CN110227471A - A kind of methanol/ethanol intersects C-C key coupling catalyst and preparation method thereof - Google Patents
A kind of methanol/ethanol intersects C-C key coupling catalyst and preparation method thereof Download PDFInfo
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- CN110227471A CN110227471A CN201910563040.XA CN201910563040A CN110227471A CN 110227471 A CN110227471 A CN 110227471A CN 201910563040 A CN201910563040 A CN 201910563040A CN 110227471 A CN110227471 A CN 110227471A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 130
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 230000008878 coupling Effects 0.000 title claims abstract description 17
- 238000010168 coupling process Methods 0.000 title claims abstract description 17
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 14
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 14
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 230000009466 transformation Effects 0.000 claims abstract description 7
- 229910002535 CuZn Inorganic materials 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 10
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000006880 cross-coupling reaction Methods 0.000 claims description 6
- 238000005275 alloying Methods 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001051 Magnalium Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims 5
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 claims 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000007790 solid phase Substances 0.000 claims 1
- 239000002028 Biomass Substances 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 36
- 229960004756 ethanol Drugs 0.000 description 33
- 239000000047 product Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- GTBPUYSGSDIIMM-UHFFFAOYSA-N phosphane;ruthenium Chemical compound P.[Ru] GTBPUYSGSDIIMM-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/23—
-
- B01J35/393—
-
- B01J35/399—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
- C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
A kind of methanol/ethanol intersects C-C coupling catalyst and preparation method thereof, and the invention belongs to biomass catalyzing transformation technology fields.The catalyst is made of that (carrier metal can be Cu Monodispersed Cu particle and oxide carrier2+、Mg2+、Zn2+、Al3+、Ce3+、Ga3+), the catalyst is by hydrotalcite precursor through H2The transformation of atmosphere topology is made.Catalyst is made by the topology transformation in situ of hydrotalcite containing Cu, and advantage is that effect of acidity and basicity is adjustable, and Cu/Zn ratio is adjustable, forms CuZn alloy.Catalyst is applied to a kind of methanol/ethanol and intersects C-C coupling, using miniature fixed-bed reactor, reaction temperature is at 150~500 DEG C, reaction pressure is 0.1~3MPa, methanol/ethanol molar ratio is 2~20, it can be achieved that ethanol conversion 90%, C-C key coupled product selection 73%.
Description
Technical field
The invention belongs to biomass catalyzing transformation technology fields, and it is coupling catalysed to provide a kind of methanol/ethanol intersection C-C key
Agent and preparation method thereof.
Background technique
Bio-ethanol can be converted into a variety of useful chemicals with high-value-use, wherein intersecting C-C key by methanol/ethanol
Coupling may be implemented carbochain and increase to obtain high valuable chemicals C3+Aldehyde, C3+Alcohol etc..Methanol/ethanol intersects the coupling of C-C key and passes through
Guerbet approach carries out, and reaction process is there are C-O key coupled product and self condenses the competitive reactions such as C-C key coupled product way
Diameter, selectivity control C-C key cross-coupling, and avoiding C-O key cross-coupling is to realize C3+The highly selective key of product.
Wass seminar report ruthenium phosphine complex outside plus sodium methoxide under the conditions of realize 75% ethanol conversion and
C greater than 99%4Alcohol selectivity (Chem.Commun., 2016,52:5202-5204).Liu seminar is urged using support type Ir
Agent is adding K outside3PO4Under conditions of, realize 50% ethanol conversion and 90% C4Selectivity (the Green of alcohol
Chem.,2016,18:2811-2818).Fixed continuous process is more advantageous to realization industrialization, suitable for urging for continuous operation
Agent attracts attention.Methanol/ethanol coupling prepares continuous solid base MgO in 380 DEG C, normal pressure, methanol/ethanol gas flow ratio
It is reacted under the conditions of being 20/1, realizes 50.3% ethanol conversion and 79.9% C3+Selectivity of product (Catal.Lett.,
1992,12:97-104).Chaudhari seminar uses CuMgAlOxCatalyst, at 250 DEG C, 0.1MPa, the gas space of alcohol
Flow velocity is 3000cm3gCatal -1h-1Under the conditions of realize C-C coupled product space-time yield be 300g kgCatal -1h-1, after reacting 5h
Catalyst activity reduces (Appl.Catal.A, Gen., 2013,455:234-246).
Summary of the invention
The object of the invention is that providing a kind of methanol/ethanol intersects C-C key coupling catalyst and preparation method thereof.Catalyst
It is made of Monodispersed Cu particle or CuZn alloying pellet and composite oxide carrier.
Catalyst of the present invention is by hydrotalcite precursor method in H2Topology transformation is made under atmosphere, and the Cu metal in catalyst contains
Amount is 1~30wt%, and Cu average grain diameter is in 1~20nm.
Catalyst of the present invention is by hydrotalcite precursor method in H2Topology transformation is made under atmosphere, the Cu/Zn ratio in catalyst
Example is 0.1~20, Cu average grain diameter in 1~20nm.
Composite oxide carrier is magnalium gallium composite oxide carrier, mangnesium-aluminium-cerium composite oxide carrier, zinc Mg-Al composite
Oxide carrier, Zn Al composite oxide carrier.
The preparation of the catalyst: the catalyst is with hydrotalcite (Layered Double Hydroxides, letter containing Cu
It is written as LDHs) it is made for precursor, neatly stone veneer bivalent cation selects Cu2+、Mg2+、Zn2+, Tricationic selection Al3+、
Ce3+、Ga3+, molar ratio M2+/(M2++M3+)=(0~5): 1, the preparation of hydrotalcite catalyst precursor uses constant pH
Method, pH value is 9~12 in preparation process.By hydrotalcite catalyst precursor obtained in H2It is restored in atmosphere, reduction temperature control
At 350~800 DEG C, the control of reduction soaking time is 2~10 DEG C/min in 0.1h~5h, heating rate, is catalyzed accordingly
Agent.
The catalyst intersects C-C coupling for methanol/ethanol, and Cu catalyst performance evaluation is in fixed-bed reactor
It realizes.Specific reaction process is as described below: weighing a certain amount of precursor of hydrotalcite catalyst containing Cu and is packed into reaction tube thermocouple
Locate in one's power, the quartz sand filling of 20~40 mesh of reaction tube rest part.Reaction tube is connect with device, is needed before use device
Reaction unit is carried out testing leakage, it is ensured that device air-tightness is good.First by catalyst precarsor in a hydrogen atmosphere from being gone back
Original, 10~100mL/min of gas flow rate, online reducing catalyst precursor obtains catalyst under condition of normal pressure, and heating rate is 2~
10 DEG C/min, rise to 350~800 DEG C of holding 0.1h~5h.By gas circuit from H after reduction2It is switched to N2(flow velocity be 10~
100mL/min), reaction temperature (150~500 DEG C) are down to temperature of reactor, by liquid feed pump by methanol/ethanol (first
Alcohol/ethyl alcohol molar ratio 2~20) mixing liquid with given pace injects reactor, and catalytic performance is carried out under the conditions of 0.1~3MPa to be commented
Valence.
The present invention has the advantage that
1. Cu particle of the present invention or CuZn alloying pellet are evenly dispersed, effect of acidity and basicity is adjustable, and Cu/Zn ratio is adjustable.It urges
Agent intersects C-C coupling for methanol/ethanol, and ethanol conversion 90%, C-C coupled product is selectively 73%.
2. reaction condition is mild, low energy consumption.Preferred reaction conditions are 150~500 DEG C, 0.1~3MPa, and catalytic performance can
Keep stable for a long time, reaction stability is maintained at 200h or more.
3. support type Cu method for preparing catalyst of the invention is simple, cost is relatively low, is conducive to apply industrial
In the process.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
Step A: constant pH method prepares catalyst precarsor;
Accurately weigh quantitative Cu (NO3)2·3H2O、Mg(NO3)2·6H2O and Ga (NO3)3·9H2O is dissolved in quantitative go
Solution A is obtained in ionized water;Accurately weigh quantitative NaOH and Na2CO3It is dissolved in quantitative deionized water and obtains solution B;It will be molten
Liquid A and B is instilled fill in the container of quantitative deionized water simultaneously, keeps the pH of system constant not in entire titration process
Become, is warming up to certain temperature, magnetic agitation crystallization.It is washed with deionized after crystallization and is precipitated to filtrate and is in neutrality, it is anhydrous
Ethanol washing filters 1 time, is put into oven drying, obtains CuMgGa-LDHs.
Step B:
The catalyst intersects C-C coupling for methanol/ethanol, and Cu catalyst performance evaluation is in fixed-bed reactor
It realizes.Specific reaction process is as described below: weighing a certain amount of precursor of hydrotalcite catalyst containing Cu and is packed into reaction tube thermocouple
Locate in one's power, the quartz sand filling of 20~40 mesh of reaction tube rest part.Reaction tube is connect with device, is needed before use device
Reaction unit is carried out testing leakage, it is ensured that device air-tightness is good.Catalyst precarsor is restored in a hydrogen atmosphere first,
10~100mL/min of gas flow rate, online reducing catalyst precursor obtains catalyst under condition of normal pressure, and heating rate is 2~10
DEG C/min, rise to 350~800 DEG C of holding 0.1h~5h.By gas circuit from H after reduction2It is switched to N2(flow velocity be 10~
100mL/min), it is down to reaction temperature to temperature of reactor, by liquid feed pump by methanol/ethanol (methanol/ethanol molar ratio
2~20) liquid mixed injects reactor with given pace, and pressure carries out catalytic performance test under the conditions of 0.1~3MPa.It urges
Change product and use gas-chromatography on-line analysis, ethanol conversion 88%, C-C key coupled product is selected as 61%.
Embodiment 2
Step A: constant pH method prepares catalyst precarsor;
Accurately weigh quantitative Cu (NO3)2·3H2O、Mg(NO3)2·6H2O、Al(NO3)3·9H2O and Ce (NO3)3·
6H2O, which is dissolved in quantitative deionized water, obtains solution A;Accurately weigh quantitative NaOH and Na2CO3It is dissolved in quantitative deionized water
In obtain solution B;Solution A and B are instilled simultaneously and filled in the four-hole boiling flask of quantitative deionized water, in entire titration process
The pH of holding system is invariable, is warming up to certain temperature, magnetic agitation crystallization.Precipitating is washed with deionized after crystallization
It is in neutrality to filtrate, dehydrated alcohol washing filters 1 time, is put into oven drying, obtains CuMgAlCe-LDHs.
Step B:
The catalyst intersects C-C coupling for methanol/ethanol, and Cu catalyst performance evaluation is in fixed-bed reactor
It realizes.Specific reaction process is as described below: weighing a certain amount of precursor of hydrotalcite catalyst containing Cu and is packed into reaction tube thermocouple
Locate in one's power, the quartz sand filling of 20~40 mesh of reaction tube rest part.Reaction tube is connect with device, is needed before use device
Reaction unit is carried out testing leakage, it is ensured that device air-tightness is good.Catalyst precarsor is restored in a hydrogen atmosphere first,
10~100mL/min of gas flow rate, online reducing catalyst precursor obtains catalyst under condition of normal pressure, and heating rate is 2~10
DEG C/min, rise to 350~800 DEG C of holding 0.1h~5h.By gas circuit from H after reduction2It is switched to N2(flow velocity be 10~
100mL/min), it is down to reaction temperature to temperature of reactor, by liquid feed pump by methanol/ethanol (methanol/ethanol molar ratio
2~20) liquid mixed injects reactor with given pace, and pressure carries out catalytic performance test under the conditions of being 0.1~3MPa.It urges
Change product and use gas-chromatography on-line analysis, ethanol conversion 85%, C-C key coupled product is selected as 64%.
Embodiment 3
Step A: constant pH method prepares catalyst precarsor;
Accurately weigh quantitative Cu (NO3)2·3H2O、Mg(NO3)2·6H2O、Zn(NO3)2·6H2O and Al (NO3)3·
9H2O, which is dissolved in quantitative deionized water, obtains solution A;Accurately weigh quantitative NaOH and Na2CO3It is dissolved in quantitative deionized water
In obtain solution B;Solution A and B are instilled simultaneously and filled in the four-hole boiling flask of quantitative deionized water, in entire titration process
The pH of holding system is invariable, is warming up to certain temperature, magnetic agitation crystallization.Precipitating is washed with deionized after crystallization
It is in neutrality to filtrate, dehydrated alcohol washing filters 1 time, is put into oven drying, obtains CuZnMgAl-LDHs.
Step B:
The catalyst intersects C-C coupling for methanol/ethanol, and Cu catalyst performance evaluation is in fixed-bed reactor
It realizes.Specific reaction process is as described below: weighing a certain amount of precursor of hydrotalcite catalyst containing Cu and is packed into reaction tube thermocouple
Locate in one's power, the quartz sand filling of 20~40 mesh of reaction tube rest part.Reaction tube is connect with device, is needed before use device
Reaction unit is carried out testing leakage, it is ensured that device air-tightness is good.Catalyst precarsor is restored in a hydrogen atmosphere first,
10~100mL/min of gas flow rate, online reducing catalyst precursor obtains catalyst under condition of normal pressure, and heating rate is 2~10
DEG C/min, rise to 350~800 DEG C of holding 0.1h~5h.By gas circuit from H after reduction2It is switched to N2(flow velocity be 10~
100mL/min), it is down to reaction temperature to temperature of reactor, by liquid feed pump by methanol/ethanol (methanol/ethanol molar ratio
2~20) mixed uniformly liquid injects reactor with given pace, and pressure carries out catalytic performance under the conditions of being 0.1~3MPa and comments
Valence.Catalysate uses gas-chromatography on-line analysis, ethanol conversion 90%, and C-C key coupled product is selected as 73%.
Embodiment 4
Step A: constant pH method prepares catalyst precarsor;
Accurately weigh quantitative Cu (NO3)2·3H2O、Zn(NO3)2·6H2O and Al (NO3)3·9H2O is dissolved in quantitative go
Solution A is obtained in ionized water;Accurately weigh quantitative NaOH and Na2CO3It is dissolved in quantitative deionized water and obtains solution B;It will be molten
Liquid A and B is instilled fill in the four-hole boiling flask of quantitative deionized water simultaneously, keeps the pH of system constant in entire titration process
It is constant, it is warming up to certain temperature, magnetic agitation crystallization.Ion-cleaning is spent after crystallization be precipitated to filtrate be in neutrality, it is anhydrous
Ethyl alcohol filtering and washing 1 time, it is put into oven drying, obtains CuZnAl-LDHs.
Step B:
The catalyst intersects C-C coupling for methanol/ethanol, and Cu catalyst performance evaluation is in fixed-bed reactor
It realizes.Specific reaction process is as described below: weighing a certain amount of precursor of hydrotalcite catalyst containing Cu and is packed into reaction tube thermocouple
Locate in one's power, the quartz sand filling of 20~40 mesh of reaction tube rest part.Reaction tube is connect with device, is needed before use device
Reaction unit is carried out testing leakage, it is ensured that device air-tightness is good.Catalyst precarsor is restored in a hydrogen atmosphere first,
10~100mL/min of gas flow rate, online reducing catalyst precursor obtains catalyst under condition of normal pressure, and heating rate is 2~10
DEG C/min, rise to 350~800 DEG C of holding 0.1h~5h.By gas circuit from H after reduction2It is switched to N2(flow velocity be 10~
100mL/min), it is down to reaction temperature to temperature of reactor, by liquid feed pump by methanol/ethanol (methanol/ethanol molar ratio
2~20) liquid mixed injects reactor with given pace, and pressure carries out catalytic performance test under the conditions of being 0.1~3MPa.It urges
Change product and use gas-chromatography on-line analysis, ethanol conversion 85%, C-C key coupled product is selected as 54%.
Claims (10)
1. a kind of methanol/ethanol C-C key cross-coupling catalyst and preparation method thereof, which is characterized in that catalyst is by Monodispersed
Cu particle or CuZn alloying pellet and composite oxide carrier composition, the catalyst is by hydrotalcite precursor through H2Topology under atmosphere
Transformation preparation.
2. a kind of methanol/ethanol C-C key cross-coupling catalyst described in accordance with the claim 1, which is characterized in that in catalyst
Cu tenor be 1~30wt%, copper mean particle size is in 1~20nm.
3. a kind of methanol/ethanol C-C key cross-coupling catalyst described in accordance with the claim 1, which is characterized in that in catalyst
Cu/Zn ratio be 0.1~20, CuZn alloying pellet average grain diameter in 1~20nm.
4. a kind of methanol/ethanol C-C key cross-coupling catalyst described in accordance with the claim 1, which is characterized in that combined oxidation
Object carrier is that magnalium gallium composite oxide carrier, mangnesium-aluminium-cerium composite oxide carrier, zinc-magnesium aluminium composite oxide carrier, zinc-aluminium are multiple
Close oxide carrier.
5. the preparation method of the described in any item catalyst of claim 1-4, which is characterized in that the catalyst is with the neatly containing Cu
Stone (Layered Double Hydroxides, be abbreviated as LDHs) is made for precursor, the selection of neatly stone veneer bivalent cation
Cu2+、Mg2+、Zn2+, Tricationic selection Al3+、Ce3+、Ga3+, molar ratio M2+/(M2++M3+)=(0~5): 1, it will make
The hydrotalcite catalyst precursor obtained is in H2It is restored in atmosphere, reduction temperature is controlled at 350~800 DEG C, reduction soaking time control
In 0.1h~5h, heating rate is 2~10 DEG C/min, obtains corresponding catalyst.
6. according to the method for claim 5, which is characterized in that effect of acidity and basicity is adjustable, and then obtains catalytic performance difference
Catalyst.It is described above adjustable to form to obtain by changing neatly stone veneer element.
7. according to the method for claim 5, it is characterised in that Cu/Zn ratio is adjustable, and then it is different to obtain catalytic performance
Catalyst.It is described above adjustable to be obtained by changing neatly stone veneer metallic element ratio.
8. the application of the described in any item catalyst of claim 1-4, the catalyst intersects C-C key for methanol/ethanol
Coupling.
9. intersecting the coupling of C-C key for solvent-free gas-solid phase methanol/ethanol according to the application of claim 8.
10. according to the application of claim 8 or 9, methanol/ethanol molar ratio is in 2~20, the charging of methanol/ethanol mixing liquid
10uL min-1~80mL min-1, methanol/ethanol mixing liquid air speed is 1~100mL gCatal -1h-1, reaction temperature 150
~500 DEG C, reaction pressure is 0.1~3MPa.
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