CN103272594B - Hydrogenation catalyst, preparation method thereof and application thereof to preparation of 10-hydroxydecanoate - Google Patents
Hydrogenation catalyst, preparation method thereof and application thereof to preparation of 10-hydroxydecanoate Download PDFInfo
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Abstract
The invention relates to the fields of catalyst technologies and fine chemical engineering, and in particular relates to a hydrogenation catalyst. The catalyst comprises a carrier and active components, wherein the carrier is mesoporous carbon pretreated by a sodium hypochlorite solution; and the active components comprise metal ruthenium and metal tin. A preparation method of the hydrogenation catalyst comprises the following steps of: soaking the mesoporous carbon in the sodium hypochlorite solution, washing the soaked mesoporous carbon by distilled water, and then filtering the washed mesoporous carbon; and soaking the carrier, namely the mesoporous carbon, by a salty solution containing the metal ruthenium and the metal tin, then washing the soaked carrier by distilled water, and performing suction filtration on the washed carrier. The invention also discloses application of the hydrogenation catalyst to preparation of 10-hydroxydecanoate. The hydrogenation catalyst has the advantages that the catalyst carrier adopts the mesoporous carbon, and compared with active carbon, the mesoporous carbon enables the target product yield to be obviously improved; compared with a catalyst with an inorganic oxide carrier, the catalyst has the advantage that the active components, namely the ruthenium and the thin, in the waste catalyst are easy to recycle; due to proper passageways, the inner diffusion resistance can be reduced, and the reaction rate is improved; by pretreatment of the sodium hypochlorite, the activity of the catalyst is obviously improved; and the hydrogenation catalyst has great industrial prospect.
Description
Technical field
The present invention relates to catalyst technology, field of fine chemical, relate to a kind of hydrogenation catalyst specifically.
Background technology
10-hydroxydecanoic acid is important source material and the intermediate of cosmetics, medical product and health products trade, can directly be added in cosmetics as sebum secretion inhibitor [multitude's Yu, Li Shanji, Lin Chunxiao, Huang Li. the research [J] of microwave catalyzed synthesis of 10-hydroxy decanonic acid by one-pot method. China brewages, and 2008 (1): 47 ~ 48.].In addition 10-hydroxydecanoic acid is also high-efficiency antioxidant agent and the important source material [Zhang Mingyue producing antibacterial in royal jelly, anticancer and radiation-resistant active ingredient E-10-hydroxy-2-decylenic acid, Gao Hong, Wang Jinfeng, Chen Yanru, Chen Xubin. the research [J] of macroreticular resin Static Adsorption 10-hydroxydecanoic acid characteristic. Guangdong chemical industry, 2010,37 (11): 28 ~ 29.].
Hargreaves [Hargreaves, G.H., Nowen, L., J.Chem.Soc., 1947, 7, 58.] the method synthesis 10-hydroxydecanoic acid of castor oil cracking is adopted, productive rate is 21%, [the Mikhalbor such as Mikhalbor, M., Godishmik Khim-Tekhnoinst, 1958, 1, 53.] after-souring method separating and cracking product is adopted, productive rate is made to bring up to 32%, Diamond [Diamond, M.J., Binder, R.G, Apple White, T.H., J.Am.Oil.Chem.Soc., 1965, 42, a large amount of 1-octanols is added or sec-n-octyl alcohol makes diluent when 882.] proposing alkali cracking, productive rate is made to be increased to 69%, this method requires to use bulk petroleum ether, and deep cooling is to-23 DEG C of Crystallization Separation products.Gao Hong, Liu Songqing [Gao Hong, Liu Songqing. microwave castor oil alkali cracking closes 10-hydroxydecanoic acid [J]. Speciality Petrochemicals, 2008,25 (3): 49 ~ 51.] adopt microwave castor oil alkali cracking synthesis 10-hydroxydecanoic acid, yield reaches 77.4%.Li Kai, Zhao Zhenhan etc. [Li Kai, Qian Wanzhu, Xu Naiqin, Cao Zengyu, Li Huagen, Huang Zhixi, Zhao Zhenhan. perfume (or spice) is trembled and essence [J], 1979,1,1.] with 95% ethanol for diluent, carry out decomposition under high pressure with autoclave, productive rate reaches 70%.Lycan and Adams [F.L.Greenwood, J.Ora.Chem., 20,803 (1955) .] to report with methyl undecylenate be raw material through the method for the four steps synthesis 10-hydroxydecanoic acids such as epoxidation, adds the reduction [N.G.Gaylord that ester group avoided by sodium borohydride in building-up process, Reduct withComplex Metal Hydrides, Interscience Publishers, Inc., New York, 1956, page500.].Binary acid selective hydrogenation is the effective ways preparing tail end hydroxycarboxylic acid, He Dehua [He Dehua, Zhu Qiming. α on ruthenium system bicomponent catalyst, the research [J] of ω-dicarboxylic acids monoesters hydrogenation synthesis 'omega '-hydroxy carboxylic acid ester. Journal of Molecular Catalysis, 1998,12 (3), 175 ~ 182.] etc. ruthenium system bicomponent catalyst catalysis α is reported, the method of ω-dicarboxylic acids monoesters hydrogenation synthesis 'omega '-hydroxy carboxylic acid, obtains good effect.But second component rhenium or molybdenum adopt corresponding carbonyl complex to be presoma in ruthenium system used bicomponent catalyst, preparation method is complicated, and preparation process is wayward; And this catalyst system and catalyzing needs first binary acid to be converted into dibasic acid monoester, just can carry out hydrogenation reaction, also need monoesters hydrolysis after reaction to obtain 'omega '-hydroxy carboxylic acid.
Summary of the invention
Corresponding carbonyl complex is adopted to be presoma for second component rhenium or molybdenum in the ruthenium system bicomponent catalyst of prior art, preparation method is complicated, the uppity deficiency of preparation process, the invention provides the reaction process of a kind of hydrogenation catalyst and decanedioic acid liquid phase catalytic hydrogenation 10-hydroxydecanoic acid.The present invention passes through to contain ruthenium salt and contains tin salt aqueous solution for presoma, and preparation method is simple, be easy to industrialization, and activity of hydrocatalyst prepared by the present invention is higher.
The present invention adopts, and to be technical scheme be: a kind of hydrogenation catalyst, and described catalyst comprises carrier and active component; Described carrier is through the pretreated mesoporous carbon of liquor natrii hypochloritis, and described active component is metal Ru and tin.
As preferably, ruthenium is 1% ~ 10% to described catalyst by mass percentage, tin is 2% ~ 11%, and surplus is mesoporous carbon;
Described mesoporous carbon carrier can adopt existing commodity, also can prepare by prior art, requires that its pore volume is 1.5-2.0mL/g, specific area is 1000-2000m
2/ g, bore dia are 3-8nm.
The preparation method of above-mentioned hydrogenation catalyst is: first by the pretreatment of mesoporous carbon clorox, concrete grammar is: mesoporous carbon added in 0.1 ~ 1M liquor natrii hypochloritis and soak 1 ~ 24 hour, then with distilled water washing, filters; Adopt the solution impregnation containing ruthenium salt and pink salt through pretreated mesoporous carbon carrier, after dipping 2 ~ 12h, with distilled water washing, suction filtration, dry, then roasting, then obtain Ru-Sn/ gold/mesoporous carbon catalyst through hydrogen reducing; The described mass percent contained containing ruthenium in the solution of ruthenium salt and pink salt is 0.3 ~ 4%, and stanniferous mass percent is 0.7 ~ 4%.
As preferably, described roasting condition is: 300 ~ 500 DEG C of roastings 2 ~ 4 hours in an inert atmosphere.
As preferably, described reducing condition is 250 ~ 500 DEG C of reductase 12 ~ 4 hour in presence of hydrogen.
Above-mentioned hydrogenation catalyst prepares the application of 10-hydroxydecanoic acid.
Above-mentioned hydrogenation catalyst prepares the application of 10-hydroxydecanoic acid, and step is as follows: take decanedioic acid as raw material, under solvent, auxiliary agent and hydrogenation catalyst existence condition, adds hydrogen and carries out catalytic reaction and prepare 10-hydroxydecanoic acid.
As preferably, described reaction condition is: reaction temperature is 210 ~ 240 DEG C, and hydrogen reaction pressure is 3 ~ 8MPa.
As preferably, described solvent is the one in methyl alcohol, water, and decanedioic acid is 1: 40 ~ 1: 100 with solvent quality ratio.
As preferably, described auxiliary agent is the one in lithium hydroxide, NaOH or potassium hydroxide, and consumption is 2% ~ 35% of decanedioic acid quality; Catalyst amount is 5% ~ 20% of decanedioic acid quality.
Specifically, compared with prior art, present invention process production 10-hydroxydecanoic acid tool has the following advantages:
1, the catalyst carrier in the present invention selects mesoporous carbon, and compared with active carbon, object product yield significantly improves; Compared with inorganic oxide carrier (as aluminium oxide), in dead catalyst, active component ruthenium and tin are easy to reclaim.
2, the catalyst carrier in the present invention selects mesoporous carbon, and its suitable duct is conducive to reducing inside diffusional resistance, improves reaction rate.
3, the catalyst carrier mesoporous carbon in the present invention is carried out after pretreatment through clorox, the activity of catalyst significantly improves, and experiment simultaneously shows, the catalyst prepared for carrier with pretreated mesoporous carbon, the yield of hydrogenation process improves further, has industrial prospect.
4, to contain ruthenium salt and to contain tin salt aqueous solution for presoma, preparation method is simple, is easy to industrialization; Catalyst of the present invention is used for decanedioic acid direct hydrogenation and prepares 10-hydroxydecanoic acid, does not need to carry out mono-esterification to raw material.
Detailed description of the invention
In order to further illustrate this invention, enumerate following examples.
The preparation of catalyst: be 1.5-2.0mL/g by pore volume, specific area is 1000-2000m
2/ g, bore dia are that the mesoporous carbon of 3-8nm adds in 0.1 ~ 1M liquor natrii hypochloritis and soaks 1-24 hour, wash with distilled water again, filter, the salt solution impregnated carrier mesoporous carbon containing ruthenium and tin is adopted according to mass ratio, mass percent containing ruthenium in dipping salting liquid is 0.3 ~ 4%, stanniferous mass percent is 0.7 ~ 4%, regulates according to catalyst ruthenium and Theil indices.Flood after 2 ~ 12 hours, with distilled water washing, suction filtration, after drying, 300 ~ 500 DEG C of roastings 2 ~ 4 hours in an inert atmosphere, then 250 ~ 500 DEG C of reductase 12 ~ 4 hour in presence of hydrogen, namely obtain Ru-Sn/ gold/mesoporous carbon catalyst.
Embodiment 1
In the autoclave that band stirs, add 10%Ru-2%Sn/ gold/mesoporous carbon catalyst (mesoporous carbon uses the process of 0.5M clorox in advance) 0.025g, decanedioic acid 0.5g, distilled water 20ml, LiOH0.01g, off-response still, with the air in nitrogen replacement reaction kettle three times, use nitrogen in hydrogen exchange reactor again three times, and then be filled with hydrogen and make the reaction pressure of reactor reach 3.0MPa, heating reactor makes reaction temperature reach 240 DEG C, start to stir, isothermal reaction is till pressure no longer declines, take out product, Filtration of catalyst, adopt liquid-phase chromatographic analysis.Analysis result lists in table 1.
Embodiment 2
In the autoclave that band stirs, add 8%Ru-3%Sn/ gold/mesoporous carbon catalyst (mesoporous carbon uses the process of 0.1M clorox in advance) 0.1g, decanedioic acid 0.5g, distilled water 50ml, NaOH0.05g, off-response still, with the air in nitrogen replacement reaction kettle three times, use nitrogen in hydrogen exchange reactor again three times, and then be filled with hydrogen and make the reaction pressure of reactor reach 5.0MPa, heating reactor makes reaction temperature reach 230 DEG C, start to stir, isothermal reaction is till pressure no longer declines, take out product, Filtration of catalyst, adopt liquid-phase chromatographic analysis.Analysis result lists in table 1.
Embodiment 3
In the autoclave that band stirs, add 5%Ru-6%Sn/ gold/mesoporous carbon catalyst (mesoporous carbon uses the process of 1M clorox in advance) 0.05g, decanedioic acid 0.5g, distilled water 50ml, KOH0.075g, off-response still, with the air in nitrogen replacement reaction kettle three times, use nitrogen in hydrogen exchange reactor again three times, and then be filled with hydrogen and make the reaction pressure of reactor reach 8.0MPa, heating reactor makes reaction temperature reach 230 DEG C, start to stir, isothermal reaction is till pressure no longer declines, take out product, Filtration of catalyst, adopt liquid-phase chromatographic analysis.Analysis result lists in table 1.
Embodiment 4
In the autoclave that band stirs, add 5%Ru-8%Sn/ gold/mesoporous carbon catalyst (mesoporous carbon uses the process of 0.2M clorox in advance) 0.05g, decanedioic acid 0.5g, distilled water 50ml, LiOH0.10g, off-response still, with the air in nitrogen replacement reaction kettle three times, use nitrogen in hydrogen exchange reactor again three times, and then be filled with hydrogen and make the reaction pressure of reactor reach 5.0MPa, heating reactor makes reaction temperature reach 210 DEG C, start to stir, isothermal reaction is till pressure no longer declines, take out product, Filtration of catalyst, adopt liquid-phase chromatographic analysis.Analysis result lists in table 1.
Embodiment 5
In the autoclave that band stirs, add 3%Ru-8%Sn/ gold/mesoporous carbon catalyst (mesoporous carbon uses the process of 0.8M clorox in advance) 0.05g, decanedioic acid 0.5g, distilled water 30ml, NaOH0.125g, off-response still, with the air in nitrogen replacement reaction kettle three times, use nitrogen in hydrogen exchange reactor again three times, and then be filled with hydrogen and make the reaction pressure of reactor reach 5.0MPa, heating reactor makes reaction temperature reach 230 DEG C, start to stir, isothermal reaction is till pressure no longer declines, take out product, Filtration of catalyst, adopt liquid-phase chromatographic analysis.Analysis result lists in table 1.
Embodiment 6
In the autoclave that band stirs, add 1%Ru-11%Sn/ gold/mesoporous carbon catalyst (mesoporous carbon uses the process of 0.5M clorox in advance) 0.05g, decanedioic acid 0.5g, methyl alcohol 50ml, KOH0.175g, off-response still, with the air in nitrogen replacement reaction kettle three times, use nitrogen in hydrogen exchange reactor again three times, and then be filled with hydrogen and make the reaction pressure of reactor reach 5.0MPa, heating reactor makes reaction temperature reach 230 DEG C, start to stir, isothermal reaction is till pressure no longer declines, take out product, Filtration of catalyst, adopt liquid-phase chromatographic analysis.Analysis result lists in table 1.
Reference example 1
In the autoclave that band stirs, add 5%Ru-6%Sn/ gold/mesoporous carbon catalyst (mesoporous carbon does not carry out pretreatment) 0.05g, decanedioic acid 0.5g, distilled water 50ml, KOH0.075g, off-response still, with the air in nitrogen replacement reaction kettle three times, use nitrogen in hydrogen exchange reactor again three times, and then be filled with hydrogen and make the reaction pressure of reactor reach 5.0MPa, heating reactor makes reaction temperature reach 230 DEG C, start to stir, isothermal reaction is till pressure no longer declines, take out product, Filtration of catalyst, adopt liquid-phase chromatographic analysis.Analysis result lists in table 1.
Reference example 2
In the autoclave that band stirs, add 5%Ru-6%Sn/ gold/mesoporous carbon catalyst (mesoporous carbon uses 10% hydrogen peroxide process in advance) 0.05g, decanedioic acid 0.5g, distilled water 50ml, KOH0.075g, off-response still, with the air in nitrogen replacement reaction kettle three times, use nitrogen in hydrogen exchange reactor again three times, and then be filled with hydrogen and make the reaction pressure of reactor reach 8.0MPa, heating reactor makes reaction temperature reach 230 DEG C, start to stir, isothermal reaction is till pressure no longer declines, take out product, Filtration of catalyst, adopt liquid-phase chromatographic analysis.Analysis result lists in table 1.
Reference example 3
In the autoclave that band stirs, add 5%Ru-6%Sn/ gold/mesoporous carbon catalyst (mesoporous carbon uses 1M HCl treatment in advance) 0.05g, decanedioic acid 0.5g, distilled water 50ml, KOH0.075g, off-response still, with the air in nitrogen replacement reaction kettle three times, use nitrogen in hydrogen exchange reactor again three times, and then be filled with hydrogen and make the reaction pressure of reactor reach 8.0MPa, heating reactor makes reaction temperature reach 230 DEG C, start to stir, isothermal reaction is till pressure no longer declines, take out product, Filtration of catalyst, adopt liquid-phase chromatographic analysis.Analysis result lists in table 1.
Reference example 4
In the autoclave that band stirs, add 5%Ru-6%Sn/ gold/mesoporous carbon catalyst (mesoporous carbon uses 1M nitric acid treatment in advance) 0.05g, decanedioic acid 0.5g, distilled water 50ml, KOH0.075g, off-response still, with the air in nitrogen replacement reaction kettle three times, use nitrogen in hydrogen exchange reactor again three times, and then be filled with hydrogen and make the reaction pressure of reactor reach 8.0MPa, heating reactor makes reaction temperature reach 230 DEG C, start to stir, isothermal reaction is till pressure no longer declines, take out product, Filtration of catalyst, adopt liquid-phase chromatographic analysis.Analysis result lists in table 1.
Reference example 5
In the autoclave that band stirs, add 5%Ru/ gold/mesoporous carbon catalyst (mesoporous carbon does not carry out pretreatment) 0.05g, decanedioic acid 0.5g, distilled water 50ml, KOH0.075g, off-response still, with the air in nitrogen replacement reaction kettle three times, then use nitrogen in hydrogen exchange reactor three times, and then be filled with hydrogen and make the reaction pressure of reactor reach 5.0MPa, heating reactor makes reaction temperature reach 230 DEG C, start to stir, isothermal reaction, till pressure no longer declines, takes out product, Filtration of catalyst, adopts liquid-phase chromatographic analysis.Analysis result lists in table 1.
Reference example 6
In the autoclave that band stirs, adding 5%Ru/ activated carbon (adopts conventional activated carbon to replace mesoporous carbon, obtain with method for preparing catalyst of the present invention) catalyst 0.05g, decanedioic acid 0.5g, distilled water 50ml, KOH0.075g, off-response still, with the air in nitrogen replacement reaction kettle three times, use nitrogen in hydrogen exchange reactor again three times, and then be filled with hydrogen and make the reaction pressure of reactor reach 5.0MPa, heating reactor makes reaction temperature reach 230 DEG C, start to stir, isothermal reaction is till pressure no longer declines, take out product, Filtration of catalyst, adopt liquid-phase chromatographic analysis.Analysis result lists in table 1.
Table 1 is according to the Performance comparision preparing 10-hydroxydecanoic acid under different technology conditions in liquid-phase chromatographic analysis acetonideexample
| Decanedioic acid conversion ratio (%) | 10-hydroxydecanoic acid yield (%) |
| Embodiment 1 | 84.8 | 56.3 |
| Embodiment 2 | 74.9 | 49.3 |
| Embodiment 3 | 83.6 | 58.2 |
| Embodiment 4 | 44.5 | 36.6 |
| Embodiment 5 | 69.3 | 47.5 |
| Embodiment 6 | 88.7 | 38.7 |
| Reference example 1 | 32.4 | 12.8 |
| Reference example 2 | 52.3 | 31.7 |
| Reference example 3 | 42.5 | 24.6 |
| Reference example 4 | 48.7 | 32.5 |
| Reference example 5 | 22.1 | 2.2 |
| Reference example 6 | 10.2 | 0.8 |
Table 1 illustrates that loaded noble metal catalyst prepared by embodiment has higher activity to sebacic-acid liquid phase hydrogenation reaction and has 10-hydroxydecanoic acid higher selective, and preparation process is simple, cheap, be the catalyst of more desirable decanedioic acid liquid phase catalytic hydrogenation 10-hydroxydecanoic acid.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (5)
1. hydrogenation catalyst prepares an application for 10-hydroxydecanoic acid, it is characterized in that: described catalyst comprises carrier and active component; Described carrier is through the pretreated mesoporous carbon of liquor natrii hypochloritis, and described active component is metal Ru and tin;
Ruthenium is 1% ~ 10% to described catalyst by mass percentage, tin is 2% ~ 11%, and surplus is mesoporous carbon;
Described carrier mesoporous carbon pore volume is 1.5-2.0mL/g, specific area is 1000-2000m
2/ g, bore dia are 3-8nm.
2. hydrogenation catalyst according to claim 1 prepares the application of 10-hydroxydecanoic acid, it is characterized in that: step is as follows: take decanedioic acid as raw material, under solvent, auxiliary agent and hydrogenation catalyst existence condition, adds hydrogen reaction and prepares 10-hydroxydecanoic acid.
3. hydrogenation catalyst according to claim 2 prepares the application of 10-hydroxydecanoic acid, it is characterized in that: described reaction condition is: reaction temperature is 210 ~ 240 DEG C, and Hydrogen Vapor Pressure is 3 ~ 8MPa.
4. hydrogenation catalyst according to claim 2 prepares the application of 10-hydroxydecanoic acid, it is characterized in that: described solvent is the one in methyl alcohol, water, and decanedioic acid is 1: 40 ~ 1: 100 with solvent quality ratio.
5. hydrogenation catalyst according to claim 2 prepares the application of 10-hydroxydecanoic acid, it is characterized in that: described auxiliary agent is the one in lithium hydroxide, NaOH or potassium hydroxide, and consumption is 2% ~ 35% of decanedioic acid quality; Catalyst amount is 5% ~ 20% of decanedioic acid quality.
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| CN102600842A (en) * | 2012-03-02 | 2012-07-25 | 山西盛驰科技有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic acid as well as preparation method and application thereof |
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