CN108586208A - A method of preparing ETBE and C8 alkene using mixing C4 and ethyl alcohol - Google Patents
A method of preparing ETBE and C8 alkene using mixing C4 and ethyl alcohol Download PDFInfo
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- CN108586208A CN108586208A CN201810551943.1A CN201810551943A CN108586208A CN 108586208 A CN108586208 A CN 108586208A CN 201810551943 A CN201810551943 A CN 201810551943A CN 108586208 A CN108586208 A CN 108586208A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/28—Catalytic processes with hydrides or organic compounds with ion-exchange resins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- C07C2531/08—Ion-exchange resins
- C07C2531/10—Ion-exchange resins sulfonated
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Abstract
The present invention relates to a kind of methods preparing ETBE and C8 alkene with ethyl alcohol using mixing C4, using the mixing C4 containing isobutene and absolute ethyl alcohol as raw material, etherification reaction and building-up reactions are carried out by continuous fixed bed reaction or continuous device under the action of solid acid catalyst, the mixing C4 uses two strands of feeding manners with absolute ethyl alcohol, the two enters in reactor jointly after mixing in a mixer reacts, the molar ratio of the absolute ethyl alcohol and isobutene is 0.05 0.5, temperature control is 20 100 DEG C when reaction, and the mass space velocity that reactant passes through reactor is 1 6h‑1.Compared with prior art, the overlapping etherification reaction of mixing C4 and ethyl alcohol proposed by the invention, by changing reaction condition, adjust the ratio of ETBE and C8 alkene in product, when keeping higher isobutene conversion, the polymerisation conversion of butylene 1 is reduced, and improves the selectivity of C8 alkene, improves the quality of heat bodied oil.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, and in particular to a kind of to prepare ETBE and C8 alkene using mixing C4 and ethyl alcohol
The method of hydrocarbon.
Background technology
In recent years, environmental requirement is more and more tighter, and quality of gasoline tends to unleaded, low aromatic hydrocarbons, low-steam pressure, high-octane rating direction
Development, at present catalytically cracked gasoline there are octane numbers it is low, alkene and sulfur content are higher the problems such as.The vapour of high-quality in order to obtain
Some addO-on therapies can be generally added in oil.Wherein, isooctane, alcohols, ethers (MTBE, ETBE) etc. are high-knock rating gasoline
AddO-on therapy, but it is found that the high water solubility of methyl tertiary butyl ether(MTBE) (MTBE) and there are potential carcinogenic nature, if used
Or storage and transportation is improper will result in serious and lasting water resource pollution, causes to seriously threaten to environment and human health, the U.S. is
Disabling comprehensively, while the states such as European Union and Japan also begin to reduce in recent years the use of MTBE.Therefore, people direct attention to second
Base tertbutyl ether (ETBE), compared with MTBE, the octane number higher of ETBE, vapour pressure is lower, and boiling point is higher, and in gasoline
Hydro carbons mutually mixes and does not generate azeotropic mixture, it is often more important that its solubility in water only has the 1/4 of MTBE, easily micro- by aerobic
Biological decomposition, therefore ETBE can become the substitute of MTBE.In addition, isooctane is also a kind of ideal gasoline addO-on therapy, it can
It is overlapped by isobutene and hydrogen is added to obtain.
Foreign countries synthesize the technology of pure ETBE comparative maturity, and industry is had been realized in West Europe and some countries of North America
Metaplasia is produced, and catalyst used is mainly macropore sulfonic acid ion exchange resin.There are two types of route of synthesis by ETBE：(1) with different
Butylene or mixing C4 containing isobutene and aqueous or absolute ethyl alcohol are raw material；(2) using ethyl alcohol and the tert-butyl alcohol as raw material, selection is closed
Suitable acidic catalyst, while the ETBE by controlling reaction process condition synthesis high-purity.Chinese patent CN103739453A
It is proposed using the C4 in liquefied gas after being etherified as raw material, with ethanol synthesis produce ETBE, and will reaction after remaining ethyl alcohol, C4 and packet
It includes the by-product including dimethyl ether and C8, the tert-butyl alcohol to separate by azeotrope tower, obtains the higher ETBE of purity.China
It is raw material that patent CN1780803A, which is mentioned with isobutene and the hydrous ethanol distilled from biological substance alcohol, mild
Under the conditions of generate ETBE and the tert-butyl alcohol.CN103044216A is proposed with isobutene and ethyl alcohol, the tert-butyl alcohol and ethyl alcohol Joint Production second
Base tertbutyl ether, isobutene and ethyl alcohol are reacted in first reaction system, and the tert-butyl alcohol and ethyl alcohol are reacted in second reaction system,
The by-product tert-butyl alcohol that the former generates enters the latter's recycling, while the isobutene that the latter generates enters first reaction system again
It utilizes.
In conclusion it is more about the research for synthesizing pure ETBE both at home and abroad, but not about isobutene and co-productiono f ethanol
The research of ETBE and C8 alkene.It is main that etherificate and polymerization (mainly dimerization) reaction occurs in the reaction system, due to ethyl alcohol
Polarity be more than isobutene and butene-1, can be preferentially adsorbed on resin activity position, accordingly, with respect to polymerisation, ethyl alcohol with
The etherification reaction of isobutene preferentially occurs, and reaction rate is very fast.Etherification reaction is a reversible reaction, and it is flat to there is chemical reaction
Weighing apparatus, after the reaction reaches balance, polymerisation becomes main reaction, and there are still unconverted ethyl alcohol in reaction system, therefore,
Ethyl alcohol is not only the reactant of etherification reaction and a kind of inhibitor, is adsorbed on resin activity position, reduces resin acid site
Intensity is conducive to the selectivity for improving C8.
It is main that etherification reaction and building-up reactions occurs in the reaction system of solid acid catalysis mixing C4 alkene and ethyl alcohol.
Etherification reaction is mainly the etherificate generation ethyl tert-butyl ether (ETBE) (ETBE) of isobutene and ethyl alcohol, and it is anti-that butene-1 is almost not involved in etherificate
It answers.Building-up reactions mainly has the dimerization reaction between isobutene, the copolymerization between isobutene and butene-1 or butene-2, butylene-
1, the dimerization of butene-2 and copolymerization etc. between the two, dimerisation products are the primary products of polymerisation, but it is possible to and alkene
The reaction was continued generates trimerization or four poly- products for hydrocarbon.It is pointed out in document, during isobutene building-up reactions, in order to improve dimer
Selectivity, a small amount of inhibitor (such as methanol, tert-butyl alcohol alcohols) can be added, since its polarity is stronger, can be preferentially adsorbed on
On the acid centre of resin, the acid capacity or acid strength of resin are reduced.For butene-1, in addition to polymerizeing between isobutene
Reaction, it also can isomery to generate cis-2-butene and Trans-2-butene, polymerisation be all that carbonium ion reacts machine with isomerization reaction
Reason, therefore have direct relation with the quantity in acid site and intensity.It is mainly 2,4,4- trimethylpentenes -1 that isobutene, which overlaps product,
With 2,4,4-TMP-2, it is the optimal product of isobutene building-up reactions, the octane number of the product after hydrogen is added to have 100.Isobutene
The product polymerizeing with butene-2 be 2,3,3- trimethylpentenes, 2,3,4- trimethylpentenes and 3,4,4- trimethylpentenes etc., this
A little products also have higher octane number, can be used as good gasoline blend component.But the product that isobutene polymerize with butene-1
For dimethyhexenes, add the product octane number after hydrogen relatively low, is not ideal high-knock rating gasoline addO-on therapy, dimethyl
The generation of hexene affects the quality of heat bodied oil, and the octane number of different C8 hydrogenation of olefins products and gasoline additive is as shown in table 1.
Therefore, in mixing C4 alkene oligomerizations reaction, polymerizeing between butene-1 and isobutene should be inhibited, reduce diformazan in product to the greatest extent
The content of base hexene reduces the polymerisation conversion of butene-1 as possible.In addition, sec-butyl alcohol can pass through n-butene (butene-1 and fourth
Alkene -2) hydration reaction be made, and sec-butyl alcohol be produce important chemical methyl ethyl ketone intermediate.Therefore, butene-1 is reduced
On the one hand polymerisation conversion can reduce the content of dimethyhexenes in C8 alkene, improve the octane number of heat bodied oil, another party
Face makes n-butene retain, and is used for other purposes, improves its utility value.
The octane number of 1 C8 hydrogenation of olefins products of table
Invention content
The purpose of the present invention be exactly to solve the above-mentioned problems and provide it is a kind of using mixing C4 and ethyl alcohol prepare ETBE and
The method of C8 alkene, using the mixing C4 containing isobutene and absolute ethyl alcohol as raw material, by overlapping-etherification reaction coproduction ETBE and
C8 alkene adjusts etherification product ETBE by changing alfin ratio and overlaps the ratio of product C8 alkene, by adjusting technique item
Part controls the conversion of butene-1, while keeping higher isobutene conversion, to reduce the polymerisation conversion of butene-1, and
The selectivity for improving C8 alkene as far as possible, reduces the generation of trimerization or four poly- side reactions, improves the quality of heat bodied oil.
The purpose of the present invention is achieved through the following technical solutions：
A method of ETBE and C8 alkene being prepared using mixing C4 and ethyl alcohol, with the mixing C4 containing isobutene and anhydrous
Ethyl alcohol is raw material, carries out etherification reaction by continuous fixed bed reaction or continuous device under the action of solid acid catalyst and overlapping is anti-
It answers, the mixing C4 enters in reactor jointly after using two strands of feeding manners, the two to mix in a mixer with absolute ethyl alcohol
Reaction, the molar ratio of the absolute ethyl alcohol and isobutene are 0.05-0.5, and temperature control is 20-100 DEG C when reaction, and reactant is logical
The mass space velocity for crossing reactor is 1-6h-1。
Preferably, the molar concentration that the isobutene accounts for mixing C4 is 10-100%, it is further preferred that the isobutene
The molar concentration for accounting for mixing C4 is 10-50%.Building-up reactions and etherification reaction are exothermic reactions, if the concentration mistake of isobutene
Height, reaction can release higher heat, cause the temperature in reactor excessively high, cause the generation of poly side reaction, therefore, generally
Part alkane can be added and make diluent.
The mixing C4 is C4 paraffins mixtures, and mixing C4 is isobutene, the mixing of iso-butane and butene-1 or different
The mixing of butylene, iso-butane, butene-1 and butene-2.
Preferably, the molar ratio of the absolute ethyl alcohol and isobutene is 0.1-0.3.After etherification reaction reaches balance, body
Still there is unconverted ethyl alcohol in system, if the amount of ethyl alcohol is excessive, excessive Ethanol Adsorption can drop significantly on resin activity center
The activity of low resin leads to lower isobutene conversion.But amount of alcohol added is very few, to the abated effect in resin acid site
Unobvious cannot improve the selectivity of C8 alkene well.
Preferably, temperature control is 30-80 DEG C when reaction.Reaction temperature has large effect, temperature to the reaction system
It spends low, although higher C8 olefine selectives can be obtained, since the conversion ratio of isobutene is too small, causes almost to collect not
To liquid product.Temperature is excessively high, and molecular motion aggravation, the easier consor of isobutene reduces the quality of heat bodied oil at C12+.
Preferably, the mass space velocity that raw material reactant passes through reactor is 2-5h-1.Too small air speed extends molecule and is urging
Residence time in agent causes the possibility that poly side reaction occurs to increase, but if air speed is excessive, part pib molecule
Have little time to convert, reaction system is just taken out of by fluid, greatly reduces the conversion ratio of isobutene.
Preferably, the solid acid catalyst uses cation exchange resin or molecular sieve.
Preferably, the solid acid catalyst uses highly acid macropore sulfuric acid resin.Macropore sulfuric acid resin has acid strength
Uniform, stability is good, it is cheap the advantages that, be excellent overlapping-catalyst for etherification.
For overlapping-etherification reaction, alfin ratio is important influence factor.Alfin ratio can influence etherification product and overlapping is produced
The ratio of object can also influence the distribution for overlapping dimerization, trimerization and four poly- products in product.The polarity of ethyl alcohol is more than isobutene and just
Therefore butylene can be preferentially adsorbed on the activated centre of resin, reduce the intensity and resin surface butylene in the acid site of resin
Concentration, reduce the rate of polymerisation, be conducive to improve C8 alkene selectivity.Ethyl alcohol preferentially occurs with reacting for isobutene,
Therefore, the production quantity that such as improve overlapping product, reduces the production quantity of ETBE, needs to control smaller alfin ratio, that is, controls second
The concentration of alcohol, but if amount of alcohol added is too small, to the abated effect unobvious in resin acid site, i.e., cannot significantly improve
The selectivity of C8 alkene.Therefore, the present invention by further investigation and repetition test, using alfin ratio 0.05-0.5 effects compared with
It is good, preferably 0.1-0.3.
In addition, etherification reaction and building-up reactions are all exothermic reactions, the former belongs to reversible reaction, and the latter belongs to can not be converse
It answers, temperature is to both having large effect.When temperature increases, it is unfavorable for the generation of etherification reaction, isobutyl in etherification reaction
Alkene equilibrium conversion reduces, but polymerisation can aggravate, therefore, it is necessary to investigate temperature to isobutene and butene-1 conversion ratio,
The influence of ETBE and C8 selectivity, the present invention are controlled at 20-100 DEG C, preferably by further investigation and repetition test, reaction temperature
It is 30-80 DEG C.
In addition, air speed can influence the residence time of reactant on a catalyst, air speed is different, and the extent of reaction of reactant is also
Difference causes isobutene different with the conversion ratio of butene-1, and the selectivity of etherification product and overlapping product is also different, and the present invention is logical
Further investigation and repetition test are crossed, air speed is controlled in 1-6h-1, preferably 2-4h-1。
Overlapping-etherification reaction of mixing C4 and absolute ethyl alcohol proposed by the present invention containing isobutene, disclose in the present invention
Process conditions under, can not only reach higher C8 selectivity, but also lower 1- butene conversions and higher different can be controlled
Butene conversion.When alfin molar ratio is 0.5, reaction temperature is 45 DEG C, air speed 2h-1, pressure be 1MPa when, isobutene it is total
Conversion ratio is 76.0%, and the total conversion of butene-1 is 4.2%, and the conversion ratio for generating the butene-1 of polymer only has 1.8%,
Ratio shared in liquid product ETBE is that shared ratio has reached 89.1% to 57.1%, C8 alkene in the polymer.
Description of the drawings
Fig. 1 is the specific reaction process device structure schematic diagram of the present invention；
In figure：1- nitrogen cylinder 2-C4 raw material steel cylinder 3- double plunger micro pump 4- ethanol raw material bottle 5- Liquid acquisition bottles
The 13- mixing of 6- airbag 7- decompression table 8- spinner flowmeter 9- triple valve 10- shut-off valve 11- pressure gauge 12- check valves
Device -14- counterbalance valve 15- microreactor 16- heating furnace 17- catalyst 18- thermocouple 19- temperature controller 20- mistakes
Filter.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
With raw material 1：The mixing C4 (molar percentage, 50% iso-butane, 25% isobutene, 25% butene-1) or original of configuration
Material 2：FCC cracking gases (wherein 52% iso-butane, 7% normal butane, 8% butene-2,16% butene-1,14% isobutene, and it is few
Measure propane) with absolute ethyl alcohol be reaction raw materials, reacted by the down-flow fixed bed continuous reaction apparatus of this field, device
As shown in Figure 1, including nitrogen cylinder 1, C4 raw materials steel cylinder 2, double plunger micro pump 3, ethanol raw material bottle 4, Liquid acquisition bottle 5, gas
Bag 6, decompression table 7, spinner flowmeter 8, triple valve 9, shut-off valve 10, pressure gauge 11, check valve 12, mixer 13, counterbalance valve 14,
Microreactor 15, heating furnace 16, catalyst 17, thermocouple 18, temperature controller 19, filter 20, microreactor 15 are
The stainless steel tube of 14mm*300mm, catalyst be mounted in reactor reaction tube constant temperature zone, rest part by same particle sizes quartz
Sand is filled, and is separated by silica wool between quartz sand and catalyst.Two gangs of raw material mixing C4 and absolute ethyl alcohol are micro- by double plunger respectively
Amount pump 3 is injected into mixer 13, enters in microreactor 15 reacted after mixing.Because the presence of water is to catalyst
Activity have large effect, therefore in the stock bottle of ethyl alcohol be added 3A molecular sieves to remove wherein micro water.Reaction
The pressure of system is controlled by counterbalance valve 14, and product is collected after gas-liquid separation, measured and respectively by gas-chromatography point after reaction
Analysis composition.The temperature of microreactor 15 is accurately measured by thermocouple 18.
Catalyst is first impregnating 5h before with ethyl alcohol, then is washed with deionized micro miscellaneous in resin to remove for several times
Matter, is then dried in vacuo 12h at 80 DEG C, and cooling is spare.Detailed process：Take 3g treated dry macropore sulfuric acid resin in
In reactor, activating pretreatment is carried out to catalyst before reaction, to remove wherein remaining moisture.Pretreatment condition：Temperature is
80 DEG C, nitrogen atmosphere, flow 50ml/min, processing time 5h cool the temperature to reaction temperature after activation, are passed through original
Material, starts to react.Using raw material 1, pressure control is 1.0MPa, air speed 2h-1, reaction temperature is 45 DEG C, by changing alfin
Than for (0.1-0.5), conversion ratio and product analysis result such as 2 institute of table of the isobutene and butene-1 of comparative example and each embodiment
Show.
2 comparative example 1-2 of table and embodiment 1-5 test results
Note：X (isobutene) is the total conversion of isobutene；X (butene-1) is the total conversion of butene-1；Xj(butene-1)
It is the conversion ratio for the butene-1 for participating in polymerisation；S (ETBE) is ETBE ratios shared in liquid product；S (C8) is C8
Shared ratio in the polymer.
It takes the 3g macropore sulfuric acid resins that treated dries in reactor, catalyst is carried out at pre-activated before reaction
Reason, to remove wherein remaining moisture.Activation temperature is 80 DEG C, nitrogen atmosphere, flow 50ml/min, processing time 5h,
Reaction temperature is cooled the temperature to after activation, is passed through raw material, starts to react.Using raw material 1, pressure 1.0MPa, air speed is
2h-1, alfin ratio 0.2, reaction temperature is 30 DEG C, 40 DEG C, 45 DEG C, 60 DEG C, the isobutene and butylene-of comparative example and each embodiment
The results are shown in Table 3 for 1 conversion ratio and product analysis.
3 comparative example 3 of table and embodiment 6-9 test results
It takes the 3g macropore sulfuric acid resins that treated dries in reactor, catalyst is carried out at pre-activated before reaction
Reason, to remove wherein remaining moisture.Activation temperature is 80 DEG C, nitrogen atmosphere, flow 50ml/min, processing time 5h,
Reaction temperature is cooled the temperature to after activation, is passed through raw material, starts to react.Using raw material 1, pressure 1.0MPa, alfin ratio
It is 0.1, reaction temperature is 45 DEG C, air speed 2h-1、3h-1、4h-1、5h-1, the isobutene of 4 each embodiment of comparative example and butene-1
The results are shown in Table 4 for conversion ratio and product analysis.
4 comparative example 4 of table and embodiment 10-13 test results
It takes the 3g macropore sulfuric acid resins that treated dries in reactor, catalyst is carried out at pre-activated before reaction
Reason, to remove wherein remaining moisture.Activation temperature is 80 DEG C, nitrogen atmosphere, flow 50ml/min, processing time 5h,
Reaction temperature is cooled the temperature to after activation, is passed through raw material, starts to react.Using raw material 2, alfin ratio 0.2,0.3,0.5,
Reaction temperature is 50 DEG C, air speed 2h-1, pressure 1.0MPa, the isobutene of comparative example (not adding ethyl alcohol) and each embodiment and
The results are shown in Table 5 for the conversion ratio and product analysis of butene-1.
5 comparative example 5-7 of table and embodiment 14-17 test results
Claims (10)
1. a kind of method preparing ETBE and C8 alkene with ethyl alcohol using mixing C4, which is characterized in that with mixed containing isobutene
It is raw material to close C4 and absolute ethyl alcohol, and etherification reaction is carried out by continuous fixed bed reaction or continuous device under the action of solid acid catalyst
And building-up reactions, the mixing C4 use two strands of feeding manners, the two to enter jointly after mixing in a mixer with absolute ethyl alcohol
It is reacted in reactor, the molar ratio of the absolute ethyl alcohol and isobutene is 0.05-0.5, and temperature control is 20-100 DEG C when reaction,
The mass space velocity that reactant passes through reactor is 1-6h-1。
2. a kind of method preparing ETBE and C8 alkene with ethyl alcohol using mixing C4 according to claim 1, feature exist
In the mixing C4 is C4 paraffins mixtures, and the molar concentration that the isobutene accounts for mixing C4 is 10-100%.
3. a kind of method preparing ETBE and C8 alkene with ethyl alcohol using mixing C4 according to claim 2, feature exist
In the molar concentration that the isobutene accounts for mixing C4 is 10-50%.
4. a kind of method preparing ETBE and C8 alkene with ethyl alcohol using mixing C4 according to claim 2, feature exist
In the mixing C4 includes isobutene, iso-butane and butene-1.
5. a kind of method preparing ETBE and C8 alkene with ethyl alcohol using mixing C4 according to claim 2, feature exist
In the mixing C4 includes isobutene, iso-butane, butene-1 and butene-2.
6. a kind of method preparing ETBE and C8 alkene with ethyl alcohol using mixing C4 according to claim 1, feature exist
In the molar ratio of the absolute ethyl alcohol and isobutene is 0.1-0.3.
7. a kind of method preparing ETBE and C8 alkene with ethyl alcohol using mixing C4 according to claim 1, feature exist
Temperature control is 30-80 DEG C when, reaction.
8. a kind of method preparing ETBE and C8 alkene with ethyl alcohol using mixing C4 according to claim 1, feature exist
In the mass space velocity that raw material reactant passes through reactor is 2-5h-1。
9. a kind of method preparing ETBE and C8 alkene with ethyl alcohol using mixing C4 according to claim 1, feature exist
In the solid acid catalyst uses cation exchange resin or molecular sieve.
10. a kind of method preparing ETBE and C8 alkene with ethyl alcohol using mixing C4 according to claim 9, feature exist
In the solid acid catalyst uses highly acid macropore sulfuric acid resin.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4377393A (en) * | 1979-11-03 | 1983-03-22 | Ec Erdolchemie Gmbh | Process for the preparation of a mixture consisting essentially of iso-butene oligomers and methyl tert.-butyl ether, its use, and fuels containing such mixture |
| CN1141908A (en) * | 1995-06-01 | 1997-02-05 | 斯南普罗吉蒂联合股票公司 | Process for joint production of ethers and hydrocarbons with high octane number |
| CN101190860A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Dimerization-etherification method for producing MTBE, isooctene and diisobutylene from C4 olefin |
-
2018
- 2018-05-31 CN CN201810551943.1A patent/CN108586208A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4377393A (en) * | 1979-11-03 | 1983-03-22 | Ec Erdolchemie Gmbh | Process for the preparation of a mixture consisting essentially of iso-butene oligomers and methyl tert.-butyl ether, its use, and fuels containing such mixture |
| CN1141908A (en) * | 1995-06-01 | 1997-02-05 | 斯南普罗吉蒂联合股票公司 | Process for joint production of ethers and hydrocarbons with high octane number |
| CN101190860A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Dimerization-etherification method for producing MTBE, isooctene and diisobutylene from C4 olefin |
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Application publication date: 20180928 |