CN103044213B - A kind of processing method preparing Ethyl Tertisry Butyl Ether - Google Patents
A kind of processing method preparing Ethyl Tertisry Butyl Ether Download PDFInfo
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Abstract
The invention provides a kind of processing method preparing Ethyl Tertisry Butyl Ether, with the rare and ethanol of isobutyl for raw material, use heteropolyacid/aluminium base composite oxides catalyzer, wherein heteropolyacid/aluminium base composite oxides catalyzer, take composite oxides as carrier, take heteropolyacid as active ingredient, described composite oxides are MgO-Al
2o
3, TiO
2-Al
2o
3and ZrO
2-Al
2o
3one or more of middle aluminium base composite oxides, described heteropolyacid is one or more in phospho-wolframic acid, silicotungstic acid, arsenowolframic acid, germanotungstic acid, phospho-molybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid etc.The present invention adopts the catalyzer of aluminium base composite oxides carried heteropoly acid, overcomes that heteropolyacid catalyst heteropolyacid structure with Keggin is easily damaged, acid amount easily runs off, shortcoming that separation difficulty and the catalyst deactivation brought, transformation efficiency reduce.
Description
Technical field
The invention provides one and be applicable to the processing method that hydrocarbon and etherified reaction prepare Ethyl Tertisry Butyl Ether (ETBE).
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 1.0MPa ~ 1.5MPa, 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), LewatitK2631, BayerK2631 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 2MPa, 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 4000, when temperature is higher than 65 DEG C, suitable with A35 of the catalytic activity of H β zeolite, at certain temperatures, even higher than the activity of A35 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 2MPa ~ 3MPa, 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 method of etherificate synthesis Ethyl Tertisry Butyl Ether (ETBE) under the catalyzer of aluminium base composite oxides carried heteropoly acid exists by iso-butylene and ethanol, the inventive method has good reactivity worth, has satisfactory stability simultaneously.
The processing method that the present invention prepares Ethyl Tertisry Butyl Ether comprises following content: with the rare and ethanol of isobutyl for raw material, and use heteropolyacid/aluminium base composite oxides catalyzer, the volume space velocity of iso-butylene is 0.5h
-1~ 6.0h
-1, the mol ratio of ethanol and iso-butylene is 1.0:1.0 ~ 5.0:1.0, temperature of reaction 60 DEG C ~ 150 DEG C, and reaction pressure is 1.0MPa ~ 3.0MPa; Wherein heteropolyacid/aluminium base composite oxides catalyzer, being carrier with composite oxides, take heteropolyacid as active ingredient, and described composite oxides are MgO-Al
2o
3, TiO
2-Al
2o
3and ZrO
2-Al
2o
3one or more of middle aluminium base composite oxides, described heteropolyacid is one or more in phospho-wolframic acid, silicotungstic acid, arsenowolframic acid, germanotungstic acid, phospho-molybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid etc.
In the inventive method, Al in aluminium base composite oxides
2o
3weight content be 20% ~ 95%, be preferably 30% ~ 90%, most preferably be 40% ~ 70%; The weight ratio of heteropolyacid and aluminium base composite oxides is 0.01:1 ~ 1:1, is preferably 0.1:1 ~ 0.9:1, most preferably is 0.3:1 ~ 0.6:1.
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, the volume space velocity of described iso-butylene is preferably 1.0h
-1~ 5.0h
-1, the mol ratio of ethanol and iso-butylene is preferably 1.0:1.0 ~ 3.0:1.0, and temperature of reaction is preferably 70 DEG C ~ 130 DEG C, and reaction pressure is preferably 1.0MPa ~ 2.5MPa.
In the inventive method, the volume space velocity of described iso-butylene most preferably is 1.0h
-1~ 2.0h
-1, the mol ratio of ethanol and iso-butylene most preferably is 1.0:1.0 ~ 2.0:1.0, and temperature of reaction most preferably is 90 DEG C ~ 110 DEG C, and reaction pressure most preferably is 2.0MPa ~ 2.5MPa.
The inventive method adopts the catalyzer of the carrier loaded heteropolyacid of a kind of aluminium base composite oxides, support of the catalyst is made to obtain suitable specific surface, aperture structure and acidity distribution, effectively can have adjusted acidity and the activity of catalyzer, overcome the carrier loaded heteropolyacid catalyst of single component porous medium due to the easy decomposes of structure with Keggin of heteropolyacid, acid amount easily run off, separation difficulty and the catalyst deactivation brought, transformation efficiency reduce shortcoming.The inventive method can realize continuous prodution, and reaction process is easy and simple to handle, and synthesizing Ethyl Tertisry Butyl Ether for iso-butylene and ethanol and have the advantages such as transformation efficiency is high, good stability, is an environmental protection novel process.
Embodiment
The present invention generates reaction mechanism and the reaction characteristics of different base sec-butyl ether (ETBE) according to iso-butylene and ethanol etherificate, adopt a kind of aluminium base composite oxides carried heteropoly acid as catalyzer, react under suitable reaction conditions, overcome that Several Typical Load type heteropolyacid catalyst heteropolyacid structure with Keggin is easily damaged, acid amount easily runs off, shortcoming that separation difficulty and the catalyst deactivation brought, transformation efficiency reduce.
Catalyzer of the present invention can be prepared by following method: the aqueous solution a of the preparation corresponding salt of aluminium base composite oxides and aluminum nitrate, preparation basic solution b(potassium hydroxide joins solution or ammoniacal liquor), under the state of normal mild stirring, solution b is added drop-wise in a, be obtained by reacting precipitation, through washing, filter, dry, then after method extruded moulding routinely, roasting obtains aluminium base composite oxides carrier.
In the preparation process of above-mentioned aluminium base composite oxides, the described reaction times is 2h ~ 20h, is preferably 4h ~ 16h, most preferably is 6h ~ 12h.Described drying temperature is 90 DEG C ~ 150 DEG C, is preferably 100 DEG C ~ 140 DEG C, most preferably is 110 DEG C ~ 130 DEG C.Described time of drying is 4h ~ 24h, is preferably 6h ~ 16h, most preferably is 10h ~ 12h.Described maturing temperature is 400 DEG C ~ 800 DEG C, is preferably 450 DEG C ~ 700 DEG C, most preferably is 500 DEG C ~ 600 DEG C.Described roasting time is 8h ~ 24h, is preferably 8h ~ 14h, most preferably is 8h ~ 12h.
By shaping rear aluminium base composite oxides carrier, the method for conveniently flooding, floods in heteropolyacid solution.Dipping time is 4h ~ 24h, is preferably 4h ~ 12h, most preferably is 6h ~ 12h.Macerate is dry 4h ~ 12h at 100 DEG C ~ 180 DEG C, is preferably dry 6h ~ 12h at 100 DEG C ~ 160 DEG C, most preferably is dry 6h ~ 8h at 100 DEG C ~ 120 DEG C.Macerate is roasting 6h ~ 24h at 250 DEG C ~ 550 DEG C, is preferably roasting 6h ~ 12h at 300 DEG C ~ 500 DEG C, most preferably is roasting 8h ~ 12h at 350 DEG C ~ 450 DEG C and obtains heteropolyacid/aluminium base composite oxides catalyzer.
Method of the present invention and effect is further illustrated below by specific embodiment.
Embodiment 1
A certain amount of aluminum nitrate and a certain amount of magnesium nitrate are mixed with aqueous solution a, aqueous solution b is configured to deionized water and a certain amount of potassium hydroxide, under the state of normal mild stirring, solution b is added drop-wise in a, reaction 6h obtains white paste precipitation, through washing, filter, at 120 DEG C of dry 10h, method extruded moulding routinely again, then at 500 DEG C, roasting 8h obtains magnesium-aluminum complex oxide carrier.
Be dissolved in by phospho-molybdic acid in deionized water, the support of the catalyst after above-mentioned shaping and roasting is dipped in assorted many solution, and dipping time is 12h, and macerate is dry 12h at 110 DEG C, roasting 8h at 350 DEG C, obtained catalyzer, and catalyzer composition is in table 1.
Iso-butylene and ethanol etherificate are carried out in the stainless steel fixed-bed reactor of Φ 18mm × 1200mm, above-mentioned catalyzer 30ml is loaded in reactor, 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, iso-butylene, ethanol metering are pumped into preheater, and reaction conditions and reaction result are in table 2.
Embodiment 2
Other condition, with embodiment 1, just changes the consumption of magnesium nitrate and phospho-molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 3
Other condition, with embodiment 1, just changes the consumption of magnesium nitrate and phospho-molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 4
Other condition, with embodiment 1, just changes the consumption of magnesium nitrate and phospho-molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 5
Other condition, with embodiment 1, just changes the consumption of magnesium nitrate and phospho-molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 6
Other condition is with embodiment 1, and just change magnesium nitrate into titanium tetrachloride, phospho-molybdic acid changes silicomolybdic acid into, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 7
Other condition, with embodiment 1, just changes the consumption of titanium tetrachloride and silicomolybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 8
Other condition, with embodiment 1, just changes the consumption of titanium tetrachloride and silicomolybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 9
Other condition, with embodiment 1, just changes the consumption of titanium tetrachloride and silicomolybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 10
Other condition, with embodiment 1, just changes the consumption of titanium tetrachloride and silicomolybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 11
Other condition is with embodiment 1, and just magnesium nitrate changes zirconium tetrachloride into, and phospho-molybdic acid changes silicomolybdic acid into, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 12
Other condition, with embodiment 1, just changes zirconium tetrachloride and silicomolybdic acid consumption, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 13
Other condition, with embodiment 1, just changes zirconium tetrachloride silicomolybdic acid consumption, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 14
Other condition, with embodiment 1, just changes zirconium tetrachloride silicomolybdic acid consumption, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 15
Other condition, with embodiment 1, just changes zirconium tetrachloride silicomolybdic acid consumption, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 16
Other condition, with embodiment 1, just changes phospho-molybdic acid into phospho-wolframic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 17
Other condition, with embodiment 1, just changes phospho-molybdic acid into silicotungstic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 18
Other condition, with embodiment 1, just changes phospho-molybdic acid into arsenowolframic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 19
Other condition, with embodiment 1, just changes phospho-molybdic acid into germanotungstic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 20
Other condition, with embodiment 1, just changes phospho-molybdic acid into arsenic molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 21
Other condition, with embodiment 1, just changes phospho-molybdic acid into germanium molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 22
By the catalyzer of embodiment 6, according to the evaluation method of embodiment 1, be 1.5h at the volume space velocity of isobutylene feed
-1, the mol ratio of ethanol and iso-butylene is 2:1, and temperature of reaction is 90 DEG C, and reaction pressure is under the condition of 2.5MPa, has carried out stability test, test-results table 3.
Comparative example 1
With a certain amount of Al of a certain amount of phospho-molybdic acid aqueous impregnation
2o
312h, dry 12h at 110 DEG C, then roasting 8h is prepared into catalyzer at 500 DEG C.Evaluating catalyst method is with embodiment 1, and catalyzer composition is in table 1, and reaction result is in table 2.
Comparative example 2
Other condition, with comparative example 1, just changes phospho-molybdic acid into phospho-wolframic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Comparative example 3
Other condition, with comparative example 1, just changes phospho-molybdic acid into silicotungstic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Comparative example 4
Other condition, with comparative example 1, just changes phospho-molybdic acid into arsenic molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Comparative example 5
Other condition, with comparative example 1, just changes phospho-molybdic acid into germanium molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Comparative example 6
Comparative example 1 catalyzer, carries out estimation of stability by the evaluation method of embodiment 22, the results are shown in Table 3.
Table 1 embodiment and comparative example catalyzer form.
| Sequence number | Aluminum oxide in composite oxides, quality % | The mass ratio of heteropolyacid and composite oxides |
| Embodiment 1 | 90 | 0.01:1.0 |
| Embodiment 2 | 80 | 0.1:1.0 |
| Embodiment 3 | 60 | 0.5:1.0 |
| Embodiment 4 | 40 | 0.7:1.0 |
| Embodiment 5 | 20 | 0.9:1.0 |
| Embodiment 6 | 65 | 0.05:1 |
| Embodiment 7 | 55 | 0.15:1 |
| Embodiment 8 | 45 | 0.35:1 |
| Embodiment 9 | 35 | 0.65:1.0 |
| Embodiment 10 | 20 | 1.0:1.0 |
| Embodiment 11 | 30 | 0.1:1.0 |
| Embodiment 12 | 40 | 0.25:1.0 |
| Embodiment 13 | 50 | 0.45:1.0 |
| Embodiment 14 | 60 | 0.65:1.0 |
| Embodiment 15 | 70 | 0.75:1.0 |
| Embodiment 16 | 85 | 0.2:1.0 |
| Embodiment 17 | 75 | 0.35:1.0 |
| Embodiment 18 | 65 | 0.55:1.0 |
| Embodiment 19 | 55 | 0.75:1.0 |
| Embodiment 20 | 45 | 1.00:1.0 |
| Embodiment 21 | 20 | 0.01:1.0 |
| Comparative example 1 | 100 | 0.10:1.0 |
| Comparative example 2 | 100 | 0.35:1.0 |
| Comparative example 3 | 100 | 0.55:1.0 |
| Comparative example 4 | 100 | 0.85:1.0 |
| Comparative example 5 | 100 | 0.90：1.0 |
The reaction conditions of table 2 embodiment and comparative example and reaction result.
| Sequence number | Reaction pressure/MPa | Temperature of reaction/DEG C | Iso-butylene volume space velocity/h -1 | Ethanol/iso-butylene (mol ratio) | Iso-butylene per pass conversion/% by mole |
| Embodiment 1 | 1.0 | 60 | 1.0 | 1.0 | 85.6 |
| Embodiment 2 | 2.0 | 80 | 2.0 | 2.0 | 89.7 |
| Embodiment 3 | 3.0 | 100 | 3.0 | 3.0 | 90.1 |
| Embodiment 4 | 1.5 | 120 | 4.0 | 4.0 | 89.8 |
| Embodiment 5 | 2.5 | 150 | 6.0 | 5.0 | 92.3 |
| Embodiment 6 | 3.0 | 140 | 5.5 | 5.0 | 93.1 |
| Embodiment 7 | 2.5 | 120 | 4.5 | 4.0 | 89.7 |
| Embodiment 8 | 2.0 | 100 | 3.5 | 3.0 | 86.8 |
| Embodiment 9 | 1.5 | 80 | 2.5 | 2.0 | 89.4 |
| Embodiment 10 | 1.0 | 60 | 1.5 | 1.0 | 90.6 |
| Embodiment 11 | 1.0 | 75 | 1.0 | 1.5 | 88.3 |
| Embodiment 12 | 1.5 | 85 | 2.0 | 2.5 | 89.1 |
| Embodiment 13 | 2.0 | 95 | 3.0 | 3.5 | 90.2 |
| Embodiment 14 | 2.5 | 105 | 4.0 | 4.5 | 87.9 |
| Embodiment 15 | 3.0 | 135 | 5.0 | 5.0 | 86.5 |
| Embodiment 16 | 3.0 | 150 | 1.5 | 4.5 | 89.8 |
| Embodiment 17 | 2.0 | 120 | 2.5 | 3.5 | 92.3 |
| Embodiment 18 | 1.0 | 100 | 3.5 | 2.5 | 93.1 |
| Embodiment 19 | 2.5 | 80 | 4.5 | 1.5 | 89.7 |
| Embodiment 20 | 1.5 | 60 | 5.0 | 1.0 | 86.8 |
| Embodiment 21 | 3.0 | 135 | 1.5 | 2.0 | 93.1 |
| Comparative example 1 | 2.5 | 100 | 1.0 | 1.0 | 75.6 |
| Comparative example 2 | 3.0 | 90 | 1.5 | 1.5 | 79.5 |
| Comparative example 3 | 1.5 | 110 | 2.0 | 2.0 | 80.1 |
| Comparative example 4 | 1.0 | 125 | 2.5 | 3.5 | 79.6 |
| Comparative example 5 | 2.0 | 135 | 3.0 | 5.0 | 80.1 |
Table 3 stability test result.
| Sequence number | Working time/h | Embodiment 22 iso-butylene per pass conversion/% by mole | Comparative example 6 iso-butylene per pass conversion/% by mole |
| 1 | 50 | 92.3 | 76.8 |
| 2 | 100 | 93.1 | 76.6 |
| 3 | 150 | 90.8 | 75.9 |
| 4 | 200 | 92.3 | 75.4 |
| 5 | 250 | 93.1 | 75.1 |
| 6 | 300 | 91.7 | 75.3 |
| 7 | 350 | 89.8 | 74.9 |
| 8 | 400 | 90.4 | 74.8 |
| 9 | 450 | 90.6 | 74.9 |
| 10 | 500 | 91.3 | 74.6 |
| 11 | 550 | 92.1 | 74.3 |
| 12 | 600 | 90.2 | 74.2 |
| 13 | 650 | 89.9 | 73.9 |
| 14 | 700 | 91.4 | 73.5 |
| 15 | 750 | 90.3 | 73.4 |
| 16 | 800 | 89.8 | 73.0 |
| 17 | 850 | 90.4 | 72.5 |
| 18 | 900 | 90.6 | 71.9 |
| 19 | 950 | 91.3 | 71.5 |
| 20 | 1000 | 92.0 | 71.4 |
Can be found out by above-mentioned data, the inventive method is synthesized Ethyl Tertisry Butyl Ether for iso-butylene and ethanol and is had the advantages such as transformation efficiency is high, good stability, is an environmental protection novel process.
Claims (10)
1. prepare a processing method for Ethyl Tertisry Butyl Ether, with iso-butylene and ethanol for raw material, it is characterized in that: use heteropolyacid/aluminium base composite oxides catalyzer, the volume space velocity of iso-butylene is 0.5h
-1~ 6.0h
-1, the mol ratio of ethanol and iso-butylene is 1.0:1.0 ~ 5.0:1.0, temperature of reaction 60 DEG C ~ 150 DEG C, and reaction pressure is 1.0MPa ~ 3.0MPa; Wherein heteropolyacid/aluminium base composite oxides catalyzer, being carrier with composite oxides, take heteropolyacid as active ingredient, and described composite oxides are MgO-Al
2o
3, TiO
2-Al
2o
3and ZrO
2-Al
2o
3one or more of middle aluminium base composite oxides, described heteropolyacid is one or more in phospho-wolframic acid, silicotungstic acid, arsenowolframic acid, germanotungstic acid, phospho-molybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid etc.; Wherein, composite oxide carrier obtains as follows: the aqueous solution a configuring the corresponding salt of described aluminium base composite oxides and aluminum nitrate, configuration basic solution b, under the state of normal mild stirring, described solution b is added drop-wise in described aqueous solution a, be obtained by reacting precipitation, after washing, filtration, drying and extruded moulding, roasting obtains aluminium base composite oxides carrier; Described basic solution b is potassium hydroxide solution or ammoniacal liquor, the reaction times of described reaction is 2h ~ 20h, and the temperature of described drying is 90 DEG C ~ 150 DEG C, and the time of described drying is 4h ~ 24h, the temperature of described roasting is 400 DEG C ~ 800 DEG C, and the time of described roasting is 8h ~ 24h.
2. in accordance with the method for claim 1, it is characterized in that: Al in aluminium base composite oxides
2o
3weight content be 20% ~ 95%.
3. in accordance with the method for claim 1, it is characterized in that: Al in aluminium base composite oxides
2o
3weight content be 30% ~ 90%.
4. in accordance with the method for claim 1, it is characterized in that: Al in aluminium base composite oxides
2o
3weight content be 40% ~ 70%.
5. according to the method according to any one of claim 1,2,3 or 4, it is characterized in that: the weight ratio of heteropolyacid and aluminium base composite oxides is 0.01:1 ~ 1:1.
6. according to the method according to any one of claim 1,2,3 or 4, it is characterized in that: the weight ratio of heteropolyacid and aluminium base composite oxides is 0.1:1 ~ 0.9:1.
7. according to the method according to any one of claim 1,2,3 or 4, it is characterized in that: the weight ratio of heteropolyacid and aluminium base composite oxides is 0.3:1 ~ 0.6:1.
8. in accordance with the method for claim 1, it is characterized in that: iso-butylene uses the hybrid C 4 raw material containing iso-butylene, or uses pure iso-butylene raw material.
9. in accordance with the method for claim 1, it is characterized in that: the volume space velocity of iso-butylene is 1.0h
-1~ 5.0h
-1, the mol ratio of ethanol and iso-butylene is 1.0:1.0 ~ 3.0:1.0, and temperature of reaction is 70 DEG C ~ 130 DEG C, and reaction pressure is 1.0MPa ~ 2.5MPa.
10. in accordance with the method for claim 1, it is characterized in that: the volume space velocity of iso-butylene is 1.0h
-1~ 2.0h
-1, the mol ratio of ethanol and iso-butylene is 1.0:1.0 ~ 2.0:1.0, and temperature of reaction is 90 DEG C ~ 110 DEG C, and reaction pressure is 2.0MPa ~ 2.5MPa.
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| CN112892584B (en) * | 2019-12-04 | 2022-07-01 | 中国科学院大连化学物理研究所 | Catalyst for preparing 3-hydroxypropionaldehyde by acrolein hydration, preparation method and application thereof |
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| TiO2 and SiO2 supported Wells-Dawson heteropolyacid H6P2W18O62 as the catalyst for ETBE formation;J. Poźniczek et al.;《Applied Catalysis A: General》;20051117;第298卷;第217-224页 * |
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