CN108855119A - A kind of production gamma-butyrolacton catalyst and preparation method - Google Patents
A kind of production gamma-butyrolacton catalyst and preparation method Download PDFInfo
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- CN108855119A CN108855119A CN201710329160.4A CN201710329160A CN108855119A CN 108855119 A CN108855119 A CN 108855119A CN 201710329160 A CN201710329160 A CN 201710329160A CN 108855119 A CN108855119 A CN 108855119A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The present invention relates to a kind of catalyst for producing gamma-butyrolacton and preparation methods, belong to catalyst technical field.Catalyst is CuO-ZnO-MnO2‑SiO2, wherein catalytic component molar ratio is Cu:Zn:Si:Mn=1~3:1~2:1:0.05.With copper nitrate, zinc nitrate, manganese nitrate solution is raw material, using alkaline solution as precipitating reagent, catalyst precursor is made by the way of co-precipitation, adds silica solution, be aged, wash, roasting, finally obtained catalyst CuO-ZnO-MnO2‑SiO2, the synergistic effect and auxiliary agent Mn, SiO of Cu-Zn2The addition of carrier improves the dispersion degree of active component, to improve activity and the service life of catalyst.
Description
Technical field
The present invention relates to a kind of production gamma-butyrolacton catalyst and preparation methods, belong to catalyst technical field.
Background technique
Gamma-butyrolacton is also known as 4 hydroxybutyric acid lactone, is a kind of important fine chemistry industry and Organic Chemicals, has height
Boiling point, dissolving power is strong, and conductivity is high, and the good feature of stability can be used for producing pyrrolidones system product, be widely used in stone
The fields such as oiling work, fiber, medicine, resin, cosmetics.In addition to this, because of its stable dissolubility and electrical conductance, γ-Ding Nei
Ester is also used for the electrolyte of lithium battery and electric appliance.With the development of relevant industries, the demand of gamma-butyrolacton is increasingly increased
Add.
Currently, there are two types of the main methods of preparation of industrialization gamma-butyrolacton：Using acetylene and formaldehyde as the 1,4- fourth two of raw material
Alcohol dehydrogenase method and using cis-butenedioic anhydride as the maleic anhydride hydrogenation method of raw material.The production of China's gamma-butyrolacton and exploitation are later, in early days with furfural and
Cis-butenedioic anhydride is raw material, based on 20 th century later new devices using 1,4-butanediol as raw material dehydrogenation prepare gamma-butyrolacton.Maleic anhydride hydrogenation
Method because catalyst production capacity is low, service life is too short, be gradually eliminated the problems such as process units fluctuation of service.1.4- fourth
For glycol dehydriding because reaction condition is mild, conversion ratio and selectivity are high, and by-product contains only a small amount of tetrahydrofuran, butanol and not
The raw material 1,4-butanediol of reaction, product is easily separated, and battery electrolyte is also met while reducing production cost and pharmacy is former
Expect the requirement to gamma-butyrolacton quality.
The dominant catalyst of early stage 1,4-butanediol dehydrogenation gamma-butyrolacton is Cu-Cr series catalysts, Japan Patent
JP0525151 prepares gamma-butyrolacton using Cu-Cr-Na and K catalyst 1,4-butanediol dehydrogenation, at 230 DEG C, 3.0h-1
Under air speed, for the conversion ratio of Isosorbide-5-Nitrae butanediol up to 87.28%, the selectivity of gamma-butyrolacton is 98.85%.The clear 61- of Japan Patent
246173, using Cu-Cr-Zn catalyst, the selectivity of gamma-butyrolacton is up to 98.2% in product.United States Patent (USP) US5210229 exists
Na or K is added in Cu-Cr-Ba or Cu-Cr-Mn-Ba, by the way that Na is added, K is modified to reduce the surface acid strength of catalyst, though
So reduce dehydration, but reduce the activity of catalyst, needs to improve reaction temperature to make up.
Although Cu-Cr series catalysts have very high gamma-butyrolacton selectivity, strong to human body because of the toxicity of Cr
Health and environment adversely affect, therefore current catalyst is attached most importance to mostly with studying the catalyst without Cr.United States Patent (USP)
US6093677 prepares Cu/SiO using infusion process2The conversion ratio of-CaO catalyst, 1,4-butanediol is greater than 99%, gamma-butyrolacton
Selectivity be greater than 97%.Patent CN1045174C uses the oxide of Cu-Zn-Al for parent, and its surface spray Pd or
Pt, at 190-290 DEG C of temperature, normal pressure, under conditions of hydrogen alcohol molar ratio is 1-6,1,4-butanediol conversion ratio is up to 100%, γ-
The selectivity of butyrolactone is up to 97%.Patent CN103044367B, catalyst is by CuO-ZnO-Al2O3And it is immersed in its surface
Auxiliary agent K and/or Li composition, at 230 ~ 250 DEG C of reaction temperature, reaction pressure is 0 ~ 0.4MPa, 1.0 ~ 2.5h of Feed space velocities-1, hydrogen
Under conditions of alcohol molar ratio is 3 ~ 10, the conversion ratio of 1,4-butanediol reaches 98%, the selectivity of gamma-butyrolacton up to 99% with
On.The above technology needs additionally to impregnate noble metal or alkaline assistant to increase to improve the conversion ratio and selectivity of catalyst mostly
Add operation step and production cost.Operation of the present invention step is simple, and the service life of catalyst is greatly improved while reducing cost.
Summary of the invention
The object of the present invention is to provide the catalyst and preparation method of a kind of 1,4- butanediol Dehydrogenation For Producing Butyrolactone.
It is characteristic of the invention that improving the activity of catalyst, and pass through auxiliary agent Mn and carrier by the synergistic effect of Cu-Zn
SiO2Addition, improve the dispersion degree of active component.
Technical solution of the invention is as follows：Produce gamma-butyrolacton catalyst, it is characterised in that the group of catalyst is divided into
CuO-ZnO-MnO2-SiO2, catalytic component molar ratio is Cu:Zn:Si:Mn=1~3:1~2:1:0.05.
The present invention also provides the preparation methods of the catalyst, and specific preparation process is as follows：
(1) first copper nitrate, zinc nitrate, manganese nitrate are dissolved in deionized water and are made into mother liquor, under agitation with alkaline sedimentation
Agent aqueous solution is co-precipitated, and pH=9 ~ 10 are controlled, and catalyst precursor is made；
(2) silica solution is added in catalyst precursor obtained in step (1), stirring ageing 1h；
(3) by products therefrom washing filtering in (2), dry, finished catalyst is finally made in roasting.
Preferably, selected alkaline precipitating agent is one of sodium hydroxide, potassium hydroxide and sodium carbonate in step (1).
Coprecipitation mode employed in step (1) is co-precipitation method.
Precipitation temperature in step (1) is 65 DEG C ~ 80 DEG C.
Aging Temperature in step (2) is 70 ~ 80 DEG C.
Drying temperature in step (3) is 100 DEG C ~ 120 DEG C, and drying time is that for 24 hours, the maturing temperature of Muffle furnace is 450
DEG C ~ 550 DEG C, calcining time is 3 ~ 6h.
Beneficial effect：
1. being free of element Cr in catalyst, environmental pollution is reduced；
2. adding auxiliary agent Mn in the catalyst, and use SiO2The specific surface area of catalyst is greatly improved as carrier, reduces activity
The partial size of component improves the service life of catalyst to alleviate the sintering of active component；
The synergistic effect of 3.Cu-Zn and higher active component dispersion degree, improve the catalytic activity of catalyst, 1,4-butanediol
Conversion ratio >=99%, selectivity >=98% of gamma-butyrolacton；
4. operating procedure is simple, production cost is substantially reduced.
Specific embodiment
Below by specific example, the present invention is further described.
Embodiment 1
According to Cu:Zn:Si:Mn=2:1:1:0.05 molar ratio weighs Cu (NO3)2·3H2O, Zn (NO3)2·6H2O solid, Mn
(NO3)2Solution (50wt%) and silica solution (40wt%), by Cu (NO3)2·3H2O, Zn (NO3)2·6H2O solid and Mn (NO3)2It is molten
Liquid dissolution is made into mother liquor in deionized water, and the solution of 1mol/l, co-precipitation are made into using sodium hydroxide as alkaline precipitating agent
To pH=9,75 DEG C of precipitation temperature, silica solution being continuously added under agitation, is aged 1h at 80 DEG C, product is washed and is filtered,
Drying for 24 hours, carries out roasting 3h, roasting particle is uniformly mixed tabletting with graphite into 3 × 3mm of Φ at 500 DEG C at 100 DEG C
Cylindrical catalyst A.At 180 DEG C, 1,4-butanediol liquid air speed 1.2h-1, than 10, operation 500h, 1,4-butanediol turns hydrogen alcohol
Rate is up to 99.2%, and the selection rate of gamma-butyrolacton is up to 98.7%, and catalyst is without obvious carbon distribution.
Embodiment 2
According to Cu:Zn:Si:Mn=3:1:1:0.05 molar ratio weighs Cu (NO3)2·3H2O, Zn (NO3)2·6H2O solid, Mn
(NO3)2Solution (50wt%) and silica solution (40wt%), by Cu (NO3)2·3H2O, Zn (NO3)2·6H2O solid and Mn (NO3)2It is molten
Liquid dissolution is made into mother liquor in deionized water, and the solution of 1mol/l, co-precipitation are made into using potassium hydroxide as alkaline precipitating agent
To pH=10,70 DEG C of precipitation temperature, silica solution is continuously added under agitation, is aged 1h at 75 DEG C, product is washed
Filter, it is dry at 120 DEG C to carry out roasting 3h at 550 DEG C for 24 hours, roasting particle be uniformly mixed with graphite tabletting at Φ 3 ×
3mm cylindrical catalyst B.At 200 DEG C, 1,4-butanediol liquid air speed 1.2h-1, hydrogen alcohol is than 12, operation 500h, 1,4-butanediol
Conversion ratio is up to 99.1%, and the selection rate of gamma-butyrolacton is up to 98.3%, and catalyst is without obvious carbon distribution.
Embodiment 3
According to Cu:Zn:Si:Mn=3:2:1:0.05 molar ratio weighs Cu (NO3)2·3H2O, Zn (NO3)2·6H2O solid, Mn
(NO3)2Solution (50wt%) and silica solution (40wt%), by Cu (NO3)2·3H2O, Zn (NO3)2·6H2O solid and Mn (NO3)2It is molten
Liquid dissolution is made into mother liquor in deionized water, the solution of 1mol/l is made into using sodium carbonate as alkaline precipitating agent, co-precipitation is extremely
PH=10 65 DEG C of precipitation temperature, continuously add silica solution under agitation, are aged 1h at 75 DEG C, and product is washed and is filtered,
Drying for 24 hours, carries out roasting 3h, roasting particle is uniformly mixed tabletting with graphite into 3 × 3mm of Φ at 450 DEG C at 100 DEG C
Cylindrical catalyst C.At 220 DEG C, 1,4-butanediol liquid air speed 1.5h-1, than 10, operation 500h, 1,4-butanediol turns hydrogen alcohol
Rate is up to 99.0%, and the selection rate of gamma-butyrolacton is up to 98.3%, and catalyst is without obvious carbon distribution.
Embodiment 4
According to Cu:Zn:Si:Mn=1:1:1:0.05 molar ratio weighs Cu (NO3)2·3H2O, Zn (NO3)2·6H2O solid, Mn
(NO3)2Solution (50wt%) and silica solution (40wt%), by Cu (NO3)2·3H2O, Zn (NO3)2·6H2O solid and Mn (NO3)2It is molten
Liquid dissolution is made into mother liquor in deionized water, the solution of 1mol/l, co-precipitation are made into using potassium hydroxide as alkaline precipitating agent
To pH=9,80 DEG C of precipitation temperature, silica solution being continuously added under agitation, is aged 1h at 70 DEG C, product is washed and is filtered,
Drying for 24 hours, carries out roasting 3h, roasting particle is uniformly mixed tabletting with graphite into 3 × 3mm of Φ at 550 DEG C at 120 DEG C
Cylindrical catalyst D.At 240 DEG C, 1,4-butanediol liquid air speed 0.8h-1, than 10, operation 500h, 1,4-butanediol turns hydrogen alcohol
Rate is up to 99.2%, and the selection rate of gamma-butyrolacton is up to 98.1%, and catalyst is without obvious carbon distribution.
Embodiment 5
According to Cu:Zn:Si:Mn=2:2:1:0.05 molar ratio weighs Cu (NO3)2·3H2O, Zn (NO3)2·6H2O solid, Mn
(NO3)2Solution (50wt%) and silica solution (40wt%), by Cu (NO3)2·3H2O, Zn (NO3)2·6H2O solid and Mn (NO3)2It is molten
Liquid dissolution is made into mother liquor in deionized water, and the solution of 1mol/l, co-precipitation are made into using sodium hydroxide as alkaline precipitating agent
To pH=10,75 DEG C of precipitation temperature, silica solution is continuously added under agitation, is aged 1h at 75 DEG C, product is washed
Filter, it is dry at 110 DEG C to carry out roasting 3h at 450 DEG C for 24 hours, roasting particle be uniformly mixed with graphite tabletting at Φ 3 ×
3mm cylindrical catalyst.At 260 DEG C, 1,4-butanediol liquid air speed 0.8h-1, hydrogen alcohol is than 12, operation 500h, 1,4-butanediol
Conversion ratio is up to 99.4%, and the selection rate of gamma-butyrolacton is up to 98.0%, and catalyst is without obvious carbon distribution.
Embodiment 6
According to Cu:Zn:Si:Mn=1:2:1:0.05 molar ratio weighs Cu (NO3)2·3H2O, Zn (NO3)2·6H2O solid, Mn
(NO3)2Solution (50wt%) and silica solution (40wt%), by Cu (NO3)2·3H2O, Zn (NO3)2·6H2O solid and Mn (NO3)2It is molten
Liquid dissolution is made into mother liquor in deionized water, and the solution of 1mol/l, co-precipitation are made into using potassium hydroxide as alkaline precipitating agent
To pH=10,75 DEG C of precipitation temperature, silica solution is continuously added under agitation, is aged 1h at 70 DEG C, product is washed
Filter, it is dry at 120 DEG C to carry out roasting 3h at 550 DEG C for 24 hours, roasting particle be uniformly mixed with graphite tabletting at Φ 3 ×
3mm cylindrical catalyst.At 220 DEG C, 1,4-butanediol liquid air speed 1.3h-1, hydrogen alcohol is than 10, operation 500h, 1,4-butanediol
Conversion ratio is up to 99.0%, and the selection rate of gamma-butyrolacton is up to 98.0%, and catalyst is without obvious carbon distribution.
Claims (7)
1. a kind of catalyst for producing gamma-butyrolacton, it is characterised in that the group of catalyst is divided into CuO-ZnO-MnO2-SiO2, catalysis
Agent component molar ratio is Cu:Zn:Si:Mn=1~3:1~2:1:0.05.
2. the preparation method of gamma-butyrolacton catalyst according to claim 1, it is characterized in that including the following steps：
(1) first copper nitrate, zinc nitrate, manganese nitrate are dissolved in deionized water and are made into mother liquor, under agitation with alkaline sedimentation
Agent aqueous solution is co-precipitated, and pH=9 ~ 10 are controlled, and catalyst precursor is made；
(2) silica solution is added in catalyst precursor obtained in step (1), stirring ageing 1h；
(3) by products therefrom washing filtering in (2), dry, finished catalyst is finally made in roasting.
3. according to the method described in claim 2, it is characterized in that, selected alkaline precipitating agent is sodium hydroxide, hydrogen in step (1)
One of potassium oxide and sodium carbonate.
4. according to the method described in claim 2, it is characterized in that, coprecipitation mode employed in step (1) is that cocurrent is coprecipitated
Shallow lake method.
5. according to the method described in claim 2, it is characterized in that, the precipitation temperature in step (1) is 65 DEG C ~ 80 DEG C.
6. according to the method described in claim 2, it is characterized in that, the Aging Temperature in step (2) is 70 ~ 80 DEG C.
7. according to the method described in claim 2, doing it is characterized in that, drying temperature in step (3) is 100 DEG C ~ 120 DEG C
The dry time is that for 24 hours, the maturing temperature of Muffle furnace is 450 DEG C ~ 550 DEG C, and calcining time is 3 ~ 6h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110773174A (en) * | 2019-09-24 | 2020-02-11 | 浙江大学 | Catalyst for preparing gamma-butyrolactone through dehydrogenation of 1, 4-butanediol and preparation method thereof |
| CN112387288A (en) * | 2019-08-15 | 2021-02-23 | 中国石油化工股份有限公司 | Medium-temperature cyclohexanol dehydrogenation catalyst and preparation method and application thereof |
| CN112844364A (en) * | 2021-02-07 | 2021-05-28 | 内蒙古久泰新材料有限公司 | Multi-metal catalyst and application thereof in preparation of lactide compound |
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| JPH02233630A (en) * | 1989-03-08 | 1990-09-17 | Tonen Corp | Production of 1,4-butanediol and tetrahydrofuran |
| CN1658970A (en) * | 2002-04-22 | 2005-08-24 | 爱敬油化株式会社 | Hydrogenation catalyst, preparation thereof, and method for the preparation of gamma-butyrolactone from maleic anhydride using the catalyst |
| CN102946994A (en) * | 2010-04-21 | 2013-02-27 | Sk新技术株式会社 | Nanometer-sized copper-based catalyst, production method thereof, and alcohol production method using the same through direct hydrogenation of carboxylic acid |
| CN103769110A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for dehydrogenating 1,4-butanediol to prepare gramma-butyrolactone and its preparation method and application |
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| US3853922A (en) * | 1968-08-10 | 1974-12-10 | Mitsubishi Chem Ind | Process for producing tetrahydrofuran |
| JPH02233630A (en) * | 1989-03-08 | 1990-09-17 | Tonen Corp | Production of 1,4-butanediol and tetrahydrofuran |
| CN1658970A (en) * | 2002-04-22 | 2005-08-24 | 爱敬油化株式会社 | Hydrogenation catalyst, preparation thereof, and method for the preparation of gamma-butyrolactone from maleic anhydride using the catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112387288A (en) * | 2019-08-15 | 2021-02-23 | 中国石油化工股份有限公司 | Medium-temperature cyclohexanol dehydrogenation catalyst and preparation method and application thereof |
| CN112387288B (en) * | 2019-08-15 | 2024-01-30 | 中国石油化工股份有限公司 | Medium-temperature cyclohexanol dehydrogenation catalyst and preparation method and application thereof |
| CN110773174A (en) * | 2019-09-24 | 2020-02-11 | 浙江大学 | Catalyst for preparing gamma-butyrolactone through dehydrogenation of 1, 4-butanediol and preparation method thereof |
| CN110773174B (en) * | 2019-09-24 | 2020-11-10 | 浙江大学 | Catalyst for preparing gamma-butyrolactone through dehydrogenation of 1, 4-butanediol and preparation method thereof |
| CN112844364A (en) * | 2021-02-07 | 2021-05-28 | 内蒙古久泰新材料有限公司 | Multi-metal catalyst and application thereof in preparation of lactide compound |
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