CN1167089A - Treatment process for acrylonitrile plant wastewater streams - Google Patents
Treatment process for acrylonitrile plant wastewater streams Download PDFInfo
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- CN1167089A CN1167089A CN96110742A CN96110742A CN1167089A CN 1167089 A CN1167089 A CN 1167089A CN 96110742 A CN96110742 A CN 96110742A CN 96110742 A CN96110742 A CN 96110742A CN 1167089 A CN1167089 A CN 1167089A
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- reactor
- catalyzer
- load
- waste water
- ammonia
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- 238000000034 method Methods 0.000 title claims abstract description 73
- 239000002351 wastewater Substances 0.000 title claims abstract description 54
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 title claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 8
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 7
- 230000006378 damage Effects 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 235000011089 carbon dioxide Nutrition 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 241000196324 Embryophyta Species 0.000 claims description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 9
- 229910052728 basic metal Inorganic materials 0.000 claims description 9
- 150000003818 basic metals Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 240000006909 Tilia x europaea Species 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 159000000009 barium salts Chemical class 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010815 organic waste Substances 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 239000006200 vaporizer Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- -1 hydrogen Chemical compound 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 238000005273 aeration Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920013649 Paracril Polymers 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- 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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- Catalysts (AREA)
Abstract
A process for the destruction of organic wastes and ammonia from acrylonitrile plant wastewater, comprising contacting volatilized wastewater with a catalyst at an elevated temperature so as to convert volatile organic compounds and ammonia to a mixture comprising hydrogen, nitrogen and carbon dioxide which are separated and removed from the stream, yielding a puried aqueous stream, substantially free of organic compounds and ammonia.
Description
The present invention relates to purify the method for vinyl cyanide plant effluent.Especially, the present invention relates to eliminate the catalysis process of organism and ammonia in this waste water.
Vinyl cyanide is a kind of (the highest the 50) of output maximum in the U.S. and the World chemical product.Nearly all vinyl cyanide all is, to be produced by propylene, oxygen and ammonia under the situation as catalyzer at BiPMo or uranium based compound.Vinyl cyanide has many purposes, comprises vinylformic acid and modified acroleic acid fiber, ABS and vinyl cyanide one styrol copolymer, paracril, cotton with the cyanoethlation of artificial soil block (SOilblocks) (polymeric vinyl cyanide in wooden oar).The vinyl cyanide that sucks is that deleterious and known vinyl cyanide is a carcinogens.
Vinyl cyanide factory produces the considerable waste water that contains organism and ammonia.The method of handling or dispose this waste water comprises heat or catalytic burning, biological treatment, wet oxidation and reduction and deep well aeration.In the U.S., the deep well aeration of the employing waste water that a large amount of contaminated wastewater substrate concentrations that vinyl cyanide factory discharges are low is handled now, and the higher waste water of foreign matter content adopts burning method.Although these treatment processs are considered to perfect and are the common industrial practices, still at other method of wastewater treatment of research, these methods have few or not influence to environment the producer of vinyl cyanide.Biological treatment is considered to the vinyl cyanide plant effluent usually and handles more promising a kind of form.Yet biological treatment is very expensive method, and removes all impurity in this waste water unsatisfactorily.
The objective of the invention is a kind of method of eliminating vinyl cyanide plant effluent organic composition and other impurity, this method from environment than deep well aeration or burn and easilier accepted by the people, and more more economical than biological treatment.
The present invention is a kind of destruction waste water, especially the organism in the vinyl cyanide plant effluent and the method for ammonia, this method comprises that evaporable waste water stream contacts the volatile organic component and the ammonia that cause in the current with catalyzer and changes into hydrogen, the mixture of nitrogen and carbonic acid gas in reactor under the temperature that improves.
More particularly, the present invention is a kind of method of destroying organic waste and ammonia in the vinyl cyanide plant effluent stream, and this method comprises
(i) the waste water volatilization is produced and contain steam, the air-flow of ammonia and volatile organic compounds.
(ii) air-flow contacts with catalyzer under the temperature that improves in reactor and causes organic compound and ammonia to change into the mixture that contains hydrogen, nitrogen and carbonic acid gas;
(iii) condensation and the effluent that separates to come autoreactor, produce a kind of based on hydrogen, the steam flow and a kind of liquid flow based on water that also contain nitrogen and carbonic acid gas make liquid flow not have organic compound and ammonia basically thereby are up-to-standard boiler feeding water.
Fig. 1 is a process flow sheet, and optimum implementation of the present invention is described, wherein water in the waste water and volatile organic component volatilized in volatilizer before adding reactor.
Those skilled in the art will appreciate that because accompanying drawing is a sketch, install project such as condenser in addition, heat exchanger, reflux accumulator, training formula reboiler, pump, vacuum pump, temperature sensor, pressure transmitter, pressure safety valve, control valve, flow director, liquid-level controller, receiving tank, storage tank etc., all be that industrial equipments is necessary in addition, the structure of this etceteras of device does not constitute a part of the present invention and is that chemical engineering is implemented routinely.
The present invention is a kind of method of eliminating organic compound and ammonia in the vinyl cyanide plant effluent, and this method changes into the mixture of hydrogeneous, nitrogen and carbonic acid gas by making described waste water volatilization that the air-flow that evaporates is contacted with catalyzer to cause volatile organic component and ammonia.The effluent of reactor comprises these reaction product and makes steam cooling with condensed steam again, so that separate and remove gaseous reaction product.The condensation product that is generated is a kind of current that do not have organic waste and ammonia basically that purified.
Vinyl cyanide factory produces the considerable organic product that produces and the waste water of by product of containing in the acrylonitrile process process, adopt the inventive method to processing be suitable.This waste water comprises one or more following ingredients: nitrile, and as vinyl cyanide and methacrylonitrile, aromatic hydrocarbons, assorted aromatic hydrocarbons, as pyridine, acid amides, organic acid, acid anhydrides, pure and mild ammonia.
Waste water stream is with volatilized before catalyzer contacts.The volatilized steam flow that becomes the volatile component that contains steam and waste water stream of waste water.Volatile organic matter and ammonia that these volatile components exist in the waste water stream typically.Waste water can (can hold the liquid of waste water and the container of vapor phase in vaporizer, wherein liquid waste water adopts heat and or vacuumizes volatilization) volatilized or before the adding reactor other operating unit or waste water be added in the reactor as a kind of liquid and be volatilized when entering reactor, but with before catalyzer contacts.If waste water volatilizees in vaporizer, the involatile constituent in the waste water stream will be concentrated subsequently in vaporizer and shift out from vaporizer.
Can use catalyzer miscellaneous and reactor in the present invention.Reactor can be the catalyticreactor of fixed bed, fluidized-bed, transfer limes or other pattern.Reactor can be follow-on reactor, and it is made up of many pipelines that contain catalyzer that are arranged in parallel.Place a stationary furnace to heat.
The condition that is adopted in the reactor can be changed significantly.Effectively any and conditions suitable that optionally the ammonia in the waste water stream and organic composition are transformed into the mixture that contains nitrogen, hydrogen and carbonic acid gas all can be used for the present invention, preferably, temperature of reaction will be in about 250 ℃-Yue 1000 ℃ scope, and scope is at about 350 ℃-Yue 800 ℃ more fortunately.The scope of pressure can be at normal atmosphere-Yue 1000psig.Yet higher pressure also can use, and the weight ratio scope of steam and hydrocarbon can be about 5: 1-about 10,000: 1.The space velocity scope of liquid is about 1,000 by the about 0.01-of every volume of catalyst per hour, the about 100 volume waste water of preferably about 1-.
In the embodiment of this invention, single or many catalyticreactors all can use.Multiple reactor can parallel connection or arranged in series.
Any effectively and optionally the ammonia that exists in the vinyl cyanide plant effluent stream and volatile organic compounds being transformed into ammonia in the presence of water vapor is that the main suitable catalyst that also contains the mixture of carbonic acid gas and nitrogen all can be used for implementing the present invention.
Typical catalyzer comprises catalyzer of (1) reduced nickel alumina load or the platinum metal catalysts of (2) load, and two kinds of catalyzer are optional with basic metal or alkaline-earth metal activation.
The preferred nickel-alumina catalyzer of nickel catalyzator that is used for present method, this catalyzer contain the nickel of 5-90 weight % and basic metal or the alkaline-earth metal of 0.5-10 weight % on the reductive basis.In this application, the value of weight % is that the gross weight by catalyzer is a benchmark.When being not aluminum oxide, other natural or synthetic contains silica batch.As diatomite, silicon-dioxide, silicon-dioxide one aluminum oxide, silicon-dioxide one zirconium dioxide, natural or synthetic crystal pure aluminium silicate etc. can both use.Basic metal or alkaline-earth metal be as oxyhydroxide, carbonate, or other soluble salt all can be used for catalyzer.Salt of wormwood is present best alkaline matter.
As mentioned above, the composition nickel of catalyzer can be reduced and stablize, and reacts with airborne oxygen on any point after preventing adding nickel.Such reductive action and static stabilization make catalyzer pack into reactor and catalyzer be used for reaction all need not reduction step.But, after catalyzer is placed reactor, be within the scope of the invention with hydrogen or other appropriate reductant (for example carbon monoxide, light hydrocarbon) reducing catalyst.
Being used for platinum metals of the present invention can be ruthenium, rhodium, osmium, iridium, platinum or palladium.The mixture of these metals and/or its compound also can use.Ruthenium is present preferential platinum metals.
The platinum metals also can be added into any known being called in the natural of carrier or the synthetic refractory inorganic oxide material, as aluminum oxide, silicon-dioxide, magnesium oxide, zirconium dioxide, titanium dioxide, carbonic acid gas one aluminum oxide, natural or crystal pure aluminium silicate etc.The amount of platinum metals in catalyst composition can change at 0.01-20 weight %, and preferred amounts is lower than about 10 weight %.The amount that basic metal or alkaline-earth metal exist in catalyzer can change to 10 weight % from 0.Basic metal or alkaline-earth metal are available as oxyhydroxide, carbonate or other soluble salt and use.Term " solubility " is used to refer to and comprises or moisture or non-aqueous solvent, although water is at present best.Salt of wormwood is current preferred as alkali or alkaline earth metal compound.
Other catalyzer that aluminium is used for the inventive method comprises chromic salt, tungstate or the molybdate of the iron family metal of load, and the iron family metal comprises iron, cobalt and nickel, and available organic acid barium salt such as barium acetate are short lives.Preferred version is, the carrier of catalyzer comprises aluminiferous solid support material such as aluminum oxide or calcium aluminate, and catalyzer contains iron group metal 1-10 weight % by oxide compound usually, contains chromic salt, tungstate or molybdate 5-25 weight %.The remainder of catalyzer is made up of carrier substance, as aluminum oxide or other alumina-bearing material.
From the effluent that reactor is discharged, moisture, nitrogen, hydrogen and carbonic acid gas.Make flow out the logistics cooling with condensed steam again divided gas flow in gas/liquid separation, get rid of at last, these gases of removing are capable of circulation to reactor, act as a fuel to be burnt or to discharge.The aqueous stream that produces does not have organism and ammonia basically, is up-to-standard boiler feeding water, can be used for producing steam or other on-the-spot purposes.
Now referring to accompanying drawing, this figure illustrates optimum implementation of the present invention.In the figure, the waste water of vinyl cyanide factory is added in the vaporizer 2 through pipeline 1.In this vaporizer, water, ammonia and volatile organic component are volatilized to enter reactor 5 through pipeline 3 discharge vaporizers then.Involatile constituent is discharged through pipeline 4 from vaporizer.In reactor, the water that evaporates, ammonia and organism pass through above appropriate catalyst under the raising temperature.Ammonia and organism reaction form nitrogen, hydrogen and carbonic acid gas.These reaction product and water vapor leave reactor through pipeline 6 and enter in the gas/liquid separation 7.In gas/liquid separation, the effluent of reactor is cooled and makes water vapor condensation, and water of condensation is discharged from separator through pipeline 9.Gaseous reaction product leaves gas/liquid separation through pipeline 8.
Specific embodiment
For the present invention is described, provide the following example.
The raw material that is used for this embodiment is the waste water that reclaims and purify part from vinyl cyanide factory.What handle is three strands of different waste water streams.The physical properties of each strand waste water is listed in the table 1.The waste water raw material is contained in the stainless steel reactor of commercial catalyst (United Catalystcll-9-02, standard is formed 12%Ni and 88% fire-resistant alumina supporter, 10-20 order particle) with the pump suction downwards.Reaction conditions is as shown in table 2.The reactor effluent heat exchanger of at first flowing through is delivered to gas/liquid separation to product mixtures then with condensed steam, divides water outlet there from product gas.The PH of assay products water, TOC, COD, volatility and semi-volatile organic matter and ammonium ion.The H of analytical reaction expellant gas
2, CO
2, CO, N
2, O
2, CH
4, C
2-C
4Hydrocarbon and NO
xTable 3 and 4 is listed the analytical results of product.
Table 1
The waste water raw material properties
TOC=total organic carbon COD=chemical oxygen demand (COD)
| Waste water stream | PH???????TOC???????COD???????NH 4 +Nitrogen total amount mg/L mg/L mg/L mg/L |
| ??A ??B ??C | 9.0?????1,100??????1,970???????94????????590 5.4?????7,180?????17,900??????520??????3,300 5.4????31,200?????74,100????3,700?????14,000 |
Table 2
Reaction conditions
| Embodiment | The feed rate ℃ PSI mL/cc catalyzer/Hr of waste water stream temperature, pressure waste water |
| ????1 ????2 ????3 | A 500 20 1.13 B 500 environment 0.87 C 750 environment 0.69 |
Table 3
The analysis of product condensation product
NA=does not analyze ND=and shows and detect
| Embodiment | The waste water stream stops COD TOC NH4+ volatility and partly waves and stay a hour PH mg/L mg/L mg/L to send out organic matter |
| ???1 ???1 ???2 ???3 | ???A??????19???5.6??6?????5????NA????????ND ???A??????71???5.9??0?????0???14.1???????ND ???B???????4???6.5??0?????0???70.0???????ND ???C???????7???4.6??1???＜40???2.2???????ND |
Table 4
Discharge the analysis of gas
NA=does not analyze ND=and does not detect
| Embodiment | The waste water stream stops H 2????CO 2????N 2?????CO??????CH 4????O 2????NO xStay a hour Vol.% Vol.% Vol.% Vol.% Vol.% Vol.% PPM |
| ???1 ???1 ???2 ???3 | ???A?????19?????66.0???25.5????6.0?????＜0.05???＜0.05???ND?????NA ???A?????71?????65.6???26.1????6.0?????＜0.05???＜0.05???ND?????NA ???B??????4?????67.1???27.3????5.5???????0.11????ND??????ND?????NA ???C??????7?????65.3???23.8????6.5???????4.4????＜0.05???ND???＜10 |
In embodiment 1, flow at 500 ℃ of vinyl cyanide plant effluents of handling low TOC down with method of the present invention.Contained organic waste all change into hydrogen, carbonic acid gas and nitrogen.The product water of condensation does not have organic carbon basically and only contains the very ammonium ion of lower concentration.
Embodiment 2 has proved the organic waste completely destroy in containing the quite high vinyl cyanide plant effluent of organic carbon load.Under 500 ℃ of temperature of reaction, it mainly is hydrogen that contained organic waste change into fully, nitrogen, and carbon dioxide.There is not organic carbon in the product water of condensation.But the ammonium ion content of product water of condensation is than higher, because the nitrogen of raw material waste water load has improved.
Embodiment 3 shows that present method is for the validity that purifies the very high acrylonitrile process purification of waste water of organic carbon and nitrogen load.Under 750 ℃, contained organic composition is owing to be converted to and be mainly hydrogen, nitrogen, carbonic acid gas and CO (carbon monoxide converter) gas and destroyed fully.Measure product gas and learn there is not NO basically
xPollutent.The product water of condensation does not have organic carbon and ammonium concentration very low basically.
Previous embodiments of the present invention only plays explanation and describes purpose.This specification sheets is not planned with detailed or limit the invention to accurate open form, and open many improvement and correction are obviously arranged is possible from above-mentioned.For example, the parameter of reactor, as type of reactor, temperature, pressure, sizes etc. depend on mutual relationship and the improvement done for these parameters and do not influence desired result basically.The description of front intention is to explain better principle of the present invention and uses in fact, can make other technician of this area with its various embodiments with utilize the present invention better under the condition of the various modifications that the special purpose that is suitable for expecting is done thus.Attempt to limit the present invention with following claim.
Claims (41)
1. a destruction is from the method for the organic compound of vinyl cyanide plant effluent, the waste water that this method comprises the moisture vapor that will evaporate and volatile organic compounds contacts with catalyzer in reactor improving under the temperature, so that being converted into, volatile organic compounds comprises hydrogen, the mixture of nitrogen and carbonic acid gas.
2. by the process of claim 1 wherein that the vinyl cyanide plant effluent includes organic compounds and ammonia and the waste water that wherein volatilized comprises water vapor, volatile organic matter and ammonia.
3. by the process of claim 1 wherein that catalyzer is selected from the nickel catalyzator by (1) load, the platinum metal catalysts of (2) load, or (3) are with chromic salt, tungstate or the molybdate of the short iron family metal load of living of barium salt.
4. by the method for claim 3, wherein catalyzer be the platinum metal catalysts of the nickel catalyzator of (1) load or (2) load and wherein catalyzer with at least a basic metal or the short work of alkaline-earth metal.
5. by the process of claim 1 wherein that reactor is selected from fixed-bed reactor, fluidized-bed reactor and transfer limes reactor.
6. by the process of claim 1 wherein that technological temperature is between about 250 ℃-Yue 1000 ℃.
7. by the process of claim 1 wherein that technological temperature is between about 350 ℃-Yue 800 ℃.
8. by the process of claim 1 wherein that operation pressure is between about 1 normal atmosphere-Yue 100psig.
By the process of claim 1 wherein steam to the weight ratio of hydrocarbon between about 5: 1-about 10,000: 1.
By the process of claim 1 wherein the liquid reactor space velocity by every volume of catalyst per hour between the waste water of about 1,000 volume of about 0.1-.
11. by the method for claim 10, wherein the liquid reactor space velocity by every volume of catalyst per hour between the waste water of about 100 volumes of about 1.0-.
12. a destruction is from the method for the ammonia and the volatile organic matter of vinyl cyanide plant effluent, this method comprises
(i) make the waste water volatilization comprise water vapor with generation, the steam flow of ammonia and volatile organic matter;
(ii) in reactor, air-flow is contacted under the temperature that improves with catalyzer, comprise hydrogen, the mixture of nitrogen and carbonic acid gas in the presence of water vapor so that volatile organic compounds and ammonia are changed into;
(iii) cool off with the effluent that separates to come autoreactor and comprise hydrogen with product, the steam flow of nitrogen and carbonic acid gas and the liquid flow that comprises the water that does not have organic compound and ammonia basically.
13. by the method for claim 12, wherein catalyzer is selected from the nickel catalyzator of (1) load, the platinum metal catalysts of (2) load, or (3) urge load chromic salt, tungstate or the molybdate of iron family metal alive with barium salt.
14. by the method for claim 13, wherein catalyzer be the platinum metal catalysts of the nickel catalyzator of (1) load or (2) load and wherein catalyzer with at least a basic metal or the short work of alkaline-earth metal.
15. by the method for claim 12, wherein reactor is selected from fixed-bed reactor, fluidized-bed reactor and transfer limes reactor.
16. by the method for claim 12, wherein technological temperature is between about 250 ℃-1000 ℃.
17. by the method for claim 16, wherein technological temperature is between about 350 ℃-Yue 800 ℃.
18. by the method for claim 12, its operation pressure is between about 1 normal atmosphere-Yue 100psig.
19. by the method for claim 12, wherein steam to the weight ratio of hydrocarbon between about 5: 1 about 10,000: 1.
20. by the method for claim 12, wherein the liquid reactor space velocity by every volume of catalyst per hour between the waste water of about 1,000 volume of about 0.1-.
21. by the method for claim 20, wherein the liquid reactor space velocity by every volume of catalyst per hour between the waste water of about 100 volumes of about 1.0-.
22. method of destroying volatile organic compounds and ammonia in the current, this method comprises the volatilization current, the moisture vapor that volatilized is contacted with catalyzer in reactor under the raising temperature, cause and to transform into hydrogen at organic compound in the air-flow that volatilized and ammonia, the mixture of nitrogen and carbonic acid gas.
23. by the method for claim 22, wherein catalyzer is selected from the nickel catalyzator of (1) load, the platinum metal catalysts of (2) load, or (3) urge load chromic salt, tungstate or the molybdate of iron family metal alive with barium salt.
24. by the method for claim 23, wherein catalyzer be selected from the platinum metal catalysts of the nickel catalyzator of (1) load or (2) load and wherein catalyzer with the catalyzer of at least a basic metal or the short work of alkaline-earth metal.
25. by the method for claim 22, wherein reactor is selected from fixed-bed reactor, fluidized-bed reactor and transfer limes reactor.
26. by the method for claim 22, technological temperature wherein is between about 250 ℃-1000 ℃.
27. by the method for claim 26, wherein technological temperature is between about 350 ℃-Yue 800 ℃.
28. by the method for claim 22, wherein operation pressure is between about 1 normal atmosphere-Yue 100psig.
29. by the method for claim 22, wherein the weight ratio of steam and hydrocarbon is between about 5: 1-about 10,000: 1.
30. by the method for claim 22, wherein the liquid reactor space velocity by every volume of catalyst per hour between the waste water of about 1000 volumes of about 0.1-.
31. by the method for claim 30, wherein the liquid reactor space velocity by every volume of catalyst per hour between the waste water of about 100 volumes of about 1.0-.
32. the method by the qualified boiler feeding water of the vinyl cyanide plant effluent quality of production, this method comprises
(i) volatilization waste water contains the water vapor of waste water and the steam flow of volatile organic component and ammonia with generation;
(ii) steam flow contact with catalyzer under the temperature that improves in reactor, causes that conversion volatile organic component and ammonia become hydrogen in the presence of water vapor.The mixture of nitrogen and carbonic acid gas.
(iii) the cooling and separate reactor in effluent with the generation hydrogen, the steam flow of nitrogen and carbonic acid gas and current, wherein current are up-to-standard boiler feeding water.
33. by the method for claim 32, wherein catalyzer is selected from the nickel catalyzator of (1) load, the platinum metal catalysts of (2) load, or (3) urge load chromic salt, tungstate or the molybdate of iron family metal alive with barium salt.
34. by the method for claim 33, wherein catalyzer be selected from the platinum metal catalysts of the nickel catalyzator of (1) load or (2) load and wherein catalyzer with the catalyzer of at least a basic metal or the short work of alkaline-earth metal.
35. by the method for claim 32, wherein reactor is selected from fixed-bed reactor, fluidized-bed reactor and transfer limes reactor.
36. by the method for claim 32, wherein technological temperature is between about 250 ℃-1000 ℃.
37. by the method for claim 36, wherein technological temperature is between about 350 ℃-Yue 800 ℃.
38. by the method for claim 32, wherein operation pressure is between about 1 normal atmosphere-Yue 100psig.
39 methods by claim 32, wherein the weight ratio of water vapor and hydrocarbon is between about 5: 1-about 10,000: 1.
40. by the method for claim 32, wherein the liquid reactor space velocity by every volume of catalyst per hour between the waste water of about 1,000 volume of about 0.1-.
41. by the method for claim 40, wherein the liquid reactor space velocity by every volume of catalyst per hour between the waste water of about 100 volumes of about 1.0-.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96110742A CN1167089A (en) | 1996-06-03 | 1996-06-03 | Treatment process for acrylonitrile plant wastewater streams |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96110742A CN1167089A (en) | 1996-06-03 | 1996-06-03 | Treatment process for acrylonitrile plant wastewater streams |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717164B (en) * | 2009-10-20 | 2011-08-03 | 无锡殷达尼龙有限公司 | Method for treating and recycling waste water of cyanation technique and device thereof |
| CN102849838A (en) * | 2012-09-24 | 2013-01-02 | 中国矿业大学(北京) | Acrylonitrile wastewater deep treatment system |
| CN103623531A (en) * | 2012-08-29 | 2014-03-12 | 中国石油化工股份有限公司 | Processing method for waste liquid containing acrylonitrile |
| CN104108780A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for treating wastewater in acrylonitrile production refining process |
| CN115990488A (en) * | 2021-10-20 | 2023-04-21 | 中国石油化工股份有限公司 | Wet oxidation catalyst, preparation method and application thereof |
-
1996
- 1996-06-03 CN CN96110742A patent/CN1167089A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717164B (en) * | 2009-10-20 | 2011-08-03 | 无锡殷达尼龙有限公司 | Method for treating and recycling waste water of cyanation technique and device thereof |
| CN103623531A (en) * | 2012-08-29 | 2014-03-12 | 中国石油化工股份有限公司 | Processing method for waste liquid containing acrylonitrile |
| CN103623531B (en) * | 2012-08-29 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of processing method of the waste liquid containing acrylonitrile |
| CN102849838A (en) * | 2012-09-24 | 2013-01-02 | 中国矿业大学(北京) | Acrylonitrile wastewater deep treatment system |
| CN104108780A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for treating wastewater in acrylonitrile production refining process |
| CN104108780B (en) * | 2013-04-16 | 2016-12-28 | 中国石油化工股份有限公司 | Method of wastewater treatment in acrylonitrile process subtractive process |
| CN115990488A (en) * | 2021-10-20 | 2023-04-21 | 中国石油化工股份有限公司 | Wet oxidation catalyst, preparation method and application thereof |
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