CN1055918C - Olefinic nitrile emergency cooling process - Google Patents
Olefinic nitrile emergency cooling process Download PDFInfo
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- CN1055918C CN1055918C CN97106711A CN97106711A CN1055918C CN 1055918 C CN1055918 C CN 1055918C CN 97106711 A CN97106711 A CN 97106711A CN 97106711 A CN97106711 A CN 97106711A CN 1055918 C CN1055918 C CN 1055918C
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The present invention relates to a quenching technology for olefinic nitrile. The technology comprises: (a) a quenching tower is composed of an upper section, a middle section and a lower section; (b) an effluent of a reactor in which ammonia conversion rate reaches 97 to 99% contact quenching liquid in a quenching system to generate a gaseous; quenching effluent; (c) the gaseous; quenching effluent contacts the quenching liquid and acetic acid in the middle section of the quenching tower; (d) after the quenching effluent is quenched and absorbed in the middle section and cooled to 25 to 45 DEG C by the quenching liquid at the upper section, condensed liquid at the upper section is sent to an extracting tower and the gaseous; quenching effluent at the upper section is sent to an absorbing tower. The quenching technology has the characteristics that the effluent of the quenching tower can be processed conveniently and the recovery rate of olefinic nitrile can be improved. The present invention can be used in industrial production.
Description
The present invention relates to olefinic nitrile emergency cooling process.
The production of ammoxidation of hydrocarbons system unsaturated nitrile is a key areas of petrochemical industry, wherein propylene and isobutene ammonia oxidizing acrylonitrile production and methacrylonitrile industrialization already, but have a common issue with, promptly unsaturated nitrile is unsettled under alkaline condition, and polymerization very easily takes place.Therefore no matter which kind of oxidative ammonolysis, the unreacted ammonia in the reactant gases all need be removed, and all adopts the sulfuric acid chilling to remove unreacted ammonia at present.This method will produce and contain nitrile sulphur ammonium sewage, intractable in a large number.Because various countries are very high to three wastes processing requirements, therefore solving by-product sulphur ammonium has become noticeable problem.
With the ammoxidating propylene to prepare acrylonitrile is example: propylene, ammonia and air generate major product vinyl cyanide and byproduct acetonitrile, prussic acid, propenal, vinylformic acid, carbon monoxide and carbonic acid gas by the fluidized-bed reactor ammonia oxidation, also have a small amount of unreacted propylene and ammonia.After reactant gases leaves reactor, enter neutralizing tower, absorb unreacted ammonia with aqueous sulfuric acid and generate the sulphur ammonium through cooling.Owing to part water vapor in the reactant gases also condensation is told, therefore produce sulphur ammonium sewage.Remove gas behind the unreacted ammonia absorption tower of anhydrating, with water at low temperature with in the gas all organism absorb.Absorption liquid goes vinyl cyanide to reclaim refining step and isolates the high-purity propylene nitrile, prussic acid and crude acetonitrile.
In aforesaid propylene nitrile production technique, very important with the unreacted ammonia that sulfuric acid is removed in the reactant gases at neutralizing tower.Because vinyl cyanide and prussic acid all are easy polymeric materials, easier polymerization under neutral and slight alkalinity condition especially.So not only cause the loss of vinyl cyanide and hydrogen cyanide product, also can pollute production unit.Produce sulphur ammonium sewage and be inevitable in existing manufacturing technique, 1 ton of vinyl cyanide of common every production can produce the sulphur ammonium sewage of 0.6 ton of 20% concentration, and 0.6 ton of reaction is a sewage, and polymer content is about 16%, intractable.
Sulphur ammonium sewage is formed very complicated, roughly comprises following a few class:
1, superpolymer: because the pH value of neutralizing tower circulated sprinkling liquid is controlled at 2～7 scopes, a certain amount of reaction product is arranged, as vinyl cyanide, prussic acid and propenal polymerization reaction take place generate superpolymer.Each material polymerization losses amount is calculated total growing amount, and vinyl cyanide is 2～5%, and prussic acid is 3～8%, and propenal is then up to 40～80%, and superpolymer content is very high in the visible sulphur ammonium sewage.Superpolymer in the sewage also has characteristics, and promptly molecular weight distribution is very wide, and a part of molecular weight of high polymer is less, dissolve in sulphur ammonium sewage, another part molecular weight of high polymer is bigger, becomes water-fast black solid, and this has just caused another layer difficulty for reclaiming the sulphur ammonium.
2, high boiling material: the neutralizing tower service temperature is generally about 80 ℃, and the vinylformic acid in the reactant gases is condensed and is present in the sulphur ammonium sewage, and in addition also having some in the reactant gases is high boiling point cyanalcohols that carbonyl compound and prussic acid condensation produce.
3, low-boiling-point substance: mainly be vinyl cyanide, acetonitrile and the prussic acid etc. that are dissolved in the sulphur ammonium sewage, its content is looked the difference of spray liquid temperature, roughly at 500～5000ppm.
4, catalyst fines: produce in the process of vinyl cyanide at fluidized-bed reactor, by the blow off catalyst fines of beds of reactant gases, the overwhelming majority is through the cyclonic separator recovery and return bed, but the little amount of catalyst fine powder is also arranged by the gas blow-out reactor, is washed at neutralizing tower.The amount of blowing out of catalyzer is about 0.2～0.7kg to produce 1 ton of vinyl cyanide.
By above explanation as can be known, it is very difficult to reclaim crystallization sulphur ammonium from sulphur ammonium sewage.If do not reclaim the sulphur ammonium it is not burnt, can produce sulfurous gas again and cause atmospheric secondary pollution, many countries do not allow direct discharging.Another problem that sulphur ammonium sewage is handled with combustion method is that temperature of combustion requires to reach 850～1100 ℃ and the prussiate in the sewage can be burnt, and therefore will consume a large amount of fuel.Owing to contain sulfurous gas in the burning gas steel are had corrosion, waste heat boiler recovery heat is set also has any problem, the direct emptying of high-temperature gas can cause thermal pollution again to atmospheric environment.
In sum, the sulphur ammonium sewage that produces in the acrylonitrile process causes very big problem, has had a strong impact on the development of vinyl cyanide process industry.Exploitation does not produce the process for production of acrylonitrile of sulphur ammonium for this reason, and promptly so-called " cleaning procedure " caused the very big attention of vinyl cyanide industry in the world.
Document US 3885928 has been introduced a kind of recovery and refining system of alkene nitrile, wherein the purpose of emergency cooling process is on the one hand reactor effluent to be cooled to certain temperature, is on the other hand to remove unreacted ammonia and the polymkeric substance and the heavy impurity that react generation in the reactor effluent.The technical scheme that is adopted in the document be water and sulfuric acid as quench liquid, the tower base stream of moisture, sour, polymkeric substance and other impurity is discharged from quenching system.Contain 10% ammonium sulfate, 16% heavy organism, a small amount of lightweight organism and water (about 74%) in these tower base streams by weight percentage approximately.Because the heavy organism contains senior nitrile substituent, and is made up of some mixtures that contain the different high boiling point organic compounds of oxidizing hydrocarbons, so the processing of these bottom streams bothers very much, needs a large amount of investment of cost to handle, as burning or recovery.In the past because the ammonia transformation efficiency is not controlled, make the easy and alkene nitrile generation side reaction of unreacted ammonia in addition, reduced the refining rate of recovery of alkene nitrile.
For overcoming the deficiency that exists in the above-mentioned document, the purpose of this invention is to provide a new olefinic nitrile emergency cooling process, this technology has chilling Tata still effluent to be handled conveniently, and can improve the characteristics of the alkene nitrile rate of recovery.
The objective of the invention is to realize by following technical scheme: a kind of olefinic nitrile emergency cooling process comprises:
A) quench tower is by last, in, following three sections compositions, wherein hypomere is a void tower;
B) the ammonia transformation efficiency reaches 97～99% reactor effluent and contacts in quench tower lower portion with aqueous quench liquid in the quenching system, generates gaseous state chilling effluent;
C) gaseous state chilling effluent contacts with acetic acid with aqueous quench liquid in the quench tower stage casing;
D) after quench tower stage casing chilling absorbed, gaseous state chilling effluent was cooled to 25～45 ℃ of temperature through quench tower epimere aqueous quench liquid again, and quench tower epimere phlegma removes extraction tower, and the gaseous state chilling effluent of epimere goes to the absorption tower.
Aqueous quench liquid can be spray water in the technique scheme, also can be recirculated water.All operate under less than 7 condition at pH value in quench tower lower portion, stage casing, and the service temperature of its quench tower lower portion is 70～90 ℃, and its preferable range is 75～85 ℃; The service temperature in quench tower stage casing is 65～75 ℃, and its preferable range is 68～72 ℃; The gaseous effluent temperature out of quench tower epimere is 30～35 ℃.At the alkene nitrile described in the technique scheme is vinyl cyanide and methacrylonitrile, then more suitable to vinyl cyanide.
The inventor obviously descends the unreacted ammonia in the reactant gases by the improvement of fluid bedreactors and catalyzer, has created prerequisite therefore for no sulphur ammonium process for production of acrylonitrile.Owing to also generate a certain amount of vinylformic acid during ammoxidation of propylene, therefore do not need to make catalyzer that the transformation efficiency of ammonia is reached 100%, if reach 97～99%, also can not add the sulfuric acid neutralization basically.
Technology of the present invention is roughly as follows; Air and propylene, ammonia are sent into the fluidized-bed reactor of special construction respectively through dispersion plate and propylene ammonia sparger, generate vinyl cyanide and various by product by the catalyst layer reaction.The a large amount of reaction heat that produce in the reaction produce high pressure steam by water-cooled tube.Temperature of reaction is 440～450 ℃, and reaction pressure is 0.4～0.8kg/cm
2, the unstripped gas proportioning is: propylene: ammonia: air=1: 1.15～1.25: 9.0～9.8.Propylene conversion is 98～99%, and the ammonia transformation efficiency is 97～98%.
After having finished oxidative ammonolysis, quenching system is refining first key point that reclaims of alkene nitrile, usually leave the high-temperature reacting gas of fluidized-bed reactor, its temperature is 430～450 ℃, and this high-temperature reacting gas at first removes quench tower after air heat exchanger is cooled to 200～250 ℃.
Quench tower is made up of for three sections upper, middle and lower, and reactant gases is cooled to 35 ℃ through quench tower and goes to the absorption tower.Quench tower lower portion is a void tower, can be used to the circulation fluid spray cooling from the stage casing, and the superfluous water of hypomere is delivered to the sewage roasting kiln and burnt.
Quench tower stage casing water circulated sprinkling further cools off reactant gases.For the pH value that keeps circulation fluid less than 7, can add acetic acid in case of necessity to regulate PH.The stage casing is provided with water cooler and removes the heat that the stage casing produces; The water of condensation that the stage casing produces is delivered to quench tower lower portion.The quench tower epimere also is a cooling section, with the recirculated water spray gas cooling is arrived room temperature.Epimere also is provided with water cooler and removes the heat that epimere produces, and the epimere phlegma removes extraction tower afterwards, and cooled reactant gases goes to the absorption tower.
Reactant gases absorbs wherein all organic products with cold water in the absorption tower.Absorption liquid removes extraction tower through preheating.Absorb afterreaction gas by absorbing cat head emptying.
From after the absorption liquid preheating on absorption tower and the phlegma of quench tower epimere merge, from extraction tower middle part charging.Vinyl cyanide, prussic acid and less water are steamed by cat head.Be divided into the profit two-phase after the condensation, water is got back to the charging of this tower, and an oil phase part is back to this column overhead, and all the other dehydrogenation cyanic acid towers are further handled.Extracting acetonitrile out from this tower feed points bottom side line, can be gas phase or liquid phase, removes the acetonitrile recovery tower, and the acetonitrile tower bottoms that boils off acetonitrile returns this tower again.
Crude acetonitrile from the extraction cat head enters prussic acid tower separation of hydrogen cyanic acid.This tower is operated under negative pressure, is got high-purity hydrogen cyanic acid, is extracted out the vinyl cyanide that contains small amount of moisture by the tower still by cat head, the water separator that after the water cooler cooling, deoils, and water layer goes back to the quench tower stage casing, and oil reservoir removes finishing column.
Finishing column also is under reduced pressure to operate.Moisture content in the crude acetonitrile becomes azeotrope to steam from cat head with low-boiling-point substance with vinyl cyanide, condensation then, oily water separation.Water layer is sent the extraction tower charging back to, and the oil reservoir major part is back to finishing column, returns extraction tower on a small quantity.Finished product acrylonitrile is extracted out by tower top, removes the finished product storage tank after the cooling, and still liquid returns extraction tower.
Being concentrated to concentration from the acetonitrile of extraction tower side line at the acetonitrile tower is 80% crude acetonitrile.Tower bottoms returns extraction tower.This acetonitrile tower can be if do not establish reboiler according to the state (liquid phase or gas phase) of acetonitrile charging.
In sum, one of key of no sulphur ammonium process for production of acrylonitrile is a quench tower.Because the transformation efficiency of ammonia has reached 97～99% in fluidized-bed reactor, so ammonia content is very low in the reactant gases.In addition, in the ammoxidation of propylene process, also generate a certain amount of vinylformic acid, yield about 0.5～2.0%.Reclaim in the treating process at vinyl cyanide simultaneously,, add acetic acid at the prussic acid tower in order to prevent the polymerization of prussic acid.Because the acetic acid that adds finally also is to get back to quench tower, therefore under normal circumstances the pH value of quench tower recirculated water can be greater than 7.
Among the present invention, regulate the quench tower pH value and be not limited to acetic acid, other organic or inorganic acid all can be used.As phosphoric acid, boric acid, formic acid can not produce other acids of nuisance after oxalic acid and the burning, but consider from price comparatively suitable with acetic acid.
Because acetic acid has certain volatility, the ammonium salt of acetic acid is very unstable yet, so the present invention adopts the syllogic quench tower, and control quench tower lower portion temperature is 70～90 ℃, is preferably 75～85 ℃.Temperature is crossed the low vinyl cyanide in the hypomere liquid effluent that then makes, and useful matter content such as prussic acid increase, and cause product loss.Temperature is too high then can to make acetic acid, and acrylic acid ammonium salt decomposes.
Quench tower stage casing temperature is 65～75 ℃, is preferably 68～72 ℃.The too high meeting of temperature makes acetic acid take epimere to, and the circulation that enters recovery system absorbs in the water.Because the recovery system equipment material mostly is carbon steel, can cause corrosion.Temperature is too low to make then that organic content increases in the drainage water of stage casing, and hypomere drainage water (being called reaction is sewage) amount is increased, and the fuel quantity that the sewage roasting kiln is consumed rises.
Quench tower epimere Outlet Gas Temperature is 25～45 ℃, is preferably 30～35 ℃.Temperature is crossed to hang down and can be made the temperature difference of epimere water recirculator heat-eliminating medium too little, needs the water cooler with big heat transfer area.The too high cold consumption that then makes circulation absorb water of temperature rises.
The present invention is owing to adopt acetic acid to replace sulfuric acid as the unreacted ammonia in the neutralization reactor effluent, making aftertreatment eliminate reaction is that the sewage burning produces sulfurous gas, atmosphere is caused secondary pollution problem, a large amount of combustions heat that simultaneously recyclable sewage roasting kiln produces.Owing to do not contain corrosive sulfurous gas in the burning gas, so can in the sewage roasting kiln, waste heat boiler be installed, reclaim the heat of high temperature (about 1000 ℃) burning gas and produce high pressure steam, also eliminated the thermal pollution of high-temperature gas to environment.Can save sulphur ammonium recovery process in addition, reduce investment cost significantly.On the other hand since the stage casing of this technology quench tower and hypomere all turn round under less than 7 condition at pH value, reduced the polymerization losses of vinyl cyanide and prussic acid, make the refining rate of recovery of vinyl cyanide 92～94% bring up to 96～98%, obtained good effect from what usually (need to reclaim ammonium sulfate method).Below just the invention will be further elaborated by embodiment.
[embodiment 1]
Propylene, ammonia and air are sent into fluidized-bed reactor, and flow is: propylene 710kg/hr (purity 93%), ammonia 307kg/hr, air 4365kg/hr.2 meters of reactor inside diameter, high 23 meters, add 9.5 tons as example 3 catalyzer in the catalyzer of example among the CN1021638C 1 and the 0.5 ton of Chinese patent 96116456.5.440 ℃ of temperature of reaction, reaction pressure 0.5kg/cm
2Reactor outlet gas sampling analysis, vinyl cyanide growing amount are 673kg/hr, acetonitrile 25.1kg/hr, prussic acid 82.5kg/hr, vinylformic acid 6.8kg/hr, unreacted ammonia 30.6kg/hr.
Temperature is that 440 ℃ reactant gases is cooled to 210 ℃ through watercooler and removes quench tower.Quench tower is a syllogic.Hypomere is a void tower, with acid hot water (pH value is about 6) circulated sprinkling reactant gases is cooled to 80 ℃.Recirculated water is from the unnecessary phlegma in quench tower stage casing, the water layer and the finished product tower bottoms of prussic acid tower still water-and-oil separator.Hypomere recirculated water does not have water cooler, and unnecessary phlegma is that sewage decontaminated water roasting kiln is burnt as reaction.
80 ℃ reactant gases enters the quench tower stage casing from hypomere, removes epimere with sour water (pH value is about 4) circulated sprinkling after being cooled to 70 ℃, and the unnecessary phlegma in stage casing is delivered to this tower hypomere.Stage casing recirculated water has water cooler, removes the heat that the stage casing condensation is produced.Inject acetic acid at the stage casing cooler outlet, add-on is regulated according to the pH value of stage casing recirculated water, is about 20kg/hr.
70 ℃ reactant gases is recycled spray liquid at epimere and further is cooled to 35 ℃, delivers to the absorption tower by cat head.Epimere recirculated water has water cooler to be used to remove the heat that the epimere condensation is produced.The unnecessary phlegma of epimere is directly delivered to compound extracting desorption tower (hereinafter to be referred as desorption tower) charging.
The absorption tower is that filler and column plate constitute.With the whole organic products in 2～4 ℃ the water at low temperature absorption reaction gas.The ratio that absorbs water and vinyl cyanide is 12～16.Reactant gases after the absorption is put to atmosphere by cat head.Acrylonitrile concentration is about 6% in the absorption liquid, removes desorption tower through preheating.
Compound extracting desorption tower (CN1014888C) has 100 porous plates.From absorbing tower bottoms, the water layer of overhead oil water separator and finished product cat head water layer mix, charging in the middle part of tower after the preheating.Extraction solvent water adds on tower top, about 50 ℃ of water temperature, and the water ratio is 6～8.Steam whole vinyl cyanide and prussic acid at cat head, wherein also contain 10% moisture of having an appointment.Condensation, oily water separation, water layer returns the charging of this tower, and the oil reservoir partial reflux is to this column overhead, and reflux ratio is about 0.7, all the other dehydrogenation cyanic acid towers.Extract acetonitrile out from Ben Ta bottom side line and remove the acetonitrile tower.This tower bottoms is a poor-water, loops back the absorption tower.
The acetonitrile tower has 50 porous plates, and opening for feed is on tower top.Steam concentration from cat head and be about 80% crude acetonitrile, partial reflux, all the other go to acetonitrile refining workshop section.Per hour can get the about 30kg of crude acetonitrile.
Dehydrogenation cyanic acid tower has 60 porous plates, and opening for feed is at the tower middle part.This tower is a negative-pressure operation, and tower top pressure is 0.75atm.Steaming high-purity hydrogen cyanic acid from cat head, refluxes in the condensation rear section, and reflux ratio is 4～5, and all the other per hour can about 75kg finished product as the discharging of prussic acid finished product.Cat head adds little acetic acid as the prussic acid stopper.Tower bottoms is a crude acetonitrile, wherein contains small amount of moisture, is cooled to 25 ℃ of water separators that deoil; Water layer removes quench tower lower portion, and oil reservoir removes finishing column.
Finishing column also is to operate under negative pressure, if cat head steams owner's vinyl cyanide and water, a small amount of low-boiling-point substance is arranged also.Water layer and part are returned the charging of extraction desorption tower after the condensation, and all the other oil reservoirs are back to the finishing column cat head.Finished product acrylonitrile is extracted out by tower top, per hour can get 650kg.Tower bottoms mainly is a cyanalcohol, also contains a small amount of high boiling material.
By above result, the refining rate of recovery of vinyl cyanide is 96.6%, and vinyl cyanide per ton consumes 1.01 tons of propylene, 0.47 ton of ammonia, acetic acid 30kg.
Claims (9)
1, a kind of olefinic nitrile emergency cooling process comprises:
A) quench tower is made up of for three sections upper, middle and lower, and wherein hypomere is a void tower;
B) the ammonia transformation efficiency reaches 97～99% reactor effluent and the aqueous quench liquid in the quenching system in quench tower lower portion
Contact generates gaseous state chilling effluent;
C) gaseous state chilling effluent contacts with acetic acid with aqueous quench liquid in the quench tower stage casing;
D) after quench tower stage casing chilling absorbed, gaseous state chilling effluent was cooled to temperature through quench tower epimere aqueous quench liquid again
Spend 25～45 ℃, quench tower epimere phlegma removes extraction tower, and the gaseous state chilling effluent of epimere goes to the absorption tower.
2,, it is characterized in that aqueous quench liquid can be spray water, recirculated water according to the described olefinic nitrile emergency cooling process of claim 1.
3,, it is characterized in that quench tower lower portion, stage casing all operate under less than 7 condition at pH value according to the described olefinic nitrile emergency cooling process of claim 1.
4, according to the described olefinic nitrile emergency cooling process of claim 1, the service temperature that it is characterized in that quench tower lower portion is 70～90 ℃.
5, according to the described olefinic nitrile emergency cooling process of claim 4, the service temperature that it is characterized in that quench tower lower portion is 75～85 ℃.
6, according to the described olefinic nitrile emergency cooling process of claim 1, the service temperature that it is characterized in that the quench tower stage casing is 65～75 ℃.
7, according to the described olefinic nitrile emergency cooling process of claim 6, the service temperature that it is characterized in that the quench tower stage casing is 68～72 ℃.
8, according to the described olefinic nitrile emergency cooling process of claim 1, the gaseous effluent temperature out that it is characterized in that the quench tower epimere is 30～35 ℃.
9,, it is characterized in that the alkene nitrile is vinyl cyanide, methacrylonitrile according to the described olefinic nitrile emergency cooling process of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106711A CN1055918C (en) | 1997-11-13 | 1997-11-13 | Olefinic nitrile emergency cooling process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106711A CN1055918C (en) | 1997-11-13 | 1997-11-13 | Olefinic nitrile emergency cooling process |
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| CN1217323A CN1217323A (en) | 1999-05-26 |
| CN1055918C true CN1055918C (en) | 2000-08-30 |
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| CN97106711A Expired - Lifetime CN1055918C (en) | 1997-11-13 | 1997-11-13 | Olefinic nitrile emergency cooling process |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102190383B (en) * | 2010-03-03 | 2012-10-10 | 中国石油化工股份有限公司 | Method for removing and recovering water from olefin material flow prepared from oxygenated compounds |
| CN109499085A (en) * | 2014-06-11 | 2019-03-22 | 英尼奥斯欧洲股份公司 | Pollution in the acetonitrile removing step of acrylonitrile recycling mitigates |
| CN105425849B (en) * | 2015-08-03 | 2020-06-26 | 英尼奥斯欧洲股份公司 | Quench tower pH control |
| CN106496070A (en) * | 2015-09-06 | 2017-03-15 | 中国石油化工股份有限公司 | The utilization of acetonitrile refining systemic acidity waste water |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5457223A (en) * | 1992-10-09 | 1995-10-10 | The Standard Oil Company | Process for elimination of waste material during manufacture of acrylonitrile |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5457223A (en) * | 1992-10-09 | 1995-10-10 | The Standard Oil Company | Process for elimination of waste material during manufacture of acrylonitrile |
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