CN109731596B - Preparation method of modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation - Google Patents
Preparation method of modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation Download PDFInfo
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 172
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 150000001879 copper Chemical class 0.000 title claims abstract description 43
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 235000019253 formic acid Nutrition 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000003607 modifier Substances 0.000 claims abstract description 17
- -1 alkali metal salt Chemical class 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 37
- 239000010949 copper Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical group [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 16
- 238000013329 compounding Methods 0.000 description 11
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 230000001172 regenerating effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
A preparation method of a modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation relates to furfuryl alcohol. The alkali metal salt modifier is first reacted with formic acid to form a solution, and the complex of copper salt and modifier salt is then regenerated by hydrogen and carbon dioxide produced by the decomposition of formic acid to form the alkali metal carbonate modified copper-based catalyst. The prepared modified copper-based catalyst has higher furfural conversion rate and furfuryl alcohol selectivity, and the furfuryl alcohol yield can reach 80-99% under the appropriate reaction conditions. Cheap carbonate is used as a carrier or is doped into a catalyst, copper salt is used as a precursor, a simple in-situ reduction method is adopted to prepare a high-activity modified copper-based catalyst, and furfural is catalyzed and hydrogenated under proper process conditions to prepare furfuryl alcohol. The preparation process of the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation is simple to operate, short in time consumption, low in cost, high in catalytic reaction activity, good in furfuryl alcohol selectivity, stable in cycle performance and wide in application prospect.
Description
Technical Field
The invention relates to furfuryl alcohol, in particular to a preparation method of a modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation, which can be prepared by regenerating an organic copper salt and alkali metal modifier salt compound by using formic acid as a dissolving agent and a regenerating agent.
Background
Furfuryl alcohol is an important fine chemical, and is widely applied to industries of synthetic fibers, rubber, resin, spices, medicine, pesticide intermediates and the like. Furfuryl alcohol is a product of selective hydrogenation of furfural carbonyl, and a Cu-Cr catalyst is mainly used industrially, but the catalyst has high toxicity, short service life and unstable activity. Noble metal-supported catalysts developed in recent years are not suitable for mass production because of their high price. The catalyst loaded by non-noble metal or metal oxide is used as a common catalyst, has simple composition and moderate price, and is widely applied to industrial production. The furfural hydrogenation catalyst mainly adopts SiO2Copper-based catalysts supported on quasi-or porous molecular sieves, these catalysts being generally prepared by coprecipitation (including cocurrent, reverse-addition, and forward-addition coprecipitation methods) or by impregnationThe impregnation method generates a precursor of the mixed metal salt, and the finished catalyst is prepared through the steps of static aging, water washing, drying, roasting, reduction and the like, and has the advantages of longer preparation period and high cost.
At present, the research of catalyst preparation mainly focuses on the optimization and improvement of the preparation method and the preparation process, and the catalyst activity is improved by changing the proportion, the grain size, the specific surface area and the pore size distribution of the catalyst components. Plum et al, chinese patent CN 104841436A (2015), disclose a preparation method of a catalyst for preparing furfuryl alcohol by furfural hydrogenation under catalysis of a copper-magnesium mixed metal oxide, wherein the preparation method comprises precipitation, crystallization, drying, calcination and reduction processes, and the whole preparation process takes about 2-3 days. Shijia Gong et al, Chinese patent CN 106749120A (2017) disclose a new compound as CaCO3And SiO2The supported copper-based catalyst is used for catalyzing furfural hydrogenation to prepare furfuryl alcohol, and the preparation of the catalyst also comprises the steps of complex precipitation, drying, roasting, reduction and the like. In patent CN 107970942 a (2018), zhuchui et al discloses an amorphous copper-based catalyst using borohydride as an in-situ reducing agent to catalyze furfural to prepare furfuryl alcohol through hydrogenation, but a mixture of a carrier and a salt solution is dried and roasted to prepare a catalyst precursor, and then the copper-based catalyst is obtained through borohydride reduction.
In summary, no method for preparing a copper-based catalyst by formic acid in-situ reduction is available at present, and the method is used for the reaction for preparing furfuryl alcohol by furfural hydrogenation; in particular, a modified catalyst for preparing furfuryl alcohol by furfural hydrogenation, which takes doped barium salt or barium salt as a carrier and copper as an active ingredient, is not used. In addition, there is no report on the process conditions under which the above-mentioned catalyst is used for producing furfuryl alcohol.
Disclosure of Invention
The invention aims to provide a preparation method of a modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation, which can be used for preparing modified furfuryl alcohol by regenerating an organic copper salt and alkali metal modifier salt compound by using formic acid as a dissolving agent and a regenerating agent. .
The alkali metal carbonate modified copper-based catalyst is formed by firstly reacting an alkali metal salt modifier with formic acid to form a solution, and then regenerating a complex of a copper salt and the modifier salt by hydrogen and carbon dioxide generated by decomposing formic acid. The prepared modified copper-based catalyst has higher furfural conversion rate and furfuryl alcohol selectivity, and the furfuryl alcohol yield can reach 80-99% under the appropriate reaction conditions.
The invention comprises the following steps:
1) putting the alkali metal salt modifier, anhydrous formic acid and a reaction solvent into a reaction kettle, and stirring for reaction to obtain an alkali metal salt modifier formate solution;
2) adding a copper salt precursor into the formate solution of the alkali metal salt modifier obtained in the step 1), and using N2Displacing the discharged air, stirring and reacting to obtain a solid-liquid mixture, separating out a solid precipitate, washing and drying to obtain the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation.
In step 1), the alkali metal salt modifier may be selected from MgCO3、CaCO3、BaCO3、Ba(CH3COO)2·H2O, etc., the mass percentage concentration of the alkali metal salt modifier can be 0.05-1%, preferably 0.1-0.5%; the reaction solvent may be at least one selected from 1, 4-dioxane, tetrahydrofuran, methanol, ethanol, water, etc., preferably 1, 4-dioxane and tetrahydrofuran; the mass percentage concentration of the anhydrous formic acid can be 0.1-10%, and preferably 0.5-5%.
In step 2), the copper salt precursor may be selected from Cu (HCOO)2·4H2O，Cu(CH3COO)2·H2O，Cu(NO3)2·4H2O and CuSO4·5H2At least one of O and the like, the mass percentage concentration of the copper salt precursor can be 0.1-5%, preferably 1-3%; said using N2Displacing the exhaust air by N2Displacing 3-5 times to discharge air in the reaction kettle; the reaction temperature can be 100-200 ℃, preferably 150-180 ℃, the reaction time can be 0.1-4 h, preferably 0.5-2 h, and the rotating speed is 500 rpm.
The reaction method of the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation for liquid-phase hydrogenation for preparing furfuryl alcohol comprises the following steps:
reacting the reactants of furfural, 1, 4-dioxane and anhydrous formic acidAnd in situ Cu-BaCO3Mixing the catalyst in a sealed high-pressure reaction kettle, wherein the mass percentage concentration of a substrate furfural is 0.15-10%, the molar ratio of anhydrous formic acid to furfural is 4: 1, and adding N2Displacing the exhaust air (or directly using H without adding anhydrous formic acid2Emptying, 0.5-3 MPa H2Replacing anhydrous formic acid as a hydrogen source to carry out reaction), wherein the reaction temperature is 150-200 ℃, the reaction time is 0.5-4 h, and the rotation speed is 500 rpm.
The invention takes cheap carbonate as a carrier or is doped into a catalyst, takes copper salt as a precursor, adopts a simple in-situ reduction method to prepare a high-activity modified copper-based catalyst, and catalyzes furfural to hydrogenate to prepare furfuryl alcohol under proper process conditions. The preparation process of the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation is simple to operate, short in time consumption, low in cost, high in catalytic reaction activity, good in furfuryl alcohol selectivity, stable in cycle performance and wide in application prospect.
Compared with the prior art, the invention has the following beneficial effects:
1. the non-noble metal salt is used as a catalyst precursor, so that the production cost is low;
2. the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation has the advantages of simple preparation process, short time consumption, good catalytic activity and high product selectivity;
3. the in-situ Cu-BaCO3The catalyst can simultaneously utilize formic acid or H2As a hydrogen source, the hydrogenation effect is good, the economic benefit is high, and the industrial application value is high.
Drawings
FIG. 1 shows Cu-BaCO prepared3X-ray diffraction (XRD) pattern of the composite catalyst.
FIG. 2 shows Cu-BaCO prepared3Scanning Electron Microscope (SEM) images of the composite catalyst.
FIG. 3 shows Cu-BaCO prepared3Scanning electron microscopy energy spectrum (SEM-EDS) picture of the composite catalyst.
Detailed Description
The present invention is further described with reference to the following examples and the accompanying drawings, which should be construed as limiting the scope of the invention.
Example 1
Accurately weighing 0.2g MgCO3Adding 1g of anhydrous formic acid and 20m of L1, 4-dioxane into a 50m L high-pressure reaction kettle, sealing, stirring at 170 ℃ for reaction for 30min, cooling, and adding 1g of Cu (NO) into the reaction solution3)2·4H2O, sealed reaction vessel, N2And (4) displacing for 3-5 times, emptying, and reacting for 30min at 170 ℃. Cooling, centrifugally separating, washing, and vacuum drying at 60 deg.C to obtain 57% Cu-MgCO3And (3) compounding a catalyst. In a similar way, the auxiliary is changed into CaCO3、BaCO3Or Ba (CH)3COO)2·H2O, copper salt precursor Cu (HCOO)2·4H2O，Cu(CH3COO)2·H2O or CuSO4·5H2And O, preparing modified Cu-based catalysts loaded by different metals or auxiliaries.
Mixing the above Cu-MgCO3Adding 0.3g of catalyst, 0.6g of furfural and 20m L parts of 1, 4-dioxane into a reaction kettle, adding 1.15g of anhydrous formic acid, mixing, sealing, and adding N2And (3) replacing 3-5 times to discharge air, reacting for 2 hours at 170 ℃, wherein the conversion rate of furfuryl alcohol is 53%, and the selectivity is 96%. Under the same conditions, 2MPa H2The conversion rate of furfural is 70% instead of formic acid, and the selectivity is 95%.
Example 2
Accurately weighing 0.08g of BaCO3Adding 1g of anhydrous formic acid and 20m of L1, 4-dioxane into a 50m L high-pressure reaction kettle, sealing, stirring at 200 ℃ for reaction for 30min, cooling, adding 0.43g of Cu (HCOO)2·4H2O, sealed reaction vessel, N2And (4) displacing for 3-5 times, emptying, and reacting for 30min at 170 ℃. Cooling, centrifugally separating, washing, and vacuum drying at 60 deg.c to obtain 60% Cu-BaCO3And (3) compounding a catalyst. In a similar manner, the changes of Cu (HCOO)2·4H2O and BaCO3To prepare Cu-BaCO with different mass fractions3And (3) compounding a catalyst.
Mixing the above Cu-BaCO3Adding 0.3g of catalyst, 0.6g of furfural and 20m L parts of 1, 4-dioxane into a reaction kettle, adding 1.15g of anhydrous formic acid, mixing and sealingBy N2And (3) displacing 3-5 times to discharge air, reacting for 2 hours at 170 ℃, wherein the conversion rate of furfuryl alcohol is 100%, and the selectivity is 99%. Under the same conditions, 2MPa H2The conversion rate of furfural is 100% instead of formic acid, and the selectivity is 99%.
Example 3
Accurately weighing 0.08g of BaCO30.02g of anhydrous formic acid and 20m of L1, 4-dioxane were put into a 50m L autoclave, sealed, stirred at 170 ℃ for 30min, cooled and then 0.43g of Cu (HCOO) was added to the reaction mixture2·4H2O, sealed reaction vessel, N2The displacement is carried out for 3 to 5 times, and the reaction is carried out for 60min at the temperature of 170 ℃. Cooling, centrifugally separating, washing, and vacuum drying at 60 deg.c to obtain 60% Cu-BaCO3And (3) compounding a catalyst.
Mixing the above Cu-BaCO3Adding 0.3g of catalyst, 0.6g of furfural and 20m L parts of 1, 4-dioxane into a reaction kettle, adding 1.15g of anhydrous formic acid, mixing, sealing, and adding N2And (3) replacing 3-5 times to discharge air, reacting for 2 hours at 170 ℃, wherein the conversion rate of furfuryl alcohol is 58%, and the selectivity is 97%. Under the same conditions, 2MPa H2The conversion rate of furfural is 41% instead of formic acid, and the selectivity is 96%.
Example 4
Accurately weighing 0.08g of BaCO30.5g of anhydrous formic acid and 20m of L1, 4-dioxane were added into a 50m L autoclave, the autoclave was sealed, stirred at 170 ℃ for 30min, cooled, and then 0.43g of Cu (HCOO) was added to the reaction mixture2·4H2O, sealed reaction vessel, N2And (4) displacing for 3-5 times, emptying, and reacting for 60min at 170 ℃. Cooling, centrifugally separating, washing, and vacuum drying at 60 deg.c to obtain 60% Cu-BaCO3And (3) compounding a catalyst.
Mixing the above Cu-BaCO3Adding 0.3g of catalyst, 0.6g of furfural and 20m L parts of 1, 4-dioxane into a reaction kettle, adding 1.15g of anhydrous formic acid, mixing, sealing, and adding N2And (3) displacing 3-5 times to discharge air, reacting for 2 hours at 170 ℃, wherein the conversion rate of furfuryl alcohol is 98%, and the selectivity is 99%. Under the same conditions, 2MPa H2The conversion rate of furfural is 99% and the selectivity is 100% instead of formic acid.
Example 5
Accurate scale0.08g of BaCO is taken30.5g of anhydrous formic acid and 20m of L1, 4-dioxane were added into a 50m L autoclave, the autoclave was sealed, stirred at 200 ℃ and reacted for 30min, after cooling, 0.43g of Cu (HCOO) was added to the reaction mixture2·4H2O, sealed reaction vessel, N2And (4) evacuating for 3-5 times by displacement, and reacting for 60min at 100 ℃. Cooling, centrifugally separating, washing, and vacuum drying at 60 deg.c to obtain 60% Cu-BaCO3And (3) compounding a catalyst.
Mixing the above Cu-BaCO3Adding 0.3g of catalyst, 0.6g of furfural and 20m L parts of 1, 4-dioxane into a reaction kettle, adding 1.15g of anhydrous formic acid, mixing, sealing, and adding N2And (3) displacing 3-5 times to discharge air, reacting for 2 hours at 170 ℃, wherein the conversion rate of furfuryl alcohol is 48%, and the selectivity is 98%. Under the same conditions, 2MPa H2The conversion rate of furfural is 56% instead of formic acid, and the selectivity is 98%.
Example 6
Accurately weighing 0.08g of BaCO30.8g of anhydrous formic acid and 20m of L1, 4-dioxane were added into a 50m L autoclave, the autoclave was sealed, stirred at 100 ℃ and reacted for 30min, after cooling, 0.43g of Cu (HCOO) was added to the reaction mixture2·4H2O, sealed reaction vessel, N2And (4) evacuating for 3-5 times by displacement, and reacting for 60min at 200 ℃. Cooling, centrifugally separating, washing, and vacuum drying at 60 deg.c to obtain 60% Cu-BaCO3And (3) compounding a catalyst.
Mixing the above Cu-BaCO3Adding 0.3g of catalyst, 0.6g of furfural and 20m L parts of 1, 4-dioxane into a reaction kettle, adding 1.15g of anhydrous formic acid, mixing, sealing, and adding N2And (3) displacing 3-5 times to discharge air, reacting for 2 hours at 170 ℃, wherein the conversion rate of furfuryl alcohol is 100%, and the selectivity is 98%. Under the same conditions, 2MPa H2The conversion rate of furfural is 100% instead of formic acid, and the selectivity is 99%.
Example 7
Accurately weighing 0.08g of BaCO30.8g of anhydrous formic acid and 20m of L1, 4-dioxane were added into a 50m L autoclave, the autoclave was sealed, stirred at 170 ℃ and reacted for 10min, after cooling, 0.43g of Cu (HCOO) was added to the reaction mixture2·4H2O, sealed reaction vessel, N2And (4) displacing for 3-5 times, emptying, and reacting for 6min at 180 ℃. Cooling downThen centrifugally separating, washing and drying in vacuum at 60 ℃ to obtain 60 percent Cu-BaCO3And (3) compounding a catalyst.
Mixing the above Cu-BaCO3Adding 0.3g of catalyst, 0.6g of furfural and 20m L parts of 1, 4-dioxane into a reaction kettle, adding 1.15g of anhydrous formic acid, mixing, sealing, and adding N2And (3) replacing 3-5 times to discharge air, reacting for 2 hours at 170 ℃, wherein the conversion rate of furfuryl alcohol is 38%, and the selectivity is 95%. Under the same conditions, 2MPa H2The conversion rate of furfural is 45% instead of formic acid, and the selectivity is 97%.
Example 8
Accurately weighing 0.08g of BaCO30.5g of anhydrous formic acid and 20m of L1, 4-dioxane were added into a 50m L autoclave, the autoclave was sealed, stirred at 170 ℃ and reacted for 60min, after cooling, 0.43g of Cu (HCOO) was added to the reaction solution2·4H2O, sealed reaction vessel, N2And (4) displacing for 3-5 times, emptying, and reacting for 60min at 170 ℃. Cooling, centrifugally separating, washing, and vacuum drying at 60 deg.c to obtain 60% Cu-BaCO3And (3) compounding a catalyst.
Mixing the above Cu-BaCO3Adding 0.3g of catalyst, 0.6g of furfural and 20m L parts of 1, 4-dioxane into a reaction kettle, adding 1.15g of anhydrous formic acid, mixing, sealing, and adding N2And (3) replacing 3-5 times to discharge air, reacting for 2 hours at 100 ℃, wherein the conversion rate of furfuryl alcohol is 100%, and the selectivity is 99%. Under the same conditions, 2MPa H2The conversion rate of furfural is 100% instead of formic acid, and the selectivity is 99%.
Example 9
Accurately weighing 0.08g of BaCO30.5g of anhydrous formic acid and 20m of L1, 4-dioxane were added into a 50m L autoclave, the autoclave was sealed, stirred at 170 ℃ for 240min, cooled, and then 0.43g of Cu (HCOO) was added to the reaction mixture2·4H2O, sealed reaction vessel, N2And (4) displacing for 3-5 times, emptying, and reacting for 120min at 180 ℃. Cooling, centrifugally separating, washing, and vacuum drying at 60 deg.c to obtain 60% Cu-BaCO3And (3) compounding a catalyst.
Mixing the above Cu-BaCO3Adding 0.3g of catalyst, 0.6g of furfural and 20m L parts of 1, 4-dioxane into a reaction kettle, adding 1.15g of anhydrous formic acid, mixing, sealing, and adding N2And (3) displacing 3-5 times to discharge air, reacting for 2 hours at 150 ℃, wherein the conversion rate of furfuryl alcohol is 80%, and the selectivity is 99%. Under the same conditions, 0.5MPa H2The conversion rate of furfural is 45% instead of formic acid, and the selectivity is 98%.
Example 10
Accurately weighing 0.08g of BaCO30.5g of anhydrous formic acid and 20m of L1, 4-dioxane were added into a 50m L autoclave, the autoclave was sealed, stirred at 170 ℃ for 240min, cooled, and then 0.43g of Cu (HCOO) was added to the reaction mixture2·4H2O, sealed reaction vessel, N2And (4) displacing for 3-5 times, emptying, and reacting for 240min at 180 ℃. Cooling, centrifugally separating, washing, and vacuum drying at 60 deg.c to obtain 60% Cu-BaCO3And (3) compounding a catalyst.
Mixing the above Cu-BaCO3Adding 0.3g of catalyst, 0.6g of furfural and 20m L parts of 1, 4-dioxane into a reaction kettle, adding 1.15g of anhydrous formic acid, mixing, sealing, and adding N2And (3) displacing 3-5 times to discharge air, reacting for 2 hours at 200 ℃, wherein the conversion rate of furfuryl alcohol is 100%, and the selectivity is 95%. Under the same conditions, with 3MPa H2The conversion rate of furfural is 100% instead of formic acid, and the selectivity is 93%.
Prepared Cu-BaCO3X-ray diffraction (XRD) pattern of the composite catalyst referring to FIG. 1, Cu-BaCO prepared3Scanning Electron Microscope (SEM) image of composite catalyst referring to FIG. 2, Cu-BaCO prepared3A scanning electron microscopy energy spectrum (SEM-EDS) image of the composite catalyst is shown in FIG. 3.
The method does not need complex steps such as precipitation, calcination, reduction and the like, has simple process flow, and greatly reduces the preparation time and cost of the catalyst. The catalyst is used in furfural hydrogenation reaction, the conversion rate can reach 80-100%, and the selectivity to the main product furfuryl alcohol reaches 90-99%. The preparation method is simple to operate, short in preparation period, good in hydrogenation effect of the catalyst, high in selectivity of the target product, capable of being repeatedly used and good in stability.
Claims (14)
1. A preparation method of a modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation is characterized by comprising the following steps:
1) putting an alkaline metal modifier, anhydrous formic acid and a reaction solvent into a reaction kettle, sealing, and stirring for reaction to obtain an alkali metal salt modifier formate solution; the alkaline metal modifier is selected from MgCO3、CaCO3、BaCO3、Ba(CH3COO)2·H2At least one of O;
2) adding a copper salt precursor into the alkaline metal salt modifier formate solution obtained in the step 1), and using N2Displacing the discharged air, stirring and reacting to obtain a solid-liquid mixture, separating out a solid precipitate, washing and drying to obtain the in-situ modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation.
2. The method for preparing the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation according to claim 1, wherein in the step 1), the mass percentage concentration of the alkali metal salt modifier is 0.05-1%.
3. The method for preparing the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation according to claim 2, wherein in the step 1), the mass percentage concentration of the alkali metal salt modifier is 0.1-0.5%.
4. The method for preparing a modified copper-based catalyst for preparing furfuryl alcohol by hydrogenating furfuryl alcohol according to claim 1, wherein in step 1), the reaction solvent is at least one selected from the group consisting of 1, 4-dioxane, tetrahydrofuran, methanol, ethanol and water.
5. The method for preparing a modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation according to claim 4, wherein in the step 1), the reaction solvent is 1, 4-dioxane and tetrahydrofuran.
6. The method for preparing the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation according to claim 1, wherein in the step 1), the anhydrous formic acid is at a concentration of 0.1 to 10% by mass.
7. The method for preparing the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation according to claim 6, wherein in the step 1), the anhydrous formic acid is at a concentration of 0.5 to 5% by mass.
8. The method for preparing the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation according to claim 1, wherein in the step 2), the copper salt precursor is selected from Cu (HCOO)2·4H2O，Cu(CH3COO)2·H2O，Cu(NO3)2·4H2O and CuSO4·5H2At least one of O.
9. The method for preparing the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation according to claim 1, wherein in the step 2), the mass percentage concentration of the copper salt precursor is 0.1-5%.
10. The method for preparing the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation according to claim 9, wherein in the step 2), the mass percentage concentration of the copper salt precursor is 1 to 3 percent.
11. The method for preparing the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation according to claim 1, wherein in the step 2), N is used2Displacing the exhaust air by N2And (4) replacing the air in the reaction kettle for 3-5 times.
12. The method for preparing the modified copper-based catalyst for preparing furfuryl alcohol through furfural hydrogenation according to claim 1, wherein in the step 2), the reaction temperature is 100-200 ℃, the reaction time is 0.1-4 h, and the rotation speed is 500 rpm.
13. The method for preparing the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation according to claim 12, wherein in the step 2), the reaction temperature is 150 to 180 ℃ and the reaction time is 0.5 to 2 hours.
14. The method for preparing the modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation according to claim 1, wherein the product prepared by the method is in-situ Cu-BaCO3The catalyst is used for a reaction method for preparing furfuryl alcohol by furfural liquid phase hydrogenation, and comprises the following steps:
reacting a reactant furfural, a 1, 4-dioxane solution, anhydrous formic acid and in-situ Cu-BaCO3Mixing the catalyst in a sealed high-pressure reaction kettle, wherein the mass percentage concentration of the furfural is 0.15-10%, the molar ratio of the anhydrous formic acid to the furfural is 4: 1, and adding N2Displacing the exhaust air, or using H directly without addition of anhydrous formic acid2Emptying, 0.5-3 MPa H2The method replaces anhydrous formic acid as a hydrogen source to carry out reaction, the reaction temperature is 150-200 ℃, the reaction time is 0.5-4 h, and the rotation speed is 500 rpm.
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