CN107866221A - Catalyst applied to the production of 1,4 diacetoxy butane - Google Patents

Catalyst applied to the production of 1,4 diacetoxy butane Download PDF

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CN107866221A
CN107866221A CN201610852203.2A CN201610852203A CN107866221A CN 107866221 A CN107866221 A CN 107866221A CN 201610852203 A CN201610852203 A CN 201610852203A CN 107866221 A CN107866221 A CN 107866221A
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catalyst
catalyst precarsor
precarsor
nitrae
isosorbide
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CN107866221B (en
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查晓钟
杨运信
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/648—Vanadium, niobium or tantalum or polonium
    • B01J23/6482—Vanadium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/648—Vanadium, niobium or tantalum or polonium
    • B01J23/6484—Niobium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/283—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds

Abstract

The present invention relates to applied to 1, the catalyst of 4 diacetoxy butane production, mainly solve in the prior art 1, the problem of yield and low selectivity of 4 diacetoxy butane, using applied to 1, the catalyst of 4 diacetoxy butane production, including carrier and active component, described carrier is activated carbon, active component includes Pt elements and promoter elements, the promoter elements include the technical scheme selected from least one of Group IIIA metal at least one of metallic element and VB races metal metallic element, preferably solves the technical problem, available for 1, in the industrial production of 4 diacetoxy butane.

Description

Catalyst applied to the production of 1,4- diacetoxies butane
Technical field
The present invention relates to the catalyst produced applied to 1,4- diacetoxies butane.
Background technology
BDO (Isosorbide-5-Nitrae-BDO) is a kind of important organic and fine chemical material, it be widely used in medicine, The fields such as chemical industry, weaving, papermaking, automobile and daily-use chemical industry.It can derive a series of fine chemical product of high added values. For example, tetrahydrofuran (THF), polybutylene terephthalate (PBT) (PBT), γ-fourth lactones (GBL) can be produced by Isosorbide-5-Nitrae-BDO With polyurethane resin (PU Resin), especially as production PBT engineering plastics and the base stock of PBT fibers, ground Study carefully the extensive concern of mechanism.
The process route of the preparation of BDO is relatively more, has acetylene, ethene, propylene, fourth from raw material used to divide The raw material route such as diene and cis-butenedioic anhydride, identical raw material also have different synthesis techniques.Because technology barriers are higher and raw material sources Limited, global Isosorbide-5-Nitrae-BDO produces Relatively centralized.2011, global Isosorbide-5-Nitrae-BDO production capacities were mainly distributed on Asia, US and European, Wherein Asia 1,4-BDO production capacities accounting is up to 56.6%.At present, Isosorbide-5-Nitrae-BDO industrialized preparing process mainly includes：1. alkynes aldehyde Method (Reppe methods)：This method does catalyst generation butynediols, butynediols using acetylene and formaldehyde as raw material, using methanol copper Two-stage hydrogenation obtains 1,4-BDO again.Its prevailing technology mainly have BASF Corp. of Germany, the U.S. DuPont exploitation Reppe methods with And the Reppe methods of improvement.2. maleic anhydride process：This method carries out two step hydrogenation to it using cis-butenedioic anhydride as raw material.The first step is urged in Ni-Re Under agent effect, maleic anhydride hydrogenation generation gamma-butyrolacton and tetrahydrofuran；Second step gamma-butyrolacton is in Mo-Cr-K2O catalyst is made 1,4-BDO is hydrogenated under.Its prevailing technology is mainly the two-stage hydrogenation work that exploitation is melted into Japanese two water chestnut oilings and Mitsubishi Skill.3. propylene method：Mainly include allyl acetate method, acryladehyde method and allyl acetate-allyl alcohol method, Kuraray company exploitation at present Allyl acetate-allyl alcohol method has obtained commercial Application, and it is the allyl alcohol liquid-phase hydrogenatin formylated generation 4- hydroxyl fourths under rhodium catalyst Aldehyde, then repeated hydrogenation generation BDO.4. butadiene process：The method that Isosorbide-5-Nitrae-BDO is produced using butadiene as raw material, main bag Butadiene acetoxylation method and butadiene chloridising are included, the technique of its main flow is melted into by Mitsubishi and Cao Da companies are in 20 generation Exploitation in 80 years of recording forms, and it successfully breaks the technology barriers and obstacle of Reppe methods.Especially butadiene acetoxylation method is excellent Gesture and prospect, the favor of domestic and international research institution is obtained.
It is well known that butadiene acetoxylation method is a three-steps process, i.e., butadiene is sent out with acetic acid, oxygen first Raw acetylization reaction, generates Isosorbide-5-Nitrae-diacetoxy butylene and accessory substance 3.4- diacetoxy butylene；Then 1,4- diacetyl Epoxide butylene catalytic hydrogenation generates Isosorbide-5-Nitrae-diene acetoxyl group butane, and reaction is finally hydrolyzed and obtains Isosorbide-5-Nitrae-BDO.In Isosorbide-5-Nitrae-fourth Diene is into BDO process route, Isosorbide-5-Nitrae-diacetoxy butylene catalytic hydrogenation generation Isosorbide-5-Nitrae-diene acetoxyl group butane As one of step, the yield and selectivity of hydrogenation products directly influence BDO relative to Isosorbide-5-Nitrae-butadiene Yield and selectivity.
Teach in the patents such as patent US4032458 (production of 1,4-butanediol) and urged using furans Agent is present, and BDO is prepared under the conditions of certain temperature and pressure.Patent CN94108094.3 (the systems of 1,4- butanediols Preparation Method) describe using cis-butenedioic anhydride as raw material, gas phase catalytic hydrogenation reaction is carried out in the presence of the catalyst specifically designed and is prepared 1,4- butanediols.Patent CN104326871A (a kind of preparation method of butanediol) is described using fixed-bed catalytic technology, will Content more than 99% 2- butylene mixed with acetic acid, nitrogen, oxygen and water vapour high temperature after be passed through in fixed bed, catalyst with 1,4- butanediols are prepared under the conditions of certain temperature, pressure etc..But there is 1,4- in the above method during 1,4-BDO is prepared The problem of BDO yields are low and selective not high.
The content of the invention
One of technical problems to be solved by the invention are that the yield of 1,4- diacetoxy butane is asked with selectively low Topic, there is provided a kind of new catalyst for being applied to Isosorbide-5-Nitrae-diacetoxy butane production, the catalyst have Isosorbide-5-Nitrae-diethyl acyl-oxygen The characteristics of base butane high income and high selectivity.
The two of the technical problems to be solved by the invention are the preparation methods of above-mentioned catalyst.
The three of the technical problems to be solved by the invention are the conjunctions using the 1,4- diacetoxy butane of above-mentioned catalyst Into method.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Applied to 1,4- diethyl acyl-oxygens The catalyst of base butane production, including carrier and active component, described carrier be activated carbon, active component include Pt elements with Promoter elements, the promoter elements are included at least one of Group IIIA metal metallic element and VB races metal At least one metallic element.
In above-mentioned technical proposal, the activated carbon is preferably ature of coal column charcoal, cocoanut active charcoal, apricot shell activated carbon and bamboo matter At least one of activated carbon.
In above-mentioned technical proposal, the specific surface area of the activated carbon is preferably 1000~1500cm2/ g, absorption pore volume are preferred For 0.60~1.00cm3/g。
In above-mentioned technical proposal, Group IIIA metal preferably is selected from least one of Al, Ga and In in the catalyst, more enters One step preferably includes In and Ga simultaneously.In and Ga is improving 1,4- diethyls acyl-oxygen butane yield and the selection of 1,4- diethyl acyl-oxygens butane Property aspect have synergy.
In above-mentioned technical proposal, VB races metal preferably is selected from least one of V, Nb and Ta in the catalyst.More enter one Step includes V, Nb simultaneously, and V, Nb have in terms of Isosorbide-5-Nitrae-diethyl acyl-oxygen butane yield and Isosorbide-5-Nitrae-diethyl acyl-oxygen butane selectivity is improved Synergy.
In above-mentioned technical proposal, the promoter elements are preferably included in Group IIIA metallic element at least simultaneously It is a kind of and selected from least one of VB races metallic element, now improved between Group IIIA metallic element and VB races metallic element 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygens butane selectivity aspect have synergy.As non-limiting act Example, such as, but not limited to gallium cooperates with niobium, and indium cooperates with niobium etc..
In above-mentioned technical proposal, Pt content is preferably 1.00~8.00g/L in the catalyst, more preferably 1.50~ 5.00g/L。
In above-mentioned technical proposal, promoter elements content is preferably 0.50~10.00g/L in the catalyst, more excellent Elect 1.00~6.00g/L as.
To solve the two of above-mentioned technical problem, technical scheme is as follows：
Method for preparing catalyst any one of the technical scheme of one of above-mentioned technical problem, comprises the following steps Process obtains：
1. mixing the solution of platiniferous element with carrier by the composition of catalyst, catalyst precarsor I is obtained；
Catalyst precarsor II is obtained after 2. catalyst precarsor I is aged；
3. being simple substance platinum by compound state platinum element reduction in catalyst precarsor II, catalyst precarsor III is obtained；
4. through washing, being dried to obtain catalyst precarsor IV；
5. the solution containing promoter elements is supported on catalyst precarsor IV using infusion process by the composition of catalyst, It is dried to obtain the catalyst.
In above-mentioned technical proposal, as non-restrictive, 1. particular compound corresponding to platinum element preferably is selected from vinegar to step At least one of sour platinum, platinum chloride, ammonium chloroplatinite, dinitroso diammonia platinum, chloroplatinic acid and four ammino platinum chlorides；More preferably Ammonium chloroplatinite.
In above-mentioned technical proposal, as non limiting example, step 5. in promoter elements Group IIIA metallic element Corresponding particular compound preferably is selected from aluminium chloride, aluminum sulfate, aluminum acetate, aluminum nitrate, aluminum oxide, gallium oxide, gallium nitrate, chlorination At least one of gallium, acetic acid gallium, inidum chloride, indium sulfate, indium nitrate and indium acetate；In more excellent free gallium nitrate and indium acetate It is at least one.
In above-mentioned technical proposal, as non limiting example, step 5. in promoter elements include VB races metal member Particular compound corresponding to element preferably be selected from vanadium trichloride, ammonium metavanadate, acetic acid vanadium, vanadic anhydride, columbium pentachloride, niobium oxalate, At least one of acetic acid niobium, acetic acid tantalum and tantalic chloride；More preferably at least one of niobium oxalate and ammonium metavanadate.
In above-mentioned technical proposal, the reducing agent of step 3. does not specially require understanding based on those skilled in the art, also Former agent can be at least one of gas or liquid, the preferred hydrogen of reducing agent, hydrazine hydrate；4. drying temperature is preferably step 30~120 DEG C, drying time is preferably 1~5 hour；5. the drying temperature is preferably 80~120 DEG C to step, more preferably 100~120 DEG C.
To solve the three of above-mentioned technical problem, technical scheme is as follows：
The synthetic method of Isosorbide-5-Nitrae-diacetoxy butane, any one of the technical scheme in one of above-mentioned technical problem In the presence of catalyst, hydrogen carries out hydrogenation reaction with Isosorbide-5-Nitrae-diacetoxy butylene and obtains Isosorbide-5-Nitrae-diacetoxy butane.
The key of the present invention is the selection of catalyst, and skilled person will know how suitable according to determination is actually needed Hydrogenation process conditions reaction temperature, the reaction time, the proportioning etc. of reaction pressure and material.But：
In above-mentioned technical proposal, the temperature of hydrogenation reaction is preferably 20~120 DEG C.
In above-mentioned technical proposal, the pressure of hydrogenation reaction is preferably 1.0~10.0MPa, more preferably 1.0~6.0MPa.
In above-mentioned technical proposal, the time of hydrogenation reaction is preferably 0.5~5.0h, more preferably 0.5~2.0h.
Isosorbide-5-Nitrae-diacetoxy butylene can obtain from commercially available channel, or butadiene Acetoxylation method can be used to synthesize.Fourth It is butadiene Acetoxylation catalyst that Pd-Te/C, which can be selected, in the synthesis of diene Acetoxylation method.Palladium in suitable Pd-Te/C catalyst The content of element preferably 2.50~5.00g/L, more preferably 3.00~4.50g/L；The content of tellurium element preferably 0.50~3.00g/ L, more preferably 1.00~2.50g/L.Suitable Acetoxylation reaction temperature is preferably 40~150 DEG C；Acetoxylation reaction pressure It is preferred that 1.0~10.0MPa；The Acetoxylation reaction time is preferably 0.5~5h；The mol ratio of butadiene and acetic acid preferably 0.010 ~2.0.After the reaction of butadiene Acetoxylation, the mixture that can be reacted butadiene Acetoxylation carries out separation acquisition target production Thing Isosorbide-5-Nitrae-diacetoxy butylene carries out hydrogenation reaction of the present invention again, can not also separate and directly carry out hydrogenation reaction.But System complexity is caused to be easy on year-on-year basis in order to exclude other impurity, specific embodiment of the invention department uses pure Isosorbide-5-Nitrae-diacetyl Epoxide butylene is as hydrogenation reaction raw material.
The product mixtures of above-mentioned hydrogenation reaction can obtain target product 1,4- diacetoxy butane through separation.
1,4- diacetoxies butane can be further used for obtaining 1,4- butanediols by method for hydrolysis.Art technology The suitable hydrolyst of the known selection of personnel and determination suitable hydrolysising reacting temperature, time and material proportion.Conventional water It can be inorganic acid, inorganic base, organic acid and organic base to solve catalyst.Such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sodium hydroxide, Potassium hydroxide, benzene sulfonic acid and ion exchange resin.Suitable hydrolysising reacting temperature is preferably 30~100 DEG C；Hydrolysis pressure Power preferably 0~2.0MPa；The preferred water of solvent.
Product mixtures after hydrogenation reaction of the present invention are analyzed through gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), by following Formula calculates the yield and selectivity of 1,4- diacetoxy butane：
Compared with prior art, key of the invention is the new catalyst that step (2) uses, and improves Isosorbide-5-Nitrae-diacetyl The yield and selectivity of oxygen butane.
Test result indicates that during using the present invention, Isosorbide-5-Nitrae-diacetoxy butane yield selectively reaches up to 82.45% 93.96%, achieve preferable technique effect.It is especially simultaneously golden including platinum, selected from Group IIIA in the active component of catalyst At least one of category metallic element and during selected from least one of VB races metal metallic element, achieves more prominent skill Art effect, available in the industrial production of BDO.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the indium acetate (In (OAc) of the In containing 1.90g3·6H2O aqueous solution 180ml) is immersed in catalyst precarsor IV On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, In contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.45%, and selectivity is 93.96%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 2】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the niobium oxalate ((C of the Nb containing 1.90g2HO4)5Nb·6H2O) it is completely dissolved in the acetic acid water that concentration is 30wt% In solution, obtain maceration extract 180ml and be immersed on catalyst precarsor IV, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Nb contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.39%, and selectivity is 94.09%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, the catalyst is obtained.
The Pt contents that the catalyst is determined through ICP are 2.05g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 75.19%, and selectivity is 91.34%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
By simultaneously, as can be seen that the present invention uses the catalyst of hydrogenation, its active component makes compared with embodiment 1~2 With the catalyst performance containing Pt, In active component while containing Pt, Nb active component than the performance containing only Pt active constituent catalysts It is more excellent, illustrate activity of hydrocatalyst component while using at least one containing Pt and in Group IIIA metal and VB races metal Kind metallic element compound, be advantageous to improve the activity and stability of hydrogenation catalyst, the yield of Isosorbide-5-Nitrae-diacetoxy butane Will be high with selectivity.
【Comparative example 2】
For【Comparative example 1】Comparative example.
The preparation of hydrogenation catalyst：
1. by the ammonium chloropalladite ((NH of the Pd containing 2.05g4)2PdCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, the catalyst is obtained.
The Pd contents that the catalyst is determined through ICP are 2.05g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 70.07%, and selectivity is 88.16%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
By can be seen that catalyst of the present invention using hydrogenation compared with comparative example 1, contained using the ratio of active component containing Pt The performance of Pd active constituent catalysts is more excellent, illustrates that activity of hydrocatalyst component is advantageous to Isosorbide-5-Nitrae-diacetoxy using Pt Butylene is hydrogenated with, and the yield and selectivity of Isosorbide-5-Nitrae-diacetoxy butane will be high.
【Embodiment 3】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the ammonium metavanadate (NH of the V containing 1.90g4VO3) aqueous solution 180ml, be immersed on catalyst precarsor IV, 110 DEG C dry 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, V content 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.37%, and selectivity is 94.08%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 4】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.60cm3/ g, specific surface area 1000cm2/ g coconut husk Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the acetic acid vanadium (V (OAc) of the V containing 1.90g3) be completely dissolved in the aqueous acetic acid that concentration is 30wt%, obtain It is immersed in maceration extract 180ml on catalyst precarsor IV, 100 DEG C of dryings 4 hours, obtains the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, V content 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.32%, and selectivity is 94.11%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 5】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 1.00cm3/ g, specific surface area 1500cm2/ g apricot shell Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the acetic acid niobium (Nb (OAc) of the Nb containing 1.90g5) be completely dissolved in the aqueous acetic acid that concentration is 30wt%, Obtain maceration extract 180ml to be immersed on catalyst precarsor IV, 120 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Nb contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.43%, and selectivity is 93.98%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 6】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g's is bamboo Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the aluminum acetate (Al (OAc) of the Al containing 1.90g3·6H2O) aqueous solution 180ml, it is immersed in catalyst precarsor IV On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Al content 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.41%, and selectivity is 93.87%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 7】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the gallium nitrate (Ga (NO of the Ga containing 1.90g3)3·8H2O) aqueous solution 180ml, it is immersed in catalyst precarsor IV On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Ga contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 50 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.50%, and selectivity is 93.99%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 8】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 1.50gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal circle Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the aluminum nitrate (Al (NO of the Al containing 1.00g3)3) aqueous solution 180ml, it is immersed on catalyst precarsor IV, 110 DEG C Dry 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 1.50g/L, Al content 1.00g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 1.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 20 DEG C, after sustained response 30min, stops anti- Should.Reactor is down to room temperature, purified removal of impurities obtains Isosorbide-5-Nitrae-diacetoxy butane.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 80.63%, and selectivity is 93.74%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 9】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 5.00g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the indium nitrate (In (NO of the In containing 6.00g3)3·4.5H2O) aqueous solution 180ml, it is immersed in catalyst precarsor IV On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 5.00g/L, In contents 6.00g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 6.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 120 DEG C, after sustained response 120min, is stopped Reaction.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.89%, and selectivity is 93.75%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 10】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by In containing the 1.18g and Ga containing 0.72g indium acetate (In (OAc)3·6H2) and gallium nitrate (Ga (NO O3)3· 8H2O aqueous solution 180ml) is immersed on catalyst precarsor IV, 110 DEG C of dryings 4 hours, obtains the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, In contents 1.18g/L, Ga content 0.72g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 83.55%, and selectivity is 94.36%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 10 and embodiment 1 and embodiment 7, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane With selective aspect, in the hydrogenation catalyst that uses of the present invention, in Group IIIA metal metallic element In and metallic element Ga have compared with Good synergy.
【Embodiment 11】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by Nb containing the 1.25g and V containing 0.65g niobium oxalate ((C2HO4)5Nb·6H2) and ammonium metavanadate (NH O4VO3) fill Divide and be dissolved in the aqueous acetic acid that concentration is 30wt%, obtain maceration extract 180ml, be immersed on catalyst precarsor IV, 110 DEG C Dry 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Nb content 1.25g/L, V content 0.65g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 83.42%, and selectivity is 94.49%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 11 and embodiment 2 and embodiment 3, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Nb and metallic element V has preferably in VB races metal Synergy.
【Embodiment 12】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by In containing the 1.05g and Nb containing 0.85g indium acetate (In (OAc)3·6H2) and niobium oxalate ((C O2HO4)5Nb· 6H2O) it is completely dissolved in the aqueous acetic acid that concentration is 30wt%, obtains maceration extract 180ml, be immersed in catalyst precarsor IV On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, In contents 1.05g/L, Nb content 0.85g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 84.62%, and selectivity is 95.19%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 2, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane In the hydrogenation catalyst used with selective aspect, the present invention, metallic element In and metal in VB races metal in Group IIIA metal Element nb has preferable synergy.
【Embodiment 13】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by Ga containing the 1.05g and Nb containing 0.85g gallium nitrate (Ga (NO3)3·8H2) and niobium oxalate ((C O2HO4)5Nb· 6H2O) it is completely dissolved in the aqueous acetic acid that concentration is 30wt%, obtains maceration extract 180ml, be immersed in catalyst precarsor IV On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Ga contents 1.05g/L, Nb content 0.85g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 84.71%, and selectivity is 95.03%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 13 and embodiment 2 and embodiment 7, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Ga and metal in VB races metal in Group IIIA metal Element nb has preferable synergy.
【Embodiment 14】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by In containing 0.65g, Ga containing 0.40g and the Nb containing 0.85g indium acetate (In (OAc)3·6H2O), gallium nitrate (Ga(NO3)3·8H2) and niobium oxalate ((C O2HO4)5Nb·6H2O) it is completely dissolved in the aqueous acetic acid that concentration is 30wt%, Maceration extract 180ml is obtained, is immersed on catalyst precarsor IV, 110 DEG C of dryings 4 hours, obtains the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, In contents 0.65g/L, Ga content 0.40g/L, Nb content 0.85g/L。
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 85.28%, and selectivity is 95.42%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13, improving the receipts of Isosorbide-5-Nitrae-diacetoxy butane In terms of rate and selectivity, in the hydrogenation catalyst that the present invention uses, in Group IIIA metal in metallic element In, Ga and VB races metal Metallic element Nb has preferable synergy.
【Embodiment 15】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by In containing 0.65g, Ga containing 0.40g and the V containing 0.85g indium acetate (In (OAc)3·6H2O), gallium nitrate (Ga (NO3)3·8H2) and ammonium metavanadate (NH O4VO3) aqueous solution 180ml, be immersed on catalyst precarsor IV, 110 DEG C of dryings 4 are small When, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, In contents 0.65g/L, Ga content 0.40g/L, V content 0.85g/L。
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 85.33%, and selectivity is 95.34%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 16】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by In containing 0.65g, Ga containing 0.40g, V containing 0.31g and the Nb containing 0.54g indium acetate (In (OAc)3· 6H2O), gallium nitrate (Ga (NO3)3·8H2O), ammonium metavanadate (NH4VO3) and niobium oxalate ((C2HO4)5Nb·6H2O) fully dissolving In the aqueous acetic acid that concentration is 30wt%, maceration extract 180ml is obtained, is immersed on catalyst precarsor IV, 110 DEG C of dryings 4 Hour, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, In contents 0.65g/L, Ga content 0.40g/L, V content For 0.31g/L, Nb contents 0.54g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 86.59%, and selectivity is 95.62%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, improving the receipts of Isosorbide-5-Nitrae-diacetoxy butane In terms of rate and selectivity, in the hydrogenation catalyst that the present invention uses, in Group IIIA metal in metallic element In, Ga and VB races metal Metallic element V, Nb have preferable synergy.
Table 1
Table 2

Claims (10)

1. applied to the catalyst of Isosorbide-5-Nitrae-diacetoxy butane production, including carrier and active component, described carrier is work Property charcoal, active component includes Pt elements and promoter elements, and the promoter elements are included in Group IIIA metal extremely A kind of at least one of few metallic element and VB race metal metallic element.
2. catalyst according to claim 1, it is characterised in that the activated carbon be ature of coal column charcoal, cocoanut active charcoal, At least one of apricot shell activated carbon and activated carbon from bamboo.
3. catalyst according to claim 1, it is characterised in that the specific surface area of the activated carbon is 1000~1500cm2/ G, absorption pore volume are 0.60~1.00cm3/g。
4. catalyst according to claim 1, it is characterised in that Group IIIA metal is selected from Al, Ga and In in the catalyst At least one of.
5. catalyst according to claim 1, it is characterised in that VB races metal is in V, Nb and Ta in the catalyst At least one.
6. catalyst according to claim 1, it is characterised in that in the catalyst Pt constituent contents be 1.00~ 8.00g/L。
7. catalyst according to claim 1, it is characterised in that in catalyst promoter elements content be 0.50~ 10.00g/L。
8. the preparation method of catalyst any one of claim 1~7, comprise the following steps：
1. mixing the solution of platiniferous element with carrier by the composition of catalyst, catalyst precarsor I is obtained；
Catalyst precarsor II is obtained after 2. catalyst precarsor I is aged；
3. being simple substance platinum by compound state platinum element reduction in catalyst precarsor II, catalyst precarsor III is obtained；
4. through washing, being dried to obtain catalyst precarsor IV；
5. being supported on the solution containing promoter elements on catalyst precarsor IV using infusion process by the composition of catalyst, dry Obtain the catalyst.
The synthetic method of 9.1,4- diacetoxy butane, in the presence of catalyst any one of claim 1~8, hydrogen Gas carries out hydrogenation reaction with 1,4- diacetoxies butylene and obtains 1,4- diacetoxy butane.
10. according to the method for claim 9, it is characterized in that hydrogenation reaction pressure is 1.0~10.0MPa, during hydrogenation reaction Between be 0.5~5.0h.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52133912A (en) * 1976-05-01 1977-11-09 Mitsubishi Chem Ind Ltd Preparation of butanediol
JPH10204011A (en) * 1997-01-29 1998-08-04 Mitsubishi Chem Corp Production of 1,4-butanediol
CN1765489A (en) * 2004-10-29 2006-05-03 中国石油化工股份有限公司 Supported type active carbon and its preparation method
CN104744204A (en) * 2015-02-04 2015-07-01 华东理工大学 Method for preparing aromatic hydrocarbon by carrying out catalytic hydrodeoxygenation on lignin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52133912A (en) * 1976-05-01 1977-11-09 Mitsubishi Chem Ind Ltd Preparation of butanediol
JPH10204011A (en) * 1997-01-29 1998-08-04 Mitsubishi Chem Corp Production of 1,4-butanediol
CN1765489A (en) * 2004-10-29 2006-05-03 中国石油化工股份有限公司 Supported type active carbon and its preparation method
CN104744204A (en) * 2015-02-04 2015-07-01 华东理工大学 Method for preparing aromatic hydrocarbon by carrying out catalytic hydrodeoxygenation on lignin

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