CN1044471C - Catalytic synthesizing process for ethers - Google Patents
Catalytic synthesizing process for ethers Download PDFInfo
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- CN1044471C CN1044471C CN95119525A CN95119525A CN1044471C CN 1044471 C CN1044471 C CN 1044471C CN 95119525 A CN95119525 A CN 95119525A CN 95119525 A CN95119525 A CN 95119525A CN 1044471 C CN1044471 C CN 1044471C
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Abstract
The present invention relates to a technology for catalyzing and synthesizing tert-amyl methyl ether (TAME) and/or tert-hexyl methyl ether (THEMES) by taking a mixture of hydrocarbon containing active isoamylene and/or active isohexene, and methanol as the raw material. The technology comprises that the raw material is in contact with a catalyst taking beta-zeolite as an active component under the conditions that the temperature is from 20 to 140 DEG C, the pressure is from 0 to 4.0MPa and the weight space velocity is from 0.2 to 0.6h<-1>. Reaction products can directly serve as proportional constituents of high octane unleaded gasoline after the stabilizing procedure, etc. is carried out to remove the methanol.
Description
The present invention relates to a kind of process for catalytic synthesis of ethers, particularly relate to the process for catalytic synthesis of a kind of tert pentyl methyl ether (TAME) and/or uncle's hexyl methyl ether (THEMES).
For reducing olefin content in gasoline, improve the gasoline oxygen level, reduce its vapour pressure, improve gasoline stability thereby reach, and the purpose of CO quantity discharged in the reduction vehicle exhaust, alcohols such as some alkene in the gasoline and methyl alcohol are reacted to generate ether compound be a kind of method preferably.Existing a lot of researchers are studied this, report that more is with resin catalyst or other solid acid catalyst catalytic synthesis of methyl tertbutyl ether (MTBE), but the content of iso-butylene in gasoline is seldom, and content more be isopentene and dissident's alkene.
The method of the synthetic tert pentyl methyl ether (TAME) of useful resin catalyst catalysis in the prior art, as USP4,193, speak of in 770 with sulfonic acid type cross-linked cationic exchange resin and make catalyzer, the raw material that will contain isopentene and methyl alcohol, carry out etherification reaction at certain pressure with under 66～116 ℃ temperature by this catalyzer, wherein the transformation efficiency of isopentene is about 35% under the air speed that industry is suitable for, than being 50～60% under the low-speed, make high-octane lead-less gasoline after reacted product and the gasoline mediation.
But making the etherification reaction catalyzer with Zeo-karb has two shortcomings, one: its use temperature can not surpass 100 ℃, otherwise can cause in the catalyzer-SO
3Coming off of H active group causes on the one hand catalyst deactivation, on the other hand can etching apparatus; Its two: the H in the catalyst activity group
+By the metal ion exchanged in the raw material and after poisoning, need that it is drawn off reactor and carry out acid treatment regeneration, operate very inconvenient.Based on above reason, seek other solid acids and occur and the formation patent as the work of etherification reaction catalyzer is continuous.As USP4, described in 605,787 and used ZSM-5, ZSM-11, ZSM-12, ZSM-23, sealumination modified Y zeolite, the catalyzer of preparations such as REY zeolite is by isobutylene etherification with methanol system methyl tertiary butyl ether (MTBE).DE3, speaking of in 813,689 with laminated clay dipping group VIII metal element is catalyzer, with the feedstock production MTBE and the TAME that contain 2-methyl butene-2, iso-butylene and methyl alcohol.These two pieces of patents have all obtained effect preferably, but the ZSM-5 catalyzer is only better to iso-butylene etherificate system MTBE effect, and to C
5And C
5Above etherification of olefins poor effect (transformation efficiency is close to zero).
The β zeolite has suitable aperture structure and active centre, with the catalyzer of its preparation to C
4 =And the etherification reaction of the alkene of higher carbon number and alcohols has catalytic performance preferably, and is especially better to the etherificate effect of isomeric olefine.
EP0,309,177A1, USP4 have described with the β zeolite to be catalyzer, to be raw material and one with the straight chain mono-olefins that the secondary alcohol reaction generates corresponding ether in the patent such as 714,87, USP5,091,590, but the etherification reaction of branched-chain alkene have not been described.
USP5 discloses a kind of method of producing tert-alkyl ether with the beta-zeolite catalyst of modification in 225,609.The purpose of this method is by water treatment reduces its acidity later on through certain condition with beta-zeolite catalyst, thereby improves the selectivity of isomeric olefine etherification reaction and reduce the olefin-copolymerization by product greatly.This method though its processing condition to preparation MTBE are described, is not carried out any description to the processing condition of preparation tert pentyl methyl ether (TAME) and uncle's hexyl methyl ether (THEMES) mainly at preparation methyl tertiary butyl ether (MTBE).On the reality, C
4Isomeric olefine and C
5And C
5Above isomeric olefine is because its molecular dimension difference, carry out the needed reaction conditions of etherification reaction with alcohols and reactivity worth widely different, be adapted to C
4The catalyzer of isomeric olefine etherification reaction and processing condition not necessarily are applicable to C
5And C
5The etherification reaction of above isomeric olefine, it is exactly like this making catalyzer with ZSM-5 as previously mentioned.
In the light component of regular price gasoline (as catalytically cracked gasoline), its isomeric olefine is mainly isopentene and a spot of dissident's alkene, and the product that itself and methanol etherification is later can be as the mediation component of high-octane lead-less gasoline.Beta-zeolite catalyst can be as the catalyzer of this etherification reaction.Comprehensive prior art, also nobody to propose with the β zeolite be any concrete processing condition that catalyst aims isopentene and/or dissident's alkene and methyl alcohol carry out etherification reaction.
The objective of the invention is to propose a kind of is catalyzer with the β zeolite, with the hydro carbons that contains isopentene and/or dissident's alkene is raw material, carries out the method that etherification reaction is produced tert pentyl methyl ether (TAME) and/or uncle's hexyl methyl ether (THEMES) with methyl alcohol under proper reaction conditions.
Method provided by the present invention comprises:
(1), to contain the hydrocarbon of active isopentene and/or active dissident's alkene and methyl alcohol and be that to feed the fixed-bed reactor that catalyzer is housed after 0.2～12.0 the mixed be 20～140 ℃ in temperature by the mol ratio of methyl alcohol/active olefin, pressure is 0～4.0 MPa, and weight space velocity is 0.2～6.0 o'clock
-1Condition under contact with this catalyzer that contains the β zeolite and to carry out etherification reaction;
(2), reaction product obtains product after operation such as stable is removed remaining methyl alcohol.
(3), when catalyzer because of carbon distribution gradually behind the inactivation, decaying catalyst can be carried out according to a conventional method continuing to use behind the coke burning regeneration in reactor.
Raw material among the present invention is light component of hydro carbons and methanol mixture, particularly gasoline and the methanol mixture that contains active isopentene and/or active dissident's alkene.Active olefin wherein is meant in the structural formula and contains
The alkene of carbon-chain structure comprises 2-methyl butene-1 and 2-methyl butene-2 as active isopentene; Active dissident's alkene comprises 2-methylpentene-1,2-methylpentene-2,3-methylpentene-2,2,3-neohexene-1,2,3-neohexene-2 and 2-ethyl butene-1.If contain other active olefins in the raw material, the inventive method also can generate corresponding ether with itself and methanol etherification simultaneously.The mol ratio of methyl alcohol and active olefin is 0.2～12.0 among the present invention, is preferably 0.5～9.0, and said active olefin is meant the summation of active isopentene and active dissident's alkene.
Raw material contacts the condition of carrying out etherification reaction and is among the present invention with catalyzer: temperature is 20～140 ℃, and pressure is 0～4.0 MPa, and weight space velocity is 0.2～6.0 o'clock
-1Wherein reaction conditions is preferably: temperature is 45～120 ℃, and pressure is 0.5～3.5 MPa, and weight space velocity is 0.5～4.5 o'clock
-1
Catalyzer among the present invention is to be active ingredient with the β zeolite, is that carrier is made by extruded moulding with a kind of binding agent.The content of β zeolite can carry out modulation as required in the catalyzer, 30-90 weight % for example, and wherein more suitable scope is 50～80 weight %.This binding agent can be an aluminum oxide, silicon-dioxide or their precursor, or their mixture, preferably aluminum oxide or its precursor.
By the present invention, the isopentene in the raw material can be converted into tert pentyl methyl ether (TAME), the dissident's alkene in the raw material can also be converted into uncle's hexyl methyl ether (THEMES) simultaneously.Under different reaction conditionss, can obtain different olefin conversions.Under suitable reaction conditions, the transformation efficiency of active isopentene can be greater than 60%, and the selectivity that generates TAME can reach 100%.Compare with the storng-acid cation exchange resin catalysis method, the active isopentene transformation efficiency of the inventive method is higher, exercisable temperature is higher, and the regeneration of zeolite catalyst compares with resin catalyst and will make things convenient for manyly in operation, and zeolite catalyst does not also have resin catalyst because pollution and the etching problem that the loss of sulfonate radical causes in the use.The product that the present invention obtains without separate can be directly as the mediation component of high-octane lead-less gasoline.
The following examples will the present invention is further illustrated.
Embodiment 1
Present embodiment provides and is applicable to two kinds of catalyzer of the present invention.
Get the 60 dried β zeolite powders of gram (Fushun No.3 Petroleum Factory's production) and put into beaker, add the NH of 300 milliliter of 5 weight %
4The Cl aqueous solution filters in 90～100 ℃ of down exchanges one hour, and filter cake press the exchange of the same terms ammonium once again, be washed till no chlorion with deionized water then and in baking oven in 120 ℃ of dryings down, obtain the β zeolite after ammonium exchanges.
The mixed that β zeolite after the exchange of this ammonium is added 16.4 gram aluminium hydroxides by per 20 gram zeolites evenly after, become the bar shaped catalyst of 1 millimeter of diameter with the aqueous nitric acid kneading extrusion of 5 weight %, through super-dry and 540 ℃ of roastings 4 hours, obtain catalyst A.
Again the mixed that the β zeolite after the exchange of this ammonium is added 11.5 gram aluminium hydroxides by per 20 gram zeolites evenly after, aqueous nitric acid with 5 weight % is mediated the bar shaped catalyst that extrusion becomes 1 millimeter of diameter, through super-dry and 540 ℃ of roastings 4 hours, obtain catalyst B.
Embodiment 2
The present embodiment explanation is applicable to the temperature of reaction of the etherification reaction among the present invention.
The used raw material a of present embodiment is the light component of a kind of gasoline, its salient features and wherein the content of some relevant components list in the table 1.
In 50 milliliters of small stationary bed bioreactors, load 20 milliliters of catalyst A, with the light component raw material of above-mentioned gasoline with after methyl alcohol mixes by a certain percentage, feed in the reactor continuously with certain air speed, under the listed condition of table 2, carry out etherification reaction, stratographic analysis is carried out in reacted product sampling, and the results are shown in Table 2 for it.
Weight space velocity after table 2 reaches in each table is to calculate by the amount of active ingredient in the catalyzer, that is:
Methyl alcohol/active olefin was meant the mol ratio of methyl alcohol and active isopentene and active dissident's alkene total amount during each was shown after table 2 reached; The selectivity of TAME is calculated by active isopentene, that is:
Table 1
| Relevant component | Content, (weight %) | Boiling range | Density in the time of 20 ℃ |
| 2-methyl butene-1 | 4.94 | 31～76 ℃ | 0.65 grams per milliliter |
| 2-methyl butene-2 | 9.74 | ||
| 3-methyl butene-1 | 0.94 | ||
| 2-methylpentene-1 | 1.46 | ||
| 2-methylpentene-2 | 1.75 | ||
| 3-methylpentene-2 | 1.03 | ||
| 2,3-neohexene-1 | 0.35 | ||
| 2,3-neohexene-2 | 0.26 | ||
| 2-ethyl butene-1 | 0.21 | ||
| Diene | 0.35 | ||
| Alkali nitrogen | 2.9ppm | ||
| Colloid | 0 |
Table 2
| Reaction pressure (MPa) | 2.0 | ||||||
| Weight space velocity (time -1) | 1.00 | ||||||
| Methyl alcohol/active olefin (mol ratio) | 1.22 | ||||||
| Temperature of reaction (℃) | 55 | 65 | 70 | 75 | 80 | 85 | 90 |
| 2-methyl butene-1 transformation efficiency (%) | 88.01 | 91.21 | 91.01 | 89.33 | 88.28 | 86.59 | 85.11 |
| 2-methyl butene-2 transformation efficiency (%) | 26.91 | 49.37 | 49.23 | 39.82 | 39.15 | 35.20 | 30.46 |
| Gross activity isopentene transformation efficiency (%) | 47.03 | 59.32 | 63.73 | 57.01 | 56.20 | 53.04 | 49.43 |
| TAME selectivity (%) | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| 2-methylpentene-1 transformation efficiency (%) | 87.00 | 89.12 | 82.62 | 86.61 | 84.09 | 79.89 | 83.23 |
| TAME content (weight %) in the product | 9.70 | 11.27 | 12.53 | 11.46 | 11.33 | 10.59 | 9.73 |
| C7 ether content (weight %) in the product | 2.11 | 2.96 | 3.13 | 2.85 | 2.85 | 2.44 | 2.44 |
Embodiment 3
The raw material b that present embodiment adopted is the higher light component of gasoline of a kind of isomeric olefine content (taking from Lanzhou oil-refining chemical head factory MIO process unit), its salient features and wherein the content of some relevant components list in the table 3.
In 50 milliliters of small stationary bed bioreactors, load 20 milliliters of catalyst B, with the light component raw material of above-mentioned gasoline b with after methyl alcohol mixes by a certain percentage, feed in the reactor continuously with certain air speed, under the listed condition of table 4, carry out etherification reaction, stratographic analysis is carried out in reacted product sampling, and the results are shown in Table 4 for it.
Table 3
| Relevant component | Content (weight %) | Boiling range | Density in the time of 20 ℃ |
| Total isoamyl olefinic carbon five dienes of 2-methyl butene-1 2-methyl butene-2 〉=C 6The total thioglycollate of component total nitrogen | 9.66 23.16 32.82 ＜0.02 11.4 1.86ppm 14.89ppm ＜2 | 29～60℃ | 0.645 grams per milliliter |
| Acidity | 0.26mgKOH/100ml | ||
| The bromine valency | 169gBr/100g | ||
Table 4
| Reaction pressure (MPa) | 1.0 | 1.20 | 1.12 | |||
| Weight space velocity (time -1) | 1.00 | 1.10 | 1.00 | |||
| Methyl alcohol/active olefin (mol ratio) | 0.95～1.10 | 1.10 | 1.10 | |||
| Temperature of reaction (℃) | 60 | 65 | 70 | 75 | 90 | 110 |
| 2-methyl butene-1 transformation efficiency (%) | 93.52 | 92.86 | 91.84 | 90.61 | 87.43 | 81.96 |
| 2-methyl butene-2 transformation efficiency (%) | 51.98 | 47.93 | 50.06 | 51.91 | 36.47 | 21.08 |
| Gross activity isopentene transformation efficiency (%) | 64.28 | 61.24 | 62.15 | 63.12 | 54.73 | 42.90 |
| TAME selectivity (%) | 100 | 100 | 100 | 100 | 100 | 100 |
| TAME content (weight %) in the product | 28.69 | 27.06 | 28.44 | 28.00 | 23.71 | 18.07 |
| C7 ether content (weight %) in the product | 1.06 | 1.07 | 0.23 | 0.22 | 0.26 | 0.19 |
Comparative Examples
This Comparative Examples is described under the method and reaction conditions identical with embodiment 2 and 3, adopts industrial 54# resin (Beijing is gone in in a big way extraordinary resin processing plant and produced) to make catalyzer and replaces catalyst A and B to carry out the situation of etherification reaction, and the results are shown in Table 5 for gained.
Table 5
| Raw material | a | b | ||||
| Reaction pressure (MPa) | 2.0 | 1.0 | ||||
| Weight space velocity (time -1) | 1.00 | 1.0 | ||||
| Methyl alcohol/active olefin (mol ratio) | 1.20 | 1.02 | ||||
| Temperature of reaction (℃) | 55 | 65 | 75 | 85 | 95 | 60 |
| 2-methyl butene-1 transformation efficiency (%) | 87.94 | 91.01 | 88.41 | 85.79 | 82.50 | 92.60 |
| 2-methyl butene-2 transformation efficiency (%) | 33.38 | 50.76 | 44.05 | 34.91 | 25.02 | 46.20 |
| Gross activity isopentene transformation efficiency (%) | 51.62 | 64.21 | 58.88 | 51.92 | 44.24 | 63.41 |
| TAME selectivity (%) | 100 | 100 | 100 | 100 | 100 | 100 |
| 2-methylpentene-1 transformation efficiency (%) | 64.20 | 93.15 | 86.27 | 82.79 | 77.53 | Do not survey |
| TAME content (weight %) in the product | 10.17 | 12.80 | 11.61 | 10.30 | 8.74 | 27.66 |
| C7 ether content (weight %) in the product | 2.18 | 3.04 | 2.75 | 2.01 | 1.94 | 0.82 |
Embodiment 4
The present embodiment explanation is applicable to the reaction pressure of the etherification reaction among the present invention.
20 milliliters of catalyst A of filling in 50 milliliters of small stationary bed bioreactors, with the light component raw material of the gasoline among the embodiment 2 a with after methyl alcohol mixes by a certain percentage, feed in the reactor continuously with certain air speed, under the listed reaction conditions of table 6, react, stratographic analysis is carried out in the reaction product sampling, and the results are shown in Table 6 for it.
Table 6
| Reaction pressure (MPa) | 0 | 0.8 | 1.0 | 2.0 |
| Weight space velocity (time -1) | 1.00 | 0.99 | 0.98 | 1.00 |
| Methyl alcohol/active olefin (mol ratio) | 1.15 | 1.16 | 1.16 | 1.16 |
| Temperature of reaction (℃) | 80 | 75 | 75 | 75 |
| 2-methyl butene-1 transformation efficiency (%) | 89.50 | 89.80 | 89.64 | 89.70 |
| 2-methyl butene-2 transformation efficiency (%) | 30.00 | 32.29 | 36.56 | 38.49 |
| Gross activity isopentene transformation efficiency (%) | 49.65 | 50.54 | 53.40 | 54.74 |
| TAME selectivity (%) | 100 | 100 | 100 | 100 |
| TAME content (weight %) in the product | 10.45 | 10.64 | 11.03 | 11.40 |
| C7 ether content (weight %) in the product | Do not survey | 2.29 | 2.20 | 2.25 |
Embodiment 5
The present embodiment explanation is applicable to the weight space velocity of the etherification reaction among the present invention.
20 milliliters of catalyst B of filling in 50 milliliters of small stationary bed bioreactors, with the light component raw material of the gasoline among the embodiment 3 with after methyl alcohol mixes by a certain percentage, feed in the reactor continuously with certain air speed, under the listed reaction conditions of table 7, react, stratographic analysis is carried out in the reaction product sampling, and the results are shown in Table 7 for it.
Table 7
| Reaction pressure (MPa) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Weight space velocity (time -1) | 4.05 | 2.85 | 1.90 | 1.07 | 0.58 |
| Methyl alcohol/active olefin (mol ratio) | 1.12 | 1.12 | 1.12 | 1.12 | 1.12 |
| Temperature of reaction (℃) | 75 | 75 | 75 | 75 | 60 |
| 2-methyl butene-1 transformation efficiency (%) | 89.3 | 89.2 | 89.6 | 89.6 | 92.92 |
| 2-methyl butene-2 transformation efficiency (%) | 50.1 | 52.5 | 55.6 | 56.1 | 62.21 |
| Gross activity isopentene transformation efficiency (%) | 61.5 | 63.1 | 65.4 | 65.8 | 71.11 |
| TAME selectivity (%) | 100 | 100 | 100 | 100 | 100 |
| TAME content (weight %) in the product | 27.9 | 28.9 | 31.55 | 31.85 | 33.48 |
| C7 ether content (weight %) in the product | 0.33 | 0.35 | 0.36 | 0.34 | 0.40 |
Embodiment 6
Present embodiment explanation is applicable to the ratio of methyl alcohol and active olefin in the raw material of the present invention.
20 milliliters of catalyst A of filling in 50 milliliters of small stationary bed bioreactors, with the light component raw material of the gasoline among the embodiment 2 a with after methyl alcohol mixes by a certain percentage, feed in the reactor continuously with certain air speed, under the listed reaction conditions of table 8, react, stratographic analysis is carried out in the reaction product sampling, and the results are shown in Table 8 for it.
Table 8
| Reaction pressure (MPa) | 1.5 | 1.5 | 1.5 |
| Weight space velocity (time -1) | 1.09 | 0.98 | 1.30 |
| Methyl alcohol/active olefin (mol ratio) | 0.79 | 1.16 | 9.85 |
| Temperature of reaction (℃) | 70 | 70 | 70 |
| 2-methyl butene-1 transformation efficiency (%) | 68.15 | 87.93 | 85.4 |
| 2-methyl butene-2 transformation efficiency (%) | 16.87 | 31.17 | 43.65 |
| Gross activity isopentene transformation efficiency (%) | 12.96 | 51.03 | 58.26 |
| TAME selectivity (%) | 26.93 | 100 | 96.43 |
| TAME content (weight %) in the product | 0.74 | 10.56 | 8.19 |
| C7 ether content (weight %) in the product | 0.21 | 1.88 | 1.86 |
Claims (10)
1. the method for the synthetic tert pentyl methyl ether of a catalysis and/or uncle's hexyl methyl ether, it is characterized in that this method comprises that be 20～140 ℃ with containing the hydrocarbon of active isopentene and/or active dissident's alkene and the raw material of methyl alcohol in temperature, pressure is 0～4.0 MPa, and weight space velocity is 0.2～6.0 o'clock
-1Condition under with a kind of be that the catalyzer of active ingredient contacts with the β zeolite.
2. by the method for claim 1, it is characterized in that the said hydrocarbon that contains active isopentene and/or active dissident's alkene is the light component of gasoline.
3. by the method for claim 1 or 2, it is characterized in that said active isopentene and active dissident's alkene are to contain in the structural formula
The alkene of carbon-chain structure.
4. by the method for claim 1, it is characterized in that the mol ratio of methyl alcohol and active olefin is 0.2～12.0 in the said raw material.
5. by the method for claim 4, it is characterized in that the mol ratio of methyl alcohol and active olefin is 0.5～9.0 in the said raw material.
6. by the method for claim 1, the condition that it is characterized in that said contact is that temperature is 45～120 ℃, and pressure is 0.5～3.5 MPa, and weight space velocity is 0.5～5.0 o'clock
-1
7. by the method for claim 1, it is characterized in that said catalyzer is is active component with the β zeolite, be that carrier is made by extruded moulding with a kind of binding agent.
8. press the method for claim 1 or 7, the content that it is characterized in that β zeolite in the said catalyzer is 30～90 weight %
9. by the method for claim 7, it is characterized in that said binding agent is an aluminum oxide, silicon-dioxide or their precursor, or their mixture.
10. by the method for claim 7, it is characterized in that said binding agent is aluminum oxide or its precursor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95119525A CN1044471C (en) | 1995-01-16 | 1995-12-20 | Catalytic synthesizing process for ethers |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95101077.8 | 1995-01-16 | ||
| CN 95101077 CN1127242A (en) | 1995-01-16 | 1995-01-16 | Catalysis synthesizing technology for ether |
| CN95119525A CN1044471C (en) | 1995-01-16 | 1995-12-20 | Catalytic synthesizing process for ethers |
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| Publication Number | Publication Date |
|---|---|
| CN1136552A CN1136552A (en) | 1996-11-27 |
| CN1044471C true CN1044471C (en) | 1999-08-04 |
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|---|---|---|---|
| CN95119525A Expired - Fee Related CN1044471C (en) | 1995-01-16 | 1995-12-20 | Catalytic synthesizing process for ethers |
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| CN106520187B (en) * | 2015-09-14 | 2018-04-06 | 中国石油天然气股份有限公司 | A kind of light petrol hydrocarbon restructuring etherificate catalytic rectification process and its device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4193770A (en) * | 1977-12-22 | 1980-03-18 | Gulf Canada Limited | Preparation of gasoline containing tertiaryamyl methyl ether |
| US4605787A (en) * | 1984-08-16 | 1986-08-12 | Mobil Oil Corporation | Process for the preparation of alkyl tert-alkyl ethers |
| EP0309177A1 (en) * | 1987-09-25 | 1989-03-29 | Mobil Oil Corporation | Ether synthesis with zeolite beta |
| US5225609A (en) * | 1991-12-17 | 1993-07-06 | Mobil Oil Corporation | Production of tertiary alkyl ether using improved zeolite catalyst |
-
1995
- 1995-12-20 CN CN95119525A patent/CN1044471C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4193770A (en) * | 1977-12-22 | 1980-03-18 | Gulf Canada Limited | Preparation of gasoline containing tertiaryamyl methyl ether |
| US4605787A (en) * | 1984-08-16 | 1986-08-12 | Mobil Oil Corporation | Process for the preparation of alkyl tert-alkyl ethers |
| EP0309177A1 (en) * | 1987-09-25 | 1989-03-29 | Mobil Oil Corporation | Ether synthesis with zeolite beta |
| US5225609A (en) * | 1991-12-17 | 1993-07-06 | Mobil Oil Corporation | Production of tertiary alkyl ether using improved zeolite catalyst |
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| CN1136552A (en) | 1996-11-27 |
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