CN1275689C - Catalyzer synthesized from ethyl lactate and hydrogen in use for 1, 2 propylene glycol, and preparation method - Google Patents
Catalyzer synthesized from ethyl lactate and hydrogen in use for 1, 2 propylene glycol, and preparation method Download PDFInfo
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- CN1275689C CN1275689C CN 200310108268 CN200310108268A CN1275689C CN 1275689 C CN1275689 C CN 1275689C CN 200310108268 CN200310108268 CN 200310108268 CN 200310108268 A CN200310108268 A CN 200310108268A CN 1275689 C CN1275689 C CN 1275689C
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- catalyst
- reaction
- ruthenium
- ethyl lactate
- hydrogenation
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Abstract
The present invention relates to a catalyst for synthesizing 1, 2-propylene glycol by hydrogenating ethyl lactate, and a preparation process thereof. The catalyst is a ruthenium-boron catalyst taking ruthenium as an active component and potassium borohydride or sodium borohydride as a reducing agent and has a non-loaded type and a loaded type. The catalyst is prepared by an improved chemical reduction method. The reaction for synthesizing the 1, 2-propylene glycol can be carried out under the moderate condition by using the catalyst. The present invention has simple preparation method for the catalyst and post-treatment technology, energy consumption reduction and no environment pollution and has high selectivity and activity on the 1, 2-propylene glycol.
Description
Technical field
The invention belongs to chemical technology field, being specifically related to a kind of is raw material with the ethyl lactate, synthesizes 1 by hydrogenation reaction under the temperate condition, the Catalysts and its preparation method of 2-propane diols.
Technical background
1, the 2-propane diols is a kind of important chemical material, and is main as the raw material of producing unsaturated-resin, epoxy resin, polyurethane resin etc., also can be used as the raw material of producing plasticizer, surfactant, emulsifying agent and demulsifier.In food industry, solvent, mould inhibitor, food emulsifying agent and the fruit that propane diols can be used as spices, the food pigment anticorrisive agent that accelerates the ripening.In medical industry, propane diols is commonly used to make solvent, softening agent and the excipient of all kinds of ointment, ointment and pill.In cosmetics industry, propane diols also can be used to produce solvent and softening agent.In addition, also alternative ethylene glycol of propane diols and glycerine are used as the antifreeze in the industry, and use (App.Catal.A:219 (2001) 89) as tobacco humidizer and heat carrier.
1, what 2-propane diols synthetic generally adopted at present is expoxy propane HTHP direct hydration process route.The expoxy propane hydration reaction can be carried out in the presence of catalyst-free or acidic catalyst.On-catalytic hydration route advantage is that equipment corrosion is little, and the product postprocessing process is simple, and the waste discharge amount is little.But reaction condition is harsh, and equipment investment is big.And for being the hydration reaction of catalyst with sulfuric acid, though reaction temperature is lower, product separation and subtractive process are complicated, and not only the energy consumption height also causes certain pollution to environment simultaneously.The raw material expoxy propane mainly adopts the chlorohydrination preparation.Produce 0.15-0.18 ton debirs in the time of 1 ton of expoxy propane of the every production of chlorohydrination, wherein dichloropropane content is at 60-85%.The dichloropropane waste liquid has stronger toxicity, and it can stimulate the eyes mucous membrane, causes dermatitis, and long-term high concentration contact can cause the liver renal necrosis.Owing to wherein contain a large amount of organochlorines, adopt burning disposal can bring serious secondary pollution.Other 1, the 2-propane diols also can adopt dichloropropane hydrolysis preparation (DE3545583, DE3718266, WO9744302, WO9744308, day disclosure special permission 0421643,04210655,04279543).Though this route has reduced production cost, alleviated and burned the environmental pollution that causes, the reaction pressure temperature is higher, and yield is lower, and complex process.
In recent years, the development of bioengineering and agricultural product deep processing makes effective and reasonable crops and the bionic accessory substance of utilizing be subjected to paying close attention to widely, and the utilization of lactic acid is exactly one of them importance.Lactic acid can be made by several carbohydrate raw material fermentations, also can be made by discarded biological leftover bits and pieces (for example cheese, whey, wood pulp).Select hydrogenation preparing 1 with lactic acid or lactate, the 2-propane diols is a green environmental protection technique route that efficiently utilizes lactic acid, but correlative study at present is few.Because the more difficult hydrogenation of organic acid, and be easy to and product alcohol generation esterification, the recovery of product influenced, so often with repeated hydrogenation after the acid estersization.But ester through hydrogenation generally need carry out under high temperature (200-300 ℃), high pressure (20-30MPa), also usually adopts the catalyst that contains Cr, as Cu-Cr, Zn-Cr etc., not only equipment is required height, also environment is caused certain infringement.In addition, contain carboxyl and hydroxyl reactive group in the lactate, the reaction temperature height can cause the generation of side reactions such as ester exchange, polymerization, dehydration.So develop a kind of catalyst efficiently, make lactate highly selective under the hydroconversion condition of gentleness prepare propane diols, be significant and challenging problem.
Summary of the invention
The object of the present invention is to provide hydrogenation catalyst of a kind of high activity and high selectivity and preparation method thereof, make ethyl lactate highly selective hydrogenation under the reaction condition of gentleness synthesize 1, the 2-propane diols.
The ethyl lactate hydrogenation that the present invention proposes is synthetic 1, the catalyst that the 2-propane diols is used, be a kind of be active constituent with the ruthenium, be the ruthenium boron catalyzer that reducing agent prepares with potassium borohydride or sodium borohydride, the molar ratio of boron and ruthenium is 1-8.
For the speed that improves hydrogenation reaction and the selectivity of reaction, also can add a kind of auxiliary agent in the ruthenium catalyst.This auxiliary agent comprises: one or more of zinc, cobalt, tin, iron, molybdenum, magnesium.The adding method of auxiliary agent can adopt the method for soaking step by step or flooding altogether with reactive metal.The addition of auxiliary agent is a benchmark with the ruthenium quality in the catalyst, the about 0.1%-100% of the mass percent of auxiliary agent and ruthenium, and that more excellent is 5-20%.
Ruthenium boron catalyzer of the present invention can be DNAcarrier free ultra-fine dust particle, also can be support type.When being loaded catalyst, this carrier can be Al
2O
3, MgO, SiO
2, TiO
2, ZrO
2Or active carbon is a kind of.The mass percent of active constituent ruthenium and carrier is between the 1-10%.
Ruthenium boron catalyzer of the present invention can prepare with the following method:
For unsupported catalyst, press the usage ratio of each component, the initiation material ruthenium trichloride is dissolved in the water, be 20-50 ℃ in temperature then, the pH value is with potassium borohydride or boron chlorination reduction, promptly under the condition of 7-9.
For loaded catalyst, elder generation in the solution of potassium borohydride or sodium borohydride, time 10-30 minute, pours out carrier impregnation with supernatant; Then, will put into the ruthenium trichloride aqueous solution, carry out reduction reaction through the carrier of dipping; When bubble not had was emerged, water to neutral, was used absolute ethanol washing to the washing of gained solids again, carried out drying at last and handled.Promptly get required ruthenium boron catalyzer.
Among the above-mentioned preparation method, can also add auxiliary agent.Specifically when carrying out reduction reaction, add the solution of above-mentioned auxiliary agent in the ruthenium trichloride solution, constitute the mixed solution of ruthenium trichloride and auxiliary agent.
Use catalyst of the present invention, the ethyl lactate hydrogenation synthesizes 1, and the technology of 2-propane diols is as follows:
Be reflected in the stainless steel autoclave of 220ml band magnetic agitation and carry out, catalyst amount is a 0.3-0.8g/ml ethyl lactate raw material, and reaction temperature is between 130-200 ℃, and is more excellent between 140-170 ℃; The pressure of hydrogen should be not less than 2.0MPa, is 3.0-6.0MPa preferably.In general, lower reaction temperature and higher pressure descend the selectivity of reaction higher.Reaction time is 4-15 hour.
Hydrogenation reaction is carried out having in the presence of the solvent, and solvent should not disturb hydrogenation reaction, can be different with the dissolubility of product to reaction.Suitable solvent comprises: aromatic compounds such as benzene, toluene, ethers such as ether, glycol dimethyl ether, alkane such as pentane, normal heptane, normal octane.Solvent load is 4-8 a times of reactant volume.
After the reaction some time, reactant mixture is taken a sample, adopt chromatogram-mass spectrum technology used in conjunction and gas-chromatography that product is carried out qualitative and quantitative analysis, thereby calculate the yield of reaction conversion ratio and product.
Catalyst provided by the invention and ethyl lactate hydrogenation reaction technology have following advantage:
1, this catalyst preparation process is simple, does not need to carry out high-temperature roasting and H
2Reduction can directly be used after washing and drying, and energy consumption is low.
2, this catalyst does not contain the composition of serious environment pollutions such as Cr, and preparation process also meets the requirement of Green Chemistry.
3, this catalyst have high by 1,2-propane diols selectivity.Side reaction is less.
4, this catalyst can have good hydrogenation activity under relatively mild condition.
The specific embodiment
Embodiment 1
With a certain amount of carrier A l
2O
3Immerse 3mol/L KBH
4After 10 minutes, pour out supernatant liquor in the solution; To be soaked with KBH
4Al
2O
3Carrier joins RuCl
33H
2In the O solution, reaction when not having bubble and emerge till.The solids of washing gained is used absolute ethanol washing three times again to neutral, and vacuum drying under the room temperature gets ruthenium boron catalyzer.Above-mentioned catalyst 2.0g and 5ml ethyl lactate and 30ml normal heptane are joined in the stainless steel autoclave that has magnetic agitation.Reaction system feeds hydrogen with 1.0MPa hydrogen exchange three times, begins during to 4.0MPa to heat up, and after temperature is raised to 140 ℃ of required temperature, pressure is adjusted to 5.0MPa, opens stirring, begins to react.Reacted 10 hours.Reactant mixture its composition of gas chromatographic analysis.The results are shown in Table 1.
Embodiment 2
Carrier A l with aequum
2O
3Immerse 3mol/L KBH
4In the solution 15 minutes, pour out supernatant liquor, will be soaked with KBH
4Al
2O
3Carrier joins RuCl
33H
2O and SnCl
22H
2In the mixed solution of O, reaction when not having bubble and emerge till.The solids of washing gained is used absolute ethanol washing three times again to neutral, and vacuum drying under the room temperature gets ruthenium boron catalyzer.Above-mentioned catalyst 2.5g and 5ml ethyl lactate and 40ml normal heptane join in the autoclave.With reaction system 1.0MPa hydrogen exchange three times, feed hydrogen.4.5MPa in time, begin to heat up, and after temperature is raised to 150 ℃ of required temperature, pressure is adjusted to 6.0MPa, opens stirring, begins reaction.Reacted 13 hours.Reactant mixture its composition of gas chromatographic analysis.The results are shown in Table 1.
Embodiment 3
The carrier active carbon of aequum is immersed 3mol/L KBH
4In the solution 20 minutes, pour out supernatant liquor, will be soaked with KBH
4Absorbent charcoal carrier join RuCl
33H
2O and FeCl
36H
2In the mixed solution of O, reaction when not having bubble and emerge till.The solids of washing gained is extremely neutral, absolute ethanol washing three times, and vacuum drying under the room temperature gets ruthenium boron catalyzer.Above-mentioned catalyst 1.5g and 5ml ethyl lactate and 20ml normal heptane join in the autoclave.With reaction system 1.0MPa hydrogen exchange three times, feed hydrogen.4.0MPa in time, begin to heat up, and after temperature is raised to 160 ℃ of required temperature, pressure is adjusted to 5.5MPa, opens stirring, begins reaction.Reacted 10 hours.Reactant mixture its composition of gas chromatographic analysis.The results are shown in Table 1.
Embodiment 4
Carrier S iO with aequum
2Immerse 3mol/L KBH
4In the solution 30 minutes, pour out supernatant liquor, will be soaked with KBH
4SiO
2Carrier joins RuCl
33H
2O and ZnCl
2Mixed solution in, reaction when not having bubble and emerge till.The solids of washing gained is to neutral, again with absolute ethanol washing three times, vacuum drying under the room temperature, ruthenium boron catalyzer.Above-mentioned catalyst 1.5g and 5ml ethyl lactate and 40ml cyclohexane join in the autoclave.With reaction system 1.0MPa hydrogen exchange three times, feed hydrogen.1.0MPa in time, begin to heat up, and after temperature is raised to 170 ℃ of required temperature, pressure is adjusted to 3.0MPa, opens stirring, begins reaction.Reacted 10 hours.Reactant mixture its composition of gas chromatographic analysis.The results are shown in Table 1.
Embodiment 5
Carrier ZrO with aequum
2Immerse 3mol/L KBH
4In the solution 25 minutes, pour out supernatant liquor, will be soaked with KBH
4ZrO
2Carrier joins RuCl
33H
2O and SnCl
22H
2In the mixed solution of O, reaction when not having bubble and emerge till.The solids of washing gained is used absolute ethanol washing three times again to neutral, and vacuum drying under the room temperature gets ruthenium boron catalyzer.Above-mentioned catalyst 3.0g and 5ml ethyl lactate and 40ml glycol dimethyl ether join in the autoclave.With reaction system 1.0MPa hydrogen exchange three times, feed hydrogen.4.0MPa in time, begin to heat up, and after temperature is raised to 150 ℃ of required temperature, pressure is adjusted to 6.0MPa, opens stirring, begins reaction.Reacted 10 hours.Reactant mixture is formed with gas chromatographic analysis.The results are shown in Table 1.
Embodiment 6
Carrier TiO with aequum
2Immerse 3mol/L KBH
4In the solution 20 minutes, pour out supernatant liquor, will be soaked with KBH
4TiO
2Carrier joins RuCl
33H
2O and CoCl
26H
2In the mixed solution of O, reaction when not having bubble and emerge till.The solids of washing gained is used absolute ethanol washing three times, vacuum drying under the room temperature again to neutral.Above-mentioned catalyst 2.5g and 5ml ethyl lactate and 40ml toluene join in the autoclave.With reaction system 1.0MPa hydrogen exchange three times, feed hydrogen.2.0MPa in time, begin to heat up, and after temperature is raised to 160 ℃ of required temperature, pressure is adjusted to 4.0MPa, opens stirring, begins reaction.Reacted 10 hours.Reactant mixture is formed with gas chromatographic analysis.The results are shown in Table 1.
Embodiment 7
Carrier A l with aequum
2O
3Immerse RuCl
33H
2O and SnCl
22H
2In the mixed solution of O, evaporating water in 75 ℃ of water-baths; Place 120 ℃ baking oven dried overnight.In above-mentioned solids, drip the KBH of 3mol/L
4Solution reaction, when not having bubble and emerge till.The solids of washing gained is used absolute ethanol washing three times again to neutral, and vacuum drying under the room temperature gets ruthenium boron catalyzer.Above-mentioned catalyst 1.5g and 5ml ethyl lactate and 20ml glycol dimethyl ether join in the autoclave.With reaction system 1.0MPa hydrogen exchange three times, feed hydrogen.4.0MPa in time, begin to heat up, and after temperature is raised to 150 ℃ of required temperature, pressure is adjusted to 6.0MPa, opens stirring, begins reaction.Reacted 10 hours.Reactant mixture its composition of gas chromatographic analysis.The results are shown in Table 1.
Table 1. embodiment and reaction result
| Embodiment | Ethyl lactate conversion ratio (mol%) | 1,2-propane diols selectivity (%) | 1,2-propane diols yield (mol%) |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 | 82.5 97.3 91.7 88.9 94.3 98.4 85.6 | 82.9 92.4 91.5 93.5 87.7 84.5 90.5 | 68.4 89.9 83.8 83.0 82.7 83.2 77.5 |
Claims (10)
1, a kind of ethyl lactate hydrogenation synthesizes 1, and the catalyst that the 2-propane diols is used is to be active constituent with the ruthenium, is the ruthenium boron catalyzer that reducing agent prepares with potassium borohydride or sodium borohydride, and the mol ratio of boron and ruthenium is 1-8.
2, according to the catalyst described in the claim 1, it is characterized in that also containing auxiliary agent, this auxiliary agent is one or more of zinc, cobalt, molybdenum, magnesium, tin or iron, the mass percent of auxiliary agent and ruthenium is 0.1-100%.
3,, it is characterized in that catalyst is DNAcarrier free ultrafine particle or loaded catalyst according to the catalyst described in the claim 1.
4, catalyst according to claim 3, the carrier that it is characterized in that described loaded catalyst is Al
2O
3, MgO, SiO
2, TiO
2, ZrO
2Or active carbon is a kind of, and the mass ratio of active constituent ruthenium and carrier is between 1-10%.
5, a kind of Preparation of catalysts method as claimed in claim 1, it is characterized in that unsupported catalyst, press the each component usage ratio, earlier the initiation material ruthenium trichloride is dissolved in the water, be 20-50 ℃ in temperature then, the pH value is with potassium borohydride or sodium borohydride reduction under the condition of 7-9.
6, a kind of Preparation of catalysts method as claimed in claim 1 is characterized in that loaded catalyst, presses the each component usage ratio, and elder generation in the solution of potassium borohydride or sodium borohydride, time 10-30 minute, pours out carrier impregnation with supernatant; Then, will put into the ruthenium trichloride aqueous solution, carry out reduction reaction through the carrier of dipping; When bubble not had was emerged, water to neutral, was used absolute ethanol washing to the washing of gained solids again, carried out drying at last and handled.
7, Preparation of catalysts method according to claim 6, one or more that it is characterized in that also adding zinc, cobalt, tin, iron, molybdenum, magnesium be as auxiliary agent, the method that the adding employing of auxiliary agent and reactive metal soak altogether or substep soaks.
8, a kind of ethyl lactate hydrogenation synthetic 1 that utilizes the described catalyst of claim 1, the reaction process of 2-propane diols, it is characterized in that catalyst amount is a 0.3-0.8g/ml ethyl lactate raw material, the temperature of hydrogenation reaction is 130-200 ℃, hydrogenation reaction pressure is for being not less than 2MPa, and the reaction time is 4-15 hour.
9, reaction process according to claim 8, the temperature that it is characterized in that hydrogenation reaction is 140-170 ℃, the pressure of hydrogenation reaction is 3-6MPa.
10, reaction process according to claim 8 is characterized in that hydrogenation reaction carries out under the situation that has solvent to exist, solvent is a kind of of alkane, aromatic compound, ethers, solvent load be the reactant volume 4-8 doubly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108268 CN1275689C (en) | 2003-10-30 | 2003-10-30 | Catalyzer synthesized from ethyl lactate and hydrogen in use for 1, 2 propylene glycol, and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108268 CN1275689C (en) | 2003-10-30 | 2003-10-30 | Catalyzer synthesized from ethyl lactate and hydrogen in use for 1, 2 propylene glycol, and preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1539551A CN1539551A (en) | 2004-10-27 |
| CN1275689C true CN1275689C (en) | 2006-09-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310108268 Expired - Fee Related CN1275689C (en) | 2003-10-30 | 2003-10-30 | Catalyzer synthesized from ethyl lactate and hydrogen in use for 1, 2 propylene glycol, and preparation method |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465144C (en) * | 2006-12-01 | 2009-03-04 | 华南理工大学 | Method for load type amorphous ruthenium boron-containing catalyst to catalyzing hydrogenating and reducing carbonyl compound to prepare alcohol |
| CN102295660A (en) * | 2011-07-04 | 2011-12-28 | 常州大学 | Synthetic technology of PMPA |
| CN106083521A (en) * | 2016-06-14 | 2016-11-09 | 东莞市联洲知识产权运营管理有限公司 | The method of 1,2 propylene glycol prepared by a kind of ethyl lactate |
| CN111905802B (en) * | 2020-06-15 | 2022-01-18 | 厦门大学 | Method for preparing lactate by using molybdenum-alkali metal/alkaline earth metal modified Lewis acid catalyst |
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