CN1349853A - Lactone preparing catalyst and lactone preparing process - Google Patents

Lactone preparing catalyst and lactone preparing process Download PDF

Info

Publication number
CN1349853A
CN1349853A CN 00130177 CN00130177A CN1349853A CN 1349853 A CN1349853 A CN 1349853A CN 00130177 CN00130177 CN 00130177 CN 00130177 A CN00130177 A CN 00130177A CN 1349853 A CN1349853 A CN 1349853A
Authority
CN
China
Prior art keywords
catalyzer
preparation
zinc
lactone
oxide
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.)
Granted
Application number
CN 00130177
Other languages
Chinese (zh)
Other versions
CN1136207C (en
Inventor
陈显彰
林福伸
许良安
蔡振琳
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.)
DALIAN CHEMICAL INDUSTRY Co Ltd
Original Assignee
DALIAN CHEMICAL INDUSTRY Co Ltd
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 DALIAN CHEMICAL INDUSTRY Co Ltd filed Critical DALIAN CHEMICAL INDUSTRY Co Ltd
Priority to CNB001301772A priority Critical patent/CN1136207C/en
Publication of CN1349853A publication Critical patent/CN1349853A/en
Application granted granted Critical
Publication of CN1136207C publication Critical patent/CN1136207C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Landscapes

  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The catalyst for preparing lactone is one on whose carrier the copper compound, zinc compound and at least one alkaline earth metal compound are carried. Said invention also relates to the method for preparing lactone, and said preparation method includes the steps of activating catalyst and making glycol implement cyclodehydrogenation reaction in gas phase in the presence of said catalyst. Said catalyst is high in activity, long in service life and high in selection rate.

Description

The catalyzer that the preparation lactone is used and the preparation method of lactone
The present invention relates to prepare the catalyzer that lactone is used, this catalyzer is to be carried with copper compound, zn cpds and at least a alkaline earth metal compound on carrier.The invention still further relates to the preparation method of lactone, this preparation method comprise aforementioned catalyzer activated after, in the presence of this catalyzer, make glycol in gas phase, carry out the dehydrocyclization reaction.
Lactone such as gamma-butyrolactone can be used as weedicide, can be the intermediate product of preparation pyrrolidone (for example N-Methyl pyrrolidone, 2-Pyrrolidone and N-vinyl pyrrolidone), hexahydropyridine, phenylbutyric acid and Thiobutyric acid or are used for pharmacy composite.Therefore, have economic benefit the gamma-butyrolactone preparation method exploitation always for industrial community required.
In the past, gamma-butyrolactone was to be carried out hydrogenation and made in liquid phase or gas phase by MALEIC ANHYDRIDE or ester, but this processing procedure needs a large amount of hydrogen and catalyst life short, therefore not ideal.
At present, gamma-butyrolactone can be by 1, and the 4-butyleneglycol carries out the dehydrocyclization reaction and makes, and generates a large amount of hydrogen by products that can be used as raw material or fuel use.This is by 1, and the preparation method that the 4-butyleneglycol carries out the gamma-butyrolactone of dehydrocyclization reaction sees Japanese kokai publication sho 58-13575, and it is to carry out liquid phase dehydrocyclization reaction with platinum/plumbous catalyzer, but its catalyst activity is low, and low to the gamma-butyrolactone selection rate; Japanese kokai publication sho 61-246173 is with 1, and 4-butyleneglycol steam obtains gamma-butyrolactone by copper/chromium/zinc catalyst, but it has produced a large amount of tetrahydrofuran (THF)s and butanols by product, and the selection rate of gamma-butyrolactone and productive rate are not high usually; Japanese kokai publication hei 3-232874 is with 1,4-butyleneglycol steam generates gamma-butyrolactone by copper/chromium/manganese or titanate catalyst, USP 5110954 is with 1, the 4-butyleneglycol adds in copper/chrome catalysts solution and obtains gamma-butyrolactone, and Japanese kokai publication hei 2-255668 is with 1, and 4-butyleneglycol steam generates gamma-butyrolactone by copper/zinc/base metal catalysts, but all very fast decline of these catalyst activities, after for some time is carried out in reaction, 1,4-butyleneglycol transformation efficiency becomes low.Therefore with regard to the commercialization processing procedure, it can't be satisfactory.
Shortcoming in view of above-mentioned known technology, an object of the present invention is to provide a kind of catalyzer that lactone is used for preparing, it is the catalyzer that is carried with copper compound, zn cpds and at least a alkaline earth metal compound on carrier, it is used in by glycol in gas phase, carries out in dehydrocyclization reaction the processing procedure with the preparation lactone, catalyst activity and life-span with raising, simultaneously the selection rate of lactone can be up to more than the 99mol%, thereby has improved the economic benefit of this processing procedure significantly;
Another object of the present invention provides a kind of preparation method of lactone.
The catalyzer that preparation lactone of the present invention is used is the catalyzer that is carried with copper compound, zn cpds and at least a alkaline earth metal compound on carrier, the solid support material that catalyzer of the present invention is suitable for has silicon-dioxide, aluminum oxide or its mixture, is preferably the mixture of silicon-dioxide and aluminum oxide.
The present invention prepares lactone and can be multiple mantoquita with the copper compound in the catalyzer, and the example is cupric nitrate, copper carbonate, neutralized verdigris, cupric chloride, copper hydroxide, cupric phosphate and copper sulfate etc.Zn cpds in the catalyzer of the present invention can be multiple zinc salt, and the example is zinc nitrate, zinc carbonate, zinc acetate, zinc chloride, zinc hydroxide and zinc sulfate etc.Alkaline earth metal compound in the catalyzer of the present invention is at least a metallic compound that is selected from beryllium, magnesium, calcium, strontium or barium, be preferably at least a metallic compound that is selected from magnesium, calcium or barium, comprise their carbonate, oxyhydroxide, silicate and phosphoric acid salt etc.
The catalyzer that preparation lactone of the present invention is used is prepared according to following method: carrier is contained be dipped in the aqueous solution of above-mentioned mantoquita and zinc salt, adjust the pH value in 8~11 with ammoniacal liquor, the precipitation of hydroxide that makes copper and zinc is on carrier; With throw out washing, drying; Impregnation is selected from the aqueous solution of aforementioned salt of one or both alkaline earth metal compounds of magnesium, calcium or barium; Then in 400~500 ℃ of calcinings 3~5 hours; If need, then can add for example graphite of molded auxiliary agent, and be molded as predetermined shape with moulding press.In the catalyzer that so makes, each metal ingredient is oxide form and exists, before the dehydrogenation reaction of carrying out glycol, need under the temperature prior to 180~250 ℃, activated in 6~20 hours, and can be used with hydrogen (ratio of hydrogen and nitrogen is heightened to all being hydrogen gradually from 1: 20 to 1: 10 initial volume ratio) reduction.
Preparing in the catalyzer that lactone uses in the present invention, the weight ratio of cupric oxide and zinc oxide is generally 6: 1~and 1: 2, be preferably 5: 1~1: 1.When use was selected from any alkaline earth metal compound of magnesium, calcium or barium, it was measured in oxide compound, is preferably 0.01~10wt% of cupric oxide and zinc oxide gross weight, more preferably 0.05~5wt%; When use was selected from any two kinds of alkaline earth metal compounds of magnesium, calcium or barium, it was measured in oxide compound, is preferably 0.5~20wt% of cupric oxide and zinc oxide gross weight, more preferably 1~10wt%.The consumption of carrier is preferably 0.5~20wt% of cupric oxide and zinc oxide gross weight, more preferably 1~10wt% in silicon-dioxide.
The preparation method of lactone provided by the invention, it comprise aforementioned catalyzer activated after, in the presence of this catalyzer, make glycol in gas phase, carry out the dehydrocyclization reaction.
The example of lactone of the present invention such as beta-propiolactone, beta-butyrolactone, gamma-butyrolactone, γ-Wu Neizhi, δ-butyrolactone, γ-Ji Neizhi, 6-caprolactone, δ-Xin Neizhi, δ-nonalactone, γ-decalactone and δ-Gui Neizhi etc.
The example of used glycol is as 1 among the lactone preparation method of the present invention, ammediol, 2-methyl isophthalic acid, ammediol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,4-pentanediol, 1,5-hexylene glycol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol and decamethylene-glycol etc.
In lactone of the present invention such as gamma-butyrolactone preparation method's dehydrocyclization reaction, temperature of reaction is generally 160~280 ℃, is preferably 180~250 ℃; If temperature of reaction can reduce by 1 too low, the transformation efficiency of 4-butyleneglycol, though and higher temperature of reaction can improve 1, the transformation efficiency of 4-butyleneglycol can make the selection rate of gamma-butyrolactone greatly reduce.
In lactone of the present invention such as gamma-butyrolactone preparation method's dehydrocyclization reaction, reaction pressure is generally 1~10atm, is preferably 1~5atm.Higher reaction pressure is easy to generate side reaction, and productive rate is reduced.
In lactone of the present invention such as gamma-butyrolactone preparation method's dehydrocyclization reaction, need be with hydrogen as vector gas, if hydrogen does not exist in the reactive system, then life of catalyst can shorten.The amount of used hydrogen need make reactive system be maintained at gas phase at least, common used hydrogen and 1, and the mol ratio of 4-butyleneglycol is 12~1, is preferably 8~1.5.
In lactone of the present invention such as gamma-butyrolactone preparation method's dehydrocyclization reaction, used 1, if the gas space flow velocity of 4-butyleneglycol is too low, then the residence time of gas in catalyst bed oversize, cause product to decompose, the selection rate of gamma-butyrolactone is reduced; And 1, the gas space flow velocity Ruo Taigao of 4-butyleneglycol, then the residence time of gas in catalyst bed too short, make 1, the transformation efficiency of 4-butyleneglycol reduces.Usually, 1, the gas space flow velocity of 4-butyleneglycol be 10~20,000 (hour) -1, be preferably 30~9,000 (hour) -1
In lactone of the present invention such as gamma-butyrolactone preparation method's dehydrocyclization reaction, used catalyst bed can be fixed bed or liquid bed.
In carrying out the reacted certain hour of dehydrocyclization, through the condensation collecting reaction product, form with HP-6890 gas chromatograph analysis outlet, calculate two alcohol conversions and lactone selection rate according to following formula (1) and (2), and obtain the productive rate of lactone.Two alcohol conversions=(the glycol mole number of the glycol mole number-discharging of charging)/
Glycol mole number * 100% (2) of the glycol mole number of charging * 100% (1) lactone selection rate=interior ester products mole number/(charging-discharging)
Following embodiments of the invention and comparative example are described in detail, but be not to be used to limit the scope of the invention.
Comparative example 1
Get commercially with copper-chromium catalyst (wherein cupric oxide accounts for 42wt%, and chromic oxide accounts for 28wt%, diameter 5mm) 30ml, filling is in the stainless steel tube reactor of internal diameter 23.5mm.With nitrogen temperature to 150 ℃, then feed the mixed gas of 10% (percent by volume) hydrogen then, beginning catalyst reduction reaction.Heighten temperature and density of hydrogen gradually, to the catalyst reduction temperature be 200 ℃ and density of hydrogen 100% (percent by volume), determine that the temperature of catalyst bed temperature and heating installation is identical after, stop reduction reaction.
Then, temperature of reactor is risen to 210 ℃, with 1, the 4-butyleneglycol is squeezed in the reactor with pump of constant delivery type, makes 1, the gas space flow velocity of 4-butyleneglycol maintain 4500 (hour) -1, to 1 mole 1, under the ratio of 4-butyleneglycol, carry out dehydrogenation reaction in 5 mol of hydrogen.The collection analysis product, the result is as shown in table 1.
Comparative example 2
Repeat the same steps as of comparative example 1, only be to use the commercial copper-zinc catalyst (G-66) of using, its composition is cupric oxide 60wt% and zinc oxide 30wt%, and the result is as shown in table 1.
Comparative example 3
Repeat the same steps as of comparative example 1, only be to use the copper/chromium/zinc catalyst according to the described method preparation of the clear 61-246173 of day disclosure special permission communique, its composition is cupric oxide 35wt%, zinc oxide 4.5wt% and chromic oxide 60wt%, and the result is as shown in table 1.
Comparative example 4
Repeat the same steps as of comparative example 1, only be to use with commerce with copper-zinc catalyst (G-66) impregnation 0.5% aqueous sodium hydroxide solution after exsiccant catalyzer again, its composition is cupric oxide 60wt%, zinc oxide 30wt% and sodium hydroxide 0.12wt%, and the result is as shown in table 1.
Table 1
Comparative example ???1 ??2 ??3 ??4
Temperature of reaction, ℃ ???210 ??210 ??210 ??210
Reaction pressure, atm ???1 ??1 ??1 ??1
1,4-butyleneglycol gas space flow velocity, (hour) -1 ???4500 ??4500 ??4500 ??4500
Hydrogen/1,4-butyleneglycol mol ratio ???5/1 ??5/1 ??5/1 ??5/1
1,4-butyleneglycol transformation efficiency, mole % ???72.50 ??91.50 ??81.30 ??97.20
The gamma-butyrolactone selection rate, mole % ???88.30 ??92.50 ??90.50 ??95.30
The gamma-butyrolactone productive rate, mole % ???64.02 ??84.64 ??73.82 ??92.63
Embodiment 1
[BET surface-area (according to the surface-area of Brunner-Emmett-Teller method mensuration) is 185m with 10 gram silicon-dioxide slowly to pour 60% copper nitrate aqueous solution, 350 grams into 40% zinc nitrate aqueous solution 220 grams 2/ g] in the mixture of powder, and keep abundant stirring, then slowly add 25% ammoniacal liquor, make the pH value of mixed aqueous solution be maintained at 10, continue to stir, after the throw out filtering separation, clean with water, then placed 100 ℃ of baking ovens dry 12 hours, obtain the complex catalyst precursor thing.This complex catalyst precursor thing moved to be heated to 450 ℃ in the tubular high temperature stove, calcined 4 hours.This catalyzer consists of cupric oxide: zinc oxide=3: 1.
Add 1.0wt% graphite in above-mentioned catalyzer, it is squeezed into the round shaped grain catalyzer of diameter 5mm.Get this catalyzer 30ml, repeat the same steps as of comparative example 1, the result is as shown in table 2.
Embodiment 2 to 7
Repeat the same steps as of embodiment 1, just the temperature of the weight ratio of cupric oxide and zinc oxide, dehydrogenation reaction and hydrogen are to 1, and the mol ratio of 4-butyleneglycol is all as shown in table 2, and its result also is shown in Table 2.
Table 2
Embodiment ??1 ??2 ??3 ??4 ??5 ??6 ??7
Cupric oxide: zinc oxide, weight ratio ??3/1 ??5/1 ??1/2 ??5/1 ??3/1 ??5/1 ??3/1
Temperature of reaction, ℃ ??210 ??210 ??210 ??210 ??210 ??230 ??230
Reaction pressure, atm ??1 ??1 ??1 ??1 ??1 ??1 ??1
BDO gas space flow velocity, (hour) -1 ??4500 ??4500 ??4500 ??4500 ??4500 ??4500 ??4500
Hydrogen/BDO, mol ratio ??5/1 ??5/1 ??5/1 ??2/1 ??2/1 ??5/1 ??5/1
The BDO transformation efficiency, mole % ??97.30 ??98.50 ??92.10 ??95.30 ??93.50 ??98.10 ??97.20
The gamma-butyrolactone selection rate, mole % ??96.10 ??97.40 ??90.50 ??97.10 ??96.50 ??91.50 ??90.30
The gamma-butyrolactone productive rate, mole % ??93.50 ??95.94 ??83.35 ??92.53 ??90.22 ??89.76 ??87.77
Embodiment 8
Behind the complex catalyst precursor thing impregnation 1.5wt% baryta water with embodiment 1, then this catalyzer is moved to and be heated to 450 ℃ in the tubular high temperature stove, calcined 4 hours.This catalyzer consists of cupric oxide 55wt%, zinc oxide 22wt% and barium oxide 1.2wt%.
Compare the same steps as of example 1 with this catalyzer, the result is as shown in table 3.
Embodiment 9
Behind the complex catalyst precursor thing impregnation 1.0wt% calcium hydroxide aqueous solution with embodiment 1, then this catalyzer is moved to and be heated to 450 ℃ in the tubular high temperature stove, calcined 4 hours.This catalyzer consists of cupric oxide 53wt%, zinc oxide 24wt% and calcium oxide 0.81wt%.
Compare the same steps as of example 1 with this catalyzer, the result is as shown in table 3.
Embodiment 10
Behind the complex catalyst precursor thing impregnation 1.0wt% magnesium hydroxide aqueous solution with embodiment 1, then this catalyzer is moved to and be heated to 450 ℃ in the tubular high temperature stove, calcined 4 hours.This catalyzer consists of cupric oxide 49wt%, zinc oxide 26wt% and magnesium oxide 0.52wt%.
Compare the same steps as of example 1 with this catalyzer, the result is as shown in table 3.
Embodiment 11
Behind the complex catalyst precursor thing impregnation 1.5wt% hydrated barta and the 0.3wt% calcium hydroxide blended aqueous solution with embodiment 1, then this catalyzer is moved to and be heated to 450 ℃ in the tubular high temperature stove, calcined 4 hours.This catalyzer consists of cupric oxide 55wt%, zinc oxide 22wt%, barium oxide 1.2wt% and calcium oxide 0.14wt%.
Compare the same steps as of example 1 with this catalyzer, the result is as shown in table 3.
Embodiment 12
Behind the complex catalyst precursor thing impregnation 1.0wt% calcium hydroxide and the 0.4wt% magnesium hydroxide blended aqueous solution with embodiment 1, then this catalyzer is moved to and be heated to 450 ℃ in the tubular high temperature stove, calcined 4 hours.This catalyzer consists of cupric oxide 53wt%, zinc oxide 24wt%, calcium oxide 0.81wt% and magnesium oxide 0.16wt%.
Compare the same steps as of example 1 with this catalyzer, the result is as shown in table 3.
Embodiment 13
Behind the complex catalyst precursor thing impregnation 1.0wt% magnesium hydroxide and the 0.2wt% hydrated barta blended aqueous solution with embodiment 1, then this catalyzer is moved to and be heated to 450 ℃ in the tubular high temperature stove, calcined 4 hours.This catalyzer consists of cupric oxide 49wt%, zinc oxide 26wt%, magnesium oxide 0.52wt% and barium oxide 0.11wt%.
Compare the same steps as of example 1 with this catalyzer, the result is as shown in table 3.
Table 3
Embodiment ????8 ????9 ????10 ????11 ????12 ????13
Temperature of reaction, ℃ ????210 ????210 ????210 ????210 ????210 ????210
Reaction pressure, atm ????1 ????1 ????1 ????1 ????1 ????1
BDO gas space flow velocity, (hour) -1 ????4500 ????4500 ????4500 ????4500 ????4500 ????4500
Hydrogen/BDO mol ratio ????5/1 ????5/1 ????5/1 ????5/1 ????5/1 ????5/1
The BDO transformation efficiency, mole % ????99.50 ????99.20 ????99.60 ????99.90 ????99.50 ????99.80
The gamma-butyrolactone selection rate, mole % ????99.10 ????98.60 ????98.10 ????99.80 ????99.10 ????99.30
The gamma-butyrolactone productive rate, mole % ????98.60 ????97.81 ????97.70 ????99.70 ????98.60 ????99.10

Claims (18)

1. one kind prepares the catalyzer that lactone is used, and it is the catalyzer that is carried with copper compound, zn cpds and at least a alkaline earth metal compound on carrier.
2. catalyzer as claimed in claim 1, the material of wherein said carrier is selected from the cohort of being made up of silicon-dioxide, aluminum oxide and composition thereof.
3. catalyzer as claimed in claim 1, wherein said copper compound is selected from the cohort of being made up of cupric nitrate, copper carbonate, neutralized verdigris, cupric chloride, copper hydroxide, cupric phosphate and copper sulfate.
4. catalyzer as claimed in claim 1, wherein said zn cpds is selected from the cohort of being made up of zinc nitrate, zinc carbonate, zinc acetate, zinc chloride, zinc hydroxide and zinc sulfate.
5. catalyzer as claimed in claim 1, wherein said alkaline earth metal compound is selected from the cohort of being made up of the carbonate of beryllium, magnesium, calcium, strontium and barium, oxyhydroxide, silicate and phosphoric acid salt.
6. catalyzer as claimed in claim 1, the weight ratio of wherein said copper compound and zn cpds in cupric oxide and zinc oxide, is 6: 1~1: 2.
7. catalyzer as claimed in claim 1, wherein when using a kind of described alkaline earth metal compound, it is measured in oxide compound, is 0.01~10wt% of cupric oxide and zinc oxide gross weight.
8. catalyzer as claimed in claim 1, wherein when using two kinds of described alkaline earth metal compounds, it is measured in oxide compound, is 0.5~20wt% of cupric oxide and zinc oxide gross weight.
9. the preparation method of a lactone, it comprise catalyzer one of any in the claim 1 to 8 activated after, in the presence of this catalyzer, make glycol in gas phase, carry out the dehydrocyclization reaction.
10. preparation method as claimed in claim 9, wherein said lactone is selected from the cohort of being made up of beta-propiolactone, beta-butyrolactone, gamma-butyrolactone, γ-Wu Neizhi, δ-butyrolactone, γ-Ji Neizhi, 6-caprolactone, δ-Xin Neizhi, δ-nonalactone, γ-decalactone and δ-Gui Neizhi.
11. preparation method as claimed in claim 9, wherein said glycol is selected from by 1, ammediol, 2-methyl isophthalic acid, ammediol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,4-pentanediol, 1,5-hexylene glycol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1, the cohort that 9-nonanediol and decamethylene-glycol are formed.
12. preparation method as claimed in claim 9, wherein said lactone is that gamma-butyrolactone and described glycol are 1, the 4-butyleneglycol.
13. preparation method as claimed in claim 9, the activation of wherein said catalyzer is under 180~250 ℃, carries out in 6~20 hours with hydrogen reducing.
14. preparation method as claimed in claim 9, wherein said dehydrocyclization reaction is carried out under 160~280 ℃.
15. as the preparation method of claim 12, wherein said dehydrocyclization reaction be in hydrogen to 1, the mol ratio of 4-butyleneglycol is 12~1 to carry out.
16. as the preparation method of claim 12, wherein said dehydrocyclization reaction is in 1, the gas space flow velocity of 4-butyleneglycol be 10~20,000 (hour) -1Carry out.
17. preparation method as claimed in claim 9, used catalyst bed is a fixed bed in the wherein said dehydrocyclization reaction.
18. preparation method as claimed in claim 9, used catalyst bed is a thermopnore in the wherein said dehydrocyclization reaction.
CNB001301772A 2000-10-19 2000-10-19 Lactone preparing catalyst and lactone preparing process Expired - Lifetime CN1136207C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB001301772A CN1136207C (en) 2000-10-19 2000-10-19 Lactone preparing catalyst and lactone preparing process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB001301772A CN1136207C (en) 2000-10-19 2000-10-19 Lactone preparing catalyst and lactone preparing process

Publications (2)

Publication Number Publication Date
CN1349853A true CN1349853A (en) 2002-05-22
CN1136207C CN1136207C (en) 2004-01-28

Family

ID=4594011

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB001301772A Expired - Lifetime CN1136207C (en) 2000-10-19 2000-10-19 Lactone preparing catalyst and lactone preparing process

Country Status (1)

Country Link
CN (1) CN1136207C (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1305193C (en) * 2001-06-15 2007-03-14 索尼公司 Multi-beam semiconductor laser
CN101157677B (en) * 2007-09-27 2011-05-04 复旦大学 Method for catalytic preparation of delta-valerolactone by using supported nano-gold catalyst
JP2012056927A (en) * 2010-09-13 2012-03-22 Chiba Univ METHOD OF PRODUCING δ-VALEROLACTONE
CN106632163A (en) * 2016-12-07 2017-05-10 合肥利夫生物科技有限公司 Preparation method of gamma-caprolactone
CN107694573A (en) * 2017-10-17 2018-02-16 聊城大学 A kind of copper zinc zirconia metallic catalyst and the method that γ valerolactones are continuously synthesized using the catalyst
CN107974445A (en) * 2017-11-20 2018-05-01 苏州艾缇克药物化学有限公司 A kind of cupric phosphate of cladding enzyme/poly-(6-caprolactone)The preparation method of crystal catalyst and the application in spiral shell producing oxindoles
CN110773174A (en) * 2019-09-24 2020-02-11 浙江大学 Catalyst for preparing gamma-butyrolactone through dehydrogenation of 1, 4-butanediol and preparation method thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1305193C (en) * 2001-06-15 2007-03-14 索尼公司 Multi-beam semiconductor laser
CN101157677B (en) * 2007-09-27 2011-05-04 复旦大学 Method for catalytic preparation of delta-valerolactone by using supported nano-gold catalyst
JP2012056927A (en) * 2010-09-13 2012-03-22 Chiba Univ METHOD OF PRODUCING δ-VALEROLACTONE
CN106632163A (en) * 2016-12-07 2017-05-10 合肥利夫生物科技有限公司 Preparation method of gamma-caprolactone
CN106632163B (en) * 2016-12-07 2019-01-01 合肥利夫生物科技有限公司 A kind of preparation method of γ-hexalactone
CN107694573A (en) * 2017-10-17 2018-02-16 聊城大学 A kind of copper zinc zirconia metallic catalyst and the method that γ valerolactones are continuously synthesized using the catalyst
CN107974445A (en) * 2017-11-20 2018-05-01 苏州艾缇克药物化学有限公司 A kind of cupric phosphate of cladding enzyme/poly-(6-caprolactone)The preparation method of crystal catalyst and the application in spiral shell producing oxindoles
CN110773174A (en) * 2019-09-24 2020-02-11 浙江大学 Catalyst for preparing gamma-butyrolactone through dehydrogenation of 1, 4-butanediol and preparation method thereof
CN110773174B (en) * 2019-09-24 2020-11-10 浙江大学 Catalyst for preparing gamma-butyrolactone through dehydrogenation of 1, 4-butanediol and preparation method thereof

Also Published As

Publication number Publication date
CN1136207C (en) 2004-01-28

Similar Documents

Publication Publication Date Title
CN1269781C (en) Alcohol producing method and catalyst thereof
CN101502803B (en) Catalyst for preparing 1,4-butanediol or tetrahydrofuran from selective hydrogenation of dimethyl maleate and preparation method thereof
CN1136207C (en) Lactone preparing catalyst and lactone preparing process
WO2010054055A2 (en) Copper catalyst for dehydrogenation application
CN1215984C (en) Iron oxides with a higher degree of refining
CN103100393A (en) Hydrogenation catalyst and preparation method thereof
CN102304021B (en) Method for preparing neopentyl glycol
CN103476492B (en) For aldehyde being hydrogenated the promoted cu zn catalyst for alcohol
CN101395112B (en) Process for hydrogenating methylolalkanals
EP0582277B1 (en) Process for producing unsaturated alcohols
KR101975914B1 (en) Hydrogenation catalysts and the preparation processes thereof
JP2001504891A (en) Improved method for producing polytetrahydrofuran
JP3763738B2 (en) Catalyst for producing lactones and method for producing lactones
CN111715238B (en) Hydrogenation catalyst, preparation method and application thereof
CN113101937A (en) Doped mixed-valence copper catalyst and preparation method and application thereof
CN101391964A (en) Method for preparing 2-amido-1-alkyl alcohol and catalyst preparation method
CN1247559C (en) Method for the selective production of tetrahydrofuran by hydrogenating maleic acid anhydride
CN110560072A (en) Catalyst for producing 1, 6-hexanediol by hydrogenation of adipate and preparation method thereof
CN112871171A (en) Preparation method for preparing multi-element low-carbon alcohol by dimethyl oxalate gas-phase hydrogenation
CN1138018A (en) Catalyst(A) for preparation of 1,4-butanediol by gas-phase hydrogenation
CN113731442B (en) Catalyst for dimethyl maleate hydrogenation reaction and preparation method and application thereof
CN1187303C (en) Solid alkali catalyst for synthesizing propanediol ether
CN114956956B (en) Method for producing neopentyl glycol
CN1137944A (en) Catalyst (B) for preparation of 1,4-butanediol by gas-phase hydrogenation
CN117443407B (en) Copper rare earth-based LDHs dehydrogenation catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1044129

Country of ref document: HK

CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20040128