CN111085220A - Catalyst, preparation method thereof and dimethyl carbonate synthesis method - Google Patents
Catalyst, preparation method thereof and dimethyl carbonate synthesis method Download PDFInfo
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- CN111085220A CN111085220A CN201911387258.0A CN201911387258A CN111085220A CN 111085220 A CN111085220 A CN 111085220A CN 201911387258 A CN201911387258 A CN 201911387258A CN 111085220 A CN111085220 A CN 111085220A
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- dimethyl carbonate
- spinel
- precursor compound
- spinel carrier
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- 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 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 69
- 239000011029 spinel Substances 0.000 claims abstract description 69
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229910002666 PdCl2 Inorganic materials 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 150000001805 chlorine compounds Chemical group 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 28
- 238000000498 ball milling Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 9
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 9
- 229940126062 Compound A Drugs 0.000 claims description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000012495 reaction gas Substances 0.000 claims 1
- 230000006315 carbonylation Effects 0.000 abstract description 11
- 238000005810 carbonylation reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 230000003993 interaction Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 24
- 239000002002 slurry Substances 0.000 description 24
- 239000012798 spherical particle Substances 0.000 description 24
- 239000007788 liquid Substances 0.000 description 23
- 239000000969 carrier Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 101150003085 Pdcl gene Proteins 0.000 description 11
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000005677 organic carbonates Chemical class 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910010215 LiAl5O8 Inorganic materials 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- -1 magnesium aluminate Chemical class 0.000 description 1
- YEYZNBKNDWPFSQ-UHFFFAOYSA-N methanol;urea Chemical compound OC.NC(N)=O YEYZNBKNDWPFSQ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
-
- 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
- B01J23/005—Spinels
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
Abstract
The invention relates to the field of industrial catalysis, and particularly discloses a catalyst, a preparation method thereof and a dimethyl carbonate synthesis method, wherein the catalyst comprises the following raw materials: spinel carrier, active component and auxiliary agent; wherein the auxiliary agent is a chloride of a transition metal element, and the active component is PdCl2The Pd content in the catalyst is 0.1-2 wt%. The catalyst provided by the embodiment of the invention has a stable structure, the spinel carrier and the active component form strong interaction, the activity and the selectivity of the catalyst are effectively improved, and the catalyst has higher methyl nitrite conversion rate and dimethyl carbonate selectivity when being used for synthesizing dimethyl carbonate, thereby solving the problem of the existing methyl nitrite gas-phase carbonylation methodThe catalyst for preparing the dimethyl carbonate has the problems of low activity and selectivity; the provided preparation method has the advantages of simplicity, reliability and simple production equipment, and is suitable for industrial large-scale production.
Description
Technical Field
The invention relates to the field of industrial catalysis, in particular to a catalyst, a preparation method thereof and a dimethyl carbonate synthesis method.
Background
Dimethyl carbonate (DMC) is an organic compound with low toxicity, excellent environmental protection performance and wide application, and has a great demand in the fields of chemical industry and energy. The dimethyl carbonate can be subjected to methylation, carbonylation, methyl esterification and other reactions to generate various fine chemicals with high added values, and is widely applied to the fields of organic synthesis, pharmaceutical synthesis, engineering plastics, green additives, detergents of color television picture tubes and the like. In recent years, with the rapid development of the lithium ion battery industry, the demand of DMC has also sharply increased as one of the main components of the lithium ion battery electrolyte.
At present, the methods for synthesizing dimethyl carbonate mainly include an ester exchange method, a methanol liquid-phase oxidation carbonylation method, a methyl nitrite gas-phase carbonylation method, a urea methanol method and the like. The methyl nitrite gas-phase carbonylation method has high atom utilization rate, accords with the green energy category, has relatively low production cost and is suitable for large-scale industrial production because the product can be recycled in the reaction.
However, in the synthesis of dimethyl carbonate by methyl nitrite gas-phase carbonylation method, the used catalyst has the problems of low activity and selectivity.
Disclosure of Invention
The embodiment of the invention aims to provide a catalyst, a preparation method thereof and a dimethyl carbonate synthesis method, so as to solve the problem that the activity and the selectivity of the existing catalyst for synthesizing dimethyl carbonate by a methyl nitrite gas-phase carbonylation method are not high in the background technology.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a catalyst comprising the following starting materials: spinel carrier, active component and auxiliary agent; wherein the auxiliary agent is a chloride of a transition metal element, and the active component is PdCl2And the Pd content in the catalyst is 0.1-2 wt%.
AsThe further scheme of the invention is as follows: the spinel carrier comprises the following raw materials: a precursor compound A and a precursor compound B; wherein the precursor compound A is MgO, ZnO or Li2O, the precursor compound B is Al2O3And the molar ratio of the precursor compound A to the precursor compound B is 0.9-1.1: 1-2.5.
As a still further scheme of the invention: the preparation method of the spinel carrier comprises the following steps: and weighing the precursor compound A and the precursor compound B according to a ratio, mixing, adding water, performing ball milling, preparing particles, and roasting to obtain the spinel carrier.
As a still further scheme of the invention: in the preparation method of the spinel carrier, the roasting temperature is 800-1500 ℃.
As a still further scheme of the invention: the shape of the particles may be spherical, cylindrical, rectangular parallelepiped, etc., and is not particularly limited.
Preferably, the shape of the particles may be spherical.
As a still further scheme of the invention: the spinel carrier is magnesium aluminate spinel MgAl2O4ZnAl, Zn-Al spinel2O4Or lithium aluminum spinel LiAl5O8One kind of (1).
As a still further scheme of the invention: the transition metal element is selected from one or more of Cu, Co, Ni or Ce.
Preferably, the transition metal element is Cu.
As a still further scheme of the invention: the content of the transition metal element in the catalyst is 0.1-5 wt%.
Another object of an embodiment of the present invention is to provide a method for preparing a catalyst, including the following steps:
1) weighing the active component and the auxiliary agent according to a ratio, adding water, uniformly mixing, and adjusting the pH value to 0.2-1.0 to obtain a mixed solution;
2) adding the spinel carrier into the mixed solution obtained in the step 1), soaking, drying and roasting to obtain the catalyst.
As a still further scheme of the invention: the pH is adjusted by any reagent for pH adjustment that is conventional in the art, such as ammonia, sodium hydroxide solution, dilute hydrochloric acid, potassium hydroxide solution, and the like, without limitation.
Preferably, the pH adjustment is performed by adding hydrochloric acid to bring the pH of the mixed solution to 0.2 to 1.0.
As a still further scheme of the invention: in the step 1), the concentration of the active component in the mixed solution is 0.025-0.5mol/L, and the concentration of the transition metal element in the auxiliary agent in the mixed solution is 0.04-2 mol/L.
As a still further scheme of the invention: in the step 2), the dipping temperature is 25-80 ℃, and the dipping time is 2-48 hours.
As a still further scheme of the invention: in the step 2), the roasting temperature is 150-400 ℃, and the roasting time is more than 2 hours.
Another object of the embodiments of the present invention is to provide a catalyst prepared by the above method for preparing a catalyst.
Another objective of the embodiments of the present invention is to provide a method for synthesizing dimethyl carbonate, where the method for synthesizing dimethyl carbonate uses the above catalyst, and specifically includes the following steps:
weighing the catalyst, and carrying out synthetic reaction by using MN (methyl nitrite) and carbon monoxide (CO) as reaction gases to obtain the dimethyl carbonate.
As a still further scheme of the invention: the space velocity of the carbon monoxide is 250-2500h-1The space velocity of the methyl nitrite is 250--1The temperature of the synthesis reaction is controlled at 100-150 ℃, and the reaction pressure of the synthesis reaction is controlled at 0.1-1 Mpa.
As a still further scheme of the invention: the synthesis method of the dimethyl carbonate also comprises the steps of adding nitrogen as balance gas and adding hydrogen chloride as chlorine supplement gas. The yield is improved by the dilution effect of nitrogen and the chlorine supplement effect of hydrogen chloride.
Preferably, the method for synthesizing the dimethyl carbonate comprises the following steps: adding the catalyst and the mixed raw material gas into a fixed reaction bed to carry out synthesis reaction, wherein the temperature of the synthesis reaction is controlled at 100-150 ℃, and the reaction pressure is controlled at 0.1-1 Mpa; wherein the mixed raw material gas is MN, CO and N2And HCl, wherein MN and CO are reaction gases, and N is2HCl is used as chlorine supplement gas as balance gas, wherein the space velocity of CO is 250--1The MN airspeed is 250-2500h-1HCl space velocity of 50-500ppm and N in mixed raw material gas2The concentration is 50% or more. Under the action of the catalyst, MN and CO are synthesized into DMC under low pressure.
The embodiment of the invention also aims to provide application of the catalyst in preparing organic carbonate. Wherein the organic carbonate can be propylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate and the like.
Compared with the prior art, the invention has the beneficial effects that:
the catalyst prepared by the embodiment of the invention has a stable structure, and the spinel carrier and the active components form strong interaction, so that the activity and the selectivity of the catalyst are effectively improved, when the catalyst is used for synthesizing dimethyl carbonate by a methyl nitrite gas-phase carbonylation method, the conversion rate of the methyl nitrite is over 70 percent, and the selectivity of the dimethyl carbonate can reach 90 percent, thereby solving the problem that the activity and the selectivity of the existing catalyst used for synthesizing the dimethyl carbonate by the methyl nitrite gas-phase carbonylation method are not high; the preparation method of the catalyst provided by the embodiment of the invention has the advantages of simplicity and reliability, simple production equipment and suitability for industrial large-scale production, the prepared catalyst has the advantages of stable structure, high compressive strength and long service life, and the catalyst can be used at low temperature and low pressure and has higher space-time yield and selectivity.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The catalyst is prepared by the following specific steps:
1) weighing 10mol of MgO powder and 10mol of Al2O3Mixing the powders, adding a small amount of water, stirring, placing in a ball mill, ball-milling to slurry, putting the slurry after ball-milling into a ball mill to prepare spherical particles, and roasting the spherical particles at 1100 ℃ for 5 hours to form spherical spinel carriers;
2) 50mmol of PdCl are weighed out2And 50mmol of CuCl2Adding the catalyst into water together, dissolving and mixing the catalyst and the water uniformly to prepare 400mL of liquid, adding hydrochloric acid to enable the pH value of the liquid to be 1 to obtain a mixed solution, heating the mixed solution to 80 ℃, putting 200g of the spinel carrier into the mixed solution, soaking for 2 hours, taking out and drying the spinel carrier, and roasting at 200 ℃ for 4 hours to obtain the catalyst, wherein the catalyst is marked as a sample 1, and the load of Pd in the sample 1 is 0.45 wt%, and the load of Cu in the sample 1 is 0.32 wt%.
Example 2
The catalyst is prepared by the following specific steps:
1) weighing 10mol of ZnO powder and 10mol of Al2O3Mixing the powders, adding a small amount of water, stirring, placing in a ball mill, ball-milling to slurry, putting the slurry after ball-milling into a ball mill to prepare spherical particles, and roasting the spherical particles at 1500 ℃ for 5 hours to form spherical spinel carriers;
2) 50mmol of PdCl are weighed out2And 50mmol of CoCl2Adding into water, dissolving and mixing to obtain 400mL liquid, adding hydrochloric acid to adjust pH to 0.5 to obtain mixed solution, heating the mixed solution to 60 deg.C, adding 200g spinel carrier into the mixed solution, soaking for 8 hr, taking out, drying, and roasting at 150 deg.C for 24 hrThe catalyst was obtained and designated as sample 2, wherein the loading of Pd in sample 2 was 0.5 wt% and the loading of Co was 0.35 wt%.
Example 3
The catalyst is prepared by the following specific steps:
1) weighing 10mol of Li2O powder and 25mol of Al2O3Mixing the powders, adding a small amount of water, stirring, placing in a ball mill, ball-milling to slurry, putting the slurry after ball-milling into a ball mill to prepare spherical particles, and roasting the spherical particles at 800 ℃ for 5 hours to form spherical spinel carriers;
2) 50mmol of PdCl are weighed out2And 50mmol of NiCl2Adding the catalyst into water together, dissolving and mixing the catalyst and the water uniformly to prepare 400mL of liquid, adding hydrochloric acid to enable the pH value of the liquid to be 0.2 to obtain a mixed solution, heating the mixed solution to 25 ℃, putting 200g of spinel carrier into the mixed solution, soaking the spinel carrier for 48 hours, taking out the spinel carrier, drying the spinel carrier, and roasting the spinel carrier for 2 hours at 400 ℃ to obtain the catalyst, namely a sample 3, wherein the load of Pd in the sample 3 is 0.48 wt%, and the load of Ni in the sample 3 is 0.34 wt%.
Example 4
The catalyst is prepared by the following specific steps:
1) weighing 10mol of MgO powder and 10mol of Al2O3Mixing the powders, adding a small amount of water, stirring, placing in a ball mill, ball-milling to slurry, putting the slurry after ball-milling into a ball mill to prepare spherical particles, and roasting the spherical particles at 1100 ℃ for 5 hours to form spherical spinel carriers;
2) 50mmol of PdCl are weighed out2And 50mmol of CeCl3Adding the catalyst into water together, dissolving and mixing the catalyst and the water uniformly to prepare 400mL of liquid, adding hydrochloric acid to enable the pH value of the liquid to be 0.5 to obtain a mixed solution, heating the mixed solution to 60 ℃, putting 200g of the spinel carrier into the mixed solution, soaking the spinel carrier for 10 hours, taking out the spinel carrier, drying the spinel carrier, and roasting the spinel carrier for 4 hours at 200 ℃ to obtain the catalyst, namely a sample 4, wherein the load of Pd in the sample 4 is 0.5 wt%, and the load of Ce in the sample 4 is 0.65 wt%.
Example 5
The catalyst is prepared by the following specific steps:
1) weighing 10mol of ZnO powder and 10mol of Al2O3Mixing the powders, adding a small amount of water, stirring, placing in a ball mill, ball-milling to slurry, putting the slurry after ball-milling into a ball mill to prepare spherical particles, and roasting the spherical particles at 1500 ℃ for 5 hours to form spherical spinel carriers;
2) 50mmol of PdCl are weighed out2And 50mmol of CuCl2Adding the catalyst into water together, dissolving and mixing the catalyst and the water uniformly to prepare 400mL of liquid, adding hydrochloric acid to enable the pH value of the liquid to be 0.5 to obtain a mixed solution, heating the mixed solution to 80 ℃, putting 200g of the spinel carrier into the mixed solution, soaking for 5 hours, taking out, drying, and roasting at 200 ℃ for 4 hours to obtain the catalyst, namely a sample 5, wherein the load of Pd in the sample 5 is 0.5 wt%, and the load of Cu is 0.35 wt%.
Example 6
The catalyst is prepared by the following specific steps:
1) weighing 10mol of Li2O powder and 25mol of Al2O3Mixing the powders, adding a small amount of water, stirring, placing in a ball mill, ball-milling to slurry, putting the slurry after ball-milling into a ball mill to prepare spherical particles, and roasting the spherical particles at 800 ℃ for 5 hours to form spherical spinel carriers;
2) 50mmol of PdCl are weighed out2And 50mmol of CuCl2Adding the catalyst into water together, dissolving and mixing the catalyst and the water uniformly to prepare 400mL of liquid, adding hydrochloric acid to enable the pH value of the liquid to be 0.5 to obtain a mixed solution, heating the mixed solution to 80 ℃, putting 200g of the spinel carrier into the mixed solution, soaking the spinel carrier for 5 hours, taking out the spinel carrier, drying the spinel carrier, and roasting the spinel carrier for 4 hours at 200 ℃ to obtain the catalyst, namely a sample 6, wherein the load of Pd in the sample 6 is 0.5 wt%, and the load of Cu in the sample 6 is 0.35 wt%.
Example 7
The catalyst is prepared by the following specific steps:
1) weighing 10mol of Li2O powder and 10mol of Al2O3Mixing the powders, adding a small amount of water, stirring, placing in a ball mill, ball-milling to slurry, putting the slurry after ball-milling into a ball mill to prepare spherical particles, and roasting the spherical particles at 800 ℃ for 5 hours to form spherical spinel carriers;
2) weighing 10mmol of PdCl2And 10mmol of CuCl2Adding the catalyst and the catalyst into water together, dissolving and mixing the catalyst and the water uniformly to prepare 400mL of liquid, adding hydrochloric acid to enable the pH value of the liquid to be 0.5 to obtain a mixed solution, heating the mixed solution to 80 ℃, putting 200g of the spinel carrier into the mixed solution, soaking the spinel carrier for 5 hours, taking out the spinel carrier, drying the spinel carrier, and roasting the spinel carrier for 4 hours at 200 ℃ to obtain the catalyst, namely a sample 7, wherein the load of Pd in the sample 7 is 0.1 wt%, and the load of Cu in the sample 7 is 0.1 wt%.
Example 8
The catalyst is prepared by the following specific steps:
1) weighing 10mol of MgO powder and 10mol of Al2O3Mixing the powders, adding a small amount of water, stirring, placing in a ball mill, ball-milling to slurry, putting the slurry after ball-milling into a ball mill to prepare spherical particles, and roasting the spherical particles at 1100 ℃ for 5 hours to form spherical spinel carriers;
2) weighing 160mmol of PdCl2And 800mmol of CuCl2Adding the catalyst into water together, dissolving and mixing the catalyst and the water uniformly to prepare 400mL of liquid, adding hydrochloric acid to enable the pH value of the liquid to be 0.5 to obtain a mixed solution, heating the mixed solution to 80 ℃, putting 200g of the spinel carrier into the mixed solution, soaking for 5 hours, taking out, drying, and roasting at 200 ℃ for 4 hours to obtain the catalyst, namely a sample 8, wherein the load of Pd in the sample 8 is 2wt%, and the load of Cu is 5 wt%.
Example 9
The catalyst is prepared by the following specific steps:
1) weighing 10mol of Li2O powder and 25mol of Al2O3Mixing the powders, adding small amount of water, stirring, and standingBall-milling the mixture in a ball mill to form slurry, putting the slurry after ball-milling into a ball mill to prepare spherical particles, and roasting the spherical particles at 800 ℃ for 5 hours to form spherical spinel carriers;
2) 50mmol of PdCl are weighed out2And 20mmol of CuCl220mmol of NiCl210mmol of CeCl3Adding the materials into water together, dissolving and mixing the materials uniformly to prepare 400mL of liquid, adding hydrochloric acid to enable the pH value of the liquid to be 0.5 to obtain a mixed solution, heating the mixed solution to 60 ℃, putting 200g of the spinel carrier into the mixed solution, soaking for 5 hours, taking out and drying, and roasting at 200 ℃ for 4 hours to obtain the catalyst, namely a sample 9, wherein the load of Pd in the sample 9 is 0.46 wt%, the load of Cu is 0.18 wt%, the load of Ni is 0.14 wt%, and the load of Ce is 0.14 wt%.
Example 10
The catalyst is prepared by the following specific steps:
1) weighing 10mol of Li2O powder and 25mol of Al2O3Mixing the powders, adding a small amount of water, stirring, placing in a ball mill, ball-milling to slurry, putting the slurry after ball-milling into a ball mill to prepare spherical particles, and roasting the spherical particles at 800 ℃ for 5 hours to form spherical spinel carriers;
2) 50mmol of PdCl are weighed out2And 25mmol of CuCl225mmol of CoCl2Adding the materials into water together, dissolving and mixing the materials uniformly to prepare 400mL of liquid, adding hydrochloric acid to enable the pH value of the liquid to be 0.5 to obtain a mixed solution, heating the mixed solution to 70 ℃, putting 200g of the spinel carrier into the mixed solution, soaking for 5 hours, taking out and drying, and roasting at 150 ℃ for 4 hours to obtain the catalyst, namely a sample 10, wherein the load of Pd in the sample 10 is 0.5 wt%, the load of Cu is 0.2 wt%, and the load of Co is 0.18 wt%.
Example 11
The catalyst is prepared by the following specific steps:
1) weighing 10mol of Li2O powder and 25mol of Al2O3Mixing the powders, adding a small amount of water, stirring, placing in a ball mill, ball-milling to slurry, putting the slurry after ball-milling into a ball mill to prepare spherical particles, and roasting the spherical particles at 800 ℃ for 5 hours to form spherical spinel carriers;
2) 50mmol of PdCl are weighed out2And 10mmol of CeCl340mmol of CoCl2Adding the catalyst into water together, dissolving and mixing the catalyst and the water uniformly to prepare 400mL of liquid, adding hydrochloric acid to enable the pH value of the liquid to be 0.5 to obtain a mixed solution, heating the mixed solution to 60 ℃, putting 200g of the spinel carrier into the mixed solution, soaking the spinel carrier for 5 hours, taking out the spinel carrier, drying the spinel carrier, and roasting the spinel carrier for 4 hours at 200 ℃ to obtain the catalyst, wherein the catalyst is marked as a sample 11, and the load of Pd in the sample 11 is 0.5 wt%, the load of Ce is 0.14 wt%, and the load of Co is 0.0.27 wt%.
Example 12
The catalyst is prepared by the following specific steps:
1) weighing 10mol of Li2O powder and 25mol of Al2O3Mixing the powders, adding a small amount of water, stirring, placing in a ball mill, ball-milling to slurry, putting the slurry after ball-milling into a ball mill to prepare spherical particles, and roasting the spherical particles at 800 ℃ for 5 hours to form spherical spinel carriers;
2) 50mmol of PdCl are weighed out2And 40mmol of CuCl210mmol of CeCl3Adding the catalyst into water together, dissolving and mixing the catalyst and the water uniformly to prepare 400mL of liquid, adding hydrochloric acid to enable the pH value of the liquid to be 0.5 to obtain a mixed solution, heating the mixed solution to 80 ℃, putting 200g of the spinel carrier into the mixed solution, soaking for 5 hours, taking out and drying the spinel carrier, and roasting at 200 ℃ for 4 hours to obtain the catalyst, namely a sample 12, wherein the load of Pd in the sample 12 is 0.5 wt%, the load of Cu is 0.38 wt%, and the load of Ce is 0.14 wt%.
Performance testing
The catalysts prepared in examples 1 to 12 were evaluated for their catalytic performance by the following specific evaluation methods: the prepared catalyst is arranged in a fixed reaction bed, wherein the fixed reaction is carried outThe inner diameter of the bed is 25mm, and the middle of the fixed reaction bed is filled with 100cm3The catalyst (bulk density 1.3 g/cm)3) 70g of inert ceramic alumina is respectively filled in the upper part and the lower part of a catalyst bed of the fixed reaction bed; the reaction raw materials are MN, CO and N2HCl and MN at a space velocity of 500h-1The space velocity of CO is 500h-1，N2Space velocity of 2000h-1The method comprises the following steps of (1) controlling the space velocity of HCl to be 100ppm, controlling the reaction temperature to be 120 +/-1 ℃, controlling the reaction pressure to be 0.2 +/-0.02 MPa, and continuing the reaction for 6 hours, and analyzing a reaction product according to gas chromatography to calculate the catalytic activity of the catalyst, wherein the DMC selectivity calculation method is directly obtained by analyzing the DMC content in the product through the gas chromatography;
the conversion of MN is calculated as:
the space-time yield calculation formula is:
the specific evaluation results of the catalytic performance are shown in table 1.
TABLE 1 evaluation results of catalytic Properties
As can be seen from the comparison of the data in Table 1, the spinel carrier and the active component form strong interaction, so that the activity and the selectivity of the catalyst are improved, and the catalyst has the advantages of stable structure, high compressive strength and long service life, and the spinel carrier is used as the carrier, and PdCl is used as the carrier2The catalyst which is used as an active component and takes the chloride of the transition metal element as an auxiliary agent can be used for synthesizing dimethyl carbonate by a methyl nitrite gas-phase carbonylation method.
The invention has the advantages that the catalyst prepared by the embodiment of the invention has stable structure, the spinel carrier is selected to load the active component, the spinel carrier and the active component form strong interaction, when the catalyst is used for synthesizing dimethyl carbonate by a methyl nitrite gas-phase carbonylation method, the conversion rate of methyl nitrite can be more than 70%, and the selectivity of dimethyl carbonate can reach 90%, so that the activity and the selectivity of the catalyst are effectively improved, and the catalyst has the advantages of stable structure, high compressive strength and long service life. Has wide market prospect.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. A catalyst, comprising the following raw materials: spinel carrier, active component and auxiliary agent; wherein the auxiliary agent is a chloride of a transition metal element, and the active component is PdCl2And the Pd content in the catalyst is 0.1-2 wt%.
2. The catalyst of claim 1, wherein the spinel support comprises the following raw materials: a precursor compound A and a precursor compound B; wherein the precursor compound A is MgO, ZnO or Li2O, the precursor compound B is Al2O3And the molar ratio of the precursor compound A to the precursor compound B is 0.9-1.1: 1-2.5.
3. The catalyst according to claim 2, wherein the spinel carrier is prepared by a method comprising: and weighing the precursor compound A and the precursor compound B according to a ratio, mixing, adding water, performing ball milling, preparing particles, and roasting to obtain the spinel carrier.
4. The catalyst as claimed in claim 3, wherein the temperature of the calcination is 800-1500 ℃ in the preparation method of the spinel carrier.
5. The catalyst of claim 1, wherein the transition metal element is selected from one or more of Cu, Co, Ni, or Ce.
6. The catalyst according to claim 1, wherein the transition metal element is contained in the catalyst in an amount of 0.1 to 5 wt%.
7. A process for preparing a catalyst as claimed in any one of claims 1 to 6, comprising the steps of:
1) weighing the active component and the auxiliary agent according to a proportion, adding water, uniformly mixing, and adjusting the pH value to 0.2-1.0 to obtain a mixed solution;
2) adding the spinel carrier into the mixed solution obtained in the step 1), soaking, drying and roasting to obtain the catalyst.
8. A catalyst prepared by the method of claim 7.
9. A method for synthesizing dimethyl carbonate, which is characterized in that the method for synthesizing dimethyl carbonate adopts the catalyst as claimed in claim 1, 2, 3, 4, 5, 6 or 8, and comprises the following steps: weighing the catalyst, and carrying out synthetic reaction by using methyl nitrite and carbon monoxide as reaction gases to obtain the dimethyl carbonate.
10. The dimethyl carbonate synthesis method according to claim 9, further comprising: nitrogen gas was added to the reaction gas as an equilibrium gas, and hydrogen chloride was added as a chlorine replenishing agent gas.
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