CN103044214B - Preparation method of ethyl tert butyl ether - Google Patents
Preparation method of ethyl tert butyl ether Download PDFInfo
- Publication number
- CN103044214B CN103044214B CN201110313293.5A CN201110313293A CN103044214B CN 103044214 B CN103044214 B CN 103044214B CN 201110313293 A CN201110313293 A CN 201110313293A CN 103044214 B CN103044214 B CN 103044214B
- Authority
- CN
- China
- Prior art keywords
- butylene
- iso
- reaction
- ethanol
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of ethyl tert butyl ether. With isobutylene and ethanol as reaction raw materials and supported caesium phosphotungstate acidic salt as a catalyst, the ethyl tert butyl ether is prepared under the reaction conditions that liquid hourly volume space velocity of isobutylene is 0.5-5.0/h, mole ratio of the ethanol to the isobutylene is (1.0-10.0):1, reaction temperature is 90-200 DEG C and reaction pressure is 2.0-6.0MPa. The preparation method provided by the invention adopts the supported caesium phosphotungstate acidic salt as the catalyst, the defect that the typical heteropolyacid phosphotungstic acid and caesium phosphotungstate acidic salt thereof are easy to run away in a using process, are difficult to separate as particles are too small and are difficult to be used on a fixed bed reactor is overcome, continuous production by virtue of a fixed bed is realized, reaction activity is high, the supported caesium phosphotungstate acidic salt is easy to recycle and can be repeatedly used, and a reaction process operation is easy, so that the preparation method provided by the invention is a new environment-friendly process.
Description
Technical field
The invention provides one and synthesize the method for Ethyl Tertisry Butyl Ether (ETBE) with iso-butylene and aqueous ethanolic solution through etherificate and/or intermolecular dehydration.
Technical background
Ethyl Tertisry Butyl Ether (ETBE) and methyl tertiary butyl ether (MTBE) are as gasoline dope, and have good Blending effect, its chemical stability is good, can be miscible with arbitrary proportion with hydrocarbon fuel, has excellent anti-seismic performance.And adding of ETBE and MTBE, the discharge of the obnoxious flavoures such as CO can be reduced, reduce the pollution of air.Compared with MTBE, the octane value of ETBE is higher, and vapour pressure is lower, and therefore, what the gasoline that with the addition of ETBE can meet xeothermic area makes it with requiring.Simultaneously because MTBE leakage can bring certain water pollution problems, therefore occur limiting its trend used.And as one of the substitute of MTBE, ETBE starts to be subject to people's attention.
ETBE production process is similar with MTBE to technique, industrial usually with iso-butylene and ethanol for raw material, liquid phase synthesis under strong acidic ion resin exists, General reactions temperature 50 C ~ 70 DEG C, pressure 1.0 MPa ~ 1.5 MPa, alcohol/alkene mol ratio is greater than 1.
Zeo-karb is the catalyst for etherification industrially extensively adopted at present, and principal item is macropore sulfonic acid ion exchange resin.Mostly adopt Amberlyst-15 (A-15), Amberlyst-35 (A-35), Lewatit K2631, Bayer K2631 type etc. abroad.Domestic, mainly adopt D-72, S-54, D005, QRE type resin catalyst etc. that China researches and develops voluntarily, these resins are all the poly styrene polymers of divinylbenzene crosslink.
EP0048893 details the method by C 4 fraction coproduction isobutylene oligomer and alkyl-tert-butyl ether (ATBE) in a reactor.The catalyzer adopted is that a kind of metal of the periodic table of elements the 7th and the 8th subgroup of using in advance is with the acidic ion exchange resin of element form partly modification.Product is separated by distillating method with unconverted C4 hydro carbons.In this kind of method, about 8% linear butylene be have lost by oligomerization.The loss amount of butene-1 is 7%.But the main drawback of the method is, do not reach the conversion completely of iso-butylene, the iso-butylene content therefore in the C 4 fraction taken out is too high so that therefrom can not get qualified butene-1.
DE2521964 describes a kind of two phase methods preparing alkyl-tert-butyl ether, wherein in the first stage, iso-butylene and alcohol react, and the ether of generation is taken out by from the product mixtures of first stage, the remnants of remaining initial hydrocarbon stream are fed into etherification stage, at this by remaining isobutene conversion.EP0071032 equally also describes the two-stage method of preparation ETBE, and the ETBE wherein generated in the first stage is taken out by from reactant between first and second stage.
CN1772848A, CN1780803A and CN101955418A all disclose a kind of method preparing ETBE mixture, are all the methods being prepared ETBE by aqueous ethanol and isobutene reaction.
CN1990443A provides a kind of method being prepared ETBE by hybrid C 4, prepare ETBE by the mixture at least comprising butene-1, iso-butylene, normal butane and butene-2, the method iso-butylene comprised contained by order react, distill take out comprise butene-1 and iso-butylene cut also make the iso-butylene wherein existed again react generation ETBE.
Petrochemical complex the 34th volume first phase in 2005, adopt with iso-butylene and ethanol for raw material, HF acid modification USY molecular sieve (HF/USY) is catalyzer, synthesizes Ethyl Tertisry Butyl Ether (ETBE) in fixed-bed reactor.Under the same operating conditions, respectively with acidic resins A-15, H beta-molecular sieve, USY molecular sieve and HF/USY for catalyzer carries out contrast experiment.Result shows, the USY molecular sieve catalyzer of HF acid modification has good activity and selectivity, and the modifying function of HF acid USY molecular sieve is obvious.Take HF/USY as catalyzer, having investigated the processing condition such as temperature, air speed, pressure respectively optionally affects ethanol conversion and ETBE, obtains the etherificate operational condition be suitable for: temperature 110 DEG C, air speed (WHSV) 5.0h
-1, pressure 1.8MPa, the transformation efficiency of iso-butylene is 78.3%.
" hydrometallurgy " 2009 the 28th volume the 2nd phase, adopt sol-gel method, by a certain amount of loaded by heteropoly acid in silica-based obtained HPWA/SiO
2catalyzer, this catalyzer can be used for the building-up reactions of catalysis Ethyl Tertisry Butyl Ether (ETBE).At temperature of reaction 110 DEG C, pressure 2 MPa, air speed 1h
-1under condition, the transformation efficiency of iso-butylene is 82.6%.
" catalysis journal " the 24th volume the 4th phase in 2003, under have studied liquid phase, pressurized conditions, adopt different zeolites Zeolite synthesis Ethyl Tertisry Butyl Ether (ETBE).The catalytic activity of H β zeolite and the suitable of A235 resin catalyst, far away higher than other zeolite [molecular sieves.On alcohol/alkene comparison H molecular sieve catalyst and A235 catalyzer, the synthesis impact of ETBE is larger.But on H beta-zeolite molecular sieve, the selectivity of ETBE is not substantially by the impact of alcohol/alkene ratio, and on alcohol/alkene comparison resin catalyst, the selectivity impact of ETBE is relatively large.After adding tackiness agent, the activity of H beta-zeolite molecular sieve catalyst declines to some extent, but after adding pore-creating agent, its activity increases.After adding 5 % Macrogol 4000s, when temperature is higher than 65 DEG C, suitable with A 35 of the catalytic activity of H β zeolite, at certain temperatures, even higher than the activity of A 35 resin catalyst.
" petroleum journal (refining of petroleum) " calendar year 2001 the 17th volume supplementary issue, adopt the catalyzer of modified beta zeolite synthesis Ethyl Tertisry Butyl Ether (ETBE), temperature of reaction 60 DEG C ~ 90 DEG C, pressure 2 MPa ~ 3 MPa, the transformation efficiency of iso-butylene is 60% ~ 93.3%.
" catalysis journal " the 25th volume the 3rd phase in 2005, adopting alkaline purification to mordenite thing phase, Acidity and Synthesis of Ethyl-tert-Butyl Ether (ETBE), is 58 % at the peak rate of conversion of about 80 DEG C iso-butylenes.
In sum, the advantage of resin catalyst is active high, and easy and product separation, less to equipment corrosion, selectivity is more high.Weak point is then mainly reflected in: 1. resin catalyst less stable, and during raised temperature (being greater than 373.15K), sulfonic acid group easily comes off, and causes catalyst deactivation, etching apparatus polluted product; 2. along with the rising of temperature, resin catalyst selectivity is deteriorated, and oligomerisation side reaction increases, and by product increases; 3. industrial in order to improve olefin conversion, suppress side reaction, often adopt higher alfin ratio, thus cause needing higher energy consumption to carry out recycling of realization response thing.
Zeolite molecular sieve is the effective catalyst of synthesis ETBE, in various zeolite molecular sieve, best with β zeolite properties.The advantage of zeolite is mainly reflected in: 1. Heat stability is good, can use at a higher temperature; 2. possess shape selective catalysis feature, thus the selectivity of object product E TBE is higher; 3. easily regenerated by roasting and activate, even if discarded also pollution-free to environment.Current main weak point is that activity is lower.
The activity of heteropolyacid catalyst itself is on the low side, less stable, limits its application.The stability deficiency of heteropolyacid catalyst is mainly manifested in bad, the water-soluble and alcohol dissolubility of thermostability.The thermostability of heteropolyacid is bad, can slowly decompose at relatively high temperatures, causes active ingredient to lose, and then activity decrease; The alcohol dissolubility of heteropolyacid, in the reaction system containing alcohol, heteropolyacid meeting loss by dissolution, and then make active reduction.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of with iso-butylene and aqueous ethanolic solution through etherificate and/or intermolecular Dehydration for the method for Ethyl Tertisry Butyl Ether (ETBE), it is characterized in that the acid salt (C adopting carried phospho-tungstic acid caesium
s2.5h
0.5pW
12o
40) as catalyzer, overcome typical heteropolyacid phospho-wolframic acid and its esters acid Tricesium dodecatungstophosphate catalyzer, in use easily run off and particle too little, cause separation difficulty, be difficult to the shortcoming be used on fixed-bed reactor, fixed-bed reactor achieve continuous prodution, and reactive behavior is high, easy recovery, and reusable.Meanwhile, the carried heteropoly acid catalyst activity that the inventive method uses is high, good stability.
The preparation method of Ethyl Tertisry Butyl Ether of the present invention comprises following process: with iso-butylene and ethanol for reaction raw materials, the acid salt (C of working load type Tricesium dodecatungstophosphate
s2.5h
0.5pW
12o
40) as catalyzer, when the liquid of iso-butylene, volume space velocity is 0.5h
-1~ 5.0h
-1, the mol ratio of ethanol and iso-butylene is 1.0:1 ~ 10.0:1, temperature of reaction 90 DEG C ~ 200 DEG C, and reaction pressure is under the reaction conditions of 2.0 MPa ~ 6.0MPa, prepares Ethyl Tertisry Butyl Ether (ETBE).
In the inventive method, the acid salt catalyzer of carried phospho-tungstic acid caesium take silica gel as carrier, and active ingredient is Tricesium dodecatungstophosphate acid salt, and the molecular formula of Tricesium dodecatungstophosphate acid salt is C
s2.5h
0.5pW
12o
40, the charge capacity of Tricesium dodecatungstophosphate acid salt is 20% ~ 50% of catalyst weight, is preferably 30% ~ 40%.
In the inventive method, described iso-butylene can use the hybrid C 4 raw material containing iso-butylene, also can use pure iso-butylene.When using hybrid C 4 raw material, in hybrid C 4 raw material, iso-butylene weight content is at least 5%, is preferably at least 10%, is most preferably at least 15%.
In the inventive method, described ethanol raw material can be the aqueous solution of dehydrated alcohol or ethanol, and when using the aqueous solution of ethanol, in the aqueous solution, the weight content of ethanol is more than 50%, is preferably more than 60%, most preferably is more than 75%.
In the inventive method, during the liquid of described iso-butylene, volume space velocity is preferably 1.0h
-1~ 4.0h
-1; The mol ratio of ethanol and iso-butylene is preferably 1.5:1 ~ 6.0:1; Temperature of reaction is preferably 100 DEG C ~ 160 DEG C; Reaction pressure is preferably 3.0 MPa ~ 6.0MPa.
In the inventive method, during the liquid of described iso-butylene, volume space velocity is preferably 1.0h
-1~ 2.5h
-1; The mol ratio of ethanol and iso-butylene is preferably 1.5:1 ~ 5.0:1; Temperature of reaction is preferably 100 DEG C ~ 150 DEG C; Reaction pressure is preferably 4.0 MPa ~ 5.0MPa.
The present invention adopts the acid salt (C of carried phospho-tungstic acid caesium
s2.5h
0.5pW
12o
40) as catalyzer, catalyst activity is high, good stability.The present invention overcomes typical heteropolyacid phospho-wolframic acid and its esters acid Tricesium dodecatungstophosphate, in use easily run off and particle too little, cause separation difficulty, be difficult to the shortcoming be used on fixed-bed reactor, fixed-bed reactor achieve continuous prodution, and reactive behavior is high, easy recovery, and reusable, reaction process is easy and simple to handle, is environmental friendliness chemical industry novel process.
Embodiment
The preparation method of the acid salt catalyzer of carried phospho-tungstic acid caesium used in the present invention, comprises following content:
(1) silica-gel carrier is got, preparation cesium carbonate solution and Salkowski's solution;
(2) with cesium carbonate solution dipping silica-gel carrier, then dry, roasting;
(3) the material dipping Salkowski's solution that obtains of step (2), then drying and roasting, obtain final catalyzer.
In the above-mentioned method for preparing catalyst of the present invention, silica-gel carrier can use common commercially available prod, also can prepare by this area ordinary method.In cesium carbonate (caesium 133) solution and Salkowski's solution, the consumption of solute is determined by the active ingredient consumption needed for final catalyzer.
In the above-mentioned method for preparing catalyst of the present invention, two impregnation steps can adopt conventional impregnation method, as incipient impregnation, spray, supersaturation impregnating.
In the above-mentioned method for preparing catalyst of the present invention, the drying of step (2) and step (3) is normal condition, as at 80 ~ 200 DEG C dry 5 ~ 20 hours, the roasting condition of step (2) is roasting 3 ~ 10 hours at 300 ~ 400 DEG C, and the roasting condition of step (3) is roasting 2 ~ 14 hours at 350 ~ 550 DEG C.
Embodiment 1
Acid salt (the C of carried phospho-tungstic acid caesium
s2.5h
0.5pW
12o
40) method for preparing catalyst:
Adopt two step equi-volume impregnatings, get appropriate cesium carbonate (C
s2cO
3) be dissolved in deionized water, carrier silica gel be dipped in above-mentioned solution, sample is dried at 120 DEG C, roasting 5 hours at 350 DEG C.
By quantitative phospho-wolframic acid (H
3pW
12o
40) be dissolved in deionized water, the sample after above-mentioned roasting is dipped in Salkowski's solution, and after drying at 120 DEG C, at 450 DEG C, roasting 4 hours, obtains catalyst A.
Through XRD analysis, the active ingredient of catalyst A is the acid salt (C of Tricesium dodecatungstophosphate
s2.5h
0.5pW
12o
40), in catalyzer, active ingredient content is by weight 38%.
Change the consumption of cesium carbonate and phospho-wolframic acid, other condition is constant, obtains catalyst B, and the acid salt mass content in the catalyst of active ingredient Tricesium dodecatungstophosphate is 20%.
Embodiment 2 ~ 15
Acid (the C of carried phospho-tungstic acid caesium prepared by embodiment 1
s2.5h
0.5pW
12o
40) catalyzer, the reaction of Ethyl Tertisry Butyl Ether is prepared for ethanol (or aqueous ethanolic solution) and iso-butylene, this reaction carries out in the stainless steel fixed-bed reactor of Φ 18mm × 1200mm, in reactor, load above-mentioned catalyzer 30ml, reactor head and bottom, be respectively charged into the quartz sand that diameter is Φ 0.5mm ~ 1.2mm, after reactor installs, with nitrogen replacement three times, and tightness test is qualified, and iso-butylene, ethanol or aqueous ethanolic solution metering are pumped into preheater.Embodiment 2 ~ 8 uses catalyst A, and embodiment 9-15 uses catalyst B.Reaction conditions and reaction result are in table 1.
Table 1 embodiment 2 ~ 15 reaction conditions and reaction result.
| Sequence number | Feed ethanol content/% | Reaction pressure/MPa | Temperature of reaction/DEG C | Volume space velocity/the h of iso-butylene -1 | Ethanol/iso-butylene | Isobutene conversion/% |
| Embodiment 2 | 50 | 2.0 | 90 | 0.5 | 1.0 | 87.6 |
| Embodiment 3 | 60 | 3.0 | 120 | 1.5 | 3.0 | 88.7 |
| Embodiment 4 | 70 | 4.0 | 150 | 2.5 | 5.0 | 90.3 |
| Embodiment 5 | 80 | 5.0 | 170 | 3.5 | 7.0 | 88.9 |
| Embodiment 6 | 90 | 6.0 | 200 | 4.5 | 10.0 | 93.2 |
| Embodiment 7 | 100 | 3.0 | 100 | 5.0 | 1.5 | 91.3 |
| Embodiment 8 | 55 | 4.0 | 110 | 1.0 | 2.5 | 87.9 |
| Embodiment 9 | 65 | 5.0 | 130 | 2.0 | 3.5 | 88.6 |
| Embodiment 10 | 75 | 4.0 | 150 | 3.0 | 4.5 | 89.5 |
| Embodiment 11 | 85 | 5.0 | 160 | 4.0 | 6.0 | 90.3 |
| Embodiment 12 | 95 | 4.0 | 100 | 1.0 | 2.0 | 88.9 |
| Embodiment 13 | 75 | 5.0 | 120 | 1.5 | 3.0 | 89.6 |
| Embodiment 14 | 85 | 4.0 | 130 | 2.0 | 4.0 | 89.2 |
| Embodiment 15 | 95 | 5.0 | 150 | 2.5 | 5.0 | 89.9 |
Comparative example
According to the method for embodiment 1, by phospho-wolframic acid load on silica-gel carrier, the weight content of phospho-wolframic acid is by 20% load.The condition identical with embodiment 9 is reacted, and reaction result such as table 2 shows institute.
Table 2 comparative example and embodiment 9 reaction result.
| Runtime | 100 hours | 800 hours | 1500 hours |
| Temperature of reaction, DEG C | 130 | 135 | 138 |
| Comparative example isobutene conversion/% | 82.1 | 80.3 | 74.6 |
| Embodiment 9 isobutene conversions/% | 88.6 | 88.7 | 88.4 |
Table 2 data can be found out, the inventive method has satisfactory stability.
Claims (7)
1. the preparation method of an Ethyl Tertisry Butyl Ether, with the hybrid C 4 raw material containing iso-butylene or pure iso-butylene and ethanol for reaction raw materials, it is characterized in that: the acid salt of working load type Tricesium dodecatungstophosphate is as catalyzer, and when the liquid of the hybrid C 4 raw material containing iso-butylene or pure iso-butylene, volume space velocity is 0.5h
-1~ 5.0h
-1, ethanol and be 1.0:1 ~ 10.0:1 containing the hybrid C 4 raw material of iso-butylene or the mol ratio of pure iso-butylene, temperature of reaction 90 DEG C ~ 200 DEG C, reaction pressure is under the reaction conditions of 2.0 MPa ~ 6.0MPa, prepares Ethyl Tertisry Butyl Ether;
Wherein, the preparation method of the acid salt catalyzer of carried phospho-tungstic acid caesium is made up of following content:
(1) silica-gel carrier is got, preparation cesium carbonate solution and Salkowski's solution;
(2) with cesium carbonate solution dipping silica-gel carrier, then at 80 ~ 200 DEG C dry 5 ~ 20 hours, 300 ~ 400 DEG C of roastings 3 ~ 10 hours;
(3) the material dipping Salkowski's solution that obtains of step (2), drier 5 ~ 20 hours and roasting 2 ~ 14 hours at 350 ~ 550 DEG C at 80 ~ 200 DEG C, obtain final catalyzer.
2. in accordance with the method for claim 1, it is characterized in that: the acid salt catalyzer of carried phospho-tungstic acid caesium take silica gel as carrier, and active ingredient is Tricesium dodecatungstophosphate acid salt, the molecular formula of Tricesium dodecatungstophosphate acid salt is Cs
2.5h
0.5pW
12o
40.
3. according to the method described in claim 1 or 2, it is characterized in that: the charge capacity of Tricesium dodecatungstophosphate acid salt is 20% ~ 50% of catalyst weight.
4. according to the method described in claim 1 or 2, it is characterized in that: the charge capacity of Tricesium dodecatungstophosphate acid salt is catalyst weight is 30% ~ 40%.
5. in accordance with the method for claim 1, it is characterized in that: ethanol raw material is the aqueous solution of dehydrated alcohol or ethanol.
6. in accordance with the method for claim 1, it is characterized in that: during the liquid of the hybrid C 4 raw material containing iso-butylene or pure iso-butylene, volume space velocity is 1.0h
-1~ 4.0h
-1, ethanol and be 1.5:1 ~ 6.0:1 containing the hybrid C 4 raw material of iso-butylene or the mol ratio of pure iso-butylene, temperature of reaction is 100 DEG C ~ 160 DEG C, and reaction pressure is 3.0 MPa ~ 6.0MPa.
7. in accordance with the method for claim 1, it is characterized in that: during the liquid of the hybrid C 4 raw material containing iso-butylene or pure iso-butylene, volume space velocity is 1.0h
-1~ 2.5h
-1, ethanol and containing the hybrid C 4 raw material of iso-butylene or the mol ratio 1.5:1 ~ 5.0:1 of pure iso-butylene, temperature of reaction is 100 DEG C ~ 150 DEG C, and reaction pressure is 4.0 MPa ~ 5.0MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110313293.5A CN103044214B (en) | 2011-10-17 | 2011-10-17 | Preparation method of ethyl tert butyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110313293.5A CN103044214B (en) | 2011-10-17 | 2011-10-17 | Preparation method of ethyl tert butyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103044214A CN103044214A (en) | 2013-04-17 |
| CN103044214B true CN103044214B (en) | 2015-07-22 |
Family
ID=48057102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110313293.5A Active CN103044214B (en) | 2011-10-17 | 2011-10-17 | Preparation method of ethyl tert butyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103044214B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110937982B (en) * | 2018-09-25 | 2023-01-10 | 中国石油化工股份有限公司 | Method for preparing p-tert-butylphenol |
| CN111375433B (en) * | 2018-12-28 | 2023-02-03 | 中国石油化工股份有限公司 | Method for oligomerization of isobutene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613559A (en) * | 2004-09-28 | 2005-05-11 | 北京化工大学 | Preparation for hydrophobic solid acid catalyst |
| CN1752003A (en) * | 2005-10-20 | 2006-03-29 | 复旦大学 | Synthesis method of solid ultrastrong acid cesium phospho-welframate |
-
2011
- 2011-10-17 CN CN201110313293.5A patent/CN103044214B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613559A (en) * | 2004-09-28 | 2005-05-11 | 北京化工大学 | Preparation for hydrophobic solid acid catalyst |
| CN1752003A (en) * | 2005-10-20 | 2006-03-29 | 复旦大学 | Synthesis method of solid ultrastrong acid cesium phospho-welframate |
Non-Patent Citations (2)
| Title |
|---|
| HPWA/SiO2催化乙基叔丁基醚合成反应的研究;班红艳等;《湿法冶金》;20090615;第28卷(第2期);116-118 * |
| 负载型Cs2.5H0.5PW12O40醚化催化剂的制备与催化性能;王海彦等;《化工学报》;20031030;第54卷(第10期);1374-1377 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103044214A (en) | 2013-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2660132C2 (en) | Method for producing olefin by catalytic conversion of at least one alcohol | |
| CN103301876B (en) | A kind of preparation method of straight-chain olefin skeleton isomerization catalyst | |
| CN101332432B (en) | Load-type solid acid catalyst with selective oligomerisation for mixed C4 | |
| JP2013522270A (en) | Simultaneous dehydration and skeletal isomerization of isobutanol over acid catalyst | |
| CN102344364A (en) | Method for producing sec-butyl acetate by synthesizing acetic acid and mixed C4 | |
| CN103044213B (en) | A kind of processing method preparing Ethyl Tertisry Butyl Ether | |
| CN103044214B (en) | Preparation method of ethyl tert butyl ether | |
| CN103785482B (en) | A kind of deactivating process for the treatment of of olefin isomerization catalyst | |
| CN101121656A (en) | Method for synthesizing sec-butyl acetate from acetic acid and linear butylene | |
| CN103508885B (en) | One utilizes C after ether 4cut prepares the method for 2-butyl acetate | |
| CN103508884B (en) | One utilizes C after ether 4cut prepares the method for 2-butyl acetate | |
| CN109092302B (en) | Method for selective hydrogenation of butadiene | |
| CN103044212B (en) | Process method for preparing ethyl tert-butyl ether | |
| CN103787843B (en) | A kind of method preparing tert amyl methyl ether(TAME) | |
| CN113024336B (en) | Method for preparing isodecene by catalyzing isoamylene dimerization | |
| CN102755903B (en) | Preparation method of acidic molecular sieve and resin composite catalyst | |
| CN102909081A (en) | Catalyst and method for preparing methyl sec-butyl ether | |
| CN103787877B (en) | Preparation method of cyclohexyl acetate | |
| CN102755904B (en) | Preparation method of acidic molecular sieve and resin composite catalyst | |
| UA106417C2 (en) | Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts | |
| CN103506151B (en) | C 4 olefin prepares 2-butyl acetate catalyst | |
| CN1307132C (en) | Catalyst for producing diesel oil from tetracarbon olefin polymerization and its preparation method and uses | |
| CN102757309B (en) | Alkene hydration method | |
| CN110639517A (en) | Catalyst for selective hydrogenation of butadiene and application thereof | |
| CN103787841B (en) | A kind of method of synthesizing tertiary amyl ethyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |