CN1136207C - Lactone preparing catalyst and lactone preparing process - Google Patents
Lactone preparing catalyst and lactone preparing process Download PDFInfo
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- CN1136207C CN1136207C CNB001301772A CN00130177A CN1136207C CN 1136207 C CN1136207 C CN 1136207C CN B001301772 A CNB001301772 A CN B001301772A CN 00130177 A CN00130177 A CN 00130177A CN 1136207 C CN1136207 C CN 1136207C
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Abstract
The present invention relates to catalyst used for preparing lactone. A carrier loads copper compound, zinc compound and at least one kind of catalyst of alkaline earth metal compound. The present invention also relates to a method for manufacturing the lactone, which comprises the following step: after the catalyst is activated, glycol carries out cyclisation dehydrogenation reaction in a gas phase under the existence of the catalyst. The catalyst of the present invention for preparing the lactone has the advantages of high activity, long service life, high product selectivity and high economic benefit.
Description
Technical field
The present invention relates to prepare the catalyzer that lactone uses and 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.
Background technology
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.
Summary of the invention
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)
Embodiment
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 (13)
1. one kind prepares the catalyzer that lactone is used, it is the catalyzer that is carried with copper compound, zn cpds and at least a alkaline earth metal compound on carrier, wherein, the material of described carrier is selected from the cohort of being made up of silicon-dioxide, aluminum oxide and composition thereof, and its content is 20wt%～30wt%; The weight ratio of described copper compound and zn cpds in cupric oxide and zinc oxide, is 6: 1～1: 2; And 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; Or 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.
2. 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.
3. 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.
4. 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.
5. the preparation method of a lactone, it comprise catalyzer one of any in the claim 1 to 4 activated after, in the presence of this catalyzer, make glycol in gas phase, carry out the dehydrocyclization reaction, the activation of wherein said catalyzer is under 180～250 ℃, carries out in 6～20 hours with hydrogen reducing.
6. preparation method as claimed in claim 5, 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.
7. preparation method as claimed in claim 5, 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.
8. preparation method as claimed in claim 5, wherein said lactone is that gamma-butyrolactone and described glycol are 1, the 4-butyleneglycol.
9. preparation method as claimed in claim 5, wherein said dehydrocyclization reaction is carried out under 160～280 ℃.
10. preparation method as claimed in claim 8, wherein said dehydrocyclization reaction be in hydrogen to 1, the mol ratio of 4-butyleneglycol is 12～1 to carry out.
11. preparation method as claimed in claim 8, wherein said dehydrocyclization reaction is in 1, the gas space flow velocity of 4-butyleneglycol be 10～20,000 (hour)
-1Carry out.
12. preparation method as claimed in claim 5, used catalyst bed is a fixed bed in the wherein said dehydrocyclization reaction.
13. preparation method as claimed in claim 5, used catalyst bed is a thermopnore in the wherein said dehydrocyclization reaction.
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 |
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| CN1349853A CN1349853A (en) | 2002-05-22 |
| CN1136207C true CN1136207C (en) | 2004-01-28 |
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| CNB001301772A Expired - Lifetime CN1136207C (en) | 2000-10-19 | 2000-10-19 | Lactone preparing catalyst and lactone preparing process |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003069152A (en) * | 2001-06-15 | 2003-03-07 | Sony Corp | Multibeam semiconductor laser element |
| 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 |
| JP5645065B2 (en) * | 2010-09-13 | 2014-12-24 | 国立大学法人 千葉大学 | Method for producing δ-valerolactone |
| 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 |
| 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 |
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