CN108014817A - Butadiene synthesizes the catalyst of 1,4- diacetoxy butane processes - Google Patents

Butadiene synthesizes the catalyst of 1,4- diacetoxy butane processes Download PDF

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CN108014817A
CN108014817A CN201610978492.0A CN201610978492A CN108014817A CN 108014817 A CN108014817 A CN 108014817A CN 201610978492 A CN201610978492 A CN 201610978492A CN 108014817 A CN108014817 A CN 108014817A
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catalyst
isosorbide
catalyst precarsor
nitrae
precarsor
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CN108014817B (en
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查晓钟
杨运信
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/644—Arsenic, antimony or bismuth
    • B01J23/6445—Antimony
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/644—Arsenic, antimony or bismuth
    • B01J23/6447—Bismuth
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    • 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
    • B01J23/70—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
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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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
    • B01J23/892—Nickel and noble metals
    • 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
    • B01J23/70—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
    • B01J23/8933—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/283—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds

Abstract

The present invention relates to the catalyst of butadiene synthesis Isosorbide-5-Nitrae diacetoxy butane process, mainly solves the problems, such as that the yield of Isosorbide-5-Nitrae diacetoxy butane in the prior art and selectivity are low, using the catalyst of butadiene synthesis Isosorbide-5-Nitrae diacetoxy butane process；Including carrier and active component, the carrier is activated carbon, active component includes Pt elements and promoter elements, the promoter elements include the technical solution selected from least one of Ferrious material at least one of metallic element and VA races metal metallic element, preferably solves the technical problem, in industrial production available for Isosorbide-5-Nitrae diacetoxy butane.

Description

Butadiene synthesizes the catalyst of 1,4- diacetoxy butane processes
Technical field
The present invention relates to the catalyst of butadiene synthesis 1,4- diacetoxy butane processes.
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 first technical problem to be solved by the present invention is that the yield of 1,4- diacetoxy butane is asked with selectively low Topic, there is provided a kind of catalyst of new butadiene synthesis Isosorbide-5-Nitrae-diacetoxy butane process, the catalyst have Isosorbide-5-Nitrae-diethyl The characteristics of acyloxy butane high income and high selectivity.
The second technical problem to be solved by the present invention is the preparation method of above-mentioned catalyst.
The third technical problem to be solved by the present invention is the conjunction using the 1,4- diacetoxy butane of above-mentioned catalyst Into method.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Butadiene synthesizes 1,4- diethyl acyl-oxygens The catalyst of base butane process；Including carrier and active component, the carrier is activated carbon, active component include Pt elements and Promoter elements, the promoter elements are included at least one of Ferrious material metallic element and VA races metal At least one 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 catalyst.Further Include Co and Ni at the same time.Co and Ni has in terms of 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane selectivity is improved There is synergistic effect.
In above-mentioned technical proposal, VA races metal preferably is selected from least one of As, Sb and Bi in the catalyst, more into one Step preferably includes Sb and Bi at the same time.Sb and Bi is improving 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygens butane selectivity Aspect has synergistic effect.
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 catalyst, more preferably 1.50~ 5.00g/L。
In above-mentioned technical proposal, promoter elements content is preferably 0.50~10.00g/L in the catalyst, more excellent Elect 1.00~6.00g/L as.
To solve the two of above-mentioned technical problem, technical scheme is as follows：
Method for preparing catalyst any one of the technical solution of one of above-mentioned technical problem, includes 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 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.
To solve the three of above-mentioned technical problem, technical scheme is as follows：
The synthetic method of Isosorbide-5-Nitrae-diacetoxy butane, any one of the technical solution in one of above-mentioned technical problem In the presence of catalyst, hydrogen obtains Isosorbide-5-Nitrae-diacetoxy butane with Isosorbide-5-Nitrae-diacetoxy butene reaction.
The key of the present invention is the selection of hydrogenation catalyst, and skilled person will know how 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.
Isosorbide-5-Nitrae-diacetoxy butylene can be obtained from commercially available channel, or butadiene Acetoxylation method can be used to synthesize.Fourth It is butadiene Acetoxylation catalyst that Pd-Te/C, which can be selected, in the synthesis of diene Acetoxylation method.Palladium in suitable Pd-Te/C catalyst The content of element preferably 2.50~5.00g/L, more preferably 3.00~4.50g/L；The content of tellurium element preferably 0.50~3.00g/ L, more preferably 1.00~2.50g/L.Suitable Acetoxylation reaction temperature is preferably 40~150 DEG C；Acetoxylation reaction pressure It is preferred that 1.0~10.0MPa；The Acetoxylation reaction time is preferably 0.5~5h；The molar ratio of butadiene and acetic acid preferably 0.010 ~2.0.After the reaction of butadiene Acetoxylation, the mixture that can be reacted butadiene Acetoxylation carries out separation acquisition target production Thing Isosorbide-5-Nitrae-diacetoxy butylene carries out hydrogenation reaction of the present invention again, can not also separate and directly carry out hydrogenation reaction.But Cause system complicated easy to year-on-year to exclude other impurity, specific embodiment of the invention department uses pure Isosorbide-5-Nitrae-diacetyl Epoxide butylene is as hydrogenation reaction raw material.
The product mixtures of above-mentioned hydrogenation reaction can obtain target product 1,4- diacetoxy butane through separation.
1,4- diacetoxies butane can be further used for obtaining 1,4- butanediols by method for hydrolysis.Art technology The suitable hydrolyst of the known selection of personnel and definite suitable hydrolysising reacting temperature, time and material proportion.Common water It can be inorganic acid, inorganic base, organic acid and organic base to solve catalyst.Such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sodium hydroxide, Potassium hydroxide, benzene sulfonic acid and ion exchange resin.Suitable hydrolysising reacting temperature is preferably 30~100 DEG C；Hydrolysis pressure Power preferably 0~2.0MPa；The preferred water of solvent.
Product mixtures after hydrogenation reaction of the present invention are analyzed through gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), by following Formula calculates the yield and selectivity of 1,4- diacetoxy butane：
Compared with prior art, catalyst of the invention improves the yield and selectivity of Isosorbide-5-Nitrae-diethyl acyl-oxygen butane.
Test result indicates that during using the present invention, Isosorbide-5-Nitrae-diacetoxy butane yield selectively reaches up to 82.45% 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.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.45%, and selectivity is 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 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.39%, and selectivity is 94.27%, 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 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 75.18%, 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.
The catalyst used by can be seen that the present invention compared with embodiment 1~2, the use at the same time of its active component contain Pt, Ni active component while catalyst performance containing Pt, Sb active component will be more than the performance containing only Pt active constituent catalysts It is excellent, illustrate that activity of hydrocatalyst component is included the use of containing Pt and selected from least one of Ferrious material and VA races metal at the same time Metallic element compound, is conducive to improve the activity and stability of catalyst, the yield of Isosorbide-5-Nitrae-diacetoxy butane and selection Property 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 70.07%, and selectivity is 88.11%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
The catalyst used by can be seen that the present invention compared with comparative example 1, is lived using the ratio of active component containing Pt containing Pd The performance of property component catalyst is more excellent, illustrates that activity of hydrocatalyst component is conducive to Isosorbide-5-Nitrae-diacetoxy butylene using Pt Hydrogenation, the yield and selectivity of Isosorbide-5-Nitrae-diacetoxy butane will be high.
【Embodiment 3】
The preparation of 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.37%, and selectivity is 94.28%, 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 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.41%, and selectivity is 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 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.40%, 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 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.46%, 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 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 50 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.44%, and selectivity is 94.13%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, the yield of Isosorbide-5-Nitrae-diacetoxy butane and selection Property is listed in Tables 1 and 2 respectively.
【Embodiment 8】
The preparation of 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 1.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 20 DEG C, after sustained response 30min, stops anti- Should.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 catalyst, reaction condition, material inlet amount, the yield of Isosorbide-5-Nitrae-diacetoxy butane and selection Property is listed in Tables 1 and 2 respectively.
【Embodiment 9】
The preparation of 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 6.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 120 DEG C, after sustained response 120min, is stopped Reaction.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.59%, and selectivity is 93.95%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, the yield of Isosorbide-5-Nitrae-diacetoxy butane and selection Property is listed in Tables 1 and 2 respectively.
【Embodiment 10】
The preparation of 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 83.41%, and selectivity is 94.38%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, the yield of Isosorbide-5-Nitrae-diacetoxy butane and selection Property 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 catalyst used with selective aspect, the present invention, metallic element Ni and metallic element Co has preferable association in Ferrious material Same-action.
【Embodiment 11】
The preparation of 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 83.34%, and selectivity is 94.49%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, the yield of Isosorbide-5-Nitrae-diacetoxy butane and selection Property 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 catalyst used with selective aspect, the present invention, metallic element Sb and metallic element Bi has preferable association in VA races metal Same-action.
【Embodiment 12】
The preparation of 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 84.36%, and selectivity is 95.12%, for the ease of Illustrate and compare, preparation, reaction condition, material inlet amount, the yield of Isosorbide-5-Nitrae-diacetoxy butane and the selection of agent will be added Property 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 catalyst used with selective aspect, the present invention, metallic element Ni and metallic element Sb in VA races metal in Ferrious material There is preferable synergistic effect.
【Embodiment 13】
The preparation of 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 84.34%, and selectivity is 95.10%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, the yield of Isosorbide-5-Nitrae-diacetoxy butane and selection Property 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 catalyst used with selective aspect, the present invention, metallic element Ni and metallic element Bi in VA races metal in Ferrious material There is preferable synergistic effect.
【Embodiment 14】
The preparation of 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 85.26%, and selectivity is 95.41%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, the yield of Isosorbide-5-Nitrae-diacetoxy butane and selection Property 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 catalyst that the present invention uses, metallic element in metallic element Ni and VA races metal in Ferrious material Sb, Bi have preferable synergistic effect.
【Embodiment 15】
The preparation of 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 85.16%, and selectivity is 95.47%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, the yield of Isosorbide-5-Nitrae-diacetoxy butane and selection Property is listed in Tables 1 and 2 respectively.
【Embodiment 16】
The preparation of 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- diacetoxies butane synthesizes：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 86.35%, and selectivity is 95.60%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, the yield of Isosorbide-5-Nitrae-diacetoxy butane and selection Property 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 catalyst that the present invention uses, metal member in metallic element Ni, Co and VA races metal in Ferrious material Plain Sb, Bi have preferable synergistic effect.
Table 1
Table 2

Claims (10)

1. butadiene synthesizes the catalyst of 1,4- diacetoxy butane processes；Including carrier and active component, the carrier For activated carbon, active component includes Pt elements and promoter elements, and the promoter elements are included in Ferrious material At least one of at least one metallic element and VA race metal metallic element.
2. catalyst according to claim 1, it is characterised in that the activated carbon for coal quality column charcoal, cocoanut active charcoal, At least one of apricot shell activated carbon and activated carbon from bamboo.
3. catalyst according to claim 1, it is characterised in that the specific surface area of the activated carbon is 1000~1500cm2/ G, absorption pore volume are 0.60~1.00cm3/g。
4. catalyst according to claim 1, it is characterised in that in the hydrogenation catalyst Ferrious material be selected from Fe, Co and At least one of Ni.
5. catalyst according to claim 1, it is characterised in that in the hydrogenation catalyst VA races metal be selected from As, Sb and At least one of Bi.
6. catalyst according to claim 1, it is characterised in that in the hydrogenation catalyst Pt constituent contents for 1.00~ 8.00g/L。
7. catalyst according to claim 1, it is characterised in that promoter elements content is 0.50 in hydrogenation catalyst ~10.00g/L.
8. the preparation method of catalyst according to claim 1, includes 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.
The synthetic method of 9.1,4- diacetoxy butane, in the presence of catalyst any one of claim 1~7, hydrogen Gas obtains 1,4- diacetoxy butane with 1,4- diacetoxies butene reaction.
10. according to the method described in claim 9, it is characterized in that hydrogenation reaction pressure is 1.0~10.0MPa, during hydrogenation reaction Between be 0.5~5.0h.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1105951A (en) * 1993-09-07 1995-08-02 昭和电工株式会社 Chromium-based fluorination catalyst, process for producing the catalyst, and fluorination process using the catalyst
CN1173168A (en) * 1994-11-24 1998-02-11 索尔维公司 Method for converting a chlorinated alkane into a less chlerinated alkene
CN1765489A (en) * 2004-10-29 2006-05-03 中国石油化工股份有限公司 Supported type active carbon and its preparation method
CN101687181A (en) * 2007-05-10 2010-03-31 巴斯夫欧洲公司 Method for producing amines

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1105951A (en) * 1993-09-07 1995-08-02 昭和电工株式会社 Chromium-based fluorination catalyst, process for producing the catalyst, and fluorination process using the catalyst
CN1173168A (en) * 1994-11-24 1998-02-11 索尔维公司 Method for converting a chlorinated alkane into a less chlerinated alkene
CN1765489A (en) * 2004-10-29 2006-05-03 中国石油化工股份有限公司 Supported type active carbon and its preparation method
CN101687181A (en) * 2007-05-10 2010-03-31 巴斯夫欧洲公司 Method for producing amines

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