CN107999064A - Butadiene synthesizes the catalyst of 1,4- diacetoxy butane courses - Google Patents

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

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CN107999064A
CN107999064A CN201610967705.XA CN201610967705A CN107999064A CN 107999064 A CN107999064 A CN 107999064A CN 201610967705 A CN201610967705 A CN 201610967705A CN 107999064 A CN107999064 A CN 107999064A
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catalyst
isosorbide
catalyst precarsor
nitrae
precarsor
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CN107999064B (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
    • B01J23/38—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
    • B01J23/58—Platinum group metals with alkali- or alkaline earth 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
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6522—Chromium
    • 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
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • 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 course, 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 course；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 alkaline-earth metal at least one of metallic element and group vib 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 courses
Technical field
The present invention relates to the catalyst of butadiene synthesis 1,4- diacetoxy butane courses.
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 course, 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.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Butadiene synthesizes 1,4- diethyls The catalyst of acyloxy butane course；Including carrier and active component, the carrier is activated carbon, and active component includes Pt members Element and promoter elements, the promoter elements are included selected from least one of alkaline-earth metal metallic element and group vib gold At least one of category 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, alkaline-earth metal preferably is selected from least one of Be, Mg, Ca, Sr and Ba in the catalyst, Still more preferably include Ba and Sr at the same time.Ba and Sr is improving 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane Selectivity aspect has synergistic effect.
In above-mentioned technical proposal, group vib metal preferably is selected from least one of Cr, Mo and W in the catalyst.More into one Step includes Cr, W at the same time.Cr, W have in terms of 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane selectivity is improved Synergistic effect.
In above-mentioned technical proposal, the promoter elements are preferably at the same time including at least one in alkali earth metal Kind and selected from least one of group vib metallic element, metal member in the metallic element in alkaline-earth metal and group vib metal at this time There is synergistic effect between element in terms of 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane selectivity is improved.As Non limiting example, such as, but not limited to strontium are cooperateed with chromium, and strontium is cooperateed with tungsten 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, step 5. in promoter elements include alkaline-earth metal member When plain, the corresponding particular compound of alkali earth metal preferably is selected from alkaline earth oxide, alkaline earth metal chloride, alkaline-earth metal At least one of sulfate, alkaline earth metal nitrate and Alkaline Earth Metal Acetate；More preferably in Alkaline Earth Metal Acetate It is at least one；Most preferably from least one of barium acetate and strontium acetate.
In above-mentioned technical proposal, as non limiting example, when step 5. in promoter elements include group vib metal During element, the corresponding particular compound of group vib metallic element preferably is selected from chromic acetate, chromic nitrate, chromium chloride, ammonium molybdate, phosphoric At least one of molybdenum, molybdenum carbonyl, molybdic acid, tungsten chloride, tungsten carbonyl, ammonium paratungstate and ammonium tungstate；More preferably from chromic acetate and tungsten At least one of sour ammonium.
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 catalyst, and skilled person will know how definite suitable according to being actually needed Hydrogenation process conditions reaction temperature, the reaction time, the proportioning etc. of reaction pressure and material.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, the catalyst used in the present invention improves yield and the selection of Isosorbide-5-Nitrae-diethyl acyl-oxygen butane Property.
Test result indicates that during using the present invention, Isosorbide-5-Nitrae-diacetoxy butane yield selectively reaches up to 82.36% 94.26%, achieve preferable technique effect.Especially include platinum at the same time, selected from alkaline earth in the active component of hydrogenation catalyst At least one of metal metallic element and during selected from least one of group vib metal metallic element, 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 strontium acetate (Sr (OAc) of the Sr containing 1.88g2·0.5H2O aqueous solution 180ml) is immersed in catalyst precarsor On 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, Sr contents 1.88g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 82.36%, and selectivity is 94.26%, 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 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 ammonium tungstate ((NH of the W containing 1.88g4)10W12O41·4H2O) it is dissolved in hot water, obtains maceration extract 180ml, soaks Stain when 110 DEG C of dryings 4 are small, obtains the catalyst on catalyst precarsor IV.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, W content 1.88g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 82.44%, and selectivity is 94.12%, 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.
【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.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 75.21%, and selectivity is 91.27%, 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.
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, Sr active component while catalyst performance containing Pt, W active component will be more than the performance containing only Pt active constituent catalysts It is excellent, illustrate that activity of hydrocatalyst component includes the use of at least one containing Pt and in alkaline-earth metal and group vib metal at the same time Kind metallic element, is conducive to improve the activity and stability of catalyst, the yield and selectivity of Isosorbide-5-Nitrae-diacetoxy butane are all Will height.
【Comparative example 2】
For【Comparative example 1】Comparative example.
The preparation of 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.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 70.14%, and selectivity is 88.09%, 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.
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 catalyst activity 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 chromic acetate (Cr (OAc) of the Cr containing 1.88g3·6H2O) it is dissolved in hot water, obtains maceration extract 180ml, impregnates 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, Cr contents 1.88g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 94.14%, 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 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 beryllium acetate (Be (OAc) of the Be containing 1.88g2·H2O) it is dissolved in hot water, obtains maceration extract 180ml, be immersed in On catalyst precarsor IV, when 100 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, Be contents 1.88g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 82.31%, and selectivity is 94.24%, 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 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 magnesium acetate (Mg (OAc) of the Mg containing 1.88g2·4H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, When 120 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, Mg contents 1.88g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 82.31%, and selectivity is 94.24%, 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 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 calcium acetate (Ca (OAc) of the Ca containing 1.88g2·H2O) 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, Ca contents 1.88g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 82.32%, and selectivity is 94.28%, 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 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 barium acetate (Ba (OAc) of the Ba containing 1.88g2·H2O) 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, Ba contents 1.88g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 82.37%, and selectivity is 94.27%, 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 strontium acetate (Sr (OAc) of the Sr containing 1.00g2·0.5H2O) 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, Sr contents 1.00g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 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 80.71%, and selectivity is 93.88%, 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 strontium acetate (Sr (OAc) of the Sr containing 6.00g2·0.5H2O) 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, Sr contents 6.00g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 82.61%, and selectivity is 93.92%, 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 strontium acetate (Sr (OAc) of Sr containing the 1.22g and Ba containing 0.66g2·0.5H2) and barium acetate (Ba O (OAc)2·H2O 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, Sr contents 1.22g/L, Ba content 0.66g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 83.29%, and selectivity is 94.50%, 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 Sr and metallic element Ba has preferable association in alkaline-earth metal 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 ammonium tungstate ((NH of W containing the 0.98g and Cr containing 0.90g4)10W12O41·4H2) and chromic acetate (Cr O (OAc)3·6H2O) it is dissolved in hot water, obtains maceration extract 180ml, be immersed on catalyst precarsor IV, when 110 DEG C of dryings 4 are small, obtains To the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, W content 0.98g/L, Cr content 0.90g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 83.43%, and selectivity is 94.33%, 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, metal elements W has preferable association with metallic element Cr in group vib 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 strontium acetate (Sr (OAc) of Sr containing the 1.04g and W containing 0.84g2·0.5H2) and ammonium tungstate ((NH O4)10W12O41·4H2O) it is dissolved in hot water, obtains maceration extract 180ml, is 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, Sr content 1.04g/L, W content 0.84g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 84.32%, and selectivity is 95.11%, 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 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 Sr and metal elements W in group vib metal in alkaline-earth metal 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 strontium acetate (Sr (OAc) of Sr containing the 1.04g and Cr containing 0.84g2·0.5H2) and chromic acetate (Cr O (OAc)3·6H2O) it is dissolved in hot water, obtains maceration extract 180ml, be immersed on catalyst precarsor IV, when 110 DEG C of dryings 4 are small, obtains To the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Sr contents 1.04g/L, Cr content 0.84g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 84.28%, and selectivity is 95.08%, 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 Sr and metallic element Cr in group vib metal in alkaline-earth metal 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 strontium acetate (Sr (OAc) of Sr containing 1.04g, W containing 0.58g and the Cr containing 0.26g2·0.5H2O), ammonium tungstate ((NH4)10W12O41·4H2) and chromic acetate (Cr (OAc) O3·6H2O) it is dissolved in hot water, obtains maceration extract 180ml, be immersed in and urge 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, Sr content 1.04g/L, W content 0.58g/L, Cr content 0.26g/L。
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 85.22%, and selectivity is 95.31%, 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 Rate and selectivity aspect, in the catalyst that uses of the present invention, metallic element in metallic element Sr and group vib metal in alkaline-earth metal W, Cr has 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 barium acetate (Ba (OAc) of Ba containing 1.04g, W containing 0.58g and the Cr containing 0.26g2·H2O), ammonium tungstate ((NH4)10W12O41·4H2) and chromic acetate (Cr (OAc) O3·6H2O) it is dissolved in hot water, obtains maceration extract 180ml, be immersed in and urge 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, Ba content 1.04g/L, W content 0.58g/L, Cr content 0.26g/L。
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 85.17%, and selectivity is 95.35%, 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 strontium acetate (Sr (OAc) of Sr containing 0.65g, Ba containing 0.39g, W containing 0.58g and the Cr containing 0.26g2· 0.5H2O), barium acetate (Ba (OAc)2·H2O), ammonium tungstate ((NH4)10W12O41·4H2) and chromic acetate (Cr (OAc) O3·6H2O) It is dissolved in hot water, obtains maceration extract 180ml, be 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, Sr contents 0.65g/L, Ba content 0.39g/L, W content 0.58g/L, Cr content 0.26g/L.
The synthesis of 1,4- diacetoxy butane：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 86.29%, and selectivity is 95.52%, 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 Rate and selectivity aspect, in the catalyst that uses of the present invention, metal in metallic element Sr, Ba and group vib metal in alkaline-earth metal Element W, Cr have preferable synergistic effect.
Table 1
Table 2

Claims (10)

1. butadiene synthesizes the catalyst of 1,4- diacetoxy butane courses；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 alkaline-earth metal At least one of at least one metallic element and group vib 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 alkaline-earth metal is selected from Be, Mg, Ca, Sr in the catalyst At least one of with Ba.
5. catalyst according to claim 1, it is characterised in that group vib metal is in Cr, Mo and W in the catalyst At least one.
6. catalyst according to claim 1, it is characterised in that in the catalyst Pt constituent contents for 1.00~ 8.00g/L。
7. catalyst according to claim 1, it is characterised in that in catalyst promoter elements content for 0.50~ 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 reaction pressure is 1.0~10.0MPa, the reaction time for 0.5~ 5.0h。
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