CN1090227C - Gas refinishing process and gas refinishing equipment - Google Patents
Gas refinishing process and gas refinishing equipment Download PDFInfo
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- CN1090227C CN1090227C CN98117907A CN98117907A CN1090227C CN 1090227 C CN1090227 C CN 1090227C CN 98117907 A CN98117907 A CN 98117907A CN 98117907 A CN98117907 A CN 98117907A CN 1090227 C CN1090227 C CN 1090227C
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- hydrogenchloride
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- 238000000034 method Methods 0.000 title claims description 34
- 230000008569 process Effects 0.000 title claims description 7
- 239000007789 gas Substances 0.000 claims abstract description 199
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 67
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 62
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 54
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 54
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 24
- 239000003245 coal Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000002309 gasification Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 238000011144 upstream manufacturing Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000007670 refining Methods 0.000 abstract description 6
- 239000003208 petroleum Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 3
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 26
- 239000007788 liquid Substances 0.000 description 24
- 238000010521 absorption reaction Methods 0.000 description 21
- 238000006477 desulfuration reaction Methods 0.000 description 20
- 230000023556 desulfurization Effects 0.000 description 20
- 230000008929 regeneration Effects 0.000 description 15
- 238000011069 regeneration method Methods 0.000 description 15
- 239000005864 Sulphur Substances 0.000 description 13
- 229910052602 gypsum Inorganic materials 0.000 description 13
- 239000010440 gypsum Substances 0.000 description 13
- -1 sulphur compound Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
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- 239000007787 solid Substances 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 238000002203 pretreatment Methods 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
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- 230000009467 reduction Effects 0.000 description 7
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- 238000005406 washing Methods 0.000 description 7
- 239000002912 waste gas Substances 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 239000000567 combustion gas Substances 0.000 description 6
- 230000008676 import Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
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- 239000002245 particle Substances 0.000 description 5
- 239000002594 sorbent Substances 0.000 description 5
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- 238000000354 decomposition reaction Methods 0.000 description 4
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- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011505 plaster Substances 0.000 description 4
- 238000009795 derivation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
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- 238000011084 recovery Methods 0.000 description 3
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- 239000000779 smoke Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 235000019628 coolness Nutrition 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003500 flue dust Substances 0.000 description 2
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- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 description 1
- UKGJZDSUJSPAJL-YPUOHESYSA-N (e)-n-[(1r)-1-[3,5-difluoro-4-(methanesulfonamido)phenyl]ethyl]-3-[2-propyl-6-(trifluoromethyl)pyridin-3-yl]prop-2-enamide Chemical compound CCCC1=NC(C(F)(F)F)=CC=C1\C=C\C(=O)N[C@H](C)C1=CC(F)=C(NS(C)(=O)=O)C(F)=C1 UKGJZDSUJSPAJL-YPUOHESYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000580063 Ipomopsis rubra Species 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
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- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Treating Waste Gases (AREA)
Abstract
The facility for refining gas, obtained by gasification of coal and petroleum, is provided with heat exchangers(2, 5)(cooling means)for cooling production gas Al at such temperature that hydrogen chloride and ammonia contained in the production gas Al are deposited as ammonium chloride and with a porous filter(6)(collection means)for collecting ammonium chloride from the production gas Al passed through the cooling means.
Description
The present invention relates to the central purification techniquess that generate gas such as coal gasification technology, particularly relate to and easily to remove the fine preparation method for gas and the equipment of processing generating hydrogen chloride in gas and ammonia.
In recent years, because petroleum resources are exhausted and price skyrockets, so the exploitation that coal and mink cell focus utilize technology has been carried out in the variation of call fuel, one of them is exactly to be directed to coal and the heavy oil gasifying technology as fuel used to generate electricity or synthesis material.And,, gazed at especially therefore by effectively utilizing the limited resources this point to set out owing to utilize gasifying gas generating and the thermal power generation relative efficiency height that utilizes coal or oil in the past.
But, in this gas that generates by gasification, contain the sulphur compound (hydrogen sulfide etc.) of hundreds of～thousands of ppm, for preventing public hazards,, be necessary to be removed perhaps for the corrosion that prevents downstream machine (for example internal combustion turbine etc.) etc.Remove method as it, known have for example resemble the spy and open the wet type fine preparation method for gas of the absorption liquid gas-to-liquid contact of being narrated in the flat 7-48584 communique that makes gas and sulphur compound and for example resemble the spy and open the dry type fine preparation method for gas of being narrated in the flat 2-75320 communique that the sulphur compound in the gas is removed with sulphided form absorption with sorbing material.
, in the fine preparation method for gas in above-mentioned past, not to being contained in other nuisance that generates in the gas, i.e. hydrogenchloride (HCl) or ammonia (NH
3) consider especially, therefore wish to improve.
That is, generally in the generation gas of coal gasification technology etc., contain for example NH of 1000ppm degree
3And for example HCl of 100ppm degree, therefore for cleaningization more, be necessary they are removed.
And hydrogenchloride is strong acid; stainless material is corrosive; viewpoint by the protection equipment and materials is set out; be necessary especially to remove at upstream side as far as possible;, also must be removed simultaneously in order to lower to be contained in the amount that mode in the smoke evacuation that generates gas burning generation in internal combustion turbine etc. is discharged to the chlorine compound in the atmosphere.
In addition, ammonia is burning in internal combustion turbine etc., generates deleterious oxynitride, makes the denitrification apparatus load that generally is located at downstream sides such as internal combustion turbine increase.
But, in above-mentioned existing fine preparation method for gas, no matter be the occasion of wet type or the occasion of dry type, all there is not to be set to especially in the upstream of thionizer to remove the equipment of de-chlorine hydride and ammonia.
And in the thionizer of wet type gas purification in the past, therefore the general absorption liquid (alkalescence) that is made of amine compound that uses is to remove ammonia hardly at least, makes the ammonia of residual volume in the gas of delivering to downstream side machine (internal combustion turbine etc.).
In addition, in the thionizer of dry type gas purification in the past, mainly only carry out the absorption of sulphur compound and remove, be that ammonia or hydrogenchloride all almost will not be removed therefore, and directly be discharged to the downstream side.
The applicant had once proposed in the wet type fine preparation method for gas, made in the thionizer upstream to generate gas and washing water gas-to-liquid contact, and impurity such as above-mentioned hydrogenchloride and ammonia are absorbed the process for purification of being removed in the washing water., can remove de-chlorine hydride and ammonia efficiently, also exist and to carry out the such shortcoming of washings draining processing though such washing procedure is set.
Therefore, the objective of the invention is to, provide a kind of and can easily remove the fine preparation method for gas and the gas refinishing equipment of processing hydrogen chloride in gas and ammonia.
For achieving the above object, fine preparation method for gas of the present invention is the fine preparation method for gas that removes de-chlorine hydride and ammonia in a kind of generation gas that is obtained by coal or oil gasification,
It is characterized in that, this method is made of following operation: cool off above-mentioned generation gas, make refrigerating work procedure that above-mentioned generation hydrogen chloride in gas and ammonia separates out with the form of ammonium chloride and the capture operation that captures the ammonium chloride in the above-mentioned generation gas after this refrigerating work procedure.
Fine preparation method for gas of the present invention, in its preferred mode, in above-mentioned refrigerating work procedure or its upstream, being provided with becomes equal direction is injected hydrogenchloride or ammonia in above-mentioned generation gas injection process towards the volumetric molar concentration that makes above-mentioned generation hydrogen chloride in gas and ammonia.
Gas refinishing equipment of the present invention is the gas refinishing equipment that removes de-chlorine hydride and ammonia in a kind of generation gas that is obtained by coal or oil gasification,
It is characterized in that, this equipment possesses with lower device: with above-mentioned generation gas cooling to the refrigerating unit of the temperature that above-mentioned generation hydrogen chloride in gas and ammonia are separated out with the form of ammonium chloride with by through capturing the capturing device of above-mentioned ammonium chloride in the above-mentioned generation gas of this refrigerating unit.
Gas refinishing equipment of the present invention, in its preferred mode, in above-mentioned refrigerating unit or its upstream, being provided with becomes equal direction is injected hydrogenchloride or ammonia in above-mentioned generation gas injection device towards the volumetric molar concentration that makes above-mentioned generation hydrogen chloride in gas and ammonia.
Fig. 1 is the figure of pre-treatment portion that shows the gas refinishing equipment of the embodiment of the invention 1.
Fig. 2 shows the desulfurization portion of same equipment and the figure of gypsum recoverer.
Fig. 3 is the figure that shows the decomposition pressure characteristic of ammonium chloride.
Fig. 4 is the figure of pre-treatment portion that shows the gas refinishing equipment of the embodiment of the invention 2.
Fig. 5 shows the pre-treatment portion of gas refinishing equipment of the embodiment of the invention 3 and the figure of desulfurization portion.
Below be each embodiment of base description embodiment of the present invention with the accompanying drawing.
Embodiment 1
At first, use embodiments of the invention 1 in wet type gas purification technology are described.Fig. 1 is the figure that shows the pre-treatment bilge construction in the gas refinishing equipment of present embodiment, and Fig. 2 shows the desulfurization portion in the same equipment and the figure of gypsum recoverer structure.
At first structure and the elemental motion to pre-treatment portion describes.In the vapourizing furnace of elliptical, for example coal gasifies as vaporized chemical with air in the drawings, produces with carbon monoxide and the hydrogen generation gas A as principal constituent.
In the generation gas A that obtains as vaporized chemical with air as raw material with coal like this, contain the H of 1000～1500ppm degree usually
2The COS (sulphur compound) of S (sulphur compound) and 100ppm degree also contains the NH of 100～1500ppm degree
3The HCl of (nitrogen compound) and 100ppm degree (chlorine compound).
In addition, generate gas A and be generally 1000 ℃～2000 ℃ after outlet of still, but carry out recovery of heat by the heat exchanger that is arranged on the outlet of still side (omitting among the figure) usually, be cooled to for example 350 ℃ degree, its pressure for example is the degree of 26ata.
This generates gas A as shown in Figure 1, at first import the cleaning apparatus 1 that tornado dust collector or porous filter constitute, make dust separation and remove, in the downstream of cleaning apparatus 1, heat exchanger 2 (refrigerating unit) is set, the gas A4 after using the heat heating of the gas A1 that derives by cleaning apparatus 1 refining.
Gas A1 is seized heat anti-phasely in this heat exchanger 2, make it to be cooled to for example 250 ℃ degree.
Then, in the downstream of heat exchanger 2, set gradually and gas A1 is cooled to ammonium chloride fully separates out the heat exchanger 5 (refrigerating unit) of temperature and the porous filter 6 (capturing device) that the capture of the ammonium chloride (solid of flue dust shape) of separating out is removed.
Wherein, temperature regulator 8 will detect the detection of the temperature sensor 9 of heat exchanger 5 outlet side gas temperatures and export as value of feedback, by the flow of the above-mentioned thermal medium B1 of above-mentioned flow control valve 7 adjustings, the gas temperature of heat exchanger 5 outlet sides is controlled at the controlled target value of regulation.
In addition, the controlled target value of this temperature regulator 8 can be redefined for the abundant low temperature (for example 120～130 ℃) that hydrogenchloride contained in the gas and ammonia major part are separated out with the ammonium chloride form on the basis of the decomposition pressure characteristic (Fig. 3 illustrates) of ammonium chloride described later.
And, the controlled target value of this temperature regulator 8, also can be in the gas A3 of the outlet side of for example porous filter 6 on the basis of hydrogen cloride concentration or ammonia concentration measured value, change to suitable necessary minimum limit value, so that hydrogen cloride concentration among this gas A3 or ammonia concentration are maintained below the target value.
In addition, porous filter 6 for example is made of the element of pottery system, can capture the solid particles of submicron, therefore at this moment, the solid particles (mainly being the flue dust of ammonium chloride) that exists in will the gas A1 via heat exchanger 5 captures and removes, and the gas A2 that removes this solid particles is discharged by top.And the solid particles C that captures is blown into the method for removing gas by making suitable vibration of element or regularly contrary aspect, by shaking on the element, is discharged by lower hopper again.
In the downstream of porous filter 6, heat exchanger 10 is set then, it will be heated to for example 230 ℃ degree by the gas A2 that porous filter 6 comes out by thermal medium 12.The thermal medium B2 of heating usefulness for example can utilize the thermal medium B1 after being heated in the aforesaid heat exchangers 5 in this heat exchanger 10.
In the downstream of this heat exchanger, the COS (carbonyl sulfide) that will be contained among the gas A2 of the 230 ℃ of degree for example of being heated to is set is transformed into H
2The transmodulator that is filled with catalyzer 3 of S, the major part that generates COS among the gas A2 converts H therein to
2S becomes the gas A3 that contains COS hardly, is derived then.
In the downstream of this umformer 3 heat exchanger 4 is set again, its formation is the gas A4 after utilization is made with extra care by the heat heating of the gas A3 of umformer 3 derivation.
Gas A3 is seized heat on the contrary in this heat exchanger 4, be cooled to for example 100 ℃ degree.
Secondly, the structure and the action of desulfurization portion are described according to Fig. 2.Desulfurization portion mainly is made of thionizer 21 and regenerator column 22.
Thionizer 21 is vapour-liquid contacting columns of downflow system, being constructed as follows of it, the absorption liquid F that stores at the hydrogen sulfide of regenerator column 22 tower bottoms is sucted by recycle pump 23, after 24 coolings of absorption liquid heat exchanger, injection spray pipe by tower top sprays, with gas A3 gas-to-liquid contact, one side flows down via packing material 26 on one side.
Remove H with absorption liquid F gas-to-liquid contact
2Gas A4 behind S refining removes the water smoke of following by mist eliminator 27, is discharged by the top of tower of this thionizer 21 then, by aforesaid heat exchangers shown in Figure 14 and heat exchanger 2 heating, becomes processed gas A5.
Processed gas A5 for example is sent to the internal combustion turbine of integrated gasification combined generating, as the gas turbine fuel utilization.In addition, the pressure of processed gas A5 for example is the degree of 25ata, and its temperature is 270 ℃ a degree, and its sulphur content (H
2The concentration of S and COS) be below the 10ppm.
On the other hand, being constructed as follows of regenerator column 22, the absorption liquid F that stores at thionizer 21 tower bottoms is sucted by recycle pump, by 24 heating of absorption liquid heat exchanger, injection spray pipe by tower top sprays then, contact with absorption composition (waste gas) with the steam of the absorption liquid F that in tower, rises on one side, via compaction material 30 flow down on one side.
The absorption liquid F of these regenerator column 22 tower bottoms by water vapor G heating, will absorb the H of composition whereby in reboiler
2S is discharged into gas one side in this regenerator column 22.
Then, this contains H
2The waste gas H of S, in mist eliminator 32, remove water smoke after, contain greater concn H through being located at the backflow portion at regenerator column 22 tops, becoming
2Waste gas H1 (the principal constituent CO of S
2), deliver to gypsum recoverer described later.
Wherein, the backflow portion at regenerator column 22 tops by water cooler 33 cooling exhaust H phlegma I that generate, that store the waste gas H in jar 34, is sprayed by injection spray pipe 26 by pump 35, the steam among the waste gas H is liquefied more, the absorption composition H in the liquid
2S diffuses more, obtain volume percent 20% degree for example high density contain H
2The waste gas H1 of S.
Below the formation and the action of gypsum recoverer described.
The gypsum recoverer that this is routine is that following two portions are combined: make waste gas H1 and air J reaction, make the H that contains
2Absorb among S incendiary roasting kiln 41 and the combustion gases H2 that produces by combustion exhaust H1 in this roasting kiln 41 and remove SO
2The desulfurizer of the wet type lime stone-gypsum method of discharging as harmless tail gas H3 behind the oxysulfides such as (sulfur dioxide gas).
Desulfurizer possesses: make and contain H
2The SO of the high density that the S burning produces
2Combustion gases H2 and the slurries K gas-to-liquid contact that contains calcium cpd that is supplied in its inside reactor 42 of discharging then, oxidation is blown into the air feeder (figure part omitted) in the slurries in this reactor 42 and will be carried out the equipment for separating liquid from solid such as separating centrifuge 44 of solid-liquid separation by the slurries M (gypsum slurries) that reactor 42 is drawn with a large amount of micro bubbles with air L.Also can possess the solids fraction M1 (plaster blocks of two hydrated gypsum) that will be obtained by this equipment for separating liquid from solid 44 in addition again is heated to 120 ℃～150 ℃ of degree and makes the gypsum heating units such as roasting kiln of hemi-hydrated plaster.
In addition, the dried up M3 of branch that the solid-liquid separation in equipment for separating liquid from solid 44 generates is as the moisture that constitutes slurries in the reactor 42, in the at this moment direct Returning reactor 42.
Wherein, the concrete formation of reactor 42 for example has and has the oxidation of being blown into possesses the gas-to-liquid contact portions such as fill-type, spraying type or fluid column formula of slurries in the jetting slurry flow container with the serum pot of air L, on the tower top of combustion gases H2 circulation the circulating so-called absorption tower of slurries at tower bottom.This reactor 42 also can be in the slurries in oxidation is blown into jar with air L and combustion gases H2, SO
2Deng the absorption and the oxidation so-called bubbling mode of in jar, carrying out entirely.And through the temperature in the reactor 42 etc. is controlled, can so that reactor 42 in the generation hemi-hydrated plaster.
In a word, in the desulfurizer that comprises reactor 42, mainly be to absorb SO
2, generate two hydrated gypsum or hemi-hydrated plaster.
Secondly, the main points for the fine preparation method for gas of being implemented in the gas refinishing equipment of above formation of the present invention describe.
In the present embodiment, carry out by aforesaid heat exchanger 2, heat exchanger 5 as the refrigerating work procedure of feature of the present invention.That is, cool off generation gas successively by these heat exchangers, this moment is through the control of temperature regulator 8, and the temperature that generates gas the most at last is cooled to hydrogen chloride in gas and ammonia with ammonium chloride (NH
4Cl) temperature fully separated out of form.
In addition, capture operation of the present invention is carried out by porous filter 6.That is,, capture the ammonium chloride particle of separating out among the generation gas A1 through carrying out filtration treatment with 6 pairs of porous filters cooled generation gas A1 in above-mentioned refrigerating work procedure.Therefore, even only have hydrogenchloride and ammonia among the composition generation gas A1 that separates out with the ammonium chloride form to be removed, the gas A2 low especially as the concentration of these impurity discharges.
The target temperature of above-mentioned refrigerating work procedure (be the controlled target value of temperature regulator 8 this moment) can be set on the basis of ammonium chloride decomposition pressure characteristic by the hydrogenchloride among the generation gas A2 after handling and the aimed concn of ammonia.For example, when gaseous tension was 25ata, the decomposition pressure characteristic of ammonium chloride as shown in Figure 3.Therefore, if for example the temperature of gas is cooled to 120～130 ℃ degree, the concentration of hydrogen chloride in gas and ammonia is counted the degree of very little 5ppm with square root (root).
Thereby, according to the fine preparation method for gas or the gas refinishing equipment of present embodiment,, obtained to remove sulphur compound (H with the high rate of removing as the gas A4, the A5 that finally obtain
2The concentration of S and COS) and the clean gas of hydrogenchloride and ammonia.And owing to remove de-chlorine hydride and ammonia does not use washing water, so do not need the draining of the trouble that for this reason causes to handle fully.
In addition, usually compare with hydrogenchloride in gas A1 and contain the more ammonia of volume, therefore in the occasion of present embodiment, be roughly 0 though hydrogen cloride concentration can ease down to, the attenuating of ammonia concentration is normally limited.
That is, ammonia is combined into ammonium chloride for 1 mole with respect to hydrogenchloride for 1 mole and separates out.Therefore, be that 100ppm ammonia concentration is when being 1000ppm for example at hydrogen cloride concentration, if ignore the part of removing ammonia,, say that in theory ammonia concentration can not drop to below the 900ppm yet even then the temperature of refrigerating work procedure fully reduces because of other factors (condensation of ammonia etc.).
Therefore, requiring extremely to reduce the extreme simultaneously occasion that reduces ammonia concentration of hydrogen cloride concentration, for the ratio of the volumetric molar concentration that makes hydrogenchloride and ammonia approaches 1 pair 1 relation, embodiment 2 is such as described later, for example also the insufficient section of hydrogenchloride can be injected to generate gas.
Below embodiments of the invention 2 are used in explanation in wet type gas purification technology.Fig. 4 is the figure that shows that pre-treatment portion constitutes in the gas refinishing equipment of present embodiment.Parts similarly to Example 1 are marked with prosign, and the repetitive description thereof will be omitted.
Present embodiment is in the upstream of the heat exchanger 5 (refrigerating unit) of embodiment 1, is provided with hydrogenchloride is injected the injection device that generates gas A1.Promptly as shown in Figure 4, it constitutes: the jar 51 that stores hydrogenchloride in generating gas A1 with the high pressure conditions that can inject is set, and the hydrogenchloride D in this jar 51 injects the gas inlet side of heat exchanger 5 by flow control valve 52.
At this moment, the injection rate of hydrogenchloride D relies on the aperture at the automatic control downward modulation rectification flow variable valve 52 of flow director 53, keeps optimum value.Promptly adopt following formation: the hydrogenchloride among the generation gas A2 and the measured value of each concentration of ammonia, by the concentration sensor 54 suitable flow directors 53 that are input to, on the basis of the difference of the measured value of these two concentration, calculate the best injection rate of hydrogenchloride D, regulate the aperture of flow rate regulating valve 52 according to this best injection rate.
For example, hydrogen cloride concentration is 100ppm, when ammonia concentration is 1000ppm, has the difference of 900ppm, therefore according to the flow of the hydrogenchloride suitable with this 900ppm, regulates flow rate regulating valve 52.
In the present embodiment, use the injection device that constitutes by above-mentioned jar 51 and flow control valve 52 etc. to carry out injection process of the present invention, will inject generation gas A2 with respect to the hydrogenchloride of ammonia insufficient section.
Therefore,, and fully reduce gas temperatures, most hydrogenchloride and ammonia are separated out with the form of ammonium chloride, capture with porous filter 6 then and remove with heat exchanger 5 as long as revise according to the hydrogenchloride among the generation gas A1 and the balance of ammonia amount.Thereby irrelevant with the proterties that generates gas, no matter the concentration of hydrogenchloride still is that ammonia concentration can both significantly reduce.
Below embodiments of the invention 3 are used in explanation in dry type gas purification technology.Fig. 5 is the figure that shows that pre-treatment portion and desulfurization portion constitute in the gas refinishing equipment of present embodiment.Parts similarly to Example 1 are marked with prosign, and the repetitive description thereof will be omitted.In addition, omitted the gypsum recoverer among the figure.
At first, formation and the action for the pre-treatment portion of present embodiment describes with Fig. 5.
Generate in the vapourizing furnace of elliptical in the drawings, then through heat exchanger recovery of heat such as (omitting among the figure), again by figure in elliptical tornado dust collector or the dust separating generation gas of porous filter A1, cooled off by heat exchanger 132 described later (refrigerating unit) this moment, then as generating gas A2 delivery heat exchanger 5 (refrigerating units), similarly to Example 1, be cooled to the temperature (refrigerating work procedure) that ammonium chloride is fully separated out.
Generate gas A2 after this and be imported into porous filter 6 (capturing device) similarly to Example 1, the ammonium chloride of separating out is captured remove (capture operation), the generation gas A3 that reduces greatly as hydrogenchloride and ammonia concentration is discharged from, and delivers to desulfurization described later portion.
Generate gas A3 and before importing desulfurization portion, also can carry out reheat by necessity.In this reheat, if the heat of using heat exchanger 5 to reclaim, then efficient is better.
In addition, different as the sulphur compound that generates among the gas A3 with embodiment 1, except that hydrogen sulfide, also contain carbonyl sulfide, remove but in desulfurization described later portion, itself and hydrogen sulfide can be adsorbed simultaneously.
Below the desulfurization portion of present embodiment is described.
As shown in Figure 5, there is the fixed-bed type thionizer 101 more than three in desulfurization portion, and the situation of three towers is shown herein.In the inside of each thionizer, filling is implemented absorption operation described later, step for regeneration and reduction operation successively by the cellular sorbent material 102 that the metal oxide of Fe, Zn, Mo, Mn, Cu, W etc. constitutes.In Fig. 5, the thionizer 101 of the thionizer 101 in left side, central authorities, the thionizer 101 on right side show the state that absorbs operation, reduction operation, step for regeneration respectively in addition.
In this desulfurization portion, as gas tube, the 1st gas introduction tube line 111 that imports generation gas A3 to be desulfurization for absorption operation described later is set, import the 2nd gas introduction tube line 112 that generates gas A3 for reduction operation described later, the pipeline 113 of generation gas A4 after the derivation desulfurization, for the regeneration gas of deriving the regeneration gas E that is discharged by thionizer 101 in the aftermentioned step for regeneration is derived pipeline 114, for importing the reprocessing cycle gas ingress pipe line 115 of supplying with the reprocessing cycle gas E1 of thionizer 101 in the aftermentioned step for regeneration, with for importing the reducing gas return line 116 of the thionizer 101 that absorbs operation by reducing reducing gas that the thionizer 101 of operation comes out.
And, valve 121,122,123 is set respectively, valve as the gas inlet that opens and closes each thionizer 101 of connection independently and above-mentioned the 1st gas introduction tube line the 111, the 2nd gas introduction tube line 112 or regeneration gas derivation gas tube 114, in addition, each thionizer is provided with valve 124,125,126 respectively, as the pneumatic outlet that opens and closes each thionizer 101 of connection independently and the valve of gas eduction tube line 113, reprocessing cycle gas ingress pipe line 115 or reducing gas return line 116.
These valves are controlled its action with elliptical control device among the figure, and it constitutes makes and can switch by the kind of the operation of carrying out in each thionizer.In addition, in Fig. 5, the diagram valve of blacking represents to be closing condition, and the valve of blacking does not represent to be in opened condition.In this occasion, adopt following formation in the desulfurization portion in addition: 2 heat exchangers 131,132 are set, in heat exchanger 131, with regeneration gas E regeneration circulation gas E1, in heat exchanger 132, with generating gas A1 regeneration circulation gas E1.
Below the action of above-mentioned desulfurization portion is described.
Import the generation gas A3 of desulfurization portion, mainly import by valve 121 and be in the reaction tower 101 (reaction tower in left side among Fig. 5) that absorbs working procedure states, with cellular sorbent material (Fe for example by the 1st gas introduction tube line 111
3O
4) contact effectively, with hydrogen sulfide (H
2S) and carbonyl sulfide (COS) absorb with the form of sulfide (FeS) and remove, discharge as the gas A4 after refining via valve 124 and gas eduction tube line 113, deliver to the downstream machine (internal combustion turbine etc.) in the power generation system etc.In addition, a part that generates gas A3 imports the reaction tower 101 (in Fig. 5 reaction tower of central authorities) that be in reduction working procedure states as reduction with gas by the 2nd gas introduction tube line 112 and valve 122, with absorption agent after the regeneration (Fe for example
2O
3) contact effectively, sorbent material is become have the state (Fe for example of receptivity through reduction reaction
3O
4).In addition, this generates the part of gas A3, is come out by the reaction tower 101 that is in the reduction working procedure states, by for example valve 126 and reducing gas return line 116, importing is in for example pars intermedia of the reaction tower 101 that absorbs working procedure states, makes hydrogen sulfide (H through above-mentioned absorption reaction
2S) and carbonyl sulfide (COS) etc. absorb and remove, via valve 124 and gas eduction tube line 113, be discharged from as the part of the generation gas A4 after refining.
In addition, with above-mentioned absorption operation and reduction operation while, in remaining reaction tower 101 (reaction tower on right side among Fig. 5), carry out the step for regeneration that roasting is the sorbent material of sulfide.That is, reprocessing cycle gas E1 is imported in the remaining reaction tower 101 by reprocessing cycle gas ingress pipe line 115 and valve 125, oxygen among this reprocessing cycle gas E1 and sorbent material generation roasting reaction make adsorbent reactivation.
The regeneration gas E that in this step for regeneration, produces, be contain high density by being absorbed the sulfur dioxide gas (SO that sulphur content is formed
2) gas, derive pipeline 114 by valve 123 and regeneration gas and send into gypsum recoverer in elliptical among the figure, become exhaust after for example using the desulfurizer of wet type lime stone-gypsum method similarly to Example 1 to absorb to remove sulfur dioxide gas, delivery of supplemental oxygen is returned desulfurization portion as reprocessing cycle gas as required.
In above-mentioned gas purification apparatus discussed above, in desulfurization portion, remove sulphur compound according to adsorbing like that in the past, adopt simultaneously and be arranged on heat exchanger 5 refrigerating units such as grade of desulfurization portion upstream and the capturing device that constitutes by porous filter 6 this moment, carry out refrigerating work procedure of the present invention similarly to Example 1 and capture operation, also will generate hydrogen chloride in gas and ammonia is removed.
Thereby, as finally obtain refining after gas A4, obtained to remove sulphur compound (H with the high rate of removing
2S and COS) and the clean gas of hydrogenchloride and ammonia.And do not use washing water for removing de-chlorine hydride and ammonia, and do not use absorption liquid for removing sulphur compound this moment in addition yet, therefore the draining processing of trouble need be set for these purposes fully.
The invention is not restricted to the embodiment of above-mentioned form, but various forms can be arranged.For example, the temperature regulation in the refrigerating work procedure needn't necessarily be undertaken by the automatic control of using controller, also can manual setting.In addition, the indeclinable occasion of proterties (concentration of hydrogenchloride and ammonia) at gas also can adopt to be fixed as the formation that certain target temperature is not adjusted.In addition in embodiment 2, example be that hydrogenchloride is injected the situation that generates gas, but, should inject ammonia certainly in the occasion that the amount of hydrogenchloride is Duoed than ammonia.In addition, the capturing device as capturing ammonium chloride also can use for example electric precipitator of wet type.But, set out by saving draining processing this point fully, preferably adopt dry gas cleaning devices such as porous filter.
By above-mentioned explanation as can be known, in the present invention, make the generation gas cooling of refrigerating work procedure (refrigerating unit), hydrogen chloride in gas and ammonia are separated out with the ammonium chloride form.Then, by the ammonium chloride in the generation gas that captures after operation (capturing device) captures refrigerating work procedure.Therefore, only there is the composition of separating out to remove generating hydrogen chloride in gas and ammonia as ammonium chloride.
Thereby just easily obtained with the high gasifying gas that the cloud rate is removed the cleaning of de-chlorine hydride and ammonia that removes.And, do not carry out the gas-to-liquid contact processing of gas and washing water for removing de-chlorine hydride and ammonia, the draining that does not therefore need trouble is set is for this reason handled.
In the mode of set hydrogenchloride or the injection process of ammonia (injection device),, in generating gas, inject hydrogenchloride or ammonia towards making the volumetric molar concentration that generates hydrogen chloride in gas and ammonia become equal direction in above-mentioned refrigerating work procedure or its upstream.
Therefore, revise, in refrigerating work procedure, fully reduce gas temperature, most hydrogenchloride and ammonia are separated out with the ammonium chloride form, in capturing operation, capture again and remove according to making the amount that generates hydrogen chloride in gas and ammonia reach the equilibrated mode.
Thereby no matter the proterties that generates gas how, no matter hydrogen cloride concentration still is an ammonia concentration can both significantly be reduced.
Claims (2)
1, fine preparation method for gas, it is the fine preparation method for gas that from the generation gas that coal or oil gasification obtain, removes de-chlorine hydride and ammonia, it is characterized in that, this fine preparation method for gas is made of following operation: with above-mentioned generation gas cooling, make the capture operation that captures the ammonium chloride in the above-mentioned generation gas after refrigerating work procedure that above-mentioned generation hydrogen chloride in gas and ammonia separates out with the ammonium chloride form and this refrigerating work procedure;
In above-mentioned refrigerating work procedure or its upstream, be provided with in above-mentioned generation gas inject hydrogenchloride or ammonia injection process so that the volumetric molar concentration of above-mentioned generation hydrogen chloride in gas and ammonia becomes equal.
2, gas refinishing equipment, it is the gas refinishing equipment that removes de-chlorine hydride and ammonium in the generation gas that obtains by coal or oil gasification, it is characterized in that, this gas refinishing equipment possesses: with above-mentioned generation gas cooling to the refrigerating unit of the temperature that above-mentioned generation hydrogen chloride in gas and ammonia are separated out with the ammonium chloride form with by capturing device through the above-mentioned ammonium chloride of above-mentioned generation gas trapping of this refrigerating unit;
In above-mentioned refrigerating unit or its upstream, be provided with in above-mentioned generation gas inject hydrogenchloride or ammonia injection device so that the concentration of above-mentioned generation hydrogen chloride in gas and ammonia becomes equal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP231710/97 | 1997-08-13 | ||
| JP9231710A JPH1157402A (en) | 1997-08-13 | 1997-08-13 | Method and facility for refining gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1213690A CN1213690A (en) | 1999-04-14 |
| CN1090227C true CN1090227C (en) | 2002-09-04 |
Family
ID=16927805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98117907A Expired - Fee Related CN1090227C (en) | 1997-08-13 | 1998-08-12 | Gas refinishing process and gas refinishing equipment |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH1157402A (en) |
| CN (1) | CN1090227C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012219225A (en) * | 2011-04-12 | 2012-11-12 | Central Research Institute Of Electric Power Industry | Dry gas purification facility and coal gasification-combined power generation facility |
| JP2012233655A (en) * | 2011-05-07 | 2012-11-29 | Denso Corp | Device for suppressing leakage of ammonia |
| JP2019189850A (en) * | 2018-04-20 | 2019-10-31 | 一般財団法人電力中央研究所 | Impurity removal device, dry type gas refining facility and coal gasification combined power generating facility |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104420A (en) * | 1985-07-02 | 1987-02-04 | 科夫工程有限公司 | Method for cooling and purifying producer gas and blast furnace gas and device for implementing the method |
-
1997
- 1997-08-13 JP JP9231710A patent/JPH1157402A/en not_active Withdrawn
-
1998
- 1998-08-12 CN CN98117907A patent/CN1090227C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104420A (en) * | 1985-07-02 | 1987-02-04 | 科夫工程有限公司 | Method for cooling and purifying producer gas and blast furnace gas and device for implementing the method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1157402A (en) | 1999-03-02 |
| CN1213690A (en) | 1999-04-14 |
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