CN1289751A - Process for preparing ether and its alcohol-ether mixture - Google Patents
Process for preparing ether and its alcohol-ether mixture Download PDFInfo
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- CN1289751A CN1289751A CN 99113275 CN99113275A CN1289751A CN 1289751 A CN1289751 A CN 1289751A CN 99113275 CN99113275 CN 99113275 CN 99113275 A CN99113275 A CN 99113275A CN 1289751 A CN1289751 A CN 1289751A
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Abstract
A process for preparing ether and its alcohol-ether mixture features that the built-up zeolite from acidic mesoporous and macroporous zeolites is used as catalyst and the light olefins (ethene, propene and butene) and their mixture take part in hydroetherifying reaction with the water and/or alcohol. Said ethers and their mixture can be used as solvent and additive of gasoline to increase the octane number and anti-knocking nature of gasoline.
Description
The present invention relates to produce the method for ether and alcohol-ether mixture thereof by the catalyzed reaction of alkene.More particularly, the present invention relates to light olefin and water and/or alcohol and under catalyst action, carry out the method that ether and alcohol-ether mixture thereof are produced in the hydration and etherification reaction.
In order to prepare ether by light olefin, need a kind of effective catalysis process, increase the high-octane rating blending supply of raw material that gasoline is used by it.The ether of lower molecular weight such as diisopropyl ether (DIPE) and knownly have a high blending octane rating all in the boiling range scope of gasoline.The stream of light olefins mixture of C2～C7 molecular weight ranges is also produced in petrochemical industry, these hydrocarbon streams or its cut are changed into various ethers and composition thereof, and these ethers also can be used as solvent and gasoline blending raw material, mix and improve its octane value and anti-knocking property in the gasoline.
Realize by the first step hydration and the second step etherificate from the synthetic ether of alkene.Hydration reaction is to generate corresponding alcohol by alkene and water reaction; Etherificate generates ether by alkene and alcohol reaction and two reactions of pure intermolecular dehydration reaction generation ether are carried out.
Making the catalytic hydration of olefins etherificate is known with the technology of producing ether and composition thereof, is widely adopted, and has the important commercial meaning.ZSM-5 is suggested in the synthetic patent US4214107 of Virahol (IPA), is a kind of mesopore SiO
2: Al
2O
3Be at least 12 crystalline aluminium hydrochlorate zeolite catalyst.Its feature is that the IPA selectivity is good, does not contain propylene dimer in the product.The recommended catalyzer as first conversion zone of ZSM-5 in the synthetic patent US 5144086 of DIPE two-stage method, olefin hydration becomes pure activity because it has preferably exactly.And under same reaction conditions, ZSM-5 and other zeolite such as ZSM-35, Y zeolite beta-zeolite etc. compare, and it is then relatively poor by the activity that IPA is converted into DIPE.
Beta-zeolite be by U.S. Mobil company in 1967 synthetic (US 3308069) at first, be a kind of crystalline aluminosilicate of macropore high silica alumina ratio.Beta-zeolite has and is better than that other is big, the light olefin hydration and etherification of mesopore zeolite becomes the activity of ether, second conversion zone by the reaction of the synthetic DIPE of IPA in by first-selected as catalyst for etherification.The patent CN 1035492 of Mobil company has listed the example of the beta-zeolite catalytic activity of many propylene hydration system IPA and DIPE, and makes comparisons so that its superiority to be described with other zeolite.Under the same terms, the etherificate catalytic activity of β zeolite is better than some known olefin hydration catalyst for etherification, as solid silicon aluminum molecular screen, solid tungsten catalyzer, the phosphoric acid etc. that is stated from liquid and other large pore zeolite, as Y zeolite, overstable gamma zeolite, mordenite etc.Not with tackiness agent blended beta-zeolite than good with the mixed beta-zeolite activity of tackiness agent.Beta-zeolite (the SiO of adhesive-free
2: Al
2O
3Be 40) under 150 ℃ of temperature, pressure 70bar, propylene WHSV 0.5, water/condition of 0.5: 1 of alkene mol ratio, the per pass conversion of propylene is 45%, wherein to the selectivity of IPA and DIPE be 97% (IPA40%, DIPE57%).
ZSM-5 and beta-zeolite are at present by preferred two kinds of catalyzer as the olefin hydration etherificate.They have many outstanding advantages than other hydration and etherification catalyzer such as resin and heteropolyacid etc.: higher to propylene conversion, better, high temperature resistant to the selectivity of pure and mild ether, insensitive, renewable to impurity in the charging (as metal ion and basic nitrogen), etching apparatus, product postprocessing are simple or the like.
But ZSM-5 and beta-zeolite respectively have the characteristics of oneself again.The restricted index of ZSM-5 is 6～8.3 (316～371 ℃), belongs to mesopore zeolite, and acid amount and strength of acid are higher, but only better to the selectivity of IPA, and be very little to the selectivity of DIPE, can not be used to produce DIPE separately.And the restricted index of beta-zeolite is 0.6～2.0 (316～399 ℃), belong to large pore zeolite, can hold the IPA molecule fully, therefore the generation of DIPE is not controlled by pore volume, but its transformation efficiency and selectivity remain further to be improved and the speed of generation ether is very fast, wayward, the easy coking of catalyzer, the work-ing life of limiting catalyst.If above-mentioned two catalyst junction are used to produce ether and composition thereof altogether, will bring into play individual advantage certainly, overcome corresponding defective, reach good effect.
The purpose of this invention is to provide all higher method of a kind of selectivity, transformation efficiency by light olefin system ether and composition thereof.
Feature of the present invention is to select for use a kind ofly to mix the composite molecular sieve that forms as catalyzer by mesopore and large pore zeolite, and the hydration and etherification of catalysis light olefin and water and/or alcohol reacts under the etherification reaction condition.More particularly, be that to adopt mesopore and large pore zeolite to mix the composite molecular sieve that forms in 2: 8～8: 2 ratio (weight ratio) be catalyzer of the present invention.Wherein the ratio of mesopore and large pore zeolite is preferably 4: 6～6: 4 (weight ratio).The tackiness agent that in catalyst preparation process, also can add 20～40% (weight).
Above-mentioned zeolite is selected from beta-zeolite, ZSM-5, X, L, Y, REY, Deal Y, ZSM-3, ZSM-4, ZSM-20 and ZSM-50, most preferably beta-zeolite and ZSM-5; Above-mentioned alkene is the mixture of ethene, propylene, butylene or above-mentioned alkene; Above-mentioned alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol or butanols, or these pure mixtures.
Catalyst compounded used tackiness agent must be able to stand temperature used in the hydration and etherification process of the present invention and other condition.Generally wish silicon-dioxide, tackiness agent such as aluminum oxide with can have high crushing strength after catalyzer combines because in plant-scale application, wish to prevent catalyst breakage powdering material here.The purpose of using these binding agents also is in order to improve the crushing strength of catalyzer.
The operational condition of these olefin hydration etherification methods is not strict especially.They comprise that temperature range is from about the envrionment temperature to 300 ℃, preferably are about 50～220 ℃, preferredly are about 90～200 ℃; The pressure of total system is at least about 0.5～20.0MPa, preferably is at least about 2.0～15.0MPa, the preferred 4.0～10.0MPa that is at least about; Air speed (WHVS) is 0.3～0.8; Water: the mol ratio of total olefin is about 0.1～30, preferably is about 0.2～15, and best is about 0.3～5; Sometimes may under the low mol ratio of water, operate total olefin, for example water to the mol ratio of total olefin less than 1 condition under.Selecting the specific operation condition will influence product by concrete charging distributes.
Etherification reaction process of the present invention can adopt intermittent type and continous way, and with a stirred-tank reactor or flow reactor of fixed bed, with liquid phase, vapour phase or vapour---liquid mixed phase condition is carried out.Used flow reactor has, trickle bed formula, liquid upper reaches flowing-type, the dirty flowing-type of liquid, counter-current flow formula and concurrent flow formula etc.Usually, wish to reclaim all unreacted alkene and/or alcohol, and make it be recirculated into reactor.
When being used for the hydration and etherification reaction of catalyzed alkene and/or alcohol with beta-zeolite and the composite catalyzer that forms of ZSM-5, the selectivity of conversion of olefines rate and DIPE is improved.In addition, ZSM-5 selects to generate alcohol, generates the speed of ether on its adding may command beta-zeolite, and ether product is output regularly, and need not other means go to control speed of reaction, can effectively utilize catalyzer, prolongs the work-ing life of catalyzer.The characteristics that the olefinic polymerization coking of ZSM-5 is few can prolong whole life of catalyst.
Following example is used to illustrate the present invention.The hydration and etherification activity of example 1 ZSM-5
ZSM-5 and 30%Al
2O
3The olefin catalytic activity of the catalyzer that powder is bonded is as follows.Numbering LZ-1 temperature, ℃ 170 pressure, MPa 8.0 water/alkene ratio, mol 1 propylene air speed, WHSV 0.5 propylene conversion, % 40 diisopropyl ether selectivity, the hydration and etherification activity of % 25 examples 2 beta-zeolites
Beta-zeolite and 30%Al
2O
3The olefin catalytic activity of the catalyzer that powder is bonded is as follows.Numbering LZ-2 temperature, ℃ 170 pressure, MPa 8.0 water/alkene ratio, mol 1 propylene air speed, WHSV 0.5 propylene conversion, % 40 diisopropyl ether selectivity, the hydration and etherification activity that % 50 examples 3 are catalyst compounded
ZSM-5 mixes back and 30%Al in varing proportions with beta-zeolite
2O
3The olefin hydration activity of the catalyzer that powder is bonded is as follows.
The catalyst compounded activity experiment result of table 1
Experiment shows that ZSM-5 and beta-zeolite are with 4: 6～6: 4 composite molecular sieve catalysts that make of ratio, and propylene hydration etherificate system diisopropyl ether is better active.Catalyst compounded hydration and etherification activity under the example 4 differing temps pressure
The hydration and etherification activity of LZ-5 catalyzer under the table 2 differing temps pressure
The stability experiment of example 5 LZ-5 catalyzer
| Temperature, ℃ | ????130 | ????150 | ????165 | ????165 | ????165 | ????175 | ????185 |
| Pressure, MPa | ????8．5 | ????6．0 | ????6．0 | ????7．0 | ????8．0 | ????8．0 | ????6．0 |
| ?WHSV．h -1 | ????0．6 | ????0．3 | ????0．5 | ????0．8 | ????0．5 | ????0．5 | ????0．4 |
| Water: alkene | ????3 | ????1 | ????1 | ????1 | ????1 | ????1 | ????2．5 |
| Propylene conversion, % | ???20．38 | ????36．81 | ????38．87 | ????34．69 | ?41．63 | ?47．65 | ??45．36 |
| The DIPE selectivity, % | ???49．37 | ????46．72 | ????52．22 | ????58．70 | ?53．98 | ?52．83 | ??54．39 |
Selectivity two aspects by propylene conversion and diisopropyl ether are taken all factors into consideration, and selected effect is LZ-5 (ZSM-5: beta-zeolite (weight)) make stability experiment preferably.Under the experiment condition of example 3, catalyzer LZ-5 continuous operation 1008 hours, transformation efficiency and selectivity all maintain higher level, transformation efficiency reduces to 41% by 45%, the diisopropyl ether selectivity reduces to 48% by 51%.
Claims (9)
1. the preparation method of ether and alcohol-ether mixture thereof, under the etherification reaction condition, carry out the hydration and etherification reaction with light olefin, it is characterized in that using in the reaction process a kind of tart to mix the composite molecular sieve that forms as catalyzer by mesopore and large pore zeolite with water and/or alcohol.
2. according to the described preparation method of claim 1, wherein mesopore and large pore zeolite compound proportion are counted 2: 8～8: 2 by weight.
3. according to claim 1 or 2 described preparation methods, wherein the ratio of mesopore and large pore zeolite is counted 4: 6～6: 4 by weight.
4. according to the described preparation method of claim 1, wherein said catalyzer contains 20～40% tackiness agent by weight.
5. according to claim 1 or 2 described preparation methods, wherein mesopore and large pore zeolite are selected from beta-zeolite, ZSM-5, X, L, Y, REY, Deal Y, ZSM-3, ZSM-4, ZSM-20 and ZSM-50.
6. according to the described preparation method of claim 5, wherein said mesopore and large pore zeolite are ZSM-5 and beta-zeolite.
7. according to the described preparation method of claim 1, its hydrating condition: temperature is a room temperature to 300 ℃; Stagnation pressure is 0.5～20.0MPa; Air speed is 0.3～0.8; Water: the mol ratio of total olefin is 0.1～30.
8. according to the described preparation method of claim 7, its operational condition: temperature is 50～220 ℃; Stagnation pressure is 2.0～15.0MPa; Air speed is 0.3～0.8; Water: the mol ratio of total olefin is 0.2～15.
9. according to the described preparation method of claim 8, its operational condition: temperature is 90～200 ℃; Stagnation pressure is 4.0～10.0MPa; Air speed is 0.3～0.8; Water: the mol ratio of total olefin is 0.3～5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113275A CN1117054C (en) | 1999-09-29 | 1999-09-29 | Process for preparing ether and its alcohol-ether mixture |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113275A CN1117054C (en) | 1999-09-29 | 1999-09-29 | Process for preparing ether and its alcohol-ether mixture |
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| Publication Number | Publication Date |
|---|---|
| CN1289751A true CN1289751A (en) | 2001-04-04 |
| CN1117054C CN1117054C (en) | 2003-08-06 |
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|---|---|---|---|
| CN99113275A Expired - Lifetime CN1117054C (en) | 1999-09-29 | 1999-09-29 | Process for preparing ether and its alcohol-ether mixture |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451757A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by using propylene |
| CN105944754A (en) * | 2016-05-24 | 2016-09-21 | 山东成泰化工有限公司 | Light oil etherification catalyst and preparation method thereof |
| CN106000457A (en) * | 2016-05-24 | 2016-10-12 | 山东成泰化工有限公司 | Composite catalyst used for gasoline etherification and preparation method thereof |
| CN114341091A (en) * | 2019-09-30 | 2022-04-12 | 陶氏环球技术有限责任公司 | Etherification process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2731203B2 (en) * | 1987-12-30 | 1998-03-25 | モービル・オイル・コーポレイション | Water addition method of olefin |
| US5102428A (en) * | 1989-10-20 | 1992-04-07 | Mobil Oil Corporation | Integrated process for the production of diisopropyl ether and gasoline |
-
1999
- 1999-09-29 CN CN99113275A patent/CN1117054C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451757A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by using propylene |
| CN102451757B (en) * | 2010-10-15 | 2013-08-28 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by using propylene |
| CN105944754A (en) * | 2016-05-24 | 2016-09-21 | 山东成泰化工有限公司 | Light oil etherification catalyst and preparation method thereof |
| CN106000457A (en) * | 2016-05-24 | 2016-10-12 | 山东成泰化工有限公司 | Composite catalyst used for gasoline etherification and preparation method thereof |
| CN114341091A (en) * | 2019-09-30 | 2022-04-12 | 陶氏环球技术有限责任公司 | Etherification process |
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| Publication number | Publication date |
|---|---|
| CN1117054C (en) | 2003-08-06 |
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Granted publication date: 20030806 |