CN105664669A - Method for processing of unreacted ammonia in acrylonitrile reaction device - Google Patents
Method for processing of unreacted ammonia in acrylonitrile reaction device Download PDFInfo
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- CN105664669A CN105664669A CN201410668291.1A CN201410668291A CN105664669A CN 105664669 A CN105664669 A CN 105664669A CN 201410668291 A CN201410668291 A CN 201410668291A CN 105664669 A CN105664669 A CN 105664669A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 212
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 42
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 title abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 100
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 95
- 238000010521 absorption reaction Methods 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000002745 absorbent Effects 0.000 claims abstract description 8
- 239000002250 absorbent Substances 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 38
- 238000005915 ammonolysis reaction Methods 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 239000000470 constituent Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000005204 segregation Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000001117 sulphuric acid Substances 0.000 claims description 8
- 235000011149 sulphuric acid Nutrition 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010791 quenching Methods 0.000 abstract 2
- 238000000926 separation method Methods 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 9
- 230000001351 cycling effect Effects 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004254 Ammonium phosphate Substances 0.000 description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 4
- 235000019289 ammonium phosphates Nutrition 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003701 inert diluent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- -1 alkene nitrile Chemical class 0.000 description 2
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- 235000019157 thiamine Nutrition 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Degasification And Air Bubble Elimination (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for processing of unreacted ammonia in an acrylonitrile reaction device, and mainly solves the problem of incomplete absorption of the unreacted ammonia in the prior art. By use of the method, the problem can be well solved, and the method is as follows: the unreacted ammonia in a high ammonia product gas stream can be absorbed by contact of the high ammonia product gas stream and a lean ammonium absorbing liquid in a quench tower to obtain an ammonium-rich absorbing liquid and a low ammonia product gas stream; volatile organic components in the ammonium-rich absorbing liquid can be removed by stripping with a stripping tower stripping gas in a stripping tower, light components floating on the upper layer and heavy components sinking into the lower layer can be removed by separation in a separation device, a crude ammonia gas stream and a lean ammonium absorbing liquid can be obtained by heating and stripping with a deabsorption tower stripping gas in a deabsorption tower, and the lean ammonium absorbing liquid is returned to the quench tower to be used for absorption of the unreacted ammonia; by catalytic wet oxidation of the crude ammonia gas stream, an ammonia-free material stream is obtained and is used for device circulation water; and the lean ammonium absorbing liquid comprises at least one absorbent selected from phosphoric acid, ammonium dihydrogen phosphate or sulfuric acid. The method can be used in acrylonitrile production.
Description
Technical field
The present invention relates to the processing method of unreacted ammonia in acrylonitrile reactor device.
Background technology
The unreacted ammonia needs having about 10% in Acrylonitrile Production are separated from reaction logistics by absorption. Although there being technology can reduce the content of reactor outlet ammonia, but still have the existence of a large amount of unreacted ammonia. Current production technology is mainly by sulfuric acid scrubbing thus absorbing unreacted ammonia, and amine wastewater of sulphuric acid is directly injected into deep-well and processes, or reclaims crystallization sulfur ammonium through thiamine recovery workshop section, or sulfur ammonium burns and makes SO3, make sulphuric acid then through absorption and return system recycling. Also partial monopoly is had to pass through in phosphoric acid, ammonium dihydrogen phosphate or the two mixture and reclaim unreacted ammonia.
Patent CN1204620A discloses a kind of for the middle method reclaiming unreacted ammonia after flowing out from the reactor producing to obtain in alkene nitrile or methacrylonitrile reaction zone, it is quenched above-mentioned reactor effluent with ammonium phosphate solution, wherein, the ratio of the ammonium ion in described solution and phosphate anion is about 0.7-1.3, it is preferred to 1.0-1.2. In order to remove the useless remaining Organic substance absorbing in liquid, adding wet oxidation unit in method, wet oxidation reaction carries out at about 200 DEG C of temperature of-650 DEG C and the pressure of 600-3000 pound/square inch.
Patent CN101027252A discloses a kind of modification method reclaimed from steam stream and circulate ammonia, and the method includes being quenched reactor effluent with the aqueous solution of ammonium phosphate at least two stage, thus the ammonia components caught in effluent. The ammonia caught in year can be reclaimed by heated phosphoric aqueous ammonium, then this ammonium phosphate solution is circulated. Before circulation, pollutant contained in ammonium phosphate solution can be removed by wet oxidation.
But in prior art, the high ammonolysis product air-flow from ammonia oxidation reactor still remains remarkable amounts of ammonia in the low ammonolysis product air-flow that lean ammonium absorbs after liquid absorption, thus affecting the raising of product quality. Prior art is realized the recycling of ammonia by rectifier unit, rectification cell and want big energy maintain, so energy consumption is high.
Summary of the invention
The technical problem to be solved is the problem that in prior art, unreacted ammonia absorbs not exclusively, energy consumption is high, it is provided that the processing method of unreacted ammonia in a kind of new acrylonitrile reactor device.The method has the advantage that ammonia absorbs completely, energy consumption is low.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows:
The absorption process of unreacted ammonia in acrylonitrile reactor device, comprises the following steps:
From ammonia oxidation reactor, high ammonolysis product air-flow 6 out absorbs liquid 14 at chilling tower 1 with lean ammonium and contact unreacted ammonia in the high ammonolysis product air-flow of absorption, obtains rich ammonium absorption liquid 8 and low ammonolysis product air-flow 7; Richness ammonium is absorbed liquid 8 in stripper 2 through stripper stripping gas 9 stripping volatile organic component 10, in segregation apparatus 3, it is separated off supernatant light component 11 again and is sunken to the heavy constituent 12 of lower floor, then heated in Analytic Tower 4 and Analytic Tower stripping gas 13 stripping obtains thick ammonia flow 15 and lean ammonium absorbs liquid 14, and lean ammonium absorbs liquid 14 and returns the chilling tower 1 absorption for unreacted ammonia; Pure ammonia logistics 17 is obtained after thick ammonia flow 15 and the reaction of oxygen-containing gas 16 catalyzed wet oxidation reaction device 5; Wherein, lean ammonium absorbs in liquid containing at least one absorbent in phosphoric acid, ammonium dihydrogen phosphate or sulphuric acid. Volatile organic constituents (10) is preferably returned to chilling tower 1. The absorbent that lean ammonium absorbs in liquid preferably includes: at least one in (a) phosphoric acid and ammonium dihydrogen phosphate; (b) sulphuric acid; More preferably lean ammonium absorbs S/P mol ratio in liquid is 0.01-0.5, and wherein S represents element sulphur, and P represents P elements; In technique scheme, lean ammonium absorption liquid pH value is preferably 2-6.5. In technique scheme, preferred lean ammonium absorbs the mass content of P element in liquid 14 is 3%～8%.
In technique scheme, segregation apparatus 3 preferably has the upper outlet discharging light component 11.
In technique scheme, segregation apparatus 3 preferably has the lower outlet discharging heavy constituent 11.
In technique scheme, lean ammonium absorbs the temperature of liquid and is preferably 50-85 DEG C.
In technique scheme, stripper stripping gas 9 and/or Analytic Tower stripping gas 13 are preferably the gas that stripping thing is inert.
In technique scheme, the gas that stripping thing is inert is preferably at least one in water vapour, air and nitrogen.
In technique scheme, described heavy constituent 12 is high polymer and/or catalyst fines.
In technique scheme, described lean ammonium absorbs liquid 14 with water for solvent.
In technique scheme, Analytic Tower temperature is preferably 150-250 DEG C.
In technique scheme, Analytic Tower pressure is preferably in the Analytic Tower under relevant temperature the saturated vapor pressure of solution.
In technique scheme, wet oxidation reaction device interior reaction temperature is preferably 150-300 DEG C, and pressure is preferably 5MPa-12MPa.
In technique scheme, oxygen-containing gas is air, pure oxygen and oxygen content is the oxygen rich gas of 35-50v%. The oxygen rich gas that oxygen content is 35-50v% can by oxygen mix in inert diluent gas, and conventional inert diluent may be incorporated for the present invention, for instance nitrogen, carbon dioxide, helium, neon, argon etc. In the embodiment of the present invention, the inert diluent in oxygen rich gas all adopts nitrogen.
In technique scheme, wet oxidation reaction used catalyst is not particularly limited, it is preferable that ammonia nitrogen has those catalyst of better clearance, for instance but be not limited to include the loaded catalyst of at least one active component in Pt, Pd, Ru and Rh. The carrier of loaded catalyst does not limit, commonly used in the art those, for instance but it is not limited to silicon oxide, aluminium oxide, titanium oxide etc.The embodiment of the present invention all adopts silica supports.
Absorbing in liquid at lean ammonium in the inventive method and place a small amount of sulphuric acid, the absorption efficiency that can make ammonia is higher with phosphoric acid and/or ammonium dihydrogen phosphate than only, and also high with sulphuric acid than only, absorbance reaches 100%, improves the quality of product air-flow.
Removing ammonia by wet oxidation method in the inventive method and substitute ammonia rectifier unit, wet oxidation reaction is exothermic reaction, and generation energy, and ammonia distillation process consumed energy, institute's energy consumption in the process of the present invention reduces.
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the present invention.
In Fig. 1,1 is chilling tower, and 2 is stripper, and 3 is segregation apparatus, and 4 is Analytic Tower, and 5 is CWO reactor; 6 is high ammonolysis product air-flow, and 7 is low ammonolysis product air-flow, and 8 is that rich ammonium absorbs liquid, and 9 is stripper stripping gas, 10 is volatile organic constituents, and 11 is light component, and 12 is heavy constituent, and 13 is Analytic Tower stripping gas, 14 is that lean ammonium absorbs liquid, and 15 is thick ammonia flow, and 16 is oxygen-containing gas, and 17 is without ammonia flow.
Flow process shown in Fig. 1 is: the high ammonolysis product air-flow 6 from ammonia oxidation reactor absorbs liquid 15 at chilling tower 1 with lean ammonium and contacts the unreacted ammonia of absorption, obtain low ammonolysis product air-flow 7 and rich ammonium absorbs liquid 8, rich ammonium absorbs liquid 8 and removes volatile organic constituents 10 at stripper 2 through stripping gas 9, in segregation apparatus 3, it is separated off supernatant light component 11 again and is sunken to the heavy constituent 12 of lower floor, then heated in Analytic Tower 4 and Analytic Tower stripping gas 13 stripping obtains thick ammonia flow 15 and lean ammonium absorbs liquid 14, lean ammonium absorbs liquid 14 and returns chilling tower 1 for being cycled to used in the absorption of unreacted ammonia, the catalyzed wet oxidation reaction device 5 of thick ammonia flow 15 is obtained by reacting without ammonia logistics 17 with oxygen-containing gas 16, can be used for device cycling use of water (not shown) without ammonia logistics 17.
Detailed description of the invention
Embodiment 1-6 and comparative example 1 and comparative example 2 are all by flow operations shown in Fig. 1, and it is water that lean ammonium absorbs the solvent adopted in liquid.
[embodiment 1]
High ammonolysis product air-flow from ammoxidation of propylene reactor contacts the unreacted ammonia of absorption at chilling tower with lean ammonium absorption liquid and obtains low ammonolysis product air-flow and rich ammonium absorption liquid, it is 0.01 that lean ammonium absorbs S/P mol ratio in liquid, P elements mass content is 6.5%, absorption liquid pH value is 2, it is 85 DEG C that lean ammonium absorbs the temperature of liquid, is detected as 0 through absorbing the content of ammonia in the low ammonolysis product air-flow obtained. Rich ammonium absorbs liquid and enters segregation apparatus after water vapour stripping gas strips at stripper, remove light component and include the heavy constituent of catalyst and/or polymer, then entering back into Analytic Tower parsing and obtain thick ammonia flow and lean ammonium absorption liquid, Analytic Tower operation temperature is 195 DEG C, and stripping gas is air. Lean ammonium absorbs liquid and returns to chilling tower for absorbing unreacted ammonia. Thick ammonia flow enters CWO reactor, obtains without ammonia logistics after removing ammonia nitrogen under the catalytic action of Pt, and reaction temperature is 150 DEG C, and reaction pressure is 5MPa, and oxygen-containing gas is purity oxygen. Logistics without ammonia can be used for device cycling use of water.
For ease of comparing, technological condition and result are listed in table 1, table 2.
[embodiment 2]
High ammonolysis product air-flow from ammoxidation of propylene reactor contacts the unreacted ammonia of absorption at chilling tower with lean ammonium absorption liquid and obtains low ammonolysis product air-flow and rich ammonium absorption liquid, it is 0.05 that lean ammonium absorbs S/P mol ratio in liquid, P elements mass content is 8.0%, absorption liquid pH value is 3.5, it is 75 DEG C that lean ammonium absorbs the temperature of liquid, is detected as 0 through absorbing the content of ammonia in the low ammonolysis product air-flow obtained.Rich ammonium absorbs liquid and enters segregation apparatus after air strips at stripper, remove light component and include the heavy constituent of catalyst and/or polymer, then entering back into Analytic Tower parsing and obtain thick ammonia flow and lean ammonium absorption liquid, Analytic Tower operation temperature is 250 DEG C, and stripping gas is nitrogen. Lean ammonium absorbs liquid and returns to chilling tower for absorbing unreacted ammonia. Thick ammonia flow enters CWO reactor, obtains without ammonia logistics after removing ammonia nitrogen under the catalytic action of Rh, and reaction temperature is 260 DEG C, and reaction pressure is 10MPa, and oxygen-containing gas is air. Logistics without ammonia can be used for device cycling use of water.
For ease of comparing, technological condition and result are listed in table 1, table 2.
[embodiment 3]
High ammonolysis product air-flow from ammoxidation of propylene reactor contacts the unreacted ammonia of absorption at chilling tower with lean ammonium absorption liquid and obtains low ammonolysis product air-flow and rich ammonium absorption liquid, it is 0.1 that lean ammonium absorbs S/P mol ratio in liquid, P elements mass content is 5.0%, absorption liquid pH value is 2.5, it is 50 DEG C that lean ammonium absorbs the temperature of liquid, is detected as 0 through absorbing the content of ammonia in the low ammonolysis product air-flow obtained. Rich ammonium absorbs liquid and enters segregation apparatus after nitrogen stripping at stripper, remove light component and include the heavy constituent of catalyst and/or polymer, then entering back into Analytic Tower parsing and obtain thick ammonia flow and lean ammonium absorption liquid, Analytic Tower operation temperature is 150 DEG C, and stripping gas is water vapour. Lean ammonium absorbs liquid and returns to chilling tower for absorbing unreacted ammonia. Thick ammonia flow enters CWO reactor, obtains without ammonia logistics after removing ammonia nitrogen under the catalytic action of Pd, and reaction temperature is 300 DEG C, and reaction pressure is 12MPa, and oxygen-containing gas is purity oxygen. Logistics without ammonia can be used for device cycling use of water.
For ease of comparing, technological condition and result are listed in table 1, table 2.
[embodiment 4]
High ammonolysis product air-flow from ammoxidation of propylene reactor contacts the unreacted ammonia of absorption at chilling tower with lean ammonium absorption liquid and obtains low ammonolysis product air-flow and rich ammonium absorption liquid, it is 0.1 that lean ammonium absorbs S/P mol ratio in liquid, P elements mass content is 6.5%, absorption liquid pH value is 5.0, it is 80 DEG C that lean ammonium absorbs the temperature of liquid, is detected as 0 through absorbing the content of ammonia in the low ammonolysis product air-flow obtained. Rich ammonium absorbs liquid and enters segregation apparatus after air strips at stripper, remove light component and include the heavy constituent of catalyst and/or polymer, then entering back into Analytic Tower parsing and obtain thick ammonia flow and lean ammonium absorption liquid, Analytic Tower operation temperature is 190 DEG C, and stripping gas is water vapour. Lean ammonium absorbs liquid and returns to chilling tower for absorbing unreacted ammonia. Thick ammonia flow enters CWO reactor, obtains lean ammonium and absorb liquid and wet oxidation tail gas under the catalytic action of Ru after removing ammonia nitrogen, and reaction temperature is 280 DEG C, and reaction pressure is 11MPa, and oxygen-containing gas is 50v% oxygen. Logistics without ammonia can be used for device cycling use of water.
For ease of comparing, technological condition and result are listed in table 1, table 2.
[embodiment 5]
High ammonolysis product air-flow from ammoxidation of propylene reactor contacts the unreacted ammonia of absorption at chilling tower with lean ammonium absorption liquid and obtains low ammonolysis product air-flow and rich ammonium absorption liquid, it is 0.3 that lean ammonium absorbs S/P mol ratio in liquid, P elements mass content is 6.0%, absorption liquid pH value is 6.5, it is 65 DEG C that lean ammonium absorbs the temperature of liquid, is detected as 0 through absorbing the content of ammonia in the low ammonolysis product air-flow obtained.Rich ammonium absorbs liquid and enters segregation apparatus after nitrogen stripping at stripper, remove light component and include the heavy constituent of catalyst and/or polymer, then entering back into Analytic Tower parsing and obtain thick ammonia flow and lean ammonium absorption liquid, Analytic Tower operation temperature is 170 DEG C, and stripping gas is water vapour. Lean ammonium absorbs liquid and returns to chilling tower for absorbing unreacted ammonia. Thick ammonia flow enters CWO reactor, obtains without ammonia logistics after removing ammonia nitrogen under the catalytic action of Pt, and reaction temperature is 230 DEG C, and reaction pressure is 9MPa, and oxygen-containing gas is 35v% oxygen. Logistics without ammonia can be used for device cycling use of water.
For ease of comparing, technological condition and result are listed in table 1, table 2.
[embodiment 6]
High ammonolysis product air-flow from ammoxidation of propylene reactor contacts the unreacted ammonia of absorption at chilling tower with lean ammonium absorption liquid and obtains low ammonolysis product air-flow and rich ammonium absorption liquid, it is 0.5 that lean ammonium absorbs S/P mol ratio in liquid, P elements mass content is 3.3%, absorption liquid pH value is 5.0, it is 70 DEG C that lean ammonium absorbs the temperature of liquid, is detected as 0 through absorbing the content of ammonia in the low ammonolysis product air-flow obtained. Rich ammonium absorbs liquid and enters segregation apparatus after air strips at stripper, remove light component and include the heavy constituent of catalyst and/or polymer, then entering back into Analytic Tower parsing and obtain thick ammonia flow and lean ammonium absorption liquid, Analytic Tower operation temperature is 165 DEG C, and stripping gas is water vapour. Lean ammonium absorbs liquid and returns to chilling tower for absorbing unreacted ammonia. Thick ammonia flow enters CWO reactor, obtains without ammonia logistics after removing ammonia nitrogen under the catalytic action of Pt, and reaction temperature is 270 DEG C, and reaction pressure is 11MPa, and oxygen-containing gas is 40v% oxygen. Logistics without ammonia can be used for device cycling use of water.
For ease of comparing, technological condition and result are listed in table 1, table 2.
[comparative example 1]
Difference from Example 4 is in that lean ammonium absorbs the character of liquid and is: S/P mol ratio is 0, pH is 5, and temperature is 80 DEG C, and P content is 6.5wt%; Other process conditions are identical with embodiment 4. Particularly as follows:
High ammonolysis product air-flow from ammoxidation of propylene reactor contacts the unreacted ammonia of absorption at chilling tower with lean ammonium absorption liquid and obtains low ammonolysis product air-flow and rich ammonium absorption liquid, is detected as 0.2wt% through absorbing the content of ammonia in the low ammonolysis product air-flow obtained. Rich ammonium absorbs liquid and enters segregation apparatus after air strips at stripper, remove light component and include the heavy constituent of catalyst and/or polymer, then entering back into Analytic Tower parsing and obtain thick ammonia flow and lean ammonium absorption liquid, Analytic Tower operation temperature is 190 DEG C, and stripping gas is water vapour. Lean ammonium absorbs liquid and returns to chilling tower for absorbing unreacted ammonia. Thick ammonia flow enters CWO reactor, obtains lean ammonium and absorb liquid and wet oxidation tail gas under the catalytic action of Ru after removing ammonia nitrogen, and reaction temperature is 280 DEG C, and reaction pressure is 11MPa, and oxygen-containing gas is 50v% oxygen. Logistics without ammonia can be used for device cycling use of water.
For ease of comparing, technological condition and result are listed in table 1, table 2.
[comparative example 2]
Difference from Example 4 is in that lean ammonium absorbs the character of liquid and is: absorbent is sulphuric acid, is 5 without P, pH, and temperature is 80 DEG C; Other process conditions are identical with embodiment 4. Particularly as follows:
High ammonolysis product air-flow from ammoxidation of propylene reactor contacts the unreacted ammonia of absorption at chilling tower with lean ammonium absorption liquid and obtains low ammonolysis product air-flow and rich ammonium absorption liquid, is detected as 0.1wt% through absorbing the content of ammonia in the low ammonolysis product air-flow obtained.Rich ammonium absorbs liquid and enters segregation apparatus after air strips at stripper, remove light component and include the heavy constituent of catalyst and/or polymer, then entering back into Analytic Tower parsing and obtain thick ammonia flow and lean ammonium absorption liquid, Analytic Tower operation temperature is 190 DEG C, and stripping gas is water vapour. Lean ammonium absorbs liquid and returns to chilling tower for absorbing unreacted ammonia. Thick ammonia flow enters CWO reactor, obtains lean ammonium and absorb liquid and wet oxidation tail gas under the catalytic action of Ru after removing ammonia nitrogen, and reaction temperature is 280 DEG C, and reaction pressure is 11MPa, and oxygen-containing gas is 50v% oxygen. Logistics without ammonia can be used for device cycling use of water.
For ease of comparing, technological condition and result are listed in table 1, table 2.
Only with the absorbent containing S or only with the absorbent containing P not as adopting simultaneously absorbent containing S and P good, this from comparative example 1 and 2 and embodiment 4 on year-on-year basis can be seen more clearly from.
Table 1
Table 2
Claims (10)
1. the processing method of unreacted ammonia in acrylonitrile reactor device, comprises the following steps:
From ammonia oxidation reactor, high ammonolysis product air-flow (6) out absorbs liquid (14) at chilling tower (1) with lean ammonium and contact unreacted ammonia in the high ammonolysis product air-flow of absorption, obtains rich ammonium absorption liquid (8) and low ammonolysis product air-flow (7); Richness ammonium is absorbed liquid (8) in stripper (2) through stripper stripping gas (9) stripping volatile organic component (10), in segregation apparatus (3), it is separated off supernatant light component (11) again and is sunken to the heavy constituent (12) of lower floor, then heated in Analytic Tower (4) and Analytic Tower stripping gas (13) stripping obtains thick ammonia flow (15) and lean ammonium absorbs liquid (14), and lean ammonium absorbs liquid (14) and returns the chilling tower (1) absorption for unreacted ammonia; Thick ammonia flow (15) and oxygen-containing gas (16) obtain without ammonia logistics (17) after wet oxidation reaction device (5) reacts; Wherein, lean ammonium absorbs in liquid containing at least one absorbent in phosphoric acid, ammonium dihydrogen phosphate or sulphuric acid.
2. method according to claim 1, it is characterised in that segregation apparatus (3) has the upper outlet discharging light component (11).
3. method according to claim 1, it is characterised in that segregation apparatus (3) has the lower outlet of discharge heavy constituent (12).
4. method according to claim 1, it is characterised in that lean ammonium absorbs the temperature of liquid and is 50-85 DEG C.
5. method according to claim 1, it is characterised in that stripper stripping gas (9) and/or Analytic Tower stripping gas (13) are the gas that stripping thing is inert.
6. method according to claim 5, it is characterised in that be at least one in water vapour, air and nitrogen to the stripping inert gas of thing.
7. according to the method described in claim 1, it is characterised in that described heavy constituent (12) is high polymer and/or catalyst fines.
8. according to the method described in claim 1, it is characterised in that described lean ammonium absorbs liquid (14) with water for solvent.
9. method according to claim 1, it is characterised in that Analytic Tower temperature is 150-250 DEG C.
10. method according to claim 1, it is characterised in that wet oxidation reaction used catalyst is include at least one loaded catalyst for active component in Pt, Pd, Ru and Rh.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106964247A (en) * | 2017-04-24 | 2017-07-21 | 中国石油化工股份有限公司 | Handling process containing ammonia flow in acrylonitrile installation |
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| US7326391B2 (en) * | 2004-07-22 | 2008-02-05 | Ineos Usa Llc | Process for recovery and recycle of ammonia from a vapor stream |
| CN101970083A (en) * | 2007-10-19 | 2011-02-09 | 依柯卡特有限公司 | Removal of ammonia from fluids |
| CN102553410A (en) * | 2010-12-22 | 2012-07-11 | 宜兰大学 | Treatment equipment for volatile low-polarity organic waste gas |
| CN103739517A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Improvement method for recycling and reusing unreacted ammonia in acrylonitrile reaction apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7326391B2 (en) * | 2004-07-22 | 2008-02-05 | Ineos Usa Llc | Process for recovery and recycle of ammonia from a vapor stream |
| CN101970083A (en) * | 2007-10-19 | 2011-02-09 | 依柯卡特有限公司 | Removal of ammonia from fluids |
| CN102553410A (en) * | 2010-12-22 | 2012-07-11 | 宜兰大学 | Treatment equipment for volatile low-polarity organic waste gas |
| CN103739517A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Improvement method for recycling and reusing unreacted ammonia in acrylonitrile reaction apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106964247A (en) * | 2017-04-24 | 2017-07-21 | 中国石油化工股份有限公司 | Handling process containing ammonia flow in acrylonitrile installation |
| CN106964247B (en) * | 2017-04-24 | 2020-10-30 | 中国石油化工股份有限公司 | Process for treating ammonia-containing gas stream in acrylonitrile plant |
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