CN1413980A - Quench process of acrylonitrile - Google Patents
Quench process of acrylonitrile Download PDFInfo
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- CN1413980A CN1413980A CN 01131954 CN01131954A CN1413980A CN 1413980 A CN1413980 A CN 1413980A CN 01131954 CN01131954 CN 01131954 CN 01131954 A CN01131954 A CN 01131954A CN 1413980 A CN1413980 A CN 1413980A
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- acid
- quench tower
- vinyl cyanide
- epimere
- tower
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000010791 quenching Methods 0.000 title claims description 78
- 238000000034 method Methods 0.000 title abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 229910021529 ammonia Inorganic materials 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 16
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 10
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 230000008521 reorganization Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 17
- 239000007789 gas Substances 0.000 description 23
- 230000004087 circulation Effects 0.000 description 19
- 239000012530 fluid Substances 0.000 description 13
- 239000000376 reactant Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 150000003863 ammonium salts Chemical class 0.000 description 7
- 239000011800 void material Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 241000282326 Felis catus Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- -1 propylene nitrile Chemical class 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- OTKOPKDCLGDHFV-UHFFFAOYSA-N azane;2-methylprop-1-ene Chemical compound N.CC(C)=C OTKOPKDCLGDHFV-UHFFFAOYSA-N 0.000 description 1
- GLAKNHGQBRSLIO-UHFFFAOYSA-N azane;prop-1-ene Chemical compound N.CC=C GLAKNHGQBRSLIO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 230000001839 systemic circulation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for suddenly cooling acrylonitrile features that the acid is directly added to tower still at lower part of suddenly cooling tower, the pH value of liquid in tower still is controlled to 7-7.5, and the water is supplemented to lower segment to control the concentration of heavy component in the liquid of tower still. Its advantage is high recovery rate of acrylonitrile.
Description
Technical field
The present invention relates to a kind of acrylonitrile quenching method.
Background technology
The production of ammoxidation of hydrocarbons system unsaturated nitrile is a key areas of petrochemical industry, wherein propylene or isobutene ammonia oxidizing acrylonitrile production or 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.
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 quench tower, absorb unreacted ammonia with aqueous sulfuric acid and generate sulphur ammonium generation sulphur ammonium sewage through cooling.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 quench tower.Because vinyl cyanide and prussic acid all are easy polymeric materials, easier polymerization under alkaline condition especially.Cause the loss of vinyl cyanide and hydrogen cyanide product like this, promptly the refining rate of recovery of vinyl cyanide is lower, generally about 90%, wherein in the loss of quench tower place vinyl cyanide just up to 8%.
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 ammonia transformation efficiency is not controlled, make the easy and alkene nitrile generation side reaction of unreacted ammonia, reduced the refining rate of recovery of alkene nitrile.The clear 55-104 of document JP, 246 have introduced a kind of quench tower quick cooling method that has multistage outer circulation water coolant, and its quench tower bottom is a filler, and top is the two-section type structure of void tower.Reactor outlet gas enters quench tower lower portion about 230 ℃, (wherein acid is sulfuric acid with unreacted ammonia in acid fully herein, add in the outer circulation liquid a part as spray liquid, do not indicate the regulation range of pH value), behind the washing reaction gas, import epimere, be cooled to derive from the top about 40 ℃ through outer circulation water coolant (10～60 ℃).One material is extracted at maximum plate place out in epimere tower inner propene nitrile concentration, without the absorption tower, directly in subsequent treatment process.Wherein to require be 10～25 times of extraction amount to the epimere quantity of circulating water.Claim that according to this patent this measure can reduce the load on absorption tower, and the energy expenditure of systemic circulation (poor-water that relates in extraction in the finger device, absorption, the evaporation of propylene ammonia and the FF reboiler system).But because it only adds acid at hypomere, it is not high to remove the ammonia effect.And the pressure-controlling in the tower requires high, and pressure is higher a little, and the polymerization losses of vinyl cyanide just increases.Therefore, this design recovery of acrylonitrile is not high.Introduced a kind of quick cooling method in the document WO 96/23765, its quench tower is the two-section type structure, and its middle and upper part is a filler, and the bottom is a void tower.Reactor outlet gas enters hypomere at 260～280 ℃, and (wherein acid is sulfuric acid, as the part of spray liquid, hypomere tower bottoms pH value is 5.5 in the adding outer circulation liquid, and hypomere tower bottoms temperature is 85 ℃), in acid and behind the unreacted ammonia, washing reaction gas, import epimere herein.After epimere is cooled to 37～39 ℃, derive from the top.Also can add further neutralization of ammonia of acid at epimere.Behind the linear speed of spray, quantity of circulating water and the pH value of controlling hypomere recirculated water, reactor outlet gas, claim that according to the document removing the ammonia effect can be more than 90%.That is to say, also have about 10% ammonia will with acrylonitrile polymerization.Therefore, the loss of vinyl cyanide is bigger in the quench tower.
Above-mentioned document all is that the hypomere at quench tower adds sulfuric acid and removes ammonia, reduce unreacted ammonia at the chance of loss of hypomere and acrylonitrile polymerization or all add acid at two sections and remove unreacted ammonia fully, the process for production of acrylonitrile of sulphur ammonium is not reclaimed in this employing, because quench tower is to operate under acidic conditions, the polymerization losses that has suppressed vinyl cyanide, vinyl cyanide is all higher in the rate of recovery of quench tower, but do the condition that must possess like this, otherwise can produce a large amount of sulfide and contaminate environment behind the ammonium salt liquid waste incineration the direct buried processing of acid ammonium salt waste liquid.In the process for production of acrylonitrile that reclaims the sulphur ammonium, must at first wash and remove the impurity such as catalyst dust, high boiling material and polymkeric substance that reactant gases is carried secretly, and in epimere adding sulfuric acid, also be reclaimed to obtain clean sulphur ammonium with unreacted ammonia at quench tower lower portion.In quenching process, if because arranging of nozzle is unreasonable, or a small amount of nozzle stops up, can cause the quench tower lower portion non-uniform spraying, the hypomere part is than strong basicity, and vinyl cyanide with polymerization reaction take place, causes the loss of quench tower vinyl cyanide to increase under alkaline condition.If enter follow-up tower in the unreacted ammonia and not exclusively in the quench tower, will have a strong impact on the operation of follow-up tower, also will increase the loss of vinyl cyanide greatly simultaneously.
Summary of the invention
Technical problem to be solved by this invention be overcome in the past that document exists must be with the direct buried processing of acid ammonium salt waste liquid, could improve recovery of acrylonitrile or since quench tower inner member problem cause non-uniform spraying, the hypomere part is than strong basicity, cause the low defective of recovery of acrylonitrile, a kind of quick cooling method of new vinyl cyanide is provided.This method has not will the direct buried processing of ammonium salt waste liquid, can reclaim the sulphur ammonium, and can improve recovery of acrylonitrile, even reduce the characteristics of environmental pollution.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of quick cooling method of vinyl cyanide may further comprise the steps successively:
A) quench tower is made up of for two sections epimere and hypomere at least, in the middle of epimere and the hypomere catch tray is arranged, and riser is arranged on the catch tray;
B) temperature is that pH value is that 7～7.5 aqueous quench liquid contacts in quench tower lower portion in 180～280 ℃ the reactor effluent that contains ammonia and vinyl cyanide and the quenching system, and wherein acid is directly to add in the quench tower lower portion tower still;
C) the gaseous state chilling effluent after the quench tower lower portion contact enters the quench tower epimere by riser;
D) the gaseous state chilling effluent that enters the quench tower epimere is with after epimere circulated sprinkling liquid contacts, part sulphur ammonium sewage desulfuration ammonium retrieving arrangement, and the gaseous state chilling effluent of quench tower epimere goes to the absorption tower.
In the technique scheme, quench tower epimere preferred version is the column plate type structure or the filler of 1～10 block of theoretical tray, and the pH value preferred version of quench tower epimere spray liquid is 2～5.The pH value preferable range of quench tower lower portion aqueous quench liquid is 7～7.3, the sour preferred version that quench tower lower portion adds is selected from least a and miscellany in acetic acid, oxalic acid, vinylformic acid, phosphoric acid, sulfuric acid, boric acid or the formic acid, and the more preferably scheme of the acid that quench tower lower portion adds is selected from least a and miscellany in acetic acid, oxalic acid or the vinylformic acid.Preferred version is for adding water in the operation of quench tower lower portion, heavy constituent concentration is 0.1～5% to the additional amount of water by weight percentage in the quench tower lower portion tower bottoms in order to make, wherein reorganization is divided into polymkeric substance of vinyl cyanide, prussic acid or propenal and composition thereof, in the tower bottoms heavy constituent concentration by weight percentage preferable range be 0.5～4.0%, more preferably scope is 0.5～2.0%.
The present invention is because therefore capable of circulation, the recovery of ammonium salt in the epimere circulation fluid can avoid the direct buried processing of ammonium salt waste liquid.Acid is directly added in the quench tower lower portion tower still, quench tower lower portion tower bottoms pH value is reduced to below 7.5, avoided to avoid the autohemagglutination and the addition polymerization loss of vinyl cyanide in addition because of hypomere spray poor effect causes the part to be more alkaline situation.Above the epimere catch tray, set up the column plate type structure or the filler of 1～10 block of theoretical tray, improved mass transfer and heat transfer between gas-liquid two-phase, improved and removed the ammonia effect, in having strengthened and efficient, improved the rate of recovery of vinyl cyanide in quench tower.Because quench tower lower portion does not reclaim with the ammonium salt that sour neutralization of ammonia produces, only doing reaction is the sewage burn processing, acid is selected from acetic acid, oxalic acid or vinylformic acid, can regulate quench tower lower portion still liquid pH value on the one hand, produce sulfurous gas after can avoiding on the other hand burning, atmosphere is caused secondary pollution problem, a large amount of combustions heat that simultaneously recyclable sewage roasting kiln produces.In the quench tower lower portion amount of makeup water, can reduce the concentration that generates heavy constituent in the hypomere tower bottoms body, reduce the polymerization losses of vinyl cyanide.Confirm that through test adopt technical scheme of the present invention, the rate of recovery of vinyl cyanide is the highest to improve 3.1%, has obtained better technical effect.
Description of drawings
Fig. 1 is the quench tower emergency cooling process flow process of the clear 55-104246 of JP.
Fig. 2 is the quench tower emergency cooling process flow process of WO96/23765.
Fig. 3 is a quench tower emergency cooling process flow process of the present invention.
1 is quench tower among Fig. 1, Fig. 2 and Fig. 3, and 2 is reactor outlet gas, and 3 is riser, 4 is column plate, and 5 is filler, and 6 is water cooler, 7 are outer circulation liquid, and 8 is Extract, and 9 is acid solution, 10 for working off one's feeling vent one's spleen, and 11 is epimere still liquid, and 12 is hypomere still liquid, 13 is gas flowfield, and 14 is nozzle, and 15 for adding water (can be pure water or recycling waste water), 16 for adding water, 17 acid solutions for adding.
Among Fig. 3, the reacting gas 2 after precooling enters quench tower lower portion, circulation fluid 7 sprays of being extracted out from tower reactor, Be quenched to 45～85 ℃ from 180～280 ℃, washing is except catalyst, high-boiling components, the polymer of deentrainment, part still simultaneously Liquid 12 blowdowns are done to burn but and are processed. Oxalic acid or acetic acid or acrylic acid etc. 17 directly joins in the tower reactor, to regulate the PH of still liquid Value. The amount of amount of makeup water 16 and circulated sprinkling liquid 7 is regulated by corresponding pump and pipeline valve. In epimere circulation fluid 7 Add the unreacted ammonia in the sulfuric acid 9 neutralization reaction gases, to obtain clean sulphur ammonium 11 for reclaiming. Reaction gas behind the chilling Body 10 enters the absorption tower, with water at low temperature coercibility organic matter is wherein absorbed.
The invention will be further elaborated below by embodiment.
Embodiment [comparative example 1]
Enter in the reactant gases of quench tower and contain vinyl cyanide 42 Grams Per Hours, temperature is 210 ℃, epimere is 5 blocks of theoretical trays, hypomere is the chilling cat head working pressure 0.036MPa of void tower, 82 ℃ of top temperature, 82 ℃ of still temperature, epimere circulated sprinkling amount is 123.6 ml/min, it is 3.5 that sulfuric acid adds in the epimere circulation fluid with control epimere circulation fluid pH value.Hypomere circulated sprinkling amount is 31.9 ml/min, and temperature is 82 ℃, blowdown flow rate 0.4 ml/min, and hypomere still liquid pH value is 7.8.Contain vinyl cyanide 38.6 Grams Per Hours in the tower top outlet gas, the quench tower recovery of acrylonitrile is 91.9%.[embodiment 1]
Enter in the reactant gases of quench tower and contain vinyl cyanide 42 Grams Per Hours, temperature is 210 ℃, epimere is 5 blocks of theoretical trays, hypomere is the chilling cat head working pressure 0.036MPa of void tower, 82 ℃ of top temperature, 82 ℃ of still temperature, epimere circulated sprinkling amount is 123.6 ml/min, it is 3.5 that sulfuric acid adds in the epimere circulation fluid with control epimere circulation fluid pH value.Hypomere circulated sprinkling amount is 31.9 ml/min, and temperature is 82 ℃, and blowdown flow rate 0.4 ml/min directly adds in the hypomere tower still with acetic acid, and regulating hypomere still liquid pH value is 7.5.Contain vinyl cyanide 38.9 Grams Per Hours in the tower top outlet gas, the quench tower recovery of acrylonitrile is 92.6%.[embodiment 2]
Enter in the reactant gases of quench tower and contain vinyl cyanide 42 Grams Per Hours, temperature is 210 ℃, epimere is 5 blocks of theoretical trays, hypomere is the chilling cat head working pressure 0.036Mpa of void tower, 82 ℃ of top temperature, 82 ℃ of still temperature, epimere circulated sprinkling amount is 123.6 ml/min, it is 3.5 that sulfuric acid adds in the epimere circulation fluid with control epimere circulation fluid pH value.Hypomere circulated sprinkling amount is 31.9 ml/min, directly join in the hypomere tower still with oxalic acid, and to regulate still liquid pH value is 7.0 blowdown flow rate 0.4 ml/min.Contain vinyl cyanide 39.7 Grams Per Hours in the tower top outlet gas, the quench tower recovery of acrylonitrile is 94.5%.[embodiment 3]
Enter in the reactant gases of quench tower and contain vinyl cyanide 42 Grams Per Hours, temperature is 210 ℃, epimere is 5 blocks of theoretical trays, hypomere is the chilling cat head working pressure 0.036MPa of void tower, 82 ℃ of top temperature, 82 ℃ of still temperature, epimere circulated sprinkling amount is 123.6 ml/min, it is 3.5 that sulfuric acid adds in the epimere circulation fluid with control epimere circulation fluid pH value.Hypomere circulated sprinkling amount is 31.9 ml/min, and to make the weight concentration of the polymkeric substance and composition thereof of vinyl cyanide, prussic acid or propenal in the tower still be 0.5% by increasing amount of makeup water, directly adds in the tower still with vinylformic acid, and regulating still liquid pH value is 7.0.Contain vinyl cyanide 39.9 Grams Per Hours in the tower top outlet gas, the quench tower recovery of acrylonitrile is 95.0%.[embodiment 4]
Enter in the reactant gases of quench tower and contain vinyl cyanide 42 Grams Per Hours, temperature is 210 ℃, epimere is 5 blocks of theoretical trays, hypomere is the chilling cat head working pressure 0.036MPa of void tower, 82 ℃ of top temperature, 82 ℃ of still temperature, epimere circulated sprinkling amount is 123.6 ml/min, it is 3.5 that sulfuric acid adds in the epimere circulation fluid with control epimere circulation fluid pH value.Hypomere circulated sprinkling amount is 31.9 ml/min, and to make the weight concentration of the polymkeric substance and composition thereof of vinyl cyanide, prussic acid or propenal in the tower still be 2.0% by increasing amount of makeup water.Directly add acetic acid in hypomere tower still, still liquid pH value is 7.3.Contain vinyl cyanide 39.4 Grams Per Hours in the tower top outlet gas, the quench tower recovery of acrylonitrile is 93.8%.
Claims (9)
1, a kind of quick cooling method of vinyl cyanide may further comprise the steps successively:
A) quench tower is made up of for two sections epimere and hypomere at least, in the middle of epimere and the hypomere catch tray is arranged, and riser is arranged on the catch tray;
B) temperature is that pH value is that 7～7.5 aqueous quench liquid contacts in quench tower lower portion in 180～280 ℃ the reactor effluent that contains ammonia and vinyl cyanide and the quenching system, and wherein acid is directly to add in the quench tower lower portion tower still;
C) the gaseous state chilling effluent after the quench tower lower portion contact enters the quench tower epimere by riser;
D) the gaseous state chilling effluent that enters the quench tower epimere is with after epimere circulated sprinkling liquid contacts, part sulphur ammonium sewage desulfuration ammonium retrieving arrangement, and the gaseous state chilling effluent of quench tower epimere goes to the absorption tower.
2, the quick cooling method of vinyl cyanide according to claim 1 is characterized in that the quench tower epimere is the column plate type structure or the filler of 1～10 block of theoretical tray.
3, the quick cooling method of vinyl cyanide according to claim 1, the pH value that it is characterized in that quench tower epimere spray liquid is 2～5.
4, the quick cooling method of vinyl cyanide according to claim 1, the pH value that it is characterized in that quench tower lower portion aqueous quench liquid is 7～7.3.
5, the quick cooling method of vinyl cyanide according to claim 1 is characterized in that acid that quench tower lower portion adds is selected from least a and miscellany in acetic acid, oxalic acid, vinylformic acid, phosphoric acid, sulfuric acid, boric acid or the formic acid.
6, the quick cooling method of vinyl cyanide according to claim 5 is characterized in that acid that quench tower lower portion adds is selected from least a and miscellany in acetic acid, oxalic acid or the vinylformic acid.
7, the quick cooling method of vinyl cyanide according to claim 1, it is characterized in that quench tower lower portion adds water, heavy constituent concentration is 0.1～5% to the additional amount of water by weight percentage in the quench tower lower portion tower bottoms in order to make, and wherein reorganization is divided into polymkeric substance of vinyl cyanide, prussic acid or propenal and composition thereof.
8, the quick cooling method of vinyl cyanide according to claim 7 is characterized in that heavy constituent concentration is 0.5～4.0% by weight percentage in the quench tower lower portion tower bottoms.
9, the quick cooling method of vinyl cyanide according to claim 8 is characterized in that heavy constituent concentration is 0.5～2.0% by weight percentage in the quench tower lower portion tower bottoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011319542A CN1161326C (en) | 2001-10-22 | 2001-10-22 | Quench process of acrylonitrile |
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|---|---|---|---|
| CNB011319542A CN1161326C (en) | 2001-10-22 | 2001-10-22 | Quench process of acrylonitrile |
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| CN1413980A true CN1413980A (en) | 2003-04-30 |
| CN1161326C CN1161326C (en) | 2004-08-11 |
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| CNB011319542A Expired - Lifetime CN1161326C (en) | 2001-10-22 | 2001-10-22 | Quench process of acrylonitrile |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386270C (en) * | 2006-06-06 | 2008-05-07 | 孙永敏 | Method for processing kettle-liquid of acrylonitrile quench tower lower portion |
| CN106430245A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Improvement method for ammonium-sulfate-free process in acrylonitrile reaction apparatus |
-
2001
- 2001-10-22 CN CNB011319542A patent/CN1161326C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386270C (en) * | 2006-06-06 | 2008-05-07 | 孙永敏 | Method for processing kettle-liquid of acrylonitrile quench tower lower portion |
| CN106430245A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Improvement method for ammonium-sulfate-free process in acrylonitrile reaction apparatus |
| CN106430245B (en) * | 2015-08-12 | 2018-10-23 | 中国石油化工股份有限公司 | Improved method without thiamine process in acrylonitrile reactor device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1161326C (en) | 2004-08-11 |
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