CN107930674A - A kind of catalyst and preparation method and application for preparing dimethyl carbonate - Google Patents
A kind of catalyst and preparation method and application for preparing dimethyl carbonate Download PDFInfo
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- CN107930674A CN107930674A CN201710965718.8A CN201710965718A CN107930674A CN 107930674 A CN107930674 A CN 107930674A CN 201710965718 A CN201710965718 A CN 201710965718A CN 107930674 A CN107930674 A CN 107930674A
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- dimethyl carbonate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 20
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 58
- 239000011148 porous material Substances 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 23
- 239000012018 catalyst precursor Substances 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 210000002268 wool Anatomy 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 24
- 230000000694 effects Effects 0.000 description 16
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 241000894007 species Species 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 238000005810 carbonylation reaction Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000006200 vaporizer Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000002502 liposome Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
A kind of catalyst for preparing dimethyl carbonate is made of 6 mesopore molecular sieves of active component Cu and Al KIT, and in terms of metal, Cu is 10 30wt%, remaining is 6 mesopore molecular sieves of Al KIT.The present invention has the advantages that catalytic activity is high.
Description
Technical field
The present invention relates to catalyst field, and in particular to a kind of catalyst for preparing dimethyl carbonate and preparation method and should
With.
Background technology
Dimethyl carbonate is a kind of low toxicity, the organic synthesis intermediate of environmental protection, using very extensive.Methanol gas-phase oxidation carbonyl
Glycosylation reaction, which prepares common Y type molecular sieve in dimethyl carbonate technique, since small cage window aperture (0.23nm) limits, to be caused
A part exchange in small cage copper species can not play its catalytic active center effect (Huang Shouying,
Industrial&Engineering Chemistry Research,2013,52(19):6349-6356.), reduce activity
The utilization rate of species；In addition, similar poromerics is since pore size limits, to macromolecule reactant absorption and product
Diffusion exerts a certain influence.
In this regard, the catalyst carrier research of the reaction at present primarily focuses on mesoporous material, wherein KIT-6 mesopore silicon oxides
With the co-continuous three-dimensional meso-hole duct connected by micropore, this material has higher specific surface area, adjustable mesoporous hole
Footpath and hydrothermal stability.It can promote the absorption of product and the diffusion of reactant compared with micro porous molecular sieve.But since pure silicon carries
Body surface surface charge balances, and the metal active species of load thereon is easy to that group occurs in catalyst preparation and reaction process
It is poly-, cause active decline, limit this material catalysis and adsorbing domain further using (Vinu Ajayan,
Chemistry Letters,2008,37(10):1016-1017.).Hetero atom is introduced into carrier framework, is to solve the problems, such as this
Most directly effective method.Dragoi et al. has found, Al ions are introduced into mesoporous silicon material, it is possible to increase carrier surface acid
Property bit number of points and acid strength (B.Dragoi, Microporous＆Mesoporous Materials, 2009.212:7-17.),
But various researchs at present are limited only to be adsorbed using the acidic site in carrier and acidic catalyst.Research there is no to show, it is miscellaneous
Can the acidic site that atom is formed promote raising of the active metal in carrier surface dispersion degree.
In addition, in the preparation method of traditional copper-based loaded catalyst of methanol oxidative carbonylation, compared to infusion process
(IWIM) and solion exchange process (LSIE), solid liposome nanoparticle method (SSIE), which can be prepared, has high-content Cu+Activity
The catalyst at center, and this method and step is simple, will not be affected by the solvent, but common CuCl copper source, it can cause
The problems such as such as equipment corrosion, catalyst life is short.Institutes Of Technology Of Taiyuan Wang Yu spring et al. (Wang Yuchun, institution of higher education's Science of Chemistry
Report, 2015 (12):2540-2549) use acetylacetone copper to be prepared for copper-based molecular sieve catalyst for copper source, avoid chlorion
Pollution to catalyst, improves the activity and stability of catalyst, but since carrier structure limits so that catalytic activity can not
Further improve.
The content of the invention
The object of the present invention is to provide a kind of high catalyst for preparing dimethyl carbonate of catalytic activity and preparation method and
Application in Oxidative Carbonylation Synthesis of DMC technique.
The present invention is the cation exchange site in unique pore passage structure and its skeleton using mesoporous Al-KIT-6 carriers,
Using the acetylacetone copper solid liposome nanoparticle method of totally chlorine free, the reunion for the active specy for being carried on its surface is reduced, is improved
Cu+Active specy content, prepares a kind of copper species high degree of dispersion, high activity, free of contamination Cu-Al-KIT-6 catalysis
Agent.
The catalyst of the present invention is made of active component Cu and Al-KIT-6 mesopore molecular sieves, in terms of metal, Cu 10-
30wt%, remaining is Al-KIT-6 mesopore molecular sieves.
The Al-KIT-6 meso-porous molecular sieve materials that the present invention uses be using soft mode version method synthesize, aluminium ion mother liquor not into
Added before brilliant, its dispensing molar ratio is：Ethyl orthosilicate:N-butanol:P123:Hydrochloric acid:Aluminium isopropoxide:Deionized water=1:1.3:
(0.008-0.053):1.84:0.013:194.Specific synthetic method is shown in (Prabhu A, Applied Catalysis A:
General,2009.360:59-65), by taking the Al-KIT-6 synthetic methods of Si/Al=40 as an example, P123 is dissolved in HCl solution
In, treat P123 be completely dissolved in backward mixed liquor add n-butanol persistently stir, be added dropwise into solution ethyl orthosilicate and
Aluminium isopropoxide, after mixed solution stirs 24h at 35-40 DEG C, pours into polytetrafluoroethylene (PTFE) crystallization kettle and carries out crystallization in 80-120 DEG C,
The filtered drying of mixture after crystallization finally obtains Al-KIT-6 molecular sieve carriers in Removal under High Temperature template.
The Al-KIT-6 molecular sieves silica alumina ratio of Al-KIT-6 Zeolite synthesis method synthesis as described above is 10-60, than
Surface area is 772.9-910.3m2/ g, aperture 7.39-9.17nm, pore volume 2.17-2.56cm3/g
The method for preparing catalyst of the present invention, comprises the following steps that：
(1) Al-KIT-6 is pressed:Acetylacetone copper mass ratio is 5:The ratio of (2.05-6.15), by both in mortar
Even mixing；
(2) by mixture be placed at 250-300 DEG C carry out 4-10 it is small when steam impregnate, obtain catalyst precursor；Make
Acetylacetone copper is highly dispersed in carrier surface and duct, while with carrier ion exchange occurs for part acetylacetone copper.
(3) by catalyst precursor in activation phenomenon, temperature programming activation, temperature programming are carried out to catalyst precursor
Speed is 2-5 DEG C/min, and when temperature reaches 600-750 DEG C, high-temperature activation when small to sample progress 4-10, treats that it is cooled to
Taken out after room temperature, obtain Cu-Al-KIT-6 catalyst.
The gaseous mixture or sky that the gas atmosphere used when being activated in preparation process as described above forms for nitrogen and oxygen
Gas, nitrogen and oxygen volume ratio are 10:(1-2).The presence of wherein oxygen is to promote organic ligand and its catabolite
Burning, so as to accelerate the progress that solid-state exchanges.
Its specific surface area of Cu-Al-KIT-6 catalyst as described above is 470.8-530.6m2/ g, pore volume 1.25-
1.78cm3/ g, mesoporous pore size 6.78-7.54nm.
The present invention prepares catalyst and is applied to methanol oxidation carbonylation, includes the following steps：
(1) catalyst and silica wool are fitted into fixed bed reactors, in a nitrogen atmosphere, by the catalyst in reactor
Bed is heated to 140-180 DEG C；(2) volume composition is CO:O2:Methanol=9:1:The preheated device of raw material of (4-6) is preheated to
120-140℃；(3) material of preheater outflow enters tubular reactor, under normal pressure, temperature 140- in the upper end of reactor
Reacted in 180 DEG C of condition, gaseous phase materials volume space velocity is 4000~6000h-1。
Catalyst as described above is 1 with silica wool weight ratio：0.5-1.
Compared with prior art, the present invention its remarkable advantage is：
(1) the Al-KIT-6 carriers that the present invention uses are prepared in DMC reactions compared to conventional methanol gas-phase oxidation/carbonylation
Frequently with Y type molecular sieve and all kinds of poromerics, there is higher specific surface area and aperture and pore volume, due to the aperture of carrier
Reach mesoporous rank, the diffusion of absorption and product of the reactant on avtive spot can be obviously promoted, and between mesoporous
There are the micropore canals being largely connected with each other, fundamentally solve conventional microporous material due to anti-caused by aperture and window size
The problem of answering thing can not be contacted with active specy.
(2) acetylacetone copper solid liposome nanoparticle method, can be in forerunner's production procedure by the acetylacetone copper after distillation
It is highly dispersed on the duct and surface of Al-KIT-6 materials, while part acetylacetone copper and the acidity on the Al-KIT-6 of part
Site exchanges；In activation step afterwards, the copper oxide species that the acetylacetone copper after decomposition is formed are exchanged in carrier
Acidic site on, and there occurs autoreduction reaction, form substantial amounts of methanol oxidative carbonylation Synthesis of dimethyl carbonate
Activated centre Cu+, be conducive to the raising of reactivity.
(3) acetylacetone copper solid liposome nanoparticle method, compared to traditional CuCl ion-exchanges, can prevent from source
Pollution of the chlorion to catalyst, and solvent auxiliary operation will not be needed as infusion process and solion exchange process, keep away
Exempt from the process such as washing, suction filtration, dry, simplify preparation process.And since preparation process does not have solvent participation, this method
Reduce the discharge of waste liquid and the pollution to environment.
(4) Cu-Al-KIT-6 catalyst prepared by the present invention, in the direct gas-phase oxidation/carbonylation carbonate synthesis diformazan of methanol
There is higher catalytic activity, the space-time yield of target product dimethyl carbonate is reachable in reaction in the reaction of ester：300.6-
890.5mg·g-1·h-1, methanol conversion is：10.8-25.3%, dimethyl carbonate selectively reach：48.2-85.2%.
Brief description of the drawings
Fig. 1 is the N of Cu-Al-KIT-6 (S) catalyst prepared by embodiment 1-52Adsorption-desorption isothermal curve.Wherein a-e
The respectively curve of embodiment 1-5.
Fig. 2 is the big angle XRD spectrum of comparative example 1,2 and embodiment 1,4,6.Wherein a and b is respectively comparative example 1 and 2
XRD spectrum, c, d, e are respectively the XRD spectrum of embodiment 1,4,6.
A-d in Fig. 3 be respectively in Al-KIT-6 carriers and embodiment 3, embodiment 5 and comparative example 1 Al-KIT-6 urge
The images of transmissive electron microscope of agent carrier.
Embodiment
Comparative example 1
Cu-Al-KIT-6 catalyst is prepared using ultrasonic immersing method, is comprised the following steps that：
(1) by 1.47g Cu (NO3)2·3H2O is dissolved in 20ml deionized waters.
(2) 5g Al-KIT-6 molecular sieves (specific surface area 798.2m is weighed2/ g, aperture 9.17nm, pore volume are
2.69cm3/ g, Si/Al=40) it is slowly added in above-mentioned solution, and mixture is put into and is cleaned by ultrasonic in instrument, surpass at room temperature
Sound impregnates 0.5h.
(3) mixture is dried into 5h at 105 DEG C, after being cooled to room temperature, obtains catalyst precursor.
(4) catalyst precursor is placed in tube furnace, when the lower 650 DEG C of roastings 4 of nitrogen protection are small.Its method of roasting category
It is as follows in temperature programming, temperature-rise period：Since room temperature, appreciated 300 DEG C with the heating rate of 3 DEG C/min, after constant temperature 0.5h, with
The speed of 5 DEG C/min is appreciated 650 DEG C, constant temperature 4h, is finally down to room temperature naturally, is obtained Cu-Al-KIT-6 (I) catalyst.With gold
Belong to meter, the load capacity of copper is 10wt%.
Activity of the catalyst in methanol gas-phase oxidation/carbonylation reaction is listed in table 1, and specific evaluation procedure is as follows：
Weigh 0.5g (1.2ml) Cu-Al-KIT-6 (I) catalyst and 0.25g silica wools load the miniature stainless steel of fixed bed
In reactor, under nitrogen protection, the temperature of catalyst bed and vaporizer is risen to 180 DEG C and 140 DEG C respectively.React sample introduction
Material rate is：CO:O2:CH3OH=9:1:4, volume space velocity 4000h-1Raw material is mixed through vaporizer, from reactor top into
Enter catalyst bed, react and continuous sample introduction analysis is carried out by Agilent 6890N types gas chromatograph, is urged for synthesis under normal pressure, product
Agent activity data takes the average value that 10h reacts.
Comparative example 2
Catalyst is prepared using solion exchange process
(1) by 1.47gCu (NO3)2·3H2O is dissolved in 50ml deionized waters, and pH value of solution=9.5 are adjusted with ammonium hydroxide, and
Constant volume 100ml, obtains the copper ammon solution of 0.08mol/L.
(2) 5g Al-KIT-6 molecular sieves (specific surface area 798.2m is weighed2/ g, aperture 9.17nm, pore volume are
2.69cm3/ g, Si/Al=40) be slowly added in above-mentioned copper ammon solution, 2h is stirred at room temperature, after the completion of, using it is enough go from
Sub- water washing filters, and filter cake is dried 10h at 105 DEG C, after being cooled to room temperature, obtains catalyst precursor.
(3) catalyst precursor is placed in tube furnace, when the lower 650 DEG C of roastings 4 of nitrogen protection are small.Its method of roasting category
It is as follows in temperature programming, temperature-rise period：Since room temperature, appreciated 300 DEG C with the heating rate of 3 DEG C/min, after constant temperature 0.5h, with
The speed of 5 DEG C/min is appreciated 650 DEG C, constant temperature 4h, is finally down to room temperature naturally, is obtained Cu-Al-KIT-6 (L) catalyst.With gold
Belong to meter, the load capacity of copper species is 10wt%.
Activity of the catalyst in methanol gas-phase oxidation/carbonylation reaction is listed in table 1, and specific evaluation procedure is as follows：
Weigh 0.5g (1.2ml) Cu-Al-KIT-6 (L) catalyst and 0.25g silica wools load the miniature stainless steel of fixed bed
In reactor, under nitrogen protection, the temperature of catalyst bed and vaporizer is risen to 180 DEG C and 140 DEG C respectively.React sample introduction
Material rate is：CO:O2:CH3OH=9:1:4, volume space velocity 4500h-1Raw material is mixed through vaporizer, from reactor top into
Enter catalyst bed, react and continuous sample introduction analysis is carried out by Agilent 6890N types gas chromatograph, is urged for synthesis under normal pressure, product
Agent activity data takes the average value that 10h reacts.
Embodiment 1
(1) 5g Al-KIT-6 molecular sieves (specific surface area 798.2m is weighed2/ g, aperture 9.17nm, pore volume are
2.69cm3/ g, Si/Al=40) uniformly mixed in agate mortar with 2.05g acetylacetone coppers, and in 250 DEG C in Muffle furnace
Lower steam impregnates 4h, and catalyst precursor is made.
(2) 2g catalyst precursors are weighed, are 10 in nitrogen and oxygen volume ratio:Into line program liter under 1 protective gas
Temperature activation, heating schedule are：Since room temperature, with the heating rate of 3 DEG C/min just, 650 DEG C are warming up to, constant temperature 10h.It is to be cooled
To room temperature, Cu-Al-KIT-6 (S) catalyst is obtained, in terms of metal, copper species load capacity is 10wt% in catalyst.Catalysis
The specific surface area of agent is 499.3m2/ g, pore volume 1.62cm3/ g, mesoporous pore size 7.02nm.
Activity of the catalyst in methanol gas-phase oxidation/carbonylation reaction is listed in table 1, and specific evaluation procedure is as follows：
Weigh 0.5g (1.2ml) Cu-Al-KIT-6 (S) catalyst and the 0.5g silica wools loading miniature stainless steel of fixed bed is anti-
Answer in device, under nitrogen protection, the temperature of catalyst bed and vaporizer is risen to 140 DEG C.Reacting sample introduction material rate is：
CO:O2:CH3OH=9:1:6, volume space velocity 6000h-1Raw material is mixed through vaporizer, enters catalyst bed from reactor top
Layer, reacts and carries out continuous sample introduction analysis, catalyst activity number by Agilent 6890N types gas chromatograph for synthesis under normal pressure, product
According to the average value for taking 10h to react.
Embodiment 2
(1) 5g Al-KIT-6 molecular sieves (specific surface area 910.3m is weighed2/ g, aperture 8.99nm, pore volume are
2.56cm3/ g, Si/Al=60) uniformly mixed in agate mortar with 3.07g acetylacetone coppers, and in 250 DEG C in Muffle furnace
Lower steam impregnates 4h, and catalyst precursor is made.
(2) 2g catalyst precursors are weighed, are 10 in nitrogen and oxygen volume ratio:Into line program liter under 1 protective gas
Temperature activation, heating schedule are：Since room temperature, with the heating rate of 3 DEG C/min just, 650 DEG C are warming up to, constant temperature 10h.It is to be cooled
To room temperature, Cu-Al-KIT-6 (S) catalyst is obtained, in terms of metal, copper species load capacity is 15wt% in catalyst.Catalysis
The specific surface area of agent is 530.6m2/ g, pore volume 1.78cm3/ g, mesoporous pore size 7.54nm.
(3) reaction bed temperature is promoted to 160 DEG C of progress evaluating catalysts, other specification and test method are as implemented
Example 1.Activity of the catalyst in methanol gas-phase oxidation/carbonylation reaction is listed in table 1.
Embodiment 3
(1) 5g Al-KIT-6 molecular sieves (specific surface area 772.9m is weighed2/ g, aperture 7.39nm, pore volume are
2.17cm3/ g, Si/Al=10) uniformly mixed in agate mortar with 3.07g acetylacetone coppers, and in 300 DEG C in Muffle furnace
Lower steam impregnates 10h, and catalyst precursor is made.
(2) 2g catalyst precursors are weighed, are 10 in nitrogen and oxygen volume ratio:Into line program liter under 2 protective gas
Temperature activation, heating schedule are：Since room temperature, with the heating rate of 3 DEG C/min just, 650 DEG C are warming up to, constant temperature 5h.It is to be cooled
To room temperature, Cu-Al-KIT-6 (S) catalyst is obtained, in terms of metal, copper species load capacity is 15wt% in catalyst.Catalysis
The specific surface area of agent is 470.8m2/ g, pore volume 1.25cm3/ g, mesoporous pore size 6.78nm.
(3) it is by reaction sample introduction material rate：CO:O2:CH3OH=9:1:5, volume space velocity 5000h-1, catalyst bed
Layer temperature is 160 DEG C, other specification and test method such as embodiment 1.Catalyst is in methanol gas-phase oxidation/carbonylation reaction
Activity is listed in table 1.
Embodiment 4
(1) 5g Al-KIT-6 molecular sieves (specific surface area 798.2m is weighed2/ g, aperture 9.17nm, pore volume are
2.69cm3/ g, Si/Al=40) uniformly mixed in agate mortar with 6.15g acetylacetone coppers, and in 250 DEG C in Muffle furnace
Lower steam impregnates 6h, and catalyst precursor is made.
(2) 2g catalyst precursors are weighed, carry out temperature programming activation in atmosphere, heating schedule is：Since room temperature,
With the heating rate of 3 DEG C/min just, 650 DEG C, when constant temperature 10 is small are warming up to.After being cooled to room temperature, Cu-Al-KIT-6 is obtained
(S) catalyst, in terms of metal, copper species load capacity is 30wt% in catalyst, and the specific surface area of catalyst is 485.6m2/ g,
Pore volume is 1.58cm3/ g, mesoporous pore size 6.68nm.
(3) it is by reaction sample introduction material rate：CO:O2:CH3OH=9:1:5, volume space velocity 5000h-1, catalyst bed
Layer temperature is 180 DEG C, other specification and test method such as embodiment 1.Catalyst is in methanol gas-phase oxidation/carbonylation reaction
Activity is listed in table 1.
Embodiment 5
(1) 5g Al-KIT-6 molecular sieves (specific surface area 910.3m is weighed2/ g, aperture 8.99nm, pore volume are
2.56cm3/ g Si/Al=60) uniformly mixed in agate mortar with 6.15g acetylacetone coppers, and in 300 DEG C in Muffle furnace
Lower steam impregnates 10h, and catalyst precursor is made.
(2) 2g catalyst precursors are weighed, are 10 in nitrogen and oxygen volume ratio:Into line program liter under 1 protective gas
Temperature activation, heating schedule are：Since room temperature, with the heating rate of 3 DEG C/min just, 750 DEG C are warming up to, constant temperature 5h.It is to be cooled
To room temperature, Cu-Al-KIT-6 (S) catalyst is obtained, in terms of metal, copper species load capacity is 30wt% in catalyst.Catalysis
The specific surface area of agent is 512.9m2/ g, pore volume 1.69cm3/ g, mesoporous pore size 6.89nm.
(3) it is by reaction sample introduction material rate：CO:O2:CH3OH=9:1:6, volume space velocity 5000h-1, catalyst bed
Layer temperature is 180 DEG C, other specification and test method such as embodiment 1.Catalyst is in methanol gas-phase oxidation/carbonylation reaction
Activity is listed in table 1.
Embodiment 6
(1) 5g Al-KIT-6 molecular sieves (specific surface area 910.3m is weighed2/ g, aperture 8.99nm, pore volume are
2.56cm3/ g, Si/Al=60) uniformly mixed in agate mortar with 6.15g acetylacetone coppers, and 10h is roasted at 300 DEG C,
Catalyst precursor is made.
(2) 2g catalyst precursors are weighed, are 10 in nitrogen and oxygen volume ratio:Into line program liter under 2 protective gas
Temperature activation, heating schedule are：Since room temperature, with the heating rate of 3 DEG C/min just, 750 DEG C are warming up to, constant temperature 5h.It is to be cooled
To room temperature, Cu-Al-KIT-6 (S) catalyst is obtained, in terms of metal, copper species load capacity is 30wt% in catalyst.Catalysis
The specific surface area of agent is 504.2m2/ g, pore volume 1.71cm3/ g, mesoporous pore size 6.94nm.
(3) it is by reaction sample introduction material rate：CO:O2:CH3OH=9:1:4, volume space velocity 6000h-1, catalyst bed
Layer temperature is 180 DEG C, other specification and test method such as embodiment 1.Catalyst is in methanol gas-phase oxidation/carbonylation reaction
Activity is listed in table 1.
Table 1
Claims (8)
1. a kind of catalyst for preparing dimethyl carbonate, it is characterised in that catalyst is by active component Cu and mesoporous point of Al-KIT-6
Sub- screen banks is into terms of metal, Cu 10-30wt%, remaining is Al-KIT-6 mesopore molecular sieves.
A kind of 2. catalyst for preparing dimethyl carbonate as claimed in claim 1, it is characterised in that Cu-Al-KIT-6 catalyst
Its specific surface area is 470.8-530.6m2/ g, pore volume 1.25-1.78cm3/ g, mesoporous pore size 6.78-7.54nm.
A kind of 3. catalyst for preparing dimethyl carbonate as claimed in claim 1 or 2, it is characterised in that mesoporous point of Al-KIT-6
The silica alumina ratio of son sieve is 10-60, specific surface area 772.9-910.3m2/ g, aperture 7.39-9.17nm, pore volume 2.17-
2.56cm3/g。
4. such as a kind of preparation method for the catalyst for preparing dimethyl carbonate of claim 1-3 any one of them, its feature exists
In including the following steps：
（1）By Al-KIT-6:Acetylacetone copper mass ratio is 5:The ratio of 2.05-6.15, both are uniformly mixed in mortar
Close；
（2）By mixture be placed in 250-300 DEG C carry out 4-10 it is small when steam impregnate, obtain catalyst precursor；
（3）By catalyst precursor in activation phenomenon, temperature programming activation, programmed rate are carried out to catalyst precursor
For 2-5 DEG C/min, when temperature reaches 600-750 DEG C, high-temperature activation when small to sample progress 4-10, treats that it is cooled to room temperature
After take out, obtain Cu-Al-KIT-6 catalyst.
A kind of 5. preparation method for the catalyst for preparing dimethyl carbonate as claimed in claim 4, it is characterised in that the work
Change gaseous mixture or air that atmosphere forms for nitrogen and oxygen.
A kind of 6. preparation method for the catalyst for preparing dimethyl carbonate as claimed in claim 5, it is characterised in that described=nitrogen
Nitrogen and oxygen volume ratio are 10 in the gaseous mixture of gas and oxygen composition:1-2.
7. such as a kind of application for the catalyst for preparing dimethyl carbonate of claim 1-3 any one of them, it is characterised in that bag
Include following steps：
(1) catalyst and silica wool are fitted into fixed bed reactors, in a nitrogen atmosphere, by the catalyst bed in reactor
It is heated to 140-180 DEG C；
(2) volume composition is CO:O2:Methanol=9:1:The preheated device of raw material of 4-6 is preheated to 120-140 DEG C；
(3) material of preheater outflow enters tubular reactor in the upper end of reactor, and under normal pressure, temperature is 140-180 DEG C
Condition in reacted.
A kind of 8. application for the catalyst for preparing dimethyl carbonate as claimed in claim 7, it is characterised in that the catalysis
Agent is 1 with silica wool weight ratio：0.5-1.
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| CN114618559A (en) * | 2022-04-11 | 2022-06-14 | 辽宁大学 | Solid acid catalyst, preparation method thereof and application of solid acid catalyst in catalyzing decarboxylation of gamma-valerolactone to butene preparation |
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