CN107778135A - The method for producing 1,4 butanediols - Google Patents
The method for producing 1,4 butanediols Download PDFInfo
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- CN107778135A CN107778135A CN201610750990.XA CN201610750990A CN107778135A CN 107778135 A CN107778135 A CN 107778135A CN 201610750990 A CN201610750990 A CN 201610750990A CN 107778135 A CN107778135 A CN 107778135A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
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- 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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- 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 production Isosorbide-5-Nitrae butanediol method, mainly solve in the prior art due to Isosorbide-5-Nitrae diacetoxy butylene be hydrogenated with after yield and poor selectivity, cause Isosorbide-5-Nitrae diacetoxy butane hydrolyze after Isosorbide-5-Nitrae butanediol yield and selectivity it is low the problem of.The method for producing Isosorbide-5-Nitrae butanediol, comprises the following steps：Using butadiene, acetic acid and oxygen as raw material, Acetoxylation reaction is carried out in the presence of Acetoxylation catalyst and obtains Isosorbide-5-Nitrae diacetoxy butylene；In the presence of a hydrogenation catalyst, hydrogen obtains Isosorbide-5-Nitrae diacetoxy butane with Isosorbide-5-Nitrae diacetoxy butene reaction；The hydrolysis of 1,4 diacetoxy butane obtains 1,4 butanediols；Wherein, described hydrogenation catalyst uses activated carbon as carrier, and active component includes Pt elements and promoter elements, and the promoter elements are included selected from least one of VA races metal and lanthanide series metal metallic element.
Description
Technical field
The present invention relates to the method for production 1,4- butanediols.
Background technology
BDO (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 BDO 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.Because technology barriers are 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, Isosorbide-5-Nitrae-BDO industrialized preparing process 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 two step hydrogenation to it 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 that exploitation is melted into Japanese two water chestnut oilings and Mitsubishi
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, and it is the allyl alcohol liquid-phase hydrogenatin formylated generation 4- hydroxyl fourths under rhodium catalyst
Aldehyde, then repeated hydrogenation generation BDO.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 main flow is melted into by Mitsubishi and Cao Da companies are in 20 generation
Exploitation in 80 years of recording forms, and it successfully breaks the technology barriers and obstacle of Reppe methods.Especially butadiene acetoxylation method is excellent
Gesture and prospect, the favor of domestic and international research institution is obtained.
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 BDO 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 BDO 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 is present, and BDO 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 synthesized under the conditions of certain temperature, pressure etc..But there is 1,4- in the above method during 1,4-BDO is prepared
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 BDO, there is provided Yi Zhongxin
Production BDO method, this method have BDO high income and selectivity it is high the characteristics of.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：The method for producing BDO, bag
Include following steps：(1) using butadiene, acetic acid and oxygen as raw material, it is anti-that Acetoxylation is carried out in the presence of Acetoxylation catalyst
1,4- diacetoxy butylene should be obtained；(2) in the presence of a hydrogenation catalyst, hydrogen and Isosorbide-5-Nitrae-diacetoxy butene reaction are made
Obtain 1,4- diacetoxy butane；(3) 1,4- diacetoxies butane hydrolysis obtains 1,4- butanediols；Wherein, it is described plus
Hydrogen catalyst uses activated carbon as carrier, and active component includes Pt elements and promoter elements, the promoter elements bag
Include selected from least one of VA races metal and lanthanide series metal metallic element.
In above-mentioned technical proposal, the activated carbon is preferably ature of coal 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, VA races metal preferably is selected from least one of As, Sb and Bi in the hydrogenation catalyst, more
Further preferably include Sb and Bi simultaneously.Sb and Bi is improving 1,4- diethyls acyl-oxygen butane yield and the choosing of 1,4- diethyl acyl-oxygens butane
There is synergy in terms of selecting property.
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.Further include Ce, Sm simultaneously.Ce, Sm are improving 1,4- diethyls acyl-oxygen butane yield and 1,4- diethyls
Acyl-oxygen butane selectivity aspect has synergy.
In above-mentioned technical proposal, the promoter elements are preferably simultaneously including at least one in VA races metallic element
Kind and selected from least one of lanthanide element, now between VA races metallic element and lanthanide element improve Isosorbide-5-Nitrae-
There is synergy in terms of diethyl acyl-oxygen butane yield and 1,4- diethyl acyl-oxygens butane.As non limiting example, such as but not
It is limited to bismuth to cooperate with cerium, bismuth cooperates with samarium etc..
In above-mentioned technical proposal, Pt content 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.
In above-mentioned technical proposal, hydrogenation catalyst can use the process comprised the following steps to obtain：
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. 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. particular compound corresponding to 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 VA races metal
During element, particular compound corresponding to VA races 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, as non limiting example, when step 5. in promoter elements include lanthanide series metal
During element, particular compound corresponding to 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 cerous acetate and acetic acid samarium.
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.
The key of the present invention is the selection of hydrogenation catalyst, and skilled person will know how basis to be actually needed determination
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.
In the method for present invention production BDO, the known suitable butadiene oxygen acetyl of selection of those skilled in the art
Change catalysts and determine suitable reaction temperature, time and material proportion.The such as, but not limited to active constituent of catalyst
Based on Pd or Rh, it is auxiliary ingredients to add Te, Se, Sb, Bi, V etc..Carrier used can be activated carbon, aluminium glue, silica gel or
Molecular sieve.
Preferred Pd-Te/C is butadiene Acetoxylation catalyst in the present invention.Palladium element in suitable Pd-Te/C catalyst
Content 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
It is preferred that 1.00~2.50g/L.Suitable Acetoxylation reaction temperature is preferably 40~150 DEG C；Acetoxylation reaction pressure is preferred
1.0~10.0MPa；The Acetoxylation reaction time is preferably 0.5~5h；The mol ratio of butadiene and acetic acid preferably 0.010~
2.0.After terminating for step (1), the mixture that butadiene Acetoxylation can be reacted carry out separation obtain target product Isosorbide-5-Nitrae-
Diacetoxy butylene carries out step (2) again, can also not separated directly after step (1) generation Isosorbide-5-Nitrae-diacetoxy butylene
Tap into row step (2).But system complexity is caused to be easy on year-on-year basis in order to exclude other impurity, specific embodiment of the invention department is equal
Step (2) is carried out using the isolated pure 1,4- diacetoxies butylene of step (1) mixture of reaction products.
After step (2) terminates, separation can be carried out to the mixture of hydrogenation reaction and obtains target product Isosorbide-5-Nitrae-diethyl acyl-oxygen
Base butane carries out step (3) again, can not also separate and is directly walked after step (2) generation Isosorbide-5-Nitrae-diacetoxy butane
Suddenly (3).The suitable hydrolyst of the known selection of those skilled in the art and determination suitable hydrolysising reacting temperature, time and thing
Material proportioning.Conventional hydrolyst 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
℃；Hydrolysis pressure preferably 0~2.0MPa；The preferred water of solvent.
Because the key of the present invention is step (2), in order to year-on-year, non-restrictive is also served as, the present invention is specific real
The step of applying mode part (1) is carried out using following specific method：
The synthesis of 1,4- butanediols：
Step (1)：By 2.10mol acetic acid, 12.8g Pd-Te/C, (Pd constituent contents are 3.80g/L, and Te constituent contents are
1.85g/L) catalyst is added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, is then passed to
Butadiene and oxygen improve mixing speed to 1000rpm until pressure 6.8MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 80 DEG C, and the mol ratio of butadiene and oxygen is 1:After 1, sustained response 5.0h, stop reaction.By reactor
Room temperature is down to, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, through rectification and purification, obtains Isosorbide-5-Nitrae-diacetyl
Epoxide butylene.
Because the key of the present invention is step (2), in order to make it easy to understand, non-restrictive is also served as, present invention tool
The step of body embodiment part (3), can use following specific method to carry out：
Step (3)：By above-mentioned 1,4- diacetoxies butane 18ml, 30ml toluene-water, (10ml toluene and 20ml water mix
Into), 0.015mol benzene sulfonic acids add 100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, rise
Temperature stirs constant temperature 5h to 30 DEG C.
Step (2) final product mixture of the present invention is 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, key of the invention is the new hydrogenation catalyst that step (2) uses, and improves Isosorbide-5-Nitrae-two
The yield and selectivity of acetyl 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 simultaneously, selected from VA races in the active component of hydrogenation catalyst
At least one of metal metallic element and during selected from least one of group of the lanthanides race metal metallic element, is achieved more prominent
Technique effect, available in the industrial production of BDO.Below by embodiment, the present invention is further elaborated.
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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
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 of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Ce contents 1.92g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
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 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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
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 of dryings 4 hours, the catalyst is obtained.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Bi contents 1.92g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.18%, and selectivity is 94.27%, for the ease of
Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of 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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, the catalyst is obtained.
The Pt contents that the catalyst is determined through ICP are 2.05g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 75.22%, and 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 simultaneously, as can be seen that the present invention uses the catalyst of hydrogenation, its active component makes compared with embodiment 1~2
With the catalyst performance containing Pt, Ce active component while containing Pt, Bi active component than the performance containing only Pt active constituent catalysts
It is more excellent, illustrate activity of hydrocatalyst component while using containing Pt and selected from least one of VA races metal and lanthanide series metal
Metallic element compound, be advantageous to improve hydrogenation catalyst activity and stability, the yield of Isosorbide-5-Nitrae-diacetoxy butane 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 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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, the catalyst is obtained.
The Pd contents that the catalyst is determined through ICP are 2.05g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 70.07%, and selectivity is 88.11%, for the ease of
Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and
Selectivity is listed in Tables 1 and 2 respectively.
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 advantageous 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 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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
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 of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Sm contents 1.92g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.53%, and selectivity is 94.10%, for the ease of
Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 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 diameters 3mm, long 2cm, pore volume 0.60cm3/ g, specific surface area 1000cm2/ g coconut husk
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
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 of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, La contents 1.92g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.48%, and 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 diameters 3mm, long 2cm, pore volume 1.00cm3/ g, specific surface area 1500cm2/ g apricot shell
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
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 of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Pr contents 1.92g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.50%, and selectivity is 94.12%, for the ease of
Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 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 diameters 3mm, long 2cm, pore volume 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. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by the acetic acid lutetium (Lu (OAc) of the Lu containing 1.92g3·6H2O) aqueous solution 180ml, it is immersed in catalyst precarsor IV
On, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Lu contents 1.92g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.54%, and selectivity is 94.15%, for the ease of
Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 7】
The preparation of 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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
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
Dry 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Sb contents 1.92g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 50 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.17%, and 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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
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 of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 1.50g/L, Nd contents 1.00g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 1.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 20 DEG C, sustained response 30min
Afterwards, reaction is stopped.Reactor 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 80.84%, and 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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, 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 on catalyst precarsor IV,
110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 5.00g/L, Yb contents 6.00g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 6.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 120 DEG C, sustained response
After 120min, stop reaction.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 82.44%, 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 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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by Bi containing the 1.21g and Sb containing 0.71g bismuth and ammonium citrate (Bi (NH3)2C6H7O7·4H2) and antimony acetate (Sb O
(OAc)3) aqueous solution 180ml be immersed on catalyst precarsor IV, 110 DEG C of dryings 4 hours, obtain the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Bi contents 1.21g/L, Sb content 0.71g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 83.39%, and 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, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane
In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Bi and metallic element Sb has preferably in VA races metal
Synergy.
【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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by Ce containing the 1.12g and Sm containing 0.80g 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, obtains the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Ce contents 1.12g/L, Sm content 0.80g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 83.60%, and 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, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane
In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Ce and metallic element Sm has preferably in lanthanide series metal
Synergy.
【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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by Bi containing the 0.98g and Ce containing 0.94g bismuth and ammonium citrate (Bi (NH3)2C6H7O7·4H2) and cerous acetate (Ce O
(OAc)3·6H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, 110 DEG C of dryings 4 hours, obtains the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Bi contents 0.98g/L, Ce content 0.94g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 84.51%, and 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, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane
In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Bi and metal member in lanthanide series metal in VA races metal
Plain Ce has preferable synergy.
【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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by Bi containing the 0.98g and Sm containing 0.94g bismuth and ammonium citrate (Bi (NH3)2C6H7O7·4H2) and acetic acid samarium (Sm O
(OAc)3·6H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, 110 DEG C of dryings 4 hours, obtains the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Bi contents 0.98g/L, Sm content 0.94g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 84.63%, and 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, improving the yield of Isosorbide-5-Nitrae-diacetoxy butane
In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Bi and metal member in lanthanide series metal in VA races metal
Plain Sm has preferable synergy.
【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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by Bi containing 0.98g, Ce containing 0.45g and bismuth and ammonium citrate (Bi (NH containing 0.49gSm3)2C6H7O7·4H2O)、
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 contents that the catalyst is determined through ICP are 2.05g/L, Bi contents 0.98g/L, Ce content 0.45g/L, Sm content
0.49g/L。
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 85.22%, and 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, improving the receipts of Isosorbide-5-Nitrae-diacetoxy butane
Rate and selectivity aspect, in the hydrogenation catalyst that uses of the present invention, metal in metallic element Bi and lanthanide series metal in VA races metal
Elements C e, Sm has preferable synergy.
【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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by Sb containing 0.98g, Ce containing 0.45g and the Sm containing 0.49g antimony acetate (Sb (OAc)3), 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 contents that the catalyst is determined through ICP are 2.05g/L, Sb contents 0.98g/L, Ce content 0.45g/L, Sm content
0.49g/L。
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 85.30%, and 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 diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal
Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. still aging 24h, obtain catalyst precarsor II；
3. with concentration for 8% (with N2H4·H2O weight ratio meters) 500ml hydrazine hydrates catalyst precarsor II is reduced
3h, obtain catalyst precarsor III；
4. through being washed to no chlorion, 50 DEG C of dryings 4 hours, catalyst precarsor IV is obtained；
5. by Bi containing 0.62g, Sb containing 0.36g, Ce containing 0.45g and the Sm containing 0.49g bismuth and ammonium citrate (Bi (NH3)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 of dryings 4 hours, obtains the catalyst.
The Pt contents that the catalyst is determined through ICP are 2.05g/L, Bi contents 0.62g/L, Sb content 0.36g/L, Ce content
0.45g/L, Sm content 0.49g/L.
Hydrogenation reaction：
Step (2)：1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst are added into 100ml
Titanium reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 3.0MPa, is improved
Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 60 DEG C, sustained response 90min
Afterwards, reaction is stopped.
The yield that Isosorbide-5-Nitrae-diacetoxy butane is calculated through analysis is 86.74%, and 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, improving the receipts of Isosorbide-5-Nitrae-diacetoxy butane
Rate and selectivity aspect, in the hydrogenation catalyst that uses of the present invention, gold in metallic element Bi, Sb and lanthanide series metal in VA races metal
Category Elements C e, Sm has preferable synergy.
Table 1
Table 2
Claims (10)
1. producing the method for BDO, comprise the following steps：(1) using butadiene, acetic acid and oxygen as raw material, in oxygen acetyl
Progress Acetoxylation reaction obtains 1,4- diacetoxy butylene in the presence of changing catalyst；(2) in the presence of a hydrogenation catalyst, make
Hydrogen obtains 1,4- diacetoxy butane with 1,4- diacetoxies butene reaction；(3) 1,4- diacetoxies butane hydrolyzes
Obtain 1,4- butanediols；Wherein, described hydrogenation catalyst uses activated carbon as carrier, and active component includes Pt elements and helped to urge
Agent element, the promoter elements are included selected from least one of VA races metal and lanthanide series metal metallic element.
2. according to the method for claim 1, it is characterised in that the activated carbon is ature of coal column charcoal, cocoanut active charcoal, apricot
At least one of shell activated carbon and activated carbon from bamboo.
3. according to the method for claim 1, it is characterised in that the specific surface area of the activated carbon is 1000~1500cm2/ g,
Absorption pore volume is 0.60~1.00cm3/g。
4. according to the method for claim 1, it is characterised in that VA races metal is selected from As, Sb and Bi in the hydrogenation catalyst
At least one of.
5. according to the method for claim 1, it is characterised in that in the hydrogenation catalyst lanthanide series metal be selected from La, Ce, Pr,
At least one of Nd, Sm, Eu, Yb and Lu.
6. according to the method for claim 1, it is characterised in that in the hydrogenation catalyst Pt constituent contents be 1.00~
8.00g/L。
7. according to the method for claim 1, it is characterised in that in hydrogenation catalyst promoter elements content be 0.50~
10.00g/L。
8. as the method described in claim 1, it is characterised in that hydrogenation catalyst is obtained using the process comprised 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 of promoter elements is supported on catalyst precarsor IV using infusion process by the composition of catalyst, dry
To the catalyst.
9. according to the method for claim 1, it is characterized in that hydrogenation reaction pressure is 1.0~10.0MPa.
10. according to the method for claim 1, it is characterized in that the hydrogenation reaction time is 0.5~5.0h.
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| CN112457156A (en) * | 2019-09-06 | 2021-03-09 | 南京延长反应技术研究院有限公司 | Reinforcing system and process for preparing 1, 4-butanediol from butadiene and acetic acid |
| CN112457155A (en) * | 2019-09-06 | 2021-03-09 | 南京延长反应技术研究院有限公司 | Intelligent enhanced production system and process of 1, 4-butanediol |
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