CN105709760B - A kind of Cu-Cr catalyst and its preparation method and application - Google Patents
A kind of Cu-Cr catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of Cu Cr catalyst, includes the following steps：（1）Prepare copper chromium mixed solution and alkaline solution；（2）By copper chromium mixed solution and alkaline solution co-precipitation；（3）Citric acid is added in remaining copper chromium solution, continues to compare step with alkaline solution co-precipitation, wherein precipitation system（2）Reaction temperature improves 10 ~ 30 DEG C, and precipitation reaction pH value improves 0.5 ~ 1.5；（4）Reaction product solution is heated to gel；（5）By gel in 120 ~ 150 DEG C, become xerogel；（6）Xerogel is ground into fine-powdered, ethyl alcohol is added and lights, the product after burning is the Cu-Cr catalyst prepared.Catalyst prepared by this method for maleic acid alkyl ester and/or succinic acid dialkyl ester Hydrogenation for Isosorbide-5-Nitrae butanediol during, activity is high, stability is good, reactor bed pressure drop is without obviously increasing.
Description
Technical field
The present invention relates to a kind of preparation methods of Cu-Cr catalyst, especially with maleic acid alkyl ester and/or fourth
Adipate is raw material, and the copper chromium of 1,4-butanediol co-producing tetrahydrofuran and gamma-butyrolacton is produced using gas phase hydrogenation
The preparation method of catalyst.
Background technology
1,4-butanediol is a kind of important sill Organic Chemicals, mainly for the production of tetrahydrofuran, is gathered to benzene two
Formic acid dibutyl ester（PBT）, gamma-butyrolacton and polyurethane（PU）.In recent years, due to thermoplastic elastic fiber and elastomer demand
It increases rapidly, the PTMEG as monomer（Polytetramethylene ether diol）、PTMG（Polytetrahydrofuran ether）It is in great demand so that
Upstream raw material 1,4-butanediol demand also rapid growth, in the world major 1,4-butanediol manufacturer such as BASF, DuPont etc.
All numerous and confused expand can be increased production.Tetrahydrofuran is a kind of excellent solvent and important Organic Chemicals, maximum purposes be with
1,4-butanediol polycondensation generates PTMG and itself polycondensation generates PTMEG.Gamma-butyrolacton is that a kind of important organic chemical industry is former
Material and fine-chemical intermediate, and one kind is functional, dissolubility is strong, good electrical property, stability are high, nontoxic, safe to use
High boiling solvent, maximum purposes be production methyl pyrrolidone.
Current industrialized 1,4- butanediols production line mainly has following 5 kinds：Using acetylene and formaldehyde as raw material
Reppe methods；2, using cis-butenedioic anhydride as the hydrogenation technique of raw material；3, the gas phase hydrogenation technique of maleate；4, using propylene as raw material
Synthesis technology；5, using butadiene as the synthesis technology of raw material.Most widely used at present is Reppe method techniques.But maleic
The gas phase hydrogenation technique of two acid esters is since the boiling point of its raw material is relatively low, and the fixed bed reaction of relative maturity can be used to fill
It sets, is increasingly taken seriously.It is more as the catalyst of main active component using CuO in the production technology of 1,4-butanediol.And this
Wherein, and mostly based on Cu-Cr systems, such as EP0143634, CN1182732A, EP0373947.
US2079414 discloses a kind of Cu-series catalyst for esters Hydrogenation alcohol, subsequently discloses many esters
Patent of hydrogenation catalyst, including US 3787334, US 3899446 etc..Such catalyst is mainly Cu-Cr catalyst.
Cu-Cr catalyst can be used for other techniques, and low-temperature liquid phase synthesis of methanol and first are used for as disclosed in CN1136979A
In sour methyl ester producing process, in the patent Cu/Cr molar ratios 0.6~1.4 are controlled to measure, filter cake obtained through drying, in N2Under
300~350 DEG C thermally decompose 2~5 hours, without molding, are directly used in one-step method low-temperature liquid phase synthesis of methanol and methyl formate life
In production. art.
CN1182732 discloses CuO-Cr2O3-A12O3Metal salt is first dissolved in deionized water by catalyst, is stirred evenly
After ammonium hydroxide is added, until pH is 5.0, precipitation is collected in filtering, washing, and catalyst is made in dry, roasting.This preparation method exists
Waste water handling problem, environment are unfriendly.
EP0143634 discloses a kind of using diethyl maleate or/and butene dioic acid diethylester gas phase hydrogenation system
The method of standby 1,4-butanediol, co-producing tetrahydrofuran and gamma-butyrolacton, catalyst used is the catalyst containing Cu-Cr.
CN1116616A discloses one kind using maleic dialkyl ester and/or succinic acid dialkyl ester as raw material gas phase hydrogenation
The method for preparing 1,4-butanediol, catalyst Formula CuaZnCrbMcOx（M is a kind of element in Group IVB, especially
Zr elements）.CN 1137944A CuCraMnbBacMdOX（M=Al or Ti）, 118263 9A CuCr of CNaZnbTicOXAdd hydrogen
Maleic anhydride and/or its ester 1,4- butanediols.The above catalyst is all made of various forms of precipitation method and is made, although it
Have higher catalytic activity and good selectivity, but the precipitation method it is intrinsic technological process it is long, consumption it is more, operation influence
The deficiencies of factor is complicated all makes the of high cost of precipitation method production catalyst.Efficiency is low, and is urged containing chromium since the precipitation method are produced
Agent filter process can also cause the loss of chromium, pollute the environment.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of hydrogenation catalyst.This method technological process
Simply, efficiently, for maleic acid alkyl ester and/or succinic acid dialkyl ester Hydrogenation for 1,4-butanediol process
In, activity is high, stability is good, reactor bed pressure drop is without obviously increasing, especially suitable for producing 1,4-butanediol co-production
The method of tetrahydrofuran and gamma-butyrolacton.
The preparation process of Cu-Cr catalyst proposed by the present invention, includes the following steps：
（1）Prepare copper chromium mixed solution and alkaline solution；
（2）At 20 ~ 70 DEG C, preferably 30 ~ 50 DEG C, by copper chromium mixed solution and alkaline solution co-precipitation, precipitation is kept
The pH value of system is 4 ~ 7, preferably 5 ~ 6, and copper chromium solution dosage used is the 30% ~ 60% of total amount, preferably 40% ~ 50%；
（3）Citric acid is added in remaining copper chromium solution, addition is with citric acid quality with remaining copper chromium solution
Volume ratio is 1.5:1-0.2:1 meter, preferably 1.1:1-1.4:1, continue and alkaline solution co-precipitation, wherein precipitation system phase
Compare step（2）Reaction temperature improves 10 ~ 30 DEG C, and preferably 15 ~ 25 DEG C, precipitation reaction pH value improves 0.5 ~ 1.5, preferably 0.8 ~ 1.2；
（4）Reaction product solution is heated to 80 ~ 100 DEG C, preferably 85 ~ 95 DEG C, being allowed to dehydration becomes gel；
（5）It is dry at preferably 130 ~ 140 DEG C by gel in 120 ~ 150 DEG C, become xerogel；
（6）Xerogel is ground into fine-powdered, ethyl alcohol is added and lights, the product after burning is the copper chromium catalysis prepared
Agent.
The method of the present invention, step（1）In, the soluble-salt of copper can be one in its nitrate, acetate or oxalates etc.
Kind is a variety of；Control a concentration of 0.5 ~ 4.0mol/L of copper；Preferably 0.8~3.0mol/L.The oxide of chromic salts or chromium includes
But it is not limited to following several：Chromic nitrate, potassium chromate, potassium bichromate, ammonium chromate, ammonium dichromate, sodium chromate, sodium dichromate, chromic acid
Acid anhydride etc. it is one or more, control a concentration of 0.5 ~ 2mol/L of chromium, preferably 1.0 ~ 1.5mol/L.
Hydrogenation catalyst prepared by the method for the present invention has following property：, on the basis of the weight of catalyst：Copper oxide
Content is 20% ~ 50%, preferably 30% ~ 40%, and specific surface area is 50 ~ 100m2/ g, preferably 60 ~ 90m2/ g, Kong Rongwei 0.20 ~
0.50mL/g, preferably 0.30 ~ 0.40mL/g of pore size distribution：Bore dia be 10~30nm shared by Kong Rong account for total pore volume 80%~
95%, preferably 85%~90%.
Above-mentioned catalyst is for maleic acid alkyl ester and/or succinic acid dialkyl ester Hydrogenation for 1,4- fourths two
Alcohol, reaction pressure are 4 ~ 8MPa, and preferably 5 ~ 6MPa, reaction temperature is 160 ~ 240 DEG C, and preferable reaction temperature is 180 ~ 200 DEG C, hydrogen
Ester molar ratio 100:1~400:1, preferred hydrogen ester molar ratio 200:1~300:1, maleic acid alkyl ester and/or succinic acid
Volume space velocity is 0.1 ~ 2.0h when the liquid of dialkyl ester-1, volume space velocity is 0.2 ~ 0.5h when preferred liquid-1。
The maleic acid alkyl ester and/or succinic acid dialkyl ester are generally the dialkyl ester of C1 ~ C4, such as along fourth
Enedioic acid dimethyl ester and/or dimethyl succinate, diethyl maleate and/or diethyl succinate, maleic acid two
Butyl ester and/or dibutyl succinate etc..
According to Cu-Cr catalyst provided by the invention, preparation flow is simple, and catalyst production efficiency is high.It is given birth to the precipitation method
Cu-Cr catalyst is produced, technological process is long, and consumption is more, but also chromium can be made to be lost in and cause environmental pollution.The present invention uses two
Section precipitates and controls the addition opportunity of citric acid, produces Cu-Cr catalyst in conjunction with self-propagating combustion, does not need complicated control
Means do not generate sewage, will not cause environmental pollution, and combustion process does not need external heat source yet, reduce energy consumption, institute
The catalyst obtained has the characteristics that Kong Rong and specific surface area are larger, and hole holds distribution and concentrates, and improves the reactivity of catalyst.
The catalyst is used for maleic acid alkyl ester and/or succinic acid dialkyl ester hydrogenation reaction, it can high selection
Property prepare 1,4-butanediol and producing tetrahydrofuran, gamma-butyrolacton, activity is high, and selectivity is good, and stability is good.
Specific implementation mode
The present invention is further described in production 1,4- butanediols and producing tetrahydrofuran, γ-fourth below by specific embodiment
The preparation of the catalyst of lactone.In the present invention, specific surface area and Kong Rong, aperture, pore size distribution use low temperature liquid nitrogen determination of adsorption method
's.
Catalyst provided by the invention can be evaluated with the following method:
Catalyst activity is evaluated in micro fixed-bed reactor.Catalyst powder after roasting is granulated to 40 ~ 60 mesh,
It is fitted into microreactor reaction tube (internal diameter 15mm), with diluted H2Gas reduction activation.Raw material maleic acid dialkyl group
Ester and/or succinic acid dialkyl ester squeeze into reaction tube, temperature reaction of then pressurizeing as reaction solution through constant-flux pump.Reaction pressure
For 4 ~ 8MPa, preferably 5 ~ 6MPa, reaction temperature is 160 ~ 240 DEG C, and preferable reaction temperature is 180 ~ 200 DEG C.Hydrogen ester molar ratio
100:1~400:1, preferred hydrogen ester molar ratio 200:1~300:1, maleic acid alkyl ester and/or succinic acid dialkyl ester
Liquid when volume space velocity be 0.1 ~ 2.0h-1, volume space velocity is 0.2 ~ 0.5h when preferred liquid-1, concrete technology condition can basis
Feedstock property and product requirement are specifically chosen by ability domain knowledge.
In the method for the present invention, reaction process is first by liquid maleic acid alkyl ester and/or succinic acid dialkyl ester
It is vaporized the vapourous mixture to be formed higher than raw material dew-point temperature in proportion in hot hydrogen logistics, which is led to
Enter in the reactor equipped with catalyst.
Embodiment 1
（1）Take 241.6g Cu (NO3)2.3H2O and 400g Cr (NO3)3.9H2O prepares 1000ml copper chromium mixed solutions；
The ammonia spirit that mass fraction is 10% is prepared simultaneously.
（2）At 25 DEG C, 500ml steps are taken（1）The copper chromium mixed solution and ammonia spirit cocurrent of middle preparation are added dropwise coprecipitated
It forms sediment, it is 5 to keep precipitation system pH value, continues constant temperature after completion of dropwise addition and stirs 60min.
（3）420.2g Citric Acid Monos are added in 500ml copper chromium mixed solutions（C6H8O7·H2O）, it stirs evenly, and
Afterwards in 45 DEG C of system temperature, under conditions of pH value is 6.5, with ammonia spirit co-precipitation, after cocurrent completion of dropwise addition, constant temperature stirs
Mix 60min.
（4）Solution is warming up to 80 DEG C, colloidal sol is made to become gel.
（5）Gel is placed in heat drying in 120 DEG C of drying box, makes xerogel.
（6）Xerogel is ground into fine-powdered, 5ml ethyl alcohol is added in wherein, lights, obtains catalyst.Catalyst is through pressure
Piece is granulated to 50 mesh, is packed into microreactor and is carried out activity rating.
Embodiment 2
（1）Take 241.6g Cu (NO3)2.3H2O and 400g Cr (NO3)3.9H2O prepares 1000ml copper chromium mixed solutions；
Prepare 1.5mol/L sal volatiles simultaneously.
（2）At 30 DEG C, 600ml steps are taken（1）The copper chromium mixed solution and sal volatile cocurrent of middle preparation are added dropwise altogether
Precipitation, it is 5.5 to keep precipitation system pH value, continues constant temperature after completion of dropwise addition and stirs 60min.
（3）420.2g Citric Acid Monos are added in 400ml copper chromium mixed solutions（C6H8O7·H2O）, it stirs evenly, and
Afterwards in 45 DEG C of system temperature, under conditions of pH value is 6.5, with sal volatile co-precipitation, after cocurrent completion of dropwise addition, constant temperature
Stir 120min.
（4）Solution is warming up to 80 DEG C, colloidal sol is made to become gel.
（5）Gel is placed in heat drying in 120 DEG C of drying box, makes xerogel.
（6）Xerogel is ground into fine-powdered, 5ml ethyl alcohol is added in wherein, lights, obtains catalyst.Catalyst is through pressure
Piece is granulated to 50 mesh, is packed into microreactor and is carried out activity rating.
Embodiment 3
（1）Take 241.6g Cu (NO3)2.3H2O and 100g Cr (NO3)3.9H2O prepares 1000ml copper chromium mixed solutions；
The ammonia spirit that mass fraction is 15% is prepared simultaneously.
（2）At 25 DEG C, 500ml steps are taken（1）The copper chromium mixed solution and ammonia spirit cocurrent of middle preparation are added dropwise coprecipitated
It forms sediment, it is 5.5 to keep precipitation system pH value, continues constant temperature after completion of dropwise addition and stirs 60min.
（3）210.1g Citric Acid Monos are added in 500ml copper chromium mixed solutions（C6H8O7·H2O）, it stirs evenly, and
Afterwards in 50 DEG C of system temperature, under conditions of pH value is 6.5, with ammonia spirit co-precipitation, after cocurrent completion of dropwise addition, constant temperature stirs
Mix 120min.
（4）Solution is warming up to 80 DEG C, colloidal sol is made to become gel.
（5）Gel is placed in heat drying in 120 DEG C of drying box, makes xerogel.
（6）Xerogel is ground into fine-powdered, 5ml ethyl alcohol is added in wherein, lights, obtains catalyst.Catalyst is through pressure
Piece is granulated to 50 mesh, is packed into microreactor and is carried out activity rating.
Comparative example 1
（1）Take 241.6g Cu (NO3)2.3H2O and 400g Cr (NO3)3.9H2O prepares 1000ml copper chromium mixed solutions；
The ammonia spirit that mass fraction is 15% is prepared simultaneously.
（2）At 30 DEG C, by step（1）Co-precipitation is added dropwise in the copper chromium mixed solution and ammonia spirit cocurrent of middle preparation, protects
It is 5.5 to hold precipitation system pH value, continues constant temperature after completion of dropwise addition and stirs 120min.
（3）Filtering is collected precipitation, the heat drying in 120 DEG C of drying box, and is roasted 3 hours at 450 DEG C, obtains
Catalyst.Catalyst is granulated through tabletting to 50 mesh, is packed into microreactor and is carried out activity rating.
Comparative example 2
（1）Take 241.6g Cu (NO3)2.3H2O and 400g Cr (NO3)3.9H2O prepares 1000ml copper chromium mixed solutions；
The ammonia spirit that mass fraction is 15% is prepared simultaneously.
（2）At 30 DEG C, 500ml steps are taken（1）The copper chromium mixed solution and ammonia spirit cocurrent of middle preparation are added dropwise coprecipitated
It forms sediment, it is 5 to keep precipitation system pH value, continues constant temperature after completion of dropwise addition and stirs 60min.
（3）Remaining 500ml copper chromium mixed solution is in 45 DEG C of system temperature, under conditions of pH value is 6.5, with ammonia spirit
Co-precipitation, after cocurrent completion of dropwise addition, constant temperature stirs 120min.
（4）Filtering is collected precipitation, the heat drying in 120 DEG C of drying box, and is roasted 3 hours at 450 DEG C, obtains
Catalyst.Catalyst is granulated through tabletting to 50 mesh, is packed into microreactor and is carried out activity rating.
Comparative example 3
（1）Take 241.6g Cu (NO3)2.3H2O, 400g Cr (NO3)3.9H2O and 420.2g Citric Acid Monos
（C6H8O7·H2O）, prepare 1000ml copper chromium-citric acid mixed solution；The ammonia spirit that mass fraction is 15% is prepared simultaneously.
（2）At 30 DEG C, by step（1）Copper chromium-citric acid the mixed solution and ammonia spirit cocurrent of middle preparation are added dropwise altogether
Precipitation, it is 5.5 to keep precipitation system pH value, continues constant temperature after completion of dropwise addition and stirs 120min.
（3）Solution is warming up to 80 DEG C, colloidal sol is made to become gel.
（4）Gel is placed in heat drying in 120 DEG C of drying box, makes xerogel.
（5）Xerogel is ground into fine-powdered, 5ml ethyl alcohol is added in wherein, lights, obtains catalyst.Catalyst is through pressure
Piece is granulated to 50 mesh, is packed into microreactor and is carried out activity rating.
Above-described embodiment, comparative example evaluation process conditions be shown in Table 1, evaluation result is shown in Table 2, and the physico-chemical property of catalyst is shown in
Table 3.
Table 1
Table 2
Note：Reaction product composition unit is mass fraction in table, and conversion ratio is molar fraction, and product overall selectivity is mole
Score.
Table 3
Claims (15)
1. a kind of preparation method of Cu-Cr catalyst, includes the following steps：
（1）Prepare copper chromium mixed solution and alkaline solution；
（2）At 20 ~ 70 DEG C, by copper chromium mixed solution and alkaline solution co-precipitation, it is 4 ~ 7 to keep the pH value of precipitation system,
Copper chromium solution dosage used is the 30% ~ 60% of total amount；
（3）Citric acid is added in remaining copper chromium solution, addition is with citric acid quality with the volume of remaining copper chromium solution
Than being 1.5:1-0.2:1 meter continues to compare step with alkaline solution co-precipitation, wherein precipitation system（2）Reaction temperature carries
10 ~ 30 DEG C high, precipitation reaction pH value improves 0.5 ~ 1.5；
（4）Reaction product solution is heated to 80 ~ 100 DEG C, being allowed to dehydration becomes gel；
（5）Gel is dry at 120 ~ 150 DEG C, become xerogel；
（6）Xerogel is ground into fine-powdered, ethyl alcohol is added and lights, the product after burning is the Cu-Cr catalyst prepared.
2. according to the method described in claim 1, it is characterized in that：Step（1）In, copper is its nitrate, acetate or oxalic acid
One or more of salt；Control a concentration of 0.5 ~ 4.0mol/L of copper.
3. according to the method described in claim 2, it is characterized in that：Control a concentration of 0.8~3.0mol/L of copper.
4. according to the method described in claim 1, it is characterized in that：Step（1）In, chromium is in the oxide of its chromic salts or chromium
It is one or more of.
5. according to the method described in claim 4, it is characterized in that：Chromium is chromic nitrate, potassium chromate, potassium bichromate, ammonium chromate, again
One or more of ammonium chromate, sodium chromate, sodium dichromate, chromic anhybride control a concentration of 0.5 ~ 2mol/L of chromium.
6. according to the method described in claim 4, it is characterized in that：A concentration of 1.0 ~ 1.5mol/L of chromium.
7. according to the method described in claim 1, it is characterized in that：Step（2）In, at 30 ~ 50 DEG C, by copper chromium mixed solution and
Alkaline solution co-precipitation, it is 5 ~ 6 to keep the pH value of precipitation system, and copper chromium solution dosage used is the 40% ~ 50% of total amount.
8. according to the method described in claim 1, it is characterized in that：Step（3）In, addition is with citric acid quality with remaining
The volume ratio of copper chromium solution is 1.1:1-1.4:1 meter, precipitation system compare step（2）Reaction temperature improves 15 ~ 25 DEG C, and precipitation is anti-
PH value is answered to improve 0.8 ~ 1.2.
9. according to the method described in claim 1, it is characterized in that：Step（4）It is middle that reaction product solution is heated to 85 ~ 95
℃。
10. according to the method described in claim 1, it is characterized in that：Step（5）It is middle that gel is dry at 130 ~ 140 DEG C.
11. catalyst prepared by claims 1 to 10 either method, it is characterised in that：On the basis of the weight of catalyst：Oxidation
The content of copper is 20% ~ 50%, and specific surface area is 50 ~ 100m20.20 ~ 0.50mL/g of/g, Kong Rongwei, bore dia are 10~30nm
Shared Kong Rong accounts for the 80%~95% of total pore volume.
12. catalyst according to claim 11, it is characterised in that：The content of copper oxide is 30% ~ 40%, and specific surface area is
60~90m20.30 ~ 0.40mL/g of/g, Kong Rongwei, bore dia be 10~30nm shared by Kong Rong account for total pore volume 85%~
90%.
13. catalyst described in claim 11 is standby for maleic acid alkyl ester and/or succinic acid dialkyl ester Hydrogenation
1,4-butanediol, it is characterised in that：Reaction pressure is 4 ~ 8MPa, and reaction temperature is 160 ~ 240 DEG C, hydrogen ester molar ratio 100:1~
400:1, volume space velocity is 0.1 ~ 2.0h when the liquid of maleic acid alkyl ester and/or succinic acid dialkyl ester-1。
14. application according to claim 13, it is characterised in that：Reaction pressure is 5 ~ 6MPa, and reaction temperature is 180 ~ 200
DEG C, hydrogen ester molar ratio 200:1~300:1, the volume space velocity when liquid of maleic acid alkyl ester and/or succinic acid dialkyl ester
For 0.2 ~ 0.5h-1。
15. application according to claim 13, it is characterised in that：Maleic acid alkyl ester and/or succinic acid dioxane
Base ester is C1~C4Dialkyl ester, including dimethyl maleate and/or dimethyl succinate, diethyl maleate
And/or diethyl succinate, dibutyl maleate and/or dibutyl succinate.
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