CN107999064B - The catalyst of butadiene synthesis 1,4- diacetoxy butane course - Google Patents

The catalyst of butadiene synthesis 1,4- diacetoxy butane course Download PDF

Info

Publication number
CN107999064B
CN107999064B CN201610967705.XA CN201610967705A CN107999064B CN 107999064 B CN107999064 B CN 107999064B CN 201610967705 A CN201610967705 A CN 201610967705A CN 107999064 B CN107999064 B CN 107999064B
Authority
CN
China
Prior art keywords
catalyst
nitrae
isosorbide
catalyst precarsor
diacetoxy butane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610967705.XA
Other languages
Chinese (zh)
Other versions
CN107999064A (en
Inventor
查晓钟
杨运信
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
Original Assignee
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Shanghai Research Institute of Petrochemical Technology, China Petrochemical Corp filed Critical Sinopec Shanghai Research Institute of Petrochemical Technology
Priority to CN201610967705.XA priority Critical patent/CN107999064B/en
Publication of CN107999064A publication Critical patent/CN107999064A/en
Application granted granted Critical
Publication of CN107999064B publication Critical patent/CN107999064B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6522—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • 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

Abstract

The present invention relates to butadiene to synthesize Isosorbide-5-Nitrae-diacetoxy butane course catalyst, mainly solves the problems, such as that Isosorbide-5-Nitrae-diacetoxy butane yield in the prior art and selectivity are low, synthesizes Isosorbide-5-Nitrae-diacetoxy butane course catalyst using butadiene；Including carrier and active component, the carrier is active carbon, active component includes Pt element and promoter elements, the promoter elements include the technical solution selected from least one of alkaline-earth metal at least one of metallic element and group vib metal metallic element, preferably solves the technical problem, it can be used in Isosorbide-5-Nitrae-diacetoxy butane industrial production.

Description

The catalyst of butadiene synthesis 1,4- diacetoxy butane course
Technical field
The present invention relates to the catalyst of butadiene synthesis 1,4- diacetoxy butane course.
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 first technical problem to be solved by the present invention is that the yield of 1,4- diacetoxy butane is asked with selectively low Topic, provides a kind of new butadiene synthesis Isosorbide-5-Nitrae-diacetoxy butane course catalyst, which has Isosorbide-5-Nitrae-diethyl Acyloxy butane high income and selective high feature.
The second technical problem to be solved by the present invention is the preparation method of above-mentioned catalyst.
The third technical problem to be solved by the present invention is the conjunction using the 1,4- diacetoxy butane of above-mentioned catalyst At method.
One of in order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: butadiene synthesizes Isosorbide-5-Nitrae-diethyl The catalyst of acyloxy butane course；Including carrier and active component, the carrier is active carbon, and active component includes Pt member Element and promoter elements, the promoter elements include selected from least one of alkaline-earth metal metallic element and group vib gold At least one of category 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, and adsorption hole holds preferred For 0.60~1.00cm3/g.
In above-mentioned technical proposal, alkaline-earth metal preferably is selected from least one of Be, Mg, Ca, Sr and Ba in the catalyst, It still more preferably simultaneously include Ba and Sr.Ba and Sr is improving 1,4- diethyl acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane Selectivity aspect has synergistic effect.
In above-mentioned technical proposal, group vib metal preferably is selected from least one of Cr, Mo and W in the catalyst.More into one It walks while including Cr, W.Cr, W have in terms of improving 1,4- diethyl acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane selectivity Synergistic effect.
In above-mentioned technical proposal, the promoter elements preferably include at least one in alkali earth metal simultaneously Kind and at least one of selected from group vib metallic element, metal member in the metallic element in alkaline-earth metal and group vib metal at this time There is in terms of improving 1,4- diethyl acyl-oxygen butane yield and 1,4- diethyl acyl-oxygen butane selectivity synergistic effect between element.As Non limiting example, such as, but not limited to strontium are cooperateed with chromium, and strontium is cooperateed with tungsten etc..
In above-mentioned technical proposal, the content of Pt is preferably 1.00~8.00g/L in the 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 catalyst, more excellent It is selected as 1.00~6.00g/L.
To solve above-mentioned technical problem two, technical scheme is as follows:
Method for preparing catalyst described in any one of technical solution of one of above-mentioned technical problem, includes 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, step 5. in promoter elements include alkaline-earth metal member When plain, the corresponding particular compound of alkali earth metal preferably is selected from alkaline earth oxide, alkaline earth metal chloride, alkaline-earth metal At least one of sulfate, alkaline earth metal nitrate and Alkaline Earth Metal Acetate；In more preferable Alkaline Earth Metal Acetate It is at least one；Most preferably from least one of barium acetate and strontium acetate.
In above-mentioned technical proposal, as non limiting example, when step 5. in promoter elements include group vib metal When element, the corresponding particular compound of group vib metallic element preferably is selected from chromic acetate, chromic nitrate, chromium chloride, ammonium molybdate, phosphoric At least one of molybdenum, molybdenum carbonyl, molybdic acid, tungsten chloride, tungsten carbonyl, ammonium paratungstate and ammonium tungstate；More preferably from chromic acetate and tungsten At least one of sour ammonium.
In above-mentioned technical proposal, the reducing agent of step 3. does not specially require understanding based on those skilled in the art, also Former agent can be at least one of gas or liquid, the preferred hydrogen of reducing agent, hydrazine hydrate；4. drying temperature is preferably step 30~120 DEG C, drying time is preferably 1~5 hour；5. the drying temperature is preferably 80~120 DEG C to step, more preferably 100~120 DEG C.
To solve above-mentioned technical problem three, technical scheme is as follows:
Isosorbide-5-Nitrae-diacetoxy butane synthetic method, described in any one of technical solution of one of above-mentioned technical problem In the presence of catalyst, hydrogen and Isosorbide-5-Nitrae-diacetoxy butene reaction obtain Isosorbide-5-Nitrae-diacetoxy butane.
Key of the invention is the selection of catalyst, and skilled person will know how suitable determine according to actual needs Hydrogenation process conditions reaction temperature, reaction time, reaction pressure and the proportion of material etc..But:
In above-mentioned technical proposal, the temperature of hydrogenation reaction is preferably 20~120 DEG C.
In above-mentioned technical proposal, the pressure of hydrogenation reaction is preferably 1.0~10.0MPa, more preferable 1.0~6.0MPa.
In above-mentioned technical proposal, the time of hydrogenation reaction is preferably 0.5~5.0h, more preferable 0.5~2.0h.
Isosorbide-5-Nitrae-diacetoxy butylene can be obtained from commercially available channel, or the synthesis of butadiene Acetoxylation method can be used.Fourth It is butadiene Acetoxylation catalyst that diene Acetoxylation method, which synthesizes and Pd-Te/C can be selected,.Palladium in suitable Pd-Te/C catalyst The content of element preferably 2.50~5.00g/L, more preferable 3.00~4.50g/L；The content of tellurium element preferably 0.50~3.00g/ L, more preferable 1.00~2.50g/L.Suitable Acetoxylation reaction temperature is preferably 40~150 DEG C；Acetoxylation reaction pressure It is preferred that 1.0~10.0MPa；The Acetoxylation reaction time is preferably 0.5~5h；The molar ratio of butadiene and acetic acid preferably 0.010 ~2.0.After the reaction of butadiene Acetoxylation, the mixture that can be reacted butadiene Acetoxylation carries out separation and obtains target production Object Isosorbide-5-Nitrae-diacetoxy butylene carries out hydrogenation reaction of the present invention again, can not also separate and directly carry out hydrogenation reaction.But Cause system complexity convenient on year-on-year basis, specific embodiment of the invention department is all made of pure Isosorbide-5-Nitrae-diacetyl to exclude other impurity Oxygroup butylene is as hydrogenation reaction raw material.
The product mixtures of above-mentioned hydrogenation reaction can obtain target product 1,4- diacetoxy butane through separation.
1,4- diacetoxy butane can be further used for obtaining 1,4- butanediol by method for hydrolysis.Art technology The suitable hydrolyst of the known selection of personnel and determining suitable hydrolysising reacting temperature, time and material proportion.Common water Solution catalyst can be inorganic acid, inorganic base, organic acid and organic base.Such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sodium hydroxide, Potassium hydroxide, benzene sulfonic acid and ion exchange resin.Suitable hydrolysising reacting temperature is preferably 30~100 DEG C；Hydrolysis pressure Power preferably 0~2.0MPa；The preferred water of solvent.
Product mixtures after hydrogenation reaction of the present invention are analyzed through gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), by following The yield and selectivity of formula calculating 1,4- diacetoxy butane:
Compared with prior art, the catalyst used in the present invention improves Isosorbide-5-Nitrae-diethyl acyl-oxygen butane yield and selection Property.
The experimental results showed that Isosorbide-5-Nitrae-diacetoxy butane yield selectively reaches up to 82.36% when using the present invention 94.26%, achieve preferable technical effect.It simultaneously include especially platinum, selected from alkaline earth in the active component of hydrogenation catalyst At least one of metal metallic element and when selected from least one of group vib metal metallic element, achieves more prominent Technical effect.Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 strontium acetate (Sr (OAc) of the Sr containing 1.88g2·0.5H2O aqueous solution 180ml) is immersed in catalyst precarsor On IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Sr content 1.88g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.36% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.26%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property is listed in Tables 1 and 2 respectively.
[embodiment 2]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the ammonium tungstate ((NH of the W containing 1.88g4)10W12O41·4H2O it) is dissolved in hot water, obtains maceration extract 180ml, soak Stain 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, W content 1.88g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.44% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.12%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property 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 containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 75.21% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 91.27%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property is listed in Tables 1 and 2 respectively.
The catalyst used by can be seen that the present invention compared with Examples 1 to 2, active component use simultaneously contain Pt, Sr active component, simultaneously the catalyst performance containing Pt, W active component than containing only the performance of Pt active constituent catalyst more It is excellent, illustrate activity of hydrocatalyst component while including using at least one containing Pt and in alkaline-earth metal and group vib metal Kind metallic element is conducive to the activity and stability that improve catalyst, and Isosorbide-5-Nitrae-diacetoxy butane yield and selectivity are all Want high.
[comparative example 2]
For the comparative example of [comparative example 1].
The preparation of catalyst:
1. by the ammonium chloropalladite ((NH containing 2.05gPd4)2PdCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 2.05g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 70.14% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 88.09%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property 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 catalyst activity component is conducive to Isosorbide-5-Nitrae-diacetoxy butylene using Pt Add hydrogen, Isosorbide-5-Nitrae-diacetoxy butane yield and selectivity will be high.
[embodiment 3]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the chromic acetate (Cr (OAc) of the Cr containing 1.88g3·6H2O it) is dissolved in hot water, obtains maceration extract 180ml, impregnate On catalyst precarsor IV, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Cr content 1.88g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.41% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.14%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property is listed in Tables 1 and 2 respectively.
[embodiment 4]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.60cm3/ g, specific surface area 1000cm2The coconut husk circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 beryllium acetate (Be (OAc) of the Be containing 1.88g2·H2O it) is dissolved in hot water, obtains maceration extract 180ml, be immersed in On catalyst precarsor IV, 100 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Be content 1.88g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.31% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.24%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property is listed in Tables 1 and 2 respectively.
[embodiment 5]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 1.00cm3/ g, specific surface area 1500cm2The apricot shell circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 magnesium acetate (Mg (OAc) of the Mg containing 1.88g2·4H2O) aqueous solution 180ml is immersed on catalyst precarsor IV, 120 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Mg content 1.88g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.31% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.24%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property is listed in Tables 1 and 2 respectively.
[embodiment 6]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The bamboo circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 calcium acetate (Ca (OAc) of the Ca containing 1.88g2·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 2.05g/L, Ca content 1.88g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.32% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.28%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property is listed in Tables 1 and 2 respectively.
[embodiment 7]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 barium acetate (Ba (OAc) of the Ba containing 1.88g2·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 2.05g/L, Ba content 1.88g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 50 DEG C, after sustained response 90min, stops anti- It answers.
It is 82.37% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.27%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property is listed in Tables 1 and 2 respectively.
[embodiment 8]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 1.50gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 strontium acetate (Sr (OAc) of the Sr containing 1.00g2·0.5H2O) 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 1.50g/L, Sr content 1.00g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 1.0MPa, improves mixing speed first with 0.5MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 20 DEG C, after sustained response 30min, stops anti- It answers.Reaction kettle is down to room temperature, purified removal of impurities obtains Isosorbide-5-Nitrae-diacetoxy butane.
It is 80.71% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 93.88%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property is listed in Tables 1 and 2 respectively.
[embodiment 9]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 5.00gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 strontium acetate (Sr (OAc) of the Sr containing 6.00g2·0.5H2O) 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 5.00g/L, Sr content 6.00g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 6.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 120 DEG C, after sustained response 120min, stops Reaction.
It is 82.61% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 93.92%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property is listed in Tables 1 and 2 respectively.
[embodiment 10]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 strontium acetate (Sr (OAc) of Sr containing the 1.22g and Ba containing 0.66g2·0.5H2) and barium acetate (Ba O (OAc)2·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 2.05g/L, Sr content 1.22g/L, Ba content 0.66g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 83.29% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.50%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property 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 catalyst used with selective aspect, the present invention, metallic element Sr and metallic element Ba have preferable association in alkaline-earth metal Same-action.
[embodiment 11]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. it is still aging for 24 hours, obtain catalyst precarsor II；
3. being 8% (with N with concentration2H4·H2O weight ratio meter) 500ml hydrazine hydrate catalyst precarsor II is restored 3h obtains catalyst precarsor III；
4. be washed to no chloride ion, 50 DEG C drying 4 hours, obtain catalyst precarsor IV；
5. by the ammonium tungstate ((NH of W containing the 0.98g and Cr containing 0.90g4)10W12O41·4H2) and chromic acetate (Cr O (OAc)3·6H2O) be dissolved in hot water, obtain maceration extract 180ml, be immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain To the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, W content 0.98g/L, Cr content 0.90g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 83.43% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 94.33%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property 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 catalyst used with selective aspect, the present invention, metal elements W and metallic element Cr have preferable association in group vib metal Same-action.
[embodiment 12]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 strontium acetate (Sr (OAc) of Sr containing the 1.04g and W containing 0.84g2·0.5H2) and ammonium tungstate ((NH O4)10W12O41·4H2O) be dissolved in hot water, obtain maceration extract 180ml, be immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, Obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Sr content 1.04g/L, W content 0.84g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 84.32% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.11%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property 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 catalyst used with selective aspect, the present invention, metallic element Sr and metal elements W in group vib metal in alkaline-earth metal There is preferable synergistic effect.
[embodiment 13]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 strontium acetate (Sr (OAc) of Sr containing the 1.04g and Cr containing 0.84g2·0.5H2) and chromic acetate (Cr O (OAc)3·6H2O) be dissolved in hot water, obtain maceration extract 180ml, be immersed on catalyst precarsor IV, 110 DEG C drying 4 hours, obtain To the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Sr content 1.04g/L, Cr content 0.84g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 84.28% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.08%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property 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 catalyst used with selective aspect, the present invention, metallic element Sr and metallic element Cr in group vib metal in alkaline-earth metal There is preferable synergistic effect.
[embodiment 14]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 strontium acetate (Sr (OAc) of Sr containing 1.04g, W containing 0.58g and the Cr containing 0.26g2·0.5H2O), ammonium tungstate ((NH4)10W12O41·4H2) and chromic acetate (Cr (OAc) O3·6H2O it) is dissolved in hot water, obtains maceration extract 180ml, be immersed in and urge On agent precursor I V, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Sr content 1.04g/L, W content 0.58g/L, Cr content 0.26g/L。
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 85.22% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.31%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property 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 catalyst that the present invention uses, metallic element in metallic element Sr and group vib metal in alkaline-earth metal W, Cr has preferable synergistic effect.
[embodiment 15]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 barium acetate (Ba (OAc) of Ba containing 1.04g, W containing 0.58g and the Cr containing 0.26g2·H2O), ammonium tungstate ((NH4)10W12O41·4H2) and chromic acetate (Cr (OAc) O3·6H2O it) is dissolved in hot water, obtains maceration extract 180ml, be immersed in and urge On agent precursor I V, 110 DEG C drying 4 hours, obtain the catalyst.
The Pt content for measuring the catalyst through ICP is 2.05g/L, Ba content 1.04g/L, W content 0.58g/L, Cr content 0.26g/L。
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 85.17% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.35%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property is listed in Tables 1 and 2 respectively.
[embodiment 16]
The preparation of catalyst:
1. by the ammonium chloroplatinite ((NH containing 2.05gPt4)2PtCl4) be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, Maceration extract 200ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality circle of/g Column-shaped active carbon carrier impregnation obtains catalyst precarsor I in above-mentioned maceration extract；
2. 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 strontium acetate (Sr (OAc) of Sr containing 0.65g, Ba containing 0.39g, W containing 0.58g and the Cr containing 0.26g2· 0.5H2O), barium acetate (Ba (OAc)2·H2O), ammonium tungstate ((NH4)10W12O41·4H2) and chromic acetate (Cr (OAc) O3·6H2O) Be dissolved in hot water, 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, Sr content 0.65g/L, Ba content 0.39g/L, W content 0.58g/L, Cr content 0.26g/L.
The synthesis of 1,4- diacetoxy butane:
The reaction of 100ml titanium is added in 1,4- diacetoxy butylene 15ml, toluene 30ml, 0.01mol hydrogenation catalyst Kettle then passes to hydrogen until pressure 3.0MPa, improves mixing speed first with 1.0MPa is pressurized to after air in argon gas discharge kettle To 600rpm, while agitating and heating is warming up to reaction temperature, and control reaction temperature is 60 DEG C, after sustained response 90min, stops anti- It answers.
It is 86.29% through analytical calculation Isosorbide-5-Nitrae-diacetoxy butane yield, selectivity is 95.52%, for the ease of Illustrate and compare, by the preparation of catalyst, reaction condition, material inlet amount, Isosorbide-5-Nitrae-diacetoxy butane yield and selection Property is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, is improving Isosorbide-5-Nitrae-diacetoxy butane receipts Rate and selectivity aspect, in the catalyst that the present invention uses, metal in metallic element Sr, Ba and group vib metal in alkaline-earth metal Element W, Cr have preferable synergistic effect.
Table 1
Table 2

Claims (7)

1. a kind of Isosorbide-5-Nitrae-diacetoxy butane synthetic method, in the presence of a catalyst, hydrogen and Isosorbide-5-Nitrae-diacetoxybut Alkene reaction obtains 1,4- diacetoxy butane；Wherein the catalyst includes carrier and active component, and the carrier is to live Property charcoal, active component include Pt element and promoter elements, the promoter elements include in alkaline-earth metal at least At least one of a kind of metallic element and group vib metal metallic element；
Wherein, Pt constituent content is 1.00 ~ 8.00g/L in the catalyst, and promoter elements content is 0.50 ~ 6.00g/L.
2. synthetic method according to claim 1, which is characterized in that the active carbon is coal quality column charcoal, coconut activated At least one of charcoal, apricot shell active carbon and activated carbon from bamboo.
3. synthetic method according to claim 1, which is characterized in that the specific surface area of the active carbon is 1000 ~ 1500 m2/ g, it is 0.60 ~ 1.00 cm that adsorption hole, which holds,3/g。
4. synthetic method according to claim 1, which is characterized in that in the catalyst alkaline-earth metal be selected from Be, Mg, At least one of Ca, Sr and Ba.
5. synthetic method according to claim 1, which is characterized in that in the catalyst group vib metal be selected from Cr, Mo and At least one of W.
6. synthetic method according to claim 1, which is characterized in that the preparation method of the catalyst, including walk as follows It is rapid:
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. synthetic method according to claim 1, which is characterized in that reaction pressure is 1.0~10.0MPa, reaction time For 0.5~5.0h.
CN201610967705.XA 2016-11-01 2016-11-01 The catalyst of butadiene synthesis 1,4- diacetoxy butane course Active CN107999064B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610967705.XA CN107999064B (en) 2016-11-01 2016-11-01 The catalyst of butadiene synthesis 1,4- diacetoxy butane course

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610967705.XA CN107999064B (en) 2016-11-01 2016-11-01 The catalyst of butadiene synthesis 1,4- diacetoxy butane course

Publications (2)

Publication Number Publication Date
CN107999064A CN107999064A (en) 2018-05-08
CN107999064B true CN107999064B (en) 2019-11-08

Family

ID=62047535

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610967705.XA Active CN107999064B (en) 2016-11-01 2016-11-01 The catalyst of butadiene synthesis 1,4- diacetoxy butane course

Country Status (1)

Country Link
CN (1) CN107999064B (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1313201C (en) * 2004-10-29 2007-05-02 中国石油化工股份有限公司 Supported type active carbon and its preparation method
CN101029245A (en) * 2007-04-13 2007-09-05 清华大学 Production of biological diesel oil by integrated hydrogenation
CN100537503C (en) * 2007-05-31 2009-09-09 上海华谊丙烯酸有限公司 Process for preparing n-propanol by hydrogenating glycerol
CN103331158B (en) * 2013-07-15 2017-08-25 上海华谊（集团）公司 The catalyst and preparation method of a kind of acetic acid preparation of ethanol by hydrogenating

Also Published As

Publication number Publication date
CN107999064A (en) 2018-05-08

Similar Documents

Publication Publication Date Title
CN108017509B (en) The method of butadiene production 1,4- butanediol
CN107778135B (en) The method for producing 1,4- butanediol
CN107999064B (en) The catalyst of butadiene synthesis 1,4- diacetoxy butane course
CN107774253B (en) For synthesizing the hydrogenation catalyst of 1,4- diacetoxy butane
CN107774336B (en) Catalyst for 1,4- diacetoxy butylene hydrogenation process
CN107774250B (en) Catalyst for 1,4- diacetoxy butylene hydrogenation technique
CN107790182B (en) 1,4- diacetoxy butylene hydrogenation process catalyst
CN107774255B (en) 1,4- diacetoxy butylene hydroprocessing catalysts
CN107778134B (en) The synthetic method of 1,4- butanediol
CN108014791A (en) Butadiene prepares the catalyst of 1,4- diacetoxy butane courses
CN107778136B (en) The method for preparing 1,4- butanediol
CN108014796A (en) The catalyst of butadiene production 1,4- diacetoxy butane courses
CN107866217B (en) Catalyst suitable for the preparation of 1,4- diacetoxy butane
CN108014794B (en) Synthesize hydrogenation catalyst used in 1,4- diacetoxy butane
CN107867971B (en) The preparation method of 1,4-butanediol
CN108002980A (en) The method that butadiene Acetoxylation synthesizes 1,4- butanediols
CN107999069A (en) Butadiene prepares the catalyst of 1,4- diacetoxy butane processes
CN107774252A (en) For producing the hydrogenation catalyst of 1,4 diacetoxy butane
CN107999068A (en) The catalyst of butadiene production 1,4- diacetoxy butane processes
CN107774254A (en) For preparing the hydrogenation catalyst of 1,4 diacetoxy butane
CN108014817A (en) Butadiene synthesizes the catalyst of 1,4- diacetoxy butane processes
CN107790180A (en) Catalyst for 1,4 diacetoxy butylene hydrogenation
CN107866218A (en) The catalyst prepared applied to 1,4 diacetoxy butane
CN107866221A (en) Catalyst applied to the production of 1,4 diacetoxy butane
CN107999065A (en) Butadiene synthesizes the catalyst of 1,4- diacetoxy butane processes

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant