CN116726922A - Catalyst for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol, preparation method and application - Google Patents
Catalyst for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol, preparation method and application Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000007791 liquid phase Substances 0.000 title claims abstract description 53
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 49
- 238000005832 oxidative carbonylation reaction Methods 0.000 title claims description 40
- 238000002360 preparation method Methods 0.000 title abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 239000013084 copper-based metal-organic framework Substances 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 230000006315 carbonylation Effects 0.000 claims abstract description 12
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 239000010949 copper Substances 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000010000 carbonizing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 150000001879 copper Chemical class 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000004090 dissolution Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000003446 ligand Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 33
- 230000000694 effects Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000013148 Cu-BTC MOF Substances 0.000 description 10
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- -1 halogen ions Chemical class 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/01—Preparation of esters of carbonic or haloformic acids from carbon monoxide and oxygen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for synthesizing dimethyl carbonate by methanol liquid phase oxidation carbonylation, a preparation method and application thereof, wherein the catalyst is MOFs derivative, metal oxide is dispersed on a carbon carrier, and the metal oxide is CuO X . MOFs derivative is CuO obtained by calcining Cu-MOF X The MOFs derivative is dispersed on the carbon carrier, and the dosage of the MOFs derivative is 1.3-3.8% of that of methanol. Compared with the prior art, the invention has the characteristics of adjustable metal node and ligand structure, large specific surface area, various structures and the like by utilizing MOFs, and the like after calcinationThe obtained derivative has the advantages of high specific surface area and high dispersion of metal oxide on the carbon carrier.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol, a preparation method and application thereof.
Background
Dimethyl carbonate, registered in europe in 1992 as a nontoxic chemical, is known as "base stone" of green synthetic chemistry, and is widely used in the fields of pesticides, medicines, plastics, dyes, electronic chemicals, food additives, and the like; can also be used as an electrolyte solvent, and the electrolyte is one of core materials of the lithium battery.
At present, the dimethyl carbonate is mainly produced by an ester exchange method in industry, the raw materials of the dimethyl carbonate are ethylene carbonate and methanol, the raw materials belong to a typical petrochemical line, the raw materials are greatly influenced by petroleum price, and meanwhile, the sales of the ethylene glycol is a byproduct, so that the operating rate of the device is limited to a certain extent. CO 2 Direct one-step synthesis of dimethyl carbonate with methanol is also of great interest to researchers, but methanol conversion is always low. In recent years, the process for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol and synthesizing dimethyl carbonate by alcoholysis of urea is mature, and pilot plant or industrial device start-up is reported successively. However, most of the reported catalysts are halogen-containing catalysts, which have low activity, low reaction efficiency and strong corrosiveness of halogen ions to stainless steel reaction kettles.
Patent application CN201610647640.0 discloses a catalyst and a method for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol. The catalyst comprises: copper halides and ionic liquids; the mass ratio of the halide of copper to the ionic liquid is 1 (1-10); the cation of the ionic liquid is imidazole type, quaternary ammonium salt type or pyridine type, and the anion is halogen ion. The catalyst of the invention has higher dimethyl carbonate selectivity which can reach 99.8 percent at most, and in addition, the corrosion to stainless steel reaction equipment can be relieved by adding ionic liquid, but the technology does not fundamentally solve the corrosion of halogen ions to the stainless steel equipment, so the development of the catalyst without halogen is particularly important.
Patent application CN201310077972.6 discloses a catalyst for synthesizing dimethyl carbonate by continuous oxidative carbonylation of liquid-phase methanol, which is prepared from active component Cu 2 O and activated carbon composition (Cu 2 O/AC), the catalyst composition is: cu (Cu) 2 5.0 to 25.0 weight percent of O and 75.0 to 95.0 weight percent of active carbon. The catalyst shows good activity and stability in DMC reaction of continuous liquid phase oxidation carbonylation synthesis of methanol, selectivity is higher than 95%, but catalyst dosage is 6.5-22.6% of methanol mass, dosage is large, and DMC space-time yield is only 300-700 mg.g -1 ·h -1 。
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol, a preparation method and application thereof, and the catalyst does not contain halogen and CuO X High dispersion on carbon supports.
The aim of the invention can be achieved by the following technical scheme: a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidizing and carbonylating methanol is prepared from MOFs (metal-organic skeleton) derivative, metal oxide (CuO) and Cu oxide (or Cu oxide) through dispersing it on carbon carrier X 。
Further, the MOFs derivative is CuO obtained by Cu-MOF calcination X Dispersed on a carbon support.
Further, provided thatThe catalyst has a topological structure, and the specific surface area is 10-150 m 2 ·g -1 The surface of the catalyst is distributed with mesoporous with the pore diameter of 4-35 nm.
The invention also provides a preparation method of the catalyst for synthesizing the dimethyl carbonate by liquid-phase oxidative carbonylation of methanol, which comprises the following steps:
s101, dissolving copper salt in deionized water to obtain a solution A;
s102, H 3 Dissolving BTC and PVP in a mixed solution of deionized water, ethanol and DMF to obtain a solution B;
s103, adding the solution B into the solution A, stirring, and fully and uniformly mixing to obtain a suspension C;
s104, transferring the suspension C into a hydrothermal kettle, and reacting for 12-36 hours at 100-150 ℃ to obtain a D solution with blue precipitate;
s105, centrifuging the solution D, and washing until the supernatant is colorless;
s106, drying the washed product to obtain blue powdery Cu-MOF;
s107 Cu-MOF at N 2 Carbonizing at high temperature under atmosphere to obtain the catalyst MOFs derivative.
The copper salt comprises Cu (NO) 3 ) 2 ·3H 2 O。
In the step S102, the volume ratio of deionized water to ethanol to DMF is 1:1:0-1.
H in step S102 3 The mass ratio of BTC to PVP is 1:0-1.1.
Copper salt and H in suspension C 3 The molar ratio of BTC is 1.5-2:1.
In the step S107, the carbonization temperature is 300-500 ℃, the heating rate is 3-6 ℃/min, and the carbonization time is 1-3 h.
The catalyst is used for synthesizing the dimethyl carbonate by liquid-phase oxidative carbonylation of methanol, and the dosage of the catalyst is 1.3-3.8% of the mass of the methanol.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst of the invention is a Metal Organic Frameworks (MOFs) derivative, and the MOFs derivativeCuO obtained by calcining Cu-MOF X Highly dispersed on carbon supports, MOFs are a novel porous inorganic-organic material consisting of metal ions or metal clusters and organic linking ligands. Has the characteristics of adjustable metal node and ligand structure, large specific surface area, various structures and the like. Because organic ligands of MOFs are easy to decompose at high temperature, MOFs derivatives prepared by high-temperature carbonization have the advantages of large specific surface area, high dispersion of metal centers, adjustable pores, easy modification and the like.
The invention designs a methyl carbonate catalyst synthesized by methanol liquid-phase oxidative carbonylation, which utilizes MOFs with periodically arranged frameworks, and the catalyst derived after calcination inherits the topological structure, and metal oxides are highly dispersed on a carbon carrier; MOFs have the characteristics of adjustable metal nodes and ligand structures, various structures and the like, and the derived catalyst has high controllability. The catalyst has no corrosion to stainless steel equipment, and has good dimethyl carbonate selectivity and no by-product.
(2) The invention selects H 3 BTC and PVP are used as raw materials and are dissolved in a mixed solution of ionized water, ethanol and DMF, wherein DMF can promote the formation of Cu-MOF crystals, PVP can protect the structure of Cu-MOF from being damaged by water in the air, promote the formation of porous carbon shells in the carbonization process, and then are mixed with a solution containing copper ions, and the Cu-MOF with high purity of crystal phase is synthesized by hydrothermal reaction -1 ·h -1 。
Drawings
FIG. 1 is an SEM image of Cu-BTC-PVP-1 of the present invention;
FIG. 2 shows CuO of the present invention X SEM image of PC-1;
FIG. 3 shows Cu-BTC-PVP-1 and CuO of the present invention X XRD pattern of PC-1;
FIG. 4 shows Cu-BTC-PVP of the present invention-1 and CuO X N of/PC-1 2 Adsorption and desorption and pore size distribution spectrograms.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1:
a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidization and carbonylation of methanol is MOFs derivative which is CuO obtained by Cu-MOF calcination X Dispersed on a carbon carrier, the catalyst is used in an amount of 1.3% by mass of methanol.
The preparation method of the catalyst for synthesizing the dimethyl carbonate by liquid-phase oxidative carbonylation of methanol comprises the following steps:
s101, 4.0g Cu (NO 3 ) 2 ·3H 2 O is dissolved in 15mL of deionized water to obtain solution A;
s102, H2.5 g 3 BTC and 2.7g PVP are dissolved in 125mL of mixed solution of deionized water, ethanol and DMF to obtain solution B, wherein the volume ratio of the deionized water to the ethanol to the DMF is 1:1:1;
s103, adding the solution B into the solution A, stirring for 10min, and fully and uniformly mixing to obtain a suspension C;
s104, transferring the suspension C into a 200mL hydrothermal kettle, and placing the hydrothermal kettle in a 120 ℃ oven for reaction for 24 hours to obtain a D solution with blue precipitate;
s105, centrifuging the solution D, and washing the solution D for a plurality of times by using deionized water and ethanol until the supernatant is colorless;
s106, placing the washed product in a baking oven at 120 ℃ for drying overnight to obtain blue powdery Cu-BTC-PVP-1;
s107, cu-BTC-PVP-1 is placed in a tube furnace, and is added in N 2 Carbonizing at 400 ℃ for 2h at a heating rate of 5 ℃/min in the atmosphere. The resulting catalyst was designated CuO X /PC-1。
An SEM image of the prepared uncarbonated Cu-BTC-PVP-1, as shown in FIG. 1, which exhibited a typical regular octahedral structure with a particle size of 2 μm; derivatized CuO X SEM image of PC-1, as shown in FIG. 2, the surface of the regular octahedron thereof is slightly shrunk inwardsThe particle size is reduced, but the basic framework structure is maintained, and a large amount of spherical CuO appears on the surface and in the graphitized carbon shell X And (3) particles.
Cu-BTC-PVP-1 and CuO X XRD pattern of PC-1, as shown in FIG. 3, XRD pattern of Cu-BTC-PVP-1 and CuO X The simulated spectrograms of the/PC-1 are highly matched, which shows that the crystal form is not affected by the PVP doped in the Cu-BTC, the diffraction peak of the Cu-BTC-PVP-1 disappears after carbonization, the characteristic diffraction peak attributed to Cu appears at 40.3 degrees, 50.5 degrees and 70.1 degrees, and the characteristic diffraction peak attributed to Cu appears at 36.4 degrees 2 Weak characteristic diffraction peak of O. Indicating Cu during carbonization 2+ Is reduced to Cu and Cu 2 O。
Cu-BTC-PVP-1 and CuO X N of/PC-1 2 Adsorption and desorption and pore size distribution spectra, as shown in FIG. 4, of CuO X Specific surface area of PC-1 is 102m 2 ·g -1 Is lower than the specific surface area of Cu-BTC-PVP-1 before carbonization (883 m 2 ·g -1 ) This is caused by structural collapse of Cu-BTC-PVP-1 after high temperature carbonization. Cu-BTC-PVP-1 and CuO derived from same X Each of PC-1 shows an isothermal adsorption line of type IV, and H appears 4 Hysteresis shows that both are mesoporous structures, but the aperture of Cu-BTC-PVP-1 is concentrated at 4nm, and carbonized CuO X Some mesopores with the size of 4-18nm are also observed in PC-1, which shows that the high-temperature carbonization process widens the pore size distribution of Cu-BTC-PVP-1, which is beneficial to the transmission of substances.
The activity of the catalyst in synthesizing dimethyl carbonate by liquid phase oxidative carbonylation of methanol was examined by using a 100mL autoclave. 10mL of methanol and 0.1g of catalyst were charged into a reaction vessel, and CO at 3.6MPa and O at 0.4MPa were charged at room temperature 2 The reaction was carried out at 300rpm at 120℃for 2 hours, then cooled to room temperature and the product composition was analyzed by gas chromatography. Dimethyl carbonate space-time yield 1188 mg.g -1 ·h -1 Dimethyl carbonate selectivity was 100%.
Example 2:
a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidization and carbonylation of methanol is MOFs derivative which is CuO obtained by Cu-MOF calcination X Dispersed on a carbon support, the catalystThe amount of (2) was 2.5% by mass of methanol.
The preparation method of the catalyst for synthesizing the dimethyl carbonate by liquid-phase oxidative carbonylation of methanol comprises the following steps:
s101, 4.0g Cu (NO 3 ) 2 ·3H 2 O is dissolved in 15mL of deionized water to obtain solution A;
s102, H2.5 g 3 BTC and 2.7g PVP are dissolved in 125mL of mixed solution of deionized water, ethanol and DMF to obtain solution B, wherein the volume ratio of the deionized water to the ethanol to the DMF is 1:1:1;
s103, adding the solution B into the solution A, stirring for 10min, and fully and uniformly mixing to obtain a suspension C;
s104, transferring the suspension C into a 200mL hydrothermal kettle, and placing the hydrothermal kettle in a 120 ℃ oven for reaction for 24 hours to obtain a D solution with blue precipitate;
s105, centrifuging the solution D, and washing the solution D for a plurality of times by using deionized water and ethanol until the supernatant is colorless;
s106, placing the washed product in a baking oven at 120 ℃ for drying overnight to obtain blue powdery Cu-BTC-PVP-1;
s107, cu-BTC-PVP-1 is placed in a tube furnace, and is added in N 2 Carbonizing at 400 ℃ for 2h at a heating rate of 5 ℃/min in the atmosphere. The resulting catalyst was designated CuO X /PC-1。
The activity of the catalyst in synthesizing dimethyl carbonate by liquid phase oxidative carbonylation of methanol was examined by using a 100mL autoclave. 10mL of methanol and 0.2g of catalyst were charged into a reactor, and CO at 3.6MPa and O at 0.4MPa were charged at room temperature 2 The reaction was carried out at 300rpm at 120℃for 2 hours, then cooled to room temperature and the product composition was analyzed by gas chromatography. Dimethyl carbonate space-time yield 605 mg.g -1 ·h -1 The conversion of methanol is 2.19%, and the selectivity of dimethyl carbonate is 100%.
Example 3:
a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidization and carbonylation of methanol is MOFs derivative which is CuO obtained by Cu-MOF calcination X Dispersed on a carbon carrier, the catalyst is used in an amount of 3% by mass of methanol.8％。
The preparation method of the catalyst for synthesizing the dimethyl carbonate by liquid-phase oxidative carbonylation of methanol comprises the following steps:
s101, 4.0g Cu (NO 3 ) 2 ·3H 2 O is dissolved in 15mL of deionized water to obtain solution A;
s102, H2.5 g 3 BTC and 2.7g PVP are dissolved in 125mL of mixed solution of deionized water, ethanol and DMF to obtain solution B, wherein the volume ratio of the deionized water to the ethanol to the DMF is 1:1:1;
s103, adding the solution B into the solution A, stirring for 10min, and fully and uniformly mixing to obtain a suspension C;
s104, transferring the suspension C into a 200mL hydrothermal kettle, and placing the hydrothermal kettle in a 120 ℃ oven for reaction for 24 hours to obtain a D solution with blue precipitate;
s105, centrifuging the solution D, and washing the solution D for a plurality of times by using deionized water and ethanol until the supernatant is colorless;
s106, placing the washed product in a baking oven at 120 ℃ for drying overnight to obtain blue powdery Cu-BTC-PVP-1;
s107, cu-BTC-PVP-1 is placed in a tube furnace, and is added in N 2 Carbonizing at 400 ℃ for 2h at a heating rate of 5 ℃/min in the atmosphere. The resulting catalyst was designated CuO X /PC-1。
The activity of the catalyst in synthesizing dimethyl carbonate by liquid phase oxidative carbonylation of methanol was examined by using a 100mL autoclave. 10mL of methanol and 0.3g of catalyst were charged into a reactor, and CO at 3.6MPa and O at 0.4MPa were charged at room temperature 2 The reaction was carried out at 300rpm at 120℃for 2 hours, then cooled to room temperature and the product composition was analyzed by gas chromatography. Dimethyl carbonate space-time yield 413 mg.g -1 ·h -1 Dimethyl carbonate selectivity was 100%.
Example 4:
a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidization and carbonylation of methanol is MOFs derivative which is CuO obtained by Cu-MOF calcination X Dispersed on a carbon carrier, the catalyst is used in an amount of 1.3% by mass of methanol.
The preparation method of the catalyst for synthesizing the dimethyl carbonate by liquid-phase oxidative carbonylation of methanol comprises the following steps:
s101, 4.0g Cu (NO 3 ) 2 ·3H 2 O is dissolved in 15mL of deionized water to obtain solution A;
s102, H2.5 g 3 BTC and 1.4g PVP are dissolved in 125mL of mixed solution of deionized water, ethanol and DMF to obtain solution B, wherein the volume ratio of the deionized water to the ethanol to the DMF is 1:1:1;
s103, adding the solution B into the solution A, stirring for 10min, and fully and uniformly mixing to obtain a suspension C;
s104, transferring the suspension C into a 200mL hydrothermal kettle, and placing the hydrothermal kettle in a 120 ℃ oven for reaction for 24 hours to obtain a D solution with blue precipitate;
s105, centrifuging the solution D, and washing the solution D for a plurality of times by using deionized water and ethanol until the supernatant is colorless;
s106, placing the washed product in a baking oven at 120 ℃ for drying overnight to obtain blue powdery Cu-BTC-PVP-2;
s107, cu-BTC-PVP-2 is placed in a tube furnace, and is added in N 2 Carbonizing at 400 ℃ for 2h at a heating rate of 5 ℃/min in the atmosphere. The resulting catalyst was designated CuO X /PC-2。
The activity of the catalyst in synthesizing dimethyl carbonate by liquid phase oxidative carbonylation of methanol was examined by using a 100mL autoclave. 10mL of methanol and 0.1g of catalyst were charged into a reaction vessel, and CO at 3.6MPa and O at 0.4MPa were charged at room temperature 2 The reaction was carried out at 300rpm at 120℃for 2 hours, then cooled to room temperature and the product composition was analyzed by gas chromatography. Space-time yield of dimethyl carbonate 1254 mg.g -1 ·h -1 Dimethyl carbonate selectivity was 100%.
Example 5:
a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidization and carbonylation of methanol is MOFs derivative which is CuO obtained by Cu-MOF calcination X Dispersed on a carbon carrier, the catalyst is used in an amount of 1.3% by mass of methanol.
The preparation method of the catalyst for synthesizing the dimethyl carbonate by liquid-phase oxidative carbonylation of methanol comprises the following steps:
s101, 4.0g Cu (NO 3 ) 2 ·3H 2 O is dissolved in 15mL of deionized water to obtain solution A;
s102, H2.5 g 3 BTC and 0.7g PVP are dissolved in 125mL of mixed solution of deionized water, ethanol and DMF to obtain solution B, wherein the volume ratio of the deionized water to the ethanol to the DMF is 1:1:1;
s103, adding the solution B into the solution A, stirring for 10min, and fully and uniformly mixing to obtain a suspension C;
s104, transferring the suspension C into a 200mL hydrothermal kettle, and placing the hydrothermal kettle in a 120 ℃ oven for reaction for 24 hours to obtain a D solution with blue precipitate;
s105, centrifuging the solution D, and washing the solution D for a plurality of times by using deionized water and ethanol until the supernatant is colorless;
s106, placing the washed product in a baking oven at 120 ℃ for drying overnight to obtain blue powdery Cu-BTC-PVP-3;
s107, cu-BTC-PVP-3 is placed in a tube furnace, and is added in N 2 Carbonizing at 400 ℃ for 2h at a heating rate of 5 ℃/min in the atmosphere. The resulting catalyst was designated CuO X /PC-3。
The activity of the catalyst in synthesizing dimethyl carbonate by liquid phase oxidative carbonylation of methanol was examined by using a 100mL autoclave. 10mL of methanol and 0.1g of catalyst were charged into a reaction vessel, and CO at 3.6MPa and O at 0.4MPa were charged at room temperature 2 The reaction was carried out at 300rpm at 120℃for 2 hours, then cooled to room temperature and the product composition was analyzed by gas chromatography. Dimethyl carbonate space-time yield 1295 mg.g -1 ·h -1 Dimethyl carbonate selectivity was 100%.
Example 6:
a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidization and carbonylation of methanol is MOFs derivative which is CuO obtained by Cu-MOF calcination X Dispersed on a carbon carrier, the catalyst is used in an amount of 1.3% by mass of methanol.
The preparation method of the catalyst for synthesizing the dimethyl carbonate by liquid-phase oxidative carbonylation of methanol comprises the following steps:
s101, 4.0g Cu (NO 3 ) 2 ·3H 2 O is dissolved in 15mL of deionized water to obtain solution A;
s102, H2.5 g 3 BTC and 0.3g PVP are dissolved in 125mL of mixed solution of deionized water, ethanol and DMF to obtain solution B, wherein the volume ratio of the deionized water to the ethanol to the DMF is 1:1:1;
s103, adding the solution B into the solution A, stirring for 10min, and fully and uniformly mixing to obtain a suspension C;
s104, transferring the suspension C into a 200mL hydrothermal kettle, and placing the hydrothermal kettle in a 120 ℃ oven for reaction for 24 hours to obtain a D solution with blue precipitate;
s105, centrifuging the solution D, and washing the solution D for a plurality of times by using deionized water and ethanol until the supernatant is colorless;
s106, placing the washed product in a baking oven at 120 ℃ for drying overnight to obtain blue powdery Cu-BTC-PVP-4;
s107, cu-BTC-PVP-4 is placed in a tube furnace, and is added in N 2 Carbonizing at 400 ℃ for 2h at a heating rate of 5 ℃/min in the atmosphere. The resulting catalyst was designated CuO X /PC-4。
The activity of the catalyst in synthesizing dimethyl carbonate by liquid phase oxidative carbonylation of methanol was examined by using a 100mL autoclave. 10mL of methanol and 0.1g of catalyst were charged into a reaction vessel, and CO at 3.6MPa and O at 0.4MPa were charged at room temperature 2 The reaction was carried out at 300rpm at 120℃for 2 hours, then cooled to room temperature and the product composition was analyzed by gas chromatography. Dimethyl carbonate space-time yield 1029mg.g -1 ·h -1 Dimethyl carbonate selectivity was 100%.
Example 7:
a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidization and carbonylation of methanol is MOFs derivative which is CuO obtained by Cu-MOF calcination X Dispersed on a carbon carrier, the catalyst is used in an amount of 1.3% by mass of methanol.
The preparation method of the catalyst for synthesizing the dimethyl carbonate by liquid-phase oxidative carbonylation of methanol comprises the following steps:
s101, 4.0g Cu(NO 3 ) 2 ·3H 2 O is dissolved in 15mL of deionized water to obtain solution A;
s102, H2.5 g 3 BTC is dissolved in 125mL of mixed solution of deionized water, ethanol and DMF to obtain solution B, wherein the volume ratio of deionized water to ethanol to DMF is 1:1:1;
s103, adding the solution B into the solution A, stirring for 10min, and fully and uniformly mixing to obtain a suspension C;
s104, transferring the suspension C into a 200mL hydrothermal kettle, and placing the hydrothermal kettle in a 120 ℃ oven for reaction for 24 hours to obtain a D solution with blue precipitate;
s105, centrifuging the solution D, and washing the solution D for a plurality of times by using deionized water and ethanol until the supernatant is colorless;
s106, placing the washed product in a baking oven at 120 ℃ for drying overnight to obtain blue powdery Cu-BTC;
s107, placing Cu-BTC in a tube furnace, and adding the Cu-BTC in N 2 Carbonizing at 400 ℃ for 2h at a heating rate of 5 ℃/min in the atmosphere. The resulting catalyst was designated CuO X /C-400。
The activity of the catalyst in synthesizing dimethyl carbonate by liquid phase oxidative carbonylation of methanol was examined by using a 100mL autoclave. 10mL of methanol and 0.1g of catalyst were charged into a reaction vessel, and CO at 3.6MPa and O at 0.4MPa were charged at room temperature 2 The reaction was carried out at 300rpm at 120℃for 2 hours, then cooled to room temperature and the product composition was analyzed by gas chromatography. Space-time yield of dimethyl carbonate 948mg.g -1 ·h -1 Dimethyl carbonate selectivity was 100%.
Example 8:
a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidization and carbonylation of methanol is MOFs derivative which is CuO obtained by Cu-MOF calcination X Dispersed on a carbon carrier, the catalyst is used in an amount of 1.3% by mass of methanol.
The preparation method of the catalyst for synthesizing the dimethyl carbonate by liquid-phase oxidative carbonylation of methanol comprises the following steps:
s101, 4.0g Cu (NO 3 ) 2 ·3H 2 O is dissolved in 15mL of deionized water to obtainSolution A;
s102, H2.5 g 3 BTC is dissolved in 125mL of mixed solution of deionized water, ethanol and DMF to obtain solution B, wherein the volume ratio of deionized water to ethanol to DMF is 1:1:1;
s103, adding the solution B into the solution A, stirring for 10min, and fully and uniformly mixing to obtain a suspension C;
s104, transferring the suspension C into a 200mL hydrothermal kettle, and placing the hydrothermal kettle in a 120 ℃ oven for reaction for 24 hours to obtain a D solution with blue precipitate;
s105, centrifuging the solution D, and washing the solution D for a plurality of times by using deionized water and ethanol until the supernatant is colorless;
s106, placing the washed product in a baking oven at 120 ℃ for drying overnight to obtain blue powdery Cu-BTC;
s107, placing Cu-BTC in a tube furnace, and adding the Cu-BTC in N 2 Carbonizing at 300 ℃ for 2h at a heating rate of 5 ℃/min in the atmosphere. The resulting catalyst was designated CuO X /C-300。
The activity of the catalyst in synthesizing dimethyl carbonate by liquid phase oxidative carbonylation of methanol was examined by using a 100mL autoclave. 10mL of methanol and 0.1g of catalyst were charged into a reaction vessel, and CO at 3.6MPa and O at 0.4MPa were charged at room temperature 2 The reaction was carried out at 300rpm at 120℃for 2 hours, then cooled to room temperature and the product composition was analyzed by gas chromatography. Dimethyl carbonate space-time yield 1166mg.g -1 ·h -1 Dimethyl carbonate selectivity was 100%.
Example 9:
a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidization and carbonylation of methanol is MOFs derivative which is CuO obtained by Cu-MOF calcination X Dispersed on a carbon carrier, the catalyst is used in an amount of 1.3% by mass of methanol.
The preparation method of the catalyst for synthesizing the dimethyl carbonate by liquid-phase oxidative carbonylation of methanol comprises the following steps:
s101, 4.0g Cu (NO 3 ) 2 ·3H 2 O is dissolved in 15mL of deionized water to obtain solution A;
s102, H2.5 g 3 BTC is dissolved in 125mL of mixed solution of deionized water, ethanol and DMF to obtain solution B, wherein the volume ratio of deionized water to ethanol to DMF is 1:1:1;
s103, adding the solution B into the solution A, stirring for 10min, and fully and uniformly mixing to obtain a suspension C;
s104, transferring the suspension C into a 200mL hydrothermal kettle, and placing the hydrothermal kettle in a 120 ℃ oven for reaction for 24 hours to obtain a D solution with blue precipitate;
s105, centrifuging the solution D, and washing the solution D for a plurality of times by using deionized water and ethanol until the supernatant is colorless;
s106, placing the washed product in a baking oven at 120 ℃ for drying overnight to obtain blue powdery Cu-BTC;
s107, placing Cu-BTC in a tube furnace, and adding the Cu-BTC in N 2 Carbonizing at 500 ℃ for 2h at a heating rate of 5 ℃/min in the atmosphere. The resulting catalyst was designated CuO X /C-500。
The activity of the catalyst in synthesizing dimethyl carbonate by liquid phase oxidative carbonylation of methanol was examined by using a 100mL autoclave. 10mL of methanol and 0.1g of catalyst were charged into a reaction vessel, and CO at 3.6MPa and O at 0.4MPa were charged at room temperature 2 The reaction was carried out at 300rpm at 120℃for 2 hours, then cooled to room temperature and the product composition was analyzed by gas chromatography. Dimethyl carbonate space-time yield 634 mg.g -1 ·h -1 Dimethyl carbonate selectivity was 100%.
As shown in table 1, the evaluation results of the reaction of synthesizing dimethyl carbonate by liquid phase oxidative carbonylation of methanol by the catalyst:
table 1: evaluation results of catalyst in methanol liquid phase oxidative carbonylation to dimethyl carbonate reaction table
As can be seen from the above table, the space-time yield of dimethyl carbonate is up to 1295 mg.g -1 ·h -1 Is superior to the existing catalysts, such as Cu 2 And an O/AC catalyst, wherein the selectivity of the dimethyl carbonate is 100%, and no by-product is generated basically.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to assist in understanding the methods of the present invention and the core ideas thereof; also, it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A catalyst for synthesizing dimethyl carbonate by liquid-phase oxidization and carbonylation of methanol is prepared from MOFs derivative, metal oxide (CuO) and carbon carrier through dispersing the metal oxide on said carbon carrier X 。
2. The catalyst for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol according to claim 1, wherein the MOFs derivative is CuO obtained by Cu-MOF calcination X Dispersed on a carbon support.
3. The catalyst for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol according to claim 1, wherein the catalyst has a topological structure and a specific surface area of 10-150 m 2 ·g -1 The surface of the catalyst is distributed with mesoporous with the pore diameter of 4-35 nm.
4. A process for preparing a catalyst for the liquid phase oxidative carbonylation of methanol to dimethyl carbonate according to any one of claims 1 to 3 comprising the steps of:
s101, dissolving copper salt in deionized water to obtain a solution A;
s102, H 3 Dissolution of BTC and PVP in De-ionizationObtaining a solution B in a mixed solution of the child water, the ethanol and the DMF;
s103, adding the solution B into the solution A, stirring, and fully and uniformly mixing to obtain a suspension C;
s104, transferring the suspension C into a hydrothermal kettle, and reacting for 12-36 hours at 100-150 ℃ to obtain a D solution with blue precipitate;
s105, centrifuging the solution D, and washing until the supernatant is colorless;
s106, drying the washed product to obtain blue powdery Cu-MOF;
s107 Cu-MOF at N 2 Carbonizing at high temperature under atmosphere to obtain the catalyst MOFs derivative.
5. The method for preparing a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol according to claim 4, wherein the copper salt comprises Cu (NO 3 ) 2 ·3H 2 O。
6. The method for preparing a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol according to claim 4, wherein the volume ratio of deionized water, ethanol and DMF in step S102 is 1:1:0-1.
7. The method for preparing a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol according to claim 4, wherein H in step S102 3 The mass ratio of BTC to PVP is 1:0-1.1.
8. The process for preparing a catalyst for the liquid-phase oxidative carbonylation of methanol to dimethyl carbonate according to claim 4, wherein the copper salt in suspension C is mixed with H 3 The mole ratio of BTC is 1.5-2: 1.
9. the method for preparing a catalyst for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol according to claim 4, wherein the carbonization temperature in step S107 is 300-500 ℃, the heating rate is 3-6 ℃/min, and the carbonization time is 1-3 h.
10. Use of the catalyst for synthesizing dimethyl carbonate by liquid phase oxidative carbonylation of methanol according to claim 1, wherein the catalyst is used for synthesizing dimethyl carbonate by liquid phase oxidative carbonylation of methanol, and the catalyst is used in an amount of 1.3-3.8% of the mass of methanol.
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