CN102145284B - Catalyst for preparing 1,3-propylene glycol by directly carrying out hydrotreating on glycerin and preparation method of catalyst - Google Patents
Catalyst for preparing 1,3-propylene glycol by directly carrying out hydrotreating on glycerin and preparation method of catalyst Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing 1,3-propylene glycol by directly carrying out hydrotreating on glycerin and a preparation method of the catalyst. The catalyst at least comprises Pt, W, Ti, SiO2 and at least one assistant component, such as La, Ce, Sn, Re, Zr, Zn, Cu, Rh and Ru. By the catalyst provided by the invention and the preparation method of the catalyst, an aqueous solution of glycerin can be converted into 1,3-propylene glycol at a certain temperature under a certain hydrogen pressure and the condition of high conversion rate or high selectivity.
Description
Technical field
The present invention relates to a kind of directly hydrogenizing glycerol system 1, the ammediol Catalysts and its preparation method.
Technical background
1, ammediol is the important source material of producing PTT.Existing 1, the ammediol technology of preparing has acrolein hydration hydrogenation method, oxirane carbonyl hydrogenation method and microbe fermentation method and directly hydrogenizing glycerol method.
Chinese patent CN96198050.8 discloses a kind of oxirane carbonyl hydrogenation legal system 1; The technology of ammediol; Oxirane and synthesis gas reaction under the condition that catalyst exists are generated the 3-hydroxy propanal; The reaction under the condition that catalyst exists of 3-hydroxy propanal and hydrogen generates 1, ammediol.
Chinese patent CN93114516.3 discloses a kind of dehydrating glycerin through acrolein hydration hydrogenation legal system 1; The technology of ammediol; Glycerine dehydration under the condition that catalyst exists is generated methacrylaldehyde; Methacrylaldehyde generates the 3-hydroxy propanal through hydration reaction, and the reaction under the condition that catalyst exists of 3-hydroxy propanal and hydrogen generates 1, ammediol.
Chinese patent CN02100233.9 discloses a kind of formaldehyde, acetaldehyde condensation through 3-hydroxy propanal hydrogenation legal system 1; The technology of ammediol; The condensation under alkali condition of formaldehyde, acetaldehyde is generated the 3-hydroxy propanal; The reaction under the condition that catalyst exists of 3-hydroxy propanal and hydrogen generates 1, ammediol.
Above-mentioned technical matters is more loaded down with trivial details, severe reaction conditions, and problem of environmental pollution is also more serious.
Document (modern chemical industry, 2002,22 (7): 34) reported to be that substrate adopts microbe fermentation method to synthesize 1, the technology of ammediol with glycerine.Because product is the very low aqueous solution of concentration, production efficiency is lower.
Document (Catalysis Communication 9 (2008) 1360-1363) has been reported directly system 1 of glycerine hydrogenation, and the new method of ammediol is with 1; 3-dimethyl-2-imidazolone is a solvent, and through making 1, ammediol contacts and removes a hydroxyl with hydrogen and obtains 1 with specific catalyst; Ammediol, but accessory substance 1, the 2-propane diols is more; And target product 1, the ammediol selectivity is lower, makes the economy of process lower.
Glycerine hydrogenation directly makes 1, and the process of ammediol is simple, and low in raw material cost is easy to get, and has development prospect.In order to make directly system 1 of glycerine hydrogenation, the process of ammediol can satisfy the requirement of commercial production to production cost, must on the prior art basis, significantly improve 1, and the selectivity of ammediol reduces by 1, the generation of accessory substances such as 2-propane diols.
Summary of the invention
The invention provides directly system 1 of a kind of glycerine hydrogenation, the ammediol Catalysts and its preparation method, compared with prior art, technology provided by the invention can significantly improve glycerol conversion yield, or improves generation 1, the selectivity of ammediol.
Below set forth in detail content of the present invention:
A kind of glycerine hydrogenation provided by the invention directly makes 1, the ammediol catalyst, and the composition of catalyst contains Pt, W, Ti, SiO
2, and contain at least a adjuvant component among La, Ce, Sn, Re, Zr, Zn, Cu, Rh and the Ru simultaneously.
The weight content of Pt is 1.0%~5.0% in the said catalyst, and the W that is contained in the catalyst amounts to into WO
3Weight content be 5.0%~10.0%, the Ti that is contained in the catalyst amounts to into TiO
2Weight content be 10.0%~15.0%, the weight content of the said adjuvant component that is contained in the catalyst is 0.2%~5.0%, said SiO
2Weight be 65~83%.
Above-mentioned Preparation of catalysts method provided by the invention comprises the steps: a) to press the weight proportion of each component in the catalyst, is modulated into maceration extract with the soluble-salt of each component; B) use the solution impregnation SiO that contains soluble T i component or contain said adjuvant component simultaneously
2And oven dry and roasting make the SiO that contains Ti or contain said adjuvant component simultaneously
2C) with containing solubility W component or containing the solution impregnation above-mentioned steps b of said adjuvant component simultaneously) obtain contain Ti or contain the SiO of said adjuvant component simultaneously
2And oven dry and roasting, obtain containing W and contain Ti or contain the SiO of said adjuvant component simultaneously
2D) with containing solubility Pt component or containing the solution impregnation above-mentioned steps c of said adjuvant component simultaneously) obtain contain W and contain Ti or contain the SiO of said adjuvant component simultaneously
2And oven dry and roasting, make catalyst.
In above-mentioned preparation method, at step b), c) and d) in said oven dry and roasting condition be: (1) drying condition: 80~150 ℃ dry 1~12 hour down; (2) roasting condition: 450~800 ℃ of following roastings 1~20 hour.
In above-mentioned preparation method, the soluble-salt of each component is its nitrate, hydrochloride or soluble transition metal hydrochlorate or ester in the said catalyst.
Directly make 1 by glycerine hydrogenation provided by the invention, the ammediol Catalysts and its preparation method, catalyst directly makes 1 to glycerine hydrogenation; The evaluation of the catalytic performance of ammediol reaction is carried out in fixed bed reactors, and the catalyst loading amount is 2g, and raw material is that to contain the glycerine weight content be 50% the aqueous solution; The hydrogenation reaction temperature is 180 ℃; Pressure is 5.0MPa, and the liquid air speed is 0.5h-1, hydrogen gas space velocity 900h-1.The Agilent7890 gas chromatographic analysis of back with equipment HP-5 capillary column collected in the liquid product cooling, and gas-phase product is with the Agilent 3000AMicroGC gas chromatographic analysis of equipment Pora-Q capillary column.
Below by specific embodiment and comparative example the present invention is further specified.
The specific embodiment
Embodiment 1
Catalyst is Pt-La
2O
3/ WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, La%=2%, WO
3%=5%, TiO
2%=10%, all the other are carrier S iO
2The Preparation of catalysts step comprises: the ethanolic solution impregnated carrier SiO that a) uses the butyl titanate of the Ti that contains requirement
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get TiO
2/ SiO
2B) TiO that a) obtains with the aqueous solution impregnation steps of ammonium metatungstate of the W that contains requirement
2/ SiO
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get WO
3/ TiO
2/ SiO
2C) with the chloroplatinic acid of the Pt that contains requirement and contain the lanthanum nitrate aqueous solution impregnation steps b of the La of requirement simultaneously) WO that obtains
3/ TiO
2/ SiO
2, 120 ℃ of dry 3h, 500 ℃ of roasting 3h get Pt-La
2O
3/ WO
3/ TiO
2/ SiO
2Catalyst.
Embodiment 2
Catalyst is Pt-La
2O
3/ WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, La%=2%, WO
3%=5%, TiO
2%=5%, all the other are carrier S iO
2Except that catalytic component content difference, the Preparation of catalysts process is identical with embodiment 1.
Embodiment 3
Catalyst is Pt-La
2O
3/ WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, La%=5%, WO
3%=5%, TiO
2%=5%, all the other are carrier S iO
2Except that catalytic component content difference, the Preparation of catalysts process is identical with embodiment 1.
Embodiment 4
Catalyst is Pt-CeO
2/ WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, Ce%=2%, WO
3%=5%, TiO
2%=10%, all the other are carrier S iO
2The Preparation of catalysts step comprises: the ethanolic solution impregnated carrier SiO that a) uses the butyl titanate of the Ti that contains requirement
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get TiO
2/ SiO
2B) TiO that a) obtains with the aqueous solution impregnation steps of ammonium metatungstate of the W that contains requirement
2/ SiO
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get WO
3/ TiO
2/ SiO
2C) with the chloroplatinic acid of the Pt that contains requirement and contain the cerous nitrate aqueous solution impregnation steps b of the Ce of requirement simultaneously) WO that obtains
3/ TiO
2/ SiO
2, 120 ℃ of dry 3h, 500 ℃ of roasting 3h get Pt-CeO
2/ WO
3/ TiO
2/ SiO
2Catalyst.
Embodiment 5
Catalyst is Pt-CeO
2/ WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, Ce%=0.5%, WO
3%=5%, TiO
2%=10%, all the other are carrier S iO
2Except that catalytic component content difference, the Preparation of catalysts process is identical with embodiment 4.
Embodiment 6
Catalyst is Pt-CeO
2/ WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, Ce%=5%, WO
3%=5%, TiO
2%=10%, all the other are carrier S iO
2Except that catalytic component content difference, the Preparation of catalysts process is identical with embodiment 4.
Embodiment 7
Catalyst is Pt-Rh/WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, Rh%=2%, WO
3%=5%, TiO
2%=10%, all the other are carrier S iO
2The Preparation of catalysts step comprises: the ethanolic solution impregnated carrier SiO that a) uses the butyl titanate of the Ti that contains requirement
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get TiO
2/ SiO
2B) TiO that a) obtains with the aqueous solution impregnation steps of ammonium metatungstate of the W that contains requirement
2/ SiO
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get WO
3/ TiO
2/ SiO
2C) with the chloroplatinic acid of the Pt that contains requirement and contain the RhCl of the Rh of requirement simultaneously
3Aqueous solution impregnation steps b) WO that obtains
3/ TiO
2/ SiO
2, 120 ℃ of dry 3h, 500 ℃ of roasting 3h get Pt-Rh/WO
3/ TiO
2/ SiO
2Catalyst.
Embodiment 8
Catalyst is Pt-Rh/WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, Rh%=0.5%, WO
3%=5%, TiO
2%=5%, all the other are carrier S iO
2Except that catalytic component content difference, the Preparation of catalysts process is identical with embodiment 7.
Embodiment 9
Catalyst is Pt-Rh/WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, Rh%=4%, WO
3%=5%, TiO
2%=5%, all the other are carrier S iO
2Except that catalytic component content difference, the Preparation of catalysts process is identical with embodiment 7.
Embodiment 10
Catalyst is Pt-Sn/WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, Sn%=2%, WO
3%=5%, TiO
2%=10%, all the other are carrier S iO
2The Preparation of catalysts step comprises: the ethanolic solution impregnated carrier SiO that a) uses the butyl titanate of the Ti that contains requirement
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get TiO
2/ SiO
2B) TiO that a) obtains with the aqueous solution impregnation steps of ammonium metatungstate of the W that contains requirement
2/ SiO
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get WO
3/ TiO
2/ SiO
2C) with the chloroplatinic acid of the Pt that contains requirement and contain the SnCl of the Sn of requirement simultaneously
3Aqueous solution impregnation steps b) WO that obtains
3/ TiO
2/ SiO
2, 120 ℃ of dry 3h, 500 ℃ of roasting 3h get Pt-Sn/WO
3/ TiO
2/ SiO
2Catalyst.
Embodiment 11
Catalyst is Pt/Re-WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, Re%=2%, WO
3%=5%, TiO
2%=10%, all the other are carrier S iO
2The Preparation of catalysts step comprises: the ethanolic solution impregnated carrier SiO that a) uses the butyl titanate of the Ti that contains requirement
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get TiO
2/ SiO
2B) with the ammonium metatungstate of the W that contains requirement and contain the TiO that the aqueous solution impregnation steps of rehenic acid ammonium of the Re of requirement a) obtains simultaneously
2/ SiO
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get Re-WO
3/ TiO
2/ SiO
2C) with the chloroplatinic acid aqueous solution impregnation steps b of Pt that contains requirement) Re-WO that obtains
3/ TiO
2/ SiO
2, 120 ℃ of dry 3h, 500 ℃ of roasting 3h get Pt/Re-WO
3/ TiO
2/ SiO
2Catalyst.
Embodiment 12
Catalyst is Pt/WO
3/ ZrO
2-TiO
2/ SiO
2, weight consists of: Pt%=2%, WO
3%=5%, ZrO
2%=2%, TiO
2%=10%, all the other are carrier S iO
2The Preparation of catalysts step comprises: a) with the butyl titanate of the Ti that contains requirement and contain the ethanolic solution impregnated carrier SiO of tetrabutyl zirconate of the Zr of requirement simultaneously
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get ZrO
2-TiO
2/ SiO
2B) ZrO that a) obtains with the aqueous solution impregnation steps of ammonium metatungstate of the W that contains requirement
2-TiO
2/ SiO
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get WO
3/ ZrO
2-TiO
2/ SiO
2C) with the chloroplatinic acid aqueous solution impregnation steps b of Pt that contains requirement) WO that obtains
3/ ZrO
2-TiO
2/ SiO
2, 120 ℃ of dry 3h, 500 ℃ of roasting 3h get Pt/WO
3/ ZrO
2-TiO
2/ SiO
2Catalyst.
Embodiment 13
Catalyst is Pt-Zn/WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, Zn%=2%, WO
3%=5%, TiO
2%=10%, all the other are carrier S iO
2The Preparation of catalysts step comprises: the ethanolic solution impregnated carrier SiO that a) uses the butyl titanate of the Ti that contains requirement
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get TiO
2/ SiO
2B) TiO that a) obtains with the aqueous solution impregnation steps of ammonium metatungstate of the W that contains requirement
2/ SiO
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get WO
3/ TiO
2/ SiO
2C) with the chloroplatinic acid of the Pt that contains requirement and contain the zinc nitrate aqueous solution impregnation steps b of the Zn of requirement simultaneously) WO that obtains
3/ TiO
2/ SiO
2, 120 ℃ of dry 3h, 500 ℃ of roasting 3h get Pt-Zn/WO
3/ TiO
2/ SiO
2Catalyst.
Embodiment 14
Catalyst is Pt-Cu/WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, Cu%=2%, WO
3%=5%, TiO
2%=10%, all the other are carrier S iO
2The Preparation of catalysts step comprises: the ethanolic solution impregnated carrier SiO that a) uses the butyl titanate of the Ti that contains requirement
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get TiO
2/ SiO
2B) TiO that a) obtains with the aqueous solution impregnation steps of ammonium metatungstate of the W that contains requirement
2/ SiO
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get WO
3/ TiO
2/ SiO
2C) with the chloroplatinic acid of the Pt that contains requirement and contain the copper nitrate aqueous solution impregnation steps b of the Cu of requirement simultaneously) WO that obtains
3/ TiO
2/ SiO
2, 120 ℃ of dry 3h, 500 ℃ of roasting 3h get Pt-Cu/WO
3/ TiO
2/ SiO
2Catalyst.
Embodiment 15
Catalyst is Pt-Ru/WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, Ru%=2%, WO
3%=5%, TiO
2%=10%, all the other are carrier S iO
2The Preparation of catalysts step comprises: the ethanolic solution impregnated carrier SiO that a) uses the butyl titanate of the Ti that contains requirement
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get TiO
2/ SiO
2B) TiO that a) obtains with the aqueous solution impregnation steps of ammonium metatungstate of the W that contains requirement
2/ SiO
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get WO
3/ TiO
2/ SiO
2C) with the chloroplatinic acid of the Pt that contains requirement and contain the RuCl of the Ru of requirement simultaneously
2Aqueous solution impregnation steps b) WO that obtains
3/ TiO
2/ SiO
2, 120 ℃ of dry 3h, 500 ℃ of roasting 3h get Pt-Ru/WO
3/ TiO
2/ SiO
2Catalyst.
Comparative example 1
Catalyst is Pt/WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, WO
3%=5%, TiO
2%=10%, all the other are carrier S iO
2The Preparation of catalysts step comprises: the ethanolic solution impregnated carrier SiO that a) uses the butyl titanate of the Ti that contains requirement
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get TiO
2/ SiO
2B) TiO that a) obtains with the aqueous solution impregnation steps of ammonium metatungstate of the W that contains requirement
2/ SiO
2, 120 ℃ of dry 3h, 600 ℃ of roasting 6h get WO
3/ TiO
2/ SiO
2C) with the chloroplatinic acid aqueous solution impregnation steps b of Pt that contains requirement) WO that obtains
3/ TiO
2/ SiO
2, 120 ℃ of dry 3h, 500 ℃ of roasting 3h obtain Pt/WO
3/ TiO
2/ SiO
2Catalyst.
Comparative example 2
Catalyst is Pt/WO
3/ TiO
2/ SiO
2, weight consists of: Pt%=2%, WO
3%=5%, TiO
2%=5%, all the other are carrier S iO
2Except that catalytic component content difference, the Preparation of catalysts process is identical with comparative example 1.
The catalyst of embodiment 1~15 and comparative example 1~2 is used for directly hydrogenizing glycerol system 1, and the catalytic performance of ammediol reaction is listed in table 1.Catalytic performance according to the catalyst of embodiment and comparative example is relatively more visible, and the catalyst of the technology preparation that provides by this patent is through at Pt/WO
3/ TiO
2/ SiO
2Add proper auxiliary agent in the catalyst, can improve glycerol conversion yield, or improve 1, the selectivity of ammediol, or make glycerol conversion yield and 1, the selectivity of ammediol all is improved.
Each embodiment of table 1. and comparative example catalyst are used for directly hydrogenizing glycerol system 1, the catalytic performance of ammediol reaction
Claims (2)
1. directly hydrogenizing glycerol system 1, the ammediol catalyst is characterized in that, contains Pt, W, Ti, SiO
2, and contain at least a adjuvant component among La, Ce, Sn, Re, Zr, Zn, Cu, Rh and the Ru, and the weight content of Pt is 1.0%~5.0% in the said catalyst, the W that is contained amounts to into WO
3Weight content be 5.0%~10.0%, the Ti that is contained amounts to into TiO
2Weight content be 10.0%~15.0%, the weight content of the said adjuvant component that is contained is 0.2%~5.0%, contained SiO
2Weight content be 65~83%.
2. said directly hydrogenizing glycerol system 1 of claim 1, ammediol Preparation of catalysts method comprises the steps: a) to press the weight proportion of each component in the catalyst, is modulated into maceration extract with the soluble-salt of each component; B) use the solution impregnation SiO that contains soluble T i component or contain said adjuvant component simultaneously
2And oven dry and roasting make the SiO that contains Ti or contain said adjuvant component simultaneously
2C) with containing solubility W component or containing the solution impregnation above-mentioned steps b of said adjuvant component simultaneously) obtain contain Ti or contain the SiO of said adjuvant component simultaneously
2And oven dry and roasting, obtain containing W and contain Ti or contain the SiO of said adjuvant component simultaneously
2D) with containing solubility Pt component or containing the solution impregnation above-mentioned steps c of said adjuvant component simultaneously) obtain contain W and contain Ti or contain the SiO of said adjuvant component simultaneously
2And oven dry and roasting, and at step b), c) and d) in said oven dry and roasting condition be:
(1) drying condition: drying is 1~12 hour under 80~150 ℃;
(2) roasting condition: 450~800 ℃ of following roastings 1~20 hour make catalyst.
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JP5886678B2 (en) * | 2012-04-19 | 2016-03-16 | 株式会社ダイセル | Process for producing 1,3-propanediol and catalyst for hydrogenation reaction of glycerin |
CN104529706A (en) * | 2014-11-06 | 2015-04-22 | 上海交通大学 | Preparation method of 1,2-propanediol using biomass derivative ethyl lactate |
CN106883098B (en) * | 2015-12-15 | 2020-09-15 | 中国科学院大连化学物理研究所 | Application of multi-active-component catalyst in preparation of 1, 3-propylene glycol by hydrogenolysis of glycerol |
CN110882709B (en) * | 2018-09-07 | 2023-04-11 | 中国石油化工股份有限公司 | Carbide-based catalyst, method for producing same, and method for hydrogenolysis of glycerin |
CN109225329B (en) * | 2018-09-26 | 2021-08-17 | 浙江恒澜科技有限公司 | Catalyst for preparing 1, 3-propylene glycol by hydrogenolysis of glycerol and application thereof |
CN109851473B (en) * | 2019-01-25 | 2022-11-25 | 华东理工大学 | Method for preparing 1,3-propylene glycol by hydrogenolysis of glycerol solution |
CN111389397B (en) * | 2020-03-03 | 2023-02-03 | 浙江镇洋发展股份有限公司 | Catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation and preparation method thereof |
CN115041193A (en) * | 2022-07-28 | 2022-09-13 | 山东京博石油化工有限公司 | Catalyst and preparation method and application thereof |
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