CN1202051C - Method of producing isobutene joint producing dimetylether and dipolyisobutene - Google Patents
Method of producing isobutene joint producing dimetylether and dipolyisobutene Download PDFInfo
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Abstract
The present invention discloses a method for preparing isobutylene and jointly producing dimethyl ether and dipolyisobutylene. The present invention uses methyl tert-butyl ether (MTBE) as raw materials for the cracking reaction of ether in a reactor filled with solid acid catalysts. The present invention has the reaction condition that reaction temperature is from 230 to 270 DGE C, reaction pressure is from 0.2 to 0.8MPa, and space velocity is from 0.8 to 2h<-1>, the conversion rate of MTBE is controlled not less than 95%, and generated partial methanol is dewatered and generates dimethyl ether. Meanwhile, partial isobutylene is further polymerized for generating dipolyisobutylene. Dimethyl ether and dipolyisobutylene can be jointly produced at the same time of the production of products of isobutylene by the method of the present invention.
Description
Technical field
The present invention relates to the method for a kind of production iso-butylene combined producing dimethyl ether and Diisobutylene (being also referred to as diisobutylene), particularly utilize the method for methyl tertiary butyl ether (MTBE) cracking preparing isobutene combined producing dimethyl ether and Diisobutylene.
Background technology
Iso-butylene is the important source material of fine chemistry industry, also is the important intermediate raw material or the monomer of synthetic rubber, synthetic resins.Diisobutylene is the intermediates of washing composition, is the important source material of producing multiple chemical industry such as octyl phenol, octyl amine and octyldiphenylamine and fine chemical product simultaneously.Dme also is an important chemical material, be widely used in agricultural chemicals, medicine, dyestuff and the daily-use chemical industry industry, it still is a kind of aerosol propellant and refrigeration agent of superior performance, it is the desirable surrogate that atmospheric layer is had the fluorochlorohydrocarbon of destruction, high-purity dimethyl ether can be used as propelling agent, the dme rerum natura is similar to liquefied petroleum gas (LPG), can replace liquefied petroleum gas (LPG) as civilian clean fuel.
The production technique of MTBE cracking preparing isobutene is that iso-butylene preparation technology adopts more a kind ofly in recent years, and it is simple that it has production technique, and independence is strong, abundant raw material, and operational condition relaxes, and equipment and material are not had particular requirement, and environmental pollution is little.Up to the present, being suitable for doing the MTBE cracking produces the catalyzer of iso-butylene an acidic catalysts such as Zeo-karb, silicon-aluminium, loading type inorganic acid salt, solid phosphoric acid catalyst, acidic molecular sieve, niobic acid and tantalic acid is arranged.
The reaction process of this technology is as follows:
Main reaction:
Side reaction:
Main reaction generates iso-butylene and methyl alcohol, and simultaneously, the methyl alcohol that reaction generates can further dewater and generate dme and water, and the iso-butylene that reaction obtains can further react and obtain Diisobutylene.At present, the preparation method of disclosed high-purity iso-butylene mainly is the generation of control side reaction thing in the patent documentation, promptly by the suitable catalyzer of selection, and by the control reaction conditions, dimethanol and Diisobutylene content in the product are more lacked better, as US 6, the preparation method of 072,095 disclosed high-purity iso-butylene, the MTBE transformation efficiency is about 90%, the dme content that ether-splitting is separated in the reaction solution is about 0.5%, Diisobutylene content about 1.1%.
Dme is the useful industrial chemicals and the intermediate of organic raw material, and its preparation method mainly contains: methyl alcohol is through the vitriol oil or solid acid dewatering preparing dimethy ether; Synthetic gas generates methods such as dme through the catalysis of solid catalyst reaction, an if newly-built cover dme production equipment, investment cost is higher relatively, and look its raw material difference, the investment situation of its production equipment is also different, generally speaking, is raw material with the synthetic gas, the gross investment of 5000 tons of/year dme production equipments is about 1,000 ten thousand yuan, equal scale be that the gross investment of the device of raw material production dme is about 7,000,000 with methyl alcohol.
Diisobutylene also is the useful industrial chemicals and the intermediate of organic raw material, its production method mainly contains the sulfuric acid extracting, methods such as the superimposed and mixed c 4 selective superposition of pure iso-butylene, all there is the sulfuric acid corrosion problem in preceding two kinds of methods, mixed c 4 selective superposition method does not have etching problem, but the product purity of Diisobutylene is not high.U.S. Pat P4,447,668 disclose a kind of method of producing high-purity iso-butylene coproduction Diisobutylene, this method is: after ether-splitting is separated the reacting rear material water extraction methyl alcohol of reactor outlet, a part enters the MTBE separation column, unreacted MTBE is separated with light constituent with iso-butylene, another part material enters a dipolymer reactor, reactor outlet material contains Diisobutylene and unreacted MTBE, and send the MTBE treating tower that is arranged on before the methyltertiarvbutyl ether reactor back to, obtain the Diisobutylene product at the bottom of this refining Tata.Though this method can obtain iso-butylene and Diisobutylene product simultaneously, owing to set up a dipolymer reactor, corresponding increase cost of equipment and process cost.
If in the MTBE cracking prepares the production equipment of iso-butylene (as at USP4,447, in the 668 disclosed technical process), do not increase dipolymer reactor, only by the suitable ether-splitting reaction conditions of control, select suitable ether-splitting to separate catalyzer simultaneously, ether-splitting is separated contained an amount of dme and Diisobutylene in the reactor product, by original separating device, make this production equipment both produce iso-butylene get back dme and Diisobutylene product, like this, can not increase under the situation of facility investment, obtain multiple useful Chemicals.
Summary of the invention
The object of the present invention is to provide a kind of method of producing iso-butylene combined producing dimethyl ether and Diisobutylene.When producing iso-butylene, can regulate the content of dme and Diisobutylene in the products therefrom with method of the present invention.
In order to achieve the above object, the invention provides the method for a kind of cracking isobutene by methyl-tert-butyl ether combined producing dimethyl ether and Diisobutylene, comprise that methyl tertiary butyl ether cracking under the solid acid catalyst effect obtains iso-butylene and methyl alcohol, wherein the further dehydration of methyl alcohol can be converted into dme, the further polymerization of iso-butylene generates Diisobutylene, split product separates through follow-up equipment, obtain the major product iso-butylene, dimethyl ether as byproduct and Diisobutylene, described solid acid catalyst contains carrier and the slightly acidic inorganic acid salt that carries thereon, and the specific surface of carrier is at least 25m
2/ g is characterized in that temperature of reaction is that 230-270 ℃, the transformation efficiency of methyl tertiary butyl ether are at least 95%, preferably are at least 97%, and methanol conversion is at least 10%, and the transformation efficiency that iso-butylene generates Diisobutylene is at least 5%.
The pressure of methyl tertiary butyl ether scission reaction and air speed can be in the variations of very wide scope, and preferred reaction pressure is that 0.2-0.8MPa, air speed are 0.8-2h
-1
When tert-alkyl ether cracking preparing isobutene, transformation efficiency and reaction conditions, particularly temperature of reaction by control MTBE, the part methyl alcohol that cracking is obtained further reacts the generation dme, the further polymerization of iso-butylene generates Diisobutylene, control methanol conversion simultaneously and be at least 10%, the transformation efficiency that iso-butylene generates Diisobutylene is at least 5%, thereby the growing amount of adjusting dme and Diisobutylene is to satisfy the demand of market to dme.
The disclosed any solid acid ether-splitting of prior art is separated catalyzer and all be can be used for the present invention, as the disclosed loading type inorganic acid salt of GB1173128 catalyzer.
Catalyzer of the present invention can make with the disclosed any suitable method of prior art, forms as drying, roasting behind the solution impregnating carrier of available mineral acid or slightly acidic inorganic acid salt.Mineral acid of the present invention is preferably sulfuric acid; Described slightly acidic inorganic acid salt is preferably vitriol, most preferably is ammonium sulfate, ferrous sulfate or ferric sulfate.
The acid group content of solid acid catalyst of the present invention can change within a large range, as being that the content of basic calculation acid group is at least more than the 10wt.% with the carrier, is preferably 18-32wt.%., most preferably be 22wt.%.
The specific surface area of described carrier is at least 25m
2/ g, be preferably 100-400m
2/ g most preferably is 200-300m
2/ g.
Described carrier can be silicon oxide or aluminum oxide, as available beta-alumina or gama-alumina, and preferred gama-alumina.
Methyl tertiary butyl ether scission reaction of the present invention can be separated in the reactor at the disclosed any ether-splitting of prior art and be carried out, and preferably carries out in calandria type fixed bed reactor.
Ether-splitting is separated reaction product after the later separation device separates is as washing, rectifying (take off gently, take off heavily), can obtain iso-butylene product, dme product and Diisobutylene product.
Describe the present invention below in detail:
Vaporization enters calandria type fixed bed reactor after MTBE raw material and the thermal barrier heat exchange, and solid acid catalyst (as vitriolated solid acid catalyst) is housed in the reactor, and control reaction temperature is between 230-270 ℃; Reaction pressure is between 0.2-0.8MPa; Air speed is 0.8-2h
-1The transformation efficiency of methyl tertiary butyl ether is at least 95%, reacted ether-splitting product mainly contains iso-butylene (IB), methyl alcohol (MeOH), dme (DME), methyl tertiary butyl ether (MTBE), Diisobutylene (DIB), water etc., it consists of: carbonatoms is that 4 alkene (not comprising iso-butylene) content is about 0.0095%, butane (C4
0) content is about 0.0050%, iso-butylene (IB) content is 54-60 (wt%), MeOH content is 15-35 (wt%), dme (DME) content is 3-15 (wt%), and MTBE content is 0.5-3 (wt%), and methyl sec-butyl ether (MSBE) content is about 0.1353 (wt%), about 0.0601 (wt%) of the trimethyl carbinol (TBA) content, Diisobutylene (DIB) content is 3-9.2 (wt%), tri-isobutylene (be also referred to as triisobutene, abbreviate TIB as) 0.1-0.3 (wt%) and H
2O content is 1-6 (wt%).Ether-splitting is separated reaction product after later separation device separates-washing, rectifying (take off gently, take off heavily), obtains iso-butylene product, dme product and Diisobutylene product.
The present invention makes it both can produce qualified iso-butylene major product by to the improvement of MTBE cracking preparing isobutene production technique, again can combined producing dimethyl ether and Diisobutylene product, and also can control the growing amount of dme and Diisobutylene as required.Produce dme with this method and can save traditionally that methyl alcohol can improve the transformation efficiency of methyl tertiary butyl ether again as the required facility investment of raw material production dme, thereby improve usage ratio of equipment; Produce Diisobutylene simultaneously with this method and can save the Diisobutylene reactor, further saved facility investment.
Embodiment
Further specify the present invention below in conjunction with embodiment, but do not limit to its scope.
The used MTBE raw material of following embodiment is composed as follows:
Component (wt%)
C4
＝ 0.005
C4
0 0.005
IB 0.000
MeOH 0.100
DME 0.000
MTBE 99.348
MSBE 0.142
TBA 0.300
DIB 0.100
TIB 0.000
H
2O 0.000
To separate the catalyzer of reactor charge be the solid acid catalyst of sulfur-bearing acid group to ether-splitting among the following embodiment, and the content of its sulfate radical is about 22% (weight percent).Its concrete preparation method is as follows:
The preparation method of embodiment 1～embodiment 6 catalyst system therefors is as follows:
The 47 gram analytical pure vitriol oils (concentration 98%) are dissolved in the distilled water, be mixed with the 200ml aqueous sulfuric acid, 150ml γ-Al
2O
3Carrier immerses in the above-mentioned solution, flooded 2 hours, the elimination raffinate, with soaked carrier in 120 ℃ of dryings 4 hours, again 550 ℃ of roastings 4 hours, subsequently this catalyzer was continued to immerse in the above-mentioned aqueous sulfuric acid 2 hours, 120 ℃ of dryings after 4 hours, 550 ℃ of roastings 4 hours, the sulfate radical content in the prepared catalyzer was 22.12wt.% again.
The preparation method of embodiment 7 catalyst system therefors is as follows:
88 gram analytical pure sulfuric acid ammoniums are dissolved in the distilled water, be mixed with the 200ml ammonium sulfate solution, 150ml γ-Al
2O
3Carrier immerses in the above-mentioned solution, flooded 2 hours, and the elimination raffinate, in 120 ℃ of dryings 4 hours, again 550 ℃ of roastings 4 hours, the sulfate radical content in the prepared catalyzer was 22.08wt.% with soaked carrier.
The preparation method of embodiment 8 catalyst system therefors is as follows:
With the ferrous (FeSO of 83 gram analytical pure sulfuric acids
47H2O) dissolve in the distilled water, be mixed with the 200ml ferrous sulfate aqueous solution, with 150ml γ-Al
2O
3Carrier immerses in the above-mentioned solution, flooded 2 hours, the elimination raffinate, with soaked carrier in 120 ℃ of dryings 4 hours, again 250 ℃ of roastings 4 hours, subsequently this catalyzer was continued to immerse in the above-mentioned ferrous sulfate aqueous solution 2 hours, 120 ℃ of dryings after 4 hours, again 250 ℃ of roastings 4 hours, the sulfate radical content 21.97wt.% in the prepared catalyzer.
Embodiment 1
The MTBE raw material carries out ether-splitting and separates reaction in the shell and tube reactor of vitriolated solid acid catalyst is housed, the sulfate radical content of catalyst system therefor is 22.12wt.%, and temperature of reaction is 230 ℃; Reaction pressure 0.8MPa; Air speed 1.2h
-1, the transformation efficiency of MTBE is 98.47%, and methanol conversion is 12.78%, and the transformation efficiency that iso-butylene generates Diisobutylene is 5.09%.With the C4 in the gas chromatographic analysis ether-splitting reaction product
=Content is 0.0095%, C4
0Content is 0.0050%, and IB content is 59.3670 (wt%), and MeOH content is 31.0281 (wt%), DME content is 3.2685 (wt%), and MTBE content is 1.5230 (wt%), and MSBE content is 0.1353 (wt%), TBA0.0601 (wt%), DIB content are 3.1670 (wt%) and H
2O content is 1.4365 (wt%), this reaction product is 99.720 (wt) % through the product purity of the iso-butylene that washing, rectifying obtain, wherein contain MTBE 5ppm, contain MeOH 5ppm, contain DME 5ppm, contain all the other C4 (carbonatoms except that iso-butylene is 4 cut, down with) 0.276 (wt%), contain DIB 5ppm, moisture 20ppm.Obtain the dme product simultaneously, its dme content is 95.20 (wt%), all the other are iso-butylene, and the purity of the Diisobutylene product that obtains is 97.53%, all the other are MTBE.
Embodiment 2
The MTBE raw material carries out ether-splitting and separates reaction in the shell and tube reactor of vitriolated solid acid catalyst is housed, catalyzer is with embodiment 1, and temperature of reaction is 240 ℃; Reaction pressure 0.6MPa; Air speed 0.8h
-1, the transformation efficiency of MTBE is 98.63%, and methanol conversion is 30.59%, and the transformation efficiency that iso-butylene generates Diisobutylene is 9.20%.With the C4 in the gas chromatographic analysis ether-splitting reaction product
=Content is 0.0095%, C4
0Content is 0.0050%, and IB content is 56.7932 (wt%), and MeOH content is 24.7331 (wt%), DME content is 7.8340 (wt%), and MTBE content is 1.3650 (wt%), and MSBE content is 0.1353 (wt%), TBA0.0601 (wt%), DIB content are 5.8416 (wt%) and H
2O content is 3.2232 (wt%), this reaction product is 99.780 (wt) % through the product purity of the iso-butylene that washing, rectifying obtain, and wherein contains MTBE5ppm, contains MeOH 4ppm, contains DME 4ppm, contains all the other C4 0.2166 (wt%), contains DIB 3ppm, moisture 18ppm.Obtain the dme product simultaneously, its dme content is 95.350 (wt%), all the other are iso-butylene, and the purity of the Diisobutylene product that obtains is 97.14%, all the other are MTBE.
Embodiment 3
The MTBE raw material carries out ether-splitting and separates reaction in the shell and tube reactor of vitriolated solid acid catalyst is housed, catalyzer is with embodiment 1, and temperature of reaction is 260 ℃; Reaction pressure 0.4MPa; Air speed 1.5h
-1, the transformation efficiency of MTBE is 99.37%, and methanol conversion is 51.22%, and the transformation efficiency that iso-butylene generates Diisobutylene is 11.18%.With the C4 in the gas chromatographic analysis ether-splitting reaction product
=Content is 0.0095%, C4
0Content is 0.0050%, IB content is 55.7650 (wt%), MeOH content is 17.5146 (wt%), DME content is 13.2160 (wt%), MTBE content is 0.6239 (wt%), and MSBE content is 0.1353 (wt%), TBA0.0601 (wt%), DIB content is 7.1250 (wt%), and TIB content is 0.2160 (wt%) and H
2O content is 5.3296 (wt%), this reaction product is 99.750 (wt) % through the product purity of the iso-butylene that washing, rectifying obtain, and wherein contains MTBE 2ppm, contains MeOH 5ppm, contains DME5ppm, contains all the other C4 0.2464 (wt%), contains DIB 5ppm, moisture 19ppm.Obtain the dme product simultaneously, its dme content is 95.430 (wt%), all the other are iso-butylene, and the purity of the Diisobutylene product that obtains is 97.52%, all the other are MTBE and tri-isobutylene.
Embodiment 4
The MTBE raw material carries out ether-splitting and separates reaction in the shell and tube reactor of vitriolated solid acid catalyst is housed, catalyzer is with embodiment 1, and temperature of reaction is 270 ℃; Reaction pressure 0.3MPa; Air speed 2h
-1, the transformation efficiency of MTBE is 99.52%, and methanol conversion is 56.22%, and the transformation efficiency that iso-butylene generates Diisobutylene is 14.21%.With the C4 in the gas chromatographic analysis ether-splitting reaction product
=Content is 0.0095%, C4
0Content is 0.0050%, IB content is 53.8789 (wt%), MeOH content is 15.7435 (wt%), DME content is 14.5276 (wt%), MTBE content is 0.4762 (wt%), and MSBE content is 0.1353 (wt%), TBA0.0601 (wt%), DIB content is 9.0381 (wt%), and TIB content is 0.2834 (wt%) and H
2O content is 5.8424 (wt%), this reaction product is 99.710 (wt) % through the product purity of the iso-butylene that washing, rectifying obtain, and wherein contains MTBE 4ppm, contains MeOH 3ppm, contains DME5ppm, contains all the other C4 0.2863 (wt%), contains DIB 5ppm, moisture 20ppm.Obtain the dme product simultaneously, its dme content is 95.180 (wt%), all the other are iso-butylene, and the purity of the Diisobutylene product that obtains is 97.38%, all the other are MTBE and tri-isobutylene.
Embodiment 5
The MTBE raw material carries out ether-splitting and separates reaction in the shell and tube reactor of vitriolated solid acid catalyst is housed, catalyzer is with embodiment 1, and temperature of reaction is 260 ℃; Reaction pressure 0.4MPa; Air speed 1.2h
-1, the transformation efficiency of MTBE is 99.37%, and methanol conversion is 51.22%, and the transformation efficiency that iso-butylene generates Diisobutylene is 11.18%.With the C4 in the gas chromatographic analysis ether-splitting reaction product
=Content is 0.0095%, C4
0Content is 0.0050%, IB content is 55.7649 (wt%), MeOH content is 17.5143 (wt%), DME content is 13.2163 (wt%), MTBE content is 0.6241 (wt%), and MSBE content is 0.1353 (wt%), TBA0.0601 (wt%), DIB content is 7.1252 (wt%), and TIB content is 0.2162 (wt%) and H
2O content is 5.3291 (wt%), this reaction product is 99.750 (wt) % through the product purity of the iso-butylene that washing, rectifying obtain, and wherein contains MTBE 2ppm, contains MeOH 5ppm, contains DME 5ppm, contains all the other C4 0.2464 (wt%), contains DIB 5ppm, moisture 19ppm.Obtain the dme product simultaneously, its dme content is 95.430 (wt%), all the other are iso-butylene, and the purity of the Diisobutylene product that obtains is 97.72%, all the other are MTBE and tri-isobutylene.
Embodiment 6
The MTBE raw material carries out ether-splitting and separates reaction in the shell and tube reactor of vitriolated solid acid catalyst is housed, catalyzer is with embodiment 1, and temperature of reaction is 260 ℃; Reaction pressure 0.6MPa; Air speed 1.5h
-1, the transformation efficiency of MTBE is 99.37%, and methanol conversion is 51.22%, and the transformation efficiency that iso-butylene generates Diisobutylene is 11.18%.With the C4 in the gas chromatographic analysis ether-splitting reaction product
=Content is 0.0095%, C4
0Content is 0.0050%, IB content is 55.7664 (wt%), MeOH content is 17.5150 (wt%), DME content is 13.2158 (wt%), MTBE content is 0.6236 (wt%), and MSBE content is 0.1353 (wt%), TBA0.0601 (wt%), DIB content is 7.1247 (wt%), and TIB content is 0.2154 (wt%) and H
2O content is 5.3292 (wt%), this reaction product is 99.750 (wt) % through the product purity of the iso-butylene that washing, rectifying obtain, and wherein contains MTBE 2ppm, contains MeOH 5ppm, contains DME 5ppm, contains all the other C4 0.2464 (wt%), contains DIB 5ppm, moisture 19ppm.Obtain the dme product simultaneously, its dme content is 95.430 (wt%), all the other are iso-butylene, and the purity of the Diisobutylene product that obtains is 97.19%, all the other are MTBE and tri-isobutylene.
Embodiment 7
The MTBE raw material carries out ether-splitting and separates reaction in the shell and tube reactor of the solid acid catalyst that the sulfur-bearing hydrochlorate is housed, the sulfate radical content of catalyst system therefor is 22.08%.Temperature of reaction is 260 ℃; Reaction pressure 0.4MPa; Air speed 2h
-1, the transformation efficiency of MTBE is 97.83%, and methanol conversion is 51.89%, and the transformation efficiency that iso-butylene generates Diisobutylene is 11.32%.With the C4 in the gas chromatographic analysis ether-splitting reaction product
=Content is 0.0095%, C4
0Content is 0.0050%, IB content is 54.8125 (wt%), MeOH content is 17.0047 (wt%), DME content is 13.1826 (wt%), MTBE content is 2.1539 (wt%), and MSBE content is 0.1353 (wt%), TBA0.0601 (wt%), DIB content is 7.0987 (wt%), and TIB content is 0.2216 (wt%) and H
2O content is 5.3161 (wt%), this reaction product is 99.750 (wt) % through the product purity of the iso-butylene that washing, rectifying obtain, and wherein contains MTBE 2ppm, contains MeOH 5ppm, contains DME 5ppm, contains all the other C4 0.2464 (wt%), contains DIB 5ppm, moisture 19ppm.Obtain the dme product simultaneously, its dme content is 95.350 (wt%), all the other are iso-butylene, and the purity of the Diisobutylene product that obtains is 97.27%, all the other are MTBE and tri-isobutylene.
Embodiment 8
MT reconnaissance BE raw material carries out ether-splitting and separates reaction in the shell and tube reactor of the solid acid catalyst that the sulfur-bearing hydrochlorate is housed, the sulfate radical content of catalyst system therefor is 21.97%.The preparation method describes in detail the front, and temperature of reaction is 260 ℃; Reaction pressure 0.3MPa; Air speed 1.5h
-1, the transformation efficiency of MTBE is 97.22%, and methanol conversion is 52.11%, and the transformation efficiency that iso-butylene generates Diisobutylene is 11.35%.With the C4 in the gas chromatographic analysis ether-splitting reaction product
=Content is 0.0095%, C4
0Content is 0.0050%, IB content is 54.4355 (wt%), MeOH content is 16.8226 (wt%), DME content is 13.1538 (wt%), MTBE content is 2.7649 (wt%), and MSBE content is 0.1353 (wt%), TBA0.0601 (wt%), DIB content is 7.0756 (wt%), and TIB content is 0.2329 (wt%) and H
2O content is 5.3048 (wt%), this reaction product is 99.710 (wt) % through the product purity of the iso-butylene that washing, rectifying obtain, and wherein contains MTBE4ppm, contains MeOH 3ppm, contains DME 5ppm, contains all the other C4 0.2863 (wt%), contains DIB 5ppm, moisture 20ppm.Obtain the dme product simultaneously, its dme content is 95.350 (wt%), all the other are iso-butylene, and the purity of the Diisobutylene product that obtains is 97.61%, all the other are MTBE and tri-isobutylene.
Claims (13)
1. the method for cracking isobutene by methyl-tert-butyl ether combined producing dimethyl ether and Diisobutylene, comprise that methyl tertiary butyl ether cracking under the solid acid catalyst effect obtains iso-butylene and methyl alcohol, wherein the further dehydration of methyl alcohol can be converted into dme, the further polymerization of iso-butylene obtains Diisobutylene, split product separates through follow-up equipment, obtain the major product iso-butylene, dimethyl ether as byproduct and Diisobutylene, described solid acid catalyst contains carrier and the metallic slightly acidic component of carrying thereon, and the specific surface of carrier is at least 25m
2/ g is characterized in that temperature of reaction is that 230-270 ℃, the transformation efficiency of methyl tertiary butyl ether are at least 95%, and methanol conversion is at least 10%, and iso-butylene generates the Diisobutylene transformation efficiency and is at least 5%.
2. method according to claim 1, the pressure that it is characterized in that the methyl tertiary butyl ether scission reaction are that 0.2-0.8MPa, air speed are 0.8-2h
-1
3. method according to claim 1 is characterized in that described metallic slightly acidic component is formed by mineral acid or slightly acidic inorganic acid salt impregnated carrier.
4. method according to claim 3 is characterized in that described mineral acid is a sulfuric acid.
5. method according to claim 3 is characterized in that described slightly acidic inorganic acid salt is a vitriol.
6. method according to claim 5 is characterized in that described vitriol is ammonium sulfate, ferrous sulfate or ferric sulfate.
7. according to each described method of claim 1-6, the acid group content that it is characterized in that described solid acid catalyst is that basic calculation is 18-32wt.% with the carrier.
8. method according to claim 7, the acid group content that it is characterized in that described solid acid catalyst are that basic calculation is 22wt.% with the carrier.
9. according to each described method of claim 1-6, the specific surface area that it is characterized in that described carrier is 100-400m
2/ g.
10. method according to claim 9, the specific surface area that it is characterized in that described carrier is 200-300m
2/ g.
11., it is characterized in that described carrier is a gama-alumina according to each described method of claim 1-6.
12., it is characterized in that the transformation efficiency of methyl tertiary butyl ether is at least 97% according to each described method of claim 1-6.
13., it is characterized in that described being reflected in the calandria type fixed bed reactor carry out according to each described method of claim 1-6.
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| CN101381273B (en) * | 2007-09-06 | 2012-08-22 | 四川古杉油脂化学有限公司 | Method for preparing isobutene by tert-butanol and apparatus |
| CN104447165B (en) * | 2013-09-16 | 2016-04-27 | 中国石油化工股份有限公司 | The method of iso-butylene and Diisobutylene is produced in a kind of methyl tertiary butyl ether cracking |
| CN105478164B (en) * | 2015-11-26 | 2018-03-02 | 王金明 | A kind of preparation method for producing isobutene catalyst |
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