CN102584518A - Industrial production method and production device of isobutene - Google Patents
Industrial production method and production device of isobutene Download PDFInfo
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Abstract
The invention discloses an industrial production method of isobutene, which takes tert-butyl alcohol (TBA) water solution with 50wt% TBA or purified TBA as a raw material. The method comprises the following steps of: heating the raw material to 160-320 DEG C; adding the heated raw material into a reactor and carrying out cracking reaction at the air space velocity of 0.1-0.7 kg/m<2>.s in the presence of a heteropolyacid catalyst, thus generating isobutene-containing mixed gas; removing most part of water and TBA with water after the mixed gas enters into a water scrubber; further removing TBA after the gas which is subjected to water-scrubbing enters into an extraction tower; and removing TBA, water and other heavy components after extracted isobutene enters into a de-heavy tower, thus obtaining a high-purity isobutene product finally. In addition, the invention also discloses a production device of isobutene. According to the invention, the production process and device are optimized, the production energy consumption is reduced, full utilization of resources is achieved, the environment is protected, the purity of the obtained isobutene product can reach 99.98%, and industrial production is easy to realize.
Description
Technical field
The present invention relates to a kind of industrialized preparing process and device of iso-butylene, be specifically related to a kind of industrialized preparing process and device for preparing iso-butylene by the trimethyl carbinol.
Background technology
Iso-butylene is the organic raw material of preparation butyl rubber, polyisobutene, isobutylene oligomer, plastics inhibitor and synthetic medicine intermediate.In industrial production; Iso-butylene is many to be existed with saturated alkane and unsaturated olefin; Because the boiling point difference is little or because low-down separation factor between them, therefore from its mixture, isolating iso-butylene through the distillatory mode is comparison difficulty and uneconomic between iso-butylene and 1-butylene and the isomer thereof.Therefore industrial production is to be converted into by the iso-butylene in the mixture of hydrocarbon to be easy to and the isolating verivate of other hydro carbons, and should be cracked into iso-butylene and derivatize agent by isolating verivate.
Form MTBE (MTBE) by iso-butylene in the C4 fraction and methyl alcohol, form the trimethyl carbinol (TBA) with water, through with can be high-purity iso-butylene through cracking catalyst again after other olefines separates.Because of TBA realizes and the separating and cracking of other olefinic product than MTBE more easily, and produce by product still less, obtain the high-purity isobutylene product so suitability for industrialized production is more prone to carry out catalytic pyrolysis with TBA.
The dehydration of TBA in gas phase has multiple patented technology; Carry out on the acidic aluminum silicate catalyst as EP0255948 is said; Perhaps carrying out on the aluminum oxide or WO93/21139 is said on zeolite, carries out as US3665048 is said; These methods can both realize TBA dehydration cracking production iso-butylene, but it exists defective to be the catalyst system therefor poor selectivity, and dimerization reaction or oligomerization by product are more in iso-butylene scission reaction process.
In DE2953583; The dehydration of TBA is carried out in tower, and fill with filler the bottom of this tower, and fill with acidic ion exchange resin on its top; Below near ion exchange resin, continuously moisture TBA solution is transported in this tower; The material that contains iso-butylene obtains as overhead product, and the rectifying acquisition purity in its another tower is 99.95% iso-butylene, and the transformation efficiency of TBA is 99%.
In CN1609082; In the fixed bed of reactor drum, arrange and realize on the strong-acid ion exchange resin that the trimethyl carbinol is cracked into iso-butylene and water; And the change of the condition through controlled temperature and pressure changes at least a portion of at least a balanced reaction product into gas phase subsequently, it is separated from reaction mixture, but can realize on this theoretical method; But the difficulty of actually operating is bigger, separates not thorough.In order to guarantee selection rate and transformation efficiency, need a plurality of reactors in series simultaneously, so promptly increased control difficulty and cost, increased energy consumption again.
A kind of method and device for preparing iso-butylene with the trimethyl carbinol disclosed in CN101381273; But it does not have to disclose the transformation efficiency and the selectivity of this kind method; And isobutene gas obtains through condensation, needs to be equipped with an other cover refrigeration system, produces the additional production cost; This method can't realize industrial and large-scale production owing to receive the restriction of equipment simultaneously.
Patent CN 101300211A discloses the method for manufacture of a kind of iso-butylene and the trimethyl carbinol, and iso-butylene carries out catalysis through the microporous aluminum oxide ball and makes in this method, and the trimethyl carbinol carries out catalysis by iso-butylene through the heteropolyacid aqueous solution and makes.
Summary of the invention
Can find out that from background technology the working method of iso-butylene or have that catalyst selectivity is not high, the unfavorable problem of trimethyl carbinol transformation efficiency in the prior art perhaps exists by product more; The problem that iso-butylene purity can not further improve; The present invention provides a kind of industrialized preparing process of iso-butylene in order to overcome these problems, and this method has been selected appropriate catalyst and process step; Improved trimethyl carbinol transformation efficiency, products obtained therefrom purity is high.
The present invention also provides the equipment that is fit to this suitability for industrialized production, and this equipment only can be accomplished reaction with a reactor drum, and equipment is succinct, cost is low, is fit to industrialized production.
A kind of industrialized preparing process of iso-butylene is characterized in that, is raw material with the trimethyl carbinol aqueous solution or the pure trimethyl carbinol of trimethyl carbinol concentration >=50wt%, may further comprise the steps:
(1) raw material is heated up through preheater preheating, vaporizer vaporization, interchanger heat exchange, suphtr successively, make the raw material outlet temperature rise to 160～320 ℃;
(2) temperature of maintenance raw material joins it in reactor drum, at gas space velocity (gaseous mass of advancing p.s. is with respect to the ratio of catalyst volume) 0.1～0.7kg/m
2Carry out scission reaction under the condition that s, heteropolyacid catalyst exist, generate the mixed gas that contains iso-butylene;
(3) mixed gas is introduced into the interchanger in the step (1), for raw material provides physics heat energy, gets into water wash column then, and water removes the most of water and the trimethyl carbinol in the mixed gas from mixed gas, and residual gas gets into next step and continues purifying;
(4) gas after the washing gets into extraction tower through being collapsed into liquid, is that extraction agent extracts the trimethyl carbinol of further removing in the iso-butylene with water;
(5) iso-butylene after the extraction gets in the weight-removing column, and rectifying removes heavy constituent such as the trimethyl carbinol and water, the final high-purity isobutylene product that gets.
Concrete, the used heteropolyacid catalyst of the present invention is H
3PMo
12O
40, H
3PW
12O
40, H
4PVW
11O
40, H
4SiW
12O
40, H
9CeW
18O
36, H
8CeMoO
42, H
5AlW
12O
40, H
3NaSiW
12O
40, H
6P
2W
18O
62And H
3KSiW
12O
40In one or more, catalyst cupport at the activated alumina ball or/and on the silicon-dioxide.Preferably, catalyzer is H
3PMo
12O
40(phospho-molybdic acid), H
3PW
12O
40(phospho-wolframic acid), H
4PVW
11O
40(phosphorus Vanadotungstic acid), H
4SiW
12O
40(silicotungstic acid), H
8CeMoO
42(cerium molybdic acid) and H
9CeW
18O
36In (cerium wolframic acid) one or more.Most preferred, catalyzer is H
3PMo
12O
40(phospho-molybdic acid), H
3PW
12O
40(phospho-wolframic acid), H
8CeMoO
42(cerium molybdic acid) and H
9CeW
18O
36In (cerium wolframic acid) one or more.
Further; The water lotion of washing back gained gets into dehydration tower in the step (3); Through heating the trimethyl carbinol is separated from water lotion, the vaporizing chamber that the higher trimethyl carbinol aqueous solution of cat head gained concentration gets into step (1) is as the raw material recycle, and the remaining high-temperature water solution of tower still gets into preheater and for the trimethyl carbinol preheating physics heat energy is provided; A cooled aqueous solution part gets into extraction tower as the extraction agent recycle, and another part is recycled as water coolant.
Further, the aqueous solution of gained entering water wash column recycles in the extraction tower; Heavy constituent such as the trimethyl carbinol in the weight-removing column tower still, water get into the vaporizing chamber of step (1) as the raw material recycle.
Further, in the water wash column, the flow velocity of mixed gas be the 2.0-2.5 ton/hour, the spray rate of water is 15～30m
3/ h, the temperature of water is 35-45 ℃; In the extraction tower, the liquid that obtains of compression with the 1.5-2.5 ton/hour speed get into extraction tower, water is 0.4-0.6 with the mass ratio of the liquid that compression obtains, the temperature of extraction tower is 20-45 ℃; In the weight-removing column, the flow velocity that iso-butylene gets into weight-removing column be the 1.5-2.5 ton/hour, the weight-removing column theoretical plate number is 20, reflux ratio is 1.0～1.5, tower still temperature is 50-100 ℃.
Preferably, the temperature of trimethyl carbinol scission reaction is 200～280 ℃, and gas space velocity (gaseous mass of advancing p.s. is with respect to the ratio of catalyst volume) is 0.30-0.55kg/m
2.s.
The present invention has assembled the industrial production device of the iso-butylene that is suitable for cutting down the consumption of energy, improve product purity and trimethyl carbinol transformation efficiency especially; It is characterized in that: the water wash column of comprise the raw material heating unit successively, carry out the reactor drum of scission reaction, the mixed gas of cracking gained being washed, to the gas after the washing carry out compressor for compressing, the extraction tower that the liquid after the compression is extracted and the weight-removing column that the gas after the extraction is carried out rectifying; Said raw material heating unit comprises successively the preheater that connects, vaporizer, be the interchanger and the suphtr of physics thermal source with the mixed gas in the reactor drum; Said suphtr is connected with reactor drum; Said reactor drum links to each other with water wash column through interchanger; Make the mixed gas in the reactor drum get into water wash column through the interchanger heat exchange, said water wash column links to each other with extraction tower through pipeline, makes the extraction liquid in the extraction tower get into water wash column; Said weight-removing column links to each other with vaporizer through pipeline, makes the entering of the heavy constituent after rectifying vaporizer in the weight-removing column.
Further, water wash column also is connected with the dehydration tower that the water lotion in its tower still is dewatered, and the top of dehydration tower connects condensing surface; Condensing surface connects backflash, and backflash links to each other with vaporizer through pipeline, and the gas at dehydration tower top is liquid through condenser condenses; Part liquid gets into dehydration tower again; Another part liquid gets into vaporizer through pipeline, and the bottom of dehydration tower links to each other with extraction tower through preheater, makes the aqueous solution in the dehydration Tata still get into extraction tower through the preheater heat exchange.
The invention provides method of producing iso-butylene and the device that is applicable to this method, whole process flow comprises three big steps, and one is the intensification of reaction raw materials, and two is the cracking of raw material, and three is refining, the purifying of later stage of reaction product.The used raw material of the present invention is the mixture or the pure trimethyl carbinol that contains the trimethyl carbinol, and in mixture, other compositions should not influence the carrying out of reaction.Raw material reaches predetermined temperature through four temperature-rise periods; At first be the preheater preheating, be vaporizer vaporization again; Be the interchanger heat exchange then; Be that suphtr is heated to preset temperature at last, why the present invention is provided with 4 heating phases is in order to make full use of the thermal source that reaction self produces, to reach the purpose of the utilization of resources, minimizing energy consumption.Preferably, the heat energy in preheater and the interchanger is that the thermal medium of technology itself realizes that do not need external heat source, the thermal source in vaporizer and the suphtr comes from extraneous thermal source.Wherein, the thermal source of preheater comes from the physics heat energy that the product later stage is refining, purifying produced, and the thermal source of interchanger comes from the physics heat energy of high-temperature gas mixture body product.Certainly, preheater and interchanger also can be used external heat source.
Material temperature after heating reaches 160-320 ℃; Satisfy the required temperature requirement of reaction; Directly get into fixed-bed reactor after raw material comes out from suphtr, be added with catalyzer in the reactor drum, under the effect of catalyzer, carry out the mixed gas that scission reaction generates iso-butylene and water; Should also contain the trace that possibly contain in water and the raw material of a small amount of responseless trimethyl carbinol raw material, generation in the additionally mixed gas does not participate in the impurity of scission reaction (these impurity is the impurity that when producing the trimethyl carbinol, is unavoidably had; For example water, C4, iso-butylene, sec-butyl alcohol etc., but C4, iso-butylene and sec-butyl alcohol content are generally below 2%, normally below 1%).Mixed gas has high heat, and being introduced into interchanger is that unreacted raw material provides heat energy, and the cooling gas entering follow-up equipment after lowering the temperature is then made with extra care, purifying.Refining, purge process is: mixed gas is washed through directly getting into water wash column behind the interchanger; Because the water and the trimethyl carbinol are all water-soluble; Therefore can most composition soluble in water wash-out from mixed gas be come out after the washing; Make iso-butylene purity rising in the mixed gas, the water in the water wash column is through the pipe distributor spray, and the spray rate of water is 15-30m
3/ h, after washing, the purity of iso-butylene is 99.8%.Be provided with recirculation cooler in the water wash column, the circulation of the water lotion at the bottom of the tower is used to wash mixed gas, practice thrift the water source; In addition, it is too high that recirculation cooler guarantees that also water temperature can not rise, to strengthen deviating from of the water and the trimethyl carbinol; General temperature of washing institute's water is below 45 ℃, usually at 35-45 ℃.Mixed gas after the washing is positioned at the top of water wash column, and water lotion is positioned at tower still bottom.The mixed gas of cat head gets into compressor, through being collapsed into liquid.Liquid after the compression with the 1.5-2.5 ton/hour speed get into extraction tower, in extraction tower, be provided with extraction agent---water, preferably keeping water and compressed liquid mass ratio in the extraction tower is 0.4-0.6; Liquid prod gets into from tower bottom; Pass the extraction agent in the tower, thereby the portion water and the trimethyl carbinol are deviate from, it is 20-45 ℃ that extraction tower keeps temperature; Gas after the compression finally also can become gas after getting into, and gets into weight-removing column from cat head.Product after the extraction gets into weight-removing column, and product is carried out last purifying, calculates the stage number and the reflux ratio of weight-removing column, and iso-butylene is come out from the cat head fractionation, further dewaters through molecular sieve then, finally obtains purity at the iso-butylene more than 99.9%.
More than be three steps that iso-butylene is produced, high according to the iso-butylene purity of this flow process gained, trimethyl carbinol transformation efficiency is high; Iso-butylene purity can reach 99.98%; Water content is less than 50ppm, and reaction process is succinct, has also utilized the energy of a part self; Cost is necessarily reduced, and is respond well.
Industriallization effect for further increase product; Can further be optimized, to obtain better effect, for example technology; Though the present invention has adopted special catalyzer; But the trimethyl carbinol still can not 100% transforms, and therefore in order to improve the transformation efficiency of the trimethyl carbinol, can unreacted tertiary butyl alcohol in the reaction product be separated and be back to reaction.For separating tert-butanol; In reaction unit, a dehydration tower can also be set; Dehydration tower is accepted the water lotion of water wash column bottom, though water lotion can recycle use that can not be unlimited; Want step entering dehydration tower, when trimethyl carbinol concentration reaches 5% in the water lotion, water lotion fed in the dehydration tower and dewater.Because trimethyl carbinol concentration is very low in the water lotion, can not directly be used for reaction raw materials 5% when following, therefore have only water lotion is further dewatered.Water lotion heats in dehydration tower makes the trimethyl carbinol and water sepn; Because the trimethyl carbinol and water are miscible; Therefore the cut that distills contains moisture; But the concentration of the trimethyl carbinol should can be used as reaction raw materials more than 50%, and the cut that cat head comes out gets into vaporizer as the raw material reuse through condensing surface, backflash.And dehydration tower bottom remainder water washing lotion is because have high temperature; Can get into preheater is that preheater provides thermal source; Cooled water lotion can get into extraction tower as extraction agent, and unnecessary water lotion can be used as cooling-water drain and utilizes to plant area's circulating water system again.
When further extracting the trimethyl carbinol; The aqueous solution in the extraction tower after the extraction can be back to the absorption tower; The aqueous solution in the extraction tower also is step entering absorption tower, and it reaches at 1% o'clock in t butanol content, changes a collection of extraction agent the last consignment of extraction liquid is back to water wash column washing mixed gas.
The tower still remaining liq that further takes off after weighing can be back to vaporizer as raw material, with further raising trimethyl carbinol transformation efficiency.
Through experimental verification, through the cyclically utilizing of the trimethyl carbinol, its transformation efficiency can reach more than 99.8%, and trimethyl carbinol cracking selection rate can reach more than 99%.
Present method is through seeking a kind of special-purpose catalyst that is more suitable for being cracked in the trimethyl carbinol iso-butylene, and selection rate reaches 99%, makes trimethyl carbinol cracking more stable; Transformation efficiency is increased to more than 99.8%; In addition, through further refining and dehydration, can reach the isobutene polymer grade of high-purity low water to iso-butylene; Iso-butylene purity can reach 99.98%, and water cut is less than 50pm.
In addition; Through optimization to technology and reaction unit; Thermal source in the reaction is back to technology itself; For example compress to the preheating of raw material with to the heat exchange of reaction mixture gas and to the gas phase iso-butylene, reduced production energy consumption, be relatively easy to realize making full use of and energy saving purposes of the energy through interchanger; Through the trimethyl carbinol dehydration tower unreacted tertiary butyl alcohol and cracking generation water are recycled, realized making full use of of resource, the protection environment, save energy has realized the Sustainable development of product; Through rational deployment and the optimization to technology, entire reaction is easy to control, and iso-butylene purity can reach 99.98%, easy realization of industrial production.
Description of drawings
Fig. 1 is the synoptic diagram of iso-butylene industrial production device of the present invention.
Embodiment
Through specific embodiment the present invention is further set forth below, should be understood that, following explanation only is in order to explain the present invention, its content not to be limited.
Embodiment 1
Fig. 1 is the best preferred synoptic diagram of apparatus of the present invention; Among the figure; The water wash column that the industrial production device of iso-butylene comprises the raw material heating unit successively, carries out the reactor drum of scission reaction, the mixed gas of cracking gained is washed, to the gas after the washing carry out compressor for compressing, the extraction tower that the liquid after the compression is extracted and the weight-removing column that the gas after the extraction is carried out rectifying; Said raw material heating unit comprises successively the preheater that connects, vaporizer, be the interchanger and the suphtr of physics thermal source with the mixed gas in the reactor drum; Said suphtr is connected with reactor drum, and said reactor drum links to each other with water wash column through interchanger, makes the mixed gas in the reactor drum get into water wash column through the interchanger heat exchange; Said water wash column is provided with recirculation cooler; Water wash column links to each other with extraction tower through pipeline, makes the extraction liquid in the extraction tower get into water wash column, and said weight-removing column links to each other with vaporizer through pipeline; Make the entering of the heavy constituent after rectifying vaporizer in the weight-removing column, the gas of last weight-removing column cat head obtains the iso-butylene product through overhead condenser, second backflash, molecular sieve.
Further; Water wash column also is connected with the dehydration tower that the water lotion in its tower still is dewatered, and the top of dehydration tower connects condensing surface, and condensing surface connects first backflash; First backflash links to each other with vaporizer through pipeline; The gas at dehydration tower top is liquid through condenser condenses, and a part of liquid gets into dehydration tower again, and another part liquid gets into vaporizer through pipeline; The bottom of dehydration tower links to each other with extraction tower through preheater, makes the aqueous solution in the dehydration Tata still get into extraction tower through the preheater heat exchange.
When producing iso-butylene, technical process is:
At first, select the trimethyl carbinol aqueous solution of concentration more than 50wt% as raw material, because there is unavoidable impurities in the relations of production in raw material, for example water, C4, sec-butyl alcohol etc., these impurity do not influence the carrying out of scission reaction, do not participate in scission reaction yet.Raw material is vaporized through preheater preheating, vaporizer; After getting into interchanger, the further heat exchange intensification of suphtr again; Raw material is warming up to 160-320 ℃; Raw material is got into fixed-bed reactor, in reactor drum, be provided with heteropllyacids catalyzer (heteropllyacids refers to the mixture of heteropolyacid or heteropolyacid), unstripped gas is at 160-320 ℃, 0.1-0.7kg/m
2.s the condition of gas space velocity is carried out scission reaction, generates the mixed gas that contains iso-butylene;
Mixed gas through interchanger cooling back with the 2.0-2.5 ton/hour flow velocity get into water wash column, the water in the water wash column sprays from cat head and has got off to absorb the partial reaction raw material (trimethyl carbinol) the mixed gas, by product (water) and impurity (sec-butyl alcohol that has in the raw material and a small amount of C4 etc.).Water in the water wash column is through the pipe distributor spray, and the spray rate of water is 15-30M
3/ h.For water saving, rise to cat head again after the water at the bottom of the tower cools off through recirculation cooler and spray, the temperature of spray institute water remains at below 45 ℃;
The purity of iso-butylene is more than 99.8% in the mixed gas after the washing; Mixed gas gets into compressor from the water wash column cat head, through be collapsed into liquid with the 1.5-2.5 ton/hour speed get in the extraction tower, the bottom of extraction tower is connected with extraction agent---water; The tower temperature remains on 20-45 ℃; Liquid after the compression gets at the bottom of tower, passes extraction agent and is vaporized into gas (the iso-butylene boiling point is very low, under 20-45 ℃, can become gaseous state) arrival cat head then; Further removed the trimethyl carbinol again through extraction, wherein the mass ratio of the liquid of water and compression is 0.4:-0.6;
The gas of extraction tower cat head discharge to get into weight-removing column from cat head, speed be the 1.5-2.5 ton/hour, in weight-removing column, gas is carried out rectifying; Further remove the trimethyl carbinol and other impurity; Best theoretical plate number is 20, and reflux ratio is 1.0～1.5, and tower still temperature is 50-100 ℃.Gas behind weight-removing column is emitted from cat head, dewaters through condenser condenses, backflash backflow, molecular sieve, finally obtains purity and reaches high-purity iso-butylene of 99.98%.
Above-mentioned is the principal reaction process of preparation iso-butylene, further for save energy, reduces cost, and improves feed stock conversion, can also carry out following optimization to technology:
1, in order to improve the transformation efficiency of the trimethyl carbinol, in equipment, can also increase by a dehydration tower, be used to reclaim unreacted tertiary butyl alcohol and be reused for reaction.Dehydration tower is connected with the bottom on absorption tower, the trimethyl carbinol in the absorption tower bottom water washing lotion of mainly purifying.Operating process is: the water cycle in the water wash column is used for the trimethyl carbinol and the water of wash-out mixed gas; The trimethyl carbinol in the water lotion at the bottom of the tower reaches 5%; Water lotion fed in the dehydration tower dewater, the process of dehydration is heating, and the trimethyl carbinol will steam from cat head and get into the vaporizer reuse then.The remaining high-temperature water solution in dehydration tower bottom then gets into vaporizer provides thermal source for it, and a refrigerative aqueous solution part gets into extraction tower as extraction agent, and it is subsequent use that rest parts can be used as water coolant, enters plant area's circulating water system.
2, also contain the trimethyl carbinol in the remaining heavy constituent at the bottom of the weight-removing column tower, in order to improve its transformation efficiency, the heavy constituent at the bottom of the tower also get into the vaporizer cyclically utilizing.
3, for water saving; The aqueous solution in the extraction tower after the extraction can be back to the absorption tower; Operation steps is: extraction liquid is that intermittent type gets into the absorption tower, and the trimethyl carbinol concentration in the aqueous solution reaches at 1% o'clock, changes a collection of extraction agent the last consignment of extraction liquid is back to water wash column washing mixed gas.
Through after the above-mentioned Optimizing operation, trimethyl carbinol transformation efficiency can reach 99.8%, and trimethyl carbinol cracking selection rate reaches 99%, can obtain mass content and reach 99.98%, and water content is less than the high-purity isobutylene product of 50ppm.
Embodiment 2
Mass content 85% trimethyl carbinol charging is 2.0 tons/hour, and through preheater preheating, vaporizer vaporization, after getting into interchanger, the further heat exchange of suphtr again and heating up, temperature reaches 260 ℃, and the raw material after the intensification gets into continuously phospho-molybdic acid (H is housed
3PMo
12O
40) the fixed-bed reactor of active silica ball in, be 0.45kg/m in this temperature, gas space velocity
2.s carry out scission reaction under the condition, generate the mixed gas that contains iso-butylene; Mixed gas is gone into the water wash column washing through interchanger cooling is laggard, get into the flow velocity 2.0-2.1 ton of water wash column/hour, the spray rate of water is 20m in the water wash column
3/ hour, water temperature is 35-45 ℃.Most of trimethyl carbinol and water in the mixed gas are removed in washing, and the extraction tower extraction is discharged, after compressor compresses is liquid phase, got into to remaining mixed gas from the water wash column top.The temperature of extraction tower is 20-45 ℃, and the admission velocity of compressed liquid is 1.69 tons/hour, and the mass ratio of water and compressed liquid is 0.4-0.6.Behind the extraction tower, mixed gas has further been removed the most of trimethyl carbinol that contains in the iso-butylene, and remaining mixed gas gets into the iso-butylene weight-removing column again and removes heavy constituent such as the trimethyl carbinol, water.The speed that gas gets into weight-removing column is 1.68 tons/hour, and the theoretical plate number of weight-removing column is 20, and reflux ratio is 1.0-1.5, and tower still temperature is 98 ℃.Gas accumulation after weight-removing column rectifying is crossed molecular sieve dehydration at cat head after condensation, promptly get the high-purity isobutylene product; The water wash column still trimethyl carbinol aqueous solution is extraction to trimethyl carbinol dehydration tower intermittently, and the dehydration cat head is the high-content trimethyl carbinol aqueous solution, and this high-content trimethyl carbinol aqueous solution and iso-butylene weight-removing column still contain heavy constituent such as the trimethyl carbinol, water and intermittently return vaporizer, recycle.Trimethyl carbinol dehydration tower still water gets into extraction tower through a heat exchange cooling back part, and all the other get into plant area's circulating water system, recycle as water coolant.Extraction tower bottom extraction water gets into water wash column and recycles.Final trimethyl carbinol transformation efficiency reaches 99.96%, and trimethyl carbinol cracking selection rate reaches more than 99.6%, can obtain mass content and reach 99.98%, and water content is less than the high-purity isobutylene product of 50ppm.
Embodiment 3
Mass content 55% trimethyl carbinol charging is 2.8 tons/hour, and through preheater preheating, vaporizer vaporization, after getting into interchanger, the further heat exchange of suphtr again and heating up, temperature reaches 200 ℃, and the raw material after the intensification gets into continuously phospho-molybdic acid (H is housed
3PMo
12O
40) the fixed-bed reactor of activated alumina ball in, be 0.25-0.30kg/m in this temperature, gas space velocity
2.s carry out scission reaction under the condition, generate the mixed gas that contains iso-butylene; Mixed gas is gone into the water wash column washing through interchanger cooling is laggard, get into the flow velocity 2.75-2.85 ton of water wash column/hour, the spray rate of water is 15m in the water wash column
3/ hour, water temperature is 35-45 ℃.Most of trimethyl carbinol and water in the mixed gas are removed in washing, and the extraction tower extraction is discharged, after compressor compresses is liquid phase, got into to remaining mixed gas from the water wash column top.The temperature of extraction tower is 20-45 ℃, and the admission velocity of compressed liquid is 1.53 tons/hour, and the mass ratio of water and compressed liquid is 0.4-0.6.Behind the extraction tower, mixed gas has further been removed the most of trimethyl carbinol that contains in the iso-butylene, and remaining mixed gas gets into the iso-butylene weight-removing column again and removes heavy constituent such as the trimethyl carbinol, water.The speed that gas gets into weight-removing column is 1.53 tons/hour, and the theoretical plate number of weight-removing column is 20, and reflux ratio is 1.0-1.5, and tower still temperature is 85 ℃.Gas accumulation after weight-removing column rectifying is crossed molecular sieve dehydration at cat head after condensation, promptly get the high-purity isobutylene product; The water wash column still trimethyl carbinol aqueous solution is extraction to trimethyl carbinol dehydration tower intermittently, and the dehydration cat head is the high-content trimethyl carbinol aqueous solution, and this high-content trimethyl carbinol aqueous solution and iso-butylene weight-removing column still contain heavy constituent such as the trimethyl carbinol, water and intermittently return vaporizer, recycle.Trimethyl carbinol dehydration tower still water gets into extraction tower through a heat exchange cooling back part, and all the other get into plant area's circulating water system, recycle as water coolant.Extraction tower bottom extraction water gets into water wash column and recycles.Final trimethyl carbinol transformation efficiency reaches 99.93%, and trimethyl carbinol cracking selection rate reaches more than 99.3%, can obtain mass content and reach 99.97%, and water content is less than the high-purity isobutylene product of 50ppm.
Embodiment 4
Mass content 90% trimethyl carbinol charging is 2.2 tons/hour, and through preheater preheating, vaporizer vaporization, after getting into interchanger, the further heat exchange of suphtr again and heating up, temperature reaches 280 ℃, and the raw material after the intensification gets into continuously phospho-molybdic acid (H is housed
3PMo
12O
40) and phospho-wolframic acid (H
3PW
12O
40) the fixed-bed reactor of activated alumina ball in, be 0.55kg/m in this temperature, gas space velocity
2.s carry out scission reaction under the condition, generate the mixed gas that contains iso-butylene; Mixed gas is gone into the water wash column washing through interchanger cooling is laggard, get into the flow velocity 2.15-2.25 ton of water wash column/hour, the spray rate of water is 30m in the water wash column
3/ hour, water temperature is 35-45 ℃.Most of trimethyl carbinol and water in the mixed gas are removed in washing, and the extraction tower extraction is discharged, after compressor compresses is liquid phase, got into to remaining mixed gas from the water wash column top.The temperature of extraction tower is 20-45 ℃, and the admission velocity of compressed liquid is 1.98 tons/hour, and the mass ratio of water and compressed liquid is 0.4-0.6.Behind the extraction tower, mixed gas has further been removed the most of trimethyl carbinol that contains in the iso-butylene, and remaining mixed gas gets into the iso-butylene weight-removing column again and removes heavy constituent such as the trimethyl carbinol, water.The speed that gas gets into weight-removing column is 1.98 tons/hour, and the theoretical plate number of weight-removing column is 20, and reflux ratio is 1.0-1.5, and tower still temperature is 60-70 ℃.Gas accumulation after weight-removing column rectifying is crossed molecular sieve dehydration at cat head after condensation, promptly get the high-purity isobutylene product; The water wash column still trimethyl carbinol aqueous solution is extraction to trimethyl carbinol dehydration tower intermittently, and the dehydration cat head is the high-content trimethyl carbinol aqueous solution, and this high-content trimethyl carbinol aqueous solution and iso-butylene weight-removing column still contain heavy constituent such as the trimethyl carbinol, water and intermittently return vaporizer, recycle.Trimethyl carbinol dehydration tower still water gets into extraction tower through a heat exchange cooling back part, and all the other get into plant area's circulating water system, recycle as water coolant.Extraction tower bottom extraction water gets into water wash column and recycles.Final trimethyl carbinol transformation efficiency reaches 99.93%, and trimethyl carbinol cracking selection rate reaches more than 99.5%, can obtain mass content and reach 99.99%, and water content is less than the high-purity isobutylene product of 50ppm.
Embodiment 5
Mass content 85% trimethyl carbinol charging is 2.5 tons/hour, and through preheater preheating, vaporizer vaporization, after getting into interchanger, the further heat exchange of suphtr again and heating up, temperature reaches 320 ℃, and the raw material after the intensification gets into continuously silicotungstic acid (H is housed
4SiW
12O
40) and phospho-wolframic acid (H
3PW
12O
40) the fixed-bed reactor of activated alumina ball in, be 0.65kg/m in this temperature, gas space velocity
2.s carry out scission reaction under the condition, generate the mixed gas that contains iso-butylene; Mixed gas is gone into the water wash column washing through interchanger cooling is laggard, get into the flow velocity 2.45-2.55 ton of water wash column/hour, the spray rate of water is 30m in the water wash column
3/ hour, water temperature is 35-45 ℃.Most of trimethyl carbinol and water in the mixed gas are removed in washing, and the extraction tower extraction is discharged, after compressor compresses is liquid phase, got into to remaining mixed gas from the water wash column top.The temperature of extraction tower is 20-45 ℃, and the admission velocity of compressed liquid is 1.80 tons/hour, and the mass ratio of water and compressed liquid is 0.4-0.6.Behind the extraction tower, mixed gas has further been removed the most of trimethyl carbinol that contains in the iso-butylene, and remaining mixed gas gets into the iso-butylene weight-removing column again and removes heavy constituent such as the trimethyl carbinol, water.The speed that gas gets into weight-removing column is 1.80 tons/hour, and the theoretical plate number of weight-removing column is 20, and reflux ratio is 1.0-1.5, and tower still temperature is 60-70 ℃.Gas accumulation after weight-removing column rectifying is crossed molecular sieve dehydration at cat head after condensation, promptly get the high-purity isobutylene product; The water wash column still trimethyl carbinol aqueous solution is extraction to trimethyl carbinol dehydration tower intermittently, and the dehydration cat head is the high-content trimethyl carbinol aqueous solution, and this high-content trimethyl carbinol aqueous solution and iso-butylene weight-removing column still contain heavy constituent such as the trimethyl carbinol, water and intermittently return vaporizer, recycle.Trimethyl carbinol dehydration tower still water gets into extraction tower through a heat exchange cooling back part, and all the other get into plant area's circulating water system, recycle as water coolant.Extraction tower bottom extraction water gets into water wash column and recycles.Final trimethyl carbinol transformation efficiency reaches 99.92%, and trimethyl carbinol cracking selection rate reaches more than 99.4%, can obtain mass content and reach 99.98%, and water content is less than the high-purity isobutylene product of 50ppm.
Embodiment 6
Mass content 65% trimethyl carbinol charging is 2.5 tons/hour, and through preheater preheating, vaporizer vaporization, after getting into interchanger, the further heat exchange of suphtr again and heating up, temperature reaches 275 ℃, and the raw material after the intensification gets into continuously cerium wolframic acid (H is housed
9CeW
18O
36), phospho-wolframic acid (H
3PW
12O
40) and aluminium wolframic acid (H
5AlW
12O
40) the fixed-bed reactor of activated alumina ball in, be 0.50kg/m in this temperature, gas space velocity
2.s carry out scission reaction under the condition, generate the mixed gas that contains iso-butylene; Mixed gas is gone into the water wash column washing through interchanger cooling is laggard, get into the flow velocity 2.45-2.55 ton of water wash column/hour, the spray rate of water is 26m in the water wash column
3/ hour, water temperature is 35-45 ℃.Most of trimethyl carbinol and water in the mixed gas are removed in washing, and the extraction tower extraction is discharged, after compressor compresses is liquid phase, got into to remaining mixed gas from the water wash column top.The temperature of extraction tower is 20-45 ℃, and the admission velocity of compressed liquid is 1.62 tons/hour, and the mass ratio of water and compressed liquid is 0.4-0.6.Behind the extraction tower, mixed gas has further been removed the most of trimethyl carbinol that contains in the iso-butylene, and remaining mixed gas gets into the iso-butylene weight-removing column again and removes heavy constituent such as the trimethyl carbinol, water.The speed that gas gets into weight-removing column is 1.62 tons/hour, and the theoretical plate number of weight-removing column is 20, and reflux ratio is 1.0-1.5, and tower still temperature is 85 ℃.Gas accumulation after weight-removing column rectifying is crossed molecular sieve dehydration at cat head after condensation, promptly get the high-purity isobutylene product; The water wash column still trimethyl carbinol aqueous solution is extraction to trimethyl carbinol dehydration tower intermittently, and the dehydration cat head is the high-content trimethyl carbinol aqueous solution, and this high-content trimethyl carbinol aqueous solution and iso-butylene weight-removing column still contain heavy constituent such as the trimethyl carbinol, water and intermittently return vaporizer, recycle.Trimethyl carbinol dehydration tower still water gets into extraction tower through a heat exchange cooling back part, and all the other get into plant area's circulating water system, recycle as water coolant.Extraction tower bottom extraction water gets into water wash column and recycles.Final trimethyl carbinol transformation efficiency reaches 99.92%, and trimethyl carbinol cracking selection rate reaches more than 99.5%, can obtain mass content and reach 99.99%, and water content is less than the high-purity isobutylene product of 50ppm.
Embodiment 7
Mass content 65% trimethyl carbinol charging is 2.0 tons/hour, and through preheater preheating, vaporizer vaporization, after getting into interchanger, the further heat exchange of suphtr again and heating up, temperature reaches 160-170 ℃, and the raw material after the intensification gets into continuously P-Mo-Wo acid (H is housed
3PMo
12O
40) and phospho-wolframic acid (H
3PW
12O
40) the fixed-bed reactor of activated alumina ball in, be 0.45kg/m in this temperature, gas space velocity
2.s carry out scission reaction under the condition, generate the mixed gas that contains iso-butylene; Mixed gas is gone into the water wash column washing through interchanger cooling is laggard, advance to put down flow velocity 1.90-2.10 ton into water wash column/hour, the spray rate of water is 20m in the water wash column
3/ hour, water temperature is 35-45 ℃.Most of trimethyl carbinol and water in the mixed gas are removed in washing, and the extraction tower extraction is discharged, after compressor compresses is liquid phase, got into to remaining mixed gas from the water wash column top.The temperature of extraction tower is 20-45 ℃, and the admission velocity of compressed liquid is 1.30 tons/hour, and the mass ratio of water and compressed liquid is 0.4-0.6.Behind the extraction tower, mixed gas has further been removed the most of trimethyl carbinol that contains in the iso-butylene, and remaining mixed gas gets into the iso-butylene weight-removing column again and removes heavy constituent such as the trimethyl carbinol, water.The speed that gas gets into weight-removing column is 1.30 tons/hour, and the theoretical plate number of weight-removing column is 20, and reflux ratio is 1.0-1.5, and tower still temperature is 85 ℃.Gas accumulation after weight-removing column rectifying is crossed molecular sieve dehydration at cat head after condensation, promptly get the high-purity isobutylene product; The water wash column still trimethyl carbinol aqueous solution is extraction to trimethyl carbinol dehydration tower intermittently, and the dehydration cat head is the high-content trimethyl carbinol aqueous solution, and this high-content trimethyl carbinol aqueous solution and iso-butylene weight-removing column still contain heavy constituent such as the trimethyl carbinol, water and intermittently return vaporizer, recycle.Trimethyl carbinol dehydration tower still water gets into extraction tower through a heat exchange cooling back part, and all the other get into plant area's circulating water system, recycle as water coolant.Extraction tower bottom extraction water gets into water wash column and recycles.Final trimethyl carbinol transformation efficiency reaches 99.90%, and trimethyl carbinol cracking selection rate reaches more than 99.2%, can obtain mass content and reach 99.97%, and water content is less than the high-purity isobutylene product of 50ppm.
Claims (10)
1. the industrialized preparing process of an iso-butylene is characterized in that, is raw material with the trimethyl carbinol aqueous solution or the pure trimethyl carbinol of trimethyl carbinol concentration >=50wt%, may further comprise the steps:
(1) raw material is heated up through preheater preheating, vaporizer vaporization, interchanger heat exchange, suphtr successively, make the raw material outlet temperature rise to 160～320 ℃;
(2) temperature of maintenance raw material joins it in reactor drum, at gas space velocity 0.1～0.7kg/m
2Carry out scission reaction under the condition that s, heteropolyacid catalyst exist, generate the mixed gas that contains iso-butylene;
(3) mixed gas is introduced into the interchanger in the step (1), for raw material provides physics heat energy, gets into water wash column then, and water removes the most of water and the trimethyl carbinol in the mixed gas from mixed gas, and residual gas gets into next step and continues purifying;
(4) gas after the washing gets into extraction tower through being collapsed into liquid, is that extraction agent extracts the trimethyl carbinol of further removing in the iso-butylene with water;
(5) iso-butylene after the extraction gets in the weight-removing column, and rectifying removes heavy constituent such as the trimethyl carbinol and water, the final high-purity isobutylene product that gets.
2. the industrialized preparing process of iso-butylene according to claim 1, it is characterized in that: in the catalyzer, said heteropolyacid is H
3PMo
12O
40, H
3PW
12O
40, H
4PVW
11O
40, H
4SiW
12O
40, H
9CeW
18O
36, H
8CeMoO
42, H
5AlW
12O
40, H
3NaSiW
12O
40, H
6P
2W
18O
62And H
3KSiW
12O
40In one or more, catalyst cupport at the activated alumina ball or/and on the silicon-dioxide.
3. the industrialized preparing process of iso-butylene according to claim 2, it is characterized in that: in the catalyzer, said heteropolyacid is H
3PMo
12O
40, H
3PW
12O
40, H
4PVW
11O
40, H
4SiW
12O
40, H
8CeMoO
42And H
9CeW
18O
36In one or more.
4. the industrialized preparing process of iso-butylene according to claim 3, it is characterized in that: in the catalyzer, said heteropolyacid is H
3PMo
12O
40, H
3PW
12O
40, H
8CeMoO
42And H
9CeW
18O
36In one or more.
5. the industrialized preparing process of iso-butylene according to claim 1; It is characterized in that: in the step (3); Water lotion in the water wash column gets into dehydration tower; Through heating the trimethyl carbinol is separated from water lotion, the vaporizing chamber that the higher trimethyl carbinol aqueous solution of cat head gained concentration gets into step (1) is as the raw material recycle, and the remaining high-temperature water solution of tower still gets into preheater and for the trimethyl carbinol preheating physics heat energy is provided; A cooled aqueous solution part gets into extraction tower as the extraction agent recycle, and another part is recycled as water coolant.
6. the industrialized preparing process of iso-butylene according to claim 1 is characterized in that: the aqueous solution of gained gets into water wash column and recycles in the extraction tower; Heavy constituent such as the trimethyl carbinol in the weight-removing column tower still, water get into the vaporizing chamber of step (1) as the raw material recycle.
7. the industrialized preparing process of iso-butylene according to claim 1, it is characterized in that: the temperature of trimethyl carbinol scission reaction is 200～280 ℃, gas space velocity is 0.30-0.55kg/m
2.s.
8. the industrialized preparing process of iso-butylene according to claim 1 is characterized in that: in the water wash column, the flow velocity of mixed gas be the 2.0-2.5 ton/hour, the spray rate of water is 15～30m
3/ h, the temperature of water is 35-45 ℃; In the extraction tower, the liquid that obtains of compression with the 1.5-2.5 ton/hour speed get into extraction tower, water is 0.4-0.6 with the mass ratio of the liquid that compression obtains, the temperature of extraction tower is 20-45 ℃; In the weight-removing column, the flow velocity that iso-butylene gets into weight-removing column be the 1.5-2.5 ton/hour, the weight-removing column theoretical plate number is 20, reflux ratio is 1.0～1.5, tower still temperature is 50-100 ℃.
9. the industrial production device of an iso-butylene; It is characterized in that: the water wash column of comprise the raw material heating unit successively, carry out the reactor drum of scission reaction, the mixed gas of cracking gained being washed, to the gas after the washing carry out compressor for compressing, the extraction tower that the liquid after the compression is extracted and the weight-removing column that the gas after the extraction is carried out rectifying; Said raw material heating unit comprises successively the preheater that connects, vaporizer, be the interchanger and the suphtr of physics thermal source with the mixed gas in the reactor drum; Said suphtr is connected with reactor drum; Said reactor drum links to each other with water wash column through interchanger; Make the mixed gas in the reactor drum get into water wash column through the interchanger heat exchange, said water wash column links to each other with extraction tower through pipeline, makes the extraction liquid in the extraction tower get into water wash column; Said weight-removing column links to each other with vaporizer through pipeline, makes the entering of the heavy constituent after rectifying vaporizer in the weight-removing column.
10. the industrial production device of iso-butylene according to claim 9; It is characterized in that: water wash column also is connected with the dehydration tower that the water lotion in its tower still is dewatered; The gas at dehydration tower top is liquid through condenser condenses, and a part of liquid gets into dehydration tower again, and another part liquid gets into vaporizer through pipeline; The bottom of dehydration tower links to each other with extraction tower through preheater, makes the aqueous solution in the dehydration Tata still get into extraction tower through the preheater heat exchange.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096026A (en) * | 2018-08-28 | 2018-12-28 | 宁波昊德化学工业股份有限公司 | A kind of production method of isobutene |
| CN111072440A (en) * | 2019-12-02 | 2020-04-28 | 浙江信汇新材料股份有限公司 | Method for improving comprehensive utilization rate of isobutene |
| CN111187137A (en) * | 2020-02-13 | 2020-05-22 | 浙江信汇新材料股份有限公司 | Process for preparing polymer-grade isobutene from TBA |
| CN114307552A (en) * | 2021-12-30 | 2022-04-12 | 山东成泰新材料有限公司 | Isobutene production method with tail gas treatment function |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024595A (en) * | 2006-02-24 | 2007-08-29 | 兰州红叶精细化工公司 | Process for cracking isobutene by methyl-tert-butyl ether |
| CN101610835A (en) * | 2006-11-22 | 2009-12-23 | 英国石油化学品有限公司 | Carried heteropoly acid catalyst and the purposes in the method for making alkene by oxygenate thereof |
| WO2011136432A1 (en) * | 2010-04-26 | 2011-11-03 | Songwon Industrial Co., Ltd | Method of preparing alkene compound |
-
2012
- 2012-02-06 CN CN 201210025023 patent/CN102584518B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024595A (en) * | 2006-02-24 | 2007-08-29 | 兰州红叶精细化工公司 | Process for cracking isobutene by methyl-tert-butyl ether |
| CN101610835A (en) * | 2006-11-22 | 2009-12-23 | 英国石油化学品有限公司 | Carried heteropoly acid catalyst and the purposes in the method for making alkene by oxygenate thereof |
| WO2011136432A1 (en) * | 2010-04-26 | 2011-11-03 | Songwon Industrial Co., Ltd | Method of preparing alkene compound |
Non-Patent Citations (2)
| Title |
|---|
| 申建华 等: "聚合级异丁烯生产技术的研究进展", 《合成橡胶工业》 * |
| 谢文华等: "固体杂多酸盐催化性能的研究 Ⅱ. 磷钨、硅钨杂多酸的合成、表征和在叔丁醇脱水反应中的催化性能", 《化学研究与应用》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096026A (en) * | 2018-08-28 | 2018-12-28 | 宁波昊德化学工业股份有限公司 | A kind of production method of isobutene |
| CN109096026B (en) * | 2018-08-28 | 2021-07-06 | 宁波昊德化学工业股份有限公司 | Production method of isobutene |
| CN111072440A (en) * | 2019-12-02 | 2020-04-28 | 浙江信汇新材料股份有限公司 | Method for improving comprehensive utilization rate of isobutene |
| CN111187137A (en) * | 2020-02-13 | 2020-05-22 | 浙江信汇新材料股份有限公司 | Process for preparing polymer-grade isobutene from TBA |
| CN111187137B (en) * | 2020-02-13 | 2024-02-09 | 浙江信汇新材料股份有限公司 | Process for preparing polymeric isobutene by TBA |
| CN114307552A (en) * | 2021-12-30 | 2022-04-12 | 山东成泰新材料有限公司 | Isobutene production method with tail gas treatment function |
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