CN110003050A - A kind of method and apparatus that HPPO technology waste gas resource utilization prepares acrylonitrile - Google Patents
A kind of method and apparatus that HPPO technology waste gas resource utilization prepares acrylonitrile Download PDFInfo
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- CN110003050A CN110003050A CN201910306562.1A CN201910306562A CN110003050A CN 110003050 A CN110003050 A CN 110003050A CN 201910306562 A CN201910306562 A CN 201910306562A CN 110003050 A CN110003050 A CN 110003050A
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- acrylonitrile
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- propylene
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 57
- HWOWEGAQDKKHDR-UHFFFAOYSA-N 4-hydroxy-6-(pyridin-3-yl)-2H-pyran-2-one Chemical compound O1C(=O)C=C(O)C=C1C1=CC=CN=C1 HWOWEGAQDKKHDR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000005516 engineering process Methods 0.000 title claims abstract description 19
- 239000002912 waste gas Substances 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000007789 gas Substances 0.000 claims abstract description 73
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 67
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 49
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 35
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000010521 absorption reaction Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 239000013589 supplement Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 29
- 239000012071 phase Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 9
- 238000004458 analytical method Methods 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- -1 Ethylene Oxide Chemical class 0.000 claims description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 239000007792 gaseous phase Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 claims 1
- 230000001502 supplementing effect Effects 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007701 flash-distillation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- IWFDZFPZDWBPHT-UHFFFAOYSA-N [Bi].[Sn](=O)=O Chemical compound [Bi].[Sn](=O)=O IWFDZFPZDWBPHT-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- GUYXXEXGKVKXAW-UHFFFAOYSA-N prop-2-enenitrile Chemical compound C=CC#N.C=CC#N GUYXXEXGKVKXAW-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/18—Preparation of carboxylic acid nitriles by reaction of ammonia or amines with compounds containing carbon-to-carbon multiple bonds other than in six-membered aromatic rings
Abstract
The present invention provides a kind of method and apparatus that HPPO technology waste gas resource utilization prepares acrylonitrile, which includes the deoxidation tower being sequentially connected, drainer, acrylonitrile reactor tower, ammonia neutralizing tower, absorption tower.The exhaust gas generated in HPPO technique is first passed through drainer and recycles higher boiling organic pollutant therein, the ammonia containing propylene, oxygen, the exhaust gas of nitrogen and supplement is passed through acrylonitrile reactor again, ammoxidation reaction occurs under the action of catalyst and generates acrylonitrile for propylene, oxygen and ammonia, consume the propylene and oxygen in exhaust gas, after separation, isolated nitrogen can return to the recycling of HPPO process section to reactant.The present invention can not only effectively reduce VOC emission, but also realize the utilization of propylene Resource Rationalization, produce the acrylonitrile of high added value, while nitrogen is recycled, improve the economy of HPPO technique.
Description
Technical field
The invention belongs to technical field of petrochemical industry, it is related to a kind of HPPO technology waste gas resource utilization and prepares acrylonitrile
A kind of method, more particularly, to side for carrying out resource utilization synthesis of acrylonitrile containing waste propylene gas for generating HPPO technique
Method.The present invention has the characteristics that technique essential safety, Resource Rationalization utilization, VOC emission amount are few.
Background technique
Propylene oxide (Propylene oxide) and acrylonitrile (Acrylonitrile) are all important basis and organise
Work raw material, propylene oxide are to be only second to the polyacrylic second largest propylene analog derivative, mainly for the production of polyether polyol, the third two
The chemical products such as alcohol, isopropanolamine.Acrylonitrile is the important monomer for producing organic high molecular polymer, is mainly used to produce poly- third
The high molecular polymers such as alkene nitrile (acrylic fibers), ABS resin, SAN resin.
Propylene oxide production process mainly includes chlorohydrination, conjugated oxidation (Halcon method) and the direct oxygen of hydrogen peroxide at present
Change method (HPPO method).Wherein, there is the disadvantages of strong, three wastes discharge amount is big to equipment corrosion in chlorohydrination, according to " industrial structure tune
Whole guidance list (sheet in 2011) " it provides, chloropharin subtraction unit has been put into limitation intermediate item, and no longer approval is newly-built in principle.
And conjugated oxidation production technology is complicated, cost of investment is high, and co-product is more, needs to take into account raw material sources and co-product market, system
About factor is more.HPPO technique is a kind of clean Synthesis of Propylene Oxide of green, which is original with hydrogen peroxide and propylene
Material, reaction generates propylene oxide and water, and compared with chlorohydrination and conjugated oxidation, HPPO technique has clean and environmental protection, no co-product
The advantages that, but there is also corresponding problems for the technique, and in epoxidization reaction process, hydrogen peroxide can inevitably decompose
Oxygen is generated, gaseous mixture is formed with fuel gas such as propylene, propane, has and fire risk, seriously threaten the essential safety of technique.
Industrially to solve this problem, it generallys use and is passed through nitrogen into reaction system, the oxygen content in control system
In explosion limit hereinafter, reaction solution is passed through deoxidation tower again, it is passed through the oxygen dissolved in a large amount of nitrogen extraction and separation reaction solution,
The quick-fried risk of sudden strain of a muscle in subsequent propylene flash distillation and propylene oxide subtractive process is reduced, but not only nitrogen consumption is big for such method,
And it can need to pass through nothing containing volatile organic contaminants (VOC) such as a large amount of propylene, methanol, propylene oxide in the exhaust gas generated
Evilization processing, is just able to satisfy the emission request of national standard " discharge standard of air pollutants " (GB16297-1996).It is existing
There is technology to mostly use the exhaust gas in the methods of burning, solvent absorption, catalysis oxidation processing HPPO technique.
It is hydrocarbonaceous that patent CN200310104990.5 discloses a kind of method processing burned after heat exchanger, electric heating heating
The method of exhaust gas, this method can effectively remove organic pollutant, but method causes propylene largely to waste, and affect the economy of technique
Property.
It is molten that patent CN02812201.1, CN201110434189.1 and CN200910187942.4 disclose a kind of liquid
The method that agent absorbs absorbs the hydrocarbons such as the propylene in tail gas, and methanol, ethyl alcohol, propylene glycol etc. is selected to be used as solvent absorption tail gas
In hydrocarbons can still be taken out of in tail gas alcohols organic pollutant (VOC) although the propylene in tail gas can be recycled, it is difficult
To meet national atmosphere pollutants emission standards, and wherein propylene, energy consumption are higher for the recycling of absorbing liquid needs.
Patent such as CN201710647740.8, CN201710647787.4, CN201610008220.8 disclose one kind
The processing method of HPPO technique oxypropylene exhaust gas is aoxidized using precious metal catalysts such as Pt, Pd, Ru and converts hydrocarbons to
CO2And H2The disadvantages of O, high altitude discharge, but this method is there are expensive catalyst, easy in inactivation.
Summary of the invention
Technical problem solved by the invention is burned waste gas, solvent absorption, catalysis oxidation etc. in existing HPPO technique
The problem that reason method economy is insufficient and nitrogen consumption is big.
The present invention provides a kind of method that HPPO technology waste gas resource utilization prepares acrylonitrile, will generate in HPPO technique
Exhaust gas be first passed through drainer and recycle higher boiling organic pollutant therein, then propylene, oxygen, the exhaust gas of nitrogen and benefit will be contained
The ammonia filled is passed through acrylonitrile reactor, and ammoxidation reaction occurs under the action of catalyst and generates propylene for propylene, oxygen and ammonia
Nitrile consumes propylene and oxygen in exhaust gas, and after separation, isolated nitrogen can return to HPPO process section circulation to be made reactant
With.The present invention can not only effectively reduce VOC emission, but also realize the utilization of propylene Resource Rationalization, produce the third of high added value
Alkene nitrile, while nitrogen is recycled, improve the economy of HPPO technique.
The purpose of the present invention is what is be realized by the following method:
One aspect of the present invention provides the device that a kind of HPPO technology waste gas resource utilization prepares acrylonitrile, including successively phase
Deoxidation tower even, drainer, acrylonitrile reactor tower, ammonia neutralizing tower, absorption tower.
Another aspect of the present invention provides a kind of method that HPPO technology waste gas resource utilization prepares acrylonitrile, specifically includes
Following steps:
(1) gas phase being discharged at the top of the deoxidation tower of HPPO technique is passed through drainer, condenses and separates the first contained in exhaust gas
The composition of exhaust gas is discharged in on-line analysis drainer, supplements a certain amount of ammonia in proportion for the high boiling point organic compounds such as alcohol, propylene oxide
Gas is passed through acrylonitrile reactor, and ammoxidation of propylene reaction occurs and generates acrylonitrile；
(2) reactant that ammoxidation of propylene reaction generates in step (1) is successively passed through into ammonia neutralizing tower and absorption tower, neutralized
Extra ammonia, absorbing reaction generate the substances such as acrylonitrile, hydrogen cyanide, and absorbing liquid enters acrylonitrile separation list from absorb the bottom of the tower
Member, the deoxidation tower in gas return step (1) that absorption tower top is discharged are recycled.
Contain propylene, water, methanol, propylene oxide, oxygen, nitrogen in deoxidation top gaseous phase described in above-mentioned steps (1)
Equal substances, in gas phase the content of each ingredient by mass percentage, propylene content 0.1%~5%, methanol content is 0.1%~
2%, water content is 0.1%~1%, and propylene oxide content is 0.1%~0.5%, and oxygen content is 0.1%~4%, nitrogen
Content is 90%~99.8%；
The temperature of drainer described in above-mentioned steps (1) is -10~10 DEG C, and the gas phase residence time is 0.1~10s；
Drainer described in above-mentioned steps (1) discharge exhaust gas in containing propylene, water, methanol, propylene oxide, oxygen,
The substances such as nitrogen, propylene content 0.1%~3% in exhaust gas, methanol content≤100ppm, water content≤250ppm, propylene oxide
Content≤50ppm, oxygen content are 0.1%~5%, and nitrogen content is 92%~99.8%；
The ratio that ammonia is supplemented described in above-mentioned steps (1) is propylene: ammonia molar ratio is equal to 1:(1~1.2)；
The catalyst loaded in acrylonitrile reactor described in above-mentioned steps (2) be BiPMo, phosphotungstic acid bismuth or Sb,
The oxide of the metals such as Mo, Bi, V, W, Ce, Fe, Co, Ni, Sn or the wherein mixing of several metal oxides；
The reaction temperature of acrylonitrile reactor described in above-mentioned steps (2) be 400~500 DEG C, reaction pressure be 0.1~
1MPa, residence time are 1~10s；
The gas composition being discharged at the top of absorption tower described in above-mentioned steps (2) is nitrogen and oxygen, wherein nitrogen content
>=99.90%.
The invention has the advantages that
(1) technique intrinsic safety is high: removing dissolved oxygen in reaction solution by being passed through nitrogen into epoxidation reaction liquid, protects
The safety of subsequent propylene flash distillation and propylene oxide separation process is demonstrate,proved；
(2) Resource Rationalization utilizes: being reacted using propylene, the oxygen in exhaust gas with ammonia and generates acrylonitrile, consumed useless
Organic matter in gas, the acrylonitrile of by-product high added value reduce the economy that VOC emission improves technique simultaneously；
(3) nitrogen is recycled: the present invention removes the Hydrocarbon Organic in exhaust gas by drainer and acrylonitrile reactor
And oxygen, it realizes the recycling of nitrogen, solves the problems, such as that nitrogen consumption is big in current industrial production.
Detailed description of the invention
Fig. 1 is the process flow chart that HPPO technology waste gas resource utilization of the present invention prepares acrylonitrile.
Wherein, 1 it is deoxidation tower, 2 be drainer, 3 be acrylonitrile reactor tower, 4 be ammonia neutralizing tower, 5 is absorption tower.
Specific embodiment
In embodiments of the present invention, the propylene oxide ring separation and acrylonitrile separation method are well-known technique, this
Place no longer refers to.
The following examples are illustrated in more detail the present invention, rather than limitation of the invention further.It removes
Non- to be otherwise noted, " % " therein is " quality % ".
Embodiment 1
The gas phase that will be discharged at the top of deoxidation tower in HPPO technique, propylene content 1.22% in gas phase, methanol content 0.84%,
Water content 0.27%, propylene oxide content 0.15%, oxygen content 0.51%, nitrogen content 96.71%, being passed through temperature is 0 DEG C
Drainer stops 2s, and the exhaust gas of condensing recovery high boiling point organic compound therein, the discharge of on-line analysis drainer forms, in exhaust gas
Propylene content 0.56%, methanol content 40ppm, water content 70ppm, propylene oxide content 25ppm, oxygen content 0.52%, nitrogen
Gas content 98.91%.Then it is equal to 1:1 by propylene and ammonia molar ratio in the exhaust gas being discharged to drainer and supplements ammonia, is passed through
In acrylonitrile reactor equipped with phosphotungstic acid bismuth catalyst, reaction pressure 0.3MPa, 420 DEG C of reaction temperature, residence time 6s, gas
Ammonia neutralizing tower and absorption tower are passed through in the discharge at the top of acrylonitrile reactor of phase product, and nitrogen contains in the gas that absorption tower top row goes out
Amount 99.91%, tower overhead gas are recycled to deoxidation tower recycling, and absorbing liquid enters acrylonitrile separator.
Embodiment 2
The gas phase that will be discharged at the top of deoxidation tower in HPPO technique, propylene content 0.86% in gas phase, methanol content 1.84%,
Water content 0.89%, propylene oxide content 0.05%, oxygen content 1.01%, nitrogen content 95.35%, being passed through temperature is -5 DEG C
Drainer stops 8s, and the exhaust gas of condensing recovery high boiling point organic compound therein, the discharge of on-line analysis drainer forms, in exhaust gas
Propylene content 0.36%, methanol content 80ppm, water content 55ppm, propylene oxide content 15ppm, oxygen content 1.04%, nitrogen
Gas content 98.59%.Then it is equal to 1:1.1 by propylene and ammonia molar ratio in the exhaust gas being discharged to drainer and supplements ammonia, leads to
Enter in the acrylonitrile reactor equipped with bismuth oxide catalyst, reaction pressure 0.5MPa, 450 DEG C of reaction temperature, residence time 3s, gas
Ammonia neutralizing tower and absorption tower are passed through in the discharge at the top of acrylonitrile reactor of phase product, absorb nitrogen content in overhead
99.94%, tower overhead gas is recycled to deoxidation tower recycling, and absorbing liquid enters acrylonitrile separator.
Embodiment 3
The gas phase that will be discharged at the top of deoxidation tower in HPPO technique, propylene content 1.86% in gas phase, methanol content 1.38%,
Water content 0.97%, propylene oxide content 0.34%, oxygen content 1.91%, nitrogen content 93.54%, being passed through temperature is -10
DEG C drainer stops 10s, condensing recovery high boiling point organic compound therein, the exhaust gas composition of on-line analysis drainer discharge, exhaust gas
Middle propylene content 0.96%, methanol content 90ppm, water content 65ppm, propylene oxide content 35ppm, oxygen content 1.94%,
Nitrogen content 97.10%.Then it is equal to 1:1.2 by propylene and ammonia molar ratio in the exhaust gas being discharged to drainer and supplements ammonia,
It is passed through equipped in bismuth oxide-tin oxide catalysts acrylonitrile reactor, reaction pressure 0.6MPa, is stopped by 480 DEG C of reaction temperature
Ammonia neutralizing tower and absorption tower, absorption tower top row outlet are passed through in time 1.5s, the discharge at the top of acrylonitrile reactor of gas phase product
Nitrogen content 99.90% in body, tower overhead gas are recycled to deoxidation tower recycling, and absorbing liquid enters acrylonitrile separator.
Embodiment 4
The gas phase that will be discharged at the top of deoxidation tower in HPPO technique, propylene content 3.26% in gas phase, methanol content 0.41%,
Water content 0.53%, propylene oxide content 0.02%, oxygen content 3.65%, nitrogen content 92.13%, being passed through temperature is -10
DEG C drainer stops 2s, condensing recovery high boiling point organic compound therein, the exhaust gas composition of on-line analysis drainer discharge, exhaust gas
Middle propylene content 2.16%, methanol content 20ppm, water content 35ppm, propylene oxide content 5ppm, oxygen content 2.66%, nitrogen
Gas content 95.18%.Then it is equal to 1:1.1 by propylene and ammonia molar ratio in the exhaust gas being discharged to drainer and supplements ammonia, leads to
Enter in the acrylonitrile reactor equipped with BiPMo catalyst, reaction pressure 0.8MPa, 410 DEG C of reaction temperature, the residence time
10s, the discharge at the top of acrylonitrile reactor of gas phase product pass through ammonia neutralizing tower and absorption tower, absorb nitrogen in overhead
Gas content 99.96%, tower overhead gas are recycled to deoxidation tower recycling, and absorbing liquid enters acrylonitrile separator.
Embodiment 5
The gas phase that will be discharged at the top of deoxidation tower in HPPO technique, propylene content 4.01% in gas phase, methanol content 0.21%,
Water content 0.58%, propylene oxide content 0.05%, oxygen content 4.87%, nitrogen content 90.28%, being passed through temperature is 5 DEG C
Drainer stops 6s, and the exhaust gas of condensing recovery high boiling point organic compound therein, the discharge of on-line analysis drainer forms, in exhaust gas
Propylene content 2.49%, methanol content 40ppm, water content 75ppm, propylene oxide content 60ppm, oxygen content 3.89%, nitrogen
Gas content 94.62%.Then it is equal to 1:1.2 by propylene and ammonia molar ratio in the exhaust gas being discharged to drainer and supplements ammonia, leads to
Enter in the acrylonitrile reactor equipped with nickel oxide catalyst, reaction pressure 0.2MPa, 500 DEG C of reaction temperature, residence time 1s, gas
Ammonia neutralizing tower and absorption tower are passed through in the discharge at the top of acrylonitrile reactor of phase product, absorb nitrogen content in overhead
99.93%, tower overhead gas is recycled to deoxidation tower recycling, and absorbing liquid enters acrylonitrile separator.
Claims (9)
1. a kind of method that HPPO technology waste gas resource utilization prepares acrylonitrile, comprising the following steps:
(1) gas phase being discharged at the top of the deoxidation tower of HPPO technique is passed through drainer, condenses and separates methanol, the ring contained in exhaust gas
The composition of exhaust gas is discharged in on-line analysis drainer, supplements a certain amount of ammonia in proportion for the high boiling point organic compounds such as Ethylene Oxide, leads to
Enter acrylonitrile reactor, ammoxidation of propylene reaction occurs and generates acrylonitrile；
(2) reactant that ammoxidation of propylene reaction generates in step (1) is successively passed through into ammonia neutralizing tower and absorption tower, it is extra to neutralize
Ammonia, acrylonitrile that absorbing reaction generates, hydrogen cyanide, absorbing liquid enters acrylonitrile separative unit from absorb the bottom of the tower, absorbs
Deoxidation tower in the gas return step (1) of top of tower discharge is recycled.
2. the method that HPPO technology waste gas resource utilization according to claim 1 prepares acrylonitrile, which is characterized in that institute
It states and contains propylene, water, methanol, propylene oxide, oxygen, nitrogen substance in deoxidation top gaseous phase described in step (1), in gas phase
By mass percentage, propylene content 0.1%~5%, methanol content is 0.1%~2% to the content of each ingredient, and water content is
0.1%~1%, propylene oxide content be 0.1%~0.5%, oxygen content be 0.1%~4%, nitrogen content be 90%~
99.8%.
3. the method that HPPO technology waste gas resource utilization according to claim 1 prepares acrylonitrile, which is characterized in that on
The temperature for stating drainer described in step (1) is -10~10 DEG C, and the gas phase residence time is 0.1~10s.
4. the method that HPPO technology waste gas resource utilization according to claim 1 prepares acrylonitrile, which is characterized in that on
It states in the exhaust gas of the discharge of drainer described in step (1) and is calculated by mass percentage including propylene content 0.1%~3%, first
Alcohol content≤100ppm, water content≤250ppm, propylene oxide content≤50ppm, oxygen content are 0.1%~5%, and nitrogen contains
Amount is 92%~99.8%.
5. the method that HPPO technology waste gas resource utilization according to claim 1 prepares acrylonitrile, which is characterized in that on
Stating and supplementing the ratio of ammonia described in step (1) is propylene: ammonia molar ratio is equal to 1:(1~1.2).
6. the method that HPPO technology waste gas resource utilization according to claim 1 prepares acrylonitrile, which is characterized in that on
State the catalyst that is loaded in acrylonitrile reactor described in step (2) be BiPMo, phosphotungstic acid bismuth or Sb, Mo, Bi, V, W,
The oxide of Ce, Fe, Co, Ni, Sn metal or the wherein mixing of several metal oxides.
7. the method that HPPO technology waste gas resource utilization according to claim 1 prepares acrylonitrile, which is characterized in that on
The reaction temperature for stating acrylonitrile reactor described in step (2) is 400~500 DEG C, and reaction pressure is 0.1~1MPa, is stopped
Time is 1~10s.
8. the method that HPPO technology waste gas resource utilization according to claim 1 prepares acrylonitrile, which is characterized in that on
State nitrogen content >=99.90% in the gas being discharged at the top of absorption tower described in step (2).
9. a kind of HPPO technology waste gas resource utilization prepares the device of acrylonitrile, including be sequentially connected deoxidation tower, drainer,
Acrylonitrile reactor tower, ammonia neutralizing tower, absorption tower.
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