CN107790182B - 1,4- diacetoxy butylene hydrogenation process catalyst - Google Patents

1,4- diacetoxy butylene hydrogenation process catalyst Download PDF

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CN107790182B
CN107790182B CN201610754456.6A CN201610754456A CN107790182B CN 107790182 B CN107790182 B CN 107790182B CN 201610754456 A CN201610754456 A CN 201610754456A CN 107790182 B CN107790182 B CN 107790182B
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catalyst
isosorbide
nitrae
catalyst precarsor
diacetoxy
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CN107790182A (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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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds

Abstract

The present invention relates to 1,4- diacetoxy butylene hydrogenation process catalyst, mainly solve in the prior art 1, the low problem of the yield and selectivity of 4- diacetoxy butane, using 1,4- diacetoxy butylene hydrogenation process catalyst, including carrier and active component, the carrier is active carbon, active component includes Pt element and promoter elements, and the promoter elements include the technical solution selected from least one of lanthanide series metal metallic element, preferably solves the technical problem, it can be used in Isosorbide-5-Nitrae-diacetoxy butane industrial production.

Description

1,4- diacetoxy butylene hydrogenation process catalyst
Technical field
The present invention relates to 1,4- diacetoxy butylene hydrogenation process catalyst.
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 Isosorbide-5-Nitrae-diacetoxy butylene hydrogenation process catalyst, which has Isosorbide-5-Nitrae-diacetoxybut Alkane 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 conjunction using the 1,4- diacetoxy butane of above-mentioned catalyst At method.
In order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: Isosorbide-5-Nitrae-diacetoxy butylene adds hydrogen Process catalyst, including carrier and active component, the carrier are active carbon, and active component includes Pt element and co-catalyst Element, the promoter elements include selected from least one of lanthanide series 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, the promoter elements can further include at least one in VA race metallic element Kind metallic element.1,4- diethyl acyl-oxygen butane yield and 1,4- are being improved between VA race metallic element and lanthanide element at this time Diethyl acyl-oxygen butane selectivity aspect has synergistic effect.As non limiting example, such as, but not limited to bismuth is cooperateed with cerium, bismuth Cooperateed with samarium etc..
In above-mentioned technical proposal, lanthanide series metal preferably is selected from La, Ce, Pr, Nd, Sm, Eu, Yb and Lu in the hydrogenation catalyst At least one of.It further simultaneously include Ce, Sm, Ce, Sm are improving Isosorbide-5-Nitrae-diethyl acyl-oxygen butane yield and Isosorbide-5-Nitrae-diethyl Acyl-oxygen butane selectivity aspect has synergistic effect.
In above-mentioned technical proposal, VA race metal preferably is selected from least one of As, Sb and Bi in the hydrogenation catalyst, more It further preferably simultaneously include Sb and Bi.Sb and Bi is improving 1,4- diethyl acyl-oxygen butane yield and the choosing of 1,4- diethyl acyl-oxygen butane There is synergistic effect in terms of selecting property.
In above-mentioned technical proposal, the content of Pt is preferably 1.00~9.00g/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. 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. being supported on the solution of promoter elements on catalyst precarsor IV using infusion process by the composition of catalyst, do It is dry 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 the corresponding specific chemical combination of lanthanide element Object preferably is selected from lanthanum acetate, lanthanum nitrate, lanthanum chloride, lanthanum sulfate, cerium chloride, cerous nitrate, cerous acetate, praseodymium acetate, praseodymium chloride, nitric acid Praseodymium, acetic acid neodymium, neodymium chloride, acetic acid samarium, samarium trichloride, samaric nitrate, Europium chloride, europium nitrate, acetic acid europium, acetic acid ytterbium, ytterbium chloride, nitric acid At least one of ytterbium, lutecium chloride, lutecium nitrate and acetic acid lutetium；More preferably from least one of cerous acetate and acetic acid samarium.
In above-mentioned technical proposal, as non limiting example, when the promoter elements of step 5. further include VA race metal When element, the corresponding particular compound of VA race metallic element preferably is selected from basic bismuth carbonate, bismuth subnitrate, bismuth and ammonium citrate, sulfuric acid At least one of bismuth, bismuth acetate, bismuth nitrate, bismuth chloride, bismuth oxide, antimony oxide, antimony sulfate, antimony acetate and antimony chloride；It is more excellent Select at least one of bismuth and ammonium citrate and antimony acetate.
In above-mentioned technical proposal, the reducing agent of step 3. does not specially require understanding based on those skilled in the art, also Former agent can be at least one of gas or liquid, the preferred hydrogen of reducing agent, hydrazine hydrate；4. drying temperature is preferably step 30~120 DEG C, 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 butene reaction 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 VA race in the active component of hydrogenation catalyst At least one of metal metallic element and when selected from least one of group of the lanthanides race metal metallic element, achieves more prominent Technical effect, 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 cerous acetate (Ce (OAc) of the Ce containing 1.92g3·6H2O 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, Ce content 1.92g/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 82.49% 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 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 bismuth and ammonium citrate (Bi (NH of the Bi containing 1.92g3)2C6H7O7·4H2O aqueous solution 180ml) is immersed in catalysis On agent precursor I V, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Bi content 1.92g/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 82.18% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.27%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[comparative example 1]
For 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 75.22% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 91.36%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
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, Ce active component, simultaneously the catalyst performance containing Pt, Bi active component than the performance containing only Pt active constituent catalyst It is more excellent, illustrate activity of hydrocatalyst component while using containing Pt and selected from least one of VA race metal and lanthanide series metal Metallic element compound, be conducive to improve hydrogenation catalyst activity and stability, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity will be high.
[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 70.07% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 88.11%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
By can be seen that 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 acetic acid samarium (Sm (OAc) of the Sm containing 1.92g3·6H2O) 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, Sm content 1.92g/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 94.10%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 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 lanthanum acetate (La (OAc) of the La containing 1.92g3·5H2O) aqueous solution 180ml is immersed 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, La content 1.92g/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 82.48% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.13%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 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 praseodymium acetate (Pr (OAc) of the Pr containing 1.92g3·5H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, 120 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Pr content 1.92g/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 82.50% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.12%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 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 acetic acid lutetium (Lu (OAc) of the Lu containing 1.92g3·6H2O) 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, Lu content 1.92g/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 94.15%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 7]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH 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 antimony acetate (Sb (OAc) of the Sb containing 1.92g3) aqueous solution 180ml 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, Sb content 1.92g/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 82.17% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.31%, 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 acetic acid neodymium (Nd (OAc) of the Nd containing 1.00g2·6H2O) 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 1.50g/L, Nd 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 80.84% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 93.78%, 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 acetic acid ytterbium (Yb (OAc) of the Yb containing 6.00g3·6H2O) 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 5.00g/L, Yb 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 82.44% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.14%, 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 bismuth and ammonium citrate (Bi (NH of Bi containing the 1.21g and Sb containing 0.71g3)2C6H7O7·4H2) and antimony acetate (Sb O (OAc)3) 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, Bi content 1.21g/L, Sb content 0.71g/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 83.39% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.56%, 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 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 Bi and metallic element Sb have preferably in VA 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 cerous acetate (Ce (OAc) of Ce containing the 1.12g and Sm containing 0.80g3·6H2) and acetic acid samarium (Sm (OAc) O3· 6H2O) 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, Ce content 1.12g/L, Sm content 0.80g/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 83.60% 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 11 and embodiment 1 and embodiment 3, is improving Isosorbide-5-Nitrae-diacetoxy butane yield In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Ce and metallic element Sm have preferably in lanthanide series 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 bismuth and ammonium citrate (Bi (NH of Bi containing the 0.98g and Ce containing 0.94g3)2C6H7O7·4H2) and cerous acetate (Ce O (OAc)3·6H2O) 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, Bi content 0.98g/L, Ce content 0.94g/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 84.51% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.24%, 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 Bi and metal member in lanthanide series metal in VA race metal Plain Ce 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 bismuth and ammonium citrate (Bi (NH of Bi containing the 0.98g and Sm containing 0.94g3)2C6H7O7·4H2) and acetic acid samarium (Sm O (OAc)3·6H2O) 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, Bi content 0.98g/L, Sm content 0.94g/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 84.63% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.10%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 13 and embodiment 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 Bi and metal member in lanthanide series metal in VA race metal Plain Sm 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 bismuth and ammonium citrate (Bi (NH of Bi containing 0.98g, Ce containing 0.45g and the Sm containing 0.49g3)2C6H7O7· 4H2O), cerous acetate (Ce (OAc)3·6H2) and acetic acid samarium (Sm (OAc) O3·6H2O) 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, Bi content 0.98g/L, Ce content 0.45g/L, Sm content 0.49g/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 85.22% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.57%, 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 Rate and selectivity aspect, in the hydrogenation catalyst that the present invention uses, metal in metallic element Bi and lanthanide series metal in VA race metal Elements C e, Sm 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 antimony acetate (Sb (OAc) of Sb containing 0.98g, Ce containing 0.45g and the Sm containing 0.49g3), cerous acetate (Ce (OAc)3·6H2) and acetic acid samarium (Sm (OAc) O3·6H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Sb content 0.98g/L, Ce content 0.45g/L, Sm content 0.49g/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 85.30% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.45%, 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 bismuth and ammonium citrate (Bi (NH of Bi containing 0.62g, Sb containing 0.36g, Ce containing 0.45g and the Sm containing 0.49g3)2C6H7O7·4H2O), antimony acetate (Sb (OAc)3), cerous acetate (Ce (OAc)3·6H2) and acetic acid samarium (Sm (OAc) O3·6H2O) water 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, Bi content 0.62g/L, Sb content 0.36g/L, Ce content 0.45g/L, Sm content 0.49g/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 86.74% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.81%, 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 Rate and selectivity aspect, in the hydrogenation catalyst that the present invention uses, gold in metallic element Bi, Sb and lanthanide series metal in VA race metal Belonging to Elements C e, Sm has preferable synergistic effect.
Table 1
Table 2

Claims (7)

1. a kind of Isosorbide-5-Nitrae-diacetoxy butane production method, in the presence of a hydrogenation catalyst, hydrogen and Isosorbide-5-Nitrae-diethyl acyl-oxygen Base butylene carries out hydrogenation reaction and obtains 1,4- diacetoxy butane；The hydrogenation catalyst, including carrier and active component, institute The carrier stated is active carbon, and active component includes Pt element and promoter elements, and the promoter elements include being selected from lanthanum It is at least one of metal metallic element；
Wherein, in the hydrogenation catalyst Pt constituent content be 1.00~9.00g/L, promoter elements content be 0.50~ 10.00g/L。
2. Isosorbide-5-Nitrae according to claim 1-diacetoxy butane production method, which is characterized in that the active carbon is At least one of coal quality column charcoal, cocoanut active charcoal, apricot shell active carbon and activated carbon from bamboo.
3. Isosorbide-5-Nitrae according to claim 1-diacetoxy butane production method, which is characterized in that the active carbon Specific surface area is 1000~1500m2/ g, it is 0.60~1.00cm that adsorption hole, which holds,3/g。
4. Isosorbide-5-Nitrae according to claim 1-diacetoxy butane production method, which is characterized in that the hydrogenation catalyst Lanthanide series metal is selected from least one of La, Ce, Pr, Nd, Sm, Eu, Yb and Lu in agent.
5. Isosorbide-5-Nitrae according to any one of claims 1 to 4-diacetoxy butane production method, which is characterized in that The hydrogenation catalyst is prepared by the following method, and 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. the solution of promoter elements is supported on catalyst precarsor IV using infusion process by the composition of catalyst, dry To the catalyst.
6. Isosorbide-5-Nitrae according to claim 1-diacetoxy butane production method, which is characterized in that the temperature of hydrogenation reaction Degree is 20~120 DEG C.
7. Isosorbide-5-Nitrae according to claim 1-diacetoxy butane production method, which is characterized in that the pressure of hydrogenation reaction Power is 1.0~10.0MPa.
CN201610754456.6A 2016-08-29 2016-08-29 1,4- diacetoxy butylene hydrogenation process catalyst Active CN107790182B (en)

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CN101905158A (en) * 2010-07-21 2010-12-08 中国日用化学工业研究院 Platinum carbon catalyst for preparing alcohol ether carboxylic acid and preparation method and application thereof
CN105435786A (en) * 2014-09-25 2016-03-30 中国石油化工股份有限公司 Catalyst for producing 3-acetoxy propionaldehyde

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