CN1123389C - Preparation of catalyst for preparing low-carbon alcohol by low-carbon oleffine hydration and its application - Google Patents
Preparation of catalyst for preparing low-carbon alcohol by low-carbon oleffine hydration and its application Download PDFInfo
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- CN1123389C CN1123389C CN98114266A CN98114266A CN1123389C CN 1123389 C CN1123389 C CN 1123389C CN 98114266 A CN98114266 A CN 98114266A CN 98114266 A CN98114266 A CN 98114266A CN 1123389 C CN1123389 C CN 1123389C
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Abstract
The present invention relates to a catalyst for preparing low-carbon alcohol by the hydration of low-carbon olefin, which is characterized in that the catalyst is prepared from a modified beta molecular sieve and an adhesive, wherein the modified element is at least one of La, B, Fe, Ge, Ni, Cr, Co, Cu, Mg, Ca, Sr and Ge; the adhesive is one of silica sol, water glass, aluminum hydroxide, boehmite, kaoline, zirconium hydroxide, titanium oxide and clay soil; the catalyst is prepared from 1 to 5 wt% of modified element, 40 to 80 wt% of beta zeolite molecular sieve and balance of adhesive. The catalyst has the advantages of no requirement for raw material purity, good activity at low temperature, long one-way life time and capability of repeated regeneration.
Description
The present invention relates to catalysis technique, a kind of low-carbon alkene hydration system low-carbon alcohol its preparation of catalyzer and application are provided especially.
The olefin hydration reaction is one of important organic catalytic reaction.In hydration reaction, what meaning represented and practical value were arranged most is that olefin hydration prepares alcohols.As important Organic Chemicals and solvent, purposes is very widely arranged as ethanol, Virahol, sec-butyl alcohol, ethanol can be used for system dye, coating, medicine, synthetic rubber, washing composition.Virahol can be used as outside synthetic glycerine, the acetone, also can be used for the synthetic of meticulous product such as agricultural chemicals, spices.The a large amount of purposes of sec-butyl alcohol are methyl ethyl ketones, or can be used as the raw material of softening agent, weedicide, dressing agent.
Above-mentioned several olefin hydration is produced corresponding alcohol, and the traditional industry method all is to adopt the indirect hydration method of sulfuric acid, this method since its to problems such as the strong corrosion effect of equipment and spent acid processing, progressively replaced by the catalysis direct hydration method.The ethene direct hydration method is to adopt up-to-date a kind of method, this method to require ethene purity higher in the present industry, because the development of the maturation of ethylene industry, it is not difficult matter that highly purified ethene is provided.This method is made catalyzer with phosphoric acid/carrier, and the corrosion situation of equipment is more light than indirect method, though the ethene per pass conversion is lower, have only about 5%, but technical maturity can adapt to maximization, modernized requirement, labour productivity height, production cost also are lower than the sulfuric acid indirect method.What the industrial production of Virahol adopted at present extensively is to be catalyzer with the phosphoric acid/kieselguhr, and at 180～260 ℃, propylene and water react and gets under 2.5～6.5MPa condition.N-butene direct hydration method production technique is the butylene-butane mixture that contains 80～85% n-butenes, with water preheat after temperature of reaction, add from groove type reactor bottom and to carry out direct hydration.Butylene is 150～170 ℃ of temperature of reaction, and during 6.0MPa, its per pass conversion is about 6%, and the transformation efficiency of circulation time reaches 90%.
Zeolite [molecular sieve is a kind of outstanding solid acid that the acid loss does not take place.Because its particular performances, making it has crucial meaning in petrochemical complex.In order to overcome the shortcoming of above-mentioned catalyzer, investigators are devoted to develop low-carbon alkene hydration zeolite catalyst in recent years.The zeolite type of being studied is a lot, such as Y-zeolite, beta-zeolite, γ-zeolite, X-zeolite, super steady Y-zeolite (USY), dealuminzation Y-zeolite, mordenite, ZSM series.
It is more to be used for olefin hydration foreign study report at relevant zeolite [molecular sieve, as U.S. US4857664,4727977,5012014, and European patent EP 210793,1986, EP323268,1988, EP323137,1989, EP458048,1991.By showing in the above-mentioned document, propylene hydration prepares in the zeolite that Virahol/isopropyl ether adopts, and the effect of β zeolite is best.The ZSM-5 zeolite is effective to ethylene hydration, and n-butylene hydration system sec-butyl alcohol employing ZSM series transformation efficiency and selectivity are all very high.
The object of the present invention is to provide a kind of low-carbon alkene hydration system low-carbon alcohol catalyzer, it is to the material purity no requirement (NR), and low temperature active is good, and the one way life-span is long, iterative regenerable.
The invention provides a kind of low-carbon alkene hydration system low-carbon alcohol catalyzer, it is characterized in that: this catalyzer is made up of the beta-molecular sieve and the binding agent of modification, modifying element is selected among La, B, Fe, Ge, Ni, Cr, Co, Cu, Mg, Ca, Sr, the Ge at least a, and binding agent is selected from a kind of of silicon sol, water glass, aluminium hydroxide, boehmite, kaolin, zirconium hydroxide, titanium oxide, clay; Catalyzer consists of (all being weight percentage among the present invention) except that special indicating
Modifying element 1～5%
Beta-zeolite molecular sieve 40～80%
The binding agent surplus
Modifying element preferably accounts for 2～4% among the present invention.Beta-zeolite molecular sieve preferably accounts for 50～70%.
The present invention also provides above-mentioned low-carbon alkene hydration system low-carbon alcohol Preparation of catalysts method, and it is characterized in that: the modification of beta-molecular sieve is undertaken by ion-exchange or dipping, remix binding agent, pore-forming material and thinner moulding; Pore-forming material is selected from sesbania powder, Walocel MT 20.000PV, and add-on is 1～10% of a catalytic amount; Thinner is selected from water, rare HNO
3, add-on is suitable to be shaped to.
Wherein thinner is preferably selected 0.5N HNO for use
3Solution.
The present invention is applicable to ethene, propylene, 1-butylene, suitable, anti--2-butylene, iso-butylene hydration system ethanol, Virahol, sec-butyl alcohol, the trimethyl carbinol.
It can be polymeric that the present invention adopts the modified beta zeolite molecular sieve use catalyzer, related propylene as propylene hydration preparing isopropanol reaction, can be rare propylene such as propylene and propane mixture also, or the propylene in the catalytic cracking, need not do the particular purification processing.
The present invention adopts modified ZSM-5 zeolite as ethylene hydration system ethanol, n-butylene hydration system sec-butyl alcohol catalyzer.Raw materials used can be pure ethylene, pure butene-1, also can be rare ethene and n-butene-1.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
Take by weighing 100g β zeolite powder (Si/Al=27), through 350 ℃ of roastings 2 hours, 550 ℃ of roastings 2 hours, burn off falls to lead phase agent tetraethyl ammonium hydroxide, uses 1N NH again
4NO
3Solution exchanges four times under 85 ℃ of conditions, and solid-to-liquid ratio is 1: 10.Use washed with de-ionized water at last four times, through airing, 120 ℃ of bakings 12 hours, 500 ℃ of following roastings 4 hours, it is standby that Na β is become the H beta-molecular sieve.Obtain sample A.
Embodiment 2
From sample A, take out 10 gram H type molecular sieve powder and industrial goods aluminium hydroxide 4.3g and 0.15g sesbania powder 1N HNO
3The mixing batter shape utilizes banded extruder to extrude the bar of diameter about for Φ 2mm, and through airing, 120 ℃ of bakings 12 hours were burnt 4 hours through 500 ℃ of bakings again, obtained catalyst B.
Embodiment 3
Sample thief A10g, nickelous nitrate 0.5g, Al (OH)
34g, sesbania powder 0.12g uses 0.5N HNO
3The furnishing pasty state is extruded into the bar that diameter is 2mm, through airing, 120 ℃ of oven dry 12 hours, 500 ℃ of roastings 4 hours, catalyzer C.
Embodiment 4
Adopt the identical method of example 3, just change nickelous nitrate into lanthanum nitrate, make catalyzer D.
Embodiment 5
Get catalyst B 3 grams, be crushed to 20～40 orders, use rare H
3BO
3Solution 4ml (contains 0.06 gram B
2O
3) dipping, airing, 120 ℃ of oven dry, catalyzer E is made in 500 ℃ of roastings 4 hours.
Embodiment 6
Sample thief A5 gram adds 28%SiO again
2Content silicon sol and sesbania powder 0.05g, extruded moulding, diameter also are Φ 2mm, again through airing, oven dry, 500 ℃ of roastings 4 hours obtain catalyzer F.
Embodiment 7
Take by weighing the synthetic former powder of ZSM-5 (Si/Al=48) of 100 gram amine processes, go through 350 ℃ 1 hour, 450 ℃ of 550 ℃ of roastings in 2 hours in 2 hours are removed and lead the molecular sieve powder of phase agent, press molecular sieve: Al (OH)
3: the sesbania powder=mixed was even in 69: 29: 2, used 1N HNO again
3The furnishing pasty state, being extruded into diameter with banded extruder is bar about 2mm, airing at room temperature, 120 ℃ of bakings 12 hours rise to 550 ℃ with 60 ℃/hour in retort furnace, and constant temperature 4 hours, will obtain ZSM-5/Al
2O
3Mixture; Be crushed to 20～40 orders, take by weighing 30g, exchange 4 times down with 1N HCl reflux conditions, be 1 hour each swap time, uses deionized water at last, washs 4 times, at room temperature airing was dried 12 hours for 120 ℃, rose to 550 ℃ and constant 4 hours with 60 ℃/hour in retort furnace, obtain moulding HZSM-5, take by weighing molded HZSM-510g, with the ca nitrate soln 10ml dipping that contains 0.2gCa, heating, drying in the water-bath, 550 ℃ of following roastings 4 hours, obtain the CaHZSM-5 sample again, note is made catalyzer G.
Embodiment 8-catalyzer application examples 1
Evaluate catalysts B on self-built continuous micro-reactor, reactor size are φ 16 * 5 * 300mm, interior dress 3g20～40 order catalyst B, and the bed type uses trickle bed, and promptly propylene and water all from reactor top charging, are used N earlier before the reaction
2400 ℃ activate 1 hour, begin into ionized water when reducing to 130 ℃, begin into propylene when hydraulic pressure reaches reaction pressure 7.0MPa, and water and propylene all adopt the charging of high pressure trace piston pump, and water/propylene molecules ratio is 30, propylene liquid air speed 0.30h
-1140～200 ℃ of temperature of reaction, reaction product liquid body and function OV-17 capillary column, flame ionization detector detects, gas Qs post, the TCD identifier is analyzed, and used chromatogram is Shanghai analytical instrument factory 103 and the Shanghai GC8810A of Kechuang chromatogram company type chromatographic instrument, and the chromatogram MPU adopts day island proper Tianjin company to produce CR-1A, in the time of 150 ℃, propylene conversion 38～50%, Virahol selectivity 95%, diisopropyl ether selectivity 5%.
Embodiment 9-catalyzer application examples 2
Evaluate catalysts B, C, D, E, F on embodiment 8 devices, catalyst-assembly is 6g.Appreciation condition is: reaction pressure 7.0MPa, 150 ℃ of temperature, water/propylene (mol)=30, propylene liquid air speed 0.30h
-1, concrete reaction result sees Table 1.
Propylene hydration preparing isopropanol result on the different catalysts
| Catalyzer | Propylene conversion % | Virahol selectivity % | Other % |
| B C D E F | 38 42.3 42.6 40.3 37.5 | 93.6 96.6 97.0 97.2 94.2 | 6.4 3.4 3.0 2.8 5.8 |
Embodiment 10-catalyzer application examples 3
Take out the catalyzer D of inactivation, in retort furnace, rise to 550 ℃ with 60 ℃/hour, and constant temperature 2 hours, on embodiment 8 devices, estimate reaction pressure 7.0MPa, 150 ℃ of temperature, water/propylene (mol)=30, propylene liquid air speed 0.30h again
-1, propylene conversion can reach 42.5%, the selectivity of Virahol＞97.0%.
Embodiment 11-catalyzer application examples 4
Take by weighing 7 controlling catalyst G6g of embodiment, estimate its reactivity worth on embodiment 8 devices, charging is 1-butylene and water, and 1-butylene liquid air speed is 0.30h
-1, water/propylene (mol)=20, reaction pressure 7.0MPa, 180 ℃ of temperature, 1-butylene transformation efficiency 27.0%, the selectivity of sec-butyl alcohol is 99.6% (wt).
Claims (6)
1. low-carbon alkene hydration system low-carbon alcohol catalyzer, it is characterized in that: this catalyzer is made up of the beta-molecular sieve and the binding agent of modification, modifying element is selected among La, B, Fe, Ge, Ni, Cr, Co, Cu, Mg, Ca, Sr, the Ge at least a, and binding agent is selected from a kind of of silicon sol, water glass, aluminium hydroxide, boehmite, kaolin, zirconium hydroxide, titanium oxide, clay; Catalyzer consists of (weight percent)
Modifying element 1～5%
Beta-zeolite molecular sieve 40～80%
The binding agent surplus
2. according to the described low-carbon alkene of claim 1 hydration system low-carbon alcohol catalyzer, it is characterized in that: modifying element accounts for 2～4%.
3. according to the described low-carbon alkene of claim 1 hydration system low-carbon alcohol catalyzer, it is characterized in that: beta-zeolite molecular sieve accounts for 50～70%.
4. the described low-carbon alkene of claim 1 hydration system low-carbon alcohol Preparation of catalysts method, it is characterized in that: the modification of beta-molecular sieve is undertaken by ion-exchange or dipping, remix binding agent, pore-forming material and thinner moulding; Pore-forming material is selected from sesbania powder, Walocel MT 20.000PV, and add-on is 1～10% of a catalytic amount; Thinner is selected from water, rare HNO
3, add-on is suitable to be shaped to.
5. according to the described low-carbon alkene of claim 4 hydration system low-carbon alcohol Preparation of catalysts method, it is characterized in that: thinner is selected 0.5N HNO for use
3Solution.
6. the described catalyzer of claim 1 is used for ethene, propylene, 1-butylene, suitable, anti--2-butylene, iso-butylene hydration system ethanol, Virahol, sec-butyl alcohol, the trimethyl carbinol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114266A CN1123389C (en) | 1998-08-26 | 1998-08-26 | Preparation of catalyst for preparing low-carbon alcohol by low-carbon oleffine hydration and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114266A CN1123389C (en) | 1998-08-26 | 1998-08-26 | Preparation of catalyst for preparing low-carbon alcohol by low-carbon oleffine hydration and its application |
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|---|---|
| CN1245738A CN1245738A (en) | 2000-03-01 |
| CN1123389C true CN1123389C (en) | 2003-10-08 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915517B (en) * | 2005-08-15 | 2010-04-28 | 中国石油化工股份有限公司 | Catalyst in use for producing cyclohexene |
| EP2104565B1 (en) * | 2007-01-03 | 2012-04-11 | Saudi Basic Industries Corporation | Zeolite-kaolin catalyst composition |
| CN105170195B (en) * | 2015-09-14 | 2018-06-12 | 新奥科技发展有限公司 | Shaping of catalyst method |
| CN109647501B (en) * | 2019-01-18 | 2021-12-28 | 中国科学院城市环境研究所 | Hierarchical porous Fe-beta molecular sieve catalyst and preparation method and application thereof |
| CN113617385A (en) * | 2021-08-18 | 2021-11-09 | 天津长芦海晶集团有限公司 | Preparation method of catalyst for olefin hydration reaction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5012014A (en) * | 1990-04-26 | 1991-04-30 | Mobil Oil Corporation | Catalyst pretreatment for olefin hydration |
| CN1140629A (en) * | 1995-07-18 | 1997-01-22 | 南开大学 | Catalyst using for process of ether and its processing method |
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- 1998-08-26 CN CN98114266A patent/CN1123389C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5012014A (en) * | 1990-04-26 | 1991-04-30 | Mobil Oil Corporation | Catalyst pretreatment for olefin hydration |
| CN1140629A (en) * | 1995-07-18 | 1997-01-22 | 南开大学 | Catalyst using for process of ether and its processing method |
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Assignee: Zhejiang Xinhua Chemical Co., Ltd. Assignor: Dalian Institute of Chemical Physics, Chinese Academy of Sciences Contract record no.: 2011330001362 Denomination of invention: Preparation of catalyst for preparing low-carbon alcohol by low-carbon oleffine hydration and its application Granted publication date: 20031008 License type: Common License Open date: 20000301 Record date: 20111111 |
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