CN107930674B - Catalyst for preparing dimethyl carbonate, preparation method and application - Google Patents
Catalyst for preparing dimethyl carbonate, preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 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 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 26
- 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 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 64
- 239000011148 porous material Substances 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 24
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 239000012018 catalyst precursor Substances 0.000 claims description 19
- 230000004913 activation Effects 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000005832 oxidative carbonylation reaction Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000005342 ion exchange Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000012494 Quartz wool Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- -1 aluminum ions Chemical class 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 238000005303 weighing Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000012229 microporous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
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- B01J35/615—
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- B01J35/617—
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- B01J35/638—
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- B01J35/647—
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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
- B01J37/02—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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- 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 catalyst for preparing dimethyl carbonate is composed of active components Cu and Al-KIT-6 mesoporous molecular sieve, wherein Cu accounts for 10-30wt% of metal, and the balance is Al-KIT-6 mesoporous molecular sieve. The invention has the advantage of high catalytic activity.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst for preparing dimethyl carbonate, a preparation method and application thereof.
Background
Dimethyl carbonate is a low-toxicity and environment-friendly organic synthesis intermediate and has wide application. The commonly used Y-type molecular sieve in the process of preparing dimethyl carbonate by methanol gas phase oxidative carbonylation is limited by the aperture (0.23nm) of a small cage window, so that a part of copper species exchanged in the small cage can not play the role of a catalytic active center (Huang Shouying, Industrial & Engineering Chemistry Research,2013,52(19):6349-6356.), thereby reducing the utilization rate of active species; in addition, similar microporous materials have certain effects on macromolecular reactant adsorption and product diffusion due to pore size limitations.
In contrast, the current catalyst carrier research of the reaction mainly focuses on mesoporous materials, wherein KIT-6 mesoporous silica has bicontinuous three-dimensional mesoporous channels connected by micropores, and the materials have high specific surface area, adjustable mesoporous aperture and hydrothermal stability. Compared with microporous molecular sieve, it can promote the adsorption of product and diffusion of reactant. However, due to the surface charge balance of the pure silicon carrier, the metal active species loaded on the pure silicon carrier is easy to agglomerate in the catalyst preparation and reaction processes, which leads to the activity reduction, and limits the further application of the material in the fields of catalysis and adsorption (Vinu Ajayan, Chemistry Letters,2008,37(10): 1016-. Incorporation of heteroatoms into the support backbone is the most straightforward and effective approach to solve this problem. Dragoi et Al found that the introduction of Al ions into Mesoporous silica Materials increased the number of acid sites and acid strength on the surface of the support (b. Dragoi, microporouus & mesorouus Materials,2009.212: 7-17), but various studies have been limited to adsorption and acid catalysis using only the acid sites in the support. No research shows whether the acidic sites formed by the heteroatoms can promote the dispersion degree of the active metals on the surface of the carrier.
In addition, in the conventional preparation method of copper-based supported catalyst for oxidative carbonylation of methanol, solid ion exchange (SSIE) can prepare copper-based supported catalyst having high Cu content compared to impregnation (IWIM) and solution ion exchange (LSIE)+The catalyst of the active center, and the method has simple steps and is not influenced by a solvent, but the common CuCl copper source can cause the problems of equipment corrosion, short service life of the catalyst and the like. The copper-based molecular sieve catalyst is prepared by adopting copper acetylacetonate as a copper source by Wangyuchun of Taiyuan university (Wangyuchun, Proc. of higher school chemistry 2015(12):2540-High.
Disclosure of Invention
The invention aims to provide a catalyst with high catalytic activity for preparing dimethyl carbonate, a preparation method thereof and application in a process for synthesizing dimethyl carbonate by methanol gas-phase oxidation and carbonylation.
The invention utilizes the unique pore channel structure of the mesoporous Al-KIT-6 carrier and the cation exchange sites in the framework thereof, adopts a completely chlorine-free copper acetylacetonate solid-state ion exchange method, reduces the agglomeration of active species loaded on the surface thereof, and improves the Cu content+The Cu-Al-KIT-6 catalyst with highly dispersed copper species, high activity and no pollution is prepared by the active species content.
The catalyst consists of active components Cu and Al-KIT-6 mesoporous molecular sieve, wherein the Cu accounts for 10-30wt% of metal, and the balance is Al-KIT-6 mesoporous molecular sieve.
The Al-KIT-6 mesoporous molecular sieve material adopted by the invention is synthesized by adopting a soft template method, aluminum ions are added before mother liquor is crystallized, and the molar ratio of the ingredients is as follows: ethyl orthosilicate, n-butanol, P123, hydrochloric acid, aluminum isopropoxide and deionized water, 1:1.3, (0.008-0.053) 1.84:0.013: 194. The specific synthesis method is shown in Prabhu A, Applied Catalysis A: General,2009.360:59-65), taking Al-KIT-6 synthesis method of Si/Al 40 as an example, dissolving P123 in HCl solution, adding n-butanol into the mixed solution after P123 is completely dissolved, continuously stirring, dropwise adding ethyl orthosilicate and aluminum isopropoxide into the solution, stirring the mixed solution for 24h at 35-40 ℃, pouring into a polytetrafluoroethylene crystallization kettle, crystallizing at 80-120 ℃, filtering and drying the crystallized mixture, removing the template agent at high temperature, and finally obtaining the Al-KIT-6 molecular sieve carrier.
The Al-KIT-6 molecular sieve synthesized by the Al-KIT-6 molecular sieve synthesis method has the silicon-aluminum ratio of 10-60 and the specific surface area of 772.9-910.3m2G, the pore diameter is 7.39-9.17nm, and the pore volume is 2.17-2.56cm3/g
The preparation method of the catalyst comprises the following specific steps:
(1) uniformly mixing the Al-KIT-6 and the copper acetylacetonate in a mortar according to the mass ratio of the Al-KIT-6 to the copper acetylacetonate of 5 to (2.05 to 6.15);
(2) placing the mixture at the temperature of 250-300 ℃ for steam impregnation for 4-10 hours to obtain a catalyst precursor; so that the copper acetylacetonate is highly dispersed on the surface and in the pore channels of the carrier, and simultaneously, part of the copper acetylacetonate and the carrier are subjected to ion exchange.
(3) And (2) performing temperature programming activation on the catalyst precursor in an activation atmosphere at the temperature programming rate of 2-5 ℃/min, performing high-temperature activation on the sample for 4-10 hours when the temperature reaches 600-750 ℃, and taking out the sample after the sample is cooled to room temperature to obtain the Cu-Al-KIT-6 catalyst.
The gas atmosphere adopted during activation in the preparation steps is a mixed gas composed of nitrogen and oxygen or air, and the volume ratio of the nitrogen to the oxygen is 10 (1-2). Wherein the oxygen is present to promote combustion of the organic ligand and its decomposition products, thereby accelerating the solid state exchange.
The specific surface area of the Cu-Al-KIT-6 catalyst is 470.8-530.6m2Per g, pore volume of 1.25-1.78cm3The mesoporous aperture is 6.78-7.54 nm.
The catalyst prepared by the invention is applied to methanol oxidative carbonylation reaction, and comprises the following steps:
(1) putting a catalyst and quartz wool into a fixed bed reactor, and heating a catalyst bed layer in the reactor to 140-180 ℃ in a nitrogen atmosphere; (2) volume composition of CO to O2Raw materials of 9:1 (4-6) of methanol are preheated to 120-; (3) the material flowing out of the preheater enters the tubular reactor at the upper end of the reactor, the reaction is carried out under the conditions of normal pressure and the temperature of 140--1。
The weight ratio of the catalyst to the quartz wool is 1: 0.5-1.
Compared with the prior art, the invention has the remarkable advantages that:
(1) compared with Y-type molecular sieves and various microporous materials commonly used in the conventional reaction for preparing DMC by methanol gas-phase oxidation carbonylation, the Al-KIT-6 carrier adopted by the invention has higher specific surface area, pore diameter and pore volume, can obviously promote the adsorption of reactants on active sites and the diffusion of products because the pore diameter of the carrier reaches the mesoporous level, and has a large number of microporous pore channels which are mutually connected among mesopores, thereby fundamentally solving the problem that the reactants can not contact with active species because of the pore diameter and the window size of the conventional microporous materials.
(2) The copper acetylacetonate solid ion exchange method can highly disperse sublimed copper acetylacetonate on the pore and the surface of the Al-KIT-6 material in the preparation process of a precursor, and simultaneously exchange partial copper acetylacetonate with partial acid sites on the Al-KIT-6 material; in the subsequent activation step, copper oxide species formed by the decomposed copper acetylacetonate are exchanged on the acidic sites of the support and undergo self-reduction reaction to form a large amount of active center Cu for synthesizing dimethyl carbonate by oxidative carbonylation of methanol+And is beneficial to improving the reaction activity.
(3) Compared with the traditional CuCl ion exchange method, the acetylacetone copper solid ion exchange method can stop the pollution of chloride ions to the catalyst from the source, does not need solvent auxiliary operation like an immersion method and a solution ion exchange method, avoids the procedures of washing, suction filtration, drying and the like, and simplifies the preparation process. And because no solvent is involved in the preparation process, the method also reduces the discharge of waste liquid and the pollution to the environment.
(4) The Cu-Al-KIT-6 catalyst prepared by the invention has higher catalytic activity in the reaction of synthesizing dimethyl carbonate by direct gas-phase oxidative carbonylation of methanol, and the space-time yield of a target product dimethyl carbonate in the reaction can reach: 300.6-890.5mg g-1·h-1The conversion rate of methanol is: 10.8-25.3%, and the selectivity of dimethyl carbonate reaches: 48.2 to 85.2 percent.
Drawings
FIG. 1 is a graph showing N of Cu-Al-KIT-6(S) catalysts prepared in examples 1 to 52Adsorption-desorption isotherm curve. Wherein a-e are curves for examples 1-5, respectively.
Figure 2 is a large angle XRD pattern of comparative examples 1, 2 and examples 1, 4, 6. Wherein a and b are the XRD patterns of comparative examples 1 and 2, respectively, and c, d, e are the XRD patterns of examples 1, 4, 6, respectively.
A-d in FIG. 3 are transmission electron microscope images of Al-KIT-6 support and Al-KIT-6 catalyst supports in example 3, example 5 and comparative example 1, respectively.
Detailed Description
Comparative example 1
The Cu-Al-KIT-6 catalyst is prepared by adopting an ultrasonic impregnation method, and the method comprises the following specific steps:
(1) 1.47g of Cu (NO)3)2·3H2O was dissolved in 20ml of deionized water.
(2) Weighing 5g of Al-KIT-6 molecular sieve (the specific surface area is 798.2 m)2G, pore diameter of 9.17nm and pore volume of 2.69cm3Si/Al 40) was slowly added to the above solution, and the mixture was placed in an ultrasonic cleaner and ultrasonically immersed at room temperature for 0.5 h.
(3) And drying the mixture at 105 ℃ for 5h, and cooling to room temperature to obtain the catalyst precursor.
(4) The catalyst precursor is placed in a tube furnace and roasted for 4 hours at 650 ℃ under the protection of nitrogen. The roasting method belongs to temperature programming, and the temperature raising process is as follows: starting from room temperature, increasing the temperature at a rate of 3 ℃/min to 300 ℃, keeping the temperature for 0.5h, increasing the temperature at a rate of 5 ℃/min to 650 ℃, keeping the temperature for 4h, and finally naturally cooling to room temperature to obtain the Cu-Al-KIT-6(I) catalyst. The loading of copper was 10 wt.% based on the metal.
The activity of the catalyst in the gas phase oxidative carbonylation of methanol is shown in Table 1, and the specific evaluation procedure is as follows:
0.5g (1.2ml) of Cu-Al-KIT-6(I) catalyst and 0.25g of quartz wool were weighed into a fixed bed stainless steel mini reactor, and the temperatures of the catalyst bed and the vaporizer were raised to 180 ℃ and 140 ℃ respectively under nitrogen protection. The reaction sample introduction raw material proportion is as follows: CO is O2:CH3OH is 9:1:4, and the volume space velocity is 4000h-1The raw materials are mixed by a gasification chamber, enter a catalyst bed layer from the upper part of a reactor, the reaction is a normal-pressure reaction, a product is subjected to continuous sample injection analysis by an Agilent 6890N-type gas chromatograph, and the activity data of the catalyst is the average value of the 10-hour reaction.
Comparative example 2
Preparation of catalyst by solution ion exchange method
(1) 1.47gCu (NO)3)2·3H2Dissolving O in 50ml of deionized water, adjusting the pH value of the solution to 9.5 by using ammonia water, and fixing the volume to 100ml to obtain a copper ammonia solution of 0.08 mol/L.
(2) Weighing 5g of Al-KIT-6 molecular sieve (the specific surface area is 798.2 m)2G, pore diameter of 9.17nm and pore volume of 2.69cm3And/g, 40% of Si/Al), slowly adding the mixture into the copper ammonia solution, stirring at room temperature for 2 hours, washing and filtering by using sufficient deionized water after the reaction is finished, drying a filter cake at 105 ℃ for 10 hours, and cooling to room temperature to obtain a catalyst precursor.
(3) The catalyst precursor is placed in a tube furnace and roasted for 4 hours at 650 ℃ under the protection of nitrogen. The roasting method belongs to temperature programming, and the temperature raising process is as follows: starting from room temperature, increasing the temperature at a rate of 3 ℃/min to 300 ℃, keeping the temperature for 0.5h, increasing the temperature at a rate of 5 ℃/min to 650 ℃, keeping the temperature for 4h, and finally naturally cooling to room temperature to obtain the Cu-Al-KIT-6(L) catalyst. The loading of copper species was 10 wt.% based on metal.
The activity of the catalyst in the gas phase oxidative carbonylation of methanol is shown in Table 1, and the specific evaluation procedure is as follows:
0.5g (1.2ml) of Cu-Al-KIT-6(L) catalyst and 0.25g of quartz wool were weighed into a fixed bed stainless steel mini reactor, and the temperatures of the catalyst bed and the vaporizer were raised to 180 ℃ and 140 ℃ respectively under nitrogen protection. The reaction sample introduction raw material proportion is as follows: CO is O2:CH3OH is 9:1:4, and the volume space velocity is 4500h-1The raw materials are mixed by a gasification chamber, enter a catalyst bed layer from the upper part of a reactor, the reaction is a normal-pressure reaction, a product is subjected to continuous sample injection analysis by an Agilent 6890N-type gas chromatograph, and the activity data of the catalyst is the average value of the 10-hour reaction.
Example 1
(1) Weighing 5g of Al-KIT-6 molecular sieve (the specific surface area is 798.2 m)2G, pore diameter of 9.17nm and pore volume of 2.69cm3Si/Al 40) was uniformly mixed with 2.05g of copper acetylacetonate in an agate mortar and steam-impregnated in a muffle furnace at 250 ℃ for 4 hours to prepare a catalyst precursor.
(2) Weighing 2g of catalystCarrying out temperature programming activation on the precursor under the protection gas with the volume ratio of nitrogen to oxygen being 10:1, wherein the temperature programming is as follows: from room temperature, the temperature is raised to 650 ℃ at a heating rate of 3 ℃/min, and the temperature is kept for 10 h. After cooling to room temperature, the Cu-Al-KIT-6(S) catalyst is obtained, and the copper species loading in the catalyst is 10 wt% in terms of metal. The specific surface area of the catalyst was 499.3m2G, pore volume of 1.62cm3The mesoporous aperture is 7.02 nm.
The activity of the catalyst in the gas phase oxidative carbonylation of methanol is shown in Table 1, and the specific evaluation procedure is as follows:
0.5g (1.2ml) of Cu-Al-KIT-6(S) catalyst and 0.5g of quartz wool were weighed into a fixed bed stainless steel mini reactor, and the temperature of the catalyst bed and the gasification chamber was raised to 140 ℃ under nitrogen protection. The reaction sample introduction raw material proportion is as follows: CO is O2:CH3OH is 9:1:6, and the volume space velocity is 6000h-1The raw materials are mixed by a gasification chamber, enter a catalyst bed layer from the upper part of a reactor, the reaction is a normal-pressure reaction, a product is subjected to continuous sample injection analysis by an Agilent 6890N-type gas chromatograph, and the activity data of the catalyst is the average value of the 10-hour reaction.
Example 2
(1) Weighing 5g of Al-KIT-6 molecular sieve (the specific surface area is 910.3 m)2G, pore diameter of 8.99nm and pore volume of 2.56cm3Si/Al 60) was uniformly mixed with 3.07g of copper acetylacetonate in an agate mortar and steam-impregnated in a muffle furnace at 250 ℃ for 4 hours to prepare a catalyst precursor.
(2) Weighing 2g of catalyst precursor, and carrying out temperature programming activation under the protection gas with the volume ratio of nitrogen to oxygen of 10:1, wherein the temperature programming is as follows: from room temperature, the temperature is raised to 650 ℃ at a heating rate of 3 ℃/min, and the temperature is kept for 10 h. After cooling to room temperature, the Cu-Al-KIT-6(S) catalyst is obtained, and the copper species loading amount in the catalyst is 15 wt% in terms of metal. The specific surface area of the catalyst was 530.6m2G, pore volume of 1.78cm3The mesoporous aperture is 7.54 nm.
(3) The catalyst bed temperature was raised to 160 ℃ for catalyst evaluation, and other parameters and test methods were as in example 1. The activity of the catalyst in the gas phase oxidative carbonylation of methanol is shown in Table 1.
Example 3
(1) 5g of Al-KIT-6 molecular sieve (the specific surface area is 772.9 m)2G, pore diameter of 7.39nm and pore volume of 2.17cm3Si/Al 10) was uniformly mixed with 3.07g of copper acetylacetonate in an agate mortar and steam-impregnated in a muffle furnace at 300 ℃ for 10 hours to prepare a catalyst precursor.
(2) Weighing 2g of catalyst precursor, and carrying out temperature programming activation under the protection gas with the volume ratio of nitrogen to oxygen of 10:2, wherein the temperature programming is as follows: from room temperature, the temperature is raised to 650 ℃ at a heating rate of 3 ℃/min, and the temperature is kept for 5 h. After cooling to room temperature, the Cu-Al-KIT-6(S) catalyst is obtained, and the copper species loading amount in the catalyst is 15 wt% in terms of metal. The specific surface area of the catalyst was 470.8m2G, pore volume of 1.25cm3The mesoporous aperture is 6.78 nm.
(3) The proportion of reaction sample introduction raw materials is as follows: CO is O2:CH3OH is 9:1:5, and the volume space velocity is 5000h-1The catalyst bed temperature was 160 ℃ and other parameters and test methods were as in example 1. The activity of the catalyst in the gas phase oxidative carbonylation of methanol is shown in Table 1.
Example 4
(1) Weighing 5g of Al-KIT-6 molecular sieve (the specific surface area is 798.2 m)2G, pore diameter of 9.17nm and pore volume of 2.69cm3Si/Al 40) was uniformly mixed with 6.15g of copper acetylacetonate in an agate mortar and steam-impregnated in a muffle furnace at 250 ℃ for 6 hours to prepare a catalyst precursor.
(2) Weighing 2g of catalyst precursor, and carrying out temperature programming activation in air, wherein the temperature programming is as follows: from room temperature, the temperature was raised to 650 ℃ at a rate of 3 ℃/min and held for 10 hours. After cooling to room temperature, obtaining the Cu-Al-KIT-6(S) catalyst, wherein the loading amount of copper species in the catalyst is 30wt% calculated by metal, and the specific surface area of the catalyst is 485.6m2Per g, pore volume of 1.58cm3The mesoporous aperture is 6.68 nm.
(3) The proportion of reaction sample introduction raw materials is as follows: CO is O2:CH3OH 9:1:5, space velocity of volumeIs 5000h-1The catalyst bed temperature was 180 ℃ and other parameters and test methods were as in example 1. The activity of the catalyst in the gas phase oxidative carbonylation of methanol is shown in Table 1.
Example 5
(1) Weighing 5g of Al-KIT-6 molecular sieve (the specific surface area is 910.3 m)2G, pore diameter of 8.99nm and pore volume of 2.56cm3Si/Al 60/g) and 6.15g of copper acetylacetonate were uniformly mixed in an agate mortar and steam-impregnated in a muffle furnace at 300 ℃ for 10 hours to prepare a catalyst precursor.
(2) Weighing 2g of catalyst precursor, and carrying out temperature programming activation under the protection gas with the volume ratio of nitrogen to oxygen of 10:1, wherein the temperature programming is as follows: from room temperature, the temperature is raised to 750 ℃ at the heating rate of 3 ℃/min, and the temperature is kept for 5 h. After cooling to room temperature, the Cu-Al-KIT-6(S) catalyst is obtained, and the copper species loading in the catalyst is 30wt% in terms of metal. The specific surface area of the catalyst was 512.9m2Per g, pore volume of 1.69cm3The mesoporous aperture is 6.89 nm.
(3) The proportion of reaction sample introduction raw materials is as follows: CO is O2:CH3OH is 9:1:6, and the volume space velocity is 5000h-1The catalyst bed temperature was 180 ℃ and other parameters and test methods were as in example 1. The activity of the catalyst in the gas phase oxidative carbonylation of methanol is shown in Table 1.
Example 6
(1) Weighing 5g of Al-KIT-6 molecular sieve (the specific surface area is 910.3 m)2G, pore diameter of 8.99nm and pore volume of 2.56cm3Si/Al 60) and 6.15g of copper acetylacetonate in an agate mortar were uniformly mixed and calcined at 300 ℃ for 10 hours to obtain a catalyst precursor.
(2) Weighing 2g of catalyst precursor, and carrying out temperature programming activation under the protection gas with the volume ratio of nitrogen to oxygen of 10:2, wherein the temperature programming is as follows: from room temperature, the temperature is raised to 750 ℃ at the heating rate of 3 ℃/min, and the temperature is kept for 5 h. After cooling to room temperature, the Cu-Al-KIT-6(S) catalyst is obtained, and the copper species loading in the catalyst is 30wt% in terms of metal. The specific surface area of the catalyst was 504.2m2Per g, pore volume of 1.71cm3Per g, the mesoporous aperture is6.94nm。
(3) The proportion of reaction sample introduction raw materials is as follows: CO is O2:CH3OH is 9:1:4, and the volume space velocity is 6000h-1The catalyst bed temperature was 180 ℃ and other parameters and test methods were as in example 1. The activity of the catalyst in the gas phase oxidative carbonylation of methanol is shown in Table 1.
TABLE 1
Claims (7)
1. A catalyst for preparing dimethyl carbonate is characterized in that the catalyst consists of active components Cu and Al-KIT-6 mesoporous molecular sieve, wherein the Cu accounts for 10-30wt% of metal, and the balance is Al-KIT-6 mesoporous molecular sieve; the Al-KIT-6 mesoporous molecular sieve has the Si/Al ratio of 10-60 and the specific surface area of 772.9-910.3m2G, the pore diameter is 7.39-9.17nm, and the pore volume is 2.17-2.56cm3/g;
The mesoporous of the Al-KIT-6 mesoporous molecular sieve is provided with interconnected microporous pore channels, and the preparation method comprises the following steps: the aluminum ions are added before mother liquor is crystallized by adopting a soft template method, and the molar ratio of the ingredients is as follows: ethyl orthosilicate, n-butanol, P123, hydrochloric acid, aluminum isopropoxide and deionized water, wherein the ratio of the ethyl orthosilicate to the hydrochloric acid to the deionized water is 1:1.3, (0.008-0.053) and 1.84:0.013: 194;
the preparation process of the catalyst comprises the steps of highly dispersing copper acetylacetonate on the pore canal and the surface of the Al-KIT-6 mesoporous molecular sieve carrier by a copper acetylacetonate solid-state ion exchange method, and exchanging part of copper acetylacetonate with acid sites on part of Al-KIT-6 mesoporous molecular sieve; then, through an activation step, copper oxide species formed by the decomposition of copper acetylacetonate are exchanged on acid sites of the carrier, and self-reduction reaction is carried out to form an active center Cu for synthesizing dimethyl carbonate through the oxidative carbonylation of methanol+。
2. The catalyst for preparing dimethyl carbonate according to claim 1, wherein the Cu-Al-KIT-6 catalyst has a specific surface area of 470.8-530.6m2Per g, pore volume of 1.25-1.78cm3The mesoporous aperture is 6.78-7.54 nm.
3. A method for preparing a catalyst for the preparation of dimethyl carbonate according to claim 1, comprising the steps of:
(1) uniformly mixing Al-KIT-6 and copper acetylacetonate in a mortar according to the mass ratio of 5: 2.05-6.15;
(2) placing the mixture at the temperature of 250-300 ℃ for steam impregnation for 4-10 hours to obtain a catalyst precursor;
(3) and (2) performing temperature programming activation on the catalyst precursor in an activation atmosphere at the temperature programming rate of 2-5 ℃/min, performing high-temperature activation on the sample for 4-10 hours when the temperature reaches 600-750 ℃, and taking out the sample after the sample is cooled to room temperature to obtain the Cu-Al-KIT-6 catalyst.
4. The method of claim 3, wherein the activated atmosphere is a mixture of nitrogen and oxygen or air.
5. The method for preparing a catalyst for preparing dimethyl carbonate according to claim 4, wherein the volume ratio of nitrogen to oxygen in the mixed gas of nitrogen and oxygen is 10: 1-2.
6. Use of a catalyst according to claim 1 for the preparation of dimethyl carbonate, comprising the steps of:
(1) putting a catalyst and quartz wool into a fixed bed reactor, and heating a catalyst bed layer in the reactor to 140-180 ℃ in a nitrogen atmosphere;
(2) volume composition of CO to O2Preheating raw materials of methanol =9:1:4-6 to 120-140 ℃ by a preheater;
(3) the material from the preheater enters the tubular reactor at the upper end of the reactor and reacts at the temperature of 140-180 ℃ under normal pressure.
7. The use of the catalyst for the preparation of dimethyl carbonate according to claim 6, wherein the weight ratio of the catalyst to the quartz wool is 1: 0.5-1.
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