CN107867972B - The production method of 1,4-butanediol - Google Patents

The production method of 1,4-butanediol Download PDF

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CN107867972B
CN107867972B CN201610853090.8A CN201610853090A CN107867972B CN 107867972 B CN107867972 B CN 107867972B CN 201610853090 A CN201610853090 A CN 201610853090A CN 107867972 B CN107867972 B CN 107867972B
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catalyst
diacetoxy
hydrogenation
nitrae
isosorbide
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CN107867972A (en
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查晓钟
杨运信
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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China Petrochemical Corp
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    • 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
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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
    • 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 the production methods of 1,4-butanediol, mainly solve since Isosorbide-5-Nitrae-diacetoxy butylene adds yield and poor selectivity after hydrogen, to cause in the prior art the problem that the yield of 1,4-butanediol and selectivity are low after Isosorbide-5-Nitrae-diacetoxy butane hydrolysis.The production method of 1,4-butanediol, comprising 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 and Isosorbide-5-Nitrae-diacetoxy butene reaction obtain Isosorbide-5-Nitrae-diacetoxy butane；The hydrolysis of 1,4- diacetoxy butane obtains 1,4- butanediol；Wherein, the hydrogenation catalyst uses active carbon for carrier, and active component includes Pt element and promoter elements, and the promoter elements include being selected from least one of IB race metal and Group IVB metal metallic element.

Description

The production method of 1,4-butanediol
Technical field
The present invention relates to the production methods of 1,4- butanediol.
Background technique
1,4-butanediol (Isosorbide-5-Nitrae-BDO) is a kind of important organic and fine chemical material, it be widely used in medicine, The fields such as chemical industry, weaving, papermaking, automobile and daily-use chemical industry.It can derive a series of fine chemical product of high added values. For example, tetrahydrofuran (THF), polybutylene terephthalate (PBT) (PBT), γ-fourth lactones (GBL) can be produced by Isosorbide-5-Nitrae-BDO It is ground with polyurethane resin (PU Resin) especially as the base stock of production PBT engineering plastics and PBT fiber Study carefully the extensive concern of mechanism.
The process route of the preparation of 1,4-butanediol is relatively more, and dividing from raw material used has acetylene, ethylene, propylene, fourth The raw material routes such as diene and cis-butenedioic anhydride, identical raw material also have different synthesis technologies.Since technical barrier is higher and raw material sources Limited, global Isosorbide-5-Nitrae-BDO produces Relatively centralized.2011, global Isosorbide-5-Nitrae-BDO production capacity was mainly distributed on Asia, US and European, Wherein Asia 1,4-BDO production capacity accounting is up to 56.6%.Currently, the industrialized preparing process of Isosorbide-5-Nitrae-BDO specifically includes that 1. alkynes aldehyde Method (Reppe method): this method makees catalyst using methanol copper and generates butynediols, butynediols using acetylene and formaldehyde as raw material Two-stage hydrogenation obtains 1,4-BDO again.Its prevailing technology mainly have BASF Corp. of Germany, the U.S. DuPont exploitation Reppe method with And the Reppe method of improvement.2. maleic anhydride process: this method carries out two steps to it and adds hydrogen using cis-butenedioic anhydride as raw material.The first step is urged in Ni-Re Under agent effect, maleic anhydride hydrogenation generates gamma-butyrolacton and tetrahydrofuran；Second step gamma-butyrolacton is in Mo-Cr-K2O catalyst is made 1,4-BDO is hydrogenated under.Its prevailing technology is mainly with the two-stage hydrogenation work of Japanese two water chestnut oilings and Mitsubishi's chemical conversion exploitation Skill.3. propylene method: mainly including allyl acetate method, acryladehyde method and allyl acetate-allyl alcohol method, Kuraray company develops at present Allyl acetate-allyl alcohol method has obtained industrial application, it is under rhodium catalyst, and allyl alcohol liquid-phase hydrogenatin formylated generates 4- hydroxyl fourth Aldehyde, then repeated hydrogenation generates 1,4-butanediol.4. butadiene process: the method that Isosorbide-5-Nitrae-BDO is produced as raw material using butadiene, it is main to wrap Butadiene acetoxylation method and butadiene chloridising are included, the technique of mainstream is by Mitsubishi chemical conversion and Cao Da company in 20 generation It records 80 years and develops, it successfully breaks the technical barrier and obstacle of Reppe method.Especially butadiene acetoxylation method is excellent Gesture and prospect have obtained the favor of domestic and international research institution.
It is well known that butadiene acetoxylation method is a three-steps process, i.e., butadiene and acetic acid, oxygen first is sent out Raw acetylization reaction, generates Isosorbide-5-Nitrae-diacetoxy butylene and by-product 3.4- diacetoxy butylene；Then 1,4- diacetyl Oxygroup butylene catalytic hydrogenation generates Isosorbide-5-Nitrae-diene acetoxyl group butane, and reaction is finally hydrolyzed and obtains Isosorbide-5-Nitrae-BDO.In Isosorbide-5-Nitrae-fourth For diene into 1,4-butanediol process route, Isosorbide-5-Nitrae-diacetoxy butylene catalytic hydrogenation generates Isosorbide-5-Nitrae-diene acetoxyl group butane As one of step, the yield and selectivity of hydrogenation products directly influence 1,4-butanediol relative to Isosorbide-5-Nitrae-butadiene Yield and selectivity.
It teaches in the patents such as patent US4032458 (production of 1,4-butanediol) and is being urged using furans Agent exists, and prepares 1,4-butanediol under the conditions of certain temperature and pressure.Patent CN94108094.3 (the system of 1,4- butanediol Preparation Method) it describes using cis-butenedioic anhydride as raw material, gas phase catalytic hydrogenation reaction preparation is carried out in the presence of the catalyst specifically designed 1,4- butanediol.Patent CN104326871A (a kind of preparation method of butanediol) is described using fixed-bed catalytic technology, will Content greater than 99% 2- butylene mixed with acetic acid, nitrogen, oxygen and water vapour high temperature after be passed through in fixed bed, catalyst with 1,4- butanediol is prepared under the conditions of certain temperature, pressure etc..But there is 1,4- during preparing 1,4-BDO in the above method The problem that BDO yield is low and selectivity is not high.
Summary of the invention
The technical problem to be solved by the present invention is to the low problems of the yield of 1,4-butanediol and selectivity, provide a kind of new 1,4-butanediol production method, this method have the characteristics that 1,4-butanediol high income and selectivity it is high.
In order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: the production method of 1,4-butanediol, packet It includes 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, make hydrogen and Isosorbide-5-Nitrae-diacetoxy butene reaction Obtain 1,4- diacetoxy butane；(3) 1,4- diacetoxy butane hydrolysis obtains 1,4- butanediol；Wherein, described plus Hydrogen catalyst uses active carbon for carrier, and active component includes Pt element and promoter elements, the promoter elements packet It includes selected from least one of IB race metal and Group IVB metal metallic element.
In above-mentioned technical proposal, the active carbon is preferably coal quality column charcoal, cocoanut active charcoal, apricot shell active carbon and bamboo matter At least one of active carbon.
In above-mentioned technical proposal, the specific surface area of the active carbon is preferably 1000~1500cm2/ g, adsorption hole hold preferred For 0.60~1.00cm3/g。
In above-mentioned technical proposal, IB race metal preferably is selected from least one of Cu, Ag and Au in the hydrogenation catalyst, more It further preferably simultaneously include Cu and Ag.Cu and Ag is improving 1,4- diethyl acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane receipts Rate and selectivity aspect have synergistic effect.
In above-mentioned technical proposal, Group IVB metal preferably is selected from least one of Ti, Zr and Hf in the hydrogenation catalyst. It further simultaneously include Ti and Zr.Ti and Zr is improving 1,4- diethyl acyl-oxygen butane yield and the selection of 1,4- diethyl acyl-oxygen butane Property aspect have synergistic effect.
In above-mentioned technical proposal, the promoter elements preferably include at least one in IB race metallic element simultaneously Kind and at least one of selected from Group IVB metallic element, at this time in IB race in metallic element and Group IVB metal between metallic element There is synergistic effect in terms of improving 1,4- diethyl acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane selectivity.As unrestricted Property citing, such as, but not limited to titanium cooperates with copper, and zirconium is cooperateed with copper 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.
In above-mentioned technical proposal, hydrogenation catalyst can be obtained using the process included the following steps:
1. mixing the solution of platiniferous element with carrier by the composition of catalyst, catalyst precarsor I is obtained；
2. obtaining catalyst precarsor II after catalyst precarsor I is aged；
3. being simple substance platinum by compound state platinum element reduction in catalyst precarsor II, catalyst precarsor III is obtained；
4. being washed, being dried to obtain catalyst precarsor IV；
5. the solution 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 IB race metal When element, the corresponding particular compound of IB race metallic element preferably is selected from copper citrate, copper acetate, copper nitrate, copper chloride, sulfuric acid At least one of copper, silver acetate, silver nitrate, actol, silver tetrafluoroborate, gold chloride, gold oxide and tetra chlorauric acid ammonium；It is more excellent Selected from least one of copper acetate and silver nitrate.
In above-mentioned technical proposal, as non limiting example, when step 5. in promoter elements include Group IVB metal When element, the corresponding particular compound of Group IVB metallic element preferably is selected from titanium tetrachloride, ammonium titanium fluoride, hexafluorotitanic acid, metatitanic acid, chlorine Change at least one of zirconium, acetic acid zirconium and oxychloride hafnium；More preferable at least one of metatitanic acid and acetic acid zirconium.
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.
Key of the invention is the selection of hydrogenation catalyst, and skilled person will know how determine according to actual needs Suitable hydrogenation process conditions reaction temperature, reaction time, reaction pressure and proportion of material etc..But:
In above-mentioned technical proposal, the temperature of hydrogenation reaction is preferably 20~120 DEG C.
In above-mentioned technical proposal, the pressure of hydrogenation reaction is preferably 1.0~10.0MPa, more preferable 1.0~6.0MPa.
In above-mentioned technical proposal, the time of hydrogenation reaction is preferably 0.5~5.0h, more preferable 0.5~2.0h.
The present invention synthesizes in the method for 1,4-butanediol, the known suitable butadiene oxygen acetyl of selection of those skilled in the art Change catalysts and determines 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 that Te, Se, Sb, Bi, V etc., which is added,.Carrier used can be active 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 preferable 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 molar ratio of butadiene and acetic acid preferably 0.010~ 2.0.After for step (1), the mixture that can be reacted butadiene Acetoxylation carries out separation and obtains target product Isosorbide-5-Nitrae- Diacetoxy butylene carries out step (2) again, does not separate directly after Isosorbide-5-Nitrae-diacetoxy butylene can also being generated with step (1) Tap into row step (2).But cause system complexity convenient on year-on-year basis, specific embodiment of the invention department is equal to exclude other impurity Step (2) are carried out using the isolated pure 1,4- diacetoxy butylene of step (1) mixture of reaction products.
After step (2), can the mixture to hydrogenation reaction carry out separation obtain target product Isosorbide-5-Nitrae-diethyl acyl-oxygen Base butane carries out step (3) again, can also directly be walked with not separating 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 determining suitable hydrolysising reacting temperature, time and object Material proportion.Common 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 key of the invention is step (2), in order to year-on-year, it is also used as non-restrictive, the present invention is specifically real The step of applying mode part (1) is all made of following specific method and carries out:
The synthesis of 1,4- butanediol:
Step (1): by 2.10mol acetic acid, 12.8g Pd-Te/C, (Pd constituent content is 3.80g/L, and Te constituent content is 1.85g/L) catalyst is added in 1L titanium reaction kettle, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, then passes to Butadiene and oxygen are up to pressure 6.8MPa, raising mixing speed to 1000rpm, while agitating and heating is warming up to reaction temperature, Controlling reaction temperature is 80 DEG C, and the molar ratio of butadiene and oxygen is 1:1, after sustained response 5.0h, stops reaction.By reaction kettle It is down to room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oily phase, through rectification and purification, obtains Isosorbide-5-Nitrae-diacetyl Oxygroup butylene.
Because key of the invention is step (2), in order to make it easy to understand, it is also used as non-restrictive, present invention tool The step of body embodiment part (3), can be used following specific method and carry out:
Step (3): by above-mentioned 1,4- diacetoxy butane 18ml, 30ml toluene-water, (10ml toluene and 20ml water are mixed Into), 0.015mol benzene sulfonic acid 100ml titanium reaction kettle is added, 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 The yield and selectivity of formula calculating 1,4- diacetoxy butane:
Compared with prior art, key of the invention is the new hydrogenation catalyst that step (2) use, and improves Isosorbide-5-Nitrae-two The yield and selectivity of acetyl oxygen butane.
The experimental results showed that Isosorbide-5-Nitrae-diacetoxy butane yield selectively reaches up to 82.37% when using the present invention 94.16%, achieve preferable technical effect.It simultaneously include especially platinum, selected from IB race in the active component of hydrogenation catalyst At least one of metal metallic element and when selected from least one of Group IVB metal metallic element, achieves more prominent Technical effect, can be used in the industrial production of 1,4-butanediol.Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the copper acetate (Cu (OAc) of the Cu containing 1.87g2·H2O aqueous solution 180ml) is immersed in catalyst precarsor IV On, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Cu content 1.87g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 82.37% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.16%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 2]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the acetic acid zirconium (Zr (OAc) of the Zr containing 1.87g4·8H2O it is water-soluble) to be completely dissolved in the acetic acid that concentration is 10wt% In liquid, obtain maceration extract 180ml and be immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Zr content 1.87g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 82.44% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.02%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 75.12% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 91.29%, 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.
By the way that, as can be seen that the present invention is using the catalyst for adding hydrogen, active component makes simultaneously compared with Examples 1 to 2 With containing Pt, Cu active component, simultaneously the catalyst performance containing Pt, Zr active component than the performance containing only Pt active constituent catalyst It is more excellent, illustrate activity of hydrocatalyst component while using at least one containing Pt and in IB race metal and Group IVB metal Kind metallic element compound is conducive to the activity and stability that improve hydrogenation catalyst, Isosorbide-5-Nitrae-diacetoxy butane yield It will be high with selectivity.
[comparative example 2]
For the comparative example of [comparative example 1].
The preparation of hydrogenation catalyst:
1. by the ammonium chloropalladite ((NH of the Pd containing 2.05g4)2PdCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 2.05g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 70.04% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 88.06%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
By can be seen that the present invention compared with comparative example 1 using the catalyst for adding hydrogen, contained using the ratio of active component containing Pt The performance of Pd active constituent catalyst is more excellent, illustrates that activity of hydrocatalyst component is conducive to Isosorbide-5-Nitrae-diacetoxy using Pt Butylene adds hydrogen, and Isosorbide-5-Nitrae-diacetoxy butane yield and selectivity will be high.
[embodiment 3]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the metatitanic acid (H of the Ti containing 1.87g4TiO4) be dissolved in the aqueous acetic acid that concentration is 10wt%, it is impregnated Liquid 180ml is immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Ti content 1.87g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 82.43% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.03%, 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.
[embodiment 4]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.60cm3/ g, specific surface area 1000cm2The coconut husk of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the copper nitrate (Cu (NO of the Cu containing 1.87g3)2) aqueous solution 180ml is immersed on catalyst precarsor IV, 100 DEG C It is 4 hours dry, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Cu content 1.87g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 82.36% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.14%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 5]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 1.00cm3/ g, specific surface area 1500cm2The apricot shell of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the copper citrate (Cu of the Cu containing 1.87g2C6H4O7·2.5H2O) it is completely dissolved in the acetic acid that concentration is 10wt% In aqueous solution, obtain maceration extract 180ml and be immersed on catalyst precarsor IV, 120 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Cu content 1.87g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 82.35% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.15%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 6]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2/ g's is bamboo Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the cupric tartrate (C of the Cu containing 1.87g4H4O6Cu·2H2O) it is completely dissolved in the acetic acid water that concentration is 10wt% In solution, obtain maceration extract 180ml and be immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Cu content 1.87g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 82.37% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, 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 7]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the silver nitrate (AgNO of the Ag containing 1.87g3) aqueous solution 180ml, it is immersed on catalyst precarsor IV, 110 DEG C are dry Dry 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Ag content 1.87g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 50 DEG C, sustained response 90min Afterwards, stop reaction.
It is 82.35% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, 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 of the Pt containing 1.50g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the copper acetate (Cu (OAc) of the Cu containing 1.00g2·H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 1.50g/L, Cu content 1.00g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 1.0MPa, is improved first with 0.5MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 20 DEG C, sustained response 30min Afterwards, stop reaction.Reaction kettle is down to room temperature, purified removal of impurities obtains Isosorbide-5-Nitrae-diacetoxy butane.
It is 80.58% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 93.87%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 9]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 5.00g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the copper acetate (Cu (OAc) of the Cu containing 6.00g2·H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 5.00g/L, Cu content 6.00g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 6.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 120 DEG C, sustained response After 120min, stop reaction.
It is 82.94% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 93.69%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 10]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the copper acetate (Cu (OAc) of Cu containing the 1.00g and Ag containing 0.87g2·H2) and silver nitrate (AgNO O3) it is water-soluble Liquid 180ml is immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Cu content 1.00g/L, Ag content 0.87g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 83.31% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.47%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 10 and embodiment 1 and embodiment 7, is improving Isosorbide-5-Nitrae-diacetoxy butane yield In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Cu and metal element A g have preferably in IB race metal Synergistic effect.
[embodiment 11]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the acetic acid zirconium (Zr (OAc) of Zr containing the 1.23g and Ti containing 0.64g4·8H2) and metatitanic acid (H O4TiO4) be dissolved in Concentration is to obtain maceration extract 180ml in the aqueous acetic acid of 10wt%, be immersed on catalyst precarsor IV, 110 DEG C of dryings 4 are small When, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Zr content 1.23g/L, Ti content 0.64g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 83.44% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.38%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 11 and embodiment 2 and embodiment 3, is improving Isosorbide-5-Nitrae-diacetoxy butane yield In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Zr and metal element Ti have preferably in Group IVB metal Synergistic effect.
[embodiment 12]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the copper acetate (Cu (OAc) of Cu containing the 1.10g and Zr containing 0.77g2·H2) and acetic acid zirconium (Zr (OAc) O4· 8H2O 180ml in aqueous solution) is immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Cu content 1.10g/L, Zr content 0.77g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 84.40% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.07%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 2, is improving Isosorbide-5-Nitrae-diacetoxy butane yield In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Cu and metal member in Group IVB metal in IB race metal Plain Zr has preferable synergistic effect.
[embodiment 13]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the copper acetate (Cu (OAc) of Cu containing the 1.10g and Ti containing 0.77g2·H2) and metatitanic acid (H O4TiO4) be dissolved in Concentration is to obtain maceration extract 180ml in the aqueous acetic acid of 10wt%, be immersed on catalyst precarsor IV, 110 DEG C of dryings 4 are small When, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Cu content 1.10g/L, Ti content 0.77g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 84.33% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.18%, 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.
Found out on year-on-year basis by embodiment 13 and embodiment 1 and embodiment 3, is improving Isosorbide-5-Nitrae-diacetoxy butane yield In the hydrogenation catalyst used with selective aspect, the present invention, metallic element Cu and metal member in Group IVB metal in IB race metal Plain Ti has preferable synergistic effect.
[embodiment 14]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the copper acetate (Cu (OAc) of Cu containing 1.10g, Zr containing 0.51g and the Ti containing 0.26g2·H2O), acetic acid zirconium (Zr (OAc)4·8H2) and metatitanic acid (H O4TiO4) be completely dissolved in the aqueous acetic acid that concentration is 10wt%, obtain maceration extract 180ml is immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Cu content 1.10g/L, Zr content 0.51g/L, Ti content 0.26g/L。
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 85.23% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.40%, 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 14 and embodiment 12 and embodiment 13, is improving Isosorbide-5-Nitrae-diacetoxy butane receipts Rate and selectivity aspect, in the hydrogenation catalyst that the present invention uses, metal in metallic element Cu and Group IVB metal in IB race metal Element Zr, Ti have preferable synergistic effect.
[embodiment 15]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the silver nitrate (AgNO of Ag containing 1.10g, Zr containing 0.51g and the Ti containing 0.26g3), acetic acid zirconium (Zr (OAc)4· 8H2) and metatitanic acid (H O4TiO4) be completely dissolved in the aqueous acetic acid that concentration is 10wt%, maceration extract 180ml is obtained, is immersed in On catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Ag content 1.10g/L, Zr content 0.51g/L, Ti content 0.26g/L。
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 85.19% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.51%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
[embodiment 16]
The preparation of hydrogenation catalyst:
1. by the ammonium chloroplatinite ((NH of the Pt containing 2.05g4)2PtCl4) it is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% In, maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g Cylindrical activated carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the copper acetate (Cu (OAc) of Cu containing 0.60g, Ag containing 0.50g, Zr containing 0.51g and the Ti containing 0.26g2· H2O), silver nitrate (AgNO3), acetic acid zirconium (Zr (OAc)4·8H2) and metatitanic acid (H O4TiO4) concentration is completely dissolved in as 10wt%'s In aqueous acetic acid, obtain maceration extract 180ml, be immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalysis Agent.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Cu content 0.60g/L, Ag content 0.50g/L, Zr content 0.51g/L, Ti content 0.26g/L.
1,4- diacetoxy butylene hydrogenation reaction:
Step (2): 100ml is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Titanium reaction kettle then passes to hydrogen until pressure 3.0MPa, is improved first with 1.0MPa is pressurized to after air in argon gas discharge kettle Mixing speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, sustained response 90min Afterwards, stop reaction.
It is 86.41% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.67%, for the ease of Illustrate and compare, by the preparation of hydrogenation catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, is improving Isosorbide-5-Nitrae-diacetoxy butane receipts In terms of rate and selectivity, in the hydrogenation catalyst that the present invention uses, in IB race metal in metallic element Cu, Ag and Group IVB metal Metallic element Zr, Ti have preferable synergistic effect.
Table 1
Table 2

Claims (8)

  1. The production method of 1.1,4- butanediols, comprising 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 and 1,4- diacetoxy butene reaction obtain 1,4- diacetoxy butane；(3) 1,4- diacetoxy butane hydrolyzes Obtain 1,4- butanediol；Wherein, the hydrogenation catalyst uses active carbon for carrier, and active component includes that Pt element and helping is urged Agent element, the promoter elements include being selected from least one of IB race metal and Group IVB metal metallic element, described Pt constituent content is 1.00 ~ 8.00g/L in hydrogenation catalyst, in the hydrogenation catalyst promoter elements content be 0.50 ~ 10.00g/L。
  2. 2. according to the method described in claim 1, it is characterized in that the active carbon is coal quality column charcoal, cocoanut active charcoal, apricot At least one of shell active carbon and activated carbon from bamboo.
  3. 3. according to the method described in claim 1, it is characterized in that the specific surface area of the active carbon is 1000 ~ 1500 m2/ g, It is 0.60 ~ 1.00 cm that adsorption hole, which holds,3/g。
  4. 4. according to the method described in claim 1, it is characterized in that IB race metal is selected from Cu, Ag and Au in the hydrogenation catalyst At least one of.
  5. 5. according to the method described in claim 1, it is characterized in that in the hydrogenation catalyst Group IVB metal be selected from Ti, Zr and At least one of Hf.
  6. 6. by method described in claim 1, it is characterised in that hydrogenation catalyst is obtained using the process included the following steps:
    1. mixing the solution of platiniferous element with carrier by the composition of catalyst, catalyst precarsor I is obtained；
    2. obtaining catalyst precarsor II after catalyst precarsor I is aged；
    3. being simple substance platinum by compound state platinum element reduction in catalyst precarsor II, catalyst precarsor III is obtained；
    4. being washed, being dried to obtain catalyst precarsor IV;
    5. the solution containing promoter elements is supported on catalyst precarsor IV using infusion process by the composition of catalyst, it is dry Obtain the catalyst.
  7. 7. according to the method described in claim 1, it is characterized in that hydrogenation reaction pressure is 1.0~10.0MPa.
  8. 8. according to the method described in claim 1, it is characterized in that the hydrogenation reaction time is 0.5~5.0h.
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