CN110003050B - Method and device for preparing acrylonitrile by recycling waste gas of HPPO process - Google Patents
Method and device for preparing acrylonitrile by recycling waste gas of HPPO process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 78
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 230000008569 process Effects 0.000 title claims abstract description 51
- 239000002912 waste gas Substances 0.000 title claims abstract description 48
- 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
- 238000004064 recycling Methods 0.000 title claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 75
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 58
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 44
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 37
- 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
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 239000007789 gas Substances 0.000 claims description 52
- 238000010521 absorption reaction Methods 0.000 claims description 36
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 29
- 229910021529 ammonia Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 230000001502 supplementing effect Effects 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 3
- 239000012808 vapor phase Substances 0.000 claims 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002699 waste material Substances 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
- 241001292396 Cirrhitidae Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene 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
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 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
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 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
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 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
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method and a device for preparing acrylonitrile by recycling waste gas of an HPPO process. Waste gas generated in the HPPO process is firstly introduced into a condensing tank to recycle high-boiling organic pollutants therein, then waste gas containing propylene, oxygen and nitrogen and supplementary ammonia gas are introduced into an acrylonitrile reactor, the propylene, the oxygen and the ammonia gas undergo ammoxidation reaction under the action of a catalyst to generate acrylonitrile, the propylene and the oxygen in the waste gas are consumed, and after the reactants are separated, the separated nitrogen gas can be returned to the HPPO process section for recycling. The invention not only can effectively reduce VOC emission, but also realizes reasonable utilization of propylene resources, produces acrylonitrile with high added value, simultaneously recycles nitrogen, and improves the economy of the HPPO process.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, relates to a method for preparing acrylonitrile by recycling waste gas generated in an HPPO process, and in particular relates to a method for synthesizing acrylonitrile by recycling propylene-containing waste gas generated in the HPPO process. The invention has the characteristics of safe process, reasonable utilization of resources, less VOC emission and the like.
Background
Propylene oxide (Propylene oxide) and Acrylonitrile (Acrylonitrile) are important basic organic chemical raw materials, and propylene oxide is second largest propylene derivative next to polypropylene, and is mainly used for producing chemical products such as polyether polyol, propylene glycol, isopropanolamine and the like. Acrylonitrile is an important monomer for producing organic high molecular polymers, and is mainly used for producing high molecular polymers such as polyacrylonitrile (acrylic fibers), ABS resin, SAN resin and the like.
The current propylene oxide production processes mainly include chlorohydrin process, co-oxidation process (Halcon process) and hydrogen peroxide direct oxidation process (HPPO process). Among them, the chlorohydrin method has the disadvantages of strong corrosion to equipment, large discharge amount of three wastes, etc., and according to the regulations of the industrial structure adjustment instruction directory (2011, the device of the chlorohydrin method is classified into a restricted item, and in principle, new construction is not approved any more. The co-oxidation method has the advantages of complex production process, high investment cost, more coproducts, and more constraint factors, and needs to consider both raw material sources and coproduct markets. The HPPO process is a green and clean propylene oxide production process, and the process takes hydrogen peroxide and propylene as raw materials to react to generate propylene oxide and water, and compared with a chlorohydrin method and a co-oxidation method, the HPPO process has the advantages of cleanness, environmental protection, no coupling product and the like, but the process also has corresponding problems, in the epoxidation reaction process, the hydrogen peroxide can be inevitably decomposed to generate oxygen, and the oxygen and the combustible gas such as propylene, propane and the like form a mixed gas, so that the explosion risk is caused, and the intrinsic safety of the process is seriously threatened.
In order to solve the problem in industry, nitrogen is generally introduced into a reaction system, the oxygen content in the system is controlled below the explosion limit, then a reaction solution is introduced into a deoxidizing tower, a large amount of nitrogen is introduced to extract and separate oxygen dissolved in the reaction solution, and the flash explosion risk in the subsequent propylene flash evaporation and epoxypropane refining process is reduced. In the prior art, methods such as incineration, solvent absorption, catalytic oxidation and the like are mostly adopted to treat waste gas in the HPPO process.
Patent CN200310104990.5 discloses a method for treating hydrocarbon-containing waste gas by a heat exchanger and an electric heating and heating method, which can effectively remove organic pollutants, but the method causes a great deal of propylene waste, which affects the economical efficiency of the process.
The patents CN02812201.1, CN201110434189.1 and CN200910187942.4 all disclose a liquid solvent absorption method for absorbing hydrocarbon substances such as propylene in tail gas, methanol, ethanol, propylene glycol and the like are selected as solvents for absorbing hydrocarbon substances in tail gas, and although propylene in tail gas can be recovered, alcohol organic pollutants (VOC) can be carried out in tail gas, so that national emission standards of atmospheric pollutants are difficult to be met, and the absorption liquid needs to recover propylene in the absorption liquid, so that energy consumption is high.
Patent numbers such as CN201710647740.8, CN201710647787.4 and CN201610008220.8 disclose a method for treating propylene oxide waste gas in an HPPO process, and hydrocarbon substances are converted into CO 2 and H 2 O by catalytic oxidation of noble metals such as Pt, pd and Ru, and the like, so that high-altitude emission is realized, but the method has the defects of high catalyst cost, easiness in deactivation and the like.
Disclosure of Invention
The invention solves the technical problems that the treatment methods such as waste gas incineration, solvent absorption, catalytic oxidation and the like in the existing HPPO process are insufficient in economy and large in nitrogen consumption.
The invention provides a method for preparing acrylonitrile by recycling waste gas of an HPPO process, which comprises the steps of firstly introducing the waste gas generated in the HPPO process into a condensing tank to recycle high-boiling organic pollutants therein, then introducing waste gas containing propylene, oxygen and nitrogen and supplementary ammonia gas into an acrylonitrile reactor, and performing ammoxidation reaction on the propylene, the oxygen and the ammonia gas under the action of a catalyst to generate acrylonitrile, wherein the propylene and the oxygen in the waste gas are consumed, and the separated nitrogen can be returned to an HPPO process section for recycling after reactants are separated. The invention not only can effectively reduce VOC emission, but also realizes reasonable utilization of propylene resources, produces acrylonitrile with high added value, simultaneously recycles nitrogen, and improves the economy of the HPPO process.
The aim of the invention is achieved by the following method:
The invention provides a device for preparing acrylonitrile by recycling waste gas of an HPPO process, which comprises a deoxidization tower, a condensation tank, an acrylonitrile reaction tower, an ammonia neutralization tower and an absorption tower which are connected in sequence.
The invention also provides a method for preparing acrylonitrile by recycling waste gas of an HPPO process, which specifically comprises the following steps:
(1) Introducing a gas phase discharged from the top of a deoxidizing tower of an HPPO process into a condensing tank, condensing and separating high boiling point organic matters such as methanol, propylene oxide and the like contained in the waste gas, analyzing the composition of the waste gas discharged from the condensing tank on line, supplementing a certain amount of ammonia gas according to a certain proportion, introducing the ammonia gas into an acrylonitrile reactor, and performing an acrylonitrile ammoxidation reaction to generate acrylonitrile;
(2) And (3) sequentially passing reactants generated in the ammoxidation reaction of the propylene in the step (1) through an ammonia neutralization tower and an absorption tower to neutralize redundant ammonia, generating substances such as acrylonitrile and hydrocyanic acid in the absorption reaction, enabling absorption liquid to enter an acrylonitrile separation unit from the bottom of the absorption tower, and returning gas discharged from the top of the absorption tower to the deoxidization tower in the step (1) for recycling.
The gas phase at the top of the deoxidizing tower in the step (1) contains substances such as propylene, water, methanol, propylene oxide, oxygen, nitrogen and the like, wherein the content of each component in the gas phase is 0.1-5% by mass, the content of methanol is 0.1-2% by mass, the content of water is 0.1-1% by mass, the content of propylene oxide is 0.1-0.5% by mass, the content of oxygen is 0.1-4% by mass, and the content of nitrogen is 90-99.8% by mass;
the temperature of the condensing tank in the step (1) is-10 ℃, and the gas phase residence time is 0.1-10 s;
the waste gas discharged from the condensing tank in the step (1) contains substances such as propylene, water, methanol, propylene oxide, oxygen, nitrogen and the like, wherein the propylene content in the waste gas is 0.1-3%, the methanol content is less than or equal to 100ppm, the water content is less than or equal to 250ppm, the propylene oxide content is less than or equal to 50ppm, the oxygen content is 0.1-5%, and the nitrogen content is 92-99.8%;
The proportion of the supplementary ammonia gas in the step (1) is propylene: ammonia molar ratio equal to 1: (1-1.2);
the catalyst filled in the acrylonitrile reactor in the step (2) is an oxide of metals such as bismuth phosphomolybdate, bismuth phosphotungstate or Sb, mo, bi, V, W, ce, fe, co, ni, sn or a mixture of several metal oxides;
the reaction temperature of the acrylonitrile reactor in the step (2) is 400-500 ℃, the reaction pressure is 0.1-1 MPa, and the residence time is 1-10 s;
The gas discharged from the top of the absorption tower in the step (2) consists of nitrogen and oxygen, wherein the nitrogen content is more than or equal to 99.90 percent.
The invention has the advantages that:
(1) The process has high intrinsic safety: the dissolved oxygen in the reaction liquid is removed by introducing nitrogen into the epoxidation reaction liquid, so that the safety of the subsequent propylene flash evaporation and propylene oxide separation process is ensured;
(2) And (3) rationalizing and utilizing resources: the acrylonitrile is generated by utilizing the reaction of propylene, oxygen and ammonia in the waste gas, so that organic matters in the waste gas are consumed, and the acrylonitrile with high added value is produced as a byproduct, thereby reducing VOC emission and improving the process economy;
(3) And (3) recycling nitrogen: according to the invention, hydrocarbon organic matters and oxygen in waste gas are removed through the condensing tank and the acrylonitrile reactor, so that the recycling of nitrogen is realized, and the problem of high nitrogen consumption in the current industrial production is solved.
Drawings
FIG. 1 is a process flow diagram for preparing acrylonitrile by recycling waste gas of the HPPO process of the invention.
Wherein, 1 is a deoxidizing tower, 2 is a condensing tank, 3 is an acrylonitrile reaction tower, 4 is an ammonia neutralization tower, and 5 is an absorption tower.
Detailed Description
In embodiments of the present invention, the propylene oxide ring separation and acrylonitrile separation methods are well known in the art and are not mentioned here.
The following examples illustrate the invention in more detail, but do not limit it further. Unless otherwise indicated, "%" is "% by mass".
Example 1
Introducing a gas phase discharged from the top of a deoxidizing tower in an HPPO process, wherein the gas phase contains 1.22% of propylene, 0.84% of methanol, 0.27% of water, 0.15% of propylene oxide, 0.51% of oxygen and 96.71% of nitrogen into a condensing tank with the temperature of 0 ℃ for 2s, condensing and recovering high-boiling-point organic matters in the gas phase, analyzing the composition of waste gas discharged from the condensing tank on line, wherein the propylene content in the waste gas is 0.56%, the methanol content is 40ppm, the water content is 70ppm, the propylene oxide content is 25ppm, the oxygen content is 0.52% and the nitrogen content is 98.91%. Then the molar ratio of propylene to ammonia in the exhaust gas discharged to the condensation tank is equal to 1:1, supplementing ammonia gas, introducing the ammonia gas into an acrylonitrile reactor filled with a bismuth phosphotungstate catalyst, wherein the reaction pressure is 0.3MPa, the reaction temperature is 420 ℃, the residence time is 6s, gas phase products are discharged from the top of the acrylonitrile reactor and pass through an ammonia neutralization tower and an absorption tower, the nitrogen content in the gas discharged from the top of the absorption tower is 99.91%, the top gas is recycled to a deoxidization tower for recycling, and the absorption liquid enters an acrylonitrile separation device.
Example 2
Introducing a gas phase discharged from the top of a deoxidizing tower in an HPPO process, wherein the gas phase contains 0.86% of propylene, 1.84% of methanol, 0.89% of water, 0.05% of propylene oxide, 1.01% of oxygen and 95.35% of nitrogen into a condensing tank with the temperature of-5 ℃ for 8 seconds, condensing and recycling high-boiling-point organic matters in the gas phase, analyzing the composition of waste gas discharged from the condensing tank on line, wherein the propylene content in the waste gas is 0.36%, the methanol content is 80ppm, the water content is 55ppm, the propylene oxide content is 15ppm, the oxygen content is 1.04% and the nitrogen content is 98.59%. Then the molar ratio of propylene to ammonia in the exhaust gas discharged to the condensation tank is equal to 1:1.1 supplementing ammonia gas, introducing the ammonia gas into an acrylonitrile reactor filled with a bismuth oxide catalyst, wherein the reaction pressure is 0.5MPa, the reaction temperature is 450 ℃, the residence time is 3s, gas phase products are discharged from the top of the acrylonitrile reactor and pass through an ammonia neutralization tower and an absorption tower, the nitrogen content in the discharged gas at the top of the absorption tower is 99.94%, the gas at the top of the absorption tower is recycled to a deoxidization tower, and the absorption liquid enters an acrylonitrile separation device.
Example 3
Introducing a gas phase discharged from the top of a deoxidizing tower in an HPPO process, wherein the gas phase contains 1.86% of propylene, 1.38% of methanol, 0.97% of water, 0.34% of propylene oxide, 1.91% of oxygen and 93.54% of nitrogen into a condensing tank with the temperature of-10 ℃ for 10s, condensing and recycling high-boiling-point organic matters in the gas phase, analyzing the composition of waste gas discharged from the condensing tank on line, wherein the propylene content in the waste gas is 0.96%, the methanol content is 90ppm, the water content is 65ppm, the propylene oxide content is 35ppm, the oxygen content is 1.94% and the nitrogen content is 97.10%. Then the molar ratio of propylene to ammonia in the exhaust gas discharged to the condensation tank is equal to 1:1.2 supplementing ammonia gas, introducing the ammonia gas into an acrylonitrile reactor with a bismuth oxide-tin oxide catalyst, wherein the reaction pressure is 0.6MPa, the reaction temperature is 480 ℃, the residence time is 1.5s, gas phase products are discharged from the top of the acrylonitrile reactor and pass through an ammonia neutralization tower and an absorption tower, the nitrogen content in the discharged gas at the top of the absorption tower is 99.90%, the top gas is recycled to a deoxidization tower for recycling, and the absorption liquid enters an acrylonitrile separation device.
Example 4
Introducing a gas phase discharged from the top of a deoxidizing tower in an HPPO process, wherein the gas phase contains 3.26% of propylene, 0.41% of methanol, 0.53% of water, 0.02% of propylene oxide, 3.65% of oxygen and 92.13% of nitrogen into a condensing tank with the temperature of-10 ℃ for 2s, condensing and recovering high-boiling-point organic matters in the gas phase, analyzing the composition of waste gas discharged from the condensing tank on line, wherein the propylene content in the waste gas is 2.16%, the methanol content is 20ppm, the water content is 35ppm, the propylene oxide content is 5ppm, the oxygen content is 2.66% and the nitrogen content is 95.18%. Then the molar ratio of propylene to ammonia in the exhaust gas discharged to the condensation tank is equal to 1:1.1 supplementing ammonia gas, introducing the ammonia gas into an acrylonitrile reactor filled with a bismuth phosphomolybdate catalyst, wherein the reaction pressure is 0.8MPa, the reaction temperature is 410 ℃, the residence time is 10s, gas phase products are discharged from the top of the acrylonitrile reactor, pass through an ammonia neutralization tower and an absorption tower, the nitrogen content in the discharged gas at the top of the absorption tower is 99.96%, the gas at the top of the absorption tower is recycled to a deoxidization tower, and the absorption liquid enters an acrylonitrile separation device.
Example 5
Introducing a gas phase discharged from the top of a deoxidizing tower in an HPPO process, wherein the gas phase contains 4.01% of propylene, 0.21% of methanol, 0.58% of water, 0.05% of propylene oxide, 4.87% of oxygen and 90.28% of nitrogen into a condensing tank with the temperature of 5 ℃ for 6s, condensing and recovering high-boiling-point organic matters in the gas phase, analyzing the composition of waste gas discharged from the condensing tank on line, wherein the propylene content in the waste gas is 2.49%, the methanol content is 40ppm, the water content is 75ppm, the propylene oxide content is 60ppm, the oxygen content is 3.89% and the nitrogen content is 94.62%. Then the molar ratio of propylene to ammonia in the exhaust gas discharged to the condensation tank is equal to 1:1.2 supplementing ammonia gas, introducing the ammonia gas into an acrylonitrile reactor filled with a nickel oxide catalyst, wherein the reaction pressure is 0.2MPa, the reaction temperature is 500 ℃, the residence time is 1s, gas phase products are discharged from the top of the acrylonitrile reactor and pass through an ammonia neutralization tower and an absorption tower, the nitrogen content in the discharged gas at the top of the absorption tower is 99.93%, the top gas is recycled to a deoxidization tower for recycling, and the absorption liquid enters an acrylonitrile separation device.
Claims (8)
1. A method for preparing acrylonitrile by recycling waste gas of HPPO process comprises the following steps:
(1) Introducing a gas phase discharged from the top of a deoxidizing tower of an HPPO process into a condensing tank, condensing and separating high-boiling-point organic matters including methanol and propylene oxide from the waste gas, analyzing the composition of the waste gas discharged from the condensing tank on line, supplementing a certain amount of ammonia gas according to a certain proportion, introducing the ammonia gas into an acrylonitrile reactor, and performing an ammoxidation reaction of propylene to generate acrylonitrile; the gas phase at the top of the deoxidizing tower contains propylene, water, methanol, propylene oxide, oxygen and nitrogen substances, wherein the content of each component in the gas phase is 0.1-5% by mass percent, the content of methanol is 0.1-2%, the content of water is 0.1-1%, the content of propylene oxide is 0.1-0.5%, the content of oxygen is 0.1-4%, and the content of nitrogen is 90-99.8%; the temperature of the condensing tank is-10 ℃;
(2) And (3) sequentially passing reactants generated in the ammoxidation reaction of the propylene in the step (1) through an ammonia neutralization tower and an absorption tower to neutralize redundant ammonia gas, absorbing acrylonitrile and hydrocyanic acid generated in the reaction, enabling absorption liquid to enter an acrylonitrile separation unit from the bottom of the absorption tower, and returning gas discharged from the top of the absorption tower to the deoxidization tower in the step (1) for recycling.
2. The method for producing acrylonitrile by recycling waste gas from HPPO process according to claim 1, wherein the vapor phase residence time of the condensing tank in the step (1) is 0.1 to 10s.
3. The method for preparing acrylonitrile by recycling waste gas of HPPO process according to claim 1, wherein the waste gas discharged from the condensing tank in the step (1) comprises 0.1% -3% of propylene, less than or equal to 100ppm of methanol, less than or equal to 250ppm of water, less than or equal to 50ppm of propylene oxide, 0.1% -5% of oxygen and 92% -99.8% of nitrogen by mass percent.
4. The method for preparing acrylonitrile by recycling waste gas from HPPO process according to claim 1, wherein the ammonia-supplementing proportion in the step (1) is propylene: ammonia molar ratio equal to 1: (1-1.2).
5. The method for preparing acrylonitrile by recycling waste gas from HPPO process according to claim 1, wherein the catalyst packed in the acrylonitrile reactor in the step (1) is bismuth phosphomolybdate, bismuth phosphotungstate or Sb, mo, bi, V, W, ce, fe, co, ni, sn metal oxide or a mixture of several metal oxides thereof.
6. The method for preparing acrylonitrile by recycling waste gas from HPPO process according to claim 1, wherein the reaction temperature of the acrylonitrile reactor in the step (1) is 400-500 ℃, the reaction pressure is 0.1-1 MPa, and the residence time is 1-10 s.
7. The method for preparing acrylonitrile by recycling waste gas from HPPO process according to claim 1, wherein the nitrogen content in the gas discharged from the top of the absorption column in the step (2) is not less than 99.90%.
8. An apparatus for producing acrylonitrile by recycling waste gas from HPPO process, characterized in that the apparatus is used in the method for producing acrylonitrile by recycling waste gas from HPPO process according to any one of claims 1 to 7, the apparatus comprising a deoxidizing column, a condensing tank, an acrylonitrile reaction column, an ammonia neutralization column, an absorption column, which are connected in this order.
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