CN100506717C - Treatment method of dilute ammonium sulfate wastewater - Google Patents
Treatment method of dilute ammonium sulfate wastewater Download PDFInfo
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- CN100506717C CN100506717C CNB2006100279053A CN200610027905A CN100506717C CN 100506717 C CN100506717 C CN 100506717C CN B2006100279053 A CNB2006100279053 A CN B2006100279053A CN 200610027905 A CN200610027905 A CN 200610027905A CN 100506717 C CN100506717 C CN 100506717C
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000002351 wastewater Substances 0.000 title claims abstract description 45
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052921 ammonium sulfate Inorganic materials 0.000 title claims abstract description 18
- 235000011130 ammonium sulphate Nutrition 0.000 title claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims abstract description 14
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 42
- 230000008569 process Effects 0.000 claims description 30
- 238000010791 quenching Methods 0.000 claims description 30
- 229910021529 ammonia Inorganic materials 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 claims description 17
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 claims description 17
- 229960003495 thiamine Drugs 0.000 claims description 17
- 235000019157 thiamine Nutrition 0.000 claims description 17
- 239000011721 thiamine Substances 0.000 claims description 17
- -1 ammonium radical ion Chemical class 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 241000282326 Felis catus Species 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 11
- 239000001099 ammonium carbonate Substances 0.000 abstract description 10
- 235000012501 ammonium carbonate Nutrition 0.000 abstract description 6
- 235000011116 calcium hydroxide Nutrition 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000003456 ion exchange resin Substances 0.000 abstract description 5
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 150000002825 nitriles Chemical class 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract 2
- 229910052925 anhydrite Inorganic materials 0.000 abstract 2
- 239000002910 solid waste Substances 0.000 abstract 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 30
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 18
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 150000004683 dihydrates Chemical class 0.000 description 10
- 229910052602 gypsum Inorganic materials 0.000 description 10
- 239000010440 gypsum Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 238000009434 installation Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 229960004424 carbon dioxide Drugs 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 210000000689 upper leg Anatomy 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241001234523 Velamen Species 0.000 description 1
- LHZBJYKURLPKBC-UHFFFAOYSA-N [Mo].[P].[Bi] Chemical class [Mo].[P].[Bi] LHZBJYKURLPKBC-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007255 decyanation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
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- Removal Of Specific Substances (AREA)
- Physical Water Treatments (AREA)
Abstract
This invention relates to a method for treating diluted ammonium sulfate wastewater. The method solves the problems of high solid waste and organic nitrile impurity contents, low ammonium sulfate concentration, and difficult ammonium sulfate recovery. The method comprises: (1) removing solid impurities from diluted ammonium sulfate wastewater, adjusting the pH value to 6.5-7.5, performing flash evaporation, stripping or rectification, removing lightweight organic fractions at the overhead, collecting heavy fractions at the bottom, and extracting the rest ammonium sulfate wastewater at 1st-5th theoretical plates from the overhead; (2) sending the rest ammonium sulfate wastewater to ion exchange reaction, and removing NH4+; (3) treating regenerated liquid of the ion exchange resin with Ca(OH)2 aqueous solution to produce CaSO4 and diluted ammonia solution, performing solid-liquid separation, reacting CaSO4 and diluted ammonia solution with CO2 to obtain ammonium carbonate or ammonium hydrogen carbonate.
Description
Technical field
The present invention relates to a kind of treatment process of wastewater of dilute thiamine, particularly about a kind of treatment process that is used to handle the wastewater of dilute thiamine that the one-part form acrylonitrile quenching technique produces.
Background technology
What most of in the world production device for acrylic nitrile adopted is the Schoio technology of BP company, and its share of market reaches more than 95%.This technology is raw material (propylene in the charging: ammonia: air=1: 1.2: 10), adopt phosphorus-molybdenum-bismuth series catalysts to produce vinyl cyanide, simultaneously by-product acetonitrile and prussic acid with chemical grade propylene and chemical fertilizer level ammonia and air.Reactor is a fluidized-bed, and temperature of reaction is 400～500 ℃, and pressure is 0.05～0.1MPa.
The refining and reclaiming technology of vinyl cyanide is to the product yield important influence of acrylonitrile installation.Usually the recovery treating process in the acrylonitrile installation is such: the reaction mixture that is come out by reactor is cooled to about 200 ℃ through the reactor aftercooler, enter quench tower and carry out the solid impurities such as catalyst dust that chilling neutralization removes excess of ammonia in the dereaction and carries secretly, quench tower ejects about 80 ℃ the reaction mixture that comes and enter organic products such as absorption tower recover acrylonitrile after the chilling aftercooler further cools off, the absorption that the absorption tower still obtains the rich solution of reaction product enter recovery tower and reclaim product, reclaim the organic streams that obtains and remove light component such as prussic acid through the decyanation tower again through the refining vinyl cyanide the finished product that obtain of product tower.
The acrylonitrile quenching Tower System is the key equipment of acrylonitrile refining, and is remarkable to the recovery of acrylonitrile influence of acrylonitrile installation.Two kinds of different emergency cooling process are arranged at present in the world, and what Chinese most of production device for acrylic nitrile adopted mostly is the two-part emergency cooling process, and epimere is a neutralizing zone, and hypomere is a quench zone.From the reactor that reactor comes, contain a certain amount of excess of ammonia, make quench liquid be alkalescence.Polymerization of acrylonitrile speed and environment PH are exponential relationship, and the high more polymerization rate of pH value is fast more.Do not add the measure that pH is transferred in acid and have in the quench zone original design in two sections emergency cooling process, therefore cause vinyl cyanide serious in the quench zone loss.And quench tower all adopts one-part form design in the external production device for acrylic nitrile, and such design is finished N-process and quenching process simultaneously, and everywhere pH value all is in lower level in the quench tower, has suppressed the polymerization of vinyl cyanide effectively.Adopt the reason of different designs to be quench liquid processing mode difference.Two-piece design can be extracted neutralizer out from neutralizing zone and remove to reclaim the sulphur ammonium behind stripping, but the sulphur ammonium that reclaims is of low quality, and color and luster is bad, does not have productivity effect.External one-part form emergency cooling process does not reclaim the sulphur ammonium, but the dark injection of quench liquid is underground.Adopt the one-part form emergency cooling process that the refining rate of recovery of acrylonitrile installation is reached more than 96%, and two-part technology through a series of technological transformation still difficulty reach this index.The reason that does not adopt the one-part form emergency cooling process is different the causing of geologic framework because of different areas.At present the processing mode of one-part form quench liquid is a kind of potential environment unsafe factor, and along with bursting day by day of the increasingly stringent of environmental regulation and water resources is weary, this processing mode will be under an embargo gradually.Therefore the solution of the handling problem of rare sulphur ammonium quench liquid is extremely urgent.
The organic cyanides that contains high density in the quench liquid that contains rare sulphur ammonium that comes out at the bottom of the quench tower is if not treated discharging with the serious harm environment, and brings serious harm to human and vegeto-animal living environment.At present organic cyanogen wastewater treatment method is mainly contained three kinds: the one, pressurized hydrolysis-biochemical treatment process, its shortcoming is can not handle to contain polymkeric substance greater than 1% cyanide wastewater, the acid and alkali consumption amount is big, ammonia-nitrogen content height in the treating water, the biochemical treatment floor space is big; The 2nd, wet oxidation process, shortcoming are that facility investment is big, temperature of reaction and pressure height; The 3rd, burning method is handled the organic cyanogen waste water of high density, this method also is to handle the universal method of high organic cyanogen content quench liquid in the present vinyl cyanide industry, this method need consume a large amount of fuel oils, and the used heat of the burning waste water in the acrylonitrile installation is generally by effective recycling, so Technological Economy is bad.In recent years the someone proposes to adopt the method for rectifying to handle the method for one section chilling waste water, from the angle of wastewater treatment certain economic benefits is arranged, but reaches the purpose that reduces the acrylonitrile polymerization loss.
For the processing of wastewater of dilute thiamine, with United States Patent (USP) 4,292,043 for the technology of representative is a heating evaporation waste water, removes the water vapor that generates, and obtains concentrated liquid and crystallization suspended substance, and make its thickening, separate solid sulphur ammonium, the liquid after concentrating carries out the vacuum cooling crystallization again, removes water vapor, separate condensing crystal, concentrated solution enters the concentration that the crystallization device further reduces the sulphur ammonium, obtains sulphur ammonium solid, and the redistillation mother liquor further removes ammonia.The clear 55-145599 disclosed method of Japanese Patent is first excessive potassium hydroxide or potassium oxide in the waste water, make sulfate ion in the solution as most of vitriolate of tartar solid precipitation, filtration, filtrate is contacted with high-temperature water vapor, remove volatile matter such as deammoniation, the evaporation raffinate that generates delivered to burn but stove, under 800～1100 ℃, burning but in the presence of oxygen, generate potassium oxide, again it is returned integral part as the neutralizing agent of sulfate.The CN87103546 disclosed method adopts following step to reclaim solid ammonium sulfate from rare sulphur ammonium: first blowing air becomes ferric ion to remove oxidation of divalent iron ion, generate dihydrate gypsum and weak ammonia with lime treatment again, dihydrate gypsum is sold as paying product through post precipitation centrifugation, washing, oven dry; Weak ammonia is by ion-exchange bed adsorbing and removing ammonia, regenerate to resin with dilute sulphuric acid in the saturated back of ammonia, rare sulphur ammonium of obtaining of regeneration neutralizes with liquefied ammonia and is concentrated in vacuo to weight again after the pH value 8.0 and remains about 50%, enters the cooling and stirring crystallizer, carries out the crystallization of chuck cooling and stirring.CN95110679.1 and CN98112743.6 disclose a kind of method of handling waste liquid in the preparing process of caprolactam, the raffinate that is characterized in the waste liquid of will discharge from ion exchange tower in the caprolactam production process and comes out from the benzene distillation tower and mix with sulphur ammonium scavenging solution from the raffinate that hexanolactam stripping extraction tower comes out, carry out vapor-liquid separation after the preheating, carry out double evaporation-cooling, cooling, layering with water vapor then and reclaim the sulphur ammonium of 5～15% hexanolactam and 35～40% and 2～8% hydroxycaproic acid.The disclosed wastewater of dilute thiamine treatment process of CN98104709.2 is to adopt magnesium salts to remove wherein ammonia nitrogen as precipitation agent.Add precipitation agent and phosphoric acid earlier in waste water, substep adds alkali lye and regulates the pH value, behind the stirring reaction certain hour, obtains crystallization suspension, and this moment, ammonia nitrogen became precipitated crystal, filtering separation, pays simultaneously and produces a kind of fertilizer.Above various rare sulphur ammonium treatment process common drawback is the treatment scheme complexity, needs to add extra treatment agent, has increased processing cost.
Summary of the invention
Technical problem to be solved by this invention is to exist in the conventional art handling wastewater of dilute thiamine energy consumption height or the high problem of processing cost, a kind of processing of new acrylonitrile quenching technique wastewater of dilute thiamine is provided but does not reclaim the novel method of sulphur ammonium.This method has energy consumption and material consumption is low, the advantage of less investment.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of treatment process of wastewater of dilute thiamine may further comprise the steps:
A) remove solid impurity and to regulate the pH value be that wastewater of dilute thiamine after 6.5～7.5 enters flashing tower, stripping tower or rectifying tower, remove organism light constituent lower in the waste water at cat head than water boiling point, obtain heavy component higher in the waste water at the tower still than water boiling point, ammonium sulfate solution is extracted out from the position side line of 1～5 block of theoretical tray in tower still top, gets logistics 1;
B) the ammonium radical ion removed wherein of logistics 1 ion exchange reaction gets logistics 2;
C) logistics 2 usefulness calcium hydroxide aqueous solutions are handled and are generated calcium sulfate and weak ammonia, get calcium sulfate and weak ammonia after solid-liquid separation, and weak ammonia generates carbonic acid ammonia or bicarbonate of ammonia with carbon dioxide reaction again.
In technique scheme, the light component preferred version of organism is to be sent to handle together in the phlegma of quench tower aftercooler to reclaim the organism product or return quench tower and handle; The used resin preferred version of ion exchange reaction is a hydrogen type cation exchange resin, and exchange capacity of resin is greater than the every gram resin of 3～12 mmoles; The tower still of flashing tower, stripping tower or rectifying tower is extracted heavy component out, and the weight percent that the amount of heavy component accounts for charging waste water is 1～20%, and preferable range is 8～18%.
In above-mentioned technical scheme, adopt centrifugal, filtration, sedimentation, eddy flow or wherein the method that combines of certain two or more technology can remove solid in the waste water effectively.Adopt the method for flash distillation, stripping or rectifying, the vinyl cyanide organic matter component in the waste water can be reclaimed, and heavy components such as polymkeric substance are removed from waste water with the form of deslagging.The ion exchange reaction device is set can be exchanged the ammonium radical ion get off with very high selectivity, makes the sulphur ammonium in the regenerated liquid behind the ion exchange resin regeneration reach high purity.And milk of lime is the most cheap industrial chemicals, can obtain to use wider Chemicals gypsum with milk of lime and the reaction of highly purified sulphur ammonium.Contain dilute sulphuric acid in the waste water after the ion-exchange, and the quality of water is better than the recirculated water that water technology obtained in the past, directly loops back the consumption that can reduce diluted acid behind the quench tower, further reduce production costs.Therefore, adopt wastewater processing technology of the present invention, can obtain high-quality recirculated water, therefore with low cost because the logistics that generates in the treating processes has all obtained effective utilization in technology, obtained better technical effect.
Description of drawings
Fig. 1 is a kind of typical process flow diagram of the present invention.
1 is the quench tower of one-part form operation among Fig. 1, the 2nd, and solid-liquid separating equipment, the 3rd, flash column or stripper or rectifying column, 4 (A, B) are the ion-exchange reactions devices, and 5,6,7 and 8 is three-way valves. Stream thigh 101 comes the reaction of autoreactor aftercooler Gas, the 102nd, the reacting gas behind chilling, the 103rd, chilling dilute sulfuric acid, the 104th, excess ammonia, poly-in the absorption reaction gas The chilling tower bottoms of compound, catalyst dust and the light component of partial organic substances, the 105th, for and 104 in superacid alkali, The 106th, remove the wastewater of dilute thiamine of solid impurity, the 107th, solid impurity, the 108th, through the 3 rare sulphur ammoniums that remove organic light component Waste water, the 109th, the dilute sulfuric acid waste water after ion-exchange removes the ammonium radical ion, the 111st, the fresh water that quench tower is added, 112 Being organic light component, mainly is acrylonitrile, methacrylaldehyde, acetonitrile and hydrogen cyanide etc., the 113rd, and ion exchange resin regeneration liquid, Chief component is saturated ammonium sulfate solution. 9,11st, mixing valve or other can be realized arbitrarily the equipment that the multiply logistics mixes, The 10th, solid-liquid separating equipment is such as centrifuge, filter, hydrocyclone etc. Stream thigh 116 is milk of lime, the 117th, contain The emulsion of dihydrate gypsum and weak aqua ammonia, the 118th, ammoniacal liquor, the 119th, carbon dioxide, the 120th, ammonium carbonate/ammonium bicarbonate solution, The 121st, wet dihydrate gypsum. Fig. 1 is one of typical flowchart of the present invention, and valve wherein and the arrangement of equipment are not shown Bright this is scheme unique among the present invention.
The present invention is described in detail below in conjunction with accompanying drawing.
In Fig. 1, the reacting gas 101 that is come by the reactor aftercooler carries out chilling in quench tower 1, be cooled to 80 Reaction gas 102 about ℃ flows out downstream unit into production device for acrylic nitrile from the chilling cat head, has absorbed in the reaction gas The urgency of excess ammonia and the light component of a small amount of organic matter (mainly being acrylonitrile, methacrylaldehyde, acetonitrile and hydrogen cyanide etc.) and catalyst dust Cold liquid 104 advances solid-liquid separating equipment 2 to carry out Separation of Solid and Liquid and removes wherein solid impurity, such as dead catalyst and polymer etc., In 2, can add in the suitable alkali and excessive acid by 105, also can not add, preferred alkali be sodium carbonate, sodium acid carbonate, NaOH, potash, saleratus, potassium hydroxide, ammonium carbonate, carbonic hydroammonium etc., preferred alkali is ammonium carbonate or carbon Acid hydrogen ammonium, the more preferably cushioning liquid of the two mixture formation that is made into by a certain percentage. Solid-liquid separating equipment can be Centrifuge, filter, hydrocyclone etc., preferred solid-liquid separating equipment is hydrocyclone. By 2 isolated solids Impurity 107 goes burning disposal, liquid material 106 go stripper 3 and its cat head 112 reclaim light organic matter component acrylonitrile, Methacrylaldehyde, acetonitrile and hydrogen cyanide etc., 112 go the downstream units equipment of production device for acrylic nitrile to process, optional mode Be that the quench tower aftercooler is processed after its condensate liquid mixes again, reclaim organic matter product wherein and pay product Product. Extract rare ammonium sulfate solution 108 deionization exchange reactors 4 (A, B) out from the tower bottom side line of this tower and process, and 3 Tower reactor goes out a small amount of residue 114 and 107 and is mixed into 115 and comes along and burn to reclaim heat. 108 ion-exchange reactions device 4 (A, B) carry out ion-exchange and remove wherein ammonium radical ion, remove 109 behind the ammonium radical ion and mix with the fresh dilute sulfuric acid of adding Become 103 to recycle. Regeneration of ion-exchange resin liquid 113 is saturated ammonium sulfate solutions, advances in 9 with milk of lime 116 The rear formation of row mixing 117 suspension enter solid-liquid separating equipment 10 and carry out Separation of Solid and Liquid. Solid-liquid separating equipment can be centrifugal Machine, filter, hydrocyclone etc., preferred solid-liquid separating equipment is hydrocyclone. By 10 solid materials that obtain Part 121 is dihydrate gypsums, can be used as after the processing such as drying to pay the product sale; Liquid part 118 is weak aqua ammonias, with two Carbonoxide 119 mixed being incorporated in equipment 11 generates ammonium carbonate or ammonium bicarbonate soln 120 in the technical process. This strand alkali lye can With the usefulness as the pH in adjusting process logistics in the Acrylonitrile Production or the equipment, because ammonium carbonate or carbonic hydroammonium are not Therefore the weak base that contains sodium ion can not make the Na ion concentration accumulation in the Acrylonitrile Production, for the longevity that prolongs waste heat oven Order very favourable.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Adopt the flow process of Fig. 1, the weight percent of one-part form acrylonitrile quenching wastewater of dilute thiamine consists of: vinyl cyanide 0.19%, and prussic acid 0.19%, water 78.36%, sulphur ammonium 13.82%, polymkeric substance 7.44% wherein also contains a spot of catalyst dust.Waste water is by after the wet cyclone solid-liquid separation, catalyst dust and most polymkeric substance have been removed, obtain quality and form vinyl cyanide 0.20%, prussic acid 0.20%, water 84.67%, the clear liquid of sulphur ammonium 14.93% and trace polymer and to regulate its pH value be 6.6, this clear liquid adopts 20 theoretical stage stripping towers to carry out stripping, the stripping tower tower top temperature is 87.5 ℃, tower still temperature is under 110 ℃ of conditions, obtain cat head weight and consist of prussic acid 35%, vinyl cyanide 30%, the organic solution of water 35%, in the 1st column plate place, tower still top side line extraction concentration expressed in percentage by weight is 18% ammonium sulfate solution, and the tower still flows out 10% ammonium sulfate solution that contains polymkeric substance.Rare ammonium sulfate solution of side line extraction is the D001[H of the every gram resin of 4.2 mmoles by exchange capacity
+] ion exchange resin bed, bed height is 500 millimeters, ammonium velamen absorption and obtain flowing out the dilute sulphuric acid of bed loops back quench tower and utilizes.Regenerate with dilute sulphuric acid in the saturated back of ion-exchange bed absorption, add lime in the ammonium sulfate solution that regeneration obtains and stir production dihydrate gypsum and ammoniacal liquor, after solid-liquid separation, obtain dihydrate gypsum precipitation and concentration expressed in percentage by weight and be 18% ammoniacal liquor, ammonia soln can be reclaimed ammonia by stripping, and recovery ammonia can loop back reaction gas and utilize.Also can in system, feed carbonic acid gas, ammoniacal liquor be changed into volatile salt or ammonium hydrogencarbonate use, the yellow soda ash that adjust pH is used in the saving original system, the accumulation of sodium ion in the reduction system as the alkali of regulating pH value in the system.
[embodiment 2]
Press each step and the operational condition of embodiment 1, just changing clear liquid pH value is 7.5, exchange capacity of resin is the every gram resin of 0.5 mmole, extract ammonium sulfate solution out at the 4th column plate place, tower still top side line, increasing stripping tower cat head produced quantity is 10% of raw material weight, obtain the cat head quality group and become prussic acid 25%, vinyl cyanide 20%, the organic solution of water 55%, it in tower still side line extraction concentration expressed in percentage by weight 25% ammonium sulfate solution, the charging waste water of surplus flows out from the tower still, add lime and stir production dihydrate gypsum and ammoniacal liquor in ammonium sulfate, obtaining concentration after solid-liquid separation is that dihydrate gypsum precipitation and concentration expressed in percentage by weight are 25% ammoniacal liquor.The treatment process of dihydrate gypsum and ammoniacal liquor is with embodiment 1.
Claims (5)
1, a kind of treatment process of wastewater of dilute thiamine may further comprise the steps:
A) remove solid impurity and to regulate the pH value be that wastewater of dilute thiamine after 6.5～7.5 enters flashing tower, stripping tower or rectifying tower, remove organism light constituent lower in the waste water at cat head than water boiling point, obtain heavy constituent higher in the waste water at the tower still than water boiling point, ammonium sulfate solution is extracted out from the position side line of 1～5 block of theoretical tray in tower still top, gets logistics 1;
B) the ammonium radical ion removed wherein of logistics 1 ion exchange reaction gets logistics 2;
C) logistics 2 usefulness calcium hydroxide aqueous solutions are handled and are generated calcium sulfate and weak ammonia, get calcium sulfate and weak ammonia after solid-liquid separation, and weak ammonia generates volatile salt or bicarbonate of ammonia with carbon dioxide reaction again.
2, the treatment process of wastewater of dilute thiamine according to claim 1 is characterized in that the organism light constituent is sent to handle together in the phlegma of quench tower aftercooler to reclaim the organism product or return quench tower and handle.
3, the treatment process of wastewater of dilute thiamine according to claim 1 is characterized in that the used resin of ion exchange reaction is a hydrogen type cation exchange resin, and exchange capacity of resin is the every gram resins of 3～12 mmoles.
4, the treatment process of wastewater of dilute thiamine according to claim 1 is characterized in that the tower still of flashing tower, stripping tower or rectifying tower is extracted heavy constituent out, and the weight percent that the amount of heavy constituent accounts for charging waste water is 1～20%.
5, the treatment process of wastewater of dilute thiamine according to claim 4, the weight percent that the amount that it is characterized in that heavy constituent accounts for charging waste water is 8～18%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010090273A1 (en) * | 2009-02-06 | 2010-08-12 | 財団法人造水促進センター | Operation management device for a vaporization device, fresh water generator provided with the operation management device, and operation management method and fresh water-generating method for vaporization devices |
| CN102452955A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for recycling unreacted ammonia in acrylonitrile reaction device |
| CN102139983A (en) * | 2011-02-16 | 2011-08-03 | 神华集团有限责任公司 | Waste water treatment method and system |
| CN102249474B (en) * | 2011-06-16 | 2013-04-03 | 浙江嘉华化工有限公司 | Treatment method for thiamine waste water produced in production process of phosethyl-Al bulk chemical |
| CN102531260A (en) * | 2011-12-28 | 2012-07-04 | 武汉科梦环境工程有限公司 | Steam stripping technology of high-concentration ammonia nitrogen effluent |
| CN103496713B (en) * | 2013-10-16 | 2016-05-04 | 重庆紫光国际化工有限责任公司 | Remove the method and system of the HCN in sulphur ammonium |
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