CN107774256A - 1,4 diacetoxy butylene hydrogenation catalysts - Google Patents

1,4 diacetoxy butylene hydrogenation catalysts Download PDF

Info

Publication number
CN107774256A
CN107774256A CN201610750989.7A CN201610750989A CN107774256A CN 107774256 A CN107774256 A CN 107774256A CN 201610750989 A CN201610750989 A CN 201610750989A CN 107774256 A CN107774256 A CN 107774256A
Authority
CN
China
Prior art keywords
catalyst
hydrogenation
diacetoxy
hydrogenation catalyst
nitrae
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610750989.7A
Other languages
Chinese (zh)
Other versions
CN107774256B (en
Inventor
查晓钟
杨运信
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201610750989.7A priority Critical patent/CN107774256B/en
Publication of CN107774256A publication Critical patent/CN107774256A/en
Application granted granted Critical
Publication of CN107774256B publication Critical patent/CN107774256B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J23/644—Arsenic, antimony or bismuth
    • B01J23/6445—Antimony
    • 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
    • B01J23/644—Arsenic, antimony or bismuth
    • B01J23/6447—Bismuth
    • 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 1, 4 diacetoxy butylene hydrogenation catalysts, mainly solve in the prior art 1, the problem of yield and low selectivity of 4 diacetoxy butane, using 1, 4 diacetoxy butylene hydrogenation catalysts, 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 VA races metal at least one of metallic element and lanthanide series metal metallic element, preferably solves the technical problem, available for 1, in the industrial production of 4 diacetoxy butane.

Description

1,4- diacetoxy butylene hydrogenation catalysts
Technical field
The present invention relates to 1,4- diacetoxy butylene hydrogenation catalysts.
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 there is Isosorbide-5-Nitrae-diacetoxy butane to receive for a kind of new Isosorbide-5-Nitrae-diacetoxy butylene hydrogenation catalyst, the catalyst The characteristics of rate is high and selective high.
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：1,4- diacetoxies butylene is hydrogenated with Catalyst, including carrier and active component, described carrier are activated carbon, and active component includes Pt elements and co-catalyst member Element, the promoter elements are included selected from least one of VA races metal at least one of metallic element and lanthanide series metal gold Belong to 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, VA races metal preferably is selected from least one of As, Sb and Bi in the hydrogenation catalyst, more Further preferably include Sb and Bi simultaneously.Sb and Bi is improving 1,4- diethyls acyl-oxygen butane yield and the choosing of 1,4- diethyl acyl-oxygens butane There is synergy in terms of selecting property.
In above-mentioned technical proposal, lanthanide series metal preferably is selected from La, Ce, Pr, Nd, Sm, Eu, Yb and Lu in the hydrogenation catalyst At least one of.Further include Ce, Sm simultaneously, Ce, Sm are improving Isosorbide-5-Nitrae-diethyl acyl-oxygen butane yield and Isosorbide-5-Nitrae-diethyl Acyl-oxygen butane selectivity aspect has synergy.
In above-mentioned technical proposal, the promoter elements are preferably simultaneously including at least one in VA races metallic element Kind and selected from least one of lanthanide element, now between VA races metallic element and lanthanide element improve Isosorbide-5-Nitrae- 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygens butane selectivity aspect have in diacetoxy butylene hydrogenation reaction Synergy.As non limiting example, such as, but not limited to bismuth cooperates with cerium, and bismuth cooperates with samarium etc..
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：
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 of promoter elements on catalyst precarsor IV using infusion process by the composition of catalyst, do It is dry 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 VA races metallic element corresponding to specific chemical combination Thing preferably is selected from basic bismuth carbonate, bismuth subnitrate, bismuth and ammonium citrate, bismuth sulfate, bismuth acetate, bismuth nitrate, bismuth chloride, bismuth oxide, oxygen Change at least one of antimony, antimony sulfate, antimony acetate and antimony chloride；More preferably at least one of bismuth and ammonium citrate and antimony acetate.
In above-mentioned technical proposal, as non limiting example, step 5. in lanthanide element corresponding to specific chemical combination Thing preferably is selected from lanthanum acetate, lanthanum nitrate, lanthanum chloride, lanthanum sulfate, cerium chloride, cerous nitrate, cerous acetate, praseodymium acetate, praseodymium chloride, nitric acid Praseodymium, acetic acid neodymium, neodymium chloride, acetic acid samarium, samarium trichloride, samaric nitrate, Europium chloride, europium nitrate, acetic acid europium, acetic acid ytterbium, ytterbium chloride, nitric acid At least one of ytterbium, lutecium chloride, lutecium nitrate and acetic acid lutetium；More preferably from least one of cerous acetate and acetic acid samarium.
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 82.49% 94.18%, achieve preferable technique effect.Especially include platinum simultaneously, selected from VA races in the active component of hydrogenation catalyst At least one of metal metallic element and during selected from least one of group of the lanthanides race 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 cerous acetate (Ce (OAc) of the Ce containing 1.92g3·6H2O 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, Ce contents 1.92g/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, is stopped Reaction.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.49%, 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 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 bismuth and ammonium citrate (Bi (NH of the Bi containing 1.92g3)2C6H7O7·4H2O aqueous solution 180ml) is immersed in catalysis On agent precursor I V, 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, Bi contents 1.92g/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 82.18%, and selectivity is 94.27%, 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 coal Matter 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 75.22%, and selectivity is 91.36%, 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.
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, Ce active component while containing Pt, Bi active component than the performance containing only Pt active constituent catalysts It is more excellent, illustrate activity of hydrocatalyst component while using containing Pt and selected from least one of VA races metal and lanthanide series metal Metallic element compound, be advantageous to improve hydrogenation catalyst activity and stability, the yield of Isosorbide-5-Nitrae-diacetoxy butane and Selectivity will be high.
【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 70.07%, and selectivity is 88.11%, 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.
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 acetic acid samarium (Sm (OAc) of the Sm containing 1.92g3·6H2O) aqueous solution 180ml is 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, Sm contents 1.92g/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 94.10%, 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 lanthanum acetate (La (OAc) of the La containing 1.92g3·5H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, 100 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, La contents 1.92g/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 82.48%, and selectivity is 94.13%, 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 praseodymium acetate (Pr (OAc) of the Pr containing 1.92g3·5H2O) aqueous solution 180ml is 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, Pr contents 1.92g/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 82.50%, and selectivity is 94.12%, 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 acetic acid lutetium (Lu (OAc) of the Lu containing 1.92g3·6H2O) 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, Lu contents 1.92g/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 94.15%, 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 antimony acetate (Sb (OAc) of the Sb containing 1.92g3) aqueous solution 180ml 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, Sb contents 1.92g/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 82.17%, and selectivity is 94.31%, 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 acetic acid neodymium (Nd (OAc) of the Nd containing 1.00g2·6H2O) aqueous solution 180ml is 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 1.50g/L, Nd 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 80.84%, and selectivity is 93.78%, 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 acetic acid ytterbium (Yb (OAc) of the Yb containing 6.00g3·6H2O) 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 5.00g/L, Yb 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 82.44%, and selectivity is 94.14%, 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 Bi containing the 1.21g and Sb containing 0.71g bismuth and ammonium citrate (Bi (NH3)2C6H7O7·4H2) and antimony acetate (Sb O (OAc)3) 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, Bi contents 1.21g/L, Sb content 0.71g/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 83.39%, and selectivity is 94.56%, 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 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 Bi and metallic element Sb has preferably in VA 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 Ce containing the 1.12g and Sm containing 0.80g cerous acetate (Ce (OAc)3·6H2) and acetic acid samarium (Sm (OAc) O3· 6H2O) 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, Ce contents 1.12g/L, Sm content 0.80g/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 83.60%, 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 11 and embodiment 1 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 Ce and metallic element Sm has preferably in lanthanide series 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 Bi containing the 0.98g and Ce containing 0.94g bismuth and ammonium citrate (Bi (NH3)2C6H7O7·4H2) and cerous acetate (Ce O (OAc)3·6H2O) 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, Bi contents 0.98g/L, Ce content 0.94g/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 84.51%, and selectivity is 95.24%, 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 Bi and metal member in lanthanide series metal in VA races metal Plain Ce 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 Bi containing the 0.98g and Sm containing 0.94g bismuth and ammonium citrate (Bi (NH3)2C6H7O7·4H2) and acetic acid samarium (Sm O (OAc)3·6H2O) 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, Bi contents 0.98g/L, Sm content 0.94g/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 84.63%, and selectivity is 95.10%, 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 3, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Bi and metal member in lanthanide series metal in VA races metal Plain Sm 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 Bi containing 0.98g, Ce containing 0.45g and the Sm containing 0.49g bismuth and ammonium citrate (Bi (NH3)2C6H7O7· 4H2O), cerous acetate (Ce (OAc)3·6H2) and acetic acid samarium (Sm (OAc) O3·6H2O) 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, Bi contents 0.98g/L, Ce content 0.45g/L, Sm content 0.49g/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 85.22%, and selectivity is 95.57%, 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 Rate and selectivity aspect, in the hydrogenation catalyst that uses of the present invention, metal in metallic element Bi and lanthanide series metal in VA races metal Elements C e, Sm 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 Sb containing 0.98g, Ce containing 0.45g and the Sm containing 0.49g antimony acetate (Sb (OAc)3), cerous acetate (Ce (OAc)3·6H2) and acetic acid samarium (Sm (OAc) O3·6H2O) aqueous solution 180ml is 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, Sb contents 0.98g/L, Ce content 0.45g/L, and Sm contains Measure 0.49g/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 85.30%, and selectivity is 95.45%, 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 Bi containing 0.62g, Sb containing 0.36g, Ce containing 0.45g and the Sm containing 0.49g bismuth and ammonium citrate (Bi (NH3)2C6H7O7·4H2O), antimony acetate (Sb (OAc)3), cerous acetate (Ce (OAc)3·6H2) and acetic acid samarium (Sm (OAc) O3·6H2O) water 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, Bi contents 0.62g/L, Sb content 0.36g/L, Ce content 0.45g/L, Sm content 0.49g/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 86.74%, and selectivity is 95.81%, 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 Rate and selectivity aspect, in the hydrogenation catalyst that uses of the present invention, gold in metallic element Bi, Sb and lanthanide series metal in VA races metal Category Elements C e, Sm has preferable synergy.
Table 1
Table 2

Claims (10)

1.1,4- diacetoxy butylene hydrogenation catalysts, including carrier and active component, described carrier are activated carbon, activity Component includes Pt elements and promoter elements, and the promoter elements are included selected from least one of VA races metal metal member At least one of element and lanthanide series 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 in the hydrogenation catalyst VA races metal be selected from As, At least one of Sb and Bi.
5. hydrogenation catalyst according to claim 1, it is characterised in that in the hydrogenation catalyst lanthanide series metal be selected from La, At least one of Ce, Pr, Nd, Sm, Eu, Yb and Lu.
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. the preparation method of any one of claim 1~6 hydrogenation catalyst, it is characterised in that co-catalysis in hydrogenation catalyst Agent constituent content is 0.50~10.00g/L.
8. as the method described in claim 1, it is characterised in that hydrogenation catalyst is obtained using the process comprised 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. the solution of promoter elements is supported on catalyst precarsor IV using infusion process by the composition of catalyst, dry To 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.
CN201610750989.7A 2016-08-29 2016-08-29 Hydrogenation catalyst of 1, 4-diacetoxybutene Active CN107774256B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610750989.7A CN107774256B (en) 2016-08-29 2016-08-29 Hydrogenation catalyst of 1, 4-diacetoxybutene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610750989.7A CN107774256B (en) 2016-08-29 2016-08-29 Hydrogenation catalyst of 1, 4-diacetoxybutene

Publications (2)

Publication Number Publication Date
CN107774256A true CN107774256A (en) 2018-03-09
CN107774256B CN107774256B (en) 2020-01-03

Family

ID=61441393

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610750989.7A Active CN107774256B (en) 2016-08-29 2016-08-29 Hydrogenation catalyst of 1, 4-diacetoxybutene

Country Status (1)

Country Link
CN (1) CN107774256B (en)

Also Published As

Publication number Publication date
CN107774256B (en) 2020-01-03

Similar Documents

Publication Publication Date Title
CN107778135B (en) The method for producing 1,4- butanediol
CN108002978B (en) The method that butadiene prepares 1,4- butanediol
CN108017509B (en) The method of butadiene production 1,4- butanediol
CN107790182B (en) 1,4- diacetoxy butylene hydrogenation process catalyst
CN108002979B (en) The method that butadiene Acetoxylation prepares 1,4- butanediol
CN107774255B (en) 1,4- diacetoxy butylene hydroprocessing catalysts
CN107774256A (en) 1,4 diacetoxy butylene hydrogenation catalysts
CN108014794B (en) Synthesize hydrogenation catalyst used in 1,4- diacetoxy butane
CN107774336B (en) Catalyst for 1,4- diacetoxy butylene hydrogenation process
CN107774250B (en) Catalyst for 1,4- diacetoxy butylene hydrogenation technique
CN107999064B (en) The catalyst of butadiene synthesis 1,4- diacetoxy butane course
CN107778134B (en) The synthetic method of 1,4- butanediol
CN107999066A (en) Butadiene prepares the catalyst of 1,4- diacetoxy butane processes
CN107999063A (en) The catalyst of butadiene production 1,4- diacetoxy butane processes
CN107999067A (en) Produce the hydrogenation catalyst used in 1,4- diacetoxy butane
CN107999065A (en) Butadiene synthesizes the catalyst of 1,4- diacetoxy butane processes
CN108014793A (en) Prepare the hydrogenation catalyst used in 1,4- diacetoxy butane
CN107790180A (en) Catalyst for 1,4 diacetoxy butylene hydrogenation
CN107790125A (en) Synthesize the hydrogenation catalyst of 1,4 diacetoxy butane
CN107774249A (en) Produce the hydrogenation catalyst of 1,4 diacetoxy butane
CN107774251A (en) Manufacture the hydrogenation catalyst of 1,4 diacetoxy butane
CN107999069A (en) Butadiene prepares the catalyst of 1,4- diacetoxy butane processes
CN107999068A (en) The catalyst of butadiene production 1,4- diacetoxy butane processes
CN108014817A (en) Butadiene synthesizes the catalyst of 1,4- diacetoxy butane processes
CN107866221A (en) Catalyst applied to the production of 1,4 diacetoxy butane

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant