CN107867971A - The preparation method of 1,4 butanediols - Google Patents

The preparation method of 1,4 butanediols Download PDF

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CN107867971A
CN107867971A CN201610853114.XA CN201610853114A CN107867971A CN 107867971 A CN107867971 A CN 107867971A CN 201610853114 A CN201610853114 A CN 201610853114A CN 107867971 A CN107867971 A CN 107867971A
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catalyst
isosorbide
nitrae
hydrogenation
diacetoxy
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CN107867971B (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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
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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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
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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
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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
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—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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    • B01J23/56—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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    • B01J23/6484—Niobium
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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Abstract

The present invention relates to the preparation method of Isosorbide-5-Nitrae butanediol, mainly solve yield and poor selectivity after being hydrogenated with the prior art due to Isosorbide-5-Nitrae diacetoxy butylene, cause Isosorbide-5-Nitrae diacetoxy butane hydrolyze after Isosorbide-5-Nitrae butanediol yield and low selectivity the problem of.The preparation method of Isosorbide-5-Nitrae butanediol, comprises the following steps：Using butadiene, acetic acid and oxygen as raw material, Acetoxylation reaction is carried out in the presence of Acetoxylation catalyst and obtains Isosorbide-5-Nitrae diacetoxy butylene；In the presence of a hydrogenation catalyst, hydrogen obtains Isosorbide-5-Nitrae diacetoxy butane with Isosorbide-5-Nitrae diacetoxy butene reaction；The hydrolysis of 1,4 diacetoxy butane obtains 1,4 butanediols；Wherein, described hydrogenation catalyst uses activated carbon as carrier, and active component includes Pt elements and promoter elements, and the promoter elements include being selected from least one of Group IIIA metal and VB races metal metallic element.

Description

The preparation method of BDO
Technical field
The present invention relates to the preparation method of 1,4- butanediols.
Background technology
BDO (Isosorbide-5-Nitrae-BDO) is a kind of important organic and fine chemical material, it be widely used in medicine, The fields such as chemical industry, weaving, papermaking, automobile and daily-use chemical industry.It can derive a series of fine chemical product of high added values. For example, tetrahydrofuran (THF), polybutylene terephthalate (PBT) (PBT), γ-fourth lactones (GBL) can be produced by Isosorbide-5-Nitrae-BDO With polyurethane resin (PU Resin), especially as production PBT engineering plastics and the base stock of PBT fibers, ground Study carefully the extensive concern of mechanism.
The process route of the preparation of BDO is relatively more, has acetylene, ethene, propylene, fourth from raw material used to divide The raw material route such as diene and cis-butenedioic anhydride, identical raw material also have different synthesis techniques.Because technology barriers are higher and raw material sources Limited, global Isosorbide-5-Nitrae-BDO produces Relatively centralized.2011, global Isosorbide-5-Nitrae-BDO production capacities were mainly distributed on Asia, US and European, Wherein Asia 1,4-BDO production capacities accounting is up to 56.6%.At present, Isosorbide-5-Nitrae-BDO industrialized preparing process mainly includes：1. alkynes aldehyde Method (Reppe methods)：This method does catalyst generation butynediols, butynediols using acetylene and formaldehyde as raw material, using methanol copper Two-stage hydrogenation obtains 1,4-BDO again.Its prevailing technology mainly have BASF Corp. of Germany, the U.S. DuPont exploitation Reppe methods with And the Reppe methods of improvement.2. maleic anhydride process：This method carries out two step hydrogenation to it using cis-butenedioic anhydride as raw material.The first step is urged in Ni-Re Under agent effect, maleic anhydride hydrogenation generation gamma-butyrolacton and tetrahydrofuran；Second step gamma-butyrolacton is in Mo-Cr-K2O catalyst is made 1,4-BDO is hydrogenated under.Its prevailing technology is mainly the two-stage hydrogenation work that exploitation is melted into Japanese two water chestnut oilings and Mitsubishi Skill.3. propylene method：Mainly include allyl acetate method, acryladehyde method and allyl acetate-allyl alcohol method, Kuraray company exploitation at present Allyl acetate-allyl alcohol method has obtained commercial Application, and it is the allyl alcohol liquid-phase hydrogenatin formylated generation 4- hydroxyl fourths under rhodium catalyst Aldehyde, then repeated hydrogenation generation BDO.4. butadiene process：The method that Isosorbide-5-Nitrae-BDO is produced using butadiene as raw material, main bag Butadiene acetoxylation method and butadiene chloridising are included, the technique of its main flow is melted into by Mitsubishi and Cao Da companies are in 20 generation Exploitation in 80 years of recording forms, and it successfully breaks the technology barriers and obstacle of Reppe methods.Especially butadiene acetoxylation method is excellent Gesture and prospect, the favor of domestic and international research institution is obtained.
It is well known that butadiene acetoxylation method is a three-steps process, i.e., butadiene is sent out with acetic acid, oxygen first Raw acetylization reaction, generates Isosorbide-5-Nitrae-diacetoxy butylene and accessory substance 3.4- diacetoxy butylene；Then 1,4- diacetyl Epoxide butylene catalytic hydrogenation generates Isosorbide-5-Nitrae-diene acetoxyl group butane, and reaction is finally hydrolyzed and obtains Isosorbide-5-Nitrae-BDO.In Isosorbide-5-Nitrae-fourth Diene is into BDO process route, Isosorbide-5-Nitrae-diacetoxy butylene catalytic hydrogenation generation Isosorbide-5-Nitrae-diene acetoxyl group butane As one of step, the yield and selectivity of hydrogenation products directly influence BDO relative to Isosorbide-5-Nitrae-butadiene Yield and selectivity.
Teach in the patents such as patent US4032458 (production of 1,4-butanediol) and urged using furans Agent is present, and BDO is prepared under the conditions of certain temperature and pressure.Patent CN94108094.3 (the systems of 1,4- butanediols Preparation Method) describe using cis-butenedioic anhydride as raw material, gas phase catalytic hydrogenation reaction is carried out in the presence of the catalyst specifically designed and is prepared 1,4- butanediols.Patent CN104326871A (a kind of preparation method of butanediol) is described using fixed-bed catalytic technology, will Content more than 99% 2- butylene mixed with acetic acid, nitrogen, oxygen and water vapour high temperature after be passed through in fixed bed, catalyst with 1,4- butanediols are prepared under the conditions of certain temperature, pressure etc..But there is 1,4- in the above method during 1,4-BDO is prepared The problem of BDO yields are low and selective not high.
The content of the invention
The problem of technical problems to be solved by the invention are the yield and low selectivity of BDO, there is provided Yi Zhongxin BDO preparation method, this method have BDO high income and selectivity it is high the characteristics of.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：The preparation method of BDO, bag Include following steps：(1) using butadiene, acetic acid and oxygen as raw material, it is anti-that Acetoxylation is carried out in the presence of Acetoxylation catalyst 1,4- diacetoxy butylene should be obtained；(2) in the presence of a hydrogenation catalyst, hydrogen and Isosorbide-5-Nitrae-diacetoxy butene reaction are made Obtain 1,4- diacetoxy butane；(3) 1,4- diacetoxies butane hydrolysis obtains 1,4- butanediols；Wherein, it is described plus Hydrogen catalyst uses activated carbon as carrier, and active component includes Pt elements and promoter elements, the promoter elements bag Include and be selected from least one of Group IIIA metal and VB races metal metallic element.
Now 1,4- diethyls acyl-oxygen butane yield and 1,4- are being improved between Group IIIA metallic element and VB races metallic element Diethyl acyl-oxygen butane selectivity aspect has synergy.As non limiting example, such as, but not limited to gallium cooperates with niobium, indium Cooperateed with niobium 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, Group IIIA metal preferably is selected from least one of Al, Ga and In in the hydrogenation catalyst, Still more preferably include In and Ga simultaneously.In and Ga 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, VB races metal preferably is selected from least one of V, Nb and Ta in the hydrogenation catalyst.More Further include V, Nb simultaneously.V, Nb is in terms of 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane selectivity is improved With 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.
In above-mentioned technical proposal, hydrogenation catalyst can use the process comprised the following steps to obtain：
1. mixing the solution of platiniferous element with carrier by the composition of catalyst, catalyst precarsor I is obtained；
Catalyst precarsor II is obtained after 2. catalyst precarsor I is aged；
3. being simple substance platinum by compound state platinum element reduction in catalyst precarsor II, catalyst precarsor III is obtained；
4. through washing, being dried to obtain catalyst precarsor IV；
5. the solution containing promoter elements is supported on catalyst precarsor IV using infusion process by the composition of catalyst, It is dried to obtain the catalyst.
In above-mentioned technical proposal, as non-restrictive, 1. particular compound corresponding to platinum element preferably is selected from vinegar to step At least one of sour platinum, platinum chloride, ammonium chloroplatinite, dinitroso diammonia platinum, chloroplatinic acid and four ammino platinum chlorides；More preferably Ammonium chloroplatinite.
In above-mentioned technical proposal, as non limiting example, when step 5. in promoter elements include Group IIIA gold When belonging to element, particular compound corresponding to Group IIIA metallic element preferably is selected from aluminium chloride, aluminum sulfate, aluminum acetate, aluminum nitrate, oxidation At least one of aluminium, gallium oxide, gallium nitrate, gallium chloride, acetic acid gallium, inidum chloride, indium sulfate, indium nitrate and indium acetate；It is more excellent At least one of free gallium nitrate and indium acetate.
In above-mentioned technical proposal, as non limiting example, when step 5. in promoter elements include VB races metal During element, particular compound corresponding to VB races metallic element preferably be selected from vanadium trichloride, ammonium metavanadate, acetic acid vanadium, vanadic anhydride, At least one of columbium pentachloride, niobium oxalate, acetic acid niobium, acetic acid tantalum and tantalic chloride；More preferably in niobium oxalate and ammonium metavanadate At least one.
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.
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.
In the method for present invention synthesis BDO, the known suitable butadiene oxygen acetyl of selection of those skilled in the art Change catalysts and determine suitable reaction temperature, time and material proportion.The such as, but not limited to active constituent of catalyst Based on Pd or Rh, it is auxiliary ingredients to add Te, Se, Sb, Bi, V etc..Carrier used can be activated carbon, aluminium glue, silica gel or Molecular sieve.
Preferred Pd-Te/C is butadiene Acetoxylation catalyst in the present invention.Palladium element in suitable Pd-Te/C catalyst Content 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 It is preferred that 1.00~2.50g/L.Suitable Acetoxylation reaction temperature is preferably 40~150 DEG C；Acetoxylation reaction pressure is preferred 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 terminating for step (1), the mixture that butadiene Acetoxylation can be reacted carry out separation obtain target product Isosorbide-5-Nitrae- Diacetoxy butylene carries out step (2) again, can also not separated directly after step (1) generation Isosorbide-5-Nitrae-diacetoxy butylene Tap into row step (2).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 is equal Step (2) is carried out using the isolated pure 1,4- diacetoxies butylene of step (1) mixture of reaction products.
After step (2) terminates, separation can be carried out to the mixture of hydrogenation reaction and obtains target product Isosorbide-5-Nitrae-diethyl acyl-oxygen Base butane carries out step (3) again, can not also separate and is directly walked after step (2) generation Isosorbide-5-Nitrae-diacetoxy butane Suddenly (3).The suitable hydrolyst of the known selection of those skilled in the art and determination suitable hydrolysising reacting temperature, time and thing Material proportioning.Conventional hydrolyst can be inorganic acid, inorganic base, organic acid and organic base.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 ℃；Hydrolysis pressure preferably 0~2.0MPa；The preferred water of solvent.
Because the key of the present invention is step (2), in order to year-on-year, non-restrictive is also served as, the present invention is specific real The step of applying mode part (1) is carried out using following specific method：
The synthesis of 1,4- butanediols：
Step (1)：By 2.10mol acetic acid, 12.8g Pd-Te/C, (Pd constituent contents are 3.80g/L, and Te constituent contents are 1.85g/L) catalyst is added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, is then passed to Butadiene and oxygen improve mixing speed to 1000rpm until pressure 6.8MPa, while agitating and heating is warming up to reaction temperature, Controlling reaction temperature is 80 DEG C, and the mol ratio of butadiene and oxygen is 1:After 1, sustained response 5.0h, stop reaction.By reactor Room temperature is down to, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, through rectification and purification, obtains Isosorbide-5-Nitrae-diacetyl Epoxide butylene.
Because the key of the present invention is step (2), in order to make it easy to understand, non-restrictive is also served as, present invention tool The step of body embodiment part (3), can use following specific method to carry out：
Step (3)：By above-mentioned 1,4- diacetoxies butane 18ml, 30ml toluene-water, (10ml toluene and 20ml water mix Into), 0.015mol benzene sulfonic acids add 100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, rise Temperature stirs constant temperature 5h to 30 DEG C.
Step (2) final product mixture of the present invention is analyzed through gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), by following Formula calculates the yield and selectivity of 1,4- diacetoxy butane：
Compared with prior art, key of the invention is the new hydrogenation catalyst that step (2) uses, and improves Isosorbide-5-Nitrae-two The yield and selectivity of acetyl oxygen butane.
Test result indicates that during using the present invention, Isosorbide-5-Nitrae-diacetoxy butane yield selectively reaches up to 82.45% 93.96%, achieve preferable technique effect.Especially include platinum simultaneously, selected from IIIA in the active component of hydrogenation catalyst At least one of race's metal metallic element and during selected from least one of VB races 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 indium acetate (In (OAc) of the In containing 1.90g3·6H2O aqueous solution 180ml) is immersed in catalyst precarsor IV On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, In contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.45%, and selectivity is 93.96%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 2】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the niobium oxalate ((C of the Nb containing 1.90g2HO4)5Nb·6H2O) it is completely dissolved in the acetic acid water that concentration is 30wt% In solution, obtain maceration extract 180ml and be immersed on catalyst precarsor IV, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Nb contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.39%, and selectivity is 94.09%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, the catalyst is obtained.
The Pt contents that the catalyst is determined through ICP are 2.05g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 75.19%, and selectivity is 91.34%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
By simultaneously, as can be seen that the present invention uses the catalyst of hydrogenation, its active component makes compared with embodiment 1~2 With the catalyst performance containing Pt, In active component while containing Pt, Nb active component than the performance containing only Pt active constituent catalysts It is more excellent, illustrate activity of hydrocatalyst component while using at least one containing Pt and in Group IIIA metal and VB races metal Kind metallic element compound, be advantageous to improve the activity and stability of hydrogenation catalyst, the yield of Isosorbide-5-Nitrae-diacetoxy butane Will be high with selectivity.
【Comparative example 2】
For【Comparative example 1】Comparative example.
The preparation of hydrogenation catalyst：
1. by the ammonium chloropalladite ((NH of the Pd containing 2.05g4)2PdCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, the catalyst is obtained.
The Pd contents that the catalyst is determined through ICP are 2.05g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 70.07%, and selectivity is 88.16%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
By can be seen that catalyst of the present invention using hydrogenation compared with comparative example 1, contained using the ratio of active component containing Pt The performance of Pd active constituent catalysts is more excellent, illustrates that activity of hydrocatalyst component is advantageous to Isosorbide-5-Nitrae-diacetoxy using Pt Butylene is hydrogenated with, and the yield and selectivity of Isosorbide-5-Nitrae-diacetoxy butane will be high.
【Embodiment 3】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the ammonium metavanadate (NH of the V containing 1.90g4VO3) aqueous solution 180ml, be immersed on catalyst precarsor IV, 110 DEG C dry 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, V content 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.37%, and selectivity is 94.08%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 4】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.60cm3/ g, specific surface area 1000cm2/ g coconut husk Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the acetic acid vanadium (V (OAc) of the V containing 1.90g3) be completely dissolved in the aqueous acetic acid that concentration is 30wt%, obtain It is immersed in maceration extract 180ml on catalyst precarsor IV, 100 DEG C of dryings 4 hours, obtains the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, V content 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.32%, and selectivity is 94.11%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 5】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 1.00cm3/ g, specific surface area 1500cm2/ g apricot shell circle Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the acetic acid niobium (Nb (OAc) of the Nb containing 1.90g5) be completely dissolved in the aqueous acetic acid that concentration is 30wt%, Obtain maceration extract 180ml to be immersed on catalyst precarsor IV, 120 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Nb contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.43%, and selectivity is 93.98%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 6】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g's is bamboo Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the aluminum acetate (Al (OAc) of the Al containing 1.90g3·6H2O) aqueous solution 180ml, it is immersed in catalyst precarsor IV On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Al content 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.41%, and selectivity is 93.87%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 7】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the gallium nitrate (Ga (NO of the Ga containing 1.90g3)3·8H2O) aqueous solution 180ml, it is immersed in catalyst precarsor IV On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Ga contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 50 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.50%, and selectivity is 93.99%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 8】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH 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 aluminum nitrate (Al (NO of the Al containing 1.00g3)3) aqueous solution 180ml, it is immersed on catalyst precarsor IV, 110 DEG C Dry 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 1.50g/L, Al content 1.00g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 1.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 20 DEG C, sustained response 30min Afterwards, reaction is stopped.Reactor is down to room temperature, purified removal of impurities obtains Isosorbide-5-Nitrae-diacetoxy butane.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 80.63%, and selectivity is 93.74%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 9】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 5.00g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the indium nitrate (In (NO of the In containing 6.00g3)3·4.5H2O) aqueous solution 180ml, it is immersed in catalyst precarsor IV On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 5.00g/L, In contents 6.00g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 6.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 120 DEG C, sustained response After 120min, stop reaction.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.89%, and selectivity is 93.75%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 10】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by In containing the 1.18g and Ga containing 0.72g indium acetate (In (OAc)3·6H2) and gallium nitrate (Ga (NO O3)3· 8H2O aqueous solution 180ml) is immersed on catalyst precarsor IV, 110 DEG C of dryings 4 hours, obtains the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, In contents 1.18g/L, Ga content 0.72g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 83.55%, and selectivity is 94.36%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 10 and embodiment 1 and embodiment 7, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane With selective aspect, in the hydrogenation catalyst that uses of the present invention, in Group IIIA metal metallic element In and metallic element Ga have compared with Good synergy.
【Embodiment 11】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by Nb containing the 1.25g and V containing 0.65g niobium oxalate ((C2HO4)5Nb·6H2) and ammonium metavanadate (NH O4VO3) fill Divide and be dissolved in the aqueous acetic acid that concentration is 30wt%, obtain maceration extract 180ml, be immersed on catalyst precarsor IV, 110 DEG C Dry 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Nb content 1.25g/L, V content 0.65g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 83.42%, and selectivity is 94.49%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 11 and embodiment 2 and embodiment 3, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Nb and metallic element V has preferably in VB races metal Synergy.
【Embodiment 12】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by In containing the 1.05g and Nb containing 0.85g indium acetate (In (OAc)3·6H2) and niobium oxalate ((C O2HO4)5Nb· 6H2O) it is completely dissolved in the aqueous acetic acid that concentration is 30wt%, obtains maceration extract 180ml, be immersed in catalyst precarsor IV On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, In contents 1.05g/L, Nb content 0.85g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 84.62%, and selectivity is 95.19%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 2, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane In the hydrogenation catalyst used with selective aspect, the present invention, metallic element In and metal in VB races metal in Group IIIA metal Element nb has preferable synergy.
【Embodiment 13】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by Ga containing the 1.05g and Nb containing 0.85g gallium nitrate (Ga (NO3)3·8H2) and niobium oxalate ((C O2HO4)5Nb· 6H2O) it is completely dissolved in the aqueous acetic acid that concentration is 30wt%, obtains maceration extract 180ml, be immersed in catalyst precarsor IV On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Ga contents 1.05g/L, Nb content 0.85g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 84.71%, and selectivity is 95.03%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 13 and embodiment 2 and embodiment 7, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Ga and metal in VB races metal in Group IIIA metal Element nb has preferable synergy.
【Embodiment 14】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by In containing 0.65g, Ga containing 0.40g and the Nb containing 0.85g indium acetate (In (OAc)3·6H2O), gallium nitrate (Ga(NO3)3·8H2) and niobium oxalate ((C O2HO4)5Nb·6H2O) it is completely dissolved in the aqueous acetic acid that concentration is 30wt%, Maceration extract 180ml is obtained, is immersed on catalyst precarsor IV, 110 DEG C of dryings 4 hours, obtains the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, In contents 0.65g/L, Ga content 0.40g/L, Nb content 0.85g/L。
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 85.28%, and selectivity is 95.42%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13, improving the receipts of Isosorbide-5-Nitrae-diacetoxy butane In terms of rate and selectivity, in the hydrogenation catalyst that the present invention uses, in Group IIIA metal in metallic element In, Ga and VB races metal Metallic element Nb has preferable synergy.
【Embodiment 15】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by In containing 0.65g, Ga containing 0.40g and the V containing 0.85g indium acetate (In (OAc)3·6H2O), gallium nitrate (Ga (NO3)3·8H2) and ammonium metavanadate (NH O4VO3) aqueous solution 180ml, be immersed on catalyst precarsor IV, 110 DEG C of dryings 4 are small When, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, In contents 0.65g/L, Ga content 0.40g/L, V content 0.85g/L。
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 85.33%, and selectivity is 95.34%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 16】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by In containing 0.65g, Ga containing 0.40g, V containing 0.31g and the Nb containing 0.54g indium acetate (In (OAc)3· 6H2O), gallium nitrate (Ga (NO3)3·8H2O), ammonium metavanadate (NH4VO3) and niobium oxalate ((C2HO4)5Nb·6H2O) fully dissolving In the aqueous acetic acid that concentration is 30wt%, maceration extract 180ml is obtained, is immersed on catalyst precarsor IV, 110 DEG C of dryings 4 Hour, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, In contents 0.65g/L, Ga content 0.40g/L, V content For 0.31g/L, Nb contents 0.54g/L.
1,4- diacetoxy butylene hydrogenation reactions：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 86.59%, and selectivity is 95.62%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, improving the receipts of Isosorbide-5-Nitrae-diacetoxy butane In terms of rate and selectivity, in the hydrogenation catalyst that the present invention uses, in Group IIIA metal in metallic element In, Ga and VB races metal Metallic element V, Nb have preferable synergy.
Table 1
Table 2

Claims (10)

  1. The preparation method of 1.1,4- butanediols, comprises the following steps：(1) using butadiene, acetic acid and oxygen as raw material, in oxygen acetyl Progress Acetoxylation reaction obtains 1,4- diacetoxy butylene in the presence of changing catalyst；(2) in the presence of a hydrogenation catalyst, make Hydrogen obtains 1,4- diacetoxy butane with 1,4- diacetoxies butene reaction；(3) 1,4- diacetoxies butane hydrolyzes Obtain 1,4- butanediols；Wherein, described hydrogenation catalyst uses activated carbon as carrier, and active component includes Pt elements and helped to urge Agent element, the promoter elements include being selected from least one of Group IIIA metal and VB races metal metallic element.
  2. 2. according to the method for claim 1, it is characterised in that the activated carbon is ature of coal column charcoal, cocoanut active charcoal, apricot At least one of shell activated carbon and activated carbon from bamboo.
  3. 3. according to the method for claim 1, it is characterised in that the specific surface area of the activated carbon is 1000~1500cm2/ g, Absorption pore volume is 0.60~1.00cm3/g。
  4. 4. according to the method for claim 1, it is characterised in that in the hydrogenation catalyst Group IIIA metal be selected from Al, Ga and At least one of In.
  5. 5. according to the method for claim 1, it is characterised in that VB races metal is selected from V, Nb and Ta in the hydrogenation catalyst At least one of.
  6. 6. according to the method for claim 1, it is characterised in that in the hydrogenation catalyst Pt constituent contents be 1.00~ 8.00g/L。
  7. 7. according to the method for claim 1, it is characterised in that in hydrogenation catalyst promoter elements content be 0.50~ 10.00g/L。
  8. 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. being supported on the solution containing promoter elements on catalyst precarsor IV using infusion process by the composition of catalyst, dry Obtain the catalyst.
  9. 9. according to the method for claim 1, it is characterized in that hydrogenation reaction pressure is 1.0~10.0MPa.
  10. 10. according to the method for claim 1, it is characterized in that the hydrogenation reaction time is 0.5~5.0h.
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Publication number Priority date Publication date Assignee Title
CN102442874A (en) * 2011-10-28 2012-05-09 山东华懋新材料有限公司 Method for preparing butadiene by oxidization and dehydrogenation of butane using constant-temperature static bed
CN102617518A (en) * 2011-01-27 2012-08-01 中科合成油技术有限公司 One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation
CN103044198A (en) * 2011-10-17 2013-04-17 中国石油化工股份有限公司 Technological method for purifying 1,4-butanediol and co-producing tetrahydrofuran
CN103044197A (en) * 2011-10-17 2013-04-17 中国石油化工股份有限公司 Technological method for purifying1,4-butanediol and co-producing gamma-butyrolactone

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102617518A (en) * 2011-01-27 2012-08-01 中科合成油技术有限公司 One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation
CN103044198A (en) * 2011-10-17 2013-04-17 中国石油化工股份有限公司 Technological method for purifying 1,4-butanediol and co-producing tetrahydrofuran
CN103044197A (en) * 2011-10-17 2013-04-17 中国石油化工股份有限公司 Technological method for purifying1,4-butanediol and co-producing gamma-butyrolactone
CN102442874A (en) * 2011-10-28 2012-05-09 山东华懋新材料有限公司 Method for preparing butadiene by oxidization and dehydrogenation of butane using constant-temperature static bed

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