CN101302133A - Method for preparing isobutene by cracking methyl tert-butyl ether - Google Patents
Method for preparing isobutene by cracking methyl tert-butyl ether Download PDFInfo
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- CN101302133A CN101302133A CNA2008100170863A CN200810017086A CN101302133A CN 101302133 A CN101302133 A CN 101302133A CN A2008100170863 A CNA2008100170863 A CN A2008100170863A CN 200810017086 A CN200810017086 A CN 200810017086A CN 101302133 A CN101302133 A CN 101302133A
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 92
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000005336 cracking Methods 0.000 title claims abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 9
- 238000007670 refining Methods 0.000 claims abstract description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000002309 gasification Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 230000009466 transformation Effects 0.000 claims description 18
- 238000010504 bond cleavage reaction Methods 0.000 claims description 15
- 230000007017 scission Effects 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 239000007791 liquid phase Substances 0.000 claims description 11
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 4
- 241000282326 Felis catus Species 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- 229930195733 hydrocarbon Natural products 0.000 abstract 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract 2
- 238000005406 washing Methods 0.000 abstract 2
- 239000011324 bead Substances 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 11
- 238000007086 side reaction Methods 0.000 description 7
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 229920002367 Polyisobutene Polymers 0.000 description 5
- 239000008187 granular material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for making isobutene by cracking methyl tert-butyl ether, in particular to a method for making the isobutene by cracking the methyl tert-butyl ether after the heavier hydrocarbon removal, the lighter hydrocarbon removal, the refining and the gasification, belonging to the chemical engineering technical field. A novel trundle bed reactor, a novel high-activity catalyst and the 'yifanwuta' technique flow are adopted, wherein, the novel trundle bed reactor is a tube array reactor with a length between 1 and 3.5 meters; the novel high-activity catalyst is the white spherical silicon oxide system catalyst which is formed by the dropping beads method, with a bulk density between 0.4 and 0.5g/cm<3> and a diameter between 3 and 4 mm; the 'yifanwuta' technique flow comprises a pyrolyzer, a methyl tert-butyl ether refining gasification tower, a water-cooling ethanol washing tower, a methanol rectifying tower, an isobutene de-heavy fractionator and an isobutene de-light fractionator, and the water-cooling ethanol washing process is finished in the same tower. The method has great production ability, high converting efficiency, high selectivity, low cost and high product quality.
Description
Technical field
The present invention relates to a kind of method by cracking isobutene by methyl-tert-butyl ether, particularly a kind of by the commodity methyl tertiary butyl ether through take off heavily take off light refining gasification after the method for cracking preparing isobutene, belong to chemical technology field.
Background technology
Iso-butylene is a kind of important chemical material, be widely used in chemical production field such as isoprene-isobutylene rubber, polyisobutene, pesticide intermediate, alkylating aromatic hydrocarbon, methacrylic acid, new industry such as isoprene-isobutylene rubber and high molecular weight polyisobutylene particularly, requirement to iso-butylene is more and more higher, impel the scientific and technical personnel that are engaged in the work of this field constantly to explore new processing unit, new catalyzer and new processing method, produce high-quality iso-butylene product with low cost, satisfy the different demand of downstream user.Early stage industrialized sulfuric acid process can be produced two kinds of products of the iso-butylene and the trimethyl carbinol simultaneously, but reason such as, poor product quality serious owing to equipment corrosion, quantity of wastewater effluent be big has withdrawed from production field.The method of trimethyl carbinol dehydration preparing isobutene, the iso-butylene quality is good, can satisfy various users' needs, and following period of time is the main method of preparation iso-butylene.China produced products such as phenolic antioxidant and triisobutyl aluminium originally, used iso-butylene is produced with this method, states such as Russia produce that the used iso-butylene of isoprene-isobutylene rubber remains with this method production so far, still have the production equipment of ton to be in operation in the world.The appearance of methyl tertiary butyl ether synthesis technique has progressively changed this situation.Etherification reaction takes place and generates methyl tertiary butyl ether, this technology transformation efficiency height under strong acid ionic resin catalyst action in iso-butylene in the mixed c 4 component and methyl alcohol, the selectivity height, less investment, output is big, cost is low, for competent raw material is provided by cracking isobutene by methyl-tert-butyl ether.
The method of cracking isobutene by methyl-tert-butyl ether is a lot, can be divided into two kinds of liquid phase method and vapor phase processs substantially.The representative technology of liquid phase method such as gondola Si Namu technology and Chinese Yanshan Petrochemical company technology, its common feature is that transformation efficiency is lower, generally between 80～90%, temperature of reaction is lower, generally at 160～230 ℃, selective isobutene is higher, and reaction pressure is higher, generally about 0.6MPa, in the technological process without compressor.The main drawback of this method is that transformation efficiency is low, and unreacted methyl tertiary butyl ether needs to recycle, and the methyl alcohol that produces contains a large amount of methyl tertiary butyl ethers, can only be used as the methyl tertiary butyl ether synthesis material.Also contain a large amount of methyl tertiary butyl ethers in the heavy component of iso-butylene weight-removing column, can only be used as fuel, product cost is increased.The representative technology of vapor phase process such as the IFP technology of France and Chinese Inst. of Jilin Chemical Industry Co technology, this method is because the transformation efficiency height, the selectivity height, good product quality, cost is low, need not rely on the methyl tertiary butyl ether synthesizer, can found the factory near the user nearby, raw material can be purchased from the market, has therefore obtained developing rapidly.But this method and people's expectation also has a certain distance, rests on for a long time between 98～99% as transformation efficiency, and selectivity is about 99%, and the liquid phase air speed is less than 1h
-1Etc. problem, perplexing the related personnel for a long time.Number of patent application is 200610041851.6 by changing the catalyst activation condition, has improved the transformation efficiency and the selectivity of catalyzer, has obtained certain progress.But this technology liquid phase air speed is 0.5～0.75h
-1The product iso-butylene is not refining, can not satisfy the needs of high-end user, it or not industrial development direction, particularly the formulation about " it also is thermo-negative reaction that the side reaction that generates DME of dewatering between DIB and methanol molecules is produced in the IB polymerization " is inaccurate in this patent, be easy to generate the misleading effect, be unfavorable for the progress of iso-butylene production technology.
The transformation efficiency of methyl tertiary butyl ether scission reaction and selectivity are the standards of weighing the state of the art height.On single numeral that is more or less the same from the transformation efficiency and the selectivity of scission reaction, influence is not very big on the performance yield, but unreacted methyl tertiary butyl ether and by product all will remove in the product purification process, to carry a large amount of iso-butylenes secretly in the process that removes, foreign matter content is high more to be carried secretly manyly more, makes the true yield of iso-butylene reduce a lot.
Summary of the invention
The object of the present invention is to provide a kind of method by cracking isobutene by methyl-tert-butyl ether, throughput is big, transformation efficiency is high, selectivity is high, cost is low, good product quality.
The present invention is on the basis of existing gas-phase process, by improving the structure of cracking reactor, adopts new catalyzer, and the optimization technical process realizes.
Method by cracking isobutene by methyl-tert-butyl ether of the present invention adopts a kind of novel trundle bed reactor, novel high-activity catalyzer and " anti-five towers " technical process to carry out, wherein:
Novel trundle bed reactor is meant the shell-and-tube reactor of 1～3.5 meter of pipe range;
The novel high-activity catalyzer is meant with dripping the moulding of ball method, bulk density 0.4～0.5g/cm
3, diameter is the white spherical silicon oxide catalyst series of 3～4mm;
Comprise in " anti-five towers " technical process that a cracker, the refining gasification of methyl tertiary butyl ether tower, a water-cooled wash pure tower, a methanol rectifying tower, an iso-butylene weight-removing column and an iso-butylene lightness-removing column, water-cooled is washed alcohol and is finished in same tower.
Specific practice is: adopt a kind of novel trundle bed reactor, adopt a kind of low density, high activated catalyst, scission reaction is carried out with having in the presence of the water vapour at lower pressure, form " anti-five towers " technical process.Method provided by the invention, liquid phase air speed 4～7h
-1, transformation efficiency is greater than 99.5%, and selective isobutene is greater than 99.5%, and the iso-butylene product purity can satisfy the specification of quality of high-end markets such as isoprene-isobutylene rubber and high molecular weight polyisobutylene to iso-butylene greater than 99.95%.
Among the present invention:
The methyl tertiary butyl ether scission reaction is to carry out in shell-and-tube reactor, and tubulation length is preferably 2～3 meters.
The model of novel high-activity catalyzer is ML-01, and forming method is for dripping the ball method.It is liquid phase air speed 4～7h that operation control requires
-1, transformation efficiency is greater than 99.5%, and selective isobutene is greater than 99.5%.
Be added with water in the methyl tertiary butyl ether scission reaction, the purpose that adds water is in order to suppress side reaction, and the suitable mol ratio of water and methyl tertiary butyl ether is 0.5～3.0, and reaction pressure is 0.01～0.10MPa, and temperature of reaction is 240～270 ℃.
" anti-five towers " technical process is: the raw material methyl tertiary butyl ether advances treating tower and removes the weight component, gas phase methyl tertiary butyl ether after refining is from the side line extraction, after the high-temperature material heat exchange of cracking reactor outlet, enter the top of cracking reactor with steam, reaction product is washed pure tower through the laggard water-cooled of heat exchange, wash pure cat head from the pure water major part of methanol rectifying tower through cooling off laggard water-cooled, water-cooled is washed the pure water major part (accounting for 70～80%) of pure tower through cooling off the middle part of laggard entry cold wash alcohol tower, another part send methanol rectifying tower, after compressing and liquefying, the compressed machine of thick iso-butylene after the dealcoholysis go the iso-butylene weight-removing column to remove heavy components such as dipolymer, go the iso-butylene lightness-removing column to remove water again, behind the light component such as dme, obtain weight content greater than 99.95% high purity, high quality iso-butylene product can satisfy the specification of quality of high-end markets such as isoprene-isobutylene rubber and high molecular weight polyisobutylene to iso-butylene.
Reaction mechanism:
From chemical reaction mechanism, the methyl tertiary butyl ether cracking is thermo-negative reaction, 25 ℃ of gas-phase reaction heat is 65.2KJ/mol, also be the volume augmenting response simultaneously, one mole methyl tertiary butyl ether is decomposed into one mole iso-butylene and one mole methyl alcohol, volume increases and is twice, and therefore, the higher temperature of reaction and the reaction pressure of reduction are favourable to improving transformation efficiency.Its side reaction is that the iso-butylene dimerization generates dipolymer and methanol dehydration generates dme, and side reaction all is thermopositive reaction, and high temperature, high pressure are beneficial to side reaction, and the existence of water can suppress side reaction.From reaction kinetics, higher methyl tertiary butyl ether gas line speed has two benefits, and one can overcome the diffusional resistance of material on the granules of catalyst outside surface, the methyl tertiary butyl ether effecting reaction concentration that arrives the granules of catalyst outside surface is improved, increased reaction power; Its two, help overcoming the heat transmission resistance that the granules of catalyst outside surface exists, as early as possible the heat that loses owing to endothermic heat of reaction of make-up catalyst, improve the temperature of granules of catalyst, improve speed of response, but too high speed can make pressure fall increase, helps side reaction.The trundle bed shell-and-tube reactor that the present invention adopts has demonstrated fully above-mentioned principle, can give full play to the ability of catalyzer.
The present invention is by the method for cracking isobutene by methyl-tert-butyl ether, reactor throughput improves 5 times, transformation efficiency is up to more than 99.5%, selective isobutene is up to more than 99.5%, and reaction process is simple and direct, thorough, and cost is low, the good product quality that obtains, purity height, weight content can satisfy the specification of quality of high-end markets such as isoprene-isobutylene rubber and high molecular weight polyisobutylene to iso-butylene up to more than 99.95%.
Description of drawings
Fig. 1, process flow diagram of the present invention.
Embodiment
The invention will be further described below in conjunction with embodiment.
Method by cracking isobutene by methyl-tert-butyl ether of the present invention, the raw material methyl tertiary butyl ether advances treating tower and removes the weight component, gas phase methyl tertiary butyl ether after refining is from the side line extraction, after the high-temperature material heat exchange of cracking reactor outlet, enter the top of cracking reactor with steam, reaction product is washed pure tower through the laggard water-cooled of heat exchange, wash pure cat head from the pure water major part of methanol rectifying tower still through cooling off laggard water-cooled, water-cooled is washed the pure water major part of pure tower through cooling off the middle part of laggard entry cold wash alcohol tower, another part send methanol rectifying tower, after compressing and liquefying, the compressed machine of thick iso-butylene after the dealcoholysis removes the iso-butylene weight-removing column, remove the dipolymer heavy component, go lightness-removing column to remove water again, light component such as dme obtains the high-purity isobutylene product.
Embodiment 1
The methyl tertiary butyl ether scission reaction is carried out in the trundle bed shell-and-tube reactor, and tubulation length is 3.5 meters, selects the ML-01 catalyzer for use, bulk density 0.5g/cm
3, diameter is the white spherical silicon oxide catalyst series of 3～4mm, the catalyst bed layer height is 2 meters, temperature of reaction is 240～270 ℃, reaction pressure is 0.08MPa, the mol ratio of water and methyl tertiary butyl ether is 1.0, other operational condition and the results are shown in Table 1.
Table 1, operational condition and result
| Project | Unit | The result |
| The water ratio | Mol ratio | 1 |
| The liquid air speed | h -1 | 5.69 |
| Temperature in | ℃ | 254 |
| Temperature out | ℃ | 259 |
| Transformation efficiency | ％ | 99.72 |
| Selective isobutene | ％ | 99.75 |
| The methyl alcohol selectivity | ％ | 99.10 |
Embodiment 2, methyl tertiary butyl ether scission reaction are carried out in the trundle bed shell-and-tube reactor, and tubulation length is 3.5 meters, select the ML-01 catalyzer for use, bulk density 0.45g/cm
3, diameter is the white spherical silicon oxide catalyst series of 3～4mm, the catalyst bed layer height is 2 meters, temperature of reaction is 240～270 ℃, reaction pressure is 0.05MPa, the mol ratio of water and methyl tertiary butyl ether is 2.0, other operational condition and the results are shown in Table 2.
Table 2, operational condition and result
| Project | Unit | The result |
| The water ratio | Mol ratio | 2.0 |
| The liquid air speed | h -1 | 5.69 |
| Temperature in | ℃ | 256 |
| Temperature out | ℃ | 260 |
| Transformation efficiency | ％ | 99.73 |
| Selective isobutene | ％ | 99.80 |
| The methyl alcohol selectivity | ％ | 99.05 |
Comparative example 1
The methyl tertiary butyl ether scission reaction is selected the ML-01 catalyzer for use, and the catalyst bed layer height is 5 meters, and temperature of reaction is 240～270 ℃, and reaction pressure is 0.08MPa, other operational condition and the results are shown in Table 3.
Table 3, operational condition and result
| Project | Unit | The result |
| The water ratio | Mol ratio | 1 |
| The liquid air speed | h -1 | 5.69 |
| Temperature in | ℃ | 253 |
| Temperature out | ℃ | 262 |
| Transformation efficiency | ％ | 99.35 |
| Selective isobutene | ％ | 96.58 |
| The methyl alcohol selectivity | ％ | 97.50 |
Comparative example 2
The methyl tertiary butyl ether scission reaction is selected the JHR-02 catalyzer for use, and the catalyst bed layer height is 5 meters, and temperature of reaction is 240～270 ℃, and reaction pressure is 0.08MPa, other operational condition and the results are shown in Table 4.
Table 4, operational condition and result
| Project | Unit | The result |
| The water ratio | Mol ratio | 0 |
| The liquid air speed | h -1 | 0.75 |
| Temperature in | ℃ | 255 |
| Temperature out | ℃ | 263 |
| Transformation efficiency | ％ | 99.26 |
| Selective isobutene | ％ | 99.18 |
| The methyl alcohol selectivity | ％ | 99.01 |
Embodiment 3
The methyl tertiary butyl ether scission reaction is carried out in the trundle bed shell-and-tube reactor, and tubulation length is 3 meters, selects the ML-01 catalyzer for use, bulk density 0.45g/cm
3, diameter is the white spherical silicon oxide catalyst series of 3～4mm, the catalyst bed layer height is 2 meters, liquid phase air speed 6h
-1, temperature of reaction is 240～270 ℃, and reaction pressure is 0.06MPa, and the mol ratio of water and methyl tertiary butyl ether is 3.0.
Embodiment 4
The methyl tertiary butyl ether scission reaction is carried out in the trundle bed shell-and-tube reactor, and tubulation length is 3 meters, selects the ML-01 catalyzer for use, bulk density 0.4g/cm
3, diameter is the white spherical silicon oxide catalyst series of 3～4mm, the catalyst bed layer height is 5 meters, liquid phase air speed 5h
-1, temperature of reaction is 240～270 ℃, and reaction pressure is 0.07MPa, and the mol ratio of water and methyl tertiary butyl ether is 1.5.
Embodiment 5
The methyl tertiary butyl ether scission reaction is carried out in the trundle bed shell-and-tube reactor, and tubulation length is 3.5 meters, selects the ML-01 catalyzer for use, bulk density 0.4g/cm
3, diameter is the white spherical silicon oxide catalyst series of 3～4mm, the catalyst bed layer height is 2 meters, liquid phase air speed 6h
-1, temperature of reaction is 240～270 ℃, and reaction pressure is 0.09MPa, and the mol ratio of water and methyl tertiary butyl ether is 2.0.
Embodiment 6
The methyl tertiary butyl ether scission reaction is carried out in the trundle bed shell-and-tube reactor, and tubulation length is 3 meters, selects the ML-01 catalyzer for use, bulk density 0.4g/cm
3, diameter is the white spherical silicon oxide catalyst series of 3～4mm, the catalyst bed layer height is 3 meters, liquid phase air speed 7h
-1, temperature of reaction is 240～270 ℃, and reaction pressure is 0.08MPa, and the mol ratio of water and methyl tertiary butyl ether is 2.5.
Claims (5)
1, a kind of method by cracking isobutene by methyl-tert-butyl ether is characterized in that adopting a kind of novel trundle bed reactor, novel high-activity catalyzer and " anti-five towers " technical process to carry out, wherein:
Novel trundle bed reactor is meant the shell-and-tube reactor of 1～3.5 meter of pipe range;
The novel high-activity catalyzer is meant with dripping the moulding of ball method, bulk density 0.4～0.5g/cm
3, diameter is the white spherical silicon oxide catalyst series of 3～4mm;
Comprise in " anti-five towers " technical process that a cracker, the refining gasification of methyl tertiary butyl ether tower, a water-cooled wash pure tower, a methanol rectifying tower, an iso-butylene weight-removing column and an iso-butylene lightness-removing column, water-cooled is washed alcohol and is finished in same tower.
2, the method by cracking isobutene by methyl-tert-butyl ether according to claim 1 is characterized in that the methyl tertiary butyl ether scission reaction is to carry out in the trundle bed shell-and-tube reactor, tubulation length is 2～3 meters.
3, the method by cracking isobutene by methyl-tert-butyl ether according to claim 1 and 2, the model that it is characterized in that the novel high-activity catalyzer is ML-01, it is liquid phase air speed 4～7h that operation control requires
-1, transformation efficiency is greater than 99.5%, and selective isobutene is greater than 99.5%.
4, the method by cracking isobutene by methyl-tert-butyl ether according to claim 3, it is characterized in that being added with water in the methyl tertiary butyl ether scission reaction, the mol ratio of water and methyl tertiary butyl ether is 0.5～3.0, and reaction pressure is 0.01～0.10MPa, and temperature of reaction is 240～270 ℃.
5, method by cracking isobutene by methyl-tert-butyl ether according to claim 4, it is characterized in that the raw material methyl tertiary butyl ether advances treating tower and removes the weight component, gas phase methyl tertiary butyl ether after refining is from the side line extraction, after the high-temperature material heat exchange of cracking reactor outlet, enter the top of cracking reactor with steam, reaction product is washed pure tower through the laggard water-cooled of heat exchange, wash pure cat head from the pure water major part of methanol rectifying tower through cooling off laggard water-cooled, water-cooled is washed the pure water major part of pure tower through cooling off the middle part of laggard entry cold wash alcohol tower, another part send methanol rectifying tower, after compressing and liquefying, the compressed machine of thick iso-butylene after the dealcoholysis go the iso-butylene weight-removing column to remove heavy component, after going the iso-butylene lightness-removing column to remove light component again, obtain high-quality iso-butylene product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130606A (en) * | 2013-03-11 | 2013-06-05 | 岳阳兴长石化股份有限公司 | Unacceptable product reprocessing technique in isobutylene production |
| CN103992202A (en) * | 2013-03-11 | 2014-08-20 | 上海蓝科石化工程技术有限公司 | System and method for cracking of methyl tertiary butyl ether to prepare high purity isobutylene |
| CN104744194A (en) * | 2015-03-29 | 2015-07-01 | 大连理工大学 | Heat integration process for isobutylene device light component removing and heavy component removing tower |
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| CN1095394C (en) * | 1996-04-10 | 2002-12-04 | 中国科学院大连化学物理研究所 | Modified silica-gel catalyst for reaction of cracking methyl-tert-butyl ether to make isobutene |
| CN100516008C (en) * | 2006-02-24 | 2009-07-22 | 兰州红叶精细化工公司 | Process for cracking isobutene by methyl-tert-butyl ether |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130606A (en) * | 2013-03-11 | 2013-06-05 | 岳阳兴长石化股份有限公司 | Unacceptable product reprocessing technique in isobutylene production |
| CN103992202A (en) * | 2013-03-11 | 2014-08-20 | 上海蓝科石化工程技术有限公司 | System and method for cracking of methyl tertiary butyl ether to prepare high purity isobutylene |
| CN103992202B (en) * | 2013-03-11 | 2016-02-03 | 上海蓝科石化环保科技股份有限公司 | A kind of methyl tertiary butyl ether cracking is for the system and method for high-purity iso-butylene |
| CN104744194A (en) * | 2015-03-29 | 2015-07-01 | 大连理工大学 | Heat integration process for isobutylene device light component removing and heavy component removing tower |
| CN104744194B (en) * | 2015-03-29 | 2016-07-06 | 大连理工大学 | A kind of isobutene. device takes off light weight-removing column and is thermally integrated technique |
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| CN101302133B (en) | 2012-01-11 |
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