CN107774253B - For synthesizing the hydrogenation catalyst of 1,4- diacetoxy butane - Google Patents

For synthesizing the hydrogenation catalyst of 1,4- diacetoxy butane Download PDF

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CN107774253B
CN107774253B CN201610751026.9A CN201610751026A CN107774253B CN 107774253 B CN107774253 B CN 107774253B CN 201610751026 A CN201610751026 A CN 201610751026A CN 107774253 B CN107774253 B CN 107774253B
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catalyst
catalyst precarsor
nitrae
isosorbide
hydrogenation
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CN107774253A (en
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查晓钟
杨运信
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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China Petrochemical Corp
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    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
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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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    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
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    • 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
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    • 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 for synthesizing 1, the hydrogenation catalyst of 4- diacetoxy butane, mainly solve in the prior art 1, the low problem of the yield and selectivity of 4- diacetoxy butane, using for synthesizing 1, the hydrogenation catalyst of 4- diacetoxy butane, including carrier and active component, the carrier is active carbon, active component includes Pt element and promoter elements, the promoter elements include the technical solution selected from least one of IVA race metal metallic element, preferably solves the technical problem, it can be used for 1, in the industrial production of 4- diacetoxy butane.

Description

For synthesizing the hydrogenation catalyst of 1,4- diacetoxy butane
Technical field
The present invention relates to the hydrogenation catalysts for synthesizing 1,4- diacetoxy butane.
Background technique
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 It is ground with polyurethane resin (PU Resin) especially as the base stock of production PBT engineering plastics and PBT fiber Study carefully the extensive concern of mechanism.
The process route of the preparation of 1,4-butanediol is relatively more, and dividing from raw material used has acetylene, ethylene, propylene, fourth The raw material routes such as diene and cis-butenedioic anhydride, identical raw material also have different synthesis technologies.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 capacity was mainly distributed on Asia, US and European, Wherein Asia 1,4-BDO production capacity accounting is up to 56.6%.Currently, the industrialized preparing process of Isosorbide-5-Nitrae-BDO specifically includes that 1. alkynes aldehyde Method (Reppe method): this method makees catalyst using methanol copper and generates butynediols, butynediols using acetylene and formaldehyde as raw material Two-stage hydrogenation obtains 1,4-BDO again.Its prevailing technology mainly have BASF Corp. of Germany, the U.S. DuPont exploitation Reppe method with And the Reppe method of improvement.2. maleic anhydride process: this method carries out two steps to it and adds hydrogen using cis-butenedioic anhydride as raw material.The first step is urged in Ni-Re Under agent effect, maleic anhydride hydrogenation generates 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 with the two-stage hydrogenation work of Japanese two water chestnut oilings and Mitsubishi's chemical conversion exploitation Skill.3. propylene method: mainly including allyl acetate method, acryladehyde method and allyl acetate-allyl alcohol method, Kuraray company develops at present Allyl acetate-allyl alcohol method has obtained industrial application, it is under rhodium catalyst, and allyl alcohol liquid-phase hydrogenatin formylated generates 4- hydroxyl fourth Aldehyde, then repeated hydrogenation generates 1,4-butanediol.4. butadiene process: the method that Isosorbide-5-Nitrae-BDO is produced as raw material using butadiene, it is main to wrap Butadiene acetoxylation method and butadiene chloridising are included, the technique of mainstream is by Mitsubishi chemical conversion and Cao Da company in 20 generation It records 80 years and develops, it successfully breaks the technical barrier and obstacle of Reppe method.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 and acetic acid, oxygen first is sent out Raw acetylization reaction, generates Isosorbide-5-Nitrae-diacetoxy butylene and by-product 3.4- diacetoxy butylene；Then 1,4- diacetyl Oxygroup 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 For diene into 1,4-butanediol process route, Isosorbide-5-Nitrae-diacetoxy butylene catalytic hydrogenation generates 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.
It teaches in the patents such as patent US4032458 (production of 1,4-butanediol) and is being urged using furans Agent exists, and prepares 1,4-butanediol under the conditions of certain temperature and pressure.Patent CN94108094.3 (the system of 1,4- butanediol Preparation Method) it describes using cis-butenedioic anhydride as raw material, gas phase catalytic hydrogenation reaction preparation is carried out in the presence of the catalyst specifically designed 1,4- butanediol.Patent CN104326871A (a kind of preparation method of butanediol) is described using fixed-bed catalytic technology, will Content greater 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- butanediol is synthesized under the conditions of certain temperature, pressure etc..But there is 1,4- during preparing 1,4-BDO in the above method The problem that BDO yield is low and selectivity is not high.
Summary 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, provides a kind of new for synthesizing Isosorbide-5-Nitrae-diacetoxy butane hydrogenation catalyst, which has Isosorbide-5-Nitrae-diacetyl Oxygroup butane high income and selective high feature.
The second technical problem to be solved by the present invention is the preparation method of above-mentioned hydrogenation catalyst.
The third technical problem to be solved by the present invention is the 1,4- diacetoxy butane using above-mentioned hydrogenation catalyst Synthetic method.
In order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: for synthesizing Isosorbide-5-Nitrae-diacetoxy The hydrogenation catalyst of butane, including carrier and active component, the carrier are active carbon, and active component includes Pt element and helps Catalyst elements, the promoter elements include selected from least one of IVA race metal metallic element.
In above-mentioned technical proposal, the active carbon is preferably coal quality column charcoal, cocoanut active charcoal, apricot shell active carbon and bamboo matter At least one of active carbon.
In above-mentioned technical proposal, the specific surface area of the active carbon is preferably 1000~1500cm2/ g, adsorption hole hold preferred For 0.60~1.00cm3/g。
In above-mentioned technical proposal, IVA race metal preferably is selected from least one of Ge, Sn and Pb in the hydrogenation catalyst, It still more preferably simultaneously include Sn and Pb.Sn and Pb is improving 1,4- diethyl acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane Selectivity aspect has synergistic effect.
In above-mentioned technical proposal, promoter elements can also further comprise at least one of group vib metal metal member Element, at this time between IVA race metallic element and group vib metallic element improve Isosorbide-5-Nitrae-diacetoxy butylene hydrogenation reaction in Isosorbide-5-Nitrae- Diethyl acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane selectivity aspect have synergistic effect.As non limiting example, example Such as, but not limited to, tin is cooperateed with molybdenum, and lead is cooperateed with molybdenum etc..
In above-mentioned technical proposal, group vib metal preferably is selected from least one of Cr, Mo and W in the hydrogenation catalyst.More It further simultaneously include Cr, Mo, Cr, Mo are improving Isosorbide-5-Nitrae-diethyl acyl-oxygen butane yield and Isosorbide-5-Nitrae-diethyl acyl-oxygen butane selectivity side Face has synergistic effect.
In above-mentioned technical proposal, the content of Pt is preferably 0.80~8.00g/L in the hydrogenation catalyst, more preferably 1.50~5.00g/L.
In above-mentioned technical proposal, promoter elements content is preferably 0.50~10.00g/L in the hydrogenation catalyst, More preferably 1.00~6.00g/L.
To solve above-mentioned technical problem two, technical scheme is as follows:
1. hydrogenation catalyst preparation method described in any one of technical solution of one of above-mentioned technical problem presses catalyst Composition the solution of platiniferous element is mixed with carrier, obtain catalyst precarsor I；
2. obtaining catalyst precarsor II after 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. being washed, being dried to obtain catalyst precarsor IV；
5. the compound of 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 corresponding particular compound of step ⑤Zhong IVA race metallic element Preferably be selected from tetraethyl germanium, tetraphenyl germanium, germanium tetrachloride, stannous oxalate, stannous chloride, nitric acid stannous, stannous oxide, lead acetate, At least one of lead stearate, basic lead carbonate, basic lead acetate and plumbi nitras；More preferably from nitric acid stannous and lead acetate It is at least one.
In above-mentioned technical proposal, as non limiting example, when step 5. in promoter elements include group vib metal When 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 molybdenum 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, drying time is preferably 1~5 hour；5. the drying temperature is preferably 80~120 DEG C to step, more preferably 100~120 DEG C.
To solve above-mentioned technical problem three, technical scheme is as follows:
Isosorbide-5-Nitrae-diacetoxy butane synthetic method, described in any one of technical solution of one of above-mentioned technical problem In the presence of hydrogenation catalyst, hydrogen and Isosorbide-5-Nitrae-diacetoxy butylene carry out that hydrogen is added to obtain Isosorbide-5-Nitrae-diacetoxy butane.
Key of the invention is the selection of hydrogenation catalyst, and skilled person will know how determine according to actual needs Suitable hydrogenation process conditions reaction temperature, reaction time, reaction pressure and proportion of 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 preferable 1.0~6.0MPa.
In above-mentioned technical proposal, the time of hydrogenation reaction is preferably 0.5~5.0h, more preferable 0.5~2.0h.
Isosorbide-5-Nitrae-diacetoxy butylene can be obtained from commercially available channel, or the synthesis of butadiene Acetoxylation method can be used.Fourth It is butadiene Acetoxylation catalyst that diene Acetoxylation method, which synthesizes and Pd-Te/C can be selected,.Palladium in suitable Pd-Te/C catalyst The content of element preferably 2.50~5.00g/L, more preferable 3.00~4.50g/L；The content of tellurium element preferably 0.50~3.00g/ L, more preferable 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 and obtains target production Object 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 complexity convenient on year-on-year basis, specific embodiment of the invention department is all made of pure Isosorbide-5-Nitrae-diacetyl to exclude other impurity Oxygroup 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- diacetoxy butane can be further used for obtaining 1,4- butanediol by method for hydrolysis.Art technology The suitable hydrolyst of the known selection of personnel and determining suitable hydrolysising reacting temperature, time and material proportion.Common water Solution catalyst can be inorganic acid, inorganic base, organic acid and organic base.Such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sodium hydroxide, Potassium hydroxide, benzene sulfonic acid and ion exchange resin.Suitable hydrolysising reacting temperature is preferably 30~100 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 The yield and selectivity of formula calculating 1,4- diacetoxy butane:
Compared with prior art, hydrogenation catalyst of the present invention improves Isosorbide-5-Nitrae-diethyl acyl-oxygen butane yield and selectivity.
The experimental results showed that Isosorbide-5-Nitrae-diacetoxy butane yield selectively reaches up to 82% or more when using the present invention 94% or more, achieve preferable technical effect.It simultaneously include especially platinum, selected from IVA in the active component of hydrogenation catalyst At least one of race's metal metallic element and when selected from least one of group vib metal metallic element, achieves more prominent Technical effect out, can be used in the industrial production of 1,4-butanediol.Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the nitric acid stannous (Sn (NO of the Sn containing 1.85g3)2) aqueous solution 180ml be immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Sn content 1.85g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.54% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 93.89%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 2]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the ammonium molybdate ((NH of the Mo containing 1.85g4)6Mo7O24·4H2O aqueous solution 180ml) is immersed in catalyst precarsor On IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Mo content 1.85g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.38% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.05%, 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 the comparative example of [embodiment 1] and [embodiment 2].
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 75.15% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 91.47%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
By the way that, as can be seen that the present invention is using the catalyst for adding hydrogen, active component makes simultaneously compared with Examples 1 to 2 With containing Pt, Sn active component, simultaneously the catalyst performance containing Pt, Mo active component than the performance containing only Pt active constituent catalyst It is more excellent, illustrate activity of hydrocatalyst component while using at least one containing Pt and in IVA race metal and group vib metal Kind metallic element compound is conducive to the activity and stability that improve hydrogenation catalyst, Isosorbide-5-Nitrae-diacetoxy butane yield It will be high with selectivity.
[comparative example 2]
For the comparative example of [comparative example 1].
The preparation of hydrogenation catalyst:
1. by the ammonium chloropalladite ((NH of the Pd containing 2.05g4)2PdCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 2.05g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 70.02% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 88.20%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
By can be seen that the present invention compared with comparative example 1 using the catalyst for adding hydrogen, contained using the ratio of active component containing Pt The performance of Pd active constituent catalyst is more excellent, illustrates that activity of hydrocatalyst component is conducive to Isosorbide-5-Nitrae-diacetoxy using Pt Butylene adds hydrogen, and Isosorbide-5-Nitrae-diacetoxy butane yield and selectivity will be high.
[embodiment 3]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the chromic acetate (Cr (OAc) of the Cr containing 1.85g3·6H2O it) is dissolved in hot water, obtains maceration extract 180ml, impregnate On catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Cr content 1.85g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.35% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.18%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 4]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.60cm3/ g, specific surface area 1000cm2The coconut husk of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the ammonium tungstate ((NH of the W containing 1.85g4)10W12O41·4H2O it) is dissolved in hot water, obtains maceration extract 180ml, soak Stain on catalyst precarsor IV, 100 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, W content 1.85g/L.
Hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 82.31% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.09%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 5]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 1.00cm3/ g, specific surface area 1500cm2The apricot shell of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the basic lead acetate (Pb (OAc) of the Pb containing 1.85g2·2Pb(OH)2) aqueous solution 180ml, it is immersed in catalyst On precursor I V, 120 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Pb content 1.85g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.53% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 93.91%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 6]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2/ g's is bamboo Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the plumbi nitras (Pb (NO of the Pb containing 1.85g3)2) aqueous solution 180ml, it is immersed on catalyst precarsor IV, 110 DEG C It is 4 hours dry, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Pb content 1.85g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.51% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 93.88%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 7]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the lead acetate (Pb (OAc) of the Pb containing 1.85g2·3H2O) aqueous solution 180ml is immersed in catalyst precarsor IV On, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Pb content 1.85g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 50 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.67% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 93.95%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 8]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 1.50g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the nitric acid stannous (Sn (NO of the Sn containing 1.00g3)2) aqueous solution 180ml, it is immersed on catalyst precarsor IV, 110 DEG C dry 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 1.50g/L, Sn content 1.00g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 1.0MPa, improves mixing speed first with 0.5MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 20 DEG C, after sustained response 30min, stops anti- It answers.Reaction kettle is down to room temperature, purified removal of impurities obtains Isosorbide-5-Nitrae-diacetoxy butane.
It is 80.74% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 93.84%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 9]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 5.00g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the nitric acid stannous (Sn (NO of the Sn containing 6.00g3)2) aqueous solution 180ml, it is immersed on catalyst precarsor IV, 110 DEG C dry 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 5.00g/L, Sn content 6.00g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 6.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 120 DEG C, after sustained response 120min, stops Reaction.
It is 82.78% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.19%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 10]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the nitric acid stannous (Sn (NO of Sn containing the 0.99g and Pb containing 0.86g3)2) and lead acetate (Pb (OAc)2·3H2O) Aqueous solution 180ml be immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Sn content 0.99g/L, Pb content 0.86g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 83.65% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.40%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 10 and embodiment 1 and embodiment 7, is improving Isosorbide-5-Nitrae-diacetoxy butane yield In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Sn and metallic element Pb have preferably in IVA race metal Synergistic effect.
[embodiment 11]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the ammonium molybdate ((NH of Mo containing the 1.20g and Cr containing 0.65g4)6Mo7O24·4H2) and chromic acetate (Cr O (OAc)3·6H2O) be dissolved in hot water, obtain maceration extract 180ml, be immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain To the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Mo content 1.20g/L, Cr content 0.65g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 83.41% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.58%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 11 and embodiment 2 and embodiment 3, is improving Isosorbide-5-Nitrae-diacetoxy butane yield In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Mo and metallic element Cr have preferably in group vib metal Synergistic effect.
[embodiment 12]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the nitric acid stannous (Sn (NO of Sn containing the 1.02g and Mo containing 0.83g3)2) and ammonium molybdate ((NH4)6Mo7O24· 4H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Sn content 1.02g/L, Mo content 0.83g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 84.67% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.21%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 2, is improving Isosorbide-5-Nitrae-diacetoxy butane yield In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Sn and metal in group vib metal in IVA race metal Elements Mo has preferable synergistic effect.
[embodiment 13]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the lead acetate (Pb (OAc) of Pb containing the 1.02g and Mo containing 0.83g2·3H2) and ammonium molybdate ((NH O4)6Mo7O24·4H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Pb content 1.02g/L, Mo content 0.83g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 84.79% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.16%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 13 and embodiment 2 and embodiment 7, is improving Isosorbide-5-Nitrae-diacetoxy butane yield In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Pb and metal in group vib metal in IVA race metal Elements Mo has preferable synergistic effect.
[embodiment 14]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the nitric acid stannous (Sn (NO of Sn containing 0.55g, Pb containing 0.47g and the Mo containing 0.83g3)2), lead acetate (Pb (OAc)2·3H2) and ammonium molybdate ((NH O4)6Mo7O24·4H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, and 110 DEG C It is 4 hours dry, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Sn content 0.55g/L, Pb content 0.47g/L, Mo content 0.83g/L。
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 85.24% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.53%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13, is improving Isosorbide-5-Nitrae-diacetoxy butane receipts In terms of rate and selectivity, in the hydrogenation catalyst that the present invention uses, in IVA race metal in metallic element Sn, Pb and group vib metal Metallic element Mo has preferable synergistic effect.
[embodiment 15]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the nitric acid stannous (Sn (NO of Sn containing 0.55g, Pb containing 0.47g and the Cr containing 0.83g3)2), lead acetate (Pb (OAc)2·3H2) and chromic acetate (Cr (OAc) O3·6H2O it) is dissolved in hot water, maceration extract 180ml is obtained, before being immersed in catalyst On body IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Sn content 0.55g/L, Pb content 0.47g/L, Cr content 0.83g/L。
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 85.35% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.44%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 16]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the nitric acid stannous (Sn (NO of Sn containing 0.55g, Pb containing 0.47g, Mo containing 0.54g and the Cr containing 0.29g3)2)、 Lead acetate (Pb (OAc)2·3H2O), ammonium molybdate ((NH4)6Mo7O24·4H2) and chromic acetate (Cr (OAc) O3·6H2O) it is dissolved in heat In water, obtain maceration extract 180ml, be immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Sn content 0.55g/L, Pb content 0.47g/L, Mo content For 0.54g/L, Cr content 0.29g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 86.68% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.84%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, is improving Isosorbide-5-Nitrae-diacetoxy butane receipts In terms of rate and selectivity, in the hydrogenation catalyst that the present invention uses, in IVA race metal in metallic element Sn, Pb and group vib metal Metallic element Mo, Cr have preferable synergistic effect.
Table 1
Table 2

Claims (7)

1. a kind of Isosorbide-5-Nitrae-diacetoxy butane synthetic method, in the presence of a hydrogenation catalyst, hydrogen and Isosorbide-5-Nitrae-diethyl acyl-oxygen Base butylene carries out plus hydrogen obtains 1,4- diacetoxy butane；The hydrogenation catalyst, including carrier and active component, it is described Carrier is active carbon, and active component includes Pt element and promoter elements, and the promoter elements include selected from IVA race gold At least one of category metallic element；
Wherein, in the hydrogenation catalyst Pt constituent content be 0.80~8.00g/L, promoter elements content be 0.50~ 10.00g/L。
2. synthetic method according to claim 1, which is characterized in that the active carbon is coal quality column charcoal, coconut activated At least one of charcoal, apricot shell active carbon and activated carbon from bamboo.
3. synthetic method according to claim 1, which is characterized in that the specific surface area of the active carbon be 1000~ 1500m2/ g, it is 0.60~1.00cm that adsorption hole, which holds,3/g。
4. synthetic method according to claim 1, which is characterized in that in the hydrogenation catalyst IVA race metal be selected from Ge, At least one of Sn and Pb.
5. synthetic method according to any one of claims 1 to 4, which is characterized in that the hydrogenation catalyst is by following Method preparation, this method comprises the following steps:
1. mixing the solution of platiniferous element with carrier by the composition of catalyst, catalyst precarsor I is obtained；
2. obtaining catalyst precarsor II after 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. being washed, being dried to obtain catalyst precarsor IV；
5. promoter elements compound is supported on catalyst precarsor IV using infusion process by the composition of catalyst, dry To the catalyst.
6. synthetic method according to claim 1, which is characterized in that the hydrogenation reaction time is 0.5~5.0h.
7. synthetic method according to claim 1, which is characterized in that hydrogenation reaction pressure is 1.0~10.0MPa.
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