CN115888779A - Catalyst for preparing succinonitrile from succinic acid and preparation method of succinonitrile - Google Patents
Catalyst for preparing succinonitrile from succinic acid and preparation method of succinonitrile Download PDFInfo
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- CN115888779A CN115888779A CN202211346560.3A CN202211346560A CN115888779A CN 115888779 A CN115888779 A CN 115888779A CN 202211346560 A CN202211346560 A CN 202211346560A CN 115888779 A CN115888779 A CN 115888779A
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- succinonitrile
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- succinic acid
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000001384 succinic acid Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 15
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 15
- 229940014800 succinic anhydride Drugs 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 239000012159 carrier gas Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 4
- 239000011541 reaction mixture Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000003682 vanadium compounds Chemical class 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 150000001845 chromium compounds Chemical class 0.000 description 3
- 150000001869 cobalt compounds Chemical class 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000005078 molybdenum compound Substances 0.000 description 3
- 150000002752 molybdenum compounds Chemical class 0.000 description 3
- -1 phosphorus compound Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229940117975 chromium trioxide Drugs 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 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
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a catalyst for preparing succinonitrile by catalytic ammoniation and a preparation method of succinonitrile. Succinic acid and the like are used as starting materials, and succinonitrile is continuously prepared by one-step reaction in the presence of a catalyst. The preparation method is simple and easy to operate, easy to control, low in pollution, high in product yield and good in quality. The catalyst has the advantages of good activity and selectivity, stable performance, long service life, high raw material conversion rate and less side reaction, and effectively reduces the production cost and the generation of three wastes.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a catalyst for preparing succinonitrile from succinic acid and a preparation method of succinonitrile.
Background
Succinonitrile, also known as 1, 2-dicyanoethane, is an important fine chemical intermediate with wide application, can be used for synthesizing quinacridone pigments, electrolyte additives for improving the performance of lithium batteries and can also be used for producing nylon.
In the industrial production, the aliphatic dinitrile is usually prepared by a carboxylic acid ammoniation method, wherein carboxylic acid or derivatives thereof are heated and dissolved in an open system, and then ammonia gas is continuously introduced into the solution, so that the system reacts in the presence of catalysts such as phosphoric acid or phosphate.
And the purification process of the succinonitrile is immature, the crude product is purified by adopting a crystallization method and an adsorption method, the equipment investment is large, the process is complex, the cost of the solvent and the adsorbent is high, the regeneration is difficult, the continuous production cannot be realized, the environment can be polluted, the health of operators is harmed, the reaction route is long, the product yield is low and the like.
Therefore, further development of the production process of succinonitrile is needed, and a preparation method of succinonitrile with environmental protection, simple process, high yield, low cost and good quality is developed.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing butanedinitrile by ammoniating succinic acid, succinic anhydride and the like serving as raw materials under the action of a catalyst. In the method, the catalyst has good activity and selectivity, stable performance and long service life, can catalyze and synthesize the succinonitrile by one step, has high product yield and high quality, can realize continuous production, has simple post-treatment process and reduces environmental pollution, thereby completing the invention.
One of the objects of the present invention is to provide a catalyst for preparing succinonitrile by catalytic ammoniation, which contains vanadium, chromium, molybdenum, cobalt and boron elements, and preferably also contains alkali metal elements.
The catalyst is prepared by preparing a compound containing vanadium, chromium, molybdenum, cobalt and boron into a mixed solution, adding a carrier, and drying to obtain a catalyst precursor. Preferably, an alkali metal compound is further added to the mixed solution.
Still another object of the present invention is to provide a method for preparing succinonitrile, in which liquid succinic acid is reacted with ammonia gas in the presence of a catalyst to prepare succinonitrile. The method comprises the following steps:
and 3, allowing the reaction mixed gas to enter a collecting device, cooling and rectifying to obtain the succinonitrile.
The catalyst for preparing succinonitrile from succinic acid and the preparation method of succinonitrile have the following beneficial effects:
(1) According to the invention, succinic acid, succinic anhydride and maleic anhydride are used as starting materials, and in the presence of the catalyst prepared in the invention, succinonitrile can be continuously prepared by one-step reaction. The preparation method is simple and easy to operate, easy to control, low in pollution, high in product yield and good in quality.
(2) The catalyst for preparing succinonitrile by catalysis provided by the invention can efficiently catalyze the ammoniation of succinic acid, succinic anhydride and maleic anhydride, has high activity and good selection, and has stable performance, long service life and effectively prolonged service life.
(3) In the preparation process of the succinonitrile, liquid materials enter the catalyst layer of the reactor, the ammonification reaction can be continuously carried out, the reaction route is short, the selectivity of the catalyst activator is good, the conversion rate of raw materials is high, the side reaction is less, and the production yield is effectively reduced.
(4) The preparation method of succinonitrile provided by the invention has the advantages of simple post-treatment process, easy purification, low separation process cost, low energy consumption, high quality of the obtained product, great reduction of process cost, effective reduction of three wastes and contribution to implementation and application in industrial production.
Drawings
FIG. 1 shows a gas chromatogram of succinonitrile produced in example 1 of the present invention.
Detailed Description
The present invention will now be described in detail by way of specific embodiments, and features and advantages of the present invention will become more apparent and apparent from the following description.
The invention provides a method for preparing butanedinitrile by ammoniation by taking succinic acid and the like as raw materials. The method adopts the vanadium-chromium catalyst, has good activity and selectivity and long service life, can catalyze and synthesize the butanedinitrile in one step, has stable reaction process, high product yield, less impurity content and simple post-treatment process, realizes continuous production, reduces environmental pollution and is beneficial to application in actual production.
The first aspect of the invention provides a catalyst for preparing succinonitrile by catalytic ammoniation, which contains vanadium, chromium, molybdenum, cobalt and boron elements, and preferably also contains alkali metal elements.
The alkali metal element is selected from one or more of potassium, sodium and cesium, preferably potassium and/or cesium, and more preferably potassium.
The molar ratio of the elements of vanadium, chromium, molybdenum, cobalt and boron is 1 (0.10-0.35): 0.7-2.1): 0.01-0.20): 0.05-0.40, preferably 1 (0.15-0.30): 1.0-1.8): 0.02-0.15): 0.10-0.30), more preferably 1 (0.2-0.25): 1.3-1.5): 0.03-0.10): 0.15-0.20.
The molar ratio of the vanadium to the alkali metal element is 1 (0.01-0.16), preferably 1 (0.03-0.13), and more preferably 1 (0.05-0.10).
The catalyst is prepared by preparing a compound containing vanadium, chromium, molybdenum, cobalt and boron into a mixed solution, adding a carrier, and drying to obtain a catalyst precursor. Preferably, an alkali metal compound is further added to the mixed solution. And calcining the catalyst precursor in an air atmosphere to obtain the catalyst.
According to the invention, the ammoniation of succinic acid, succinic anhydride or maleic anhydride can be realized by using vanadium, chromium, molybdenum, cobalt and boron compounds, preferably adding alkali metal compounds, and the ammoniation has high activity and good selectivity. By adding the boron element, the desorption of reactants is promoted, the service life of the catalyst is effectively prolonged in the preparation process of the succinonitrile, and simultaneously, the activity and the selectivity of the catalyst are improved, so that the succinonitrile is prepared with high yield, the side reaction is less, the refining process is simplified, and the product quality is effectively improved.
In a preferred embodiment of the present invention, a vanadium compound and a chromium compound are added to an oxalic acid solution to be dissolved, then a boron compound and a phosphorus compound are added, after the dissolution, a molybdenum compound and a cobalt compound, preferably an alkali metal compound are sequentially added, and after the complete dissolution, a mixed solution is obtained.
The vanadium compound is selected from oxides of vanadium, such as vanadium pentoxide.
The chromium compound is selected from a chromium salt or an oxide of chromium, preferably an oxide of chromium, such as chromium trioxide.
The boron compound is selected from boric acid or organoboron, preferably boric acid.
The phosphorus compound is selected from phosphoric acid, an oxide of phosphorus or organic phosphorus, preferably phosphoric acid.
The molybdenum compound is selected from molybdate or molybdenum trioxide, preferably ammonium paramolybdate ((NH) 4 ) 2 MoO 4 )。
The cobalt compound is selected from a cobalt salt or an oxide of cobalt, preferably a cobalt salt, such as cobalt acetate.
The alkali metal compound is selected from alkali metal salts.
The molar ratio of the vanadium compound, the chromium compound, the molybdenum compound, the cobalt compound and the boron compound is 1 (0.10-0.35): (0.7-2.1): 0.01-0.20): 0.05-0.40), preferably 1 (0.15-0.30): 1.0-1.8): 0.02-0.15): 0.10-0.30), more preferably 1 (0.2-0.25): 1.3-1.5): 0.03-0.10): 0.15-0.20, based on the molar amount of vanadium, chromium, molybdenum, cobalt and boron contained therein.
The molar ratio of the vanadium compound to the alkali metal compound is 1 (0.01-0.16), preferably 1 (0.03-0.13), more preferably 1 (0.05-0.10), based on the molar amount of vanadium and alkali metal contained therein.
The carrier is selected from silica gel, titanium oxide or alumina, and is preferably silica gel. Preferably, the carrier is preheated first, then the carrier is added to the mixed solution, stirred, left to stand and filtered.
The preheating temperature of the carrier is 60-110 ℃, and preferably 80-95 ℃. The particle size of the carrier is 60-150 meshes, and preferably 80-120 meshes.
The mass ratio of the carrier to the vanadium source is 100 (2-35), preferably 100 (5-25), and more preferably 100 (8-12).
The calcination temperature is from 500 to 900 ℃, preferably from 550 to 800 ℃, more preferably from 600 to 700 ℃, e.g. 650 ℃; the calcination time is from 7 to 16h, preferably from 8 to 14h, more preferably from 9 to 12h, e.g. 10h. Preferably, the catalyst precursor is subjected to a precalcination followed by the calcination described above. The pre-calcination temperature is 200-500 deg.C, preferably 250-450 deg.C, more preferably 300-400 deg.C, such as 350 deg.C, and the pre-calcination time is 1.5-4.5h, preferably 2-4h, more preferably 2.5-3.5h, such as 3h.
The precalcination can remove the chemical combination water, volatile impurities and the chemical valence state of stable components in the precursor, so that the crystal phase of the load material is transformed to control the size of crystal grains, and the uneven size of direct high-temperature crystal grains is avoided.
In a second aspect, the invention provides a method for preparing succinonitrile, wherein one or more of liquid succinic acid, succinic anhydride and maleic anhydride are reacted with ammonia gas in the presence of a catalyst to prepare succinonitrile.
In the method, one or more of succinic acid, succinic anhydride and maleic anhydride are used for preparing succinonitrile, and succinic acid is preferred.
The method comprises the following steps:
The preheating temperature is higher than the melting point of the material to be melted, preferably is 5-20 ℃ higher than the melting point of the material to be melted, and more preferably is 10-15 ℃ higher than the melting point of the material to be melted. For example, when succinic acid is to be melted, the preheating temperature is 195-200 ℃.
The invention adopts succinic acid, succinic anhydride and maleic anhydride as starting raw materials, has high raw material safety, can realize high yield and high purity, improves the utilization rate of the raw materials, has less three wastes, is a green process and is environment-friendly.
And 2, introducing the molten liquid and ammonia gas into a reactor with a catalyst layer, optionally introducing carrier gas, and reacting at high temperature to obtain reaction mixed gas.
The catalyst is as described in the first aspect.
The carrier gas is one or more selected from helium, argon, xenon, ammonia, nitrogen and carbon dioxide, and is preferably nitrogen. According to the invention, succinic acid, succinic anhydride and maleic anhydride are reacted with ammonia gas to prepare succinonitrile, oxidizing gas is not used, impurities generated by over-oxidation are avoided, and the reaction yield is reduced.
The volume ratio of the carrier gas to the ammonia gas is (0.5-10): 1, preferably (1-7): 1, and more preferably (2-5): 1.
Preferably, the ammonia or carrier gas is first preheated to 310-380 deg.C, preferably 330-350 deg.C, and then introduced into the reactor.
The molar ratio of the total mole of succinic acid, succinic anhydride and maleic anhydride to ammonia gas is 1 (2-30), preferably 1 (4-25), more preferably 1 (5-20), such as 1. The alkaline state in the system can avoid the hydrolysis reaction of the product, and the excess ammonia gas is controlled in the preferable condition
The reaction temperature is 335 to 390 ℃, preferably 345 to 380 ℃ and more preferably 355 to 370 ℃. Too low a temperature results in a catalyst with low catalytic activity and too high a temperature results in decomposition of the product.
The flow rate of the melt into the reactor is 1.5 to 5.0g/h, preferably 2.0 to 4.0g/h, more preferably 2.5 to 3.5g/h.
The residence time of the melt in the reactor is 10 to 26s, preferably 12 to 22s, more preferably 14 to 18s. The raw materials are decomposed after the residence time is long, and the raw materials are incompletely reacted after the residence time is short.
The pressure of the reaction system is 0.01 to 0.12MPa, preferably 0.03 to 0.09MPa, and more preferably 0.04 to 0.07MPa.
The weight load (WWH) of the catalyst is from 1.5 to 5.0g/100g per hour, preferably from 2.0 to 4.0g/100g per hour, more preferably from 2.5 to 3.5g/100g per hour.
The reactor is preferably a fluidized bed reactor.
And 3, enabling the reaction mixed gas to enter a collecting device, cooling and rectifying to obtain the succinonitrile.
And (3) enabling the reaction mixed gas coming out of the reactor to enter a collecting device, cooling and then obtaining a crude product of the succinonitrile in the collecting device. The tail gas mainly contains carrier gas, excessive ammonia and water vapor, and the carrier gas is also contained when the carrier gas is introduced into the reactor. The excessive ammonia gas and/or carrier gas can be recycled after absorbing water vapor. Or the absorption device can be used for absorbing the excessive ammonia gas and then discharging the tail gas. The whole production process generates less three wastes and is environment-friendly.
The collecting device and the tail gas absorption device can be completed by adopting the prior art, such as a catcher, and the acid absorption liquid absorbs excessive ammonia in the tail gas.
And (3) rectifying the crude succinonitrile product at high temperature under reduced pressure in a rectifying tower to obtain the succinonitrile. The rectification is carried out under the conditions that the system pressure is 30mmHg and the temperature is 145 ℃.
According to the preparation method of the succinonitrile, succinic acid, succinic anhydride and maleic anhydride are used as starting materials, and the succinonitrile can be continuously prepared through one-step reaction in the presence of the catalyst prepared in the invention. The preparation method is simple and easy to operate, easy to control, low in pollution, high in product yield and good in quality. The catalyst has the advantages of stable performance, long service cycle, good activity and selectivity, high raw material conversion rate, less side reaction, effective reduction of production cost and effective reduction of three wastes.
Examples
Example 1
48g of vanadium pentoxide and 11.6g of chromium trioxide were added to 858g of an 11.4% by weight oxalic acid solution and dissolved with stirring. Then, 6.2g of boric acid and 90g of concentrated phosphoric acid having a concentration of 85.54wt% were sequentially added thereto, and stirred for 2 hours, and then 8.4g of ammonium orthomolybdate ((NH) 4 ) 2 MoO 4 ) And potassium chloride (2.9 g) were stirred for 2 hours. Then, 3.2g of cobalt acetate was added thereto, and the mixture was stirred for 1 hour to obtain a mixed solution.
Then 450g of silica gel having a particle size of 40 to 80 mesh was added, and after stirring and mixing, the mixture was immersed for 24 hours. And (3) spray-drying the slurry in a spray dryer to obtain a catalyst precursor. The molar ratio of the metal elements added is V: cr: P: mo: K: co: B = 1.22.
And placing the catalyst precursor in a muffle furnace at 350 ℃ for calcining for 3 hours, gradually heating to 650 ℃, preserving heat for 10 hours, and cooling to room temperature to obtain the catalyst.
100g of the above catalyst was charged
In a fluidized bed reactor with the height of 600mm, ammonia gas is preheated at 340 ℃ and then enters the fluidized bed reactor, succinic acid is liquefied at 195 ℃ and then enters the fluidized bed reactor, the flow of the liquefied succinic acid entering the reactor is 3.0g/h, the system pressure in the reactor is 0.05MPa, and the reaction temperature is 360 +/-5 ℃. Wherein the mol ratio of ammonia gas to succinic acid is about 16, the catalytic treatment capacity of the catalyst is that every 100g of catalyst can catalytically treat 3.0g of succinic acid per hour, and the retention time of the succinic acid is 16s. And (3) directly allowing a product desorbed from the surface of the catalyst to enter a trapping device along with reaction gas, and collecting and weighing the trapped crude succinonitrile, and detecting the content and the moisture. The conversion rate of the succinic acid is about 100 percent and the selectivity of the succinonitrile is 95.7 percent through gas chromatography test.
And (3) cooling the crude succinonitrile collected by the catcher to room temperature, putting the crude succinonitrile into a rectifying tower for vacuum rectification treatment, and carrying out vacuum rectification at the temperature of 145 ℃ under the pressure of 30mmHg to obtain a succinonitrile product, wherein the separation yield of the succinonitrile is 94.2%, the final molar yield of the succinonitrile is 90.15%, and the purity of the gas chromatography is 99.668%. The gas chromatogram is shown in FIG. 1.
The service life of the tested catalyst is 3522h.
Example 2
100g of the catalyst prepared in the embodiment 1 is loaded into a fluidized bed reactor with the diameter of 38mm and the height of 600mm, nitrogen and ammonia gas enter the fluidized bed reactor after being preheated at 340 ℃, succinic acid enters the fluidized bed reactor after being liquefied at the temperature of 195 ℃, the flow of the liquefied succinic acid entering the reactor is 3.0g/h, the system pressure in the reactor is 0.05MPa, and the reaction temperature is 360 +/-5 ℃. Wherein, the mol ratio of ammonia gas to succinic acid is about 6, the volume ratio of nitrogen gas to ammonia gas is 2:1, the catalytic treatment capacity of the catalyst is that every 100g of the catalyst can be used for catalytically treating 3.0g of succinic acid per hour, and the retention time of the succinic acid is 15-16s. And (3) directly enabling a product desorbed from the surface of the catalyst to enter a trapping device along with reaction gas, collecting a succinonitrile crude product obtained by trapping, weighing, and detecting the content and the moisture. The conversion rate of the succinic acid is about 100 percent and the selectivity of the succinonitrile is 93.2 percent through gas chromatography test.
The invention has been described in detail with reference to specific embodiments and/or illustrative examples and the accompanying drawings, which, however, should not be construed as limiting the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A catalyst for preparing succinonitrile by catalytic ammoniation, which contains vanadium, chromium, molybdenum, cobalt and boron elements, and preferably also contains alkali metal elements.
2. The catalyst according to claim 1, wherein the catalyst is prepared by preparing a compound containing vanadium, chromium, molybdenum, cobalt and boron elements into a mixed solution, adding a carrier, and drying to obtain a catalyst precursor, preferably, adding an alkali metal compound into the mixed solution;
and calcining the catalyst precursor in an air atmosphere to obtain the catalyst.
3. The catalyst according to claim 1,
the molar ratio of the elements of vanadium, chromium, molybdenum, cobalt and boron is 1 (0.10-0.35): 0.7-2.1): 0.01-0.20): 0.05-0.40, preferably 1 (0.15-0.30): 1.0-1.8): 0.02-0.15): 0.10-0.30), more preferably 1 (0.2-0.25): 1.3-1.5): 0.03-0.10): 0.15-0.20;
the molar ratio of the vanadium to the alkali metal element is 1 (0.01-0.16), preferably 1 (0.03-0.13), and more preferably 1 (0.05-0.10).
4. A process for the preparation of succinonitrile, wherein one or more of liquid succinic acid, succinic anhydride and maleic anhydride are reacted with ammonia gas in the presence of a catalyst according to any one of claims 1 to 3 to produce succinonitrile, preferably succinic acid.
5. Method according to claim 4, characterized in that it comprises the following steps:
step 1, preheating and melting one or more of succinic acid, succinic anhydride and maleic anhydride to form molten liquid;
step 2, introducing the molten liquid and ammonia gas into a reactor with a catalyst layer, optionally introducing carrier gas, and reacting at high temperature to obtain reaction mixed gas;
and 3, enabling the reaction mixed gas to enter a collecting device, cooling and rectifying to obtain the succinonitrile.
6. The method according to claim 5, wherein in the step 2, the molar ratio of the total mole of the succinic acid, the succinic anhydride and the maleic anhydride to the ammonia gas is 1 (2-30), preferably 1 (4-25), and more preferably 1 (5-20).
7. The process according to claim 5, wherein in step 2, the reaction temperature is 335 to 390 ℃, preferably 345 to 380 ℃, more preferably 355 to 370 ℃.
8. The process according to claim 5, characterized in that in step 2, the weight load (WWH) of the catalyst is from 1.5 to 5g/100g per hour, preferably from 2.0 to 4.0g/100g per hour, more preferably from 2.5 to 3.5g/100g per hour.
9. The method according to claim 5, wherein in step 2, the flow rate of the molten liquid into the reactor is 1.5 to 5g/h, preferably 2.0 to 4.0g/h, more preferably 2.5 to 3.5g/h; the residence time in the reactor is from 10 to 26s, preferably from 12 to 22s, more preferably from 14 to 18s.
10. The method of claim 5, wherein in step 3, the reaction mixture from the reactor is fed to a collecting device, and after cooling, crude succinonitrile is obtained in the collecting device; carrying out high-temperature reduced pressure rectification on the succinonitrile crude product by a rectifying tower to obtain succinonitrile;
the excessive ammonia gas is recovered and reused after absorbing water vapor.
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| US6143690A (en) * | 1998-05-07 | 2000-11-07 | Asahi Kasei Kogyo Kabushiki Kaisha | Ammoxidation catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane |
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| CN111293360A (en) * | 2018-12-10 | 2020-06-16 | 三星电子株式会社 | Electrolyte and lithium secondary battery comprising the same |
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| US6143690A (en) * | 1998-05-07 | 2000-11-07 | Asahi Kasei Kogyo Kabushiki Kaisha | Ammoxidation catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane |
| US20090234158A1 (en) * | 2005-03-29 | 2009-09-17 | Atsushi Sudo | Catalyst for use in production of methacrylic acid and method for manufacturing the same |
| CN103896807A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Preparation method of terephthalonitrile through ammonium oxidation |
| CN107915660A (en) * | 2016-10-10 | 2018-04-17 | 惠州市宙邦化工有限公司 | A kind of method of purification of succinonitrile |
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