CN1357409A - Catalyst for dehydrogenating 1,4-butanediol to prepare gramma-butyrolactone and its prepn - Google Patents
Catalyst for dehydrogenating 1,4-butanediol to prepare gramma-butyrolactone and its prepn Download PDFInfo
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- CN1357409A CN1357409A CN 01138003 CN01138003A CN1357409A CN 1357409 A CN1357409 A CN 1357409A CN 01138003 CN01138003 CN 01138003 CN 01138003 A CN01138003 A CN 01138003A CN 1357409 A CN1357409 A CN 1357409A
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- catalyst
- butanediol
- butyrolacton
- dehydrogenation system
- precipitation
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Abstract
The present invention belongs to the field of catalyst technology and the catalyst for dehydrogenating 1, 4-butanediol to prepare gamma-butyrolactone consists of CuO 20-80 wt%, ZnO 20-75 wt% and Al2O3 1-40 wt%. It is prepared through two-step deposition process. The catalyst prepared through said process has its performance superior to that prepared through conventional process and reaching or even superior to that of Cu-Cr catalyst.
Description
Technical field: the invention belongs to catalyst technical field, being specifically related to is the catalyst of 1,4 butanediol dehydrogenation system gamma-butyrolacton of a kind of Cu of containing, Zn, Al.
Background technology: the gamma-butyrolacton production method is more, but be mainly two big classes: a class is the hydrogenation of maleic acid method, one class is 1,4-butanediol dehydrogenation method, although the cis-butenedioic anhydride method has the low advantage of obvious cost of material, but short and not perfect its actual cost that causes of production technology rises significantly because of its catalyst life, and manufacturer does not close the door or changes the line of production because of technology passes a test.And the latter is still industrial production method commonly used.
1, the 4-butanediol dehydrogenation prepares gamma-butyrolacton technology two kinds: batch (-type) and continuous gas-phase dehydrogenation.Batch (-type) makes its production cost higher owing to adopt noble metal to make catalyst.Continuous gas-phase dehydrogenation technology is to face under the hydrogen state, adopts the Cu-Cr series catalysts, adopts the Cu-Cr series catalysts, as EP523774A, CN1173492, and CN1194268, CN1169428, CN1220186A etc.But adopt the Cu-Cr series catalysts because of containing poisonous element Cr in the catalyst, bring environmental pollution damage in can and using in Catalyst Production.With regard to industrialized Cu-Zn-Cr-Zr catalyst, not only exist and use noxious material Cr, and used the more expensive zr element of price.
In recent years, in order to overcome the harm of Cr, Chinese scholars has attempted mainly that nontoxic or low toxicity element (as elements such as Zr, Ba, Ti) replaces poisonous element Cr with some.But compare with containing the Cr catalyst, these catalyst have gap aspect catalytic performance, and because of containing Zr, Ti etc. than precious metal element, and the catalyst cost is increased.
Summary of the invention: the objective of the invention is to research and develop that a kind of high-performance, cost are lower, nontoxic pollution-free 1, the environment-friendly type catalyst of 4-butanediol dehydrogenation system gamma-butyrolacton.
Catalyst of the present invention consists of cupric oxide, zinc oxide, aluminium oxide, and its key property is not add poisonous component and noble metal the 4th component.Content in the catalytic component of the present invention (wt%) is respectively: cupric oxide 20-80%, and value preferably is 25-80%, zinc oxide 20-75%, value preferably is 25-75%, aluminium oxide 1-40%, value preferably is 5-20%.
Catalyst of the present invention adopts the method for precipitation to be prepared.Its key property is to adopt the method for two-step precipitation to prepare this catalyst.This method may further comprise the steps:
(1) the nitrate mixed liquor of copper zinc and aluminium and suitable precipitating reagent are carried out precipitation reaction respectively.The soluble-salt of Cu, Zn and Al, the nitrate of Cu, Zn, Al preferably, proportion of composing according to catalyst is dissolved in the deionized water respectively, make the solution that Cu, Zn salt mixture concentration and Al salinity are respectively 0.5-2.0M, 0.05-1.0M, at a certain temperature with suitable precipitant mix co-precipitation respectively, control PH=5.0-9.0, precipitating reagent can be Na
2CO
3, NH
4HCO
2, (NH
4)
2CO
3, NaOH, NaHCO
3, one or more alkali in the ammoniacal liquor are composite.The control precipitation temperature is 20-80 ℃, after precipitation is finished, at 40-90 ℃ of ageing 20-50min, filter, wash, dry 10-20h under 80-120 ℃ calcines 2-5h down at 200-500 ℃, and last compressing tablet becomes the cylindrical catalyst of Φ 5 * 5mm or the tablet of any specification.
(2) catalyst that makes needs can use after reduction, and reducing condition is: at 2-5%H
2-N
2In the air-flow, under 0.05-2.0MPa pressure in 120-300 ℃ of following temperature programmed reduction 10-40h.
The invention provides 1, the method for 4-butanediol dehydrogenation system butyrolactone is: after above-mentioned catalyst reduction, with 1, the 4-butanediol is a raw material, enters reactor through vaporization and carries out 1, the reaction of 4-butanediol dehydrogenation, be reflected at 150-300 ℃, 0.1-1.0MPa, 1,4-butanediol liquid air speed 0.5-10.0h
-1Condition under carry out, reaction condition preferably is 160-280 ℃, 0.1-0.5MPa, 1,4-butanediol liquid air speed 1.0-9.0h
-1
Reaction back effluent goes out purpose product gamma-butyrolacton through condensation separation.
One of catalyst outstanding feature of the present invention is that the catalyst activity component is CuO-ZnO-Al
2O
3, in catalyst preparation process, do not add and contain poisonous elemental constituent or more expensive metal the 4th active component, be a kind of environment-friendly type catalyst cheaply that has.
Catalyst second characteristics of the present invention are to adopt the method for unique two-step precipitation to prepare this catalyst.
Catalyst the 3rd characteristics of the present invention are catalyst activity height, 1, and 4-butanediol conversion ratio and gamma-butyrolacton selectivity height, its catalytic stability is good.
Catalyst of the present invention carries out 1, during 4-butanediol dehydrogenation prepared in reaction gamma-butyrolacton, because the function admirable of catalyst, its catalytic performance reaches the performance of the Cu-Cr series catalysts of domestic better performances, both can improve yield, reducing production costs, do not have the worry of environmental protection again, is the new varieties of a kind of superior performance/price ratio.
The specific embodiment: following example and comparative example can the invention will be further described.Example 1 neutralizes with the sodium carbonate liquor of 1M mixed liquors such as the nitrate of 1M copper zinc and 1M aluminum nitrate respectively under 10～80 ℃, strong mixing, control terminal point PH=5.0～9.0, after precipitation is finished, at 30～90 ℃ of following ageing 30min, the solids that filters gained after the ageing washs repeatedly with desalted water under 20～80 ℃, after the assay was approved above-mentioned two kinds of solution hybrid filterings is become filter cake with diphenylamine sulfate.Washed filter cake is dried by the fire 16～20h down at 60～120 ℃, and again at 200～500 ℃ of following roasting 2h, the particle that roasting is good mixes the cylindrical catalyst A that the back compressing tablet becomes Φ 5 * 5 with shaping assistant.Example 2 is with the nitrate mixed liquor of copper, zinc, aluminium and the catalyst B of sodium carbonate liquor prepared by co-precipitation, and all the other preparation conditions are with example 1.Example 3 is with the nitrate mixed liquor and the anti-catalyst C that adds the precipitation preparation of sodium carbonate liquor of copper, zinc, aluminium, and all the other preparation conditions are with example 1.
In the tubular reactor of Φ 30 * 5000mm, Φ 5 * 5mm catalyst 50ml that packs into, 1,4-butanediol liquid air speed is 1.20h
-1, carry out the performance evaluation of catalyst under 180 ℃ the condition.The performance of catalyst A, B, C of pressing example 1, example 2, the preparation of example 3 methods is as shown in table 1.
Table 1 preparation method is to the influence of the catalytic performance of catalyst
| Catalyst | Conversion ratio, % | Selectivity, % | Yield, % |
| ????A | ????65.31 | ????99.25 | ????64.82 |
| ????B | ????65.06 | ????97.56 | ????64.00 |
| ????C | ????58.20 | ????97.42 | ????56.7 |
By table 1 as seen, adopt the catalyst performance of method for preparing catalyst of the present invention (example 1) preparation obviously to be better than adopting the performance of the preparation catalyst of conventional method.Mainly show gamma-butyrolacton selectivity height and 1,4-butanediol conversion ratio height.The embodiment of the invention and domestic goods activity of such catalysts are compared as follows:
The catalyst and the contrast of domestic catalyst performance of amplifying preparation by example 1 method see Table 2.The performance measurement condition of catalyst is with example 1, heat-resisting condition: 380 ℃, and 4h.
Claims (6)
1, a kind of 1, the catalyst of 4 butanediol dehydrogenation system gamma-butyrolactons, consist of cupric oxide, zinc oxide, aluminium oxide, it is characterized in that not adding and contain poisonous elemental constituent or more expensive metal the 4th active component, catalytic component content (wt%) is: cupric oxide 20-80%, zinc oxide 20-75%, aluminium oxide 1-40%.
2, a kind of 1,4 butanediol dehydrogenation system gamma-butyrolacton Preparation of catalysts method adopts the method preparation of two-step precipitation, it is characterized in that it may further comprise the steps:
(1) with the soluble-salt of Cu, Zn and Al, proportion of composing according to catalyst is dissolved in the deionized water, make the solution that Cu, Zn salt mixture concentration and Al salinity are respectively 0.5-2.0M, 0.05-1.0M, at a certain temperature with suitable precipitant mix co-precipitation respectively, control PH=5.0-9.0, precipitating reagent can be Na
2CO
3, NH
4HCO
3, (NH
4)
2CO
3, NaOH, NaHCO
3, one or more alkali in the ammoniacal liquor are composite, the control precipitation temperature is 20-80 ℃, after precipitation is finished, at 40-90 ℃ of ageing 20-50min, filter, wash, dry 10-20h under 80-120 ℃ calcines 2-5h down at 200-500 ℃, and last compressing tablet becomes the cylindrical catalyst of Φ 5 * 5mm or the tablet of any specification;
(2) catalyst that makes needs can use after reduction, and reducing condition is: at 2-5%H
2-N
2In the air-flow, under 0.05-2.0MPa pressure, in 120-300 ℃ of following temperature programmed reduction 10-40h.
3, a kind of 1,4 butanediol dehydrogenation system gamma-butyrolacton catalyst as claimed in claim 1 is characterized in that 150-300 ℃, 0.1-1.0Mpa, 1, the 4 butanediol liquid air speed 0.5-10.0h of being reflected at of this catalyst
-1Condition under carry out.
4, a kind of 1,4 butanediol dehydrogenation system gamma-butyrolacton catalyst as claimed in claim 1 is characterized in that content in the catalytic component (wt%) is respectively: cupric oxide 25-80%, zinc oxide 25-75%, aluminium oxide 5-20%.
5, a kind of as 1,4 butanediol dehydrogenation system gamma-butyrolacton Preparation of catalysts method as described in the claim 2, the soluble-salt that it is characterized in that Cu, Zn and Al is the nitrate of Cu, Zn and Al.
6, a kind of catalyst of 1,4 butanediol dehydrogenation system gamma-butyrolacton as claimed in claim 3 is characterized in that the reaction condition of this catalyst is: 160-280 ℃, 0.1-0.5MPa, 1,4-butanediol liquid air speed 1.0-9.0h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01138003 CN1199728C (en) | 2001-12-20 | 2001-12-20 | Catalyst for dehydrogenating 1,4-butanediol to prepare gramma-butyrolactone and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01138003 CN1199728C (en) | 2001-12-20 | 2001-12-20 | Catalyst for dehydrogenating 1,4-butanediol to prepare gramma-butyrolactone and its prepn |
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| Publication Number | Publication Date |
|---|---|
| CN1357409A true CN1357409A (en) | 2002-07-10 |
| CN1199728C CN1199728C (en) | 2005-05-04 |
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|---|---|---|---|
| CN 01138003 Expired - Fee Related CN1199728C (en) | 2001-12-20 | 2001-12-20 | Catalyst for dehydrogenating 1,4-butanediol to prepare gramma-butyrolactone and its prepn |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044197A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Technological method for purifying1,4-butanediol and co-producing gamma-butyrolactone |
| CN103877981A (en) * | 2014-01-07 | 2014-06-25 | 濮阳迈奇科技有限公司 | Catalyst for preparing gamma-butyrolactone by gaseous phase dehydrogenation of 1, 4-butanediol under normal pressure and preparation method thereof |
| CN115814794A (en) * | 2022-12-01 | 2023-03-21 | 西安凯立新材料股份有限公司 | Copper/silicon oxide catalyst and preparation method and application thereof |
| CN115814794B (en) * | 2022-12-01 | 2024-06-04 | 西安凯立新材料股份有限公司 | Copper/silicon oxide catalyst and preparation method and application thereof |
-
2001
- 2001-12-20 CN CN 01138003 patent/CN1199728C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044197A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Technological method for purifying1,4-butanediol and co-producing gamma-butyrolactone |
| CN103044197B (en) * | 2011-10-17 | 2015-07-22 | 中国石油化工股份有限公司 | Technological method for purifying1,4-butanediol and co-producing gamma-butyrolactone |
| CN103877981A (en) * | 2014-01-07 | 2014-06-25 | 濮阳迈奇科技有限公司 | Catalyst for preparing gamma-butyrolactone by gaseous phase dehydrogenation of 1, 4-butanediol under normal pressure and preparation method thereof |
| CN115814794A (en) * | 2022-12-01 | 2023-03-21 | 西安凯立新材料股份有限公司 | Copper/silicon oxide catalyst and preparation method and application thereof |
| CN115814794B (en) * | 2022-12-01 | 2024-06-04 | 西安凯立新材料股份有限公司 | Copper/silicon oxide catalyst and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1199728C (en) | 2005-05-04 |
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