CN109395723B - Catalysis system for preparing gamma-valerolactone Ru-Al by hydrogenation of levulinic acid, and preparation method and application thereof - Google Patents
Catalysis system for preparing gamma-valerolactone Ru-Al by hydrogenation of levulinic acid, and preparation method and application thereof Download PDFInfo
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- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 title claims abstract description 70
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229940040102 levulinic acid Drugs 0.000 title claims abstract description 35
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 title description 2
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 105
- 239000002244 precipitate Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 239000012153 distilled water Substances 0.000 claims description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 12
- 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 description 11
- 235000019253 formic acid Nutrition 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910000856 hastalloy Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- KLUDQUOLAFVLOL-UHFFFAOYSA-N acetyl propanoate Chemical compound CCC(=O)OC(C)=O KLUDQUOLAFVLOL-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- AVMNFQHJOOYCAP-UHFFFAOYSA-N acetic acid;propanoic acid Chemical compound CC(O)=O.CCC(O)=O AVMNFQHJOOYCAP-UHFFFAOYSA-N 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalytic system for preparing gamma-valerolactone Ru-Al by hydrogenation of levulinic acid, which consists of a Ru salt and Al sol; wherein, the Ru salt and the Al sol are calculated by the atomic number of the metal elements, and the atomic number of Ru is 1, so the atomic ratio of each component in the catalyst is Ru 1 and Al 0.5-2.0. The invention provides a novel preparation method of a catalytic system for preparing gamma-valerolactone by hydrogenation of levulinic acid, and the method can provide a Ru catalytic system for preparing gamma-valerolactone by hydrogenation of levulinic acid, wherein Ru catalyst does not need to be prepared independently, and the catalyst shows high activity and high gamma-valerolactone selectivity.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a catalytic system for preparing gamma-valerolactone Ru-Al by propionyl acetate hydrogenation, and a preparation method and application thereof.
Background
Levulinic acid can be prepared from renewable biomass resources such as lignocellulose, agricultural wastes and the like through acid catalytic hydrolysis, and is an important biomass platform compound. A series of high value-added chemicals such as gamma-valerolactone, 1, 4-pentanediol, 2-methylfuran, valerate and the like can be synthesized by hydrogenating levulinic acid. Wherein, the gamma-valerolactone is widely applied to the fields of food additives, fuel additives, solvents, gasoline, diesel oil, synthesis of various chemical intermediates and the like, and is a biological-based intermediate with the most potential for producing renewable fuels and chemical products.
Disclosure of Invention
The invention aims to provide a catalytic system for preparing gamma-valerolactone Ru-Al by propionyl acetate hydrogenation and a preparation method and application thereof.
The object of the invention is achieved in the following way:
a catalytic system for preparing gamma-valerolactone Ru-Al by hydrogenation of levulinic acid consists of a Ru salt and a sol of Al; wherein, the Ru salt and the Al sol are calculated by the atomic number of the metal elements, and the atomic number of Ru is 1, so the atomic ratio of each component in the catalyst is Ru 1 and Al 0.5-2.0.
The preparation method of the catalytic system for preparing cyclohexene Ru-Zn through benzene selective hydrogenation comprises the following specific steps: taking RuCl3·3H2Adding O into distilled water to prepare RuCl3Dissolving NaOH in distilled water to obtain NaOH solution, mixing NaOH with RuCl3·3H2The mass ratio of O is (3-10): 1, rapidly pouring NaOH solution into the RuCl while stirring at 70-90 deg.C3Continuously stirring for 10-60min to completely precipitate; then, the precipitate is filtered until the filtrate is neutral, thus obtaining Ru (OH)3Precipitating;
taking AlCl3The solution is added into distilled water, 4 mol/L NaOH solution is dripped into AlCl3In the solution until no precipitate is generated; adding 4 mol/L NaOH solution into the solution with complete precipitation until the precipitation is completely dissolved to obtain Al sol;
mixing the prepared Ru (OH)3Precipitation andthe Al sol is added into a reaction kettle, and the reaction can be used for preparing the gamma-valerolactone by hydrogenation of levulinic acid.
The raw material RuCl3·3H2O and AlCl3The mixture ratio of the components is controlled in a molar ratio of Al: ru = (0.5-2.00): 1.
for example, in the application of the catalyst in the preparation of gamma-valerolactone by catalyzing the hydrogenation of levulinic acid in a stirred batch or continuous Hastelloy autoclave, hydrogen or formic acid and the like can be used as a hydrogen source.
The hydrogen is used as a hydrogen source, and the catalyst catalyzes the selective hydrogenation reaction of the levulinic acid in the batch reactor, and the steps are as follows: ru (OH) prepared by the method of claim 23Adding the precipitate and Al sol into a reaction kettle, replacing air in the reaction kettle with nitrogen, then maintaining the hydrogen pressure at 0.5-2MPa, controlling the temperature rise rate at 1 ℃/min, stirring at the stirring rate of 200-.
The method takes formic acid as a hydrogen source, and the steps of the selective hydrogenation reaction of the levulinic acid catalyzed by the catalyst in a batch reactor are as follows: mixing formic acid, prepared Ru (OH)3Adding the precipitate and Al sol into a reaction kettle, adding distilled water, controlling the temperature rise rate at 1 ℃/min, stirring at the speed of 200-.
Compared with the prior art, the invention provides a novel preparation method of a catalytic system for preparing gamma-valerolactone by hydrogenating levulinic acid, the method can provide a Ru catalytic system for preparing gamma-valerolactone by hydrogenating levulinic acid, the Ru catalyst does not need to be prepared separately, and the catalyst shows high activity and high gamma-valerolactone selectivity.
Detailed Description
A catalytic system for preparing gamma-valerolactone Ru-Al by hydrogenation of levulinic acid consists of a Ru salt and a sol of Al; wherein, the Ru salt and the Al sol are calculated by the atomic number of the metal elements, and the atomic number of Ru is 1, so the atomic ratio of each component in the catalyst is Ru 1 and Al 0.5-2.0.
The preparation method of the catalytic system for preparing cyclohexene Ru-Zn through benzene selective hydrogenation comprises the following specific steps: taking RuCl3·3H2Adding O into distilled water to prepare RuCl3Dissolving NaOH in distilled water to obtain NaOH solution, mixing NaOH with RuCl3·3H2The mass ratio of O is (3-10): 1, rapidly pouring NaOH solution into the RuCl while stirring at 70-90 deg.C3Continuously stirring for 10-60min to completely precipitate; then, the precipitate is filtered until the filtrate is neutral, thus obtaining Ru (OH)3Precipitating;
taking AlCl3The solution is added into distilled water, 4 mol/L NaOH solution is dripped into AlCl3In the solution until no precipitate is generated; adding 4 mol/L NaOH solution into the solution with complete precipitation until the precipitation is completely dissolved to obtain Al sol;
mixing the prepared Ru (OH)3Adding the precipitate and Al sol into a reaction kettle, and then using the reaction for preparing gamma-valerolactone by hydrogenation of levulinic acid.
The raw material RuCl3·3H2O and AlCl3The mixture ratio of the components is controlled in a molar ratio of Al: ru = (0.5-2.00): 1.
for example, in the application of the catalyst in the preparation of gamma-valerolactone by catalyzing the hydrogenation of levulinic acid in a stirred batch or continuous Hastelloy autoclave, hydrogen or formic acid and the like can be used as a hydrogen source.
The hydrogen is used as a hydrogen source, and the catalyst catalyzes the selective hydrogenation reaction of the levulinic acid in the batch reactor, and the steps are as follows: ru (OH) prepared by the method of claim 23Adding the precipitate and Al sol into a reaction kettle, replacing air in the reaction kettle with nitrogen, then maintaining the hydrogen pressure at 0.5-2MPa, controlling the temperature rise rate at 1 ℃/min, stirring at the stirring rate of 200-.
The method takes formic acid as a hydrogen source, and the steps of the selective hydrogenation reaction of the levulinic acid catalyzed by the catalyst in a batch reactor are as follows: mixing formic acid, prepared Ru (OH)3Precipitation ofAnd adding the Al sol into a reaction kettle, adding distilled water, controlling the temperature rise rate at 1 ℃/min, controlling the stirring rate at 200-.
Example 1:
2.63g of RuCl was taken3·3H2Adding O into 100mL of distilled water to prepare a solution, dissolving 2.0g of NaOH into 100mL of distilled water to prepare a solution, and mixing the NaOH and RuCl3·3H2The mass ratio of O is 5: 1, NaOH solution was poured rapidly into the RuCl mentioned above with stirring at 80 deg.C3·3H2In O solution. Stirring is continued for 30 min at 80 ℃ to complete the precipitation. Then, the precipitate is filtered until the filtrate is neutral, thus obtaining Ru (OH)3And (4) precipitating. Taking 1.1g AlCl3Dissolved in 250mL of distilled water, Al: the atomic ratio of Ru is 0.8: 1, 4 mol/L NaOH solution is added dropwise to AlCl3In solution until no more precipitate is formed. Adding 4 mol/L NaOH solution into AlCl3Dissolving the solution until the precipitate is completely dissolved to obtain the Al sol. Reacting Ru (OH)3Adding the precipitate, Al sol and 12.5g of levulinic acid into a reaction kettle, replacing the air in the kettle with nitrogen, maintaining the hydrogen pressure at 1MPa, controlling the temperature rise rate at 1 ℃/min, stirring at 800 r/min, and raising the temperature to 150 ℃. The product composition was analyzed by gas chromatograph, the product concentration was calculated by FID detector and area calibration, and the conversion of levulinic acid and the selectivity of gamma valerolactone were calculated, the results are shown in table 1.
Example 2:
the reaction steps of catalyzing levulinic acid hydrogenation to prepare gamma-valerolactone in a batch reaction kettle by using formic acid as a hydrogen source catalyst are as follows: ru (OH) prepared in example 13Adding the precipitate, Al sol, 10.4g acetic acid propionic acid and 1.4g formic acid into a reaction kettle, controlling the heating rate at 1 ℃/min, stirring at the speed of 800 r/min, and heating to 150 ℃. The product composition was analyzed by gas chromatograph, the product concentration was calculated by FID detector and area calibration, and the conversion of levulinic acid and the selectivity of gamma valerolactone were calculated, the results are shown in table 1.
Example 3:
1.1g of AlCl from example 13Change to 0.7g AlCl3The other conditions were the same as in example 1. The evaluation results are shown in Table 1.
Example 4:
1.1g of AlCl from example 13Change to 2.0g AlCl3The other conditions were the same as in example 1. The evaluation results are shown in Table 1.
Example 5:
1.1g of AlCl from example 13Change to 2.75g AlCl3The other conditions were the same as in example 1. The evaluation results are shown in Table 1.
As can be seen from the results in Table 1, the catalytic system prepared by the method takes hydrogen as a hydrogen source, the conversion rate of 5h levulinic acid reaches 100%, and the selectivity of gamma-valerolactone reaches 99.7%; formic acid is used as a hydrogen source, the conversion rate of the levulinic acid reaches 100% in 24 hours, and the selectivity of gamma-valerolactone reaches 99.6%. This shows that the catalytic system prepared by the invention has important industrial application value. From examples 3-5 it can be seen that the Al sol affects the conversion of levulinic acid and the selectivity for gamma valerolactone.
Example 6:
2.63g of RuCl was taken3·3H2Adding O into 100mL of distilled water to prepare a solution, dissolving 1.2g of NaOH into 100mL of distilled water to prepare a solution, and mixing the NaOH and RuCl3·3H2The mass ratio of O is 3: 1, NaOH solution was poured rapidly into the RuCl mentioned above with stirring at 80 deg.C3·3H2In O solution. Stirring is continued for 60min at 70 ℃ to complete the precipitation. Then, the precipitate is filtered until the filtrate is neutral, thus obtaining Ru (OH)3And (4) precipitating. Taking 1.1g AlCl3Dissolved in 250mL of distilled water, Al: the atomic ratio of Ru is 0.8: 1, 4 mol/L NaOH solution is added dropwise to AlCl3In solution until no more precipitate is formed. Adding 4 mol/L NaOH solution into AlCl3Dissolving the solution until the precipitate is completely dissolved to obtain the Al sol. Reacting Ru (OH)3Precipitation, sol of Al and addition of levulinic acidAnd (3) putting the mixture into a reaction kettle, and then using the mixture for preparing the gamma-valerolactone by hydrogenation of levulinic acid.
Example 7:
2.63g of RuCl was taken3·3H2Adding O into 100mL of distilled water to prepare a solution, dissolving 4.0g of NaOH into 100mL of distilled water to prepare a solution, and mixing the NaOH and RuCl3·3H2The mass ratio of O is 10: 1, NaOH solution was poured rapidly into the RuCl mentioned above with stirring at 80 deg.C3·3H2In O solution. Stirring is continued for 10 min at 90 ℃ to complete the precipitation. Then, the precipitate is filtered until the filtrate is neutral, thus obtaining Ru (OH)3And (4) precipitating. Taking 1.1g AlCl3Dissolved in 250mL of distilled water, Al: the atomic ratio of Ru is 0.8: 1, 4 mol/L NaOH solution is added dropwise to AlCl3In solution until no more precipitate is formed. Adding 4 mol/L NaOH solution into AlCl3Dissolving the solution until the precipitate is completely dissolved to obtain the Al sol. Reacting Ru (OH)3And adding the precipitate, Al sol and levulinic acid into a reaction kettle, and then using the reaction for preparing the gamma-valerolactone by hydrogenation of the levulinic acid.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the overall concept of the present invention, and these should also be considered as the protection scope of the present invention.
Claims (6)
1. A catalytic system for preparing gamma-valerolactone Ru-Al by hydrogenation of levulinic acid is characterized in that: it is composed of Ru (OH)3And sol of Al; the sol of Al is: taking AlCl3Dissolving in distilled water, and dropwise adding 4 mol/L NaOH solution to AlCl3In the solution until no precipitate is generated; adding 4 mol/L NaOH solution into the solution with complete precipitation until the precipitation is completely dissolved, and obtaining Al sol; wherein Ru (OH)3And Al sol is calculated by the atomic number of metal elements, and the atomic number of Ru is 1, so that the atomic ratio of each component in the catalyst is Ru 1, and Al is 0.5-2.0.
2. Acetylpropanone of claim 1The preparation method of the catalytic system for preparing the gamma-valerolactone Ru-Al by acid hydrogenation is characterized by comprising the following steps: the method comprises the following specific steps: taking RuCl3·3H2Adding O into distilled water to prepare RuCl3Dissolving NaOH in distilled water to obtain NaOH solution, mixing NaOH with RuCl3·3H2The mass ratio of O is (3-10): 1, rapidly pouring NaOH solution into the RuCl while stirring at 70-90 deg.C3Continuously stirring for 10-60min to completely precipitate; then, the precipitate is filtered until the filtrate is neutral, thus obtaining Ru (OH)3Precipitating;
taking AlCl3Dissolving in distilled water, and dropwise adding 4 mol/L NaOH solution to AlCl3In the solution until no precipitate is generated; adding 4 mol/L NaOH solution into the solution with complete precipitation until the precipitation is completely dissolved, and obtaining Al sol;
mixing the prepared Ru (OH)3Adding the precipitate and Al sol into a reaction kettle, and then using the reaction for preparing gamma-valerolactone by hydrogenation of levulinic acid.
3. The method for preparing the catalytic system for preparing the gamma-valerolactone Ru-Al by hydrogenating the levulinic acid according to claim 2, wherein the catalytic system comprises: the raw material RuCl3·3H2O and AlCl3The mixture ratio of the components is controlled in a molar ratio of Al: ru = (0.5-2.00): 1.
4. the use of the catalytic system of claim 1 in the catalytic hydrogenation of levulinic acid to gamma valerolactone in a stirred batch or continuous hastelloy autoclave.
5. Use according to claim 4, characterized in that: the hydrogen is used as a hydrogen source, and the catalyst catalyzes the selective hydrogenation reaction of the levulinic acid in the batch reactor, and the steps are as follows: ru (OH) prepared by the method of claim 23Adding the precipitate and Al sol into a reaction kettle, replacing air in the reaction kettle with nitrogen, maintaining the hydrogen pressure at 0.5-2MPa, controlling the temperature rise rate at 1 ℃/min, stirring at the stirring rate of 200-The speed is increased to 1200-1600 r/min to eliminate the influence of the out-diffusion.
6. Use according to claim 4, characterized in that: the method takes formic acid as a hydrogen source, and the steps of the selective hydrogenation reaction of the levulinic acid catalyzed by the catalyst in a batch reactor are as follows: mixing formic acid, Ru (OH) prepared as described in claim 23Adding the precipitate and Al sol into a reaction kettle, adding distilled water, controlling the temperature rise rate at 1 ℃/min, stirring at the speed of 200-.
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| CN1424293A (en) * | 2002-12-12 | 2003-06-18 | 复旦大学 | Benzene selective hydrogenation carried ruthenium based catalyst and its preparation |
| CN1498215A (en) * | 2001-03-16 | 2004-05-19 | 纳幕尔杜邦公司 | Process for preparing 5-methylbuty rolactone from levalinic acid |
| CN101376650A (en) * | 2008-09-08 | 2009-03-04 | 中国科学技术大学 | Method for directly preparing gamma-valerolactone from acetylpropionic acid and aminic acid |
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| CN103785379A (en) * | 2014-03-04 | 2014-05-14 | 河北石焦化工有限公司 | Preparation method and production device of catalyst for cyclohexene preparation through benzene selective hydrogenation |
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