CN102389827A - Loaded metal hydrogenation catalyst, its preparation method and application in ethylene glycol preparation - Google Patents
Loaded metal hydrogenation catalyst, its preparation method and application in ethylene glycol preparation Download PDFInfo
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Abstract
The invention relates to a loaded metal hydrogenation catalyst, its preparation method and application in ethylene glycol preparation. With a spherical SiC/C molecular sieve as a carrier and a metal loading capacity of 0.1-15 wt%, the catalyst adopts nickel as a main metal catalyst, and contains the metal auxiliary agents of Zn, Cu, Co, Fe, Cr, Sn, Bi, Re, La, Ce, Nd, Sm, and Gd. In a catalytic process, a certain amount of methyl oxalate, glycolic acid and the above loaded metal hydrogenation catalyst are added into a solvent, under a hydrogen atmosphere as well as a certain temperature and pressure, ethylene glycol can be prepared. The catalyst of the invention is suitable for the gas-solid phase or liquid-solid phase catalytic hydrogenation process of methyl oxalate and glycolic acid, and the catalytic process is characterized by high activity and selectivity to ethylene glycol. Meanwhile, the catalyst provided in the invention has excellent stability, and is suitable for a long time reaction process of batches.
Description
Technical field
The invention belongs to catalyst technical field, is the spherical molecular sieve carried nickel series duplex metal of a kind of SiC/C or many metal hydrogenation catalysts and preparation method thereof specifically, with and in the application of catalytically synthesizing glycol.
Background technology
Ethylene glycol (ethylene glycol is called for short EG) has another name called glycol, 1, and the 2-ethylidene glycol, is used always in the pharmaceuticals industry and made solvent as hydrating agents at leather industry.The preparation process is made progress as follows: 1859, Wurtz made ethylene glycol with ethylene acetate and potassium hydroxide reaction first, and next year is developed the method that is made ethylene glycol by the oxirane direct hydration.Nineteen thirty-seven U.S. UCC company has built up in the world, and first cover is the ethylene gas phase oxidation production oxirane commercial plant of oxidant with the air; It is the industrialization ethylene oxide production plant of catalyst with oxygen that U.S. Shell company in 1958 has set up first cover, makes the production of ethylene glycol turn to the hydrating process route.Up to the present, the legal main method of producing ethylene glycol in the world at present that is still of epoxyethane water.Du Pout company finds under high pressure CO and H in the 1950's
2Reaction can synthesizing glycol.UCC and Mitsui improve the synthesis gas direct synthesis technique subsequently.But the industrialization of all being unrealized.Also have several types to be the indirect synthesizing glycol of basic material in addition, comprising: oxalate method, formaldehyde hydroformylation method, glycolic acid method, formaldehyde carbonylation method with the synthesis gas.According to the difference of raw material, can be divided into: petroleum path and synthesis gas route.The synthesis gas route is all by two steps: the synthetic and hydrogenation process subsequently of oxalate and glycolic acid or glycolic acid esters, wherein hydrogenation process is the key problem in technology step of synthesis gas route synthesizing glycol.Efficient hydrogenation catalyst system exploitation is to realize one of key problem of synthesis gas synthesizing glycol.
Summary of the invention
The object of the present invention is to provide a kind of load type metal hydrogenation catalyst.
Another object of the present invention is to provide a kind of preparation method of load type metal hydrogenation catalyst.
A further object of the present invention is to provide the application of load type metal hydrogenation catalyst catalytically synthesizing glycol.
Technical scheme below the present invention has adopted realizes:
A kind of load type metal hydrogenation catalyst is characterized in that containing following component: Ni-M1-M2/SiC/C, and main metallic catalyst M1 is a nickel, and metal promoter M1, M2 are: Zn, Cu, Co, Fe, Cr, Sn, Bi, Re, La, Ce, Nd, Sm, Gd any or mixture.
A kind of preparation method of load type metal hydrogenation catalyst is characterized in that comprising the steps:
(1), macromolecule/SiO
2The preparation of spherical compound: be that cetyltrimethylammonium chloride is dissolved in the deionized water, add the silica precursor tetraethyl orthosilicate then, preserve more than 24 hours at 35-45 ℃; Be cooled to below 5 ℃;, as polymerizing template the toluene solution that is dissolved with vinylidene chloride and azodiisobutyronitrile is directly added with cetyltrimethylammonium chloride and tetraethyl orthosilicate hydrolytic sol, stir fast; Be warming up to 40 ℃ of polymerizations more than 24 hours, obtain macromolecule/SiO thus
2Spherical compound.
The concentration range of cetyltrimethylammonium chloride is 0.1-0.15g/ml, is preferably 0.12g/ml;
It is 10-20% that tetraethyl orthosilicate accounts for reactant mixture thing gross mass, is preferably 9.0%;
The concentration of vinylidene chloride is 20-30wt%, and the concentration that is preferably 25wt%, azodiisobutyronitrile is 1.0-2.0wt%, is preferably 1.5wt%; The volume of toluene solution is 5-10ml, is the 25-50% of cetyltrimethylammonium chloride, tetraethyl orthosilicate liquor capacity;
(2), the preparation of the spherical molecular sieve of SiC/C: with the macromolecule/SiO of step (1) acquisition
2The temperature programming carbonization in nitrogen or argon stream of spherical compound promptly makes the spherical molecular sieve of SiC/C;
Described carburizing temperature is 150 ℃ of reaction 3h; 200 ℃ of reaction 1h, 400 ℃ of reaction 1h, 600 ℃ of reaction 1h, 800 ℃ of reaction 1h, 1000 ℃ of reaction 2h;
(3), the dipping of the spherical molecular sieve of SiC/C is aging: the spherical molecular sieve of SiC/C is used nitric acid dousing, spends the night, and concentration of nitric acid is 30%; The spherical molecular sieve of SiC/C uses the initial vacuum dry, and dipping contains the water or the methanol solution of Ni-M1-M2 ion and nitrilotriacetic acid, after the drying; In air, be heated to 120-150 ℃ of aging 1-3 hour; Before the use, 300-350 ℃ of activation 3 hours, measure forming of load multimetal reforming catalyst by the x-ray photoelectron power spectrum with hydrogen;
Described M1, M2 are Zn, Cu, Co, Fe, Cr, Sn, Bi, Re, La, Ce, Nd, Sm, Gd any or mixture; The load capacity 1-15wt% of Ni, the load capacity of M1 is 0.1-5wt%, and the load capacity of M2 is 0-5wt%, and the precursor of M1, M2 is a nitrate; The concentration of nitrilotriacetic acid is 1-5wt%;
The application of load type metal hydrogenation catalyst catalytically synthesizing glycol is in solvent, to add a certain amount of methyl oxalate, glycolic acid and above-mentioned load type metal hydrogenation catalyst, at hydrogen with under uniform temperature and pressure, makes ethylene glycol.Reaction temperature is 100-220 ℃, and Hydrogen Vapor Pressure is 1-10MPa, and the liquid hourly space velocity (LHSV) of reaction is 0.3-9.0g/g-catalh, and catalyst consumption is the 1-5wt% of total reactant quality, and described solvent is alcohol or water.
Beneficial effect of the present invention is: as polymerizing template, obtain macromolecule/SiO with vinylidene chloride and 0 ℃ of polymerization of initator more than 24 hours with cetyltrimethylammonium chloride and tetraethyl orthosilicate hydrolytic sol
2Spherical compound.Macromolecule/SiO
2The temperature programming carbonization in nitrogen or argon stream of spherical compound makes the spherical molecular sieve of SiC/C and has very high mechanical strength and resistance to elevated temperatures, and its particle diameter is about 100-150um, and specific area is greater than 1000m
2/ g.
The load type metal hydrogenation catalyst is major catalyst with nickel, and M1, M2 are that the precursor of metal is a nitrate for the aided metal catalyst.The gas-solid that catalyst is applicable to methyl oxalate and glycolic acid mutually or liquid-solid phase catalytic hydrogenation process, catalytic process has very high active and to the selectivity of ethylene glycol, catalyst has excellent stability simultaneously, is suitable for long-time multiple batches of course of reaction.
Description of drawings
Fig. 1 is the Electronic Speculum figure of the spherical molecular sieve of the SiC/C for preparing of the embodiment of the invention 1.
The specific embodiment
This part mainly combines the argumentation specific embodiments of the invention of experimental detail is further specified.
Embodiment 1 Ni-Cu-La/SiC-C catalyst
1, macromolecule/SiO
2The preparation of spherical compound:
The cetyltrimethylammonium chloride of 2.4g is dissolved in the 20ml deionized water; The tetraethyl orthosilicate that adds 9.0g was then preserved 24 hours at 35 ℃, was cooled to 5 ℃; To be dissolved with vinylidene chloride (25wt%) and ABVN (1.5wt%) toluene solution 5ml directly adds; Stir fast, be warming up to 40 ℃ of polymerizations 24 hours, obtain macromolecule/SiO thus
2Spherical compound;
2, the preparation of the spherical molecular sieve of SiC/C:
With macromolecule/SiO
2The temperature programming carbonization in argon stream of spherical compound, described carburizing temperature are 150 ℃ of reaction 3h; 200 ℃ of reaction 1h, 400 ℃ of reaction 1h, 600 ℃ of reaction 1h, 800 ℃ of reaction 1h, 1000 ℃ of reaction 2h promptly make the spherical molecular sieve of SiC/C, and profile is as shown in Figure 1.
3, the dipping of the spherical molecular sieve of SiC/C is aging:
The spherical molecular sieve 24h of nitric acid dousing SiC/C with 30% cleans vacuum drying then with deionized water.Get Ni (NO
3)
2, Cu (NO
3)
2, La (NO
3)
3Be made into nitrilotriacetic acid and consist of (Ni:2.0wt%, Cu:0.5wt%, La:0.5wt%; Nitrilotriacetic acid: methanol solution 1.0wt%), then with the spherical molecular sieve dipping of SiC/C, after the drying; In air, being heated to 150 ℃ wore out 3 hours; 350 ℃ of activation 3 hours, obtain the load type metal hydrogenation catalyst with hydrogen, measure by the x-ray photoelectron power spectrum.
The application of load type metal hydrogenation catalyst catalytically synthesizing glycol at the 100ml autoclave, is a solvent with methyl alcohol; Add methyl oxalate or glycolic acid and 1.5g Ni-Cu-La/SiC-C catalyst; The reactive hydrogen atmospheric pressure is about 5.0MPa, and reaction temperature is 150-220 ℃, with the carrying out of gas-chromatography monitoring reaction; The conversion ratio of reaction substrate reaches 90%, to the selectivity of ethylene glycol greater than 91%.
Embodiment 2 Ni-Cu-Zn-La/SiC-C Preparation of catalysts:
The dipping of the spherical molecular sieve of SiC/C is aging: the spherical molecular sieve of the nitric acid treatment SiC/C with 30% spends the night, and cleans vacuum drying then with deionized water.Get Ni (NO
3)
2, Cu (NO
3)
2, Zn (NO
3)
2, La (NO
3)
3Be made into nitrilotriacetic acid and consist of (Ni:1.5wt%, Cu:0.5wt%, Zn:0.5wt%; La:0.5wt%, nitrilotriacetic acid: methanol solution 1.5wt%), then with the spherical molecular sieve dipping of SiC/C; After the drying; In air, be heated to 150 ℃ and wore out 3 hours, 350 ℃ of activation 3 hours, obtain the load type metal hydrogenation catalyst with hydrogen.
At the 100ml autoclave; With methyl alcohol is solvent, adds the catalyst of methyl oxalate or glycolic acid and 1.5g, and the reactive hydrogen atmospheric pressure is 5.0MPa; Reaction temperature is 150-220 ℃; With the carrying out of gas-chromatography monitoring reaction, the conversion ratio of reaction substrate reaches 95%, to the selectivity of ethylene glycol greater than 96%.
Except the content of above record, all the other are with embodiment 1.
Embodiment 3Ni-Co-Zn-La/SiC-C catalyst:
The dipping of the spherical molecular sieve of SiC/C is aging: the spherical molecular sieve of the nitric acid treatment SiC/C with 30%, clean vacuum drying then with deionized water.Get Ni (NO
3)
2, Co (NO
3)
2, Zn (NO
3)
2, La (NO
3)
3Be made into nitrilotriacetic acid and consist of (Ni:1.5wt%, Co:0.5wt%, Zn:0.5wt%; La:0.5wt%, nitrilotriacetic acid: methanol solution 1.5wt%), then with the spherical molecular sieve dipping of SiC/C; After the drying; In air, be heated to 150 ℃ and wore out 3 hours, 350 ℃ of activation 3 hours, obtain the load type metal hydrogenation catalyst with hydrogen.
At the 100ml autoclave; With methyl alcohol is solvent, adds the catalyst of methyl oxalate or glycolic acid and 1.5g, and the reactive hydrogen atmospheric pressure is about 5.0MPa; Reaction temperature is Si0-220 ℃; With the carrying out of gas-chromatography monitoring reaction, the conversion ratio of reaction substrate reaches 98%, to the selectivity of ethylene glycol greater than 99%.
Except the content of above record, all the other are with embodiment 1.
Embodiment 4 Ni-Cu-Re-Ce/SiC-C catalyst:
The dipping of the spherical molecular sieve of SiC/C is aging: the spherical molecular sieve of the nitric acid treatment SiC/C with 30%, clean vacuum drying then with deionized water.Get Ni (NO
3)
2, Cu (NO
3)
2, K
2ReO
4, Ce (NO
3)
3Be made into nitrilotriacetic acid and consist of (Ni:1.5wt%, Cu:0.5wt%, Re:0.5wt%; Ce:0.5wt%, nitrilotriacetic acid: methanol solution 1.5wt%), then with the spherical molecular sieve dipping of SiC/C; After the drying; In air, be heated to 150 ℃ and wore out 3 hours, 350 ℃ of activation 3 hours, obtain the load type metal hydrogenation catalyst with hydrogen.
At the 100ml autoclave; With methyl alcohol is solvent, adds the catalyst of methyl oxalate or glycolic acid and 1.5g, and the reactive hydrogen atmospheric pressure is about 5.0MPa; Reaction temperature is 150-220 ℃; With the carrying out of gas-chromatography monitoring reaction, the conversion ratio of reaction substrate reaches 99%, to the selectivity of ethylene glycol greater than 99%.Except the content of above record, all the other are with embodiment 1.
Embodiment 5 Ni-Cu-Re-Ce/SiC-C catalyst:
The dipping of the spherical molecular sieve of SiC/C is aging: the spherical molecular sieve of the nitric acid treatment SiC/C with 30%, clean vacuum drying then with deionized water.Get Ni (NO
3)
2, Cu (NO
3)
2, K
2ReO
4, Ce (NO
3)
3Be made into nitrilotriacetic acid and consist of (Ni:1.5wt%, Cu:0.5wt%, Re:0.5wt%; Ce:0.5wt%, nitrilotriacetic acid: methanol solution 1.5wt%), then with the spherical molecular sieve dipping of SiC/C; After the drying; In air, be heated to 150 ℃ and wore out 3 hours, 350 ℃ of activation 3 hours, obtain the load type metal hydrogenation catalyst with hydrogen.
At the 100ml autoclave; With methyl alcohol is solvent, adds the catalyst of methyl oxalate or glycolic acid and 1.5g, and the reactive hydrogen atmospheric pressure is about 5.0MPa; Reaction temperature is 150-220 ℃; With the carrying out of gas-chromatography monitoring reaction, the conversion ratio of reaction substrate reaches 99%, to the selectivity of ethylene glycol greater than 99%.After the reaction, with catalyst filtration, with small amount of methanol wash-out three times, air drying, investigate the recycling of catalyst, through nearly 20 batches investigation, the conversion ratio of reaction substrate is all more than 90%, to the selectivity of ethylene glycol all greater than 95%.Except the content of above record, all the other are with embodiment 1.
The response parameter that embodiment 6-9 is adopted is as shown in table 1, and except the content of being put down in writing, all the other are all with embodiment 1.The M1 that relates to, M2 are the mixture of different chemical component, quality such as are and mix.
Table 1
The above-mentioned specific embodiment does not limit technical scheme of the present invention in any form, and the technical scheme that mode obtained that every employing is equal to replacement or equivalent transformation all drops on protection scope of the present invention.
Claims (5)
1. a load type metal hydrogenation catalyst is characterized in that consisting of Ni-M1-M2/SiC/C, and main metallic catalyst is Ni, and metal promoter M1, M2 are: Zn, Cu, Co; Fe, Cr, Sn, Bi, Re; La, Ce, Nd, Sm, any of Gd or mixture.
2. the preparation method of a load type metal hydrogenation catalyst is characterized in that comprising the steps:
(1), macromolecule/SiO
2The preparation of spherical compound: be that cetyltrimethylammonium chloride is dissolved in the deionized water; Add tetraethyl orthosilicate then, preserve more than 24 hours, be cooled to below 5 ℃ at 35-45 ℃; The toluene solution that is dissolved with vinylidene chloride and azodiisobutyronitrile is directly added; Stir fast, be warming up to 40 ℃ of polymerizations more than 24 hours, obtain macromolecule/SiO thus
2Spherical compound;
(2), the preparation of the spherical molecular sieve of SiC/C: with the macromolecule/SiO of step (1) acquisition
2The temperature programming carbonization in nitrogen or argon stream of spherical compound promptly makes the spherical molecular sieve of SiC/C;
(3) dipping of the spherical molecular sieve of SiC/C is aging: the spherical molecular sieve of SiC/C is used nitric acid treatment; Dipping contains the water or the methanol solution of Ni-M1-M2 ion and nitrilotriacetic acid; After the drying, in air, be heated to 120-150 ℃ of aging 1-3 hour, obtain the load type metal hydrogenation catalyst; Described M1, M2 are Zn, Cu, Co, Fe, Cr, Sn, Bi, Re, La, Ce, Nd, Sm, any of Gd or mixture.
3. the preparation method of load type metal hydrogenation catalyst according to claim 2 is characterized in that
The concentration range of cetyltrimethylammonium chloride is 0.1-0.15 g/ml in the step (1); It is 10-20% that tetraethyl orthosilicate accounts for the reactant mixture gross mass; The concentration of vinylidene chloride is 20-30 wt%; The concentration of azodiisobutyronitrile is 1.0-2.0 wt%; The volume of toluene solution is the 25-50% of cetyltrimethylammonium chloride, tetraethyl orthosilicate liquor capacity;
The temperature and time of the temperature programming carbonization described in the step (2) is: 150 ℃ of reaction 3h; 200 ℃ of reaction 1h, 400 ℃ of reaction 1h, 600 ℃ of reaction 1h, 800 ℃ of reaction 1h, 1000 ℃ of reaction 2h;
In the said step (3): the spherical molecular sieve of SiC/C uses the initial vacuum dry; The load capacity 1-15wt% of Ni, the load capacity of M1 is 0.1-5wt%, and the load capacity of M2 is 0-5wt%, and the precursor of M1, M2 is a nitrate; The concentration of nitrilotriacetic acid is 1-5wt%.
4. based on the application of the load type metal hydrogenation catalyst catalytically synthesizing glycol of claim 1; It is characterized in that it being in solvent, to add a certain amount of methyl oxalate, glycolic acid and above-mentioned load type metal hydrogenation catalyst; Under atmosphere of hydrogen; Under uniform temperature and pressure, make ethylene glycol.
5. the application of load type metal hydrogenation catalyst catalytically synthesizing glycol according to claim 4; It is characterized in that reaction temperature is 100-220 ℃; Pressure is 1-10MPa; The liquid hourly space velocity (LHSV) of reaction is 0.3-9.0g/g-catalh, and catalyst consumption is the 1-5wt% of total reactant quality, and described solvent is alcohol or water.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013481A (en) * | 2014-04-15 | 2015-11-04 | 中国石化扬子石油化工有限公司 | C-SiC loaded platinum-based catalyst, preparation method and applications thereof |
| CN109701541A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of methyl glycollate adds the catalyst and its preparation method and application of hydrogen preparing ethylene glycol |
| CN111057170A (en) * | 2019-12-06 | 2020-04-24 | 中玺新材料（安徽）有限公司 | Chromium-neodymium-cobalt-loaded trimetal catalyst and preparation method and application thereof |
| CN111203252A (en) * | 2020-03-24 | 2020-05-29 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Copper catalyst for preparing ethylene glycol and ethanol from oxalate and preparation method thereof |
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| CN101757915A (en) * | 2010-01-08 | 2010-06-30 | 厦门大学 | Catalyst used for preparing glycol from hydrogenation of oxalates and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013481A (en) * | 2014-04-15 | 2015-11-04 | 中国石化扬子石油化工有限公司 | C-SiC loaded platinum-based catalyst, preparation method and applications thereof |
| CN105013481B (en) * | 2014-04-15 | 2018-02-06 | 中国石化扬子石油化工有限公司 | A kind of C SiC itself and preparation method and application of load type platinum based catalyst again |
| CN109701541A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of methyl glycollate adds the catalyst and its preparation method and application of hydrogen preparing ethylene glycol |
| CN109701541B (en) * | 2017-10-26 | 2022-03-15 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol by hydrogenating methyl glycolate and preparation method and application thereof |
| CN111057170A (en) * | 2019-12-06 | 2020-04-24 | 中玺新材料（安徽）有限公司 | Chromium-neodymium-cobalt-loaded trimetal catalyst and preparation method and application thereof |
| CN111203252A (en) * | 2020-03-24 | 2020-05-29 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Copper catalyst for preparing ethylene glycol and ethanol from oxalate and preparation method thereof |
| CN111203252B (en) * | 2020-03-24 | 2023-07-14 | 新疆至臻化工工程研究中心有限公司 | Copper catalyst for preparing glycol and ethanol from oxalate and preparation method thereof |
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