CN117599818A - Sodium super-ion conductor catalyst containing metal oxide coating and preparation method and application thereof - Google Patents
Sodium super-ion conductor catalyst containing metal oxide coating and preparation method and application thereof Download PDFInfo
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- CN117599818A CN117599818A CN202311540977.8A CN202311540977A CN117599818A CN 117599818 A CN117599818 A CN 117599818A CN 202311540977 A CN202311540977 A CN 202311540977A CN 117599818 A CN117599818 A CN 117599818A
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- ion conductor
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 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 title claims abstract description 63
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 63
- 239000011734 sodium Substances 0.000 title claims abstract description 63
- 239000010416 ion conductor Substances 0.000 title claims abstract description 62
- 239000011248 coating agent Substances 0.000 title claims abstract description 56
- 238000000576 coating method Methods 0.000 title claims abstract description 56
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 39
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 135
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 123
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 46
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 19
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- 238000000034 method Methods 0.000 claims abstract description 11
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 239000002202 Polyethylene glycol Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 11
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- 238000000227 grinding Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000007873 sieving Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002228 NASICON Substances 0.000 claims description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 claims description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 2
- 239000006004 Quartz sand Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 18
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 18
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 18
- 229910010413 TiO 2 Inorganic materials 0.000 description 18
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 18
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 9
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 9
- 238000011049 filling Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 235000019260 propionic acid Nutrition 0.000 description 9
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000002524 electron diffraction data Methods 0.000 description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
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- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- JCGCKSUCGVTMNB-UHFFFAOYSA-N acetic acid;formaldehyde Chemical compound O=C.CC(O)=O JCGCKSUCGVTMNB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- BDVMTRCCIQHRBL-UHFFFAOYSA-J phosphonato phosphate;titanium(4+) Chemical compound [Ti+4].[O-]P([O-])(=O)OP([O-])([O-])=O BDVMTRCCIQHRBL-UHFFFAOYSA-J 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1804—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a sodium super-ion conductor catalyst containing a metal oxide coating, a preparation method and application thereof, wherein the catalyst comprises Ti, zr and Ce metal oxide coating components and element components Ti, P, S, O, H forming a main body structure of the sodium super-ion conductor, and the mass percentage of the catalyst is MeO 2 ：2.5%‑20%；H 1‑x Ti 2 (PO 4 ) 3‑x (SO 4 ) x :80% -97.5%, wherein the metal Me in the coating component is one or any two of Ti, zr and Ce, and x=0.4-1. The invention uses metal for the first timeThe catalyst is prepared by oxidizing the coating and the sodium super-ion conductor, and the external coating structure can play a role in self dehydrogenation, and the coating effect can play a role in promoting subsequent reactions; the method for synthesizing the catalyst is simple, has low synthesis cost and is easy for mass production; the catalyst is used for directly synthesizing acrylic acid and methyl acrylate from methanol and acetic acid, and has high product selectivity, easy separation and wide industrial application prospect.
Description
Technical Field
The invention relates to a sodium super-ion conductor catalyst containing a metal oxide coating and a preparation method and application thereof, belonging to the technical field of catalyst preparation and application.
Background
Acrylic acid is used as the simplest unsaturated carboxylic acid and is widely used in the fields of paint, chemical fiber, water-absorbent resin, adhesive, leather, papermaking and the like. For a long time, research on acrylic acid production processes has been paid attention to all countries around the world. At present, the production of the acrylic acid is mainly realized through a propylene two-step oxidation process route. The propylene as a raw material in the route is greatly influenced by petroleum price fluctuation. And as the economy further progresses, the demand for acrylic acid increases over the years. It is important to search for synthetic routes of coal-based acrylic acid represented by methanol/formaldehyde and acetic acid condensation.
For coal-based routes, a lot of technological routes for preparing acrylic acid by condensing formaldehyde and aldol acetate are studied. As reported in the literature, the acidic catalyst represented by VPO [ M.Ai, J.Catal.124 (1990) 293-296. M.Ai, J.Catal., 124 (1990) 293-296] and the basic catalyst represented by Cs-based catalyst [ M.Ai, et al, appl. Catal. A-Gen., 288 (2005) 211-215] exhibited good catalytic activity. [ M.ai, et al Bull, chem. Soc. Jpn., 63 (1990), 199-202; X.Z. Feng, et al, 314 (2014) 132-141]. However, in the process route, formaldehyde is active in chemical property and easy to polymerize, and storage and transportation can be realized only by adopting a water solution with lower concentration. When acrylic acid is synthesized from aqueous formaldehyde, a large amount of water in the system may cause pulverization of the VPO catalyst to clog the reactor. In addition, the high reaction temperature causes part of the unreacted formaldehyde to escape from the solution and polymerize in the line to cause clogging, which limits its large-scale application.
Compared with the method for directly synthesizing the acrylic acid from the methanol and the acetic acid, the method has the advantages of shortening the reaction flow, reducing the cost, and improving the safety and the stability of the methanol over formaldehyde, so that the method has obvious advantages and is a potential technical route for extending the industrial chain of the methanol. Direct synthesis of acrylic acid from methanol and acetic acid involves two main steps, dehydrogenation of methanol to formaldehyde, and condensation of formaldehyde acetic acid to acrylic acid. The two reactions need different active centers, and the reaction temperatures are greatly different, so that the process is realized, and the requirement on the versatility of the catalyst is high. A small number of documents report that methanol and acetic acid are directly synthesized into acrylic acid (methyl ester), and the catalyst takes VPO catalyst as main material [ M.Ai, et al Bull. Chem. Soc. Jpn., 63 (1990), 199-202; X.Z. Feng, et al, 314 (2014) 132-141; L.Q.Shen, et al (97) 2019 2699-2707]. The related results show that the selectivity of the target product acrylic acid and methyl acrylate is lower than 30%. Chinese patent CN109364967A discloses a technology for synthesizing acrylic acid by using sodium super-ionic conductor catalytic material for synthesizing methanol and methyl acetate, wherein the multifunctional catalytic material modified by low-load vanadium oxide is prepared in the patent, the one-step synthesis of acrylic acid and methyl acrylate by using methanol and methyl acetate is realized, and a small amount of V element with high toxicity is still introduced in the invention. The development of a novel catalyst for directly synthesizing acrylic acid from methanol and acetic acid, which has low toxicity, high activity, high stability and low price, is very necessary. Chinese patent CN115090308A discloses a metal doped sodium super-ionic catalyst, and a preparation method and application thereof, and the patent further improves the preparation method of the catalyst, and the Mn, Y, mo, bi, re and other metals are doped into the sodium super-ionic conductor material in situ, so that better catalytic performance of synthesizing acrylic acid and methyl acrylate in one step from methanol and acetic acid is obtained. However, most of these introduced components are noble metals, and the realization of equivalent catalytic performance using inexpensive metals is significant in reducing production costs.
Therefore, the continuous improvement of the catalyst preparation method or the exploration of a new catalyst preparation method, and the more efficient synthesis of target products are the stages which are necessary to realize industrialization.
Disclosure of Invention
The invention aims to provide a sodium super-ion conductor catalyst containing a metal oxide coating, a preparation method and application thereof, and the catalyst has the advantages of simple preparation process, low cost, high thermal stability and high activity. The catalyst of the invention is H with a sodium super-ion structure 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x @MeO 2 (wherein, me=Ti, zr, ce and the like, and x=0.4-1), and the catalyst can be used for directly synthesizing the acrylic acid and the methyl acrylate from methanol and acetic acid.
In the invention, the catalytic material of the sodium super-ion conductor catalyst containing the metal oxide coating mainly comprises a main structure of the sodium super-ion conductor and a metal oxide coating component. The material has the remarkable characteristics that the coating is tightly contacted with the inner core to form a good coating effect, and can simultaneously provide double functional active sites of methanol dehydrogenation and aldol condensation; the active sites have good matching property and are efficiently cooperated within the temperature range of 340-380 ℃. The catalyst obtained by the invention has excellent catalytic effect on direct synthesis of acrylic acid and methyl acrylate from methanol and acetic acid. The catalyst components are common metal salts and oxides, the preparation conditions are simple and convenient, the repeatability of the catalyst preparation is good, the coating structure of the catalyst is novel, the preparation method does not involve complex operation, and the cost can be effectively reduced.
The invention provides a sodium super-ion conductor catalyst (H) containing a metal oxide coating 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x @MeO 2 ) Comprises Ti, zr, ce metal oxide coating components and element components Ti, P, S, O, H for forming a main body structure of the sodium super-ion conductor, wherein the mass percentage of the element components is MeO 2 ：2.5%-20%；H 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x :80% -97.5%, wherein the metal Me in the coating component is one or any two of Ti, zr and Ce, and x=0.4-1.
The invention provides a preparation method of the sodium super-ion conductor catalyst containing the metal oxide coating, which comprises the following steps:
(1) Preparation of sodium super ion conductor
Weighing titanyl sulfate TiOSO 4 Dissolving a solid sample in deionized water, performing ultrasonic dissolution to prepare a solution with the concentration range of 1.0-2.0 mol/L, adding 30wt% hydrogen peroxide as a stabilizer and polyethylene glycol (PEG) as a dispersing agent, and continuing ultrasonic treatment; dropping concentrated phosphoric acid with the concentration of 85 percent by weight for one time, and strongly stirring; placing the obtained solution in water bath, standing, and aging for 24-48 h; roasting the obtained dry gel at 500-700 deg.C for 5-10H to obtain sodium super ion conductor (H) 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x ) Raw material powder; raw materials of the synthetic mother solution, namely titanyl sulfate: water: hydrogen peroxide: polyethylene glycol: the mass ratio of the phosphoric acid is as follows: 10:10-20:6-15:3-5:5-10.
(2) Preparation of sodium super-ion conductor catalyst containing metal oxide coating
Placing 5.0. 5.0 g of the sodium super ion conductor material raw powder obtained in the step (1) in 100 mL absolute ethyl alcohol, adding 0.3-0.5 mL ammonia water, and performing ultrasonic dispersion for 15 min; then dropwise adding 0.255-5.10 g metal organic compound into the mixed solution, and stirring in a water bath at 30-60 ℃ for 12-24 h; performing centrifugal separation and drying to obtain white powder, and roasting at 400-600 ℃ for 2-6 h; and tabletting, grinding and sieving the roasted sample into particles with 20-40 meshes to obtain the catalyst. Wherein the metal oxide MeO 2 The coating accounts for 2.5 to 20 weight percent of the catalyst.
The metal organic compound comprises one or two of n-butyl titanate, titanium acetylacetonate, zirconium n-butoxide, zirconium acetylacetonate, cerium acetate or tricyclopentadienyl cerium; when two kinds of materials are selected, the ratio is arbitrary.
The invention provides application of the sodium super-ion conductor catalyst containing the metal oxide coating in direct synthesis of acrylic acid and methyl acrylate from methanol and acetic acid.
The application of the catalyst comprises the following steps: the catalyst is applied to the reaction of directly synthesizing the acrylic acid and the methyl acrylate from the methanol and the acetic acid. The catalytic reaction is carried out in a continuous flow fixed bed reactor, the catalyst is arranged in the middle position of the reactor, and the upper layer is filled with quartz sand preheating sections. The reaction carrier gas is oxygen-nitrogen mixed gas, and the volume fraction of oxygen is 2-20%. When the catalytic reaction is carried out, the reaction temperature is controlled to be 340-380 ℃, the reaction pressure is normal pressure, and the gas flow rate of the carried gas is controlled to be 5-15 mL min corresponding to each gram of catalyst -1 The molar ratio of raw material methanol to acetic acid is controlled to be 0.5-3:1, and the space velocity of reaction liquid is controlled to be 1-3 mL g -1 ·h -1 The liquid raw material is introduced by a plunger pump.
The invention has the beneficial effects that:
(1) The invention uses the concept and thought of coating catalysis, firstly prepares the catalyst by the metal oxide coating and the sodium super-ion conductor, and the external coating structure can not only play a role in self dehydrogenation, but also play a role in promoting subsequent reactions by the coating effect.
(2) The raw materials of the synthetic catalyst are easy to obtain, the preparation method is simple, the requirements on equipment are low, the synthetic cost is low, and the mass production is easy.
(3) The catalyst of the invention can be used for directly and efficiently converting methanol and acetic acid into acrylic acid and methyl acrylate, the conversion rate of acetic acid is more than 60 percent, the selectivity of acrylic acid and methyl acrylate is more than 70 percent, and the space-time yield is 5.4 mmol.g -1 ·h -1 The above. The process can convert the methanol and the acetic acid with severely excessive productivity into the acrylic acid and the methyl acrylate with high added value, the reaction operation condition is mild, the high temperature and the high pressure are not involved, the process route is simple, the equipment requirement is low, the product selectivity is high, the separation is easy, and the industrialized application prospect is wide.
Drawings
Fig. 1 is a TEM image of the catalyst prepared in example 1.
Figure 2 is an XRD spectrum of the catalyst prepared in example 2.
Fig. 3 is an XRD spectrum of the catalyst prepared in example 3.
Fig. 4 is an XRD spectrum of the catalyst prepared in example 4.
Fig. 5 is an XRD spectrum of the catalyst prepared in example 5.
Fig. 6 is an XRD spectrum of the catalyst prepared in example 6.
Fig. 7 is a TEM image of the catalyst prepared in example 7.
Fig. 8 is an XRD spectrum of the catalyst prepared in example 8.
Fig. 9 is an XRD spectrum of the catalyst prepared in example 9.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1
(1) Preparation of sodium super ion conductor
Weighing 17.60. 17.60g titanyl sulfate TiOSO 4 Adding deionized water 35.2. 35.2 g into the solid sample, sequentially adding 26.4 g of 30wt% hydrogen peroxide as a stabilizer and 8.8 g polyethylene glycol PEG as a dispersing agent, and performing ultrasonic dissolution; concentrated phosphoric acid, 14.46. 14.46 g% strength by weight, was added dropwise again with vigorous stirring. The solution was dried in a 45℃water bath and aged for 48h. Roasting the obtained dry gel at 600 ℃ for 10H to finally obtain the sodium super ion conductor (H) 1-x Ti 2 (PO 4 ) 3-x (SO 4)x ) Raw material powder.
(2) Containing TiO 2 Preparation of sodium super-ion conductor catalyst with metal oxide coating
Placing 5.0. 5.0 g of the sodium super-ion conductor raw powder obtained in the step (1) in 100 ml absolute ethyl alcohol, adding 0.3ml ammonia water, and performing ultrasonic dispersion for 15 min; then adding 1.60g n-butyl titanate into the mixed solution, and stirring in a water bath at 30 ℃ for 24h; the white powder obtained was subjected to centrifugal separation and drying, and was calcined at 500℃for 2 h. And tabletting, grinding and sieving the roasted sample into particles with 20-40 meshes to obtain the catalyst. Wherein the metal oxide TiO 2 The coating was 7.0% in the catalyst.
FIG. 1 shows a TEM spectrum of a catalyst prepared according to this example, where it can be generatedMost of the TiO 2 Coating on the surface of NASICON catalyst in the form of coating layer, and concomitantly very small amount of TiO 2 The particles have less effect on catalytic activity.
The reaction of synthesizing acrylic acid from methanol and acetic acid is realized in a fixed bed reaction. Placing 2g of the catalyst in the middle of a reactor, filling the upper part with a magnetic ring, and controlling the temperature to be 30 mL min -1 Heating to 380 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 20%, and mixing the methanol and the acetic acid with the molar ratio of 2:1 to obtain a mixed raw material of 1.5 mL h -1 ·g -1 The space velocity of the feed is controlled to be 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2h, the product was collected and analyzed. The conversion of acetic acid was 76%, the selectivity of acrylic acid and methyl acrylate in the main product was 80.3%, and the space-time yield was 6.58 mmol.g -1 ·h -1 Methyl acetate selectivity was 9.6%, dimethyl ether selectivity was 4.5%, methyl formate selectivity was 2.1%, propionaldehyde selectivity was 0.2%, acrolein selectivity was 0.3%, propionic acid selectivity was 0.4%, and gas phase product selectivity was 2.6%.
Example 2
(1) Preparation of sodium super ion conductor
Weighing 14.80. 14.80 g titanyl sulfate TiOSO 4 Adding 24.84g of deionized water into the solid sample, sequentially adding 13.8g of 30wt% hydrogen peroxide serving as a stabilizer and 4.41 g polyethylene glycol PEG serving as a dispersing agent, and continuing ultrasonic dissolution; 10.48g of concentrated phosphoric acid having a concentration of 85% by weight are added dropwise again and stirred vigorously. The solution is dried in a water bath at 45 ℃ and aged for 24 hours. Roasting the obtained dry gel at 550 ℃ to 6H to finally obtain the sodium super ion conductor (H) 1-x Ti 2 (PO 4 ) 3-x (SO 4)x ) Raw material powder.
(2) CeO-containing 2 Preparation of sodium super-ion conductor catalyst with metal oxide coating
Placing 5.0. 5.0 g of the sodium super-ion conductor raw powder obtained in the step (1) in 100 ml absolute ethyl alcohol, adding 0.3ml of ammonia water, and performing ultrasonic dispersion for 15 min; subsequently, 0.23 is added into the mixed solutiong cerium acetate (Ce (C) 2 H 3 O 2 ) 3 ·nH 2 O), stirring in a water bath at 40 ℃ for 24 hours; the white powder obtained was subjected to centrifugal separation and drying, and was calcined at 400℃for 4 hours. And tabletting, grinding and sieving the roasted sample into particles with 20-40 meshes to obtain the catalyst. Wherein, the metal oxide is CeO 2 The coating was 2.5% of the catalyst. The X-ray electron diffraction pattern of the prepared catalyst was as follows:
FIG. 2 shows an XRD pattern of the catalyst prepared in this example, which shows that the catalyst is mainly based on NASICON phase, but the degree of crystallization is poor and CeO is not observed 2 Is a characteristic diffraction peak of (2).
The reaction of synthesizing acrylic acid from methanol and acetic acid is realized in a fixed bed reaction. Placing 2g of the catalyst in the middle of a reactor, filling the upper part with a magnetic ring, and 25 mL min -1 Heating to 360 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 10%, and mixing the raw materials of methanol and acetic acid with the molar ratio of 1:1 according to the ratio of 2 mL h -1 ·g -1 Is injected into the reaction system, and the reaction pressure is controlled to be 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2h, the product was collected and analyzed. The conversion of acetic acid was 73.5%, the selectivity of acrylic acid and methyl acrylate in the main product was 79.3%, and the space-time yield was 11.77 mmol.g -1 ·h -1 Methyl acetate selectivity was 15.5%, dimethyl ether selectivity was 0.1%, methyl formate selectivity was 0.2%, propionaldehyde selectivity was 0.3%, acrolein selectivity was 1.2%, propionic acid selectivity was 0.4%, and gas phase product selectivity was 3.0%.
Example 3
(1) Preparation of sodium super ion conductor
21.93g of titanyl sulfate TiOSO was weighed 4 Adding 21.12g of deionized water into the solid sample, sequentially adding 15.84g of 30wt% hydrogen peroxide as a stabilizer and 7.04 g polyethylene glycol PEG as a dispersing agent, and performing ultrasonic dissolution; concentrated phosphoric acid, 13.24. 13.24 g% strength by weight, was added dropwise again with vigorous stirring. The solution is dried in a water bath at 50 ℃ and aged for 36 hours. The obtained dry productRoasting the gel at 500 deg.c for 8H to obtain sodium super ion conductor (H) 1-x Ti 2 (PO 4 ) 3-x (SO 4)x ) Raw material powder.
(2) Containing TiO 2 Preparation of sodium super-ion conductor catalyst with metal oxide coating
Placing 5.0. 5.0 g of the sodium super-ion conductor raw powder obtained in the step (1) in 100 ml absolute ethyl alcohol, adding 0.3ml of ammonia water, and performing ultrasonic dispersion for 15 min; then adding 2.1 g n-butyl titanate into the mixed solution, and stirring for 18h in a water bath at 50 ℃; the white powder obtained was subjected to centrifugal separation and drying, and was calcined at 700℃for 2 h. And tabletting, grinding and sieving the roasted sample into particles with 20-40 meshes to obtain the catalyst. Wherein the metal oxide TiO 2 The coating was 9.0% in the catalyst. The X-ray electron diffraction pattern of the catalyst was prepared as follows
FIG. 3 shows an XRD pattern of the catalyst prepared in this example, showing that the synthesized catalyst shows good NASICON crystalline phase diffraction peaks, and no coating TiO is observed 2 Characteristic peaks of (2) indicate good dispersion.
The reaction of synthesizing acrylic acid from methanol and acetic acid is realized in a fixed bed reaction. Placing 2g of the catalyst in the middle of a reactor, filling the upper part with a magnetic ring, and controlling the temperature to be 12 mL min -1 Heating to 380 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 15%, and mixing the methanol and acetic acid mixed raw materials with the molar ratio of 3:1 according to the ratio of 3mL h -1 ·g -1 Is injected into the reaction system, and the reaction pressure is controlled to be 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2h, the product was collected and analyzed. The conversion of acetic acid was 63%, the selectivity of acrylic acid and methyl acrylate in the main product was 76.2%, and the space-time yield was 8.11 mmol.g -1 ·h -1 Methyl acetate selectivity was 15.1%, dimethyl ether selectivity was 3.3%, methyl formate selectivity was 1.2%, propionaldehyde selectivity was 0.4%, acrolein selectivity was 0.6%, propionic acid selectivity was 0.4%, and gas phase product selectivity was 2.8%.
Example 4
(1) Preparation of sodium super ion conductor
28.92g of titanyl sulfate TiOSO was weighed 4 Adding 21.35g of deionized water into the solid sample, sequentially adding 22.53g of 30wt% hydrogen peroxide as a stabilizer and 5.93g of polyethylene glycol PEG as a dispersing agent, and performing ultrasonic dissolution; 14.46g of concentrated phosphoric acid having a concentration of 85% by weight are added dropwise again and stirred vigorously. The solution was dried in a 60 ℃ water bath and aged 36h. Roasting the obtained dry gel at 600 ℃ for 5H to finally obtain the sodium super ion conductor (H) 1-x Ti 2 (PO 4 ) 3-x (SO 4)x ) Raw material powder.
(2) Containing TiO 2 Preparation of sodium super-ion conductor catalyst with metal oxide coating
Placing 5.0. 5.0 g of the sodium super-ion conductor raw powder obtained in the step (1) in 100 ml absolute ethyl alcohol, adding 0.5ml of ammonia water, and performing ultrasonic dispersion for 15 min; then adding 1.12g of n-butyl titanate into the mixed solution, and stirring for 12 hours in a water bath at 40 ℃; the white powder obtained was subjected to centrifugal separation and drying, and then calcined at 600℃for 6h. And tabletting, grinding and sieving the roasted sample into particles with 20-40 meshes to obtain the catalyst. Wherein the metal oxide TiO 2 The coating was 5.0% in the catalyst. The X-ray electron diffraction pattern of the prepared catalyst was as follows:
FIG. 4 shows an XRD pattern of the catalyst prepared in this example, showing that increasing the Ti/P ratio of the synthesized NASICON material further enhances the degree of crystallization of the sample, and no incorporated TiO was observed 2 Characteristic peaks of the coating.
The reaction of synthesizing acrylic acid from methanol and acetic acid is realized in a fixed bed reaction. Placing 2g of the catalyst in the middle of a reactor, filling the upper part with a magnetic ring, and 22 mL min -1 Heating the mixture to 360 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 8%, and mixing the raw materials of methanol and acetic acid with the molar ratio of 1:1 at the rate of 1 mL.h -1 ·g -1 Is injected into the reaction system, and the reaction pressure is controlled to be 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2h, the product was collected and analyzed. Conversion of acetic acidThe selectivity of acrylic acid and methyl acrylate in the main product is 73.2%, and the space-time yield is 5.99 mmol.g -1 ·h -1 Methyl acetate selectivity was 12.3%, dimethyl ether selectivity was 7.56%, methyl formate selectivity was 2.1%, propionaldehyde selectivity was 0.1%, acrolein selectivity was 0.5%, propionic acid selectivity was 0.3%, and gas phase product selectivity was 3.94%.
Example 5
(1) Preparation of sodium super ion conductor
26.72g of titanyl sulfate TiOSO was weighed 4 Adding deionized water 29.39 g into the solid sample, sequentially adding 24.05g of 30wt% hydrogen peroxide as a stabilizer and 10.69. 10.69 g polyethylene glycol PEG as a dispersing agent, and continuing ultrasonic dissolution; 20.23g of concentrated phosphoric acid having a concentration of 85% by weight were added dropwise again and stirred vigorously. The solution was dried in a 55℃water bath and aged 36h. Roasting the obtained dry gel at 600 ℃ for 10H to finally obtain the sodium super ion conductor (H) 1-x Ti 2 (PO 4 ) 3-x (SO 4)x ) Raw material powder.
(2) Containing ZrO 2 Preparation of sodium super-ion conductor catalyst with metal oxide coating
Placing 5.0. 5.0 g of the sodium super-ion conductor raw powder obtained in the step (1) in 100 ml absolute ethyl alcohol, adding 0.3ml of ammonia water, and performing ultrasonic dispersion for 15 min; then adding 1.2g of zirconium n-butoxide into the mixed solution, and stirring in a water bath at 60 ℃ for 24h; the white powder obtained was subjected to centrifugal separation and drying, and was calcined at 500℃for 6 hours. And tabletting, grinding and sieving the roasted sample into particles with 20-40 meshes to obtain the catalyst. Wherein the metal oxide ZrO 2 The coating was 7.14% in the catalyst. The X-ray electron diffraction pattern of the prepared catalyst was as follows:
FIG. 5 shows XRD patterns of the catalyst prepared in this example, which shows ZrO 2 No characteristic peaks were found after the coating was introduced.
The reaction of synthesizing acrylic acid from methanol and acetic acid is realized in a fixed bed reaction. Placing 2g of the catalyst in the middle of a reactor, filling the upper part with a magnetic ring, and measuring 10 mL min -1 Heating to 3 in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 15%60. Mixing methanol and acetic acid with the mol ratio of 2:1 at the temperature of 2 mL h -1 ·g -1 Is injected into the reaction system, and the reaction pressure is controlled to be 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2h, the product was collected and analyzed. The conversion of acetic acid was 73.5%, the selectivity of acrylic acid and methyl acrylate in the main product was 70.3%, and the space-time yield was 7.43 mmol.g -1 ·h -1 Methyl acetate selectivity was 11.5%, dimethyl ether selectivity was 3.6%, methyl formate selectivity was 1.5%, propionaldehyde selectivity was 0.7%, acrolein selectivity was 1.8%, propionic acid selectivity was 1.9%, and gas phase product selectivity was 8.7%.
Example 6
(1) Preparation of sodium super ion conductor
22.73g of titanyl sulfate TiOSO was weighed 4 Adding 55.46g of deionized water into the solid sample, adding 41.60g of 30wt% hydrogen peroxide as a stabilizer, 8.319g of polyethylene glycol PEG as a dispersing agent, and performing ultrasonic dissolution; 18.91g of concentrated phosphoric acid having a concentration of 85% by weight are added dropwise again and stirred vigorously. The resulting solution was dried in a 55℃water bath and aged 24. 24h. Roasting the obtained dry gel at 500 ℃ for 10 hours to finally obtain the sodium super ion conductor (H) 1-x Ti 2 (PO 4 ) 3-x (SO 4)x ) Raw material powder.
(2) Containing TiO 2 Preparation of sodium super-ion conductor catalyst with metal oxide coating
Placing 5.0. 5.0 g of the sodium super-ion conductor raw powder obtained in the step (1) in 100 ml absolute ethyl alcohol, adding 0.4ml of ammonia water, and performing ultrasonic dispersion for 15 min; then adding 5.32g of n-butyl titanate into the mixed solution, and stirring for 20 hours in a water bath at 50 ℃; the white powder obtained was subjected to centrifugal separation and drying, and was calcined at 400℃to 4h. And tabletting, grinding and sieving the roasted sample into particles with 20-40 meshes to obtain the catalyst. Wherein the metal oxide TiO 2 The coating was 20% in the catalyst. The X-ray electron diffraction pattern of the prepared catalyst was as follows:
FIG. 6 shows XRD spectra of the catalyst prepared in this exampleThe figure shows the incorporation of a large amount of TiO 2 The coating (20%) was observed with a characteristic peak indicating an elevated loading of TiO 2 Will crystallize and nucleate to produce TiO 2 And (5) a crystal form.
The reaction of synthesizing acrylic acid from methanol and acetic acid is realized in a fixed bed reaction. Placing 2g of the catalyst in the middle of a reactor, filling the upper part with a magnetic ring, and controlling the temperature to be 30 mL min -1 Heating to 360 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 4%, and mixing the raw materials of methanol and acetic acid with the molar ratio of 2:1 at the speed of 1.4 mL.h -1 ·g -1 Is injected into the reaction system, and the reaction pressure is controlled to be 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2h, the product was collected and analyzed. The conversion of acetic acid was 79.8%, the selectivity of acrylic acid and methyl acrylate in the main product was 70.3%, and the space-time yield was 5.45 mmol.g -1 ·h -1 Methyl acetate selectivity was 12.7%, dimethyl ether selectivity was 9.5%, methyl formate selectivity was 1.3%, propionaldehyde selectivity was 0.7%, acrolein selectivity was 0.3%, propionic acid selectivity was 0.6%, and gas phase product selectivity was 4.6%.
Example 7
(1) Preparation of sodium super ion conductor
31.76g of titanyl sulfate TiOSO was weighed 4 Adding 47.64g of deionized water into the solid sample, adding 23.82g of 30wt% hydrogen peroxide as a stabilizer, and 14.29g of polyethylene glycol PEG as a dispersing agent, and performing ultrasonic dissolution; 22.65g of concentrated phosphoric acid having a concentration of 85% by weight was added dropwise again with vigorous stirring. The resulting solution was dried in a water bath at 50℃and aged for 48h. Roasting the obtained dry gel at 600 ℃ for 10 hours to finally obtain the sodium super ion conductor (H) 1-x Ti 2 (PO 4 ) 3-x (SO 4)x ) Raw material powder.
(2) Containing TiO 2 Preparation of sodium super-ion conductor catalyst with metal oxide coating
Placing 5.0. 5.0 g of the sodium super-ion conductor raw powder obtained in the step (1) in 100 ml absolute ethyl alcohol, adding 0.3ml of ammonia water, and performing ultrasonic dispersion for 15 min; then the mixed solution is prepared1.60g of n-butyl titanate is added, and the mixture is stirred for 12 hours in a water bath at 50 ℃; the white powder obtained was subjected to centrifugal separation and drying, and was calcined at 650℃to 5 h. And tabletting, grinding and sieving the roasted sample into particles with 20-40 meshes to obtain the catalyst. Wherein the metal oxide TiO 2 The coating was 7.5% of the catalyst. SEM of the prepared samples are shown in the figure:
FIG. 7 shows a TEM spectrum of the catalyst prepared in this example, in which a majority of the TiO is found 2 Coating the NASICON material to form a good coating.
The reaction of synthesizing acrylic acid from methanol and acetic acid is realized in a fixed bed reaction. Placing 2g of the catalyst in the middle of a reactor, filling the upper part with a magnetic ring, and carrying out 16 mL min -1 Heating to 340 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 4%, and mixing the raw materials of methanol and acetic acid with the molar ratio of 1:1 according to the ratio of 2 mL h -1 ·g -1 Is injected into the reaction system, and the reaction pressure is controlled to be 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2h, the product was collected and analyzed. The conversion of acetic acid was 76.5%, the selectivity of acrylic acid and methyl acrylate in the main product was 70.0%, and the space-time yield was 10.81 mmol.g -1 ·h -1 Methyl acetate selectivity was 21.7%, dimethyl ether selectivity was 1.1%, methyl formate selectivity was 0.8%, propionaldehyde selectivity was 1.7%, acrolein selectivity was 0.2%, propionic acid selectivity was 0.7%, and gas phase product selectivity was 3.8%.
Example 8
(1) Preparation of sodium super ion conductor
17.60g of titanyl sulfate TiOSO was weighed 4 Adding 20.58g of deionized water into the solid sample, sequentially adding 22.92g of 30wt% hydrogen peroxide serving as a stabilizer and 7.56g of polyethylene glycol (PEG) serving as a dispersing agent, and continuing ultrasonic dissolution; 14.64g of concentrated phosphoric acid having a concentration of 85% by weight are added dropwise again and stirred vigorously. The solution is dried in a water bath at 50 ℃ and aged for 36 hours. Roasting the obtained dry gel at 600 ℃ to 7H to finally obtain the sodium super ion conductor (H) 1-x Ti 2 (PO 4 ) 3-x (SO 4)x ) Raw material powder.
(2) Containing ZrO 2 Preparation of sodium super-ion conductor catalyst with metal oxide coating
Placing 5.0. 5.0 g of the sodium super-ion conductor raw powder obtained in the step (1) in 100 ml absolute ethyl alcohol, adding 0.3ml of ammonia water, and performing ultrasonic dispersion for 15 min; adding 1.0 g zirconium n-butoxide into the mixed solution, and stirring in a water bath at 60 ℃ for 24 hours; the white powder obtained was subjected to centrifugal separation and drying, and calcined at 550℃for 3 hours. And tabletting, grinding and sieving the roasted sample into particles with 20-40 meshes to obtain the catalyst. Wherein the metal oxide ZrO 2 The coating was 6.0% in the catalyst. The X-ray electron diffraction pattern of the prepared catalyst was as follows:
FIG. 8 shows the XRD patterns of the catalyst prepared in this example, showing that no ZrO was present after the addition of the coating layer 2 Characteristic peaks.
The reaction of synthesizing acrylic acid from methanol and acetic acid is realized in a fixed bed reaction. Placing 2g of the catalyst in the middle of a reactor, filling the upper part with a magnetic ring, and carrying out 16 mL min -1 Heating to 380 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 4%, and mixing the methanol and acetic acid mixed raw materials with the molar ratio of 1:1 at the rate of 1 mL h -1 ·g -1 Is injected into the reaction system, and the reaction pressure is controlled to be 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2h, the product was collected and analyzed. The conversion of acetic acid was 78.3%, the selectivity of acrylic acid and methyl acrylate in the main product was 70.1%, and the space-time yield was 5.54 mmol.g -1 ·h -1 The selectivity to methyl acetate was 19.5%, the selectivity to dimethyl ether was 0.5%, the selectivity to methyl formate was 0.6%, the selectivity to propionaldehyde was 1.3%, the selectivity to acrolein was 1.5%, the selectivity to propionic acid was 0.7%, and the selectivity to gas phase product was 5.8%.
Example 9
(1) Preparation of sodium super ion conductor
28.56g of titanyl sulfate TiOSO was weighed 4 Solid sample, followed by adding 42.84g of deionized water to the sample, andadding 25.70 g of 30wt% hydrogen peroxide as a stabilizer and 11.42g of polyethylene glycol PEG as a dispersing agent, and continuing ultrasonic dissolution; 25.37g of concentrated phosphoric acid having a concentration of 85% by weight are added dropwise again and stirred vigorously. The solution was dried in a water bath at 50℃and aged 48. 48h. The obtained dry gel is baked at 650 ℃ for 6H, and finally the sodium super ion conductor (H) 1-x Ti 2 (PO 4 ) 3-x (SO 4)x ) Raw material powder.
(2) Containing TiO 2 With CeO 2 Preparation of sodium super-ion conductor catalyst with metal oxide coating
Placing 5.0. 5.0 g of the sodium super-ion conductor raw powder obtained in the step (1) in 100 ml absolute ethyl alcohol, adding 0.5ml of ammonia water, and performing ultrasonic dispersion for 15 min; then adding 0.50 g cerium acetate and 0.60g of n-butyl titanate into the mixed solution at the same time, and stirring for 24 hours in a water bath at 45 ℃; the white powder obtained was subjected to centrifugal separation and drying, and was calcined at 500℃for 2 h. And tabletting, grinding and sieving the roasted sample into particles with 20-40 meshes to obtain the catalyst. Wherein the metal oxide TiO 2 -CeO 2 The mixed coating had a 7.6% ratio of catalyst. The X-ray electron diffraction pattern of the prepared catalyst was as follows:
FIG. 9 shows XRD patterns of the catalyst prepared in this example, showing that the NASICON crystal form is reduced after Ti/P reduction, many titanium pyrophosphate crystal phases are present and no CeO is present after the coating addition 2 With TiO 2 Characteristic peaks.
The reaction of synthesizing acrylic acid from methanol and acetic acid is realized in a fixed bed reaction. Placing 2g of the catalyst in the middle of a reactor, filling the upper part with a magnetic ring, and performing 28 ml min -1 Heating to 380 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 12%, and mixing the methanol and acetic acid mixed raw materials with the molar ratio of 1:1 at the rate of 1 mL h -1 ·g -1 The space velocity of the feed is controlled to be 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2h, the product was collected and analyzed. The conversion of acetic acid was 79.34%, the choice of acrylic acid and methyl acrylate in the main productThe property was 78.2% and the space-time yield was 6.27 mmol.g -1 ·h -1 Methyl acetate selectivity was 12.4%, dimethyl ether selectivity was 2.2%, methyl formate selectivity was 0.4%, propionaldehyde selectivity was 1.3%, acrolein selectivity was 0.2%, propionic acid selectivity was 0.8%, and gas phase product selectivity was 4.5%.
Claims (6)
1. A sodium super-ionic conductor catalyst comprising a metal oxide coating, characterized by: comprises Ti, zr, ce metal oxide coating components and element components Ti, P, S, O, H for composing the main body structure of the sodium super-ion conductor, wherein the mass percentage of the element components are MeO 2 ：2.5%-20%；H 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x :80% -97.5%, wherein the metal Me in the coating component is one or any two of Ti, zr and Ce, and x=0.4-1.
2. A method of preparing the metal oxide coated sodium super ion conductor catalyst of claim 1, comprising the steps of:
(1) Preparing a sodium super ion conductor:
weighing titanyl sulfate TiOSO 4 Dissolving a solid sample in deionized water, performing ultrasonic dissolution to prepare a solution with the concentration range of 1.0-2.0 mol/L, adding 30wt% hydrogen peroxide as a stabilizer and polyethylene glycol (PEG) as a dispersing agent, and continuing ultrasonic treatment; dropping concentrated phosphoric acid with the concentration of 85 percent by weight for one time, and strongly stirring; placing the obtained solution in water bath, standing, and aging for 24-48 h; roasting the obtained dry gel at 500-700 deg.C for 5-10H to obtain sodium super ion conductor H 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Raw material powder; raw materials of the synthetic mother solution, namely titanyl sulfate: water: hydrogen peroxide: polyethylene glycol: the mass ratio of the phosphoric acid is as follows: 10:10-20:6-15:3-5:5-10;
(2) Preparing a sodium super ion conductor catalyst containing a metal oxide coating:
placing 5.0. 5.0 g of the sodium super ion conductor material raw powder obtained in the step (1) in 100 mL absolute ethyl alcohol, adding 0.3-0.5 mL ammonia water, and performing ultrasonic dispersion for 15 min; then dropwise adding 0.255-5.10 g metal organic compound into the mixed solution, and stirring in a water bath at 30-60 ℃ for 12-24 h; performing centrifugal separation and drying to obtain white powder, and roasting at 400-600 ℃ for 2-6 h; and tabletting, grinding and sieving the roasted sample into particles with 20-40 meshes to obtain the catalyst.
3. The method for preparing a metal oxide-coated sodium-super-ion conductor catalyst according to claim 2, wherein: the metal organic compound comprises one or two of n-butyl titanate, titanium acetylacetonate, zirconium n-butoxide, zirconium acetylacetonate, cerium acetate or tricyclopentadienyl cerium; when two kinds of materials are selected, the two kinds of materials are in any proportion.
4. Use of the metal oxide coated sodium super ion conductor catalyst of claim 1 in direct synthesis of acrylic acid and methyl acrylate from methanol and acetic acid.
5. The use according to claim 4, characterized by the steps of: the catalyst is applied to the reaction of directly synthesizing acrylic acid and methyl acrylate from methanol and acetic acid, the catalytic reaction is carried out in a continuous flow fixed bed reactor, the catalyst is arranged in the middle position of the reactor, and a quartz sand preheating section is filled in the upper layer; the reaction carrier gas is oxygen-nitrogen mixed gas, and the volume fraction of oxygen is 2-20%; when the catalytic reaction is carried out, the reaction temperature is controlled to be 340-380 ℃, the reaction pressure is normal pressure, and the gas flow rate of the carried gas is controlled to be 5-15 mL min corresponding to each gram of catalyst -1 The molar ratio of raw material methanol to acetic acid is controlled to be 0.5-3:1, and the space velocity of reaction liquid is controlled to be 1-3 mL g -1 ·h -1 The liquid raw material is introduced by a plunger pump.
6. The use according to claim 5, characterized in that: the acetic acid conversion rate is more than 60%, the selectivity of acrylic acid and methyl acrylate is more than 70%, and the space-time yield is 5.4 mmol.g -1 ·h -1 The above.
Priority Applications (1)
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