CN108017509A - The method of butadiene production 1,4- butanediols - Google Patents

The method of butadiene production 1,4- butanediols Download PDF

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CN108017509A
CN108017509A CN201610966463.2A CN201610966463A CN108017509A CN 108017509 A CN108017509 A CN 108017509A CN 201610966463 A CN201610966463 A CN 201610966463A CN 108017509 A CN108017509 A CN 108017509A
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catalyst
isosorbide
nitrae
hydrogenation
diacetoxy
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CN108017509B (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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    • 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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    • 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
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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
    • B01J23/644—Arsenic, antimony or bismuth
    • B01J23/6447—Bismuth
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8973—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony or bismuth
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
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    • 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 the method for butadiene production 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 method of butadiene production 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, the 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 Ferrious material and VA races metal metallic element.

Description

The method of butadiene production 1,4- butanediols
Technical field
The present invention relates to the method for butadiene production 1,4- butanediols.
Background technology
1,4-butanediol (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 1,4-butanediol 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.Since technical barrier is 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, the industrialized preparing process of Isosorbide-5-Nitrae-BDO 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 it two step hydrogenation 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 with Japanese two water chestnut oilings and Mitsubishi's chemical conversion exploitation 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, it is the allyl alcohol liquid-phase hydrogenatin formylated generation 4- hydroxyl fourths under rhodium catalyst Aldehyde, then repeated hydrogenation generation 1,4-butanediol.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 mainstream is melted into by Mitsubishi and Cao Da companies are in 20 generation Exploitation in 80 years of recording forms, it successfully breaks the technical barrier and obstacle of Reppe methods.Especially butadiene acetoxylation method is excellent Gesture and prospect, have obtained the favor of domestic and international research institution.
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 1,4-butanediol 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 1,4-butanediol 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 exists, and 1,4-butanediol 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 are 1,4- during 1,4-BDO is prepared for the above method 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 1,4-butanediol, there is provided Yi Zhongxin Butadiene production 1,4-butanediol method, this method has the characteristics that 1,4-butanediol high income and high selectivity.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Butadiene production 1,4- butanediols Production method, comprises the following steps：(1) using butadiene, acetic acid and oxygen as raw material, carried out in the presence of Acetoxylation catalyst Acetoxylation reaction obtains 1,4- diacetoxy butylene；(2) in the presence of a hydrogenation catalyst, hydrogen and Isosorbide-5-Nitrae-diethyl acyl-oxygen are made Base butene reaction obtains 1,4- diacetoxy butane；(3) 1,4- diacetoxies butane hydrolysis obtains 1,4- butanediols；Its In, the hydrogenation catalyst uses activated carbon as carrier, and active component includes Pt elements and promoter elements, and described help is urged Agent element includes being selected from least one of Tie Xi races metal and VA races metal metallic element.
In above-mentioned technical proposal, the activated carbon is preferably coal quality 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, and absorption pore volume is preferred For 0.60~1.00cm3/g.
In above-mentioned technical proposal, Ferrious material is selected from least one of Fe, Co and Ni in the hydrogenation catalyst.More into One step includes Co and Ni at the same time.Co and Ni is improving 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane selectivity side Face has synergistic effect.
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 at the same time.Sb and Bi is improving 1,4- diethyls acyl-oxygen butane yield and the choosing of 1,4- diethyl acyl-oxygens butane There is synergistic effect in terms of selecting property.
In above-mentioned technical proposal, the promoter elements are preferably at the same time including at least one in Ferrious material element Kind and selected from least one of VA races metallic element, at this time in the metallic element in iron system and VA races metal between metallic element There is synergistic effect in terms of 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane selectivity is improved.As unrestricted Property citing, such as, but not limited to nickel cooperates with antimony, and nickel is cooperateed with bismuth etc..
In above-mentioned technical proposal, the content of Pt 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 included 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. the corresponding particular compound of 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, the step 5. corresponding particular compound of middle Ferrious material element It preferably is selected from ferrous acetate, ferrocene, iron chloride, ferric sulfate, ferrous nitrate, carbonyl cobalt, cobalt acetate, cobalt chloride, cobalt nitrate, carbonyl At least one of nickel, nickel acetate, nickel nitrate, nickel sulfate and nickel chloride；The acetate of more excellent Ferrious material element；Most preferably from At least one of cobalt acetate and nickel acetate.
In above-mentioned technical proposal, as non limiting example, step 5. in promoter elements include VA races metal member When plain, the corresponding particular compound of VA races metallic element preferably be selected from basic bismuth carbonate, bismuth subnitrate, bismuth and ammonium citrate, bismuth sulfate, At least one of bismuth acetate, bismuth nitrate, bismuth chloride, bismuth oxide, antimony oxide, antimony sulfate, antimony acetate and antimony chloride；More preferably lemon At least one of lemon acid bismuth ammonium and antimony acetate.
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, when drying time is preferably 1~5 small；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 definite according to being actually needed 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 1,4-butanediol, 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 molar ratio of butadiene and acetic acid preferably 0.010~ 2.0.After 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 cause system complicated easy to year-on-year 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), 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 definite suitable hydrolysising reacting temperature, time and thing Material proportioning.Common 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 reaction kettles, 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 molar ratio of butadiene and oxygen is 1:After 1, sustained response 5.0h, stop reaction.By reaction kettle 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 reaction kettles, 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% 94.10%, achieve preferable technique effect.Especially include platinum at the same time, selected from iron system in the active component of hydrogenation catalyst At least one of metal metallic element and during selected from least one of VA races metal metallic element, achieves more prominent Technique effect, available in the industrial production of 1,4-butanediol.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
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 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the nickel acetate (Ni (OAc) of the Ni containing 1.98g2·4H2O aqueous solution 180ml) is immersed in catalyst precarsor IV On, when 110 DEG C of dryings 4 are small, obtain the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Ni contents 1.98g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 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 2】
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 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the antimony acetate (Sb (OAc) of the Sb containing 1.98g3) aqueous solution 180ml is immersed on catalyst precarsor IV, 110 DEG C When drying 4 is small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Sb contents 1.98g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 94.27%, 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 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 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, the catalyst is obtained.
The Pt contents that the catalyst is measured 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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 75.18%, and selectivity is 91.35%, 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 the way that, as can be seen that the present invention uses the catalyst of hydrogenation, its active component makes at the same time compared with embodiment 1~2 With the catalyst performance containing Pt, Ni active component while containing Pt, Sb active component than the performance containing only Pt active constituent catalysts It is more excellent, illustrate activity of hydrocatalyst component include the use of at the same time containing Pt and in Ferrious material and VA races metal at least A kind of metallic element compound, is conducive to improve the activity and stability of hydrogenation catalyst, the receipts of Isosorbide-5-Nitrae-diacetoxy butane Rate 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 containing 2.05gPd4)2PdCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, the catalyst is obtained.
The Pd contents that the catalyst is measured 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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 88.11%, 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 conducive 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 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 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the bismuth and ammonium citrate (Bi (NH of the Bi containing 1.98g3)2C6H7O7·4H2O aqueous solution 180ml), is immersed in and urges On agent precursor I V, when 110 DEG C of dryings 4 are small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Bi contents 1.98g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 94.28%, 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 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 0.60cm3/ g, specific surface area 1000cm2The coconut husk circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the ferrous acetate (Fe (OAc) of the Fe containing 1.98g2·4H2O) aqueous solution 180ml is immersed in catalyst precarsor IV On, when 100 DEG C of dryings 4 are small, obtain the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Fe contents 1.98g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 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 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 1500cm2The apricot shell circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the ferrous nitrate (Fe (NO of the Fe containing 1.98g3)2·6H2O) aqueous solution 180ml is immersed in catalyst precarsor IV On, when 120 DEG C of dryings 4 are small, obtain the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Fe contents 1.98g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 82.40%, 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 6】
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 0.80cm3/ g, specific surface area 1200cm2The bamboo circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the nickel nitrate (Ni (NO of the Ni containing 1.98g3)2·6H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, When 110 DEG C of dryings 4 are small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Ni contents 1.98g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 82.46%, 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 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 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the cobalt acetate (Co (OAc) of the Co containing 1.98g2·4H2O) aqueous solution 180ml, is immersed in catalyst precarsor IV On, when 110 DEG C of dryings 4 are small, obtain the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Co contents 1.98g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 82.44%, 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 8】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 1.50gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the cobalt nitrate (Co (NO of the Co containing 1.00g3)2·6H2O) aqueous solution 180ml, is immersed in catalyst precarsor IV On, when 110 DEG C of dryings 4 are small, obtain the catalyst.
The Pt contents that the catalyst is measured through ICP are 1.50g/L, Co contents 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 reaction kettle, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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.Reaction kettle 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 80.70%, and selectivity is 93.91%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 9】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 5.00gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the nickel acetate (Ni (OAc) of the Ni containing 6.00g2·4H2O) aqueous solution 180ml, is immersed in catalyst precarsor IV On, when 110 DEG C of dryings 4 are small, obtain the catalyst.
The Pt contents that the catalyst is measured through ICP are 5.00g/L, Ni 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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 82.59%, and selectivity is 93.95%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 10】
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 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the nickel acetate (Ni (OAc) of Ni containing the 1.30g and Co containing 0.68g2·6H2) and cobalt acetate (Co (OAc) O2· 4H2O aqueous solution 180ml) is immersed on catalyst precarsor IV, when 110 DEG C of dryings 4 are small, obtains the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Ni contents 1.30g/L, Co content 0.68g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 83.41%, and selectivity is 94.38%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 10 and embodiment 1 and embodiment 7, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Ni and metallic element Co has preferably in Ferrious material Synergistic effect.
【Embodiment 11】
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 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the antimony acetate (Sb (OAc) of Sb containing the 1.24g and Bi containing 0.74g3) and bismuth and ammonium citrate (Bi (NH3)2C6H7O7·4H2O aqueous solution 180ml), is immersed on catalyst precarsor IV, when 110 DEG C of dryings 4 are small, obtains the catalysis Agent.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Sb contents 1.24g/L, Bi content 0.74g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 83.34%, 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 Sb and metallic element Bi has preferably in VA races metal Synergistic effect.
【Embodiment 12】
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 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the nickel acetate (Ni (OAc) of Ni containing the 0.96g and Sb containing 1.02g2·6H2) and antimony acetate (Sb (OAc) O3) 180ml in aqueous solution, is immersed on catalyst precarsor IV, when 110 DEG C of dryings 4 are small, obtains the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Ni contents 0.96g/L, Sb content 1.02g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 84.36%, and selectivity is 95.12%, 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.
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 Ni and metal member in VA races metal in Ferrious material Plain Sb has preferable synergistic effect.
【Embodiment 13】
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 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the nickel acetate (Ni (OAc) of Ni containing the 0.96g and Bi containing 1.02g2·6H2) and bismuth and ammonium citrate (Bi O (NH3)2C6H7O7·4H2O aqueous solution 180ml), is immersed on catalyst precarsor IV, when 110 DEG C of dryings 4 are small, obtains described urge Agent.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Ni contents 0.96g/L, Bi content 1.02g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 84.34%, 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 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 Ni and metal member in VA races metal in Ferrious material Plain Bi has preferable synergistic effect.
【Embodiment 14】
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 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the nickel acetate (Ni (OAc) of Ni containing 0.96g, Sb containing 0.64g and the Bi containing 0.38g2·6H2O), antimony acetate (Sb(OAc)3) and bismuth and ammonium citrate (Bi (NH3)2C6H7O7·4H2O aqueous solution 180ml), is immersed on catalyst precarsor IV, When 110 DEG C of dryings 4 are small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Ni contents 0.96g/L, Sb content 0.64g/L, Bi content 0.38g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 85.26%, and selectivity is 95.41%, 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, metal in metallic element Ni and VA races metal in Ferrious material Element sb, Bi have preferable synergistic effect.
【Embodiment 15】
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 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the cobalt acetate (Co (OAc) of Co containing 0.96g, Sb containing 0.64g and the Bi containing 0.38g2·4H2O), antimony acetate (Sb(OAc)3) and bismuth and ammonium citrate (Bi (NH3)2C6H7O7·4H2O aqueous solution 180ml), is immersed on catalyst precarsor IV, When 110 DEG C of dryings 4 are small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Co contents 0.96g/L, Sb content 0.64g/L, Bi content 0.38g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 85.16%, and selectivity is 95.47%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 16】
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 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the nickel acetate (Ni (OAc) of Ni containing 0.61g, Co containing 0.35g, Sb containing 0.64g and the Bi containing 0.38g2· 6H2O), cobalt acetate (Co (OAc)2·4H2O), antimony acetate (Sb (OAc)3) and bismuth and ammonium citrate (Bi (NH3)2C6H7O7·4H2O) Aqueous solution 180ml, be immersed on catalyst precarsor IV, when 110 DEG C of dryings 4 are small, obtain the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Ni contents 0.61g/L, Co content 0.35g/L, Sb content 0.64g/L, Bi content 0.38g/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 reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen 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 86.35%, and selectivity is 95.60%, 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 It is golden in metallic element Ni, Co and VA races metal in Ferrious material in the hydrogenation catalyst that the present invention uses in terms of rate and selectivity Belong to element sb, Bi has preferable synergistic effect.
Table 1
Table 2

Claims (10)

1. the method for butadiene production 1,4-butanediol, comprises the following steps：(1) using butadiene, acetic acid and oxygen as raw material, Acetoxylation reaction is carried out in the presence of Acetoxylation catalyst and obtains 1,4- diacetoxy butylene；(2) deposited in hydrogenation catalyst Under, hydrogen is set to obtain Isosorbide-5-Nitrae-diacetoxy butane with Isosorbide-5-Nitrae-diacetoxy butene reaction；(3) 1,4- diacetoxybuts Alkane hydrolysis obtains 1,4- butanediols；Wherein, the hydrogenation catalyst uses activated carbon as carrier, and active component includes Pt elements And promoter elements, the promoter elements are included selected from least one of Ferrious material and VA races metal metal member Element.
2. according to the method described in claim 1, it is characterized in that the activated carbon is coal quality column charcoal, cocoanut active charcoal, apricot At least one of shell activated carbon and activated carbon from bamboo.
3. according to the method described in claim 1, it is characterized in that the specific surface area of the activated carbon is 1000~1500cm2/ g, Absorption pore volume is 0.60~1.00cm3/g。
4. according to the method described in claim 1, it is characterized in that Ferrious material is selected from Fe, Co and Ni in the hydrogenation catalyst At least one of.
5. according to the method described in claim 1, it is characterized in that VA races metal is selected from As, Sb and Bi in the hydrogenation catalyst At least one of.
6. according to the method described in claim 1, it is characterized in that in the hydrogenation catalyst Pt constituent contents for 1.00~ 8.00g/L。
7. according to the method described in claim 1, it is characterized in that in hydrogenation catalyst promoter elements content for 0.50~ 10.00g/L。
8. according to the method described in claim 1, it is characterized in that hydrogenation catalyst is obtained using the process included 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 containing promoter elements is supported on catalyst precarsor IV using infusion process by the composition of catalyst, it is dry Obtain the catalyst.
9. according to the method described in claim 1, it is characterized in that hydrogenation reaction pressure is 1.0~10.0MPa.
10. according to the method described in claim 1, it is characterized in that the hydrogenation reaction time is 0.5~5.0h.
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