CN105797732A - Pre-hydrogenation catalyst for preparing 1,4-butanediol, preparation method and application thereof - Google Patents
Pre-hydrogenation catalyst for preparing 1,4-butanediol, preparation method and application thereof Download PDFInfo
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- CN105797732A CN105797732A CN201610115810.0A CN201610115810A CN105797732A CN 105797732 A CN105797732 A CN 105797732A CN 201610115810 A CN201610115810 A CN 201610115810A CN 105797732 A CN105797732 A CN 105797732A
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- 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
- B01J23/78—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 alkali- or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a dimethyl succinate pre-hydrogenation catalyst for preparing 1,4-butanediol, a preparation method and application thereof. The catalyst provided by the invention can be used for effectively removing few amount of impurities, such as formic acid, acetic acid and dimethyl succinate existing in the process of preparing succinic acid in dimethyl succinate through a fermentation method and the catalyst poisoning and breaking can be prevented.
Description
Technical field
The invention belongs to the Hydrofining Technology field of biochemical product, in particular, it relates to a kind of for fourth two
Dimethyl phthalate Hydrogenation is for the catalyst for pre-hydrogenation and preparation method thereof of 1,4-butanediol.
Background technology
BDO is a kind of important basic organic chemical industry and fine chemical material, is widely used as solvent, medicine, change
The fields such as cosmetic, plasticizer, firming agent, pesticide, herbicide, artificial leather, fiber, engineering plastics, it still produces
Oxolane (THF), gamma-butyrolacton (GBL), N-methyl give a tongue-lashing the base of the products such as pyrrolidone (NMP), polyurethane elastomer
Plinth raw material.The world market demand of 1,4-butanediol is at 1,300,000 tons/year at present.
The production of BDO and succinic acid at present is all based on non-renewable petroleum, energy consumption in its production process
Material consumption is high, seriously polluted, and the energy and environment are caused huge load and destruction.It addition, current petroleum base Isosorbide-5-Nitrae-fourth two
The price of alcohol and succinic acid is high, causes the production cost of poly butylene succinate (PBS) plastics to remain high, seriously makes
About its popularization and application.And be succinic acid and BDO by non-grain biomass material Efficient Conversion, oil money can be broken away from
Source relies on, and reduces its production cost, promotes the popularization and application of PBS plastics, it is achieved bio-based succinic acid, BDO,
The industrialization of poly butylene succinate (PBS) produces, and positive leading and show is played in the popularization and application for bio-based materials
Model effect.
Chinese patent CN103769157B (preparation method of a kind of hydrogenation catalyst) discloses a kind of succinic acid dialkyl ester and adds
Hydrogen prepares the preparation method of the hydrogenation catalyst of BDO.This catalyst is Cu-Al-A-B-O catalyst, wherein A
For one or more in Zn, Mo, W, B is one or more in Ba, Mn, Mg, Ti, Ce, Zr.The present invention
Method use part Cu, A and remainder Cu, Al, B two step carry out parallel-flow precipitation at different conditions, second step remains
Remaining part divides Cu, Al, B precipitation to carry out on the basis of the first step precipitates, and is so conducive to catalyst to be formed stable
Framing structure, and use Supercritical Drying Technology, make the catalyst of preparation have bigger specific surface and the hole more concentrated is divided
Cloth, there is not the clustering phenomena of nanoparticle in metal component during being dried, the grain size in catalyst is relatively simultaneously
Uniformly, pore size distribution is relatively concentrated, and for succinic acid dialkyl ester Hydrogenation in the course of reaction of BDO, improves
The reactivity of catalyst and selectivity and stability.
Chinese patent CN103100393B (a kind of hydrogenation catalyst and preparation method thereof) discloses a kind of succinic acid dialkyl ester
Hydrogenation is for the hydrogenation catalyst and preparation method thereof of 1,4-butanediol.The preparation method of this catalyst and Chinese patent
CN103769157B is similar to, and catalyst has suitable acid amount and acid distribution, improves reactivity and the selection of catalyst
Property and stability.
Chinese patent CN102786389B (a kind of ammonium succinate esterification Hydrogenation is for the method for 1,4-butanediol) relates to a kind of fourth
Diacid ammonium esterification Hydrogenation is for the method for BDO, and the method includes esterification process and hydrogenation process.The method suppresses
The generation of by-product, it is ensured that in product, nitrogen content is at below 100ppm, improve yield and the purity of product.
Chinese patent CN102784651B (urges for the high selective hydration of 1,4-butanediol for dimethyl succinate Hydrogenation
Agent, its preparation method and application thereof) disclose a kind of for dimethyl succinate Hydrogenation for the high selection of 1,4-butanediol
Property catalyst, is made by the steps: 1) copper, zinc, the soluble-salt mixed dissolution of cerium are made into metal ion solution；
2) in metal ion solution, carrier is added；3) preparation precipitant solution；4) under stirring, precipitant aqueous solution is added drop-wise to
Step 2) in gained metal ion solution, controlling temperature in precipitation process is 60～90 DEG C, control the pH value of solution be 6～
8, completion of dropwise addition, constant temperature stirring 2h, it is aged 1～12h, filters to obtain catalyst precursor precipitation；5) deionized water is used
Washing presoma precipitation removes foreign ion, and roasting 5～10h at 90～130 DEG C, then with 5～10 DEG C/min
Temperature programming, to 450～550 DEG C of roastings 5～20h, obtains catalyst Precursors；6) prepared catalyst Precursors is become
Type processes；7) catalyst after molding is reduced.
Chinese patent CN 1493569A (preparing gamma-butyrolacton and/or the method for 1,4-butanediol with chromium-less catalyst) is public
Having opened the method preparing gamma-butyrolacton and/or BDO with chromium-less catalyst, the catalyst used by the method is
Cu-Mn-Al catalyst, its preparation method: Cu-Mn-Al soluble-salt is dissolved in deionized water, at 20～50 DEG C,
With alkali precipitation to pH=5～8, the most aging, filter, wash, roasting i.e. obtains catalyst.Catalysis prepared by described method
The initial activity of agent is good, but less stable, evaluate the catalyst after 500h and there will be intensity reduction, partial catalyst
There will be powder phenomenon-tion.
United States Patent (USP) US20090137825A1 (method of production a carboxy lic a lkyl ester) is reported
A kind of ammonium succinate in road and esterified by butyl alcohol prepare dimethyl succinate, dimethyl succinate by Hydrogenation for oxolane
New technology.The method uses reactive distillation process in Esterification Stage, and the yield of dimethyl succinate is 80～100%,
The yield of oxolane reaches more than 90%.
But, the dimethyl succinate Hydrogenation that the copper-based catalysts of prior art is prepared for bioanalysis is for BDO
During there is catalyst and be easily poisoned and the defect such as crush, its main cause is to use fermentation method to prepare succinic acid two
The contaminant formic acid of a small amount of by-product, acetic acid is there is during methyl ester feedstocks succinic acid.On the other hand, it was esterified at succinic acid
, there is the incomplete monomethyl succinate impurity of a small amount of esterification in Cheng Zhong.These carboxylic acid impurities are securely attached to catalyst table
Face or react with catalyst, causes catalyst poisoning or catalyst efflorescence, cause feed stock conversion to reduce or
Reactor bed pressure drop increases, and power consumption increases.
Summary of the invention
For prior art copper-based catalysts for bio-based dimethyl succinate Hydrogenation for 1,4-butanediol during
There is catalyst be easily poisoned and the defect such as crush, it is an object of the invention to provide one can effectively remove with bio-based
Dimethyl succinate prepares the formic acid of generation, acetic acid, the catalyst for pre-hydrogenation of monomethyl succinate during BDO,
Part dimethyl succinate being hydrogenated to BDO, to reach to extend major catalyst service life, reduction is sponsored simultaneously
The purpose of agent operational load.
Detailed description of the invention:
Dimethyl succinate Hydrogenation is by Al for the catalyst for pre-hydrogenation of BDO, described catalyst2O3, CuO and
Alkali metal oxide forms；
Before dimethyl succinate is hydrogenated with, first passing through catalyst for pre-hydrogenation, described catalyst includes Al2O3, CuO and alkali gold
Belonging to oxide, in terms of the quality of catalyst, the mass content of CuO is 1～30%, and preferably content is 5～20%；Alkali gold
The mass content belonging to oxide is 1～15%, and preferably content is 5～10%；Al2O3Mass content be 55～98%, relatively
Excellent content is 70～90%；The pore volume of catalyst is 0.3～2.0cm3/ g, preferably pore volume are 0.6～1.2cm3/g；
It is 30～80% that the pore volume of aperture macropore between 100～1000nm accounts for the ratio of total pore volume, preferably ratio be 50～
70%.
Described catalyst for pre-hydrogenation, described alkali metal oxide is K2O、Na2Any one in O or a combination thereof.
Described catalyst for pre-hydrogenation, described alkali metal oxide mass content in terms of catalyst quality is 1～15%, this
The bright change by alkali metal content regulates quantity and the intensity of the basic center on catalyst, and basic center is good
The corresponding carboxylate transition state product that the hydroxy-acid group of adsorbing contaminant formic acid, acetic acid and monomethyl succinate is formed, at pre-hydrogenation
Under catalyst effect, promote that carboxylate transition state decomposition product becomes CO, CO2、H2, thus effectively remove in raw material
Formic acid, acetic acid, the acid impurities such as monomethyl succinate.
Alkali metal oxide mass content preferably content is 5～10% further；
Described catalyst for pre-hydrogenation, the mass content of described active center CuO is 1～30%, preferably content be 5～
20%；
Described catalyst for pre-hydrogenation, described Al2O3Mass content be 55～98%, preferably content is 70～90%；
Described catalyst for pre-hydrogenation, described Al2O3For particle diameter 200～500 μm, 50～200 μm, 10～50 μm
Three kinds of Al2O3The grating of powder body, be conducive to improve catalyst pore volume, especially aperture between 100～1000nm it
Between the pore volume of macropore；The preparation method of described catalyst for pre-hydrogenation, comprises the following steps:
(1) according to the ratio that mass ratio is 50～70:10～20:10～40, weigh respectively particle diameter range be 200～
500 μm, 50～200 μm, 10～50 three kinds of Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body gross mass is 2%
Binding agent hydroxypropyl methyl cellulose, mix homogeneously, obtain material I；
(2) adding the aqueous solution containing alkali metal oxide presoma in material I, after kneading, extrusion molding is bar,
Drying, roasting obtain material II；
(3) material II impregnates the aqueous solution of cupric presoma, and drying 1, roasting obtain the catalyst of the present invention.
The preparation method of described catalyst for pre-hydrogenation, the presoma of the alkali metal oxide described in step (2) be KOH,
KNO3、K2CO3, potassium acetate, NaOH, NaNO3、Na2CO3, any one or a combination thereof in sodium acetate.
The preparation method of described catalyst for pre-hydrogenation, the cupric presoma described in step (3) be copper nitrate, Schweinfurt green,
Any one in copper citrate or a combination thereof.
The application of described catalyst for pre-hydrogenation hydrotreating dimethyl succinate, the reaction condition of described pre-hydrogenation is pressure
4～6MPa, temperature 150～250 DEG C, the volume space velocity 0.2～1.0h of dimethyl succinate-1, hydrogen and succinic acid two
The mol ratio 100～300:1 of methyl ester.
Described catalyst for pre-hydrogenation, except succinic acid in the dimethyl succinate raw material handled by described catalyst for pre-hydrogenation
Outside dimethyl ester, possibly together with the succinic acid list first of impurity 0.01～the acetic acid of the formic acid of 0.1%, 0.01～0.1%, 1.0～2.0%
Ester.
The application of described catalyst for pre-hydrogenation, needs to use hydrogen reducing before use, and reduction temperature is 250 DEG C, the recovery time
For 4h, this is well known to those skilled in the art.
The thinking of the employing of the present invention is: come on regulating catalyst by the mass content of the alkali metal oxide of regulating catalyst
The quantity of basic center and intensity, utilize basic center adsorbing contaminant formic acid, acetic acid, the carboxylic acid group of monomethyl succinate
Group forms corresponding carboxylate transition state product, under the catalytic action at activity Cu center, promotes carboxylate transition state product
Resolve into CO, CO2、H2, thus effectively remove the acid impurities in raw material.On the other hand, activity Cu center also can make
A part of dimethyl succinate is hydrogenated to BDO, thus reduces the operational load of follow-up major catalyst.
Technique effect
For prior art, the invention have the advantage that one, the pore volume of catalyst is relatively big, and especially aperture is situated between
The pore volume of the macropore between 100～1000nm accounts for the ratio of total pore volume and can reach 50～70% so that catalyst has very
The ability of big adsorbing contaminant, i.e. removing formic acid acetic acid monomethyl succinate ability strong.Its two, catalyst has concurrently in alkalescence
The heart and hydrogenation both active center, center, also have adding of good dimethyl succinate while removing carboxylic acid impurities
Hydrogen Energy power, alleviates the load of dimethyl succinate hydrogenation catalyst, saves catalyst amount, reduce cost.
Embodiment
Below the detailed description of the invention of the present invention is described in detail, it should be noted however that the protection model of the present invention
Enclose the most limited to these specific embodiments, but determined by claims.
Embodiment 1
The preparation of catalyst:
(1) be the ratio of 50:10:40 according to mass ratio, weigh respectively particle diameter range be 200～500 μm, 50～
200 μm, 10～50 Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body gross mass is the binding agent hydroxypropyl methyl of 2%
Cellulose, mix homogeneously, obtain material I；
(2) adding the aqueous solution containing KOH in material I, after kneading, extrusion molding is the bar of diameter 2mm, warp
100 DEG C of dry 10h, 600 DEG C of roasting 4h obtain material II；
(3) material II is impregnated the aqueous solution containing copper nitrate, obtain this through 100 DEG C of dry 10h, 400 DEG C of roasting 4h
The catalyst of embodiment.
The composition of the catalyst that the present embodiment obtains, pore volume, macropore (100～1000nm) pore volume proportion are shown in Table 1.
The evaluation of catalyst:
In the dimethyl succinate raw material used during evaluating catalyst in addition to dimethyl succinate, possibly together with the first of 0.01%
Acid, the acetic acid of 0.01%, the monomethyl succinate of 1.0%.The catalyst for pre-hydrogenation of the present embodiment is loaded in hydrogenation reactor
Carrying out hydrogen reducing process, reduction temperature is 250 DEG C, and the recovery time is 4h.After reduction terminates, carry out succinic acid two
The pre-hydrotreating reaction of methyl ester feedstocks, reaction condition is pressure 4MPa, temperature 150 DEG C, and the volume of dimethyl succinate is empty
Speed 1.0h-1, hydrogen and mol ratio 100:1 of dimethyl succinate.
In hydrogenation products, formic acid, acetic acid, monomethyl succinate, the conversion ratio of dimethyl succinate are shown in Table 1.
Embodiment 2
The preparation of catalyst:
(1) be the ratio of 70:20:10 according to mass ratio, weigh respectively particle diameter range be 200～500 μm, 50～
200 μm, 10～50 Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body gross mass is the binding agent hydroxypropyl methyl of 2%
Cellulose, mix homogeneously, obtain material I；
(2) add containing KNO in material I3Aqueous solution, after kneading, extrusion molding is the bar of diameter 2mm, warp
100 DEG C of dry 10h, 600 DEG C of roasting 4h obtain material II；
(3) material II is impregnated the aqueous solution containing Schweinfurt green, obtain this through 100 DEG C of dry 10h, 400 DEG C of roasting 4h
The catalyst of embodiment.
The composition of the catalyst that the present embodiment obtains, pore volume, macropore (100～1000nm) pore volume proportion are shown in Table 1.
The evaluation of catalyst:
In the dimethyl succinate raw material used during evaluating catalyst in addition to dimethyl succinate, possibly together with the first of 0.1%
Acid, the acetic acid of 0.1%, the monomethyl succinate of 2.0%.The catalyst for pre-hydrogenation of the present embodiment is loaded in hydrogenation reactor
Carrying out hydrogen reducing process, reduction temperature is 250 DEG C, and the recovery time is 4h.After reduction terminates, carry out succinic acid two
The pre-hydrotreating reaction of methyl ester feedstocks, reaction condition is pressure 6MPa, temperature 250 DEG C, and the volume of dimethyl succinate is empty
Speed 0.2h-1, hydrogen and mol ratio 300:1 of dimethyl succinate.
In hydrogenation products, formic acid, acetic acid, monomethyl succinate, the conversion ratio of dimethyl succinate are shown in Table 1.
Embodiment 3
The preparation of catalyst:
(1) be the ratio of 60:10:30 according to mass ratio, weigh respectively particle diameter range be 200～500 μm, 50～
200 μm, 10～50 Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body gross mass is the binding agent hydroxypropyl methyl of 2%
Cellulose, mix homogeneously, obtain material I；
(2) add containing K in material I2CO3Aqueous solution, after kneading, extrusion molding is the bar of diameter 2mm,
Material II is obtained through 100 DEG C of dry 10h, 600 DEG C of roasting 4h；
(3) material II is impregnated the aqueous solution containing copper citrate, obtain through 100 DEG C of dry 10h, 400 DEG C of roasting 4h
The catalyst of the present embodiment.
The composition of the catalyst that the present embodiment obtains, pore volume, macropore (100～1000nm) pore volume proportion are shown in Table 1.
The evaluation of catalyst:
In the dimethyl succinate raw material used during evaluating catalyst in addition to dimethyl succinate, possibly together with the first of 0.03%
Acid, the acetic acid of 0.06%, the monomethyl succinate of 1.5%.The catalyst for pre-hydrogenation of the present embodiment is loaded in hydrogenation reactor
Carrying out hydrogen reducing process, reduction temperature is 250 DEG C, and the recovery time is 4h.After reduction terminates, carry out succinic acid two
The pre-hydrotreating reaction of methyl ester feedstocks, reaction condition is pressure 5MPa, temperature 200 DEG C, and the volume of dimethyl succinate is empty
Speed 0.5h-1, hydrogen and mol ratio 200:1 of dimethyl succinate.
In hydrogenation products, formic acid, acetic acid, monomethyl succinate, the conversion ratio of dimethyl succinate are shown in Table 1.
Embodiment 4
The preparation of catalyst:
(1) be the ratio of 60:20:20 according to mass ratio, weigh respectively particle diameter range be 200～500 μm, 50～
200 μm, 10～50 Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body gross mass is the binding agent hydroxypropyl methyl of 2%
Cellulose, mix homogeneously, obtain material I；
(2) adding the aqueous solution containing potassium acetate in material I, after kneading, extrusion molding is the bar of diameter 2mm,
Material II is obtained through 100 DEG C of dry 10h, 600 DEG C of roasting 4h；
(3) material II is impregnated the aqueous solution containing copper nitrate, obtain this through 100 DEG C of dry 10h, 400 DEG C of roasting 4h
The catalyst of embodiment.
The composition of the catalyst that the present embodiment obtains, pore volume, macropore (100～1000nm) pore volume proportion are shown in Table 1.
The evaluation of catalyst:
In the dimethyl succinate raw material used during evaluating catalyst in addition to dimethyl succinate, possibly together with the first of 0.02%
Acid, the acetic acid of 0.03%, the monomethyl succinate of 1.2%.The catalyst for pre-hydrogenation of the present embodiment is loaded in hydrogenation reactor
Carrying out hydrogen reducing process, reduction temperature is 250 DEG C, and the recovery time is 4h.After reduction terminates, carry out succinic acid two
The pre-hydrotreating reaction of methyl ester feedstocks, reaction condition is pressure 4.5MPa, temperature 180 DEG C, the volume of dimethyl succinate
Air speed 0.3h-1, hydrogen and mol ratio 150:1 of dimethyl succinate.
In hydrogenation products, formic acid, acetic acid, monomethyl succinate, the conversion ratio of dimethyl succinate are shown in Table 1.
Embodiment 5
The preparation of catalyst:
(1) be the ratio of 55:15:30 according to mass ratio, weigh respectively particle diameter range be 200～500 μm, 50～
200 μm, 10～50 Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body gross mass is the binding agent hydroxypropyl methyl of 2%
Cellulose, mix homogeneously, obtain material I；
(2) adding the aqueous solution containing NaOH in material I, after kneading, extrusion molding is the bar of diameter 2mm,
Material II is obtained through 100 DEG C of dry 10h, 600 DEG C of roasting 4h；
(3) material II is impregnated the aqueous solution containing copper nitrate, obtain this through 100 DEG C of dry 10h, 400 DEG C of roasting 4h
The catalyst of embodiment.
The composition of the catalyst that the present embodiment obtains, pore volume, macropore (100～1000nm) pore volume proportion are shown in Table 1.
The evaluation of catalyst:
In the dimethyl succinate raw material used during evaluating catalyst in addition to dimethyl succinate, possibly together with the first of 0.07%
Acid, the acetic acid of 0.08%, the monomethyl succinate of 1.8%.The catalyst for pre-hydrogenation of the present embodiment is loaded in hydrogenation reactor
Carrying out hydrogen reducing process, reduction temperature is 250 DEG C, and the recovery time is 4h.After reduction terminates, carry out succinic acid two
The pre-hydrotreating reaction of methyl ester feedstocks, reaction condition is pressure 5.5MPa, temperature 230 DEG C, the volume of dimethyl succinate
Air speed 0.0.7h-1, hydrogen and mol ratio 250:1 of dimethyl succinate.
In hydrogenation products, formic acid, acetic acid, monomethyl succinate, the conversion ratio of dimethyl succinate are shown in Table 1.
Embodiment 6
The preparation of catalyst:
(1) be the ratio of 55:10:35 according to mass ratio, weigh respectively particle diameter range be 200～500 μm, 50～
200 μm, 10～50 Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body gross mass is the binding agent hydroxypropyl methyl of 2%
Cellulose, mix homogeneously, obtain material I；
(2) add containing NaNO in material I3Aqueous solution, after kneading, extrusion molding is the bar of diameter 2mm,
Material II is obtained through 100 DEG C of dry 10h, 600 DEG C of roasting 4h；
(3) material II is impregnated the aqueous solution containing Schweinfurt green, obtain this through 100 DEG C of dry 10h, 400 DEG C of roasting 4h
The catalyst of embodiment.
The composition of the catalyst that the present embodiment obtains, pore volume, macropore (100～1000nm) pore volume proportion are shown in Table 1.
The evaluation procedure of catalyst is same as in Example 3, formic acid, acetic acid, monomethyl succinate, fourth two in hydrogenation products
The conversion ratio of dimethyl phthalate is shown in Table 1.
Embodiment 7
The preparation of catalyst:
(1) be the ratio of 65:10:25 according to mass ratio, weigh respectively particle diameter range be 200～500 μm, 50～
200 μm, 10～50 Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body gross mass is the binding agent hydroxypropyl methyl of 2%
Cellulose, mix homogeneously, obtain material I；
(2) add containing Na in material I2CO3Aqueous solution, after kneading, extrusion molding is the bar of diameter 2mm,
Material II is obtained through 100 DEG C of dry 10h, 600 DEG C of roasting 4h；
(3) material II is impregnated containing copper nitrate and the aqueous solution of Schweinfurt green (the two mass ratio 1:1), be dried through 100 DEG C
10h, 400 DEG C of roasting 4h obtain the catalyst of the present embodiment.
The composition of the catalyst that the present embodiment obtains, pore volume, macropore (100～1000nm) pore volume proportion are shown in Table 1.
The evaluation procedure of catalyst is same as in Example 3, formic acid, acetic acid, monomethyl succinate, fourth two in hydrogenation products
The conversion ratio of dimethyl phthalate is shown in Table 1.
Embodiment 8
The preparation of catalyst:
(1) be the ratio of 65:15:20 according to mass ratio, weigh respectively particle diameter range be 200～500 μm, 50～
200 μm, 10～50 Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body gross mass is the binding agent hydroxypropyl methyl of 2%
Cellulose, mix homogeneously, obtain material I；
(2) adding the aqueous solution containing sodium acetate in material I, after kneading, extrusion molding is the bar of diameter 2mm,
Material II is obtained through 100 DEG C of dry 10h, 600 DEG C of roasting 4h；
(3) material II is impregnated containing copper nitrate and the aqueous solution of Schweinfurt green (the two mass ratio 1:2), be dried through 100 DEG C
10h, 400 DEG C of roasting 4h obtain the catalyst of the present embodiment.
The composition of the catalyst that the present embodiment obtains, pore volume, macropore (100～1000nm) pore volume proportion are shown in Table 1.
The evaluation procedure of catalyst is same as in Example 3, formic acid, acetic acid, monomethyl succinate, fourth two in hydrogenation products
The conversion ratio of dimethyl phthalate is shown in Table 1.
Embodiment 9
The preparation of catalyst:
(1) be the ratio of 70:15:15 according to mass ratio, weigh respectively particle diameter range be 200～500 μm, 50～
200 μm, 10～50 Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body gross mass is the binding agent hydroxypropyl methyl of 2%
Cellulose, mix homogeneously, obtain material I；
(2) add containing KOH and K in material I2CO3The aqueous solution of (the two mass ratio 1:1), is extruded into after kneading
Type is the bar of diameter 2mm, obtains material II through 100 DEG C of dry 10h, 600 DEG C of roasting 4h；
(3) material II is impregnated containing copper nitrate and the aqueous solution of Schweinfurt green (the two mass ratio 1:1), be dried through 100 DEG C
10h, 400 DEG C of roasting 4h obtain the catalyst of the present embodiment.
The composition of the catalyst that the present embodiment obtains, pore volume, macropore (100～1000nm) pore volume proportion are shown in Table 1.
The evaluation procedure of catalyst is same as in Example 3, formic acid, acetic acid, monomethyl succinate, fourth two in hydrogenation products
The conversion ratio of dimethyl phthalate is shown in Table 1.
Embodiment 10
The preparation of catalyst:
(1) be the ratio of 50:15:35 according to mass ratio, weigh respectively particle diameter range be 200～500 μm, 50～
200 μm, 10～50 Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body gross mass is the binding agent hydroxypropyl methyl of 2%
Cellulose, mix homogeneously, obtain material I；
(2) add containing KOH and Na in material I2CO3The aqueous solution of (the two mass ratio 1:2), extrudes after kneading
It is shaped to the bar of diameter 2mm, obtains material II through 100 DEG C of dry 10h, 600 DEG C of roasting 4h；
(3) material II is impregnated containing copper nitrate and the aqueous solution of copper citrate (the two mass ratio 1:2), do through 100 DEG C
Dry 10h, 400 DEG C of roasting 4h obtain the catalyst of the present embodiment.
The composition of the catalyst that the present embodiment obtains, pore volume, macropore (100～1000nm) pore volume proportion are shown in Table 1.
The evaluation procedure of catalyst is same as in Example 3, formic acid, acetic acid, monomethyl succinate, fourth two in hydrogenation products
The conversion ratio of dimethyl phthalate is shown in Table 1.
Embodiment 11
The preparation of catalyst:
(1) be the ratio of 50:20:30 according to mass ratio, weigh respectively particle diameter range be 200～500 μm, 50～
200 μm, 10～50 Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body gross mass is the binding agent hydroxypropyl methyl of 2%
Cellulose, mix homogeneously, obtain material I；
(2) add in material I containing potassium acetate and the aqueous solution of sodium acetate (the two mass ratio 2:1), squeeze after kneading
Go out to be shaped to the bar of diameter 2mm, obtain material II through 100 DEG C of dry 10h, 600 DEG C of roasting 4h；
(3) material II is impregnated containing copper nitrate and the aqueous solution of Schweinfurt green (the two mass ratio 2:1), be dried through 100 DEG C
10h, 400 DEG C of roasting 4h obtain the catalyst of the present embodiment.
The composition of the catalyst that the present embodiment obtains, pore volume, macropore (100～1000nm) pore volume proportion are shown in Table 1.
The evaluation procedure of catalyst is same as in Example 3, formic acid, acetic acid, monomethyl succinate, fourth two in hydrogenation products
The conversion ratio of dimethyl phthalate is shown in Table 1.
Comparative example 1
According to " Speciality Petrochemicals " volume 25 the 1st phase the 21-24 page in 2008 " diethyl succinate Hydrogenation is standby
The technical study of 1,4-butanediol " coprecipitation that provides prepares catalyst.
The preparation of catalyst:
Consisting of according to catalyst: ω (copper oxide)=50%, ω (zinc oxide)=40%, ω (aluminium oxide)=10%, will
A certain amount of copper nitrate, zinc nitrate and aluminum nitrate are dissolved in deionized water and are configured to metal ion liquid, then prepare the denseest
The sodium carbonate liquor of degree is as precipitant, and in 60 DEG C of water-baths, also drip adds the two solution, and stirring, during dropping
Solution ph 7～8 to be controlled, stands aging 12h after dropping, filter, and washing dries 12h at l10 DEG C,
450 DEG C of roasting 4h, molding.The composition of the catalyst that this comparative example obtains, pore volume, macropore (100～1000nm) pore volume
Proportion is shown in Table 1.
The evaluation procedure of catalyst is same as in Example 3, formic acid, acetic acid, monomethyl succinate, fourth two in hydrogenation products
The conversion ratio of dimethyl phthalate is shown in Table 1.
Composition, character and the activity of table 1 catalyst
Compared with comparative example, the catalyst for pre-hydrogenation of the present invention has basic center and hydrogenation both active center, center concurrently,
The pore volume of catalyst, the especially aperture pore volume between 100～1000nm is bigger so that catalyst has the biggest
Accommodate the ability of carboxylate transition state impurity in products, it is possible to formic acid in efficient removal dimethyl succinate raw material, acetic acid,
The acid impurities such as monomethyl succinate.Catalyst also has the hydrogenation capability of certain dimethyl succinate simultaneously, thus drops
The low operational load of follow-up major catalyst.The catalyst of comparative example is as a kind of major catalyst, although succinic acid diformazan
The hydrogenation capability of ester is relatively strong, but poor to the removal effect of the acid impurities such as formic acid, acetic acid, monomethyl succinate, and this is right
The long-term operation of major catalyst is the most disadvantageous.
Claims (12)
1. dimethyl succinate Hydrogenation is for the catalyst for pre-hydrogenation of BDO, it is characterised in that: described
Catalyst be by Al2O3, CuO and alkali metal oxide composition, in terms of the quality of catalyst, the quality of CuO
Content is 1～30%, and the mass content of alkali metal oxide is 1～15%, Al2O3Mass content be 55～98%.
Catalyst the most according to claim 1, it is characterised in that: described CuO mass content is 5～20%.
Catalyst the most according to claim 1, it is characterised in that: described alkali metal oxide is K2O、
Na2Any one in O or a combination thereof.
Catalyst the most according to claim 1, it is characterised in that: described alkali metal oxide quality contains
Amount is 5～10%.
Catalyst the most according to claim 1, it is characterised in that: described Al2O3Mass content be 70～
90%.
Catalyst the most according to claim 1, it is characterised in that: the pore volume of described catalyst be 0.3～
2.0cm3/ g, it is 30～80% that the pore volume of aperture macropore between 100～1000nm accounts for the ratio of total pore volume.
Catalyst the most according to claim 5, it is characterised in that: described catalyst pore volume is 0.6～1.2
cm3/ g, it is 50～70% that the pore volume of aperture macropore between 100～1000nm accounts for the ratio of total pore volume.
8. according to the catalyst described in claim 1 and 11, it is characterised in that: described catalyst for pre-hydrogenation
In handled dimethyl succinate raw material in addition to dimethyl succinate, possibly together with 0.01～the formic acid of 0.1%,
0.01～the monomethyl succinate of the acetic acid of 0.1%, 1.0～2.0%.
9. the preparation method of the catalyst for pre-hydrogenation described in claim 1, comprises the following steps:
(1) according to the ratio that mass ratio is 50～70:10～20:10～40, particle diameter range is weighed respectively
It is 200～500 μm, 50～200 μm, 10～50 Al of μm2O3Powder body；Weigh again and account for Al2O3Powder body is total
Quality is the binding agent hydroxypropyl methyl cellulose of 2%, and mix homogeneously obtains material I；
(2) adding the aqueous solution containing alkali metal oxide presoma in material I, after kneading, extrusion molding is
Bar, dry, roasting obtains material II；
(3) material II impregnates the aqueous solution of cupric presoma, and drying, roasting obtain the catalyst of the present invention.
10. according to the preparation method described in claim 9, it is characterised in that: the alkali gold described in step (2)
The presoma belonging to oxide is KOH, KNO3、K2CO3, potassium acetate, NaOH, NaNO3、Na2CO3, sodium acetate
In any one or a combination thereof.
11. according to the preparation method of the catalyst for pre-hydrogenation described in claim 9, it is characterised in that: step
(3) the cupric presoma described in is any one in copper nitrate, Schweinfurt green, copper citrate or a combination thereof.
12. according to the application of the catalyst described in claim 1, it is characterised in that: described pre-hydrogenation
Reaction condition is pressure 4～6MPa, temperature 150～250 DEG C, the volume space velocity 0.2 of dimethyl succinate～
1.0h-1, hydrogen and the mol ratio 100～300:1 of dimethyl succinate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108623457A (en) * | 2017-03-15 | 2018-10-09 | 成都汇嘉春天科技有限公司 | The catalytic decomposition process of formic acid |
| CN109453763A (en) * | 2017-09-06 | 2019-03-12 | 中国石化扬子石油化工有限公司 | A kind of succinic acid water phase adds the catalyst and preparation method thereof of hydrogen 1,4- butanediol |
| CN110357765A (en) * | 2018-04-09 | 2019-10-22 | 中国石化扬子石油化工有限公司 | Dimethyl succinate hydrogenation method |
| CN111018669A (en) * | 2018-10-09 | 2020-04-17 | 中国石油化工股份有限公司 | Continuous preparation method of 1, 4-butanediol |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB995174A (en) * | 1962-04-30 | 1965-06-16 | Shell Int Research | Hydrogenative cracking of hydrocarbon oils |
| KR20010046301A (en) * | 1999-11-11 | 2001-06-15 | 김충섭 | Catalyst for preparing hydrocarbon |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
| CN102775299A (en) * | 2012-08-03 | 2012-11-14 | 兖矿国泰化工有限公司 | Method for indirectly preparing ethyl acetate by hydrogenating acetic acid |
| CN104383929A (en) * | 2014-11-18 | 2015-03-04 | 沈阳化工大学 | 2-methyl furan catalyst and preparation method thereof |
-
2016
- 2016-03-01 CN CN201610115810.0A patent/CN105797732B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB995174A (en) * | 1962-04-30 | 1965-06-16 | Shell Int Research | Hydrogenative cracking of hydrocarbon oils |
| KR20010046301A (en) * | 1999-11-11 | 2001-06-15 | 김충섭 | Catalyst for preparing hydrocarbon |
| CN102775299A (en) * | 2012-08-03 | 2012-11-14 | 兖矿国泰化工有限公司 | Method for indirectly preparing ethyl acetate by hydrogenating acetic acid |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
| CN104383929A (en) * | 2014-11-18 | 2015-03-04 | 沈阳化工大学 | 2-methyl furan catalyst and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108623457A (en) * | 2017-03-15 | 2018-10-09 | 成都汇嘉春天科技有限公司 | The catalytic decomposition process of formic acid |
| CN109453763A (en) * | 2017-09-06 | 2019-03-12 | 中国石化扬子石油化工有限公司 | A kind of succinic acid water phase adds the catalyst and preparation method thereof of hydrogen 1,4- butanediol |
| CN109453763B (en) * | 2017-09-06 | 2021-06-01 | 中国石化扬子石油化工有限公司 | Catalyst for preparing 1, 4-butanediol by aqueous phase hydrogenation of succinic acid and preparation method thereof |
| CN110357765A (en) * | 2018-04-09 | 2019-10-22 | 中国石化扬子石油化工有限公司 | Dimethyl succinate hydrogenation method |
| CN110357765B (en) * | 2018-04-09 | 2022-05-13 | 中国石化扬子石油化工有限公司 | Dimethyl succinate hydrogenation method |
| CN111018669A (en) * | 2018-10-09 | 2020-04-17 | 中国石油化工股份有限公司 | Continuous preparation method of 1, 4-butanediol |
| CN111018669B (en) * | 2018-10-09 | 2022-10-04 | 中国石油化工股份有限公司 | Continuous preparation method of 1, 4-butanediol |
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