CN107774254A - For preparing the hydrogenation catalyst of 1,4 diacetoxy butane - Google Patents

For preparing the hydrogenation catalyst of 1,4 diacetoxy butane Download PDF

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CN107774254A
CN107774254A CN201610754465.5A CN201610754465A CN107774254A CN 107774254 A CN107774254 A CN 107774254A CN 201610754465 A CN201610754465 A CN 201610754465A CN 107774254 A CN107774254 A CN 107774254A
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catalyst
hydrogenation catalyst
hydrogenation
nitrae
isosorbide
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CN107774254B (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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • 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
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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    • 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
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    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/628—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
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    • 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
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    • B01J23/6527—Tungsten
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    • 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
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Abstract

The present invention relates to for preparing 1, the hydrogenation catalyst of 4 diacetoxy butane, mainly solve in the prior art 1, the problem of yield and low selectivity of 4 diacetoxy butane, using preparation 1, the hydrogenation catalyst of 4 diacetoxy butane, 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 IVA races metal at least one of metallic element and group vib metal metallic element, preferably solves the technical problem, available for 1, in the industrial production of 4 diacetoxy butane.

Description

For preparing the hydrogenation catalyst of 1,4- diacetoxy butane
Technical field
The present invention relates to the hydrogenation catalyst for preparing 1,4- diacetoxy 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 synthesized 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 hydrogenation catalyst for being used to prepare Isosorbide-5-Nitrae-diacetoxy butane, the catalyst have Isosorbide-5-Nitrae-diacetyl The characteristics of epoxide 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 hydrogenation catalyst.
The three of the technical problems to be solved by the invention are the 1,4- diacetoxy butane using above-mentioned hydrogenation catalyst Synthetic method.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：For preparing 1,4- diacetoxies The hydrogenation catalyst of butane, including carrier and active component, described carrier are activated carbon, and active component includes Pt elements and helped Catalyst elements, the promoter elements are included at least one of IVA races metal metallic element and group vib metal At least one metallic element.
In above-mentioned technical proposal, the promoter elements are preferably included in IVA races metallic element at least simultaneously It is a kind of and selected from least one of group vib metallic element, now carried between IVA races metallic element and group vib metallic element 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygens the butane selectivity of high 1,4- diacetoxies butylene hydrogenation catalyst Aspect has synergy.As non limiting example, such as, but not limited to tin cooperates with molybdenum, and lead cooperates with molybdenum etc..
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, IVA races metal preferably is selected from least one of Ge, Sn and Pb in the hydrogenation catalyst, Still more preferably include Sn and Pb simultaneously.Sn and Pb is improving 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane Selectivity aspect has synergy.
In above-mentioned technical proposal, group vib metal preferably is selected from least one of Cr, Mo and W in the hydrogenation catalyst.More Further include Cr, Mo simultaneously, Cr, Mo are improving Isosorbide-5-Nitrae-diethyl acyl-oxygen butane yield and Isosorbide-5-Nitrae-diethyl acyl-oxygen butane selectivity side Face has synergy.
In above-mentioned technical proposal, Pt content is preferably 1.00~8.00g/L in the hydrogenation 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 hydrogenation catalyst, More preferably 1.00~6.00g/L.
To solve the two of above-mentioned technical problem, technical scheme is as follows：
Hydrogenation catalyst preparation method any one of the technical scheme of one of above-mentioned technical problem, 1. by catalyst Composition the solution of platiniferous element is mixed with carrier, obtain catalyst precarsor I；
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 compound containing promoter elements is supported on catalyst precarsor IV using infusion process by the composition of catalyst On, 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, when specific chemical combination corresponding to step ⑤Zhong IVA races metallic element Thing preferably is selected from tetraethyl germanium, tetraphenyl germanium, germanium tetrachloride, stannous oxalate, stannous chloride, nitric acid stannous, stannous oxide, acetic acid At least one of lead, lead stearate, basic lead carbonate, basic lead acetate and plumbi nitras；More preferably from nitric acid stannous and lead acetate At least one of.
In above-mentioned technical proposal, as non limiting example, when step 5. specific chemical combination corresponding to middle group vib metallic element Thing preferably is selected from chromic acetate, chromic nitrate, chromium chloride, ammonium molybdate, molybdenum pentachloride, molybdenum carbonyl, molybdic acid, tungsten chloride, tungsten carbonyl, para-tungstic acid At least one of ammonium and ammonium tungstate；More preferably from least one of chromic acetate and ammonium molybdate.
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 hydrogenation catalyst, hydrogen obtains Isosorbide-5-Nitrae-diacetoxy butane with Isosorbide-5-Nitrae-diacetoxy butene reaction.
The key of the present invention is the selection of hydrogenation catalyst, and skilled person will know how basis to be actually needed determination Suitably proportioning of hydrogenation process conditions reaction temperature, reaction time, reaction pressure and material etc..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, hydrogenation catalyst of the present invention improves the yield and selectivity of Isosorbide-5-Nitrae-diethyl acyl-oxygen butane.
Test result indicates that during using the present invention, Isosorbide-5-Nitrae-diacetoxy butane yield selectively reaches up to 82.54% 93.89%, achieve preferable technique effect.Especially include platinum simultaneously, selected from IVA races in the active component of hydrogenation catalyst At least one of metal metallic element and during selected from least one of group vib metal metallic element, is achieved more prominent Technique 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 nitric acid stannous (Sn (NO of the Sn containing 1.85g3)2) aqueous solution 180ml 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, Sn contents 1.85g/L.
The synthesis of 1,4- diacetoxy butane：
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 82.54%, and selectivity is 93.89%, 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 ammonium molybdate ((NH of the Mo containing 1.85g4)6Mo7O24·4H2O aqueous solution 180ml) is immersed in catalyst precarsor On IV, 110 DEG C of dryings 4 hours, the catalyst is obtained.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Mo contents 1.85g/L.
The synthesis of 1,4- diacetoxy butane：
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 82.38%, and selectivity is 94.05%, 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.
The synthesis of 1,4- diacetoxy butane：
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 75.15%, and selectivity is 91.47%, 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, Sn active component while containing Pt, Mo 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 IVA races metal and group vib 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.
The synthesis of 1,4- diacetoxy butane：
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 70.02%, and selectivity is 88.20%, 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 chromic acetate (Cr (OAc) of the Cr containing 1.85g3·6H2O) it is dissolved in hot water, obtains maceration extract 180ml, impregnates On catalyst precarsor IV, 110 DEG C of dryings 4 hours, the catalyst is obtained.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Cr contents 1.85g/L.
The synthesis of 1,4- diacetoxy butane：
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 82.35%, and selectivity is 94.18%, 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 ammonium tungstate ((NH of the W containing 1.85g4)10W12O41·4H2O) it is dissolved in hot water, obtains maceration extract 180ml, soaks Stain 100 DEG C of dryings 4 hours, obtains the catalyst on catalyst precarsor IV.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, W content 1.85g/L.
The synthesis of 1,4- diacetoxy butane：
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 82.31%, 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.
【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 basic lead acetate (Pb (OAc) of the Pb containing 1.85g2·2Pb(OH)2) aqueous solution 180ml, it is immersed in catalyst On precursor I V, 120 DEG C of dryings 4 hours, the catalyst is obtained.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Pb contents 1.85g/L.
The synthesis of 1,4- diacetoxy butane：
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 82.53%, and selectivity is 93.91%, 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 plumbi nitras (Pb (NO of the Pb containing 1.85g3)2) 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 2.05g/L, Pb contents 1.85g/L.
The synthesis of 1,4- diacetoxy butane：
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 82.51%, and selectivity is 93.88%, 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 lead acetate (Pb (OAc) of the Pb containing 1.85g2·3H2O) 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, Pb contents 1.85g/L.
The synthesis of 1,4- diacetoxy butane：
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 82.67%, and selectivity is 93.95%, 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 of the Pt containing 1.50g4)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 nitric acid stannous (Sn (NO of the Sn containing 1.00g3)2) 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, Sn contents 1.00g/L.
The synthesis of 1,4- diacetoxy butane：
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 80.74%, and selectivity is 93.84%, 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 nitric acid stannous (Sn (NO of the Sn containing 6.00g3)2) 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 5.00g/L, Sn contents 6.00g/L.
The synthesis of 1,4- diacetoxy butane：
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 82.78%, and selectivity is 94.19%, 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.
【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 Sn containing 0.99g and the nitric acid stannous (Sn (NO containing 0.86gPb3)2) and lead acetate (Pb (OAc)2·3H2O) Aqueous solution 180ml 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, Sn contents 0.99g/L, Pb content 0.86g/L.
The synthesis of 1,4- diacetoxy butane：
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 83.65%, and selectivity is 94.40%, 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 In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Sn and metallic element Pb has preferably in IVA races metal 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 Mo containing the 1.20g and Cr containing 0.65g ammonium molybdate ((NH4)6Mo7O24·4H2) and chromic acetate (Cr O (OAc)3·6H2O) it is dissolved in hot water, obtains maceration extract 180ml, be immersed on catalyst precarsor IV, 110 DEG C of dryings 4 hours, obtains To the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Mo contents 1.20g/L, Cr content 0.65g/L.
The synthesis of 1,4- diacetoxy butane：
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 83.41%, and selectivity is 94.58%, 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 Mo and metallic element Cr has preferably in group vib 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 Sn containing the 1.02g and Mo containing 0.83g nitric acid stannous (Sn (NO3)2) and ammonium molybdate ((NH4)6Mo7O24· 4H2O) aqueous solution 180ml, it 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, Sn contents 1.02g/L, Mo content 0.83g/L.
The synthesis of 1,4- diacetoxy butane：
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 84.67%, and selectivity is 95.21%, 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 Sn and metal in group vib metal in IVA races metal Elements Mo 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 Pb containing the 1.02g and Mo containing 0.83g lead acetate (Pb (OAc)2·3H2) and ammonium molybdate ((NH O4)6Mo7O24·4H2O) aqueous solution 180ml, it 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, Pb contents 1.02g/L, Mo content 0.83g/L.
The synthesis of 1,4- diacetoxy butane：
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 84.79%, and selectivity is 95.16%, 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.
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 Pb and metal in group vib metal in IVA races metal Elements Mo 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 Sn containing 0.55g, Pb containing 0.47g and the Mo containing 0.83g nitric acid stannous (Sn (NO3)2), lead acetate (Pb (OAc)2·3H2) and ammonium molybdate ((NH O4)6Mo7O24·4H2O) 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 2.05g/L, Sn contents 0.55g/L, Pb content 0.47g/L, Mo content 0.83g/L。
The synthesis of 1,4- diacetoxy butane：
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 85.24%, and selectivity is 95.53%, 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 IVA races metal in metallic element Sn, Pb and group vib metal Metallic element Mo 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 Sn containing 0.55g, Pb containing 0.47g and the Cr containing 0.83g nitric acid stannous (Sn (NO3)2), lead acetate (Pb (OAc)2·3H2) and chromic acetate (Cr (OAc) O3·6H2O) it is dissolved in hot water, maceration extract 180ml is obtained, before being immersed in catalyst On body IV, 110 DEG C of dryings 4 hours, the catalyst is obtained.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Sn contents 0.55g/L, Pb content 0.47g/L, Cr content 0.83g/L。
The synthesis of 1,4- diacetoxy butane：
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 85.35%, and selectivity is 95.44%, 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 Sn containing 0.55g, Pb containing 0.47g, Mo containing 0.54g and the Cr containing 0.29g nitric acid stannous (Sn (NO3)2)、 Lead acetate (Pb (OAc)2·3H2O), ammonium molybdate ((NH4)6Mo7O24·4H2) and chromic acetate (Cr (OAc) O3·6H2O) it is dissolved in heat In water, 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, Sn contents 0.55g/L, Pb content 0.47g/L, Mo content For 0.54g/L, Cr contents 0.29g/L.
The synthesis of 1,4- diacetoxy butane：
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 86.68%, and selectivity is 95.84%, 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 IVA races metal in metallic element Sn, Pb and group vib metal Metallic element Mo, Cr have preferable synergy.
Table 1
Table 2

Claims (10)

1. it is used for the hydrogenation catalyst for preparing Isosorbide-5-Nitrae-diacetoxy butane, including carrier and active component, described carrier are Activated carbon, active component include Pt elements and promoter elements, and the promoter elements are included in IVA races metal extremely A kind of at least one of few metallic element and group vib metal metallic element.
2. hydrogenation catalyst according to claim 1, it is characterised in that the activated carbon is ature of coal column charcoal, coconut activated At least one of charcoal, apricot shell activated carbon and activated carbon from bamboo.
3. hydrogenation catalyst according to claim 1, it is characterised in that the specific surface area of the activated carbon be 1000~ 1500cm2/ g, absorption pore volume are 0.60~1.00cm3/g。
4. hydrogenation catalyst according to claim 1, it is characterised in that IVA races metal is selected from the hydrogenation catalyst At least one of Ge, Sn and Pb.
5. hydrogenation catalyst according to claim 1, it is characterised in that group vib metal is selected from the hydrogenation catalyst At least one of Cr, Mo and W.
6. hydrogenation catalyst according to claim 1, it is characterised in that Pt constituent contents are in the hydrogenation catalyst 1.00~8.00g/L.
7. hydrogenation catalyst according to claim 1, it is characterised in that promoter elements content is in hydrogenation catalyst 0.50~10.00g/L.
8. as the preparation method of the hydrogenation catalyst described in claim 1, 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 compound containing promoter elements on catalyst precarsor IV using infusion process by the composition of catalyst, do It is dry to obtain the catalyst.
The synthetic method of 9.1,4- diacetoxy butane, exists in hydrogenation catalyst any one of claim 1~7 Under, hydrogen obtains Isosorbide-5-Nitrae-diacetoxy butane with Isosorbide-5-Nitrae-diacetoxy butene reaction.
10. synthetic method according to claim 9, it is characterized in that the hydrogenation reaction time is 0.5~5.0h, hydrogenation reaction pressure Power is 1.0~10.0MPa.
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CN103301838A (en) * 2012-03-15 2013-09-18 清华大学 Catalyst and application as well as preparation method thereof
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CN104874406A (en) * 2015-05-22 2015-09-02 南京红宝丽股份有限公司 Hydrogenolysis catalyst and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN103285876A (en) * 2012-02-27 2013-09-11 清华大学 Vinyl acetylene hydrogenation catalyst and preparation method and applications thereof
CN103301838A (en) * 2012-03-15 2013-09-18 清华大学 Catalyst and application as well as preparation method thereof
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