CN103962141A - Catalyst for synthesizing neopentyl glycol from hydroxypivalaldehyde by virtue of hydrogenation - Google Patents
Catalyst for synthesizing neopentyl glycol from hydroxypivalaldehyde by virtue of hydrogenation Download PDFInfo
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- CN103962141A CN103962141A CN201410207994.4A CN201410207994A CN103962141A CN 103962141 A CN103962141 A CN 103962141A CN 201410207994 A CN201410207994 A CN 201410207994A CN 103962141 A CN103962141 A CN 103962141A
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Abstract
The invention discloses a catalyst for synthesizing neopentyl glycol from hydroxypivalaldehyde by virtue of hydrogenation and belongs to the technical field of catalysts. The catalyst comprises the following components in percentage by weight: 3.2%-21.8% of copper, 3.2%-21.8% of nickel, 0%-3.2% of cobalt or iron and 75.0%-90.4% of aluminum oxide or silicon oxide. The catalyst is prepared by virtue of a one-step precipitation method or an impregnation method and has the advantages of low cost, high activity, environmental friendliness, short flow, good stability and the like. The catalyst can be used for preparing the neopentyl glycol at the temperature of 80 DEG C and the hydrogen pressure of 3MPa by virtue of a liquid phase hydrogenation manner by taking water as a solvent, and the yield of the neopentyl glycol can reach above 96%.
Description
Technical field
The present invention relates to a kind of catalyst by the synthetic neopentyl glycol of hydroxy pivalin aldehyde hydrogenation, belong to catalyst technical field.
Background technology
Neopentyl glycol is a kind of important dihydroxylic alcohols, has good chemical reactivity, can be used for production various kinds of resin and fine chemicals.At present industrially by the synthetic neopentyl glycol of new penta hydroxy aldehyde, mainly contain formaldehyde disproportionation and two kinds of methods of catalytic hydrogenation, wherein discrimination method is made reducing agent with formaldehyde, consumes more formaldehyde and liquid caustic soda, the sodium formate that by-product is a large amount of, the problems such as product quality is poor, but also exists energy consumption higher, seriously polluted; And catalytic hydrogenation adopts solid hydrogenation catalyst, product is easily separated, and quality is high, is a kind of green reaction technique of preparing neopentyl glycol, has good economy and application prospect.
By new penta hydroxy aldehyde catalytic hydrogenation, prepare the hydrogenation catalyst that neopentyl glycol adopts and generally have noble metal, nickel system and Cu-series catalyst.Noble metal catalyst mainly contain two kinds of Pt-Ru-W/C and Ru-Pd/C [Ning Chunli, Wang Jian, Zhang Meng, Shi Kaimin, Zhang Chunlei. the research of hydroxy pivalin aldehyde Hydrogenation neopentyl glycol catalyst. Shanghai Normal University's journal, 2009:68-69.], catalyst cost is high, nickel catalyst be take Raney's nickel or be representative with the catalyst of the modifications such as Mo, Co, but activity and less stable, and preparation and process all more complicated [CN101993351A, CN102513107B], in Cu-series catalyst, take Cu-Cr catalyst as main, conventionally add Mn or Ba auxiliary agent to improve the catalytic activity of aldehyde hydrogenation, although shown good activity and selectivity in the technique at Hydrogenation for neopentyl glycol, but in its process, produce a large amount of containing Cr waste water, environment is caused to severe contamination [US4250337, US4855515], in addition, copper zinc catalyst is also showing good activity and selectivity aspect the catalytic hydrogenation of new penta hydroxy aldehyde, CN201110187555.8 discloses two-stage hydrogenation and has prepared NPG, in the first hydrogenation reactor, use copper, three kinds of metallic elements of zinc and aluminium, in the second hydrogenation reactor, use copper, zinc, aluminium and four kinds of metallic elements of manganese, the mass space velocity of the first hydrogenation reaction is 0.3-1.5g/gcat/hr, and the mass space velocity of the second hydrogenation reaction is 0.01-0.3g/gcat/hr, but its flow process is comparatively complicated.
In sum, in existing hydroxy pivalin aldehyde catalytic hydrogenation technology, there is following problem 1 in its catalyst adopting) cost is high, 2) catalyst preparation and process complicated, 3) produce chromate waste water, 4) hydrogenation needs segmentation to carry out.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, the object of the present invention is to provide a kind of catalyst by the synthetic neopentyl glycol of hydroxy pivalin aldehyde hydrogenation, take water as solvent, 80
ounder the Hydrogen Vapor Pressure of the temperature of C and 3 MPa, neopentyl glycol is prepared in liquid-phase hydrogenatin, and the yield of neopentyl glycol reaches more than 96%, and catalyst has the advantages such as low, active high, the environmental friendliness of cost, flow process are short, good stability.
A kind of consisting of by the synthetic neopentyl glycol catalyst of hydroxy pivalin aldehyde hydrogenation: copper 3.2%-21.8%, nickel 3.2%-21.8%, cobalt or iron 0%-3.2%, aluminium oxide or silica 75.0%-90.4%, be more than weight percentage.The preparation method of this catalyst is the step precipitation method or an infusion process.The active component presoma that the one step precipitation method adopt is respectively copper nitrate, nickel nitrate, cobalt nitrate or ferric nitrate, aluminum nitrate or ethyl orthosilicate, precipitating reagent is the carbonate of NaOH, KOH, Na or K or one or both in bicarbonate, course of reaction requires pH between 9.5-10.5, and reaction finishes rear aging 8-24 hour; Infusion process is that copper nitrate, nickel nitrate, cobalt nitrate or ferric nitrate be impregnated on the aluminium oxide or silica of required weight by the mixed aqueous solution of required percentage by weight preparation.Roasting after the sample drying that two kinds of methods prepare, sintering temperature is 400-800
oc.The agent of preparation, for the synthetic neopentyl glycol reaction of hydroxy pivalin aldehyde gas phase hydrogenation, be take to water as solvent, and reaction temperature is 60-140
oc, preferably 80-100
oc; Hydrogen Vapor Pressure is 2-5 MPa, preferably 3-4 MPa; The weight ratio of catalyst and hydroxy pivalin aldehyde is 1:(2-100), preferred 1:(25-50); The weight ratio of hydroxy pivalin aldehyde and solvent is 1:(10-50), preferred 1:(20-40).
Compared with the prior art, advantage of the present invention is as follows: catalyst is not containing noble metal, and cost is low; , containing chromium metal, do not produce chromate waste water, environmental friendliness; Can under gentle condition, take water as solvent, hydroxy pivalin aldehyde one step hydrogenation obtains the yield of 96% above neopentyl glycol, and catalyst activity is high, good stability, and hydrogenation technique flow process is short.
The specific embodiment
Should be understood that these embodiment are only for the present invention is described, but not limit the scope of the invention.
Embodiment 1
Method for preparing catalyst of the present invention is as follows:
Take 17.72g Cu (NO
3)
2, 42.61g Ni (NO
3)
2, 4.18g Fe (NO
3)
3, 198.38g Al (NO
3)
3mix to solution clarification with 5000mL deionized water.The Na of configuration 1mol/L
2cO
3solution, pours in constant pressure funnel and is then added drop-wise in the solution mixing, and makes the final pH value of solution between 9.5-10.5.Dropwise, pour solution in PP bottle aged at room temperature 12h, aging good emulsion is carried out to suction filtration, after suction filtration is good, with deionized water washing ten times, filter cake puts into 120
oc oven drying 12h.Then gained solid is put into Muffle furnace 600
o4h is standby in C roasting.Before each hydrogenation reaction, need catalyst reduction activation, reduction temperature is 350
oc(sample 1).
Embodiment 2
The addition of the nitrate of Cu, Ni, Fe, with embodiment 1, adds 193.72g ethyl orthosilicate, and the preparation method of catalyst is with the catalyst of embodiment 1, aged at room temperature 18h, sintering temperature 500
oc, makes sample 2.
Embodiment 3
The addition of the nitrate of Cu, Ni, Al, with embodiment 1, adds 4.23g Co (NO
3)
3, the preparation method of catalyst is with the catalyst of embodiment 1, and precipitating reagent is NaOH, makes sample 3.
Embodiment 4(comparative example)
The addition of the nitrate of Cu, Al, Fe, with embodiment 1, does not add the nitrate of Ni, and the preparation method of catalyst, with the catalyst of embodiment 1, makes sample 4.
Embodiment 5
Take 17.72g Cu (NO
3)
2, 42.61g Ni (NO
3)
2, 4.18g Fe (NO
3)
3mix to solution clarification with 5000mL deionized water, impregnated in 25.15 g alumina powders.After drying at room temperature, gained solid is put into Muffle furnace 600
o4h is standby in C roasting.Before each hydrogenation reaction, need catalyst reduction activation, reduction temperature is 350
oc(sample 5).
Embodiment 6
The addition of the nitrate of Cu, Ni, Fe, with embodiment 5, impregnated in 24.32g SiO 2 powder, and the preparation method of catalyst is with the catalyst of embodiment 5, sintering temperature 700
oc, makes sample 6.
Embodiment 7(comparative example)
The addition of the nitrate of Ni, Al, Fe, with embodiment 5, does not add the nitrate of Cu, and the preparation method of catalyst, with the catalyst of embodiment 5, makes sample 7.
Through the Hydrogenation of the hydroxy pivalin aldehyde of said method gained catalyst as table 1.Reaction condition is, water is solvent, 80
othe Hydrogen Vapor Pressure of the temperature of C and 3 MPa, the weight ratio of catalyst and hydroxy pivalin aldehyde is 1:25, the weight ratio of hydroxy pivalin aldehyde and solvent is 1:20.
The Hydrogenation of hydroxy pivalin aldehyde in table 1 different catalysts
Embodiment 8
Catalytic hydrogenation reaction by sample 2 for hydroxy pivalin aldehyde, water is solvent, 100
othe Hydrogen Vapor Pressure of the temperature of C and 3 MPa, the weight ratio of catalyst and hydroxy pivalin aldehyde is 1:25, the weight ratio of hydroxy pivalin aldehyde and solvent is 1:20.
Embodiment 9
Catalytic hydrogenation reaction by sample 2 for hydroxy pivalin aldehyde, water is solvent, 120
othe Hydrogen Vapor Pressure of the temperature of C and 3 MPa, the weight ratio of catalyst and hydroxy pivalin aldehyde is 1:30, the weight ratio of hydroxy pivalin aldehyde and solvent is 1:30.
Embodiment 10
Catalytic hydrogenation reaction by sample 2 for hydroxy pivalin aldehyde, water is solvent, 100
othe Hydrogen Vapor Pressure of the temperature of C and 2 MPa, the weight ratio of catalyst and hydroxy pivalin aldehyde is 1:45, the weight ratio of hydroxy pivalin aldehyde and solvent is 1:40.
Embodiment 11
Catalytic hydrogenation reaction by sample 2 for hydroxy pivalin aldehyde, water is solvent, 80
othe temperature of C and the Hydrogen Vapor Pressure of 5MPa, the weight ratio of catalyst and hydroxy pivalin aldehyde is 1:65, the weight ratio of hydroxy pivalin aldehyde and solvent is 1:20.
Embodiment 12
Catalytic hydrogenation reaction by sample 2 for hydroxy pivalin aldehyde, water is solvent, 110
othe Hydrogen Vapor Pressure of the temperature of C and 4 MPa, the weight ratio of catalyst and hydroxy pivalin aldehyde is 1:10, the weight ratio of hydroxy pivalin aldehyde and solvent is 1:20.
Embodiment 13
Catalytic hydrogenation reaction by sample 2 for hydroxy pivalin aldehyde, water is solvent, 90
othe Hydrogen Vapor Pressure of the temperature of C and 2 MPa, the weight ratio of catalyst and hydroxy pivalin aldehyde is 1:50, the weight ratio of hydroxy pivalin aldehyde and solvent is 1:40.
Embodiment 14
Catalytic hydrogenation reaction by sample 2 for hydroxy pivalin aldehyde, water is solvent, 60
othe Hydrogen Vapor Pressure of the temperature of C and 5 MPa, the weight ratio of catalyst and hydroxy pivalin aldehyde is 1:40, the weight ratio of hydroxy pivalin aldehyde and solvent is 1:10.
Embodiment 15
Catalytic hydrogenation reaction by sample 2 for hydroxy pivalin aldehyde, water is solvent, 100
othe Hydrogen Vapor Pressure of the temperature of C and 3 MPa, the weight ratio of catalyst and hydroxy pivalin aldehyde is 1:5, the weight ratio of hydroxy pivalin aldehyde and solvent is 1:50.
Through the Hydrogenation of the hydroxy pivalin aldehyde of above-mentioned reaction condition gained catalyst as table 2.
The hydroxy pivalin aldehyde Hydrogenation of catalyst under table 2 differential responses condition
Claims (3)
1. by a catalyst for the synthetic neopentyl glycol of hydroxy pivalin aldehyde hydrogenation, it is characterized in that the consisting of of this catalyst: copper 3.2%-21.8%, nickel 3.2%-21.8%, cobalt or iron 0%-3.2%, aluminium oxide or silica 75.0%-90.4%, be more than weight percentage.
2. catalyst according to claim 1, its preparation method is the step precipitation method or an infusion process, preparation method is characterised in that, the active component presoma that the one step precipitation method adopt is respectively copper nitrate, nickel nitrate, cobalt nitrate or ferric nitrate, aluminum nitrate or ethyl orthosilicate, precipitating reagent is the carbonate of NaOH, KOH, Na or K or one or both in bicarbonate, course of reaction requires the final pH value of solution between 9.5-10.5, and reaction finishes rear aging 8-24 hour; Infusion process is that copper nitrate, nickel nitrate, cobalt nitrate or ferric nitrate be impregnated on the aluminium oxide or silica of required weight by the mixed aqueous solution of required percentage by weight preparation, roasting after the sample drying that two kinds of methods prepare, and sintering temperature is 400-800
oc.
3. catalyst according to claim 1, for the synthetic neopentyl glycol reaction of hydroxy pivalin aldehyde gas phase hydrogenation, is characterized in that, take water as solvent, reaction temperature is 60-140
oc, preferably 80-100
oc; Hydrogen Vapor Pressure is 2-5 MPa, preferably 3-4 MPa; The weight ratio of catalyst and new penta hydroxy aldehyde is 1:(2-100), preferred 1:(25-50); The weight ratio of new penta hydroxy aldehyde and solvent is 1:(10-50), preferred 1:(20-40).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664956A (en) * | 2016-01-07 | 2016-06-15 | 上海华谊（集团）公司 | Catalyst for preparing neopentyl glycol through hydrogenation of hydroxyl pivalaldehyde and preparing method thereof, and method |
| CN107540521A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The method of hydroxy pivalin aldehyde Hydrogenation neopentyl glycol |
| CN111099965A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Liquid-phase hydrofining method of 1, 5-pentanediol |
| CN113121308A (en) * | 2021-04-21 | 2021-07-16 | 云南恒罡科技有限公司 | Method for synthesizing neopentyl glycol by catalytic hydrogenation of hydroxypentanal |
| CN115069268A (en) * | 2022-08-02 | 2022-09-20 | 山东鲁新设计工程有限公司 | Catalyst for preparing neopentyl glycol by high pressure method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664956A (en) * | 2016-01-07 | 2016-06-15 | 上海华谊（集团）公司 | Catalyst for preparing neopentyl glycol through hydrogenation of hydroxyl pivalaldehyde and preparing method thereof, and method |
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| CN111099965A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Liquid-phase hydrofining method of 1, 5-pentanediol |
| CN111099965B (en) * | 2018-10-25 | 2024-03-12 | 中国石油化工股份有限公司 | Liquid-phase hydrofining method of 1, 5-pentanediol |
| CN113121308A (en) * | 2021-04-21 | 2021-07-16 | 云南恒罡科技有限公司 | Method for synthesizing neopentyl glycol by catalytic hydrogenation of hydroxypentanal |
| CN115069268A (en) * | 2022-08-02 | 2022-09-20 | 山东鲁新设计工程有限公司 | Catalyst for preparing neopentyl glycol by high pressure method |
| CN115069268B (en) * | 2022-08-02 | 2024-05-14 | 山东鲁新设计工程股份有限公司 | Catalyst for preparing neopentyl glycol by high-pressure method |
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Application publication date: 20140806 |