CA1067678A - Treatment of flue gases - Google Patents
Treatment of flue gasesInfo
- Publication number
- CA1067678A CA1067678A CA268,371A CA268371A CA1067678A CA 1067678 A CA1067678 A CA 1067678A CA 268371 A CA268371 A CA 268371A CA 1067678 A CA1067678 A CA 1067678A
- Authority
- CA
- Canada
- Prior art keywords
- gas
- packing
- slurry
- enclosure
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003546 flue gas Substances 0.000 title description 18
- 239000007789 gas Substances 0.000 claims abstract description 186
- 238000000034 method Methods 0.000 claims abstract description 83
- 230000008569 process Effects 0.000 claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000012856 packing Methods 0.000 claims abstract description 64
- 239000002002 slurry Substances 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 alkyl mercaptans Chemical class 0.000 claims abstract description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 230000006872 improvement Effects 0.000 claims abstract description 5
- 230000001706 oxygenating effect Effects 0.000 claims abstract 3
- 238000005201 scrubbing Methods 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000011084 recovery Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 238000011144 upstream manufacturing Methods 0.000 claims description 13
- 230000003134 recirculating effect Effects 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 230000006911 nucleation Effects 0.000 claims description 9
- 238000010899 nucleation Methods 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000003518 caustics Substances 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 6
- 150000003464 sulfur compounds Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 238000009738 saturating Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 description 17
- 239000007921 spray Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052815 sulfur oxide Inorganic materials 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 5
- 239000012717 electrostatic precipitator Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000306 component Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical compound [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001237728 Precis Species 0.000 description 1
- NQHAZTDQFIYTQD-UHFFFAOYSA-N SOS Chemical class SOS NQHAZTDQFIYTQD-UHFFFAOYSA-N 0.000 description 1
- 101100054666 Streptomyces halstedii sch3 gene Proteins 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- SURLGNKAQXKNSP-DBLYXWCISA-N chlorin Chemical compound C\1=C/2\N/C(=C\C3=N/C(=C\C=4NC(/C=C\5/C=CC/1=N/5)=CC=4)/C=C3)/CC\2 SURLGNKAQXKNSP-DBLYXWCISA-N 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007775 late Effects 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
- B01D47/14—Packed scrubbers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1462—Removing mixtures of hydrogen sulfide and carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Treating Waste Gases (AREA)
Abstract
ABSTRACT OF DISCLOSURE
This invention relates to a relatively simple, efficient and economical improvement in the process for recovering odoriferous sulfur-containing compounds from a gas stream containing a member selected from the group consisting of hydrogen sulfide, lower alkyl mercaptans, lower alkyl sulfides and lower alkyl disulfides by contact with an aqueous alkaline slurry of activated carbon. The improvement comprises oxygenating said slurry and intro-ducing it to the top of an enclosure containing packing and passing it downwardly over said packing under laminar flow conditions, said gas being passed transversely through the packing in contact with said slurry, whereby the carbon has a greater effective concen ?tion at the contacting surface than in the bulk of said slurry. An apparatus is also described for carrying out the process.
This invention relates to a relatively simple, efficient and economical improvement in the process for recovering odoriferous sulfur-containing compounds from a gas stream containing a member selected from the group consisting of hydrogen sulfide, lower alkyl mercaptans, lower alkyl sulfides and lower alkyl disulfides by contact with an aqueous alkaline slurry of activated carbon. The improvement comprises oxygenating said slurry and intro-ducing it to the top of an enclosure containing packing and passing it downwardly over said packing under laminar flow conditions, said gas being passed transversely through the packing in contact with said slurry, whereby the carbon has a greater effective concen ?tion at the contacting surface than in the bulk of said slurry. An apparatus is also described for carrying out the process.
Description
10~7~78 .
This invention relates to a relatively simple efficientand economical process for removing particulates and gases such as sulfur oxides, hydrogen sulfide and organic sulfur compounds from an industrial gas stream. ~ixed emissions of this type are commonly found, for example, in Kraft and sulfite recovery processes in the pulp and paper industries. Prior art processes teach various methods of removing these types of emissions individually, however, none of the prior art teaches an econo-mical coordinated process for the removal of all of these compo-nents. Furthermore, in some cases, a prior art process for the removal of one component interferes with or reduces the efficiency of subsequent removal steps for other components.
For e~ample, emissions from Kraft recovery boilers typically consist of hydrogen sulfide and organic sulfur compounds (designated "TRS" for total reduced sulfur), S02 and ~articulates.
The organic su]fur compounds typically consist of mercaptans such as methyl mercaptan (C113SH), mercapto ethers such as dimethyl sulfide (CH3SCH3), and disulfides such as dimethyl disulfide (CH3S SCH3). Some references indicate the presence of carbonyl sulfide (COS). The quan~ity and composition of emissions are a function of boiler feed and loading, boiler operation, and proce su]~idity.
` . - .
~ ~ p~qe 3 1~:;7678 Emissions from boilers are g~nerally in the broad range of:
TRS: 10-2500 PPM (parts per million) Particuiatcs: 1-7 ~r/sdcf ~grains per standard dry cubic foot) S2: 10-200 PPM (parts per million) The permissible emissions from recovery boilers are, increasingly, being restricted by government authorities.
Although the level of restriction varies with the specific authority, the emerging standards for 1977 appear to be TRS
less than 5 PPM and particulates less than 0.08 to 0.04 gr/sdcf.
In some new boiler designs, TRS emissions can be controlled to 3-10 PPM when operating at 80-100% of design capacity, but only with close combustion control and decreased thermal efficiency. Also, particulate emissions present moré
of a problem with this type of design. Black liquor oxidation processes in combination with existlng furnaces can, with close control, maintain TRS emissions at 4-30 PPM when operating at 80-100% of design capacity, but the particulate emissions problem still exists. Electrostatic precipitators in existing recovery boilers, after an extended period of operation such as 3-5 years, are reducing particulate emissions tO levels OL O.10- .
0.25 gr/sdcf at 80-100% of design capacity. When the boilers are operated at 120% of design capacity, however, the parti-¦ culate emissions level in many cases increases to more than 1 gr/sdcf. None of these systems can readily accommodate fluctuating boiler load levels. Furthermore, electrostatic precipitators in themselves do not control TRS emissions.
'7~ ~
I`here~fore, it appears tha-t neither elec-trostatic precipitators alone, black liquor oxidation alone, nor a combination of these two wel~evaluated systems, are consistently capable of meeting the overall environmental regulations.
Recently, experimental work has been conducted on the absorption of sulfur oxides and other sulfur compounds in alkaline slurries of activated carbon. In particular, U.S. Patent Nos.
3,701,824; 2,823,766; 3,486,852; and 3,824,163 teach that water slurries of activated carbon can be used to scrub sulfur dioxide, hydrogen sulfide, and organic sulfur compounds such as mercaptans and alkyl sulfides from a gas stream. These patents appear to depend on a combination of sorption and oxidation processes. In general, these patents teach a carbon slurry concentration of about 0.1-10% by weight or higher for the cocurrent or counter-current scrubbing of sulfurous gases having hydrogen sulfide or organic sulfur compound concentrations on the order of 100-5000 PPM. These patents do not discuss the problem of the removal of particulates.
Other prior art patents disclosing alkaline scrubbing reactions are U.S. Patent Nos. 3,852,408; 3,852,409 and 3,755,990.
; U.S. Patent No. 3,324,630 teaches a process for removal of particulates from a gas stream which utilizes a crossflow scrubbing technique, The process disclosed is capable of removing very small particulates on the order of 0.1-10 microns in size.
In the U.S. Patent No. 3,957,464 issued May 18, 1976, an improvement in scrubbing is disclosed wherein the particulate-laden gas stream is first treated under substan-tially adiabatic conditions to increase its turbulence and to increase its humidity substantially to saturation at a temperature :........... . ..
~agc 5 li 10~7~78 ~1 ," , above about ~50F to initiate nucleation of sn~all particulates by condensatiol) and/or agglomeration. ~hcreafter the ~as is contacted with a scrubbing liquor-which can be recirculated through a packed enclosure, usually at a substantially constant temperature. This improvement normally eliminates the need for cooling the recirculating liquor at a savinq in material and I energy costs.
¦¦OBJECTS OF TI~E INVENTION .
Accordingly, it is a primary object of the present invention to provide a coordinated and economic process for the ~-removal of particulates and acid qases from a hot effluent Igas stream.
¦ It is specifically an object of this invention to l provide a process for scrubbing particulates, sulfur dioxide, ¦ hydrogen sulfide and organic sulfur compounds from a gas stream with an aqueous alkaline carbon slurry in a process which requires ¦!a lesser concentration of carbon than has heretofore been possible .
¦ It is also an object of this invention to provide ¦¦a wet scrubbing process for the removal of particulates which ¦ does not normally require the cooling of recycled scrubbing . ¦ liquor.
It is further an object of this invention to provide ~ a process for scrubbing particulates and sulfurous gases from ;' la gas stream as described wherein efficient removal is obtained ¦ at a minimum caustic and carbon consumption, witll reduced re-quirements for heat and power and with a lower initial cost of ~equipment.
These and other objects of the invention will become apparent from the following description.
I a page 6 ¦! ~0~7~7~3 .
BRIEF l)l~:SCRIPTION Ol;' Tlll~ DR~WINGS
FIG. 1 is a flow sheet illustrating the evaporation and recovcry boilcr portions of a typical pulping process ¦producing an effluent flue gas containin~ particulates and ¦ sulfur-containin~ gases;
¦ FIG. 2 is a schematie view of one embodiment of gas treatment apparatus of this invention;
FIG. 3 is a partially-cutaway perspective view which illustrates the structure of one form of the appara~us shown sehematically in FIG. 2;
FIG. 4 is a graph comparing the efficiency of TRS
¦~removal by laminar eontact serubbin~ with that by a turbulent contaetor;
FIG. 5 is a graph comparing the efficieney of parti-eulate removal in the process of this invention at different gas stream dew point temperatures; and ¦ FIG 6 is a schematic view of a further embodiment of ¦ gas treatment apparatus aeeording to this invention illustrating ¦optional additional treatment steps and apparatus.
This invention relates to a relatively simple efficientand economical process for removing particulates and gases such as sulfur oxides, hydrogen sulfide and organic sulfur compounds from an industrial gas stream. ~ixed emissions of this type are commonly found, for example, in Kraft and sulfite recovery processes in the pulp and paper industries. Prior art processes teach various methods of removing these types of emissions individually, however, none of the prior art teaches an econo-mical coordinated process for the removal of all of these compo-nents. Furthermore, in some cases, a prior art process for the removal of one component interferes with or reduces the efficiency of subsequent removal steps for other components.
For e~ample, emissions from Kraft recovery boilers typically consist of hydrogen sulfide and organic sulfur compounds (designated "TRS" for total reduced sulfur), S02 and ~articulates.
The organic su]fur compounds typically consist of mercaptans such as methyl mercaptan (C113SH), mercapto ethers such as dimethyl sulfide (CH3SCH3), and disulfides such as dimethyl disulfide (CH3S SCH3). Some references indicate the presence of carbonyl sulfide (COS). The quan~ity and composition of emissions are a function of boiler feed and loading, boiler operation, and proce su]~idity.
` . - .
~ ~ p~qe 3 1~:;7678 Emissions from boilers are g~nerally in the broad range of:
TRS: 10-2500 PPM (parts per million) Particuiatcs: 1-7 ~r/sdcf ~grains per standard dry cubic foot) S2: 10-200 PPM (parts per million) The permissible emissions from recovery boilers are, increasingly, being restricted by government authorities.
Although the level of restriction varies with the specific authority, the emerging standards for 1977 appear to be TRS
less than 5 PPM and particulates less than 0.08 to 0.04 gr/sdcf.
In some new boiler designs, TRS emissions can be controlled to 3-10 PPM when operating at 80-100% of design capacity, but only with close combustion control and decreased thermal efficiency. Also, particulate emissions present moré
of a problem with this type of design. Black liquor oxidation processes in combination with existlng furnaces can, with close control, maintain TRS emissions at 4-30 PPM when operating at 80-100% of design capacity, but the particulate emissions problem still exists. Electrostatic precipitators in existing recovery boilers, after an extended period of operation such as 3-5 years, are reducing particulate emissions tO levels OL O.10- .
0.25 gr/sdcf at 80-100% of design capacity. When the boilers are operated at 120% of design capacity, however, the parti-¦ culate emissions level in many cases increases to more than 1 gr/sdcf. None of these systems can readily accommodate fluctuating boiler load levels. Furthermore, electrostatic precipitators in themselves do not control TRS emissions.
'7~ ~
I`here~fore, it appears tha-t neither elec-trostatic precipitators alone, black liquor oxidation alone, nor a combination of these two wel~evaluated systems, are consistently capable of meeting the overall environmental regulations.
Recently, experimental work has been conducted on the absorption of sulfur oxides and other sulfur compounds in alkaline slurries of activated carbon. In particular, U.S. Patent Nos.
3,701,824; 2,823,766; 3,486,852; and 3,824,163 teach that water slurries of activated carbon can be used to scrub sulfur dioxide, hydrogen sulfide, and organic sulfur compounds such as mercaptans and alkyl sulfides from a gas stream. These patents appear to depend on a combination of sorption and oxidation processes. In general, these patents teach a carbon slurry concentration of about 0.1-10% by weight or higher for the cocurrent or counter-current scrubbing of sulfurous gases having hydrogen sulfide or organic sulfur compound concentrations on the order of 100-5000 PPM. These patents do not discuss the problem of the removal of particulates.
Other prior art patents disclosing alkaline scrubbing reactions are U.S. Patent Nos. 3,852,408; 3,852,409 and 3,755,990.
; U.S. Patent No. 3,324,630 teaches a process for removal of particulates from a gas stream which utilizes a crossflow scrubbing technique, The process disclosed is capable of removing very small particulates on the order of 0.1-10 microns in size.
In the U.S. Patent No. 3,957,464 issued May 18, 1976, an improvement in scrubbing is disclosed wherein the particulate-laden gas stream is first treated under substan-tially adiabatic conditions to increase its turbulence and to increase its humidity substantially to saturation at a temperature :........... . ..
~agc 5 li 10~7~78 ~1 ," , above about ~50F to initiate nucleation of sn~all particulates by condensatiol) and/or agglomeration. ~hcreafter the ~as is contacted with a scrubbing liquor-which can be recirculated through a packed enclosure, usually at a substantially constant temperature. This improvement normally eliminates the need for cooling the recirculating liquor at a savinq in material and I energy costs.
¦¦OBJECTS OF TI~E INVENTION .
Accordingly, it is a primary object of the present invention to provide a coordinated and economic process for the ~-removal of particulates and acid qases from a hot effluent Igas stream.
¦ It is specifically an object of this invention to l provide a process for scrubbing particulates, sulfur dioxide, ¦ hydrogen sulfide and organic sulfur compounds from a gas stream with an aqueous alkaline carbon slurry in a process which requires ¦!a lesser concentration of carbon than has heretofore been possible .
¦ It is also an object of this invention to provide ¦¦a wet scrubbing process for the removal of particulates which ¦ does not normally require the cooling of recycled scrubbing . ¦ liquor.
It is further an object of this invention to provide ~ a process for scrubbing particulates and sulfurous gases from ;' la gas stream as described wherein efficient removal is obtained ¦ at a minimum caustic and carbon consumption, witll reduced re-quirements for heat and power and with a lower initial cost of ~equipment.
These and other objects of the invention will become apparent from the following description.
I a page 6 ¦! ~0~7~7~3 .
BRIEF l)l~:SCRIPTION Ol;' Tlll~ DR~WINGS
FIG. 1 is a flow sheet illustrating the evaporation and recovcry boilcr portions of a typical pulping process ¦producing an effluent flue gas containin~ particulates and ¦ sulfur-containin~ gases;
¦ FIG. 2 is a schematie view of one embodiment of gas treatment apparatus of this invention;
FIG. 3 is a partially-cutaway perspective view which illustrates the structure of one form of the appara~us shown sehematically in FIG. 2;
FIG. 4 is a graph comparing the efficiency of TRS
¦~removal by laminar eontact serubbin~ with that by a turbulent contaetor;
FIG. 5 is a graph comparing the efficieney of parti-eulate removal in the process of this invention at different gas stream dew point temperatures; and ¦ FIG 6 is a schematic view of a further embodiment of ¦ gas treatment apparatus aeeording to this invention illustrating ¦optional additional treatment steps and apparatus.
2 0 ¦ . FURTHER DESCRIPTION OF THE DRAWINGS
FIG. 1 sehematieally illustrates one type of reeovery Iboiler operation as employed in pulp manufacture. The liquid ,containing sulfur eompounds and eellulose-lignin organie materials ¦ealled "black liquor", from a digester (not shown) is fed into a black liquor oxidation chamber 10 where it is exposed to oxygen.
The oxidized black liquor is then fed to a stream-heated evapora-tor 12 and a direct contact evaporator 14 where water is evapo-rated to concentrate organic material to combustible levels. The eoneentrated black liquor is then sprayed into a reeovery boiler 16 where the organic material is burned to recover heat and I chemieals. The hot effluent exhaust gases, treatment of which ~lis one o~)jec~ o~ e pres~nt invention, ~re then ~ed baek 1, ~
~I
pD~e 7 1 ~067~78 ! to evaporator 1~ to recover heat, and thcnce through an electro-st~tic preci~ or l8 to rcmove pa~ticul.ltes. The ~as exiting the elcctrostatic precipitator (not always em~loyed) contains l particula~es, SO2 and TRS, principally hydrogen sulfide but also S ¦ frequcntly containin~ organic sulfur coMpounds as hereinbefore described.
Referring now to FIG. 2, the hot inlet qas stream Si is typically at a temperature of about 300-500F and a dew l point of about 150-185~F. The gas stream may have previously ¦ been treated for preliminary particle removal by conventional I ¦ methods discussed hereinafter. The stream Si is directed by î m~ans of a washed fan 100 at a velocity of about 50 fps into a ¦ venturi 101. The gas is subjected to a liquid spray quench 102 I prior to and/or simultaneously with reaching the venturi throat ¦ 103. A plug 104 having an essentially diamond-shaped cross-section may be inserted in the venturi throat and has been found to improve the efficiency of recovery. Venturi 101 is operated iat a lower pressure drop of the gas therethrough than more conventional venturis heretofore employed to remove particulates.
The pressure drop of the gas therethrough is less than 20 and preferably less than about 10 inches of water. In particular, ; I the use of a venturi with a diamond-shaped plug as shown has been found to faeilitate the removal of intermediate-sized ¦ particles larger than about 0.8 microns at this stage of the process, and such partieles drop out of the gas stream either by action of qravity or by impinqinq contact with the spray formed in the venturi throat 103. The captured particles form ¦ D slurry in tl quench liquor, or, if soluble, dissolve ~hcrein.
i~7~7~
I`he turblllent gas stream S, cooled but still at a temperature above 150 F and moisturized to near saturation by the action of the liquid quench, is next channeled through a set of baffles 105 which are continuously washed by a wash liquor from nozzles 106. The wash liquor is drained to the bottom of the apparatus where the solids may be separated by conventional means such as screen or settling tank means or left to f`orm a slurry. The wash liquor is combined with the liquor from the venturi in sump 108 and is recirculated by pump 109.
Emerging from the baffle system, the gas is substan-tially saturated with water vapor at a temperature of at least about 150F to 212 F and nucleation of sub-micron particles occurs. It should be noted that the increase in turbulence and saturation of the gas within the enclosure defined by venturi 101, baffles 105 and the walls of housing 107 occurs under substantially adiabatic or isoenthalpic conditions. No significant heat is added to or withdrawn from the gas, the heat of the gas being employed to vaporize the small amount of moisture required and the vaporization cooling the gas by lowering its dry bulb temperature. Under equilibrium operation, with recirculating quench and wash liquor, the temperature of the liquor and gas will be near the wet bulb temperature of the incoming gas.
The gas together with the entrained, nucleated particles is then passed in an essentially horizontal path through scrubber bed 111, packed with any suitable packing material, preferably the packing material disclosed in U.S. Patent No. 2,867,425, also described in U.S. Patent No. 3,324,630, and available page 9 1~ti7ti78 commcrcially unc~er the trademark "1lellcrettes", more fully describcd hereinafter, whcre it is brouc3ht into crossflow ! contact witl~ ~I)e scrubbing liquor which is continuously sprayed , into scr~hhirlg section 111 by nozzlcs 112, 113 and 114. Al-though FIG. 2 S~IOWS a singlc scrubbinq section with three sets of nozzles, the number of sections, the size of the sections, and the number of nozzles per section ls not critical and may ¦¦ be varied to suit individual process requirements. The gas is i then passed through a second packed section 115 which is washed ¦ with recirculating wash liquid and makeup water from nozzles 116 ¦ to remove any entrained liquor containing TRS and solids. The ¦ sections shown in FIG. 2 are inclined at an angle of about 8-13 from the vertical in the direction in which the gas is moving.
¦ Such a construction is not critical but helps to prevent maldis-I tribution of the liquor in the packing and thus insures full use ¦ of the packed section. The scrubbing liquor and washing liqu~d ¦ from sections 111 and 115, respectively, together with particu-¦ lates, are drained to the bottom of the respective sections through packing support gratings which are of such size that the packing is supported while the liquid and suspended particulates pass through and into collection sumps 108 and 117 respectively.
Pumps 118 and 119 are used to recirculate the scrubbing liquar and washing liquid respectively. If desired, a single collection sump below the packed sections and venturi can replace sumps 108 and 117 and the liquor collected in the single sump can be recirculated by one or more pumps. Where two sumps are employed as shown, they can ~e separated by an overflow weir 120 whereby excess recirculating liquid, including fresh makeup water, can flow into sump 108. By this means, the concentration of salts and solids in the wash liquid in sump 117 can be maintained at ¦ a lowcr concentration than in thc liquor in sump 108.
Il pa~le l O
106767~
To replace liquids lost with tlle gas and withdrawn with slipstream 121, and to maintain thc desired concentration of carbon ancl al}:~]i during use, ail as more fully explained I)ereina~t~r, rr~sl~ ma~eup water i:; s~ ]led at 122, concentrated caustic is added at 123, and carbon slurry is added at 124.
Also as more fully explained hereinafter, activated carbon in the liquor slurry in sump 108 is aerated through submerged nozzles 125 within the sump and fed at 126 through a compressor (not shown).
Advantageously, after leaving the scrubbing section 115, the gas stream is passed through an open drainage zone 127 to allow drippage of entrained water droplets followed by a demisting chamber 128. The demisting chamber is packed with any suitable packing material, preferably the same material used to pack the scrubbers. ~ subsequent ~emisting chamber .
may also be employed. The treated gas SO from the second enclosure defined by baffles 105 and the walls of housing 107, is~substantially free of particulates larger than about 0.1 micron.
As shown in FIG. 2, a single pump 109 can be used to recirculate liquor for the baffle sprays 106 and the venturi quench 102. As a further pre-treatment, prior to the venturi - and baffles, the gas stream can optionally be passed through washed fan 100 for additional increases in humidity and turbulence and to improve the wetting of the particulates.
The fan c~n b washcd with a portion of one oE the , 10 . ,, ,7~7~
recycled aqueous liquids, for example, the makeup water from pump 119 as shown in FIG. 2.
FIG. 3 is a partially cut-away perspective view of a ground level installation similar to FIG. Z and wherein like parts have like numbers. Pumps 109 and 118 have been rearranged to pumps 130 and 131. This figure illustrates that apparatus according to this invention can be combined in a single compact housing. FIGS. 4, 5 and 6 are described hereinafter.
DESCRIPTION OF_THE PREFERRED EMBODIMENT
General Description In general, the present invention comprises the following steps:
1) In a preliminary~step, the hot particulate-laden gas containing a mixture of sulfur oxides, hydrogen sulfide, and organic sulfur compounds is treated by conventional means for the removal of particles larger than about 5 microns.
Such means are well known in the art and include a cyclone separator, a spray tower, a venturi, an electrostatic preci-pitator, and a tray column, either alone or in combination.
For example, the combination of a cyclone separator for the preliminary removal of particles and a crossflow scrubbing apparatus for the removal of very small particles is illustrated in U.S. Patent No. 3,324,630. This step is optional since the subsequent steps set forth below will remove large as well as relatively small particles. However, if a significant quantity of particles larger than about 10 microns are present, the preliminary separation step will be more economical.
~ pa~c 12 1 ~0~767~3 ¦ 2) Thc hot gas, preferably containing only particles smaller than 10 microns in size together with various sulfur contaminants, is n~xt subjected to a liquid quench immediately prior to or simultaneous with its passa~e through the low energy venturi. This treatment cools (althou~h maintaining the tempera-ture above 150F) and moisturizes the gas to a point approaching saturation conditions and introduces additional turbulence in the gas. A wetted inlet fan can also be employed prior to the venturi.
FIG. 1 sehematieally illustrates one type of reeovery Iboiler operation as employed in pulp manufacture. The liquid ,containing sulfur eompounds and eellulose-lignin organie materials ¦ealled "black liquor", from a digester (not shown) is fed into a black liquor oxidation chamber 10 where it is exposed to oxygen.
The oxidized black liquor is then fed to a stream-heated evapora-tor 12 and a direct contact evaporator 14 where water is evapo-rated to concentrate organic material to combustible levels. The eoneentrated black liquor is then sprayed into a reeovery boiler 16 where the organic material is burned to recover heat and I chemieals. The hot effluent exhaust gases, treatment of which ~lis one o~)jec~ o~ e pres~nt invention, ~re then ~ed baek 1, ~
~I
pD~e 7 1 ~067~78 ! to evaporator 1~ to recover heat, and thcnce through an electro-st~tic preci~ or l8 to rcmove pa~ticul.ltes. The ~as exiting the elcctrostatic precipitator (not always em~loyed) contains l particula~es, SO2 and TRS, principally hydrogen sulfide but also S ¦ frequcntly containin~ organic sulfur coMpounds as hereinbefore described.
Referring now to FIG. 2, the hot inlet qas stream Si is typically at a temperature of about 300-500F and a dew l point of about 150-185~F. The gas stream may have previously ¦ been treated for preliminary particle removal by conventional I ¦ methods discussed hereinafter. The stream Si is directed by î m~ans of a washed fan 100 at a velocity of about 50 fps into a ¦ venturi 101. The gas is subjected to a liquid spray quench 102 I prior to and/or simultaneously with reaching the venturi throat ¦ 103. A plug 104 having an essentially diamond-shaped cross-section may be inserted in the venturi throat and has been found to improve the efficiency of recovery. Venturi 101 is operated iat a lower pressure drop of the gas therethrough than more conventional venturis heretofore employed to remove particulates.
The pressure drop of the gas therethrough is less than 20 and preferably less than about 10 inches of water. In particular, ; I the use of a venturi with a diamond-shaped plug as shown has been found to faeilitate the removal of intermediate-sized ¦ particles larger than about 0.8 microns at this stage of the process, and such partieles drop out of the gas stream either by action of qravity or by impinqinq contact with the spray formed in the venturi throat 103. The captured particles form ¦ D slurry in tl quench liquor, or, if soluble, dissolve ~hcrein.
i~7~7~
I`he turblllent gas stream S, cooled but still at a temperature above 150 F and moisturized to near saturation by the action of the liquid quench, is next channeled through a set of baffles 105 which are continuously washed by a wash liquor from nozzles 106. The wash liquor is drained to the bottom of the apparatus where the solids may be separated by conventional means such as screen or settling tank means or left to f`orm a slurry. The wash liquor is combined with the liquor from the venturi in sump 108 and is recirculated by pump 109.
Emerging from the baffle system, the gas is substan-tially saturated with water vapor at a temperature of at least about 150F to 212 F and nucleation of sub-micron particles occurs. It should be noted that the increase in turbulence and saturation of the gas within the enclosure defined by venturi 101, baffles 105 and the walls of housing 107 occurs under substantially adiabatic or isoenthalpic conditions. No significant heat is added to or withdrawn from the gas, the heat of the gas being employed to vaporize the small amount of moisture required and the vaporization cooling the gas by lowering its dry bulb temperature. Under equilibrium operation, with recirculating quench and wash liquor, the temperature of the liquor and gas will be near the wet bulb temperature of the incoming gas.
The gas together with the entrained, nucleated particles is then passed in an essentially horizontal path through scrubber bed 111, packed with any suitable packing material, preferably the packing material disclosed in U.S. Patent No. 2,867,425, also described in U.S. Patent No. 3,324,630, and available page 9 1~ti7ti78 commcrcially unc~er the trademark "1lellcrettes", more fully describcd hereinafter, whcre it is brouc3ht into crossflow ! contact witl~ ~I)e scrubbing liquor which is continuously sprayed , into scr~hhirlg section 111 by nozzlcs 112, 113 and 114. Al-though FIG. 2 S~IOWS a singlc scrubbinq section with three sets of nozzles, the number of sections, the size of the sections, and the number of nozzles per section ls not critical and may ¦¦ be varied to suit individual process requirements. The gas is i then passed through a second packed section 115 which is washed ¦ with recirculating wash liquid and makeup water from nozzles 116 ¦ to remove any entrained liquor containing TRS and solids. The ¦ sections shown in FIG. 2 are inclined at an angle of about 8-13 from the vertical in the direction in which the gas is moving.
¦ Such a construction is not critical but helps to prevent maldis-I tribution of the liquor in the packing and thus insures full use ¦ of the packed section. The scrubbing liquor and washing liqu~d ¦ from sections 111 and 115, respectively, together with particu-¦ lates, are drained to the bottom of the respective sections through packing support gratings which are of such size that the packing is supported while the liquid and suspended particulates pass through and into collection sumps 108 and 117 respectively.
Pumps 118 and 119 are used to recirculate the scrubbing liquar and washing liquid respectively. If desired, a single collection sump below the packed sections and venturi can replace sumps 108 and 117 and the liquor collected in the single sump can be recirculated by one or more pumps. Where two sumps are employed as shown, they can ~e separated by an overflow weir 120 whereby excess recirculating liquid, including fresh makeup water, can flow into sump 108. By this means, the concentration of salts and solids in the wash liquid in sump 117 can be maintained at ¦ a lowcr concentration than in thc liquor in sump 108.
Il pa~le l O
106767~
To replace liquids lost with tlle gas and withdrawn with slipstream 121, and to maintain thc desired concentration of carbon ancl al}:~]i during use, ail as more fully explained I)ereina~t~r, rr~sl~ ma~eup water i:; s~ ]led at 122, concentrated caustic is added at 123, and carbon slurry is added at 124.
Also as more fully explained hereinafter, activated carbon in the liquor slurry in sump 108 is aerated through submerged nozzles 125 within the sump and fed at 126 through a compressor (not shown).
Advantageously, after leaving the scrubbing section 115, the gas stream is passed through an open drainage zone 127 to allow drippage of entrained water droplets followed by a demisting chamber 128. The demisting chamber is packed with any suitable packing material, preferably the same material used to pack the scrubbers. ~ subsequent ~emisting chamber .
may also be employed. The treated gas SO from the second enclosure defined by baffles 105 and the walls of housing 107, is~substantially free of particulates larger than about 0.1 micron.
As shown in FIG. 2, a single pump 109 can be used to recirculate liquor for the baffle sprays 106 and the venturi quench 102. As a further pre-treatment, prior to the venturi - and baffles, the gas stream can optionally be passed through washed fan 100 for additional increases in humidity and turbulence and to improve the wetting of the particulates.
The fan c~n b washcd with a portion of one oE the , 10 . ,, ,7~7~
recycled aqueous liquids, for example, the makeup water from pump 119 as shown in FIG. 2.
FIG. 3 is a partially cut-away perspective view of a ground level installation similar to FIG. Z and wherein like parts have like numbers. Pumps 109 and 118 have been rearranged to pumps 130 and 131. This figure illustrates that apparatus according to this invention can be combined in a single compact housing. FIGS. 4, 5 and 6 are described hereinafter.
DESCRIPTION OF_THE PREFERRED EMBODIMENT
General Description In general, the present invention comprises the following steps:
1) In a preliminary~step, the hot particulate-laden gas containing a mixture of sulfur oxides, hydrogen sulfide, and organic sulfur compounds is treated by conventional means for the removal of particles larger than about 5 microns.
Such means are well known in the art and include a cyclone separator, a spray tower, a venturi, an electrostatic preci-pitator, and a tray column, either alone or in combination.
For example, the combination of a cyclone separator for the preliminary removal of particles and a crossflow scrubbing apparatus for the removal of very small particles is illustrated in U.S. Patent No. 3,324,630. This step is optional since the subsequent steps set forth below will remove large as well as relatively small particles. However, if a significant quantity of particles larger than about 10 microns are present, the preliminary separation step will be more economical.
~ pa~c 12 1 ~0~767~3 ¦ 2) Thc hot gas, preferably containing only particles smaller than 10 microns in size together with various sulfur contaminants, is n~xt subjected to a liquid quench immediately prior to or simultaneous with its passa~e through the low energy venturi. This treatment cools (althou~h maintaining the tempera-ture above 150F) and moisturizes the gas to a point approaching saturation conditions and introduces additional turbulence in the gas. A wetted inlet fan can also be employed prior to the venturi.
3) The gas is next passed through a liquor-washed baffle system. This further cools (although still maintaining the saturation temperature above 150F) and moisturizes the gas to substantial saturation and also creates additional mixing in the gas stream.
j ~) On leaving the baffle system the substantially ¦saturated gas is at a temperature above about 150F and these conditions have promoted rapid nucleation among particles down to an initial size of about 0.1 microns or less.
5) The gas stream is next passed through one or a plurality of packed scrubbing beds in crossflow contact with a scrubbing liquor. The preferred scrubbing liquor for this inven-tion comprises an aqueous, alkaline suspension or slurry of activated carbon as more fully described hereinafter.
6) The gas stream is recovered from the scrubber unit essentially free of entrained particulate matter larger than about 0.30 microns and essentially free of sulfur compounds, the TRS
concentration being generally less than about 5 PPM. The gas may then be exhausted to the atmosphere or further treated as follows.
7) Optionally, before discharge to the atmosphere, the residual TRS in the gas stream can be further reduced by a second oxidation and scrubbing step, described and illustrated hereinafter, and/or the gas can be passed through a further I 12 ~ ~, 11 "-,;, 1~ p~J~
10~7~7~3 I
packcd croc;s~low ;cction washcd with cool water to recover hcat and furth~r r~duc~ p~rticulates. Ther~after, if desired, the c3as can be ~a~scd through a suitable d~mistin~ chamber to remove entrained droplcts of liquid, for example, a unit packed with the same matcrial as the scrubbcrs but which is not washed with any liquid.
Although the nucleation mechanism for fine particulates is not thoroughly understood, it is believed to involve conden-: sation of moisture on the fine particles and their agglomeration by collision with and bonding to other such particles, thereby increasing their effective size. Fine particulates are also thought to have a surface electrostatic charge by virtue of their high surface to mass ratio; Such charges are believed to ¦assist in the nucleation process.
!5 Adiabatic or isoenthalpic nucleation as herein dis-closed and as disclosed in U~S. Patent Mo. 3,957,464 (May 18, 1976)/ is a function of essentially three variables, the moisture content of the gas, the turbulence of the gas, and the Itemperature of the gas. Thus it has been found that adiabatic ¦nucleation is not effective below abou~ i50 saturation tempera-ture and that higher gas saturation temperatures compensate, in part, for a lesser degree of turbulence in the gas and vice versa. An increase in turbulence in the incoming gas, to a Reynolds number of at least 3000, and pre~erably of at least 10,000 or more at the time of coolin~ to saturation is necessary.
With higher satuxation gas temperatures, either the venturi or baffles, or both, can in some applications be omitted, although both are preferred. Thus, where the incomin~ gas has a saturation :', . .' . ' ', , .' '' " ' '', : ~3 . ,,1.
. .
10~i7~78 temperature o~` ahout 190F -to 2]2 F, the venturi can be omitted.
At close to 212 F saturatlon temperature, both the venturi and baffles can be omitted and a series of water jets employed. For a given set of operating conditions, the turbulence of the gas can be varied experimentally to optimize results. While it is technically feasible to raise the saturation temperature of an -incoming gas stream to a point requiring minimum turbulence, the cost of doing so is ordinarily prohibitive. Turbulence, however, can be increased comparatively inexpensively.
The packing elements or units that operate most satis-factorily in the process and apparatus of this invention are disclosed in applicant's U.S. Patent Nos. 2,867~425 and 3,324,630 and are available commercially under the trademark "Tellerettes".
"Tellerettes" provide a filamentous packing having little con-tinuous extensive surface and about 80-85% free volume therein;
the packing consisting of randomly arranged, interlocked tower packing units, the units being made up of approximately circular, integrally connected filament portions having their axes approximately tangent to a circle at approximately evenly spaced points therearound, the number of such spaced approximately circular portions being from 6 to 12 and the diameter of such circle being approximately equal to the diameter of one of such approximately circular filament portions plus the diameter of a smaller circle whose circumference is not less than the cross-sectional dimension of the filament portion in the direction ofits axis times the number of such filament portions and not greater than the circumference of one of such approximately circular filament portions. Such packing units are hereinafter referred to in the description and claims as "toroidal elements".
I`he preferred scrubbing liquor for this invention is alkaline aqueous slurry of activated carbon having a particle size range perferably in the range of 0.05-10 microns and a pH of about 8-13, more preferably 8-9.5, and most preferably S about 9.0-9.3. The alkaline material in the scrubbing liquid may be soluble sodium or potassium salt such as sodium hydroxide, sodium carbonate, or the like or a relatively insoluble alkaline earth metal salt such as lime or calcium carbonate in slurry form. Sodium hydroxide is preferred.
The removal of S0z and TRS by the scrubbing liquor is based on sorption and chemical reaction with hydroxide and oxygen.
S2 is converted to sulfates and TRS to oxidized sulfur compounds.
H2S for example is converted at least in part to Na2S203. Such compounds are not volatile and can be recirculated in the scrubbing liquor as dissolved or suspended salts. In addition to the oxidized materials, the scrubbed particulates, principally carbonates and sulfates of sodium, recirculate with the scrubbing liquor.
Maximum recirculation of scrubbing liquor is an impor-tant part of the present invention for reasons of cost andefficiency. With prior art processes the highest solids or non-volatile content, i.e. the content of materials which are essentially non-volatile at 212 F, that can be recirculated is about 15% by weight. With the present process, however, the non-volatile content may be as high as 25% and is preferably in the range of 20-25% by weight. The crossflow scrubber of this invention is stable at such high content.
Crossflow scrubbing has other important advantages in the present invention. The ratio of scrubbing liquor to gas flow rates can be varied along the depth of the packing, i.e. in the 7~78 direction of gas flow, as can the size of the packing elements.
Also different liquors of different composition or concentration can be employed and recirculated. Preferably, higher flow rates of the same scrubbing liquor are employed in upstream portions of the packing where the S02 and TRS concentrations in the gas are highest. Thus the ratio of alkali (and oxygen) to S02 and TRS (and acid particulates such as NaHS04) concentrations in the gas can be varied with the depth of packing. For example, in FIG. 2, the valves controlling nozzles 112, 113 and 114 can be adjusted to provide a high flow rate through nozzle 112, a lower rate through nozzle 113, and still a lower rate through nozzle 114. Under some conditions it has been found that, based on the same total flow rate, such a distribution of scrubbing liquor will be more efficient than an even distribution.
Similarly, it is sometimes desirable to employ larger packing elements, e.g. 2 inch toroidal elements, in upstream portlons of the packing and smaller elements, e.g. 1 inch toroidal elements in downstream portions.
Sufficient alkali and carbon are required for efficient reaction and removal of contaminants b~t excess should be avoided for economy and to limit corrosion. Alkaline pH isnecessary but the pH should be below about 9.5, and preferably 9.3, to ~;
avoid reaction with C02. With well-oxygenated, activated carbon, a carbon content between about 0.03% and 0.20% by weight is suitable and about 0.05% to 0.15% is preferred. These values are lower, for given removal efficiency, with the present invention than with prior processes because the scrubbing liquor flow in the crossflow scrubber is laminar over the packing, rather than turbulent. With laminar flow it is believed that the , :
1067~78 pn~Je 17 suspcnded c~r~on migrates to the surface of the flowing liquor and concentrates in the most active portion of the scrubber liquor, that is, the portion in contact witll the gas. Below about 200 PPM of TI~S in the gas, it has been found that a bulk concentration of carbon in the weight range of about 0.03% to 0.07%is sufficient and above 200 PPM TRS, a range of about 0.0~Oto 0.15%is sufficient. Thus a carbon concentration range between about 0.0~ to about 0.20~ by weight is preferred, the particular value selected being a function of operating conditions and TRS inlet concentration in the gas.
To maintain the non-volatile concentration in the recirculated scrubbing liquor, a slipstream of liquor is bled off and returned for processing to the material balance of the pulp process. The high non-volatile concentration in the slip-stream permitted by this invention is advantageous because a minimum of carbon and unreacted alkali are thereby withdrawn with the slipstream and less heat is required to remove water for concéntrating the salts recovered in the slipstream. Fresh makeup water and fresh alkali and carbon are added as required to maintain pH and carbon concentration in the scrubbing liquor.
For the reasons given above, the consumption of alkali and carbon in the present invention are low, generally in the range of 0.3 to 0.6 pounds carbon and about 9 to 25 pounds of alkali, measured as NaOI~, per ton of air dried pulp processed, depending on the specific process conditions and control, and the type of wood being pulped. These relatively low values are important since such consumption is estimated to constitute the .
lar~est single item of cost in operating the process, including page 18 ~067ti78 amorti~ation of equipment. Properly operated, it is estimated that the econonlic valuc of recovered salts returned to the pulp-ing proc~ss can excc~d tllc total cost of operating the flue gas ¦ treatincJ process o~ this invention.
~rlle presen~ invention also has a low cost for power and heat since the nucleation step requires low power and essentlally no heat, while the scrubbing step preferably is operated without significant cooling of either the gas or scrubbing liquor, except incidentally in withdrawing of slip-stream and adding of makeup materials. Crossflow scrubbing also has an islherently low pressure drop for the gas such that the entire process can be operated with a gas pressure drop below about 30 inches of water, and typically less. Thus the entire process is substantially adiabatic throughout and, so operated, can reduce the particulates in the exhaust gas to about 0.03gr/sdcf. If further reduction is desired, the gas can be exposed to a cooling liquid, either the scrubbing liquor itself as shown in U.S. Patent No. 3,324,630, or fresh makeup water as described herein, in either the whole of the packing of the ¦ scrubber, a portion thereof, or a separate packed section. By such cooling, where desired, particulates can be further reduced ¦ to about 0.01 ~r/sdcf.
¦ The cross sectional area of the packed scrubber is ¦ chosen to accommodate the flow rate of gas to be treated and the depth of packing, with respect to the direction of flow of the gas, is chosen to provide the required removai of contaminants to the extellt desired, greater depth providing increased r~moval within the limits of the process. The required depth pJ-JC ~9 1067~7~3 can be provide(l in continuous or separat~d sections. Scrubbing liquor flow ratcs are chosen to maintain laminar liquid flow over tIle slIrfacc of tI~c ~cking, aI-cI can be varied along the deL~tIl of ~acking as describcd.
The following examples further illustrate the present invention.
EXA;IPLE I
A series of tests were performed in an integrated recovery apparatus as illustrated in FIG. 2 with flue gases from a Kraft recovery process as illustrated in FIG. 1. Gas and~
process operating conditions are given in TABLE 1. The pressure drop of the gas in the venturi was in the range between 4 and 10 inches of water, and in the total scrubber between 7 and 13 inches of water. The depth of the packing was about 5 feet and the scrubbing liquor flow rate was varied along the depth to provide greater flow upstream of the gas than downstream.
The system was found to be capable of a 2:1 turndown, providing desirable flexibility of operation, and was relatively insensitive to variations in liquid and gas flow rates. During ¦ testing, including operation 24 hours per day 7 days per week, ¦ no solids build up, no increase in pressure drop, and no adverse I conditions such as undue foaming were observed.
1~ 3i0~7~78 P~3~ ~0 'r~131.1` 1 I
_ __~.
Gas Conclitions Inlet Outlet _ . __ _ Gas Flow 235,000 200,000 (acfm) _ _ l Temp. 300 163 l (~) , .-COIlCj SOxl 50-150 5-10 . . . -I
Conc. Particulates 1.5 0.02-0.06 (gr/sdcf) .
(PPM) , . .
1 - SOx is used to denote mixed sulfur oxides, predominantly SO2.
i .
Scrubbing Liquid Inlet Outlet . _ I
! Liquid Flow 3760 3713 , (gpm) (F) 167 167 , Venturi quench liquid - 2200 gpm at 163F
! Baffle wash liquld 700 gpm ' ~lake-up water - 50 gpm ~lake-up NaOI{ - 200-1000 lbs./hr.
! Make-up carbon - 5-15 lbs./hr.
i Air for oxygenation - approx. 1500 cfm Recycle liquid: 20 gpm 22~ soli~s i 0.1~ carbon l Pl~ 9.3 i .
! acfm - actual cubic fcet p~r minute , Pl~l - Parts per millio1l 1 rjscdf - ~3rains per stand~rd dry cubic foot of gas qpm - ~allol~s per minut~
1~RX ~ Pdllc~(l s~
_ __ _ _ _ _ _ _ ~0 I h.
.. ........... _.__.
I pa~e 21 7~78 I~X~MI'I.~ II
Tl~e purposc of this cxanlplc was to comparc the process ¦of this invention with that taught by U.S. Patent No. 3,701,824, l¦and in particlllar, to compare the efficiel-cy of a turbulcnt ¦ cantactor with the crossflow'scrubbing process of this invention l at low levels of TRS emissions. The data for this example were ¦ obtained from tests at TRS levels of about 10-100 PPM using two crossflow scrubbers and one turbulent contactor having the l following characteristics:
~ TABLE 2 ¦ Recovery Unit ~PCarbon Slurry - wt.-~
II Crossflow Scrubber 10 0.03-0.06 ¦¦ Turbulent Contactor 16 0.5 ,The results of these tests were plotted,on the basis of efficiency (on a logarithmic scale) against TRS concentration as shown in FIG. 4 wherein the solid curve represents the cross-flow data and the broken curve the turbulent contactor data.
These tests demonstrate the superior efficiency of the cross10w scrubber in removal of TRS emissions despite a ten-fold reduction in the concentration of carbon in the slurry. Furthermore, these data show tllat'the crossflow scrubbers operated at about a 30%'less pressure drop, therefore requiring less power than the turbulent contactor.
EX~MPL~ III
The purpose of this example is to,demonstrate the variation of caustic consumption and tllermal requiremcnts at varying concentrations of dissolved solids (non-volatiles) in the recycle scrubbing liquor in the stable crossflow scrubber of this invention. The data pa~e 22 i J.0ti7678 ¦Iwas obtainc~ ~rom a llit3h emi!;sion boilcr having the followiny ¦¦characteristics:
O~)cratincJ Lcvcl - G00 Tl~D
¦ TRS - 500 PPM a~.
I~arl:i culate - 1. 5 c3r/sdcf l Gas Flow - 200,000 acfm 160F Sat.
I The results are shown in Table 3 below:
T~BL~ 3 Recycle Liquor - Slip- UnreactedThermal Load Dissolved Solids stream NaOH loss For Conc. to (~ Concentration) rate (lb/ton 50% Solids (GPM)* of pulp) (BTU/}lr.) 90.5 2642.8 x 106 1 10 47.6 13.721.5 x 106 27.0 7.811.1 x 106 19.1 - 5.57.2 x 106 ?5 - 14.3 4.14.8 x 106 * Required to maintain solids concentration EXAMPLE IV
This example demonstrates the effectiveness of this invention in particulate removal, the variation of effectiveness with gas saturation temperature, and the criticality of a gas temperature above about 15 0F.
A series of tests were conducted at different gas satura-tion temperatures between 155F to 172F,without cooling the recycled scrubbing liquid, and with particulate loading ranging from 0.17 to 0.54 gr/sdcf. The recovery boiler effluent was pre-trcated with an electrostatic precipitator to remove larger particles prior to entering the scrubbing unit. These results ~ pa~e 23 ~L06~7678 are plotted in FIG. 5. The smothcd curve indicates a parti-culate emission ranging from 0.050 gr/sdcf at an operating temperature of 155F to 0.024 gr/sdcf at an operating temperature ¦of 172F, well within the proposed 1977 standard of 0.08 gr/sdcf.
EXAMPLE V
Tests similar to EXAMPLE IV were conducted with a recovery boiler effluent gas pre-treated in a direct contact evaporator. Duct thermal loss prevented conducting tests at adiabatic temperatures above 162F. However, with inlet loadings ranging from 0.8 to 3.0 gr/sdcf and with the scrubber system operating at 16 to 19 inches of waterl particulate emissions were reduced to 0.11 gr/sdcf. The particles from the evaporation were found to have hydrophobic coatings; therefore, to accelerate the initial wetting of these particles, additional turbulence was induced in the gas prior to the scrubber. ~1ith added turbulence prior to scrubbing, particulate emissions were reduced to the order of 0.03 to 0.04 gr/sdcf, again well within proposed 1977 standards.
By means of the process steps and apparatus illustrated and described above, the treated flue gases will be at a saturated temperature above about 150F and have a low con-centration of particulates and TRS, suitable for exhausting in compliance with existing governmental regulations. However, the treated gases contain valuable heat. Also, it may be desirabl ¦ in some cases to reduce TRS and/or particulates still further.
¦ Optional steps to recover heat and/or further reduce TRS and I particulates are described below.
'~3 I page 24 ~Of~7~78 Wastc heat may be recovered by passing it in heat exchange relation to a cooling fluid. In the present invention, ¦it is both convcnient and advantageous to recover heat by Ipassin~ thc gas in crossflow contact with another packed section of scrubber w~shed with clean, or relatively clean, cool water.
The additional scrubber section or enclosure can~be provided in the same housing as the other sections and the heated watex can be sent to the pulp process for utilization. The thus heated water, after extraction of its heat to re-cool it, can be -` 10 ~recirculated if desired. Compared with conventional heat-exchangers or co-current or counter-current towers, the cross-Iflow recovery unit is smaller, cheaper, less subject to ¦¦corrosion and has a lower pressure-drop and power requirement.
ilAlso, the water can be heated to approximately the temperature ¦ of the inlet gases to the section, unlike conventional exchanges and co-current towers. Further, the sump below the.
unit for collecting the heated water can be segregated into two or more portions along the direction of gas flow to provide Il water of increasing purity, downstream portions being less contaminated than upstream portions. The cool water will remove addition particulates from the gas and become contaminated thereby, especially if the water is recirculated.
It has been further discovered that the TRS in the treated flue gases, generally below about 5 PPM, can be further reduced by a second oxidative treatment by means of an oxidizing agent more powerful than oxygen. The products of this second oxidation, together with any excess oxidizing agent, are scrubbed from the gas in an additional crossflow scrubber :106'7671~ page 25 section with a recirculating alkaline scrubbing liquid similar to the scrubbing liquor employed in the previous sections, but omitting activated carbon.
Preferably, the oxidizing agent means employed in the second oxidation is a chlorine-containing gas, such as C12 ox ClO2, which is often employed in bleaching operations in pulp processing. This gas can be mixed with the previously treated flue gases in advance of the additional scrubbing section. A
slip-stream of the recirculating scrubbing liquid can be sent to the pulp bleaching operations for use, especially where the oxidizing agent employed is the same as that used in the bleachin~
process. Alternatively, bleaching agent means such as an alkali metal, preferably sodium or potassium, or alkaline earth metal, hypochlorite, permanganate or chromate; or chromic acid can be dissolved or dispersed in the alkaline scrubbing liquid employed in the additional scrubblng section.
1 Further oxidative reduction of TRS concentration and ¦~ the recovery of heat are both illustrated in FIG. 6. Flue gases 1l Si are fed by means of fan 100' into venturi 101' having a ~ diamond-shaped insert 104'. Thereafter the gases S are passed q ¦~ through baffles 105' which in this embodiment comprise a crossflow section packed with elements, preferably toroidal elements, which Ii are larger, e.g. three inches in diameter, than the elements ¦l employed in succeeding sections. In passing through ventuxi 101' !l and baffles 105l, the tuxbulence of the flue gases is increased and they are cooled to saturation, causing nucleated particulates to form.
Following passage through baffles 105', the flue gases Il pass through scrubbing sections 111' and 111" packed with 1, toroidal elements, e.g. two inch and one inch elements, respec-I tively. Sections 111' and 111" are washed with an alkaline ., ~ , . . .
page 26 ~0~7~78 aqucous liquor conta1nin~ ~xygenated, activated carbon as more fully described in connection with thc preceding embodiment.
The scrubbinq liquor is collected and recirculated from a single sump 108' and no separate washing section (115 of FIG. 2) is employed. I.iquor from sump 108' is circulated by means of pumps 201, 202 and 203 to sprays ],02' for the venturi 101', spray 204 for baffles 105', sprays 205 and 206 for scrubbing sections 111' and 111", and spray 207 for the blades of fan 100'.
To maintain liquor concentration, a slipstream 121' is returned 1 to the pulp process, and fresh caustic and carbon are added as needed at 123' and 124', respectively. Compressed air from a compres.sor (not shown) is introduced at 126' to nozzles 125' submerged in scrubbing liquor in sump 108'. ' The flue gases exiting from primary oxidizing scrubbers lll' and 111" will generally contain residual TRS, less than about 5 PPM, and a low concentration of fine particulates.
To further reduce these concentrations, an oxidizing gas more powerful than oxygen is fed at 210 into the space 211 between scrubbing sections 111" and 212. Preferably, this gas is chlorin~ , ¦ which mixes with the flue gas and causes further oxidation of the residual TRS. Sufficient chlorine should be employed for~
oxidation, but the required amounts are small in view of the low concentrations of TRS being treated.
Following admixture and treatment with oxidizing gas, ¦ the flue gases are passed through another crossflow scrubbing ¦ section 212, also containing packing, preferably one inch toroidal elements. Section 212 is washed with scrubbing liquid introduced at 213 and drains into sump 214 from whence it is recirculated by means of pump 215. This scrubbing liquid is preferably an aqueous caustic solution with the same p~l and otherwise simi.lar ~o the li uor in Sull~p 10~', cxcept that it ~ . ~ .
page 27 ~;7678 contains no ~ctivated carbon. Excess oxidizin~ gas and the l products o~ oxidation are scru~bcd from ~hc gas in section 212.
¦¦ A slipstre~m 216 of the liquicl, including scrubbcd particulates, I! the products of oxidation, and excess chlorine, is bled off and ¦ returned to the bleaching portion of the pulp process, and additional concentrated caustic added at 217 to maintain pH
and volu~e.
The twice-oxidized flue gas exi~ing from section 212 ! is then passed through another crossflow scrubbing section 220, !l also filled with packing material, preferably one inch toroidal ¦ elementsO Section 220 serves as the convenient and efficient ¦ heat exchange chamber in which the hot incoming gases contact ¦ a cool fluid, either fresh cool water or recycled cool water ¦ from the pulp facility, which is sprayed into the top of the section by means of nozzles 221 and which drains and collects by gravity into sump 222. The hot water collected in sump 222 is withdrawn by means of pump 223 to the main pulp process for recovery of heat via pipe 224. A portion of the hot water is ~ also pumped by means of pipe 225 to the inlet duct 226 for the flue gases in advance of the fan lO0'. Such relatively pure water for cooling and moisturizing the incoming gases in advance of the fan is preferable to the liquor from sump 108' to avoid the collection of precipitated solids on the walls of the ¦ incoming duct. Such collection is not normally a problem with ¦ respect to components of the apparatus downstream of the fan.
An emer~ency inlet plpe 227 is also provided to admit cooling water to quench surges of unduly hot incoming gas.
¦ As previously indicated, cooling the gases in chamber ¦ 220 will remove additional residual particulates and suspended ¦ liquids from the gas. The concentrations thereof will often be I
~ 7 page 28 too s~all to cause problems when fresh cooling water is employed, ~ut may build up with time where the cooling water is recycled.
Under such conditions, or where relatively pure water is otherwis~
desir~d, the sump 222 may be segregated into two or more sumps of increasing purity downstream in the direction of gas movement, downstream sumps providing increasingly pure water for such use.
Also, the cooling water flow rate can be adjusted to provide any desired outlet temperature for the heated water up to approximately the temperature of the gases exiting from section 212. Such heat recovery is an important part in the total economics of the process and can reduce the cost of operation considerably. In one design for treating the flue gases exiting ¦ from a 600-ton per day pulp mill, it has been found that 1.6 x 108 BTU!HR can be recovered in the form of hot water at a temperature approximating saturation temperature of the flue gases, for example 160F. .
While FIG. 6 illustrates the optional secondary oxidative treatment by means of an oxidizing gas, other suitable nongaseous oxidizing agents may be added to the liquid circulating through scrubbing section 212 through spray nozzles 213 and sump 214. Gases containing chlorine are preferred since they are effective and conveniently used, and since these are the materials commonly employed in bleaching portions of pulp processes. Excess gas, recovered in the scrubbing liquid! can be sent to such bleaching operations for use.
EXAMPLE VI
A typical design for the integrated recovery apparatus ¦ illustrated in FIG. 6, with flue gases from a pulp process as illustrated in FIG. l, has the operating conditions as shown in TABLE II be]ow, wherein the terms employed have the units and definitions stated in TABLE I.
~8 10~i7678 page 29 ,' ' ' . I
TABLE II
; Gas Conditions: Inlet (si) Outlet (So , _ Flow, ACFM 275,000 148,800 ~:Temp., dry bulb 300F. 100F.
~wet bulb 160F. 100F.
: Concentration, SOx Particulates 1.5 0.04 TRS 600 2 or less Treating Materials: Flow Rate:
, : Sump 108 (at about 163F.): :
Fan Wash (207) 150 gpm Venturi spray, top 1750 gpm Venturi insert (104') spray 750 gpm Baffle spray (204) 825 gpm Scrubbing spray (205) 3735 gpm ; Scrubbing spray (206) 3465 gpm i ; Slipstream (121') 24 gpm at about 20%
' non-volatiles Make-up carbon (124') 5-20 lbs/hr NaOH make-up (123') - 250-1200 lbs/hr , Compressed air (126') about 2000 acfm at 10 PSIG
Chlorine gas (210) 2-10 acfm Sumps 214 and 222:
Scrubbing liquid (213) 400 gpm at about 163F.
I Slipstream (216) 0.5 gpm l NaOH make-up (217) 25-125 lbs/hr Cooling Water (221) 3600 gpm at about 51F.
i Hot Water (224) . 3870 gpm at- about 156F.
I Hot Water Spray (225) 80 gpm I ~
¦¦ lbs/hr - pounds per hour PSIG - pounds per square inch gauge ¦l All gallons are U.S. measure ~ .
hile demister 128' is shown in FIG. 6 as the last packed section in the process, it can precede heat exhange section 220. Where clean water is required such position reversal ~has the advantage that entrained liquids with any impurities icontained therein are removed in advance of heat recovery. Where ~1 !
, . , 101~7~;78 p~ge 30 the units 128' and 220 are thus reversed, sump 222 can be divided into two sumps, the first (in the direction of gas flow) receiving the entrained liquid drainging from demister 128', with a separate discharge, and the second receiving the heated ~ water as shown in FIG. 2, but omitting any demister drainage.
One form of crossflow heat-exhange apparatus is described in l U.S. Patent No. 3,759,496.
In the foregoing description of concentrations of activated carbon, the concentrations stated, and the comparisons !, with prior art given, were for activated carbon of low density, made for example from wood bark. Activated carbons vary in density from about 0.0~ to about 0.5. By low density as used herein are meant those having density below about 0.2. Where Il more dense forms of activated carbon are employed, for example 1 activated carbon made from coal, the carbon concentration should be increased two to three times to compensate for its lower 1 surface area and greater tendency to settle in the slurry.
il Thus the preferred range for low density carbon is from 0.03 ~I to about 0.2% by weight of slurry as stated. The upper limit ) for high density carbons should be increased to about 0.6~.
i A similar increase is required with prior art processes and the I present invention has the advantage of lower requirements when ¦~ activated carbons of equal densities are compared. Higher ¦l amounts of carbon can be used but are not required and do not 1I provide benefits to warrant the increased cost.
I ~aving described the invention, what is claimed is:
~ i .
,, .
j ~) On leaving the baffle system the substantially ¦saturated gas is at a temperature above about 150F and these conditions have promoted rapid nucleation among particles down to an initial size of about 0.1 microns or less.
5) The gas stream is next passed through one or a plurality of packed scrubbing beds in crossflow contact with a scrubbing liquor. The preferred scrubbing liquor for this inven-tion comprises an aqueous, alkaline suspension or slurry of activated carbon as more fully described hereinafter.
6) The gas stream is recovered from the scrubber unit essentially free of entrained particulate matter larger than about 0.30 microns and essentially free of sulfur compounds, the TRS
concentration being generally less than about 5 PPM. The gas may then be exhausted to the atmosphere or further treated as follows.
7) Optionally, before discharge to the atmosphere, the residual TRS in the gas stream can be further reduced by a second oxidation and scrubbing step, described and illustrated hereinafter, and/or the gas can be passed through a further I 12 ~ ~, 11 "-,;, 1~ p~J~
10~7~7~3 I
packcd croc;s~low ;cction washcd with cool water to recover hcat and furth~r r~duc~ p~rticulates. Ther~after, if desired, the c3as can be ~a~scd through a suitable d~mistin~ chamber to remove entrained droplcts of liquid, for example, a unit packed with the same matcrial as the scrubbcrs but which is not washed with any liquid.
Although the nucleation mechanism for fine particulates is not thoroughly understood, it is believed to involve conden-: sation of moisture on the fine particles and their agglomeration by collision with and bonding to other such particles, thereby increasing their effective size. Fine particulates are also thought to have a surface electrostatic charge by virtue of their high surface to mass ratio; Such charges are believed to ¦assist in the nucleation process.
!5 Adiabatic or isoenthalpic nucleation as herein dis-closed and as disclosed in U~S. Patent Mo. 3,957,464 (May 18, 1976)/ is a function of essentially three variables, the moisture content of the gas, the turbulence of the gas, and the Itemperature of the gas. Thus it has been found that adiabatic ¦nucleation is not effective below abou~ i50 saturation tempera-ture and that higher gas saturation temperatures compensate, in part, for a lesser degree of turbulence in the gas and vice versa. An increase in turbulence in the incoming gas, to a Reynolds number of at least 3000, and pre~erably of at least 10,000 or more at the time of coolin~ to saturation is necessary.
With higher satuxation gas temperatures, either the venturi or baffles, or both, can in some applications be omitted, although both are preferred. Thus, where the incomin~ gas has a saturation :', . .' . ' ', , .' '' " ' '', : ~3 . ,,1.
. .
10~i7~78 temperature o~` ahout 190F -to 2]2 F, the venturi can be omitted.
At close to 212 F saturatlon temperature, both the venturi and baffles can be omitted and a series of water jets employed. For a given set of operating conditions, the turbulence of the gas can be varied experimentally to optimize results. While it is technically feasible to raise the saturation temperature of an -incoming gas stream to a point requiring minimum turbulence, the cost of doing so is ordinarily prohibitive. Turbulence, however, can be increased comparatively inexpensively.
The packing elements or units that operate most satis-factorily in the process and apparatus of this invention are disclosed in applicant's U.S. Patent Nos. 2,867~425 and 3,324,630 and are available commercially under the trademark "Tellerettes".
"Tellerettes" provide a filamentous packing having little con-tinuous extensive surface and about 80-85% free volume therein;
the packing consisting of randomly arranged, interlocked tower packing units, the units being made up of approximately circular, integrally connected filament portions having their axes approximately tangent to a circle at approximately evenly spaced points therearound, the number of such spaced approximately circular portions being from 6 to 12 and the diameter of such circle being approximately equal to the diameter of one of such approximately circular filament portions plus the diameter of a smaller circle whose circumference is not less than the cross-sectional dimension of the filament portion in the direction ofits axis times the number of such filament portions and not greater than the circumference of one of such approximately circular filament portions. Such packing units are hereinafter referred to in the description and claims as "toroidal elements".
I`he preferred scrubbing liquor for this invention is alkaline aqueous slurry of activated carbon having a particle size range perferably in the range of 0.05-10 microns and a pH of about 8-13, more preferably 8-9.5, and most preferably S about 9.0-9.3. The alkaline material in the scrubbing liquid may be soluble sodium or potassium salt such as sodium hydroxide, sodium carbonate, or the like or a relatively insoluble alkaline earth metal salt such as lime or calcium carbonate in slurry form. Sodium hydroxide is preferred.
The removal of S0z and TRS by the scrubbing liquor is based on sorption and chemical reaction with hydroxide and oxygen.
S2 is converted to sulfates and TRS to oxidized sulfur compounds.
H2S for example is converted at least in part to Na2S203. Such compounds are not volatile and can be recirculated in the scrubbing liquor as dissolved or suspended salts. In addition to the oxidized materials, the scrubbed particulates, principally carbonates and sulfates of sodium, recirculate with the scrubbing liquor.
Maximum recirculation of scrubbing liquor is an impor-tant part of the present invention for reasons of cost andefficiency. With prior art processes the highest solids or non-volatile content, i.e. the content of materials which are essentially non-volatile at 212 F, that can be recirculated is about 15% by weight. With the present process, however, the non-volatile content may be as high as 25% and is preferably in the range of 20-25% by weight. The crossflow scrubber of this invention is stable at such high content.
Crossflow scrubbing has other important advantages in the present invention. The ratio of scrubbing liquor to gas flow rates can be varied along the depth of the packing, i.e. in the 7~78 direction of gas flow, as can the size of the packing elements.
Also different liquors of different composition or concentration can be employed and recirculated. Preferably, higher flow rates of the same scrubbing liquor are employed in upstream portions of the packing where the S02 and TRS concentrations in the gas are highest. Thus the ratio of alkali (and oxygen) to S02 and TRS (and acid particulates such as NaHS04) concentrations in the gas can be varied with the depth of packing. For example, in FIG. 2, the valves controlling nozzles 112, 113 and 114 can be adjusted to provide a high flow rate through nozzle 112, a lower rate through nozzle 113, and still a lower rate through nozzle 114. Under some conditions it has been found that, based on the same total flow rate, such a distribution of scrubbing liquor will be more efficient than an even distribution.
Similarly, it is sometimes desirable to employ larger packing elements, e.g. 2 inch toroidal elements, in upstream portlons of the packing and smaller elements, e.g. 1 inch toroidal elements in downstream portions.
Sufficient alkali and carbon are required for efficient reaction and removal of contaminants b~t excess should be avoided for economy and to limit corrosion. Alkaline pH isnecessary but the pH should be below about 9.5, and preferably 9.3, to ~;
avoid reaction with C02. With well-oxygenated, activated carbon, a carbon content between about 0.03% and 0.20% by weight is suitable and about 0.05% to 0.15% is preferred. These values are lower, for given removal efficiency, with the present invention than with prior processes because the scrubbing liquor flow in the crossflow scrubber is laminar over the packing, rather than turbulent. With laminar flow it is believed that the , :
1067~78 pn~Je 17 suspcnded c~r~on migrates to the surface of the flowing liquor and concentrates in the most active portion of the scrubber liquor, that is, the portion in contact witll the gas. Below about 200 PPM of TI~S in the gas, it has been found that a bulk concentration of carbon in the weight range of about 0.03% to 0.07%is sufficient and above 200 PPM TRS, a range of about 0.0~Oto 0.15%is sufficient. Thus a carbon concentration range between about 0.0~ to about 0.20~ by weight is preferred, the particular value selected being a function of operating conditions and TRS inlet concentration in the gas.
To maintain the non-volatile concentration in the recirculated scrubbing liquor, a slipstream of liquor is bled off and returned for processing to the material balance of the pulp process. The high non-volatile concentration in the slip-stream permitted by this invention is advantageous because a minimum of carbon and unreacted alkali are thereby withdrawn with the slipstream and less heat is required to remove water for concéntrating the salts recovered in the slipstream. Fresh makeup water and fresh alkali and carbon are added as required to maintain pH and carbon concentration in the scrubbing liquor.
For the reasons given above, the consumption of alkali and carbon in the present invention are low, generally in the range of 0.3 to 0.6 pounds carbon and about 9 to 25 pounds of alkali, measured as NaOI~, per ton of air dried pulp processed, depending on the specific process conditions and control, and the type of wood being pulped. These relatively low values are important since such consumption is estimated to constitute the .
lar~est single item of cost in operating the process, including page 18 ~067ti78 amorti~ation of equipment. Properly operated, it is estimated that the econonlic valuc of recovered salts returned to the pulp-ing proc~ss can excc~d tllc total cost of operating the flue gas ¦ treatincJ process o~ this invention.
~rlle presen~ invention also has a low cost for power and heat since the nucleation step requires low power and essentlally no heat, while the scrubbing step preferably is operated without significant cooling of either the gas or scrubbing liquor, except incidentally in withdrawing of slip-stream and adding of makeup materials. Crossflow scrubbing also has an islherently low pressure drop for the gas such that the entire process can be operated with a gas pressure drop below about 30 inches of water, and typically less. Thus the entire process is substantially adiabatic throughout and, so operated, can reduce the particulates in the exhaust gas to about 0.03gr/sdcf. If further reduction is desired, the gas can be exposed to a cooling liquid, either the scrubbing liquor itself as shown in U.S. Patent No. 3,324,630, or fresh makeup water as described herein, in either the whole of the packing of the ¦ scrubber, a portion thereof, or a separate packed section. By such cooling, where desired, particulates can be further reduced ¦ to about 0.01 ~r/sdcf.
¦ The cross sectional area of the packed scrubber is ¦ chosen to accommodate the flow rate of gas to be treated and the depth of packing, with respect to the direction of flow of the gas, is chosen to provide the required removai of contaminants to the extellt desired, greater depth providing increased r~moval within the limits of the process. The required depth pJ-JC ~9 1067~7~3 can be provide(l in continuous or separat~d sections. Scrubbing liquor flow ratcs are chosen to maintain laminar liquid flow over tIle slIrfacc of tI~c ~cking, aI-cI can be varied along the deL~tIl of ~acking as describcd.
The following examples further illustrate the present invention.
EXA;IPLE I
A series of tests were performed in an integrated recovery apparatus as illustrated in FIG. 2 with flue gases from a Kraft recovery process as illustrated in FIG. 1. Gas and~
process operating conditions are given in TABLE 1. The pressure drop of the gas in the venturi was in the range between 4 and 10 inches of water, and in the total scrubber between 7 and 13 inches of water. The depth of the packing was about 5 feet and the scrubbing liquor flow rate was varied along the depth to provide greater flow upstream of the gas than downstream.
The system was found to be capable of a 2:1 turndown, providing desirable flexibility of operation, and was relatively insensitive to variations in liquid and gas flow rates. During ¦ testing, including operation 24 hours per day 7 days per week, ¦ no solids build up, no increase in pressure drop, and no adverse I conditions such as undue foaming were observed.
1~ 3i0~7~78 P~3~ ~0 'r~131.1` 1 I
_ __~.
Gas Conclitions Inlet Outlet _ . __ _ Gas Flow 235,000 200,000 (acfm) _ _ l Temp. 300 163 l (~) , .-COIlCj SOxl 50-150 5-10 . . . -I
Conc. Particulates 1.5 0.02-0.06 (gr/sdcf) .
(PPM) , . .
1 - SOx is used to denote mixed sulfur oxides, predominantly SO2.
i .
Scrubbing Liquid Inlet Outlet . _ I
! Liquid Flow 3760 3713 , (gpm) (F) 167 167 , Venturi quench liquid - 2200 gpm at 163F
! Baffle wash liquld 700 gpm ' ~lake-up water - 50 gpm ~lake-up NaOI{ - 200-1000 lbs./hr.
! Make-up carbon - 5-15 lbs./hr.
i Air for oxygenation - approx. 1500 cfm Recycle liquid: 20 gpm 22~ soli~s i 0.1~ carbon l Pl~ 9.3 i .
! acfm - actual cubic fcet p~r minute , Pl~l - Parts per millio1l 1 rjscdf - ~3rains per stand~rd dry cubic foot of gas qpm - ~allol~s per minut~
1~RX ~ Pdllc~(l s~
_ __ _ _ _ _ _ _ ~0 I h.
.. ........... _.__.
I pa~e 21 7~78 I~X~MI'I.~ II
Tl~e purposc of this cxanlplc was to comparc the process ¦of this invention with that taught by U.S. Patent No. 3,701,824, l¦and in particlllar, to compare the efficiel-cy of a turbulcnt ¦ cantactor with the crossflow'scrubbing process of this invention l at low levels of TRS emissions. The data for this example were ¦ obtained from tests at TRS levels of about 10-100 PPM using two crossflow scrubbers and one turbulent contactor having the l following characteristics:
~ TABLE 2 ¦ Recovery Unit ~PCarbon Slurry - wt.-~
II Crossflow Scrubber 10 0.03-0.06 ¦¦ Turbulent Contactor 16 0.5 ,The results of these tests were plotted,on the basis of efficiency (on a logarithmic scale) against TRS concentration as shown in FIG. 4 wherein the solid curve represents the cross-flow data and the broken curve the turbulent contactor data.
These tests demonstrate the superior efficiency of the cross10w scrubber in removal of TRS emissions despite a ten-fold reduction in the concentration of carbon in the slurry. Furthermore, these data show tllat'the crossflow scrubbers operated at about a 30%'less pressure drop, therefore requiring less power than the turbulent contactor.
EX~MPL~ III
The purpose of this example is to,demonstrate the variation of caustic consumption and tllermal requiremcnts at varying concentrations of dissolved solids (non-volatiles) in the recycle scrubbing liquor in the stable crossflow scrubber of this invention. The data pa~e 22 i J.0ti7678 ¦Iwas obtainc~ ~rom a llit3h emi!;sion boilcr having the followiny ¦¦characteristics:
O~)cratincJ Lcvcl - G00 Tl~D
¦ TRS - 500 PPM a~.
I~arl:i culate - 1. 5 c3r/sdcf l Gas Flow - 200,000 acfm 160F Sat.
I The results are shown in Table 3 below:
T~BL~ 3 Recycle Liquor - Slip- UnreactedThermal Load Dissolved Solids stream NaOH loss For Conc. to (~ Concentration) rate (lb/ton 50% Solids (GPM)* of pulp) (BTU/}lr.) 90.5 2642.8 x 106 1 10 47.6 13.721.5 x 106 27.0 7.811.1 x 106 19.1 - 5.57.2 x 106 ?5 - 14.3 4.14.8 x 106 * Required to maintain solids concentration EXAMPLE IV
This example demonstrates the effectiveness of this invention in particulate removal, the variation of effectiveness with gas saturation temperature, and the criticality of a gas temperature above about 15 0F.
A series of tests were conducted at different gas satura-tion temperatures between 155F to 172F,without cooling the recycled scrubbing liquid, and with particulate loading ranging from 0.17 to 0.54 gr/sdcf. The recovery boiler effluent was pre-trcated with an electrostatic precipitator to remove larger particles prior to entering the scrubbing unit. These results ~ pa~e 23 ~L06~7678 are plotted in FIG. 5. The smothcd curve indicates a parti-culate emission ranging from 0.050 gr/sdcf at an operating temperature of 155F to 0.024 gr/sdcf at an operating temperature ¦of 172F, well within the proposed 1977 standard of 0.08 gr/sdcf.
EXAMPLE V
Tests similar to EXAMPLE IV were conducted with a recovery boiler effluent gas pre-treated in a direct contact evaporator. Duct thermal loss prevented conducting tests at adiabatic temperatures above 162F. However, with inlet loadings ranging from 0.8 to 3.0 gr/sdcf and with the scrubber system operating at 16 to 19 inches of waterl particulate emissions were reduced to 0.11 gr/sdcf. The particles from the evaporation were found to have hydrophobic coatings; therefore, to accelerate the initial wetting of these particles, additional turbulence was induced in the gas prior to the scrubber. ~1ith added turbulence prior to scrubbing, particulate emissions were reduced to the order of 0.03 to 0.04 gr/sdcf, again well within proposed 1977 standards.
By means of the process steps and apparatus illustrated and described above, the treated flue gases will be at a saturated temperature above about 150F and have a low con-centration of particulates and TRS, suitable for exhausting in compliance with existing governmental regulations. However, the treated gases contain valuable heat. Also, it may be desirabl ¦ in some cases to reduce TRS and/or particulates still further.
¦ Optional steps to recover heat and/or further reduce TRS and I particulates are described below.
'~3 I page 24 ~Of~7~78 Wastc heat may be recovered by passing it in heat exchange relation to a cooling fluid. In the present invention, ¦it is both convcnient and advantageous to recover heat by Ipassin~ thc gas in crossflow contact with another packed section of scrubber w~shed with clean, or relatively clean, cool water.
The additional scrubber section or enclosure can~be provided in the same housing as the other sections and the heated watex can be sent to the pulp process for utilization. The thus heated water, after extraction of its heat to re-cool it, can be -` 10 ~recirculated if desired. Compared with conventional heat-exchangers or co-current or counter-current towers, the cross-Iflow recovery unit is smaller, cheaper, less subject to ¦¦corrosion and has a lower pressure-drop and power requirement.
ilAlso, the water can be heated to approximately the temperature ¦ of the inlet gases to the section, unlike conventional exchanges and co-current towers. Further, the sump below the.
unit for collecting the heated water can be segregated into two or more portions along the direction of gas flow to provide Il water of increasing purity, downstream portions being less contaminated than upstream portions. The cool water will remove addition particulates from the gas and become contaminated thereby, especially if the water is recirculated.
It has been further discovered that the TRS in the treated flue gases, generally below about 5 PPM, can be further reduced by a second oxidative treatment by means of an oxidizing agent more powerful than oxygen. The products of this second oxidation, together with any excess oxidizing agent, are scrubbed from the gas in an additional crossflow scrubber :106'7671~ page 25 section with a recirculating alkaline scrubbing liquid similar to the scrubbing liquor employed in the previous sections, but omitting activated carbon.
Preferably, the oxidizing agent means employed in the second oxidation is a chlorine-containing gas, such as C12 ox ClO2, which is often employed in bleaching operations in pulp processing. This gas can be mixed with the previously treated flue gases in advance of the additional scrubbing section. A
slip-stream of the recirculating scrubbing liquid can be sent to the pulp bleaching operations for use, especially where the oxidizing agent employed is the same as that used in the bleachin~
process. Alternatively, bleaching agent means such as an alkali metal, preferably sodium or potassium, or alkaline earth metal, hypochlorite, permanganate or chromate; or chromic acid can be dissolved or dispersed in the alkaline scrubbing liquid employed in the additional scrubblng section.
1 Further oxidative reduction of TRS concentration and ¦~ the recovery of heat are both illustrated in FIG. 6. Flue gases 1l Si are fed by means of fan 100' into venturi 101' having a ~ diamond-shaped insert 104'. Thereafter the gases S are passed q ¦~ through baffles 105' which in this embodiment comprise a crossflow section packed with elements, preferably toroidal elements, which Ii are larger, e.g. three inches in diameter, than the elements ¦l employed in succeeding sections. In passing through ventuxi 101' !l and baffles 105l, the tuxbulence of the flue gases is increased and they are cooled to saturation, causing nucleated particulates to form.
Following passage through baffles 105', the flue gases Il pass through scrubbing sections 111' and 111" packed with 1, toroidal elements, e.g. two inch and one inch elements, respec-I tively. Sections 111' and 111" are washed with an alkaline ., ~ , . . .
page 26 ~0~7~78 aqucous liquor conta1nin~ ~xygenated, activated carbon as more fully described in connection with thc preceding embodiment.
The scrubbinq liquor is collected and recirculated from a single sump 108' and no separate washing section (115 of FIG. 2) is employed. I.iquor from sump 108' is circulated by means of pumps 201, 202 and 203 to sprays ],02' for the venturi 101', spray 204 for baffles 105', sprays 205 and 206 for scrubbing sections 111' and 111", and spray 207 for the blades of fan 100'.
To maintain liquor concentration, a slipstream 121' is returned 1 to the pulp process, and fresh caustic and carbon are added as needed at 123' and 124', respectively. Compressed air from a compres.sor (not shown) is introduced at 126' to nozzles 125' submerged in scrubbing liquor in sump 108'. ' The flue gases exiting from primary oxidizing scrubbers lll' and 111" will generally contain residual TRS, less than about 5 PPM, and a low concentration of fine particulates.
To further reduce these concentrations, an oxidizing gas more powerful than oxygen is fed at 210 into the space 211 between scrubbing sections 111" and 212. Preferably, this gas is chlorin~ , ¦ which mixes with the flue gas and causes further oxidation of the residual TRS. Sufficient chlorine should be employed for~
oxidation, but the required amounts are small in view of the low concentrations of TRS being treated.
Following admixture and treatment with oxidizing gas, ¦ the flue gases are passed through another crossflow scrubbing ¦ section 212, also containing packing, preferably one inch toroidal elements. Section 212 is washed with scrubbing liquid introduced at 213 and drains into sump 214 from whence it is recirculated by means of pump 215. This scrubbing liquid is preferably an aqueous caustic solution with the same p~l and otherwise simi.lar ~o the li uor in Sull~p 10~', cxcept that it ~ . ~ .
page 27 ~;7678 contains no ~ctivated carbon. Excess oxidizin~ gas and the l products o~ oxidation are scru~bcd from ~hc gas in section 212.
¦¦ A slipstre~m 216 of the liquicl, including scrubbcd particulates, I! the products of oxidation, and excess chlorine, is bled off and ¦ returned to the bleaching portion of the pulp process, and additional concentrated caustic added at 217 to maintain pH
and volu~e.
The twice-oxidized flue gas exi~ing from section 212 ! is then passed through another crossflow scrubbing section 220, !l also filled with packing material, preferably one inch toroidal ¦ elementsO Section 220 serves as the convenient and efficient ¦ heat exchange chamber in which the hot incoming gases contact ¦ a cool fluid, either fresh cool water or recycled cool water ¦ from the pulp facility, which is sprayed into the top of the section by means of nozzles 221 and which drains and collects by gravity into sump 222. The hot water collected in sump 222 is withdrawn by means of pump 223 to the main pulp process for recovery of heat via pipe 224. A portion of the hot water is ~ also pumped by means of pipe 225 to the inlet duct 226 for the flue gases in advance of the fan lO0'. Such relatively pure water for cooling and moisturizing the incoming gases in advance of the fan is preferable to the liquor from sump 108' to avoid the collection of precipitated solids on the walls of the ¦ incoming duct. Such collection is not normally a problem with ¦ respect to components of the apparatus downstream of the fan.
An emer~ency inlet plpe 227 is also provided to admit cooling water to quench surges of unduly hot incoming gas.
¦ As previously indicated, cooling the gases in chamber ¦ 220 will remove additional residual particulates and suspended ¦ liquids from the gas. The concentrations thereof will often be I
~ 7 page 28 too s~all to cause problems when fresh cooling water is employed, ~ut may build up with time where the cooling water is recycled.
Under such conditions, or where relatively pure water is otherwis~
desir~d, the sump 222 may be segregated into two or more sumps of increasing purity downstream in the direction of gas movement, downstream sumps providing increasingly pure water for such use.
Also, the cooling water flow rate can be adjusted to provide any desired outlet temperature for the heated water up to approximately the temperature of the gases exiting from section 212. Such heat recovery is an important part in the total economics of the process and can reduce the cost of operation considerably. In one design for treating the flue gases exiting ¦ from a 600-ton per day pulp mill, it has been found that 1.6 x 108 BTU!HR can be recovered in the form of hot water at a temperature approximating saturation temperature of the flue gases, for example 160F. .
While FIG. 6 illustrates the optional secondary oxidative treatment by means of an oxidizing gas, other suitable nongaseous oxidizing agents may be added to the liquid circulating through scrubbing section 212 through spray nozzles 213 and sump 214. Gases containing chlorine are preferred since they are effective and conveniently used, and since these are the materials commonly employed in bleaching portions of pulp processes. Excess gas, recovered in the scrubbing liquid! can be sent to such bleaching operations for use.
EXAMPLE VI
A typical design for the integrated recovery apparatus ¦ illustrated in FIG. 6, with flue gases from a pulp process as illustrated in FIG. l, has the operating conditions as shown in TABLE II be]ow, wherein the terms employed have the units and definitions stated in TABLE I.
~8 10~i7678 page 29 ,' ' ' . I
TABLE II
; Gas Conditions: Inlet (si) Outlet (So , _ Flow, ACFM 275,000 148,800 ~:Temp., dry bulb 300F. 100F.
~wet bulb 160F. 100F.
: Concentration, SOx Particulates 1.5 0.04 TRS 600 2 or less Treating Materials: Flow Rate:
, : Sump 108 (at about 163F.): :
Fan Wash (207) 150 gpm Venturi spray, top 1750 gpm Venturi insert (104') spray 750 gpm Baffle spray (204) 825 gpm Scrubbing spray (205) 3735 gpm ; Scrubbing spray (206) 3465 gpm i ; Slipstream (121') 24 gpm at about 20%
' non-volatiles Make-up carbon (124') 5-20 lbs/hr NaOH make-up (123') - 250-1200 lbs/hr , Compressed air (126') about 2000 acfm at 10 PSIG
Chlorine gas (210) 2-10 acfm Sumps 214 and 222:
Scrubbing liquid (213) 400 gpm at about 163F.
I Slipstream (216) 0.5 gpm l NaOH make-up (217) 25-125 lbs/hr Cooling Water (221) 3600 gpm at about 51F.
i Hot Water (224) . 3870 gpm at- about 156F.
I Hot Water Spray (225) 80 gpm I ~
¦¦ lbs/hr - pounds per hour PSIG - pounds per square inch gauge ¦l All gallons are U.S. measure ~ .
hile demister 128' is shown in FIG. 6 as the last packed section in the process, it can precede heat exhange section 220. Where clean water is required such position reversal ~has the advantage that entrained liquids with any impurities icontained therein are removed in advance of heat recovery. Where ~1 !
, . , 101~7~;78 p~ge 30 the units 128' and 220 are thus reversed, sump 222 can be divided into two sumps, the first (in the direction of gas flow) receiving the entrained liquid drainging from demister 128', with a separate discharge, and the second receiving the heated ~ water as shown in FIG. 2, but omitting any demister drainage.
One form of crossflow heat-exhange apparatus is described in l U.S. Patent No. 3,759,496.
In the foregoing description of concentrations of activated carbon, the concentrations stated, and the comparisons !, with prior art given, were for activated carbon of low density, made for example from wood bark. Activated carbons vary in density from about 0.0~ to about 0.5. By low density as used herein are meant those having density below about 0.2. Where Il more dense forms of activated carbon are employed, for example 1 activated carbon made from coal, the carbon concentration should be increased two to three times to compensate for its lower 1 surface area and greater tendency to settle in the slurry.
il Thus the preferred range for low density carbon is from 0.03 ~I to about 0.2% by weight of slurry as stated. The upper limit ) for high density carbons should be increased to about 0.6~.
i A similar increase is required with prior art processes and the I present invention has the advantage of lower requirements when ¦~ activated carbons of equal densities are compared. Higher ¦l amounts of carbon can be used but are not required and do not 1I provide benefits to warrant the increased cost.
I ~aving described the invention, what is claimed is:
~ i .
,, .
Claims (37)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for treating an effluent gas contain-ing entrained particulates a portion of which are below 1 micron in size, acid gas components, and a compound selected from the group consisting of H2S, lower alkyl mercaptans, lower alkyl sulfides and lower alkyl disul-fides, said gas having a temperature above 150°F., which comprises:
a. initiating nucleation of the particulates in a first enclosure by treating the gas to increase its turbu-lence and to increase its humidity substantially to saturation at a temperature above about 150°F. to about 212°F. under substantially adiabatic conditions, the pressure drop of said gas in said first enclosure being less than about 20 inches of water;
b. passing said saturated gas which is at a temperature above about 150°F. to about 212°F. in a substantially horizontal path through a second enclosure containing packing;
c. passing a scrubbing liquor comprising an aqueous alkaline slurry of activated, oxygenated carbon down-wardly over said packing under laminar flow conditions;
d. exhausting said gas from said second enclosure;
and, e. collecting at least a portion of said liquid after passage through said packing and recirculating said liquid portion to said packing, said recirculating liquid portion containing at least about 15% non-volatile material by weight.
a. initiating nucleation of the particulates in a first enclosure by treating the gas to increase its turbu-lence and to increase its humidity substantially to saturation at a temperature above about 150°F. to about 212°F. under substantially adiabatic conditions, the pressure drop of said gas in said first enclosure being less than about 20 inches of water;
b. passing said saturated gas which is at a temperature above about 150°F. to about 212°F. in a substantially horizontal path through a second enclosure containing packing;
c. passing a scrubbing liquor comprising an aqueous alkaline slurry of activated, oxygenated carbon down-wardly over said packing under laminar flow conditions;
d. exhausting said gas from said second enclosure;
and, e. collecting at least a portion of said liquid after passage through said packing and recirculating said liquid portion to said packing, said recirculating liquid portion containing at least about 15% non-volatile material by weight.
2. The process of claim i wherein the increase in turbulence of the gas stream is sufficient to reduce the particulate content of said exhausted gas to not more than about 0.08 gr/sdcf.
3. The process according to claim 1 wherein the turbulence of the gas is increased in said first enclosure to a Reynolds number greater than about 10,000 the pressure drop of the gas in passing through said first enclosure being below about 20 inches of water.
4. The process of claim 3 wherein said increase in turbulence and increase in humidity is by the step of pass-ing said gas stream through a venturi and simultaneously quenching it by contact with an aqueous quenching liquor.
5. The process of claim 3 wherein said increase in turbulence and increase in humidity is by the step of pass-ing said gas stream through a set of baffles which are con-tinuously washed with an aqueous washing liquor.
6. The process of claim 3 wherein said increase in turbulence and increase in humidity is by the steps of passing said gas stream through a venturi and simultaneously quenching it by contact with a recirculated portion of said scrubbing liquor and passing the gas stream through a set of baffles which are continuously washed with a recirculated portion of said scrubbing liquor.
7. The process according to claim 1 wherein said slurry has a pH below about 9.5 and a concentration of acti-vated carbon between about 0.03% and about 0.6% by weight.
8. The process according to claim 1 wherein said slurry is recirculated through said packing at a substan-tially constant temperature, which is approximately the same as the gas which is above about 150°F. to about 212°F.
9. The process of claim 1 comprising the further step of bringing said gas from said second enclosure into contact with an aqueous washing liquid which is at a temp-erature below that of the gas to remove a further portion of residual contaminants.
10. The process according to claim 1 wherein a portion of said slurry is recirculated to said first enclo-sure to provide moisture for saturation therein, said another portion of said slurry is recirculated through said packing, said slurry having a constant heat content except for withdrawal of a slipstream and addition of makeup materials sufficient to maintain the volume, concentrations and pH thereof.
11. The process according to claim 1 wherein the flow rate of slurry is greater in upstream portions of said pack-ing than in downstream portions of said packing, said upstream and downstream portions being with respect to the direction of flow of the gas, whereby greater amounts of alkali and carbon contact the gas at locations where the gas has relatively high concentrations of components to be removed therefrom.
12. The process according to claim 1 wherein said slurry is collected in a sump below said packing and wherein said carbon is oxygenated in said sump.
13. The process according to claim 11 wherein the pack-ing comprises a plurality of toroidal elements, said elements being larger in upstream portions than in downstream portions of said packing, said upstream and downstream portions being with respect to the direction of flow of the gas therethrough.
14. The process of claim 1 wherein contact between said effluent gas and said slurry causes oxidation and removal of at least a portion of said sulfur compounds, the process including as a further step, subsequently contacting said effluent gas with oxidizing agent means more powerful than oxygen and scrubbing the gas with an alkaline aqueous liquid to remove additional sulfur compounds therefrom.
15. The process of claim 14 wherein said oxidizing agent means is chromic acid, a chlorine containing gas, or an alkali metal or alkaline earth metal hypochlorite, permanganate or chromate.
16. The process of claim 15 wherein said oxidizing agent means is chlorine and said alkaline aqueous liquid has a pH less than about 9.5.
17. A process for treating effluent gases from a pulp recovery boiler, said gas containing particulates a portion of which are below 1 micron in size, oxides of sulfur, hyd-rogen sulfide and organic sulfur compounds, said effluent gases having a temperature above about 150°F., said process comprising as steps:
a. treating said gas in a first enclosure to increase its turbulence to a Reynolds number of at least about 10,000 and to increase its humidity to satura-tion at a temperature above about 150°F. and under substantially adiabatic conditions, said first enclosure including a low energy venturi, the pressure drop of the gas in passing through said first enclo-sure being less than about 20 inches of water, b. thereafter passing said gas in a substantially hori-zontal path through a second enclosure containing packing elements, c. passing an aqueous alkaline slurry of oxygenated, activated carbon downwardly over said packing and through said second enclosure under substantially laminar flow conditions, the flow rate of the slurry through upstream portions of the packing exceeds the flow rate through downstream portions of the packing, said upstream and downstream portions being with respect to the direction of gas flow through the packing, d. recirculating said slurry at a pH of less than about 9.5, at a non-volatile content of between at least about 15% by weight, a carbon concentration of between about 0.03% to 0.6% by weight, and at a substantially constant temperature approximately the same as said gas saturation temperature which is above about 150°F to about 212°F., and e. exhausting said gas from the second en-closure.
a. treating said gas in a first enclosure to increase its turbulence to a Reynolds number of at least about 10,000 and to increase its humidity to satura-tion at a temperature above about 150°F. and under substantially adiabatic conditions, said first enclosure including a low energy venturi, the pressure drop of the gas in passing through said first enclo-sure being less than about 20 inches of water, b. thereafter passing said gas in a substantially hori-zontal path through a second enclosure containing packing elements, c. passing an aqueous alkaline slurry of oxygenated, activated carbon downwardly over said packing and through said second enclosure under substantially laminar flow conditions, the flow rate of the slurry through upstream portions of the packing exceeds the flow rate through downstream portions of the packing, said upstream and downstream portions being with respect to the direction of gas flow through the packing, d. recirculating said slurry at a pH of less than about 9.5, at a non-volatile content of between at least about 15% by weight, a carbon concentration of between about 0.03% to 0.6% by weight, and at a substantially constant temperature approximately the same as said gas saturation temperature which is above about 150°F to about 212°F., and e. exhausting said gas from the second en-closure.
18. The process according to claim 17 wherein the consumption of carbon is less than about 0.6 pounds and the consumption of caustic as NaOH is less than about 25 pounds per ton of air dried pulp processed.
19. The process according to claim 17 wherein a portion of said slurry is recirculated to said first enclo-sure to provide the water to saturate said gas, the slurry being recirculated at constant heat content except for withdrawal of a slipstream and addition of makeup sufficient to maintain volume, concentration and pH thereof.
20. The process according to claim 19 wherein said slurry is collected in a sump below at least one of said enclosures and wherein said carbon is oxygenated in said sump.
21. The process according to claim 17 wherein the packing elements in an upstream portion of the packing are larger than the elements in a downstream portion.
22. The process of claim 17 comprising the further step of bringing said gas from said second enclosure into contact with an aqueous washing liquid which is at a temperature below that of the gas to remove a further portion of residual contaminants.
23. The process according to claim 17 wherein said gas is introduced into said first enclosure by means of a fan wetted with an aqueous liquid.
24. The process of claim 17 comprising as a further subsequent step, mixing chlorine with the gas and scrubbing additional sulfur compounds therefrom with an alkaline aqueous liquid having a pH less than about 9.5.
25. The process of claim 1 comprising the further subsequent step of passing said gas horizontally through an additional enclosure containing packing, and passing a fluid cooler than said gas downwardly over said packing to recover heat from the gas.
26. The method according to claim 17 wherein said slurry has a concentration of activated carbon of low density between about 0.03% and about 0.2% by weight.
27. Apparatus for treating effluent gas having a temperature above about 150°F. and containing contaminants to be removed, said apparatus comprising (a) a first enclo-sure and within said first enclosure, a washed venturi for increasing the turbulence of the gas and for saturating the gas with moisture under substantially adiabatic conditions at a temperature above about 150°F. up to about 212°F., said venturi having a gas pressure drop therethrough less than about 20 inches of water; (b) a second enclosure and, within said second enclosure, a packing material; means for passing said gas in a substantially horizontally path through said second enclosure; means for passing an aqueous alkaline carbon slurry downwardly over said packing in substantially laminar flow, means for varying the flow rate of slurry over said packing such that portions of the packing upstream can receive a greater flow than down-stream portions, said upstream and downstream portions being with respect to the direction of gas flow therethrough;
(c) means for collecting and recirculating said slurry;
(d) means for oxygenating said carbon; (e) means for withdrawing portions of said slurry and means for adding fresh alkali and carbon to maintain a predetermined volume of slurry in the apparatus and to maintain the pH, the carbon concentration, and the non-volatile content; (f) a third enclosure filled with packing material downstream of said second enclosure with respect to the gas flow path, said third enclosure being disposed substantially vertically across the horizontal flow path of said gas, and means for passing water at a temperature below the temperature of the gas downwardly over said packing in the additional enclosure in heat exchange contact with the gas; and (g) means for exhausting said gas.
(c) means for collecting and recirculating said slurry;
(d) means for oxygenating said carbon; (e) means for withdrawing portions of said slurry and means for adding fresh alkali and carbon to maintain a predetermined volume of slurry in the apparatus and to maintain the pH, the carbon concentration, and the non-volatile content; (f) a third enclosure filled with packing material downstream of said second enclosure with respect to the gas flow path, said third enclosure being disposed substantially vertically across the horizontal flow path of said gas, and means for passing water at a temperature below the temperature of the gas downwardly over said packing in the additional enclosure in heat exchange contact with the gas; and (g) means for exhausting said gas.
28. Apparatus according to claim 27 wherein said apparatus is housed in a single, compact housing and wherein the means for collecting the slurry comprises a sump within the housing and below at least one of said enclosures, the means for oxygenating said carbon being located in said sump.
29. Apparatus according to claim 27 further comprising an additional enclosure containing packing material, said additional enclosure being disposed substantially vertically across the horizontally flow path of said gas downstream of said second enclosure means for passing an aqueous alka-line liquid downwardly over said packing, means for collecting and recirculating said liquid, means for con-tacting said gas with an oxidizing agent in the third enclosure or in a space between said second and third enclo-sures, and means for adding fresh alkali to said liquid to maintain substantially constant volume and pH.
30. A process for treating an effluent gas at a temp-erature above about 150°F. and containing particulates a portion of which are below 1 micron in size, acid gas components, and oxidizable hydrogen and lower alkyl compounds of sulfur, the process comprising as steps:
a. treating said gas in a first enclosure to increase its turbulence to a Reynolds number of at least about 10,000 and to increase its humidity to satur-ation at a temperature above about 150°F. and under substantially adiabatic conditions, the pressure drop of the gas in passing through said first enclosure being less than about 20 inches of water;
b. thereafter passing said gas in a substantially hori-zontal path through a second enclosure containing packing;
c. passing an aqueous alkaline slurry of oxygenated, activated carbon downwardly over said packing and through said second enclosure under substantially laminar flow conditions;
d. recirculating at least a portion of said slurry at a substantially constant temperature approximately the same as said gas saturation temperature, approximately the same as the saturated gas which is above about 150°F.
to about 212°F, a pH of less than about 9.5, a non-volatile content of at least about 15% by weight, and a carbon concentration of between about 0.03 per cent to 0. 6 per cent by weight;
e. passing said gas in a substantially horizontal path through an additional enclosure containing packing in heat exchange relation with water cooler than said gas, said water passing downwardly over said packing; and f. exhausting said gas.
a. treating said gas in a first enclosure to increase its turbulence to a Reynolds number of at least about 10,000 and to increase its humidity to satur-ation at a temperature above about 150°F. and under substantially adiabatic conditions, the pressure drop of the gas in passing through said first enclosure being less than about 20 inches of water;
b. thereafter passing said gas in a substantially hori-zontal path through a second enclosure containing packing;
c. passing an aqueous alkaline slurry of oxygenated, activated carbon downwardly over said packing and through said second enclosure under substantially laminar flow conditions;
d. recirculating at least a portion of said slurry at a substantially constant temperature approximately the same as said gas saturation temperature, approximately the same as the saturated gas which is above about 150°F.
to about 212°F, a pH of less than about 9.5, a non-volatile content of at least about 15% by weight, and a carbon concentration of between about 0.03 per cent to 0. 6 per cent by weight;
e. passing said gas in a substantially horizontal path through an additional enclosure containing packing in heat exchange relation with water cooler than said gas, said water passing downwardly over said packing; and f. exhausting said gas.
31. The process of claim 30 comprising the additional step, after passage through said second enclosure, of con-tacting the gas with oxidizing means more powerful than oxygen and cross-flow scrubbing additional oxidized com-pounds of sulfur from the gas with an alkaline aqueous liquid.
32. The process of claim 31 wherein said oxidizing means is chlorine.
33. In a process for the adsorption, oxidation and removal of odoriferous sulfur-containing compounds from a gas stream containing a member selected from the group con-sisting of H2S, lower alkyl mercaptans, lower alkyl sulfides, and lower alkyl disulfides by contact with an aqueous alka-line slurry of activated carbon, the improvement wherein said slurry is oxygenated and introduced to the top of an enclo-sure containing packing and passed downwardly over said packing under laminar flow conditions, and said gas is passed transversely through the packing in contact with said slurry; whereby the carbon has a greater effective concen-tration at the contacting surface than in the bulk of said slurry.
34. The process according to claim 33 wherein said packing comprises a plurality of toroidal packing elements.
35. The process according to claim 33, wherein the carbon concentration in said slurry is between about 0.03 and about 0.6% by weight, the slurry has a pH below about 9.5, and said slurry is recycled at a substantially constant temperature with a non-volatile content of at least about 15% by weight.
36. The process according to claim 33 comprising the further step of recovering heat by passing said gas, after contact with said alkaline carbon slurry, transversely through another packed enclosure, and passing water cooler than the gas downwardly over said packing in heat exchange contact with the gas.
37. The process according to claim 33 comprising a second oxidative step of contacting said gas, subsequent to exposure to said carbon slurry, with an oxidizing agent more powerful than oxygen and cross-flow scrubbing additional compounds of sulfur therefrom with an alkaline aqueous liquid.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/652,634 US4049399A (en) | 1975-04-08 | 1976-01-26 | Treatment of flue gases |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1067678A true CA1067678A (en) | 1979-12-11 |
Family
ID=24617564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA268,371A Expired CA1067678A (en) | 1976-01-26 | 1976-12-21 | Treatment of flue gases |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5291777A (en) |
| AU (1) | AU514657B2 (en) |
| CA (1) | CA1067678A (en) |
| SE (1) | SE7700581L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116891297A (en) * | 2023-09-08 | 2023-10-17 | 北京泷涛环境科技有限公司 | Recyclable cyclic treatment method based on iron-sulfur morphology transformation and treated filler |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5920370B2 (en) * | 1979-06-20 | 1984-05-12 | 株式会社東芝 | How to purify foul-smelling gas |
| JPS56115618A (en) * | 1980-02-16 | 1981-09-10 | Toshiba Corp | Malodorous gas cleaning method |
| JPS5756023A (en) * | 1980-09-22 | 1982-04-03 | Toshiba Corp | Method and device for removing malodorous gas |
-
1976
- 1976-12-21 CA CA268,371A patent/CA1067678A/en not_active Expired
-
1977
- 1977-01-04 AU AU21018/77A patent/AU514657B2/en not_active Ceased
- 1977-01-20 SE SE7700581A patent/SE7700581L/en not_active Application Discontinuation
- 1977-01-25 JP JP721477A patent/JPS5291777A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116891297A (en) * | 2023-09-08 | 2023-10-17 | 北京泷涛环境科技有限公司 | Recyclable cyclic treatment method based on iron-sulfur morphology transformation and treated filler |
| CN116891297B (en) * | 2023-09-08 | 2023-12-01 | 北京泷涛环境科技有限公司 | Recyclable cyclic treatment method based on iron-sulfur morphology transformation and treated filler |
Also Published As
| Publication number | Publication date |
|---|---|
| SE7700581L (en) | 1977-07-27 |
| JPS5291777A (en) | 1977-08-02 |
| AU514657B2 (en) | 1981-02-19 |
| AU2101877A (en) | 1978-07-13 |
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