CN108014794A - Synthesize the hydrogenation catalyst used in 1,4- diacetoxy butane - Google Patents

Synthesize the hydrogenation catalyst used in 1,4- diacetoxy butane Download PDF

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CN108014794A
CN108014794A CN201610967708.3A CN201610967708A CN108014794A CN 108014794 A CN108014794 A CN 108014794A CN 201610967708 A CN201610967708 A CN 201610967708A CN 108014794 A CN108014794 A CN 108014794A
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catalyst
hydrogenation catalyst
hydrogenation
nitrae
isosorbide
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CN108014794B (en
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查晓钟
杨运信
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—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
    • B01J23/628—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with lead
    • 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

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Abstract

The present invention relates to synthesis 1, hydrogenation catalyst used in 4 diacetoxy butane, mainly solve in the prior art 1, the problem of yield and low selectivity of 4 diacetoxy butane, using synthesis 1, hydrogenation catalyst used in 4 diacetoxy butane, including carrier and active component, the carrier is activated carbon, active component includes Pt elements and promoter elements, the promoter elements include the technical solution selected from least one of lanthanide series metal at least one of metallic element and IVA races metal metallic element, preferably solves the technical problem, available for 1, in the industrial production of 4 diacetoxy butane.

Description

Synthesize the hydrogenation catalyst used in 1,4- diacetoxy butane
Technical field
The present invention relates to the hydrogenation catalyst used in synthesis 1,4- diacetoxy butane.
Background technology
1,4-butanediol (Isosorbide-5-Nitrae-BDO) is a kind of important organic and fine chemical material, it be widely used in medicine, The fields such as chemical industry, weaving, papermaking, automobile and daily-use chemical industry.It can derive a series of fine chemical product of high added values. For example, tetrahydrofuran (THF), polybutylene terephthalate (PBT) (PBT), γ-fourth lactones (GBL) can be produced by Isosorbide-5-Nitrae-BDO With polyurethane resin (PU Resin), especially as production PBT engineering plastics and the base stock of PBT fibers, ground Study carefully the extensive concern of mechanism.
The process route of the preparation of 1,4-butanediol is relatively more, has acetylene, ethene, propylene, fourth from raw material used to divide The raw material route such as diene and cis-butenedioic anhydride, identical raw material also have different synthesis techniques.Since technical barrier is higher and raw material sources Limited, global Isosorbide-5-Nitrae-BDO produces Relatively centralized.2011, global Isosorbide-5-Nitrae-BDO production capacities were mainly distributed on Asia, US and European, Wherein Asia 1,4-BDO production capacities accounting is up to 56.6%.At present, the industrialized preparing process of Isosorbide-5-Nitrae-BDO mainly includes：1. alkynes aldehyde Method (Reppe methods)：This method does catalyst generation butynediols, butynediols using acetylene and formaldehyde as raw material, using methanol copper Two-stage hydrogenation obtains 1,4-BDO again.Its prevailing technology mainly have BASF Corp. of Germany, the U.S. DuPont exploitation Reppe methods with And the Reppe methods of improvement.2. maleic anhydride process：This method carries out it two step hydrogenation using cis-butenedioic anhydride as raw material.The first step is urged in Ni-Re Under agent effect, maleic anhydride hydrogenation generation gamma-butyrolacton and tetrahydrofuran；Second step gamma-butyrolacton is in Mo-Cr-K2O catalyst is made 1,4-BDO is hydrogenated under.Its prevailing technology is mainly the two-stage hydrogenation work with Japanese two water chestnut oilings and Mitsubishi's chemical conversion exploitation Skill.3. propylene method：Mainly include allyl acetate method, acryladehyde method and allyl acetate-allyl alcohol method, Kuraray company exploitation at present Allyl acetate-allyl alcohol method has obtained commercial Application, it is the allyl alcohol liquid-phase hydrogenatin formylated generation 4- hydroxyl fourths under rhodium catalyst Aldehyde, then repeated hydrogenation generation 1,4-butanediol.4. butadiene process：The method that Isosorbide-5-Nitrae-BDO is produced using butadiene as raw material, main bag Butadiene acetoxylation method and butadiene chloridising are included, the technique of its mainstream is melted into by Mitsubishi and Cao Da companies are in 20 generation Exploitation in 80 years of recording forms, it successfully breaks the technical barrier and obstacle of Reppe methods.Especially butadiene acetoxylation method is excellent Gesture and prospect, have obtained the favor of domestic and international research institution.
It is well known that butadiene acetoxylation method is a three-steps process, i.e., butadiene is sent out with acetic acid, oxygen first Raw acetylization reaction, generates Isosorbide-5-Nitrae-diacetoxy butylene and accessory substance 3.4- diacetoxy butylene；Then 1,4- diacetyl Epoxide butylene catalytic hydrogenation generates Isosorbide-5-Nitrae-diene acetoxyl group butane, and reaction is finally hydrolyzed and obtains Isosorbide-5-Nitrae-BDO.In Isosorbide-5-Nitrae-fourth Diene is into 1,4-butanediol process route, Isosorbide-5-Nitrae-diacetoxy butylene catalytic hydrogenation generation Isosorbide-5-Nitrae-diene acetoxyl group butane As one of step, the yield and selectivity of hydrogenation products directly influence 1,4-butanediol relative to Isosorbide-5-Nitrae-butadiene Yield and selectivity.
Teach in the patents such as patent US4032458 (production of 1,4-butanediol) and urged using furans Agent exists, and 1,4-butanediol is prepared under the conditions of certain temperature and pressure.Patent CN94108094.3 (the systems of 1,4- butanediols Preparation Method) describe using cis-butenedioic anhydride as raw material, gas phase catalytic hydrogenation reaction is carried out in the presence of the catalyst specifically designed and is prepared 1,4- butanediols.Patent CN104326871A (a kind of preparation method of butanediol) is described using fixed-bed catalytic technology, will Content more than 99% 2- butylene mixed with acetic acid, nitrogen, oxygen and water vapour high temperature after be passed through in fixed bed, catalyst with 1,4- butanediols are prepared under the conditions of certain temperature, pressure etc..But there are 1,4- during 1,4-BDO is prepared for the above method The problem of BDO yields are low and selective not high.
The content of the invention
The problem of technical problems to be solved by the invention are the yield and low selectivity of 1,4-butanediol, there is provided Yi Zhongxin Synthesis Isosorbide-5-Nitrae-diacetoxy butane used in hydrogenation catalyst, which has Isosorbide-5-Nitrae-diacetoxy butane high income And the characteristics of high selectivity.
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.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Synthesize 1,4- diacetoxies Hydrogenation catalyst used in butane, including carrier and active component, the carrier are activated carbon, and active component includes Pt elements And promoter elements, the promoter elements are included selected from least one of lanthanide series metal metallic element and IVA races metal At least one of metallic element.
In above-mentioned technical proposal, the activated carbon is preferably coal quality column charcoal, cocoanut active charcoal, apricot shell activated carbon and bamboo matter At least one of activated carbon.
In above-mentioned technical proposal, the specific surface area of the activated carbon is preferably 1000~1500cm2/ g, absorption pore volume are preferred For 0.60~1.00cm3/g。
In above-mentioned technical proposal, in the hydrogenation catalyst group of the lanthanides race metal preferably be selected from La, Ce, Pr, Nd, Sm, Eu, Yb and At least one of Lu.Further include La, Lu at the same time.La, Lu are improving 1,4- diethyls acyl-oxygen butane yield and 1,4- bis- Acetyl oxygen butane selectivity aspect has synergistic effect.
In above-mentioned technical proposal, IVA races metal is selected from least one of Ge, Sn and Pb in the hydrogenation catalyst, more Further preferably include Sn and Pb at the same time.Sn and Pb is improving 1,4- diethyls acyl-oxygen butane yield and the choosing of 1,4- diethyl acyl-oxygens butane There is synergistic effect in terms of selecting property.
In above-mentioned technical proposal, the promoter elements are preferably at the same time including at least one in lanthanide element Kind and selected from least one of IVA races metallic element, at this time in the metallic element in group of the lanthanides and IVA races metal metallic element it Between there is synergistic effect in terms of 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane selectivity is improved.As non-limit Property citing processed, such as, but not limited to lanthanum are cooperateed with tin, and lanthanum is cooperateed with lead etc..
In above-mentioned technical proposal, the content of Pt is preferably 1.00~8.00g/L in the hydrogenation catalyst, more preferably 1.50~5.00g/L.
In above-mentioned technical proposal, promoter elements content is preferably 0.50~10.00g/L in the hydrogenation catalyst, More preferably 1.00~6.00g/L.
To solve the two of above-mentioned technical problem, technical scheme is as follows：
Hydrogenation catalyst preparation method any one of the technical solution of one of above-mentioned technical problem, including following step Suddenly：
1. mixing the solution of platiniferous element with carrier by the composition of catalyst, catalyst precarsor I is obtained；
Catalyst precarsor II is obtained after 2. catalyst precarsor I is aged；
3. being simple substance platinum by compound state platinum element reduction in catalyst precarsor II, catalyst precarsor III is obtained；
4. through washing, being dried to obtain catalyst precarsor IV；
5. the solution containing promoter elements is supported on catalyst precarsor IV using infusion process by the composition of catalyst, It is dried to obtain the catalyst.
In above-mentioned technical proposal, as non-restrictive, 1. the corresponding particular compound of platinum element preferably is selected from vinegar to step At least one of sour platinum, platinum chloride, ammonium chloroplatinite, dinitroso diammonia platinum, chloroplatinic acid and four ammino platinum chlorides；More preferably Ammonium chloroplatinite.
In above-mentioned technical proposal, as non limiting example, when step 5. in promoter elements include lanthanide series metal During element, the corresponding particular compound of lanthanide element preferably be selected from lanthanum acetate, lanthanum nitrate, lanthanum chloride, lanthanum sulfate, cerium chloride, Cerous nitrate, cerous acetate, praseodymium acetate, praseodymium chloride, praseodymium nitrate, acetic acid neodymium, neodymium chloride, acetic acid samarium, samarium trichloride, samaric nitrate, Europium chloride, At least one of europium nitrate, acetic acid europium, acetic acid ytterbium, ytterbium chloride, ytterbium nitrate, lutecium chloride, lutecium nitrate and acetic acid lutetium；More preferably certainly At least one of lanthanum acetate and acetic acid lutetium.
In above-mentioned technical proposal, as non limiting example, when step 5. in promoter elements include IVA races metal During element, it is sub- that the corresponding particular compound of IVA races metallic element preferably is selected from tetraethyl germanium, tetraphenyl germanium, germanium tetrachloride, oxalic acid Tin, stannous chloride, nitric acid stannous, stannous acetate, stannous oxide, lead acetate, lead stearate, basic lead carbonate, basic lead acetate At least one of with plumbi nitras；More preferably from least one of stannous acetate and lead acetate.
In above-mentioned technical proposal, the reducing agent of step 3. does not specially require understanding based on those skilled in the art, also Former agent can be at least one of gas or liquid, the preferred hydrogen of reducing agent, hydrazine hydrate；4. drying temperature is preferably step 30~120 DEG C, when drying time is preferably 1~5 small；5. the drying temperature is preferably 80~120 DEG C to step, more preferably 100~120 DEG C.
To solve the three of above-mentioned technical problem, technical scheme is as follows：
The synthetic method of Isosorbide-5-Nitrae-diacetoxy butane, any one of the technical solution in one of above-mentioned technical problem In the presence of hydrogenation catalyst, hydrogen obtains Isosorbide-5-Nitrae-diacetoxy butane with Isosorbide-5-Nitrae-diacetoxy butene reaction.
The key of the present invention is the selection of hydrogenation catalyst, and skilled person will know how definite according to being actually needed Suitably proportioning of hydrogenation process conditions reaction temperature, reaction time, reaction pressure and material etc..But：
In above-mentioned technical proposal, the temperature of hydrogenation reaction is preferably 20~120 DEG C.
In above-mentioned technical proposal, the pressure of hydrogenation reaction is preferably 1.0~10.0MPa, more preferably 1.0~6.0MPa.
In above-mentioned technical proposal, the time of hydrogenation reaction is preferably 0.5~5.0h, more preferably 0.5~2.0h.
Isosorbide-5-Nitrae-diacetoxy butylene can be obtained from commercially available channel, or butadiene Acetoxylation method can be used to synthesize.Fourth It is butadiene Acetoxylation catalyst that Pd-Te/C, which can be selected, in the synthesis of diene Acetoxylation method.Palladium in suitable Pd-Te/C catalyst The content of element preferably 2.50~5.00g/L, more preferably 3.00~4.50g/L；The content of tellurium element preferably 0.50~3.00g/ L, more preferably 1.00~2.50g/L.Suitable Acetoxylation reaction temperature is preferably 40~150 DEG C；Acetoxylation reaction pressure It is preferred that 1.0~10.0MPa；The Acetoxylation reaction time is preferably 0.5~5h；The molar ratio of butadiene and acetic acid preferably 0.010 ~2.0.After the reaction of butadiene Acetoxylation, the mixture that can be reacted butadiene Acetoxylation carries out separation acquisition target production Thing Isosorbide-5-Nitrae-diacetoxy butylene carries out hydrogenation reaction of the present invention again, can not also separate and directly carry out hydrogenation reaction.But Cause system complicated easy to year-on-year to exclude other impurity, specific embodiment of the invention department uses pure Isosorbide-5-Nitrae-diacetyl Epoxide butylene is as hydrogenation reaction raw material.
The product mixtures of above-mentioned hydrogenation reaction can obtain target product 1,4- diacetoxy butane through separation.
1,4- diacetoxies butane can be further used for obtaining 1,4- butanediols by method for hydrolysis.Art technology The suitable hydrolyst of the known selection of personnel and definite suitable hydrolysising reacting temperature, time and material proportion.Common water It can be inorganic acid, inorganic base, organic acid and organic base to solve catalyst.Such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sodium hydroxide, Potassium hydroxide, benzene sulfonic acid and ion exchange resin.Suitable hydrolysising reacting temperature is preferably 30~100 DEG C；Hydrolysis pressure Power preferably 0~2.0MPa；The preferred water of solvent.
Product mixtures after hydrogenation reaction of the present invention are analyzed through gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), by following Formula calculates the yield and selectivity of 1,4- diacetoxy butane：
Compared with prior art, hydrogenation catalyst of the present invention improves the yield and selectivity of Isosorbide-5-Nitrae-diethyl acyl-oxygen butane.
Test result indicates that during using the present invention, Isosorbide-5-Nitrae-diacetoxy butane yield selectively reaches up to 82.49% 94.18%, achieve preferable technique effect.Especially include platinum at the same time, selected from group of the lanthanides in the active component of hydrogenation catalyst At least one of metal metallic element and during selected from least one of IVA races metal metallic element, achieves more prominent Technique effect.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the lanthanum acetate (La (OAc) of the La containing 1.90g3·5H2O aqueous solution 180ml) is immersed in catalyst precarsor IV On, when 110 DEG C of dryings 4 are small, obtain the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, La contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.49%, and 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 containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the lead acetate (Pb (OAc) of the Pb containing 1.90g2·3H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, When 110 DEG C of dryings 4 are small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Pb contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.35%, and selectivity is 94.24%, 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.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 75.15%, and selectivity is 91.33%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
By the way that, as can be seen that the present invention uses the catalyst of hydrogenation, its active component makes at the same time compared with embodiment 1~2 With the catalyst performance containing Pt, La active component while containing Pt, Pb active component than the performance containing only Pt active constituent catalysts It is more excellent, illustrate activity of hydrocatalyst component include the use of at the same time containing Pt and in lanthanide series metal and IVA races metal extremely A kind of few metallic element compound, is conducive to improve the activity and stability of hydrogenation catalyst, Isosorbide-5-Nitrae-diacetoxy butane Yield and selectivity will be high.
【Comparative example 2】
For【Comparative example 1】Comparative example.
The preparation of hydrogenation catalyst：
1. by the ammonium chloropalladite ((NH containing 2.05gPd4)2PdCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, the catalyst is obtained.
The Pd contents that the catalyst is measured through ICP are 2.05g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 70.10%, and selectivity is 88.03%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
By can be seen that catalyst of the present invention using hydrogenation compared with comparative example 1, contained using the ratio of active component containing Pt The performance of Pd active constituent catalysts is more excellent, illustrates that activity of hydrocatalyst component is conducive to Isosorbide-5-Nitrae-diacetoxy using Pt Butylene is hydrogenated with, and the yield and selectivity of Isosorbide-5-Nitrae-diacetoxy butane will be high.
【Embodiment 3】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the stannous acetate (Sn (OAc) of the Sn containing 1.90g2·2H2O) it is dissolved in the aqueous acetic acid that concentration is 10wt% In, maceration extract 180ml is obtained, is immersed on catalyst precarsor IV, when 110 DEG C of dryings 4 are small, obtains the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Sn contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.38%, and selectivity is 94.29%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 4】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.60cm3/ g, specific surface area 1000cm2The coconut husk circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the cerous acetate (Ce (OAc) of the Ce containing 1.90g3·6H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, When 100 DEG C of dryings 4 are small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Ce contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.46%, and selectivity is 94.14%, 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 5】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 1.00cm3/ g, specific surface area 1500cm2The apricot shell circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the praseodymium acetate (Pr (OAc) of the Pr containing 1.90g3·5H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, When 120 DEG C of dryings 4 are small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Pr contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.45%, and selectivity is 94.17%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 6】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The bamboo circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the acetic acid neodymium (Nd (OAc) of the Nd containing 1.90g2·6H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, When 110 DEG C of dryings 4 are small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Nd contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.47%, and 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 7】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the acetic acid lutetium (Lu (OAc) of the Lu containing 1.90g3·6H2O) aqueous solution 180ml, is immersed in catalyst precarsor IV On, when 110 DEG C of dryings 4 are small, obtain the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Lu contents 1.90g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 50 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.45%, and selectivity is 94.20%, 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.
【Embodiment 8】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 1.50gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the acetic acid europium (Eu (OAc) of the Eu containing 1.00g3·6H2O) aqueous solution 180ml, is immersed in catalyst precarsor IV On, when 110 DEG C of dryings 4 are small, obtain the catalyst.
The Pt contents that the catalyst is measured through ICP are 1.50g/L, Eu contents 1.00g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 1.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 20 DEG C, after sustained response 30min, stops anti- Should.Reaction kettle is down to room temperature, purified removal of impurities obtains Isosorbide-5-Nitrae-diacetoxy butane.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 80.62%, and selectivity is 93.92%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 9】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 5.00gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the acetic acid ytterbium (Yb (OAc) of the Yb containing 6.00g3·6H2O) aqueous solution 180ml, is immersed in catalyst precarsor IV On, when 110 DEG C of dryings 4 are small, obtain the catalyst.
The Pt contents that the catalyst is measured through ICP are 5.00g/L, Yb contents 6.00g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 6.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 120 DEG C, after sustained response 120min, is stopped Reaction.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.54%, and 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 10】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the lanthanum acetate (La (OAc) of La containing the 1.20g and Lu containing 0.70g3·5H2) and acetic acid lutetium (Lu (OAc) O3· 6H2O aqueous solution 180ml) is immersed on catalyst precarsor IV, when 110 DEG C of dryings 4 are small, obtains the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, La contents 1.20g/L, Lu content 0.70g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 83.43%, and selectivity is 94.35%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 10 and embodiment 1 and embodiment 7, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane In the hydrogenation catalyst used with selective aspect, the present invention, metallic element La and metallic element Lu has preferably in lanthanide series metal Synergistic effect.
【Embodiment 11】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the lead acetate (Pb (OAc) of Pb containing the 0.90g and Sn containing 1.00g2·3H2) and stannous acetate (Sn O (OAc)2·2H2O) it is dissolved in the aqueous acetic acid that concentration is 10wt%, obtains maceration extract 180ml, be immersed in catalyst precarsor On IV, when 110 DEG C of dryings 4 are small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Pb contents 0.90g/L, Sn content 1.00g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 83.31%, and selectivity is 94.46%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 11 and embodiment 2 and embodiment 3, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Pb and metallic element Sn has preferably in IVA races metal Synergistic effect.
【Embodiment 12】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the lanthanum acetate (La (OAc) of La containing the 1.09g and Pb containing 0.81g3·5H2) and lead acetate (Pb (OAc) O2· 3H2O 180ml in aqueous solution), is immersed on catalyst precarsor IV, when 110 DEG C of dryings 4 are small, obtains the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, La contents 1.09g/L, Pb content 0.81g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 84.39%, and selectivity is 95.03%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 2, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane In the hydrogenation catalyst used with selective aspect, the present invention, metallic element La and metal member in IVA races metal in lanthanide series metal Plain Pb has preferable synergistic effect.
【Embodiment 13】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the lanthanum acetate (La (OAc) of La containing the 1.09g and Sn containing 0.81g3·5H2) and stannous acetate (Sn O (OAc)2·2H2O) it is dissolved in the aqueous acetic acid that concentration is 10wt%, obtains maceration extract 180ml, be immersed in catalyst precarsor On IV, when 110 DEG C of dryings 4 are small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, La contents 1.09g/L, Sn content 0.81g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 84.33%, and selectivity is 95.11%, 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.
Found out on year-on-year basis by embodiment 13 and embodiment 1 and embodiment 3, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane In the hydrogenation catalyst used with selective aspect, the present invention, metallic element La and metal member in IVA races metal in lanthanide series metal Plain Sn has preferable synergistic effect.
【Embodiment 14】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the lanthanum acetate (La (OAc) of La containing 1.09g, Pb containing 0.35g and the Sn containing 0.46g3·5H2O), lead acetate (Pb(OAc)2·3H2) and stannous acetate (Sn (OAc) O2·2H2O) it is completely dissolved in the aqueous acetic acid that concentration is 10wt% In, maceration extract 180ml is obtained, is immersed on catalyst precarsor IV, when 110 DEG C of dryings 4 are small, obtains the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, La contents 1.09g/L, Pb content 0.35g/L, Sn content 0.46g/L。
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 85.27%, and 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.
Found out on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13, improving the receipts of Isosorbide-5-Nitrae-diacetoxy butane In terms of rate and selectivity, in the hydrogenation catalyst that the present invention uses, metal in metallic element La and IVA races metal in lanthanide series metal Elements Pb, Sn have preferable synergistic effect.
【Embodiment 15】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the acetic acid lutetium (Lu (OAc) of Lu containing 1.09g, Pb containing 0.35g and the Sn containing 0.46g3·6H2O), lead acetate (Pb(OAc)2·3H2) and stannous acetate (Sn (OAc) O2·2H2O) it is completely dissolved in the aqueous acetic acid that concentration is 10wt% In, maceration extract 180ml is obtained, is immersed on catalyst precarsor IV, when 110 DEG C of dryings 4 are small, obtains the catalyst.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, Lu contents 1.09g/L, Pb content 0.35g/L, Sn content 0.46g/L。
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 85.17%, and selectivity is 95.48%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 16】
The preparation of hydrogenation catalyst：
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtains catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced 3h, obtains catalyst precarsor III；
4. through being washed to no chlorion, when 50 DEG C of dryings 4 are small, catalyst precarsor IV is obtained；
5. by the lanthanum acetate (La (OAc) of La containing 0.69g, Lu containing 0.40g, Pb containing 0.35g and the Sn containing 0.46g3· 5H2O), acetic acid lutetium (Lu (OAc)3·6H2O), lead acetate (Pb (OAc)2·3H2) and stannous acetate (Sn (OAc) O2·2H2O) fill Divide and be dissolved in the aqueous acetic acid that concentration is 10wt%, obtain maceration extract 180ml, be immersed on catalyst precarsor IV, 110 DEG C When drying 4 is small, the catalyst is obtained.
The Pt contents that the catalyst is measured through ICP are 2.05g/L, La contents 0.69g/L, Lu content 0.40g/L, Pb content 0.35g/L, Sn content 0.46g/L.
1,4- diacetoxy butylene hydrogenation reactions：
1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into the reaction of 100ml titaniums Kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to hydrogen until pressure 3.0MPa, improves mixing speed To 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, after sustained response 90min, stops anti- Should.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 86.37%, and selectivity is 95.59%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, improving the receipts of Isosorbide-5-Nitrae-diacetoxy butane In terms of rate and selectivity, in the hydrogenation catalyst that the present invention uses, in lanthanide series metal in metallic element La, Lu and IVA races metal Metallic element Pb, Sn have preferable synergistic effect.
Table 1
Table 2

Claims (9)

1. the hydrogenation catalyst used in Isosorbide-5-Nitrae-diacetoxy butane is synthesized, including carrier and active component, the carrier are Activated carbon, active component include Pt elements and promoter elements, and the promoter elements are included in lanthanide series metal extremely A kind of at least one of few metallic element and IVA race metal metallic element.
2. hydrogenation catalyst according to claim 1, it is characterised in that the activated carbon is coal quality column charcoal, coconut activated At least one of charcoal, apricot shell activated carbon and activated carbon from bamboo.
3. hydrogenation catalyst according to claim 1, it is characterised in that the specific surface area of the activated carbon for 1000~ 1500cm2/ g, absorption pore volume are 0.60~1.00cm3/g。
4. hydrogenation catalyst according to claim 1, it is characterised in that in the hydrogenation catalyst lanthanide series metal be selected from La, At least one of Ce, Pr, Nd, Sm, Eu, Yb and Lu.
5. hydrogenation catalyst according to claim 1, it is characterised in that IVA races metal is selected from the hydrogenation catalyst At least one of Ge, Sn and Pb.
6. hydrogenation catalyst according to claim 1, it is characterised in that Pt constituent contents are in the hydrogenation catalyst 1.00~8.00g/L.
7. hydrogenation catalyst according to claim 1, it is characterised in that promoter elements content is in hydrogenation catalyst 0.50~10.00g/L.
8. the preparation method of the hydrogenation catalyst described in claim 1, includes the following steps：
1. mixing the solution of platiniferous element with carrier by the composition of catalyst, catalyst precarsor I is obtained；
Catalyst precarsor II is obtained after 2. catalyst precarsor I is aged；
3. being simple substance platinum by compound state platinum element reduction in catalyst precarsor II, catalyst precarsor III is obtained；
4. through washing, being dried to obtain catalyst precarsor IV；
5. the solution containing promoter elements is supported on catalyst precarsor IV using infusion process by the composition of catalyst, it is dry Obtain the catalyst.
The synthetic method of 9.1,4- diacetoxy butane, exists in hydrogenation catalyst any one of claim 1~7 Under, hydrogen obtains Isosorbide-5-Nitrae-diacetoxy butane with Isosorbide-5-Nitrae-diacetoxy butene reaction.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN104368364A (en) * 2014-11-10 2015-02-25 华玉叶 Preparation method of catalyst for preparing propylene by virtue of propane dehydrogenation
CN104971740A (en) * 2015-07-18 2015-10-14 西安凯立化工有限公司 Catalyst for continuously preparing N-isopropyl-4-fluoroanilines, and preparation method and application of catalyst
CN105148935A (en) * 2015-07-18 2015-12-16 西安凯立化工有限公司 Catalyst for producing 2,3,4-trifluoroaniline and preparation method therefor and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104368364A (en) * 2014-11-10 2015-02-25 华玉叶 Preparation method of catalyst for preparing propylene by virtue of propane dehydrogenation
CN104971740A (en) * 2015-07-18 2015-10-14 西安凯立化工有限公司 Catalyst for continuously preparing N-isopropyl-4-fluoroanilines, and preparation method and application of catalyst
CN105148935A (en) * 2015-07-18 2015-12-16 西安凯立化工有限公司 Catalyst for producing 2,3,4-trifluoroaniline and preparation method therefor and application thereof

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