CN117181295A - Heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst, preparation and application - Google Patents
Heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst, preparation and application Download PDFInfo
- Publication number
- CN117181295A CN117181295A CN202311072103.4A CN202311072103A CN117181295A CN 117181295 A CN117181295 A CN 117181295A CN 202311072103 A CN202311072103 A CN 202311072103A CN 117181295 A CN117181295 A CN 117181295A
- Authority
- CN
- China
- Prior art keywords
- aipo
- heteroatom
- methyl salicylate
- composite catalyst
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 38
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 35
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 claims description 84
- 229960001047 methyl salicylate Drugs 0.000 claims description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 241000282326 Felis catus Species 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229940001007 aluminium phosphate Drugs 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000007210 heterogeneous catalysis Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000011949 solid catalyst Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000011160 research Methods 0.000 description 7
- 150000001408 amides Chemical class 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 3
- 238000005915 ammonolysis reaction Methods 0.000 description 3
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 3
- 229910000149 boron phosphate Inorganic materials 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- AREPHAPHABGCQP-UHFFFAOYSA-N 1-(dimethylamino)-3-[2-[2-(4-methoxyphenyl)ethyl]phenoxy]propan-2-ol Chemical compound C1=CC(OC)=CC=C1CCC1=CC=CC=C1OCC(O)CN(C)C AREPHAPHABGCQP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SKZKKFZAGNVIMN-UHFFFAOYSA-N Salicilamide Chemical compound NC(=O)C1=CC=CC=C1O SKZKKFZAGNVIMN-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229960000581 salicylamide Drugs 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- LQAQMOIBXDELJX-UHFFFAOYSA-N 2-methoxyprop-2-enoic acid Chemical compound COC(=C)C(O)=O LQAQMOIBXDELJX-UHFFFAOYSA-N 0.000 description 1
- 206010002383 Angina Pectoris Diseases 0.000 description 1
- 239000005730 Azoxystrobin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108091028732 Concatemer Proteins 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- -1 M 1 Organic compounds Chemical class 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- AJJBCQJUDJPUJP-UHFFFAOYSA-K aluminum cobalt(2+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Al+3].[Co+2] AJJBCQJUDJPUJP-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229950004443 bunolol Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- IXHBTMCLRNMKHZ-LBPRGKRZSA-N levobunolol Chemical compound O=C1CCCC2=C1C=CC=C2OC[C@@H](O)CNC(C)(C)C IXHBTMCLRNMKHZ-LBPRGKRZSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The application belongs to the field of solid catalyst preparation and application, and particularly discloses a heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst, preparation and application.
Description
Technical Field
The application relates to the technical field of supported molecular sieve catalysts, in particular to a heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst, preparation and application.
Background
The salicylonitrile is an important intermediate, is mainly used for synthesizing methoxy acrylic acid ester bactericide-azoxystrobin, and injection medicine bunolol for hypertension and angina pectoris, and has wide application in industries such as medicine, pesticide, dye, liquid crystal material synthesis and the like. At present, salicylamide is used as a reaction raw material in the industrial synthesis of salicylonitrile, phosgene or solid light is used as a dehydrating agent, a part of water in the molecule of salicylamide is removed to be converted into salicylnitrile, and a large amount of waste acid, waste gas, waste water and the like are generated in the process. In recent years, the preparation of salicylonitrile by using methyl salicylate, ammonia or urea as raw materials and adopting a solid acid heterogeneous catalysis method has been reported, wherein a common gas-solid or pressurized liquid-solid two-phase fixed bed reactor is mainly adopted, and the reported solid catalyst comprises supported boron phosphate (Z.J. Kong, et al, efficient preparation of salicylonitrile from methyl salicylate over supported boron phosphate catalyst in a continuous fixed bed reactor [ J ], chemical Papers, 2021, 76, 1365-1375), phosphorus-aluminum solid acid (Chen Guanhu and the like, and the phosphorus-aluminum solid acid catalyzes the research of preparing the salicylonitrile by using the methyl salicylate [ J ], modern Chemical industry, 2020, 40,3:143-151;CN 104549378A) and SYR-05 (Chen Erzhong and the like), and the green process [ J ] for synthesizing the o-hydroxybenzonitrile by using the methyl salicylate in one step method is adopted for pesticide, 2018, 57, 27:870-872. However, these systems have a large catalyst loading, a small liquid space velocity (0.18 to 0.3 h-1), and a low space-time yield of catalyst (0.162~0.27 gnitrile. Gcat-1. H-1). In addition, since the catalyst loading is large in the fixed bed reactor, the particle type gap is small, and the product or carbon deposit easily causes a large bed pressure drop, resulting in the bed blockage.
Zeolite molecular sieves, which are generally crystalline aluminosilicates having micropores (less than 2 nm), have large specific surface areas and pore volumes, and are tunable in acidity and basicity, are a solid catalyst widely used for heterogeneous catalysis. The advent of aluminum phosphate (AIPO-n, n to distinguish the structural types of molecular sieves) zeolite molecular sieves has not only enriched the family of molecular sieves, but has broken the traditional notion that zeolite molecular sieves consist of silicon oxygen tetrahedra (SiO 4) and aluminum oxygen tetrahedra (AlO 4). The AIPO-5 aluminum phosphate zeolite molecular sieve belongs to an AFI structure, consists of a phosphorus-oxygen tetrahedron (PO 4) and an aluminum-oxygen tetrahedron (AlO 4), has a 12-membered ring, has a pore diameter of 0.73x0. nm, and is neutral and lacks an acid center due to charge cancellation of a pentavalent phosphorus center and a trivalent aluminum center. Research shows that doping other hetero atoms into the AIPO-5 aluminum phosphate zeolite molecular sieve skeleton can regulate skeleton charge distribution, regulate the acidity of molecular sieve further and realize the application in heterogeneous catalytic reaction. For example, the institute Tian Peng of great concatemers has metal atoms doped in the AIPO-5 framework (Tian Peng, heteroatom aluminum phosphate molecular sieves and their low temperature catalytic hydrocarbon oxidation studies, doctor's school of China, 2004); F. dawaymeh et al (Molecular Catalysis 501 (2021) 111371) report on metal doped AIPO-5 catalyzed esterification of acetic acid and ethanol.
The process of generating the salicylonitrile by the reaction of methyl salicylate and ammonia is essentially catalytic coupling of ammonolysis of ester and dehydration of amide, and researches show that the metal oxide can effectively adsorb and activate organic ester and ammonia molecules and generate S N 2 nucleophilic attack to form an amide, which is then dehydrated at an acidic or basic center to form a nitrile. The application reports that the hetero atom M 2 AIPO-5 aluminum phosphate molecular sieve supported metal oxide active component for catalyzing methyl salicylate and ammonia to synthesize salicylonitrile in gas-solid multiphase reaction, wherein the metal oxide component is used for ammonolysis of ester, M 2 AIPO-5 is used for the dehydration of amide to form nitrile, and the double-function composite catalyst can realize continuous synthesis of salicylnitrile in a one-stage fixed bed reactor and has higher space-time yield. The application has not been reported.
Disclosure of Invention
The application provides a heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst M 1 O/M 2 The AIPO-5 catalyst has the double functions of catalyzing ammonolysis of methyl salicylate and amide dehydration, can be used for gas-solid multiphase continuous synthesis of salicylonitrile in a one-stage fixed bed, and has the advantages of simple reaction device, high efficiency of the catalytic reaction process and high space-time yield of the salicylnitrile.
One aspect of the application provides a heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst M 1 O/M 2 -AIPO-5, said M 1 O is a metal oxide, M 1 O includes CuO, znO, fe 2 O 3 、MgO、CeO 2 、TiO 2 Or ZrO(s) 2 ，M 2 Is a doped heteroatom, M 2 Including B, in, ga, cr, fe, V, si or Ti.
Preferably, said M 2 Doped in the AIPO-5 molecular sieve framework.
In another aspect, the present application provides a heteroatom aluminum phosphate fractionSub-sieve supported metal oxide composite catalyst M 1 O/M 2 -AIPO-5 for the gas-solid heterogeneous catalytic preparation of salicylnitrile from methyl salicylate, said M 1 O/M 2 AIPO-5 catalyzes the ammonolysis-dehydration reaction coupling of methyl salicylate to form salicylnitrile.
Preferably, the ammonolysis-dehydration reaction is carried out in a one-stage fixed bed reactor, methyl salicylate enters the fixed bed reactor to react with ammonia gas under the condition of nitrogen gas as carrier gas, and at least one of the following conditions is satisfied:
(1) The reaction temperature of the fixed bed reactor is 300-500 ℃;
(2) The liquid flow rate of the methyl salicylate is 0.01-0.08 mL/min, the flow rate of the nitrogen is 15-80 mL/min, and the flow rate of the ammonia is 15-80 mL/min;
(3) The molar ratio of the ammonia gas to the methyl salicylate is (2-8): 1, a step of;
(4) The liquid space velocity of the methyl salicylate is 2.362-18.896 g g -1 ·h -1 ；
(5) The total airspeed of the methyl salicylate, ammonia and nitrogen gas is 6000-32000 mL g -1 ·h -1 。
Preferably, the conversion rate of the methyl salicylate is 50-95%, the yield of the salicylonitrile is 40-85%, and the space-time yield of the composite catalyst is 2.50~6.30 gnitrile gcat -1 ·h -1 。
A third aspect of the present application provides a method for producing a composite catalyst comprising adding a metal element M 1 Uniformly mixing the compound of (C) with a heteroatom aluminum phosphate molecular sieve, and calcining to obtain M 1 O/M 2 -AIPO-5, said M 1 Is a metal element, M 1 Comprising Cu, zn, fe, mg, ce, ti or Zr, M 2 Is a doped heteroatom, M 2 Including B, in, ga, cr, fe, V, si or Ti.
Preferably, the metal-containing element M 1 The compound of (2) comprises a metal element M 1 An oxyacid salt, organic matter or hydroxide of (a).
Preferably, the metal-containing element M 1 Compound of (2) and heteroatom aluminium phosphate moleculeThe sieves are uniformly mixed through solid-phase grinding, the grinding rotating speed is 400-800 rmp, the grinding period is that each rotation is 60 min, 30 min is stopped, and the grinding time is 4-12 h.
Preferably, the metal-containing element M 1 Compound of (2) and heteroatom aluminium phosphate molecular sieve M 2 AIPO-5 according to the metal oxide M 1 The load of O is 3% -10% and mixed.
Preferably, the conditions of calcination include calcination at 500-700 ℃ for 2-6 h.
Compared with the prior art, the application has the beneficial effects that:
the surface of the composite catalyst has the dual-function characteristic, and the metal oxide can effectively adsorb and activate ammonia gas to enable the ammonia gas and carbonyl of the ester to generate S N 2 nucleophilic attack to produce amide, and then the amide is dehydrated in the acid or alkali center of the surface of the heteroatom aluminum phosphate molecular sieve to produce nitrile.
The catalyst can be used for catalyzing ammonolysis-dehydration reaction coupling of methyl salicylate to generate salicylonitrile in a one-stage fixed bed reactor, and has the advantages of simple reaction device, high efficiency of catalytic reaction process and high space-time yield of the salicylonitrile.
The catalyst is prepared by adopting solid-phase grinding and calcining thermal decomposition, does not need a solvent, and has the advantages of green and simple preparation method.
Drawings
The following drawings are illustrative of the application and are not intended to limit the scope of the application, in which:
fig. 1: the structure of the composite catalyst is schematically shown;
fig. 2: XRD spectra of the composite catalysts of examples 1-2;
fig. 3: the reaction performance results of the composite catalyst of example 1;
fig. 4: example 2 results of the reactivity of the composite catalyst;
fig. 5: example 3 results of the reactivity of the composite catalyst;
fig. 6: space-time yields of catalysts are preferred in the examples;
description of the embodiments
The following detailed description of the present application will provide further details in order to make the above-mentioned objects, features and advantages of the present application more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. The present application may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the application, whereby the application is not limited to the specific embodiments disclosed below.
In the description of the present application, unless otherwise defined, terms of art and words of art which have not been specifically described have the same meanings as commonly understood by those skilled in the art, and are common general knowledge to those skilled in the art, and methods which have not been specifically described are conventional methods which are well known to those skilled in the art. In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
One aspect of the application provides a heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst M 1 O/M 2 -AIPO-5, said M 1 O is a metal oxide, M 1 O includes CuO, znO, fe 2 O 3 、MgO、CeO 2 、TiO 2 Or ZrO(s) 2 ，M 2 Is a doped heteroatom, M 2 Including B, in, ga, cr, fe, V, si or Ti.
In some embodiments, the M 2 Doped in the AIPO-5 molecular sieve framework.
In another aspect of the application, a heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst M is protected 1 O/M 2 -AIPO-5 for the gas-solid heterogeneous catalytic preparation of salicylnitrile from methyl salicylate, said M 1 O/M 2 AIPO-5 catalyzes the ammonolysis-dehydration reaction coupling of methyl salicylate to form salicylnitrile.
In some embodiments, the reaction is carried out in a one-stage fixed bed reactor, methyl salicylate is carried into the fixed bed reactor as carrier gas to react with ammonia gas, and at least one of the following conditions is satisfied:
(1) The reaction temperature of the fixed bed reactor is 300-500 ℃;
(2) The liquid flow rate of the methyl salicylate is 0.01-0.08 mL/min, the flow rate of the nitrogen is 15-80 mL/min, and the flow rate of the ammonia is 15-80 mL/min;
(3) The molar ratio of the ammonia gas to the methyl salicylate is (2-8): 1, a step of;
(4) The liquid space velocity of the methyl salicylate is 2.362-18.896 g g -1 ·h -1 ；
(5) The total airspeed of the methyl salicylate, ammonia and nitrogen gas is 6000-32000 mL g -1 ·h -1 。
In some embodiments, the methyl salicylate has a conversion of 50-95%, the salicylnitrile has a yield of 40-85%, and the composite catalyst has a space-time yield of 2.50-6.30 g nitrile ·g cat -1 ·h -1 。
The third aspect of the application provides a heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst M 1 O/M 2 A process for preparing AIPO-5, comprising reacting a metal-containing element M 1 Uniformly mixing the compound of (C) with a heteroatom aluminum phosphate molecular sieve, and calcining to obtain M 1 O/M 2 -AIPO-5，M 1 Is a metal element, M 1 Comprising Cu, zn, fe, mg, ce, ti or Zr, M 2 Is a doped heteroatom, M 2 Including B, in, ga, cr, fe, V, si or Ti.
It will be appreciated that M is as described 1 O/M 2 the-AIPO-5 catalyst comprises CuO/In-AIPO-5, cuO/Ga-AIPO-5, cuO/Fe-AIPO-5, cuO/Cr-AIPO-5, cuO/V-AIPO-5, cuO/Si-AIPO-5, cuO/Ti-AIPO-5, fe 2 O 3 Ga-AIPO-5, znO/Ga-AIPO-5, mgO/Ga-AIPO-5, etc.
In some embodiments, the M-containing 1 The compound of (C) includes M-containing 1 Salts of oxyacids of (C) containing M 1 Organic compounds and hydroxides of (a). It will be appreciated that the M-containing 1 The salts of oxyacids of (a) include nitrates, sulfates, carbonates, and the like.
In some embodiments, the M-containing 1 Is mixed with heteroatom aluminum phosphate molecular sieve by solid phase grindingAnd (3) uniformly mixing, wherein the grinding rotating speed is 400-800 rmp, the grinding period is that each rotation is stopped for 30 min at 60 min, and the grinding time is 4-12 h. It will be appreciated that the solid phase milling is carried out in a ball mill.
In some embodiments, the metal-containing element M 1 According to metal oxide M 1 The load of O is 3% -10% and mixed.
In some embodiments, the conditions of calcination include calcination at 500-700 ℃ for 2-6 h.
In the application, the preparation method of the heteroatom aluminum phosphate molecular sieve can adopt direct hydrothermal synthesis and a solid-phase method (for example, reference document Zhu, research on catalytic performance and reaction mechanism of methane selective catalytic reduction cobalt aluminum phosphate molecular sieve, in 2012, tian Peng, research on heteroatom aluminum phosphate molecular sieve and low-temperature catalytic hydrocarbon oxidation reaction thereof, doctor's academy of China, 2004, hu Gushun, preparation of MeAPO-5 molecular sieve, research on arene hydrogenation ring opening performance, in 2019, Y.Jin, et al, chem. Eur. J.2014, 20, 17616-17charge, F.Dawaymeh, et al, mol. Catal, 2021, 501, 111371). The preparation of the heteroatom aluminum phosphate molecular sieve is not limited to the above method, and other preparation methods may be employed.
According to the application, a large amount of experimental researches are carried out under the conditions that the reaction temperature of a fixed bed reactor is 300-500 ℃, the methyl salicylate liquid flow is 0.01-0.08 mL/min, the nitrogen flow is 15-80 mL/min and the ammonia gas flow is 15-80 mL/min, the reaction conditions in the embodiment are controlled to be 2.4 mL/h, the nitrogen flow is 1800 mL/h, the ammonia gas flow is 3600 mL/h, and the reaction temperature of the fixed bed reactor is 480 ℃.
Examples
1.0 g of B-AIPO-5, ga-AIPO-5 or In-AIPO-5 heteroatom aluminum phosphate molecular sieve carrier is respectively weighed, respectively mixed with 0.1175 g copper nitrate and put into a ball mill, the rotation speed of the ball mill is controlled to 800 rmp, the grinding period is stopped for 30 min every 60 min, and the total time is 8 h; placing the ground sample In an air atmosphere muffle furnace, heating to 600 ℃ and calcining for 4 hours to obtain a 5% CuO/B-AIPO-5, a 5% CuO/In-AIPO-5 and a 5% CuO/Ga-AIPO-5 catalyst; the catalyst of 0.3 g is weighed and placed in a fixed bed reactor respectively for three groups of reactions, the liquid flow of methyl salicylate is set to be 2.4 mL/h, the nitrogen flow is 1800 mL/h, the ammonia flow is 3600 mL/h, and the reaction temperature is 480 ℃. The catalytic performance results are shown in FIG. 3, the conversion rate of methyl salicylate of the three groups of catalysts is 70% -95%, the yield of salicylonitrile is 60% -85%, and the catalytic activity of the 5% CuO/Ga-AIPO-5 catalyst is the best.
Examples
1.0 g of B-AIPO-5, ga-AIPO-5 or In-AIPO-5 heteroatom aluminum phosphate molecular sieve carrier is respectively weighed, respectively mixed with 0.2350 g copper nitrate and put into a ball mill, the rotation speed of the ball mill is controlled to be 800 rmp, the grinding period is stopped for 30 min every 60 min, and the total time is 8 h; placing the ground sample In an air atmosphere muffle furnace, heating to 600 ℃ and calcining for 4 hours to obtain a 10% CuO/B-AIPO-5, a 10% CuO/In-AIPO-5 and a 10% CuO/Ga-AIPO-5 catalyst; the catalyst of 0.3 and g is respectively weighed and placed in a fixed bed reactor, the liquid flow rate of methyl salicylate is set to be 2.4 mL/h, the nitrogen flow rate is 1800 mL/h, the ammonia flow rate is 3600 mL/h, and the reaction temperature is 480 ℃. The results of the catalytic performance are shown in FIG. 4. The conversion rate of methyl salicylate of the three groups of catalysts is 50% -80%, the yield of salicylonitrile is 40% -65%, and the catalytic activity of the 10% CuO/Ga-AIPO-5 catalyst is the best.
As shown in FIG. 2, the XRD test results of the six groups of catalysts of examples 1-2 show that the crystal structure of the hetero atom AIPO-5 catalyst is not changed by the load of the metal oxide, and the metal oxide is well loaded on the AIPO-5 catalyst.
Examples
1.0 g of Ga-AIPO-5 aluminum phosphate molecular sieve carrier is weighed, respectively mixed with 0.1167 g zinc nitrate, 0.0756 g iron nitrate and 0.1850 g magnesium nitrate, and put into a ball mill, the rotation speed of the ball mill is controlled to be 800 rmp, the grinding period is stopped for 30 min every 60 min, and the total time is 8 h; placing the ground sample in an air atmosphere muffle furnace, heating to 600 ℃ and calcining 4 h to obtain 5% ZnO/Ga-AIPO-5 and 5% Fe 2 O 3 Ga-AIPO-5 and 5% MgO/Ga-AIPO-5 catalyst; distribution weighing 0.3 g catalystAnd the mixture is placed in a fixed bed reactor, the liquid flow of methyl salicylate is set to be 2.4 mL/h, the nitrogen flow is set to be 1800 mL/h, the ammonia flow is set to be 3600 mL/h, and the reaction temperature is set to be 480 ℃. The results of the catalytic performance are shown in FIG. 5. The conversion rate of methyl salicylate of the three groups of catalysts is 70% -90%, the yield of salicylonitrile is 50% -70%, and the catalytic activity of the 5% ZnO/Ga-AIPO-5 catalyst is the best.
As can be seen from FIGS. 3-5, the 5% CuO/Ga-AIPO-5 catalyst gives the highest salicylnitrile yield under optimum process conditions, calculated as shown in FIG. 6 (6.30 g) cat h -1 ) And is significantly higher than the space-time yields reported in the literature single-stage reaction processes (z.j. Kong, et al Efficient preparation of salicylonitrile from methyl salicylate over supported boron phosphate catalyst in a continuous fixed bed reactor [ J)]Chemical Papers, 2021, 76, 1365-1375; chen Guanhu et al, study of phosphorus aluminum solid acid catalyzed preparation of methyl salicylate into salicylonitrile [ J]Modern chemical industry, 2020, 40,3:143-151; CN 104549378A; chen Erzhong Green technology [ J ] for synthesizing o-hydroxybenzonitrile by methyl salicylate one-step method]Pesticides, 2018, 57, 27:870-872; these documents report a low space-time yield of about 0.162 to 0.27 g nitrile ·g cat -1 ·h -1 ）
The above description of the embodiments is only for aiding in the understanding of the method of the present application and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the application can be made without departing from the principles of the application and these modifications and adaptations are intended to be within the scope of the application as defined in the following claims.
The foregoing is only a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art, who is within the scope of the present application, should make equivalent substitutions or modifications according to the technical scheme of the present application and the inventive concept thereof, and should be covered by the scope of the present application.
Claims (10)
1. Heteroatom aluminum phosphateSub-sieve supported metal oxide composite catalyst M 1 O/M 2 -AIPO-5, characterized in that said M 1 O is a metal oxide, M 1 O includes CuO, znO, fe 2 O 3 、MgO、CeO 2 、TiO 2 Or ZrO(s) 2 ，M 2 Is a doped heteroatom, M 2 Including B, in, ga, cr, fe, V, si or Ti.
2. The composite catalyst according to claim 1, wherein: the M is 2 Doped in the AIPO-5 molecular sieve framework.
3. A method for preparing salicylonitrile by using the composite catalyst of any one of claims 1-2 in gas-solid heterogeneous catalysis of methyl salicylate, which is characterized in that: the M is 1 O/M 2 AIPO-5 catalyzes the ammonolysis-dehydration reaction coupling of methyl salicylate to form salicylnitrile.
4. A method according to claim 3, characterized in that: the ammonolysis-dehydration reaction is carried out in a one-stage fixed bed reactor, methyl salicylate enters the fixed bed reactor to react with ammonia gas under the condition that nitrogen is taken as carrier gas, and at least one of the following conditions is met:
(1) The reaction temperature of the fixed bed reactor is 300-500 ℃;
(2) The liquid flow rate of the methyl salicylate is 0.01-0.08 mL/min, the flow rate of the nitrogen is 15-80 mL/min, and the flow rate of the ammonia is 15-80 mL/min;
(3) The molar ratio of the ammonia gas to the methyl salicylate is (2-8): 1, a step of;
(4) The liquid space velocity of the methyl salicylate is 2.362-18.896 g g -1 ·h -1 ；
(5) The total airspeed of the methyl salicylate, ammonia and nitrogen gas is 6000-32000 mL g -1 ·h -1 。
5. The method according to claim 4, wherein: the conversion rate of the methyl salicylate is 50-95%, and the salicylic nitrileThe yield of the catalyst is 40-85%, and the space-time yield of the composite catalyst is 2.50-6.30 g nitrile ·g cat -1 ·h -1 。
6. A process for producing a composite catalyst according to any one of claims 1 to 2 or a composite catalyst used in a process according to any one of claims 3 to 5, comprising reacting a metal-containing element M 1 The compound of (2) is evenly mixed with the heteroatom aluminum phosphate molecular sieve and calcined to obtain the composite catalyst M 1 O/M 2 -AIPO-5，M 1 Is a metal element, M 1 Comprising Cu, zn, fe, mg, ce, ti or Zr, M 2 Is a doped heteroatom, M 2 Including B, in, ga, cr, fe, V, si or Ti.
7. The preparation method according to claim 6, wherein the metal element M is contained 1 The compound of (2) comprises a metal element M 1 An oxyacid salt, organic matter or hydroxide of (a).
8. The preparation method according to claim 6, wherein the metal-containing element M 1 The compound and the heteroatom aluminum phosphate molecular sieve are uniformly mixed through solid phase grinding, the grinding rotating speed is 400-800 rmp, the grinding period is stopped for 30 min every 60 min, and the grinding time is 4-12 h.
9. The preparation method according to claim 6, wherein the metal element M is contained 1 Compound of (2) and heteroatom aluminium phosphate molecular sieve M 2 AIPO-5 according to the metal oxide M 1 The load of O is 3% -10% and mixed.
10. The method of claim 6, wherein the calcination conditions include calcination at 500-700 ℃ for 2-6 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311072103.4A CN117181295A (en) | 2023-08-24 | 2023-08-24 | Heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst, preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311072103.4A CN117181295A (en) | 2023-08-24 | 2023-08-24 | Heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst, preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117181295A true CN117181295A (en) | 2023-12-08 |
Family
ID=88982734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311072103.4A Pending CN117181295A (en) | 2023-08-24 | 2023-08-24 | Heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst, preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117181295A (en) |
-
2023
- 2023-08-24 CN CN202311072103.4A patent/CN117181295A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7232836B2 (en) | Catalyst for direct production of para-xylene from synthesis gas, production method and use thereof | |
| CN109794276B (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
| CN110227539A (en) | A kind of synthesis gas directly converts bifunctional catalyst, the preparation method and application of producing light olefins | |
| CN108380216B (en) | Preparation method and application of cobalt-based catalyst for catalyzing carbon dioxide to prepare ethanol | |
| CN104837799B (en) | Catalytic conversion of biomass-derived aliphatic alcohols to valuable olefins or oxygenates | |
| CN104607219A (en) | Vanadium-phosphorus oxide catalyst for preparing maleic anhydride through butane oxidation, and preparation method thereof | |
| CN108940355B (en) | Alkali modified catalyst and method for preparing ethylene through carbon monoxide hydrogenation reaction | |
| CN103418421A (en) | Catalyst used for synthesis of paraxylene through alkylation reactions between coking benzene and methanol and preparation method thereof | |
| CN103201031A (en) | Novel glycerol dehydration catalyst and production method therefor | |
| CN108927132B (en) | Bifunctional catalyst and method for preparing ethylene by carbon monoxide hydrogenation | |
| CA2522183C (en) | Catalyst for dimethyl carbonate synthesis | |
| EP2915582B1 (en) | Composite oxide, preparation method for same, and application thereof | |
| CN108568311B (en) | Catalyst and method for preparing ethylene by directly converting synthesis gas | |
| CN117181295A (en) | Heteroatom aluminum phosphate molecular sieve supported metal oxide composite catalyst, preparation and application | |
| KR101825495B1 (en) | Cobalt-supported catalyst for low-temperature methane reformation using carbon dioxide, and the fabrication method thereof | |
| RU2749513C1 (en) | Organic base-modified composite catalyst and method for synthesis of ethylene by hydrogenation of carbon monoxide | |
| CN104707646A (en) | Catalyst for toluene preparation through oxidative dehydrogenation of dimethyl ether, preparation method and applications thereof | |
| CN111111757B (en) | Monolithic catalyst, preparation method and use method thereof | |
| Yamaguchi et al. | Cyanosilylation of benzaldehyde with TMSCN over perovskite-type oxide catalyst prepared by thermal decomposition of heteronuclear cyano complex precursors | |
| CN112939783B (en) | Method for preparing aldehyde or ketone by selectively oxidizing alcohol with oxygen | |
| CN111744488B (en) | Catalyst for preparing dimethyl ether from slurry bed synthesis gas and preparation method thereof | |
| CN111111751B (en) | Multi-component catalyst, preparation method and application thereof | |
| CN113070094A (en) | Catalyst for carbon dioxide hydrogenation and toluene aromatic ring alkylation and preparation method and application thereof | |
| CN111153801A (en) | Preparation method of aromatic carboxylic ester compound | |
| CN109939669B (en) | Alkali-modified composite catalyst and method for preparing ethylene through carbon monoxide hydrogenation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |