CN1660488A - Preparing catalyst of tetrahydrofuran by adding hydrogen to maleic anhydride in gas phase and preparation method - Google Patents
Preparing catalyst of tetrahydrofuran by adding hydrogen to maleic anhydride in gas phase and preparation method Download PDFInfo
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- CN1660488A CN1660488A CN 200410065882 CN200410065882A CN1660488A CN 1660488 A CN1660488 A CN 1660488A CN 200410065882 CN200410065882 CN 200410065882 CN 200410065882 A CN200410065882 A CN 200410065882A CN 1660488 A CN1660488 A CN 1660488A
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- maleic anhydride
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- oxolane
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Abstract
A catalyst for preparing the tetrahydrofuran from maleic anhydride or its derivative by gas-phase hydrogenation cnotains Cu, Zn and Al. It is prepared from copper oxide, zinc oxide, aluminium oxide and shaping assistant through co-deposition. Its advantages are no toxic components and the forth activating component, and high conversion rate selectivity.
Description
Technical field:
The invention belongs to catalyst field, relate to the environment-friendly type catalyst that a kind of catalytic hydrogenation maleic anhydride and derivative thereof prepare oxolane, is the maleic anhydride of a kind of Cu of containing, Zn, Al and the catalyst of derivative hydrogenation system oxolane thereof.
Background technology:
Oxolane is a kind of broad-spectrum low boiling point solvent and organic matter intermediate.In recent years, because the purposes and the consumption of oxolane constantly increase, people deepen continuously to the oxolane production technology research, and industrialized production method mainly contains 1.4-butanediol evaporation, maleic anhydride hydrogenation by-product method, furfural method, maleic anhydride hydrogenation method.1.4-although butanediol evaporation process route is short, its cost height; Although the present domestic raw material of furfural method is abundanter, its raw material is subjected to the influence of the Nature bigger, and process route is long, and this method is eliminated abroad; Maleic anhydride hydrogenation method amount of by-products is generally less, is a process route with good industrial prospect.
Come acid anhydrides and derivative thereof to prepare succinic anhydride (SA), γ-Ding lactones (GBL) and 1.4-butanediol (BDO) by catalysis hydrogen dapple, confirmed by many documents.But particularly patent report is less to be used for further preparing the report of oxolane.Catalyst in the hydrogenation contains chromium (as US3065243, described in the CN99804254B) usually, and the catalytic performance of catalyst is not good.At the maleic anhydride and the derivative hydrogenation preparing oxolane CuO-ZnO-Al thereof that reported in the past
2O
3The preparation method of three-way catalyst has two kinds: a kind of is cladding process, as CN01820322A etc., not only has complex manufacturing, and technical difficulty is bigger, and reaction temperature is higher; Another kind is a coprecipitation, but this catalyst only has higher selectivity to product GBL when hydrogenation of maleic anhydride and derivative thereof, must have solvent to have oxolane selectivity≤87% when not having solvent to exist when the preparation oxolane.Therefore, from industrial point of view, the exploitation have greater activity and optionally maleic anhydride hydrogenation preparing oxolane environment-friendly type catalyst have tangible economy and social effect.
Summary of the invention:
The base metal environment-friendly type Catalysts and its preparation method that the purpose of this invention is to provide a kind of high-performance maleic anhydride hydrogenation preparing oxolane.Catalyst provided by the invention does not add the 4th active component that contains poisonous elemental constituent or precious metal, uses this catalyst can obtain higher maleic anhydride conversion ratio and oxolane selectivity.
Catalyst of the present invention is the catalyst of maleic anhydride hydrogenation system oxolane, it consists of cupric oxide, zinc oxide, aluminium oxide, its key property is not add the 4th active component that contains poisonous elemental constituent or precious metal, catalytic component content (wt%) is respectively: cupric oxide 30%～60%, zinc oxide 30%～60%, aluminium oxide 5%～30%, surplus is shaping assistant.
Catalyst of the present invention adopts the method preparation of co-precipitation, and this method may further comprise the steps:
Soluble-salt with Cu, Zn, Al, the nitrate of Cu, Zn, Al preferably, proportion of composing according to catalyst is dissolved in the deionized water, make the solution that mixture concentration is 0.5M～1.5M, under 20 ℃～80 ℃ temperature, be 0.5M～1.5M precipitant mix co-precipitation with concentration, 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 compounds in the ammoniacal liquor; After precipitation is finished, at 40 ℃～90 ℃ ageing 20min～50min, filter, wash dry 10h～20h under 80 ℃～120 ℃, calcine 2h～5h down at 200 ℃～500 ℃, last compressing tablet becomes the cylindrical catalyst of Φ 5mm * 5mm.Perhaps with the soluble-salt of Cu, Zn, the nitrate of Cu, Zn preferably, by preceding method after finishing filtration, washing, mode with making beating adds aluminium oxide through acid treatment, acid can be organic acid or inorganic acid, and as nitric acid, citric acid, oxalic acid etc., subsequent processing steps and condition are the same.
Can use after the catalyst need that make are activated, activation condition is: containing 2%～5%H
2Hydrogen nitrogen mixed gas or flow of pure hydrogen in, under 0.05MPa～2.0MPa pressure, in 120 ℃～300 ℃ following temperature programmings activation 10h～40h.
The using method of the adding hydrogen to maleic anhydride in gas phase system of the invention provides oxolane is: after the activation of above-mentioned catalyst, make the unstripped gas of certain hydrogen/acid anhydride mol ratio with hot hydrogen band maleic anhydride, react by fixed bed reactors continuously.Be reflected at 200 ℃～300 ℃, 1.0MPa～4.0MPa, hydrogen acid anhydride than 50～500, maleic anhydride liquid air speed 0.02h
-1～2.0h
-1Condition under carry out, reaction back effluent goes out purpose product oxolane through condensation separation.Optimum reaction condition is: 220 ℃～280 ℃, 1.5MPa～2.5MPa, hydrogen acid anhydride are than 100～300, maleic anhydride liquid air speed 0.05h
-1～1.0h
-1
One of distinguishing feature of catalyst of the present invention is that the catalyst activity component is CuO-ZnO-Al
2O
3, in catalyst preparation process, do not add the 4th active component that contains poisonous elemental constituent or precious metal, be a kind of catalyst of environment-friendly type cheaply.
The catalytic performance that second distinguishing feature of catalyst of the present invention is catalyst is good, maleic anhydride conversion ratio and oxolane selectivity height.
When catalyst of the present invention is used for adding hydrogen to maleic anhydride in gas phase prepared in reaction oxolane, because the function admirable of catalyst both can improve yield, reducing production costs, do not have the worry of environmental protection again, is the higher new product of a kind of ratio of performance to price.
The specific embodiment: the invention will be further described below in conjunction with embodiment and comparative example.
Example 1:
With the sodium carbonate liquor of the nitrate mixed liquor of 1.2MCu, Zn, Al and 0.8M 20 ℃～80 ℃, stir under neutralization, control terminal point pH=5.5～8.5, after precipitation is finished, at 40 ℃～80 ℃ following ageing 20min, the solids that filters gained after the ageing spends deionised water repeatedly under 40 ℃～70 ℃, be filtered into filter cake after the assay was approved with diphenylamine sulfate.With washed filter cake dry 16h under 80 ℃～120 ℃, again at 200 ℃～500 ℃ following roasting 2h, the particle that roasting is good mixes the cylindrical catalyst that the back compressing tablet becomes Φ 5mm * 5mm with shaping assistant, the catalyst that makes consists of cupric oxide 40.2%, zinc oxide 37.8%, aluminium oxide 14.5%, shaping assistant 7.5%.
In the tubular reactor of Φ 10 * 1mm, 20 orders of packing into～40 purpose catalyst 2ml.This catalyst need activate before reaction, and activation is adopted and contained 2%～5%H
2Hydrogen nitrogen mixed gas at 120 ℃～300 ℃ following temperature programmings activation 10h～30h.In maleic anhydride liquid air speed is 0.1h
-1, reaction pressure is 2.0MPa, and reaction temperature is 240 ℃, and hydrogen/acid anhydride ratio is the performance evaluation of carrying out catalyst under 150: 1 the condition.Performance by the catalyst A of example 1 method preparation is as shown in table 1.
Example 2:
The preparation method is with example 1, and the catalyst that makes is a catalyst B, and it consists of cupric oxide 32.5%, zinc oxide 32.9%, aluminium oxide 29.6%, shaping assistant 5.0%.Its performance sees Table 1.
Example 3:
The preparation method is with example 1, and the catalyst that makes is catalyst C, and it consists of cupric oxide 57.0%, zinc oxide 30.0%, aluminium oxide 7.5%, shaping assistant 5.5%.Its performance sees Table 1.
Example 4:
Except that the precursor of aluminium for mixing, grind the aluminium oxide of processing such as material, oven dry, pulverizing through 5% (wt) citric acid and after washing is finished, adding in the mode of pulling an oar, surplus with method 1, the catalyst that makes is catalyst D, its performance sees Table 1.
Example 5:
In specification is in the tubular reactor of Φ 32 * 2mm, packs into and amplifies the Φ 5mm * 5mm catalyst 50ml of preparation by example 1 method, and hydrogen acid anhydride ratio is 150: 1, and reaction pressure is 2.0MPa, and reaction temperature is 260 ℃, and maleic anhydride liquid air speed is 0.1h
-1, all the other conditions are with example 1, and self-control is amplified sample E catalyst performance and is seen Table 1.
The contrast of table 1 catalyst performance
| Catalyst | Maleic anhydride conversion ratio (%) | Oxolane selectivity (%) |
| ????A ????B ????C ????D ????E | ????100 ????99.2 ????100 ????100 ????99.0 | ????98.2 ????99.1 ????96.5 ????95.5 ????98.0 |
As can be seen from Table 1, activity of such catalysts of the present invention, selectivity ratios are higher, show that catalyst of the present invention has higher activity, selectivity.
Claims (8)
1. the catalyst of an adding hydrogen to maleic anhydride in gas phase system oxolane, consist of cupric oxide, zinc oxide, aluminium oxide, it is characterized in that not adding the 4th active component that contains poisonous elemental constituent or precious metal, catalytic component content (wt%) is: cupric oxide 30%～60%, zinc oxide 30%～60%, aluminium oxide 5%～30%, surplus is shaping assistant.
2. the Preparation of catalysts method of an adding hydrogen to maleic anhydride in gas phase system oxolane as claimed in claim 1 is coprecipitation, it is characterized in that it may further comprise the steps:
Soluble-salt with Cu, Zn, Al, proportion of composing according to catalyst is dissolved in the deionized water, makes the solution that mixture concentration is 0.5M-1.5M, is the precipitant mix co-precipitation of 0.5M-1.5M with concentration down at 20 ℃～80 ℃, control pH=5.0～9.0, precipitating reagent is Na
2CO
3, NH
4HCO
3, (NH
4)
2CO
3, NaOH, NaHCO
3, one or more alkali compounds in the ammoniacal liquor, after precipitation is finished, at 40 ℃～90 ℃ ageing 20min～50min, filter, wash, dry 10h～20h under 80 ℃～120 ℃ calcines 2h～5h down at 200 ℃～500 ℃, and last compressing tablet becomes the cylindrical catalyst of φ 5mm * 5mm; Perhaps with the soluble-salt of Cu, Zn, after finishing filtration, washing, add the aluminium oxide of crossing through organic acid or mineral acid treatment by preceding method in the mode of making beating, all the other steps are the same.
3. the Preparation of catalysts method of an adding hydrogen to maleic anhydride in gas phase system oxolane as claimed in claim 2, the precursor that it is characterized in that Cu, Zn, Al is separately solubility nitrate.
4. the Preparation of catalysts method of an adding hydrogen to maleic anhydride in gas phase system oxolane as claimed in claim 2 is characterized in that aluminium oxide mixes, grinds material, oven dry, pulverization process through 5% (wt) citric acid and crosses.
5. the Preparation of catalysts method of an adding hydrogen to maleic anhydride in gas phase system oxolane as claimed in claim 2 is characterized in that described alkali is one or both mixed bases in sodium carbonate, sodium acid carbonate or the ammoniacal liquor.
6. the Preparation of catalysts method of an adding hydrogen to maleic anhydride in gas phase system oxolane as claimed in claim 2, pH is 5.5～8.5 when it is characterized in that co-precipitation.
7. the Application of Catalyst of an adding hydrogen to maleic anhydride in gas phase system oxolane as claimed in claim 1 is characterized in that the catalyst that makes needs activated back to use, and activation condition is: containing 2%～5%H
2Hydrogen nitrogen mixed gas or flow of pure hydrogen in, under 0.05MPa～2.0MPa pressure, in 120 ℃～300 ℃ following temperature programmings activation 10h～40h; Reaction condition is: 200 ℃～300 ℃, 1.0MPa～4.0MPa, hydrogen acid anhydride than 50～500, maleic anhydride liquid air speed 0.02h
-1～2.0h
-1
8. the Application of Catalyst of an adding hydrogen to maleic anhydride in gas phase system oxolane as claimed in claim 7 is characterized in that reaction condition is: 220 ℃～280 ℃, 1.5MPa～2.5MPa, hydrogen acid anhydride are than 100～300, maleic anhydride liquid air speed 0.05h
-1～1.0h
-1
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617518A (en) * | 2011-01-27 | 2012-08-01 | 中科合成油技术有限公司 | One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation |
| CN101747149B (en) * | 2008-12-11 | 2013-02-20 | 浙江杭州鑫富药业股份有限公司 | Method for preparing 1,4-butanediol by two-section hydrogenation of maleic acid dialkyl ester |
| CN103638931A (en) * | 2013-12-04 | 2014-03-19 | 江苏清泉化学有限公司 | Nickel-containing catalyst for hydrogenation of 2,5-dimethoxy-2,5-dihydrofuran and preparation method of nickel-containing catalyst |
| CN103724300A (en) * | 2013-12-18 | 2014-04-16 | 江苏大学 | Method for preparing tetrahydrofuran by coupling maleic anhydride hydrogenation and alcohol dehydrogenation |
-
2004
- 2004-12-24 CN CN 200410065882 patent/CN1660488A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747149B (en) * | 2008-12-11 | 2013-02-20 | 浙江杭州鑫富药业股份有限公司 | Method for preparing 1,4-butanediol by two-section hydrogenation of maleic acid dialkyl ester |
| CN102617518A (en) * | 2011-01-27 | 2012-08-01 | 中科合成油技术有限公司 | One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation |
| CN102617518B (en) * | 2011-01-27 | 2014-10-01 | 中科合成油技术有限公司 | One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation |
| CN103638931A (en) * | 2013-12-04 | 2014-03-19 | 江苏清泉化学有限公司 | Nickel-containing catalyst for hydrogenation of 2,5-dimethoxy-2,5-dihydrofuran and preparation method of nickel-containing catalyst |
| CN103724300A (en) * | 2013-12-18 | 2014-04-16 | 江苏大学 | Method for preparing tetrahydrofuran by coupling maleic anhydride hydrogenation and alcohol dehydrogenation |
| CN103724300B (en) * | 2013-12-18 | 2016-01-13 | 江苏大学 | A kind of maleic anhydride hydrogenation is coupled with alcohol dehydrogenase and prepares the method for tetrahydrofuran (THF) |
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