CN104030874B - A kind of technique based on the positive isomery butylene of carbon molecular sieve fractionation by adsorption - Google Patents
A kind of technique based on the positive isomery butylene of carbon molecular sieve fractionation by adsorption Download PDFInfo
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Abstract
The present invention relates to a kind of technique based on the positive isomery butylene of carbon molecular sieve fractionation by adsorption.This technique adopts the carbon molecular sieve through toning hole to be sorbent material, based on non-equilibrium adsorption effect, has very high adsorption selectivity to n-butene and iso-butylene.Technical process is: passed into by positive isomery butylene mixed gas in the adsorption tower that is equipped with and adjusts hole carbon molecular sieve, adopt three towers or multi-tower variable pressure adsorption technology, carry out active adsorption by nonequilibrium effect to n-butene, outlet can obtain the iso-butylene that purity is 99% ~ 99.5%; The high purity being realized positive isomery butylene by displacement step is separated with high yield.Utilize this technique positive isomery butylene mixed system can be carried out fractionation by adsorption, obtain highly purified n-butene and the pure component of iso-butylene, thus improve the utilization ratio of positive isomery butylene in C-4-fraction.
Description
Technical field
The invention belongs to gas adsorption separation technology field, relate to a kind of technique based on the positive isomery butylene of carbon molecular sieve fractionation by adsorption, carbon molecular sieve through toning hole aligns isomery butylene Molecular Geometries and has very high adsorption selectivity, by being with the pressure-swing adsorption process of displacement step to be effectively separated by positive isomery butylene, thus obtain highly purified n-butene and iso-butylene product.
Background technology
In petrochemical production process, usually along with the generation of positive isomery hydrocarbon mixture.Due to the boiling point of quite a few positive isomery hydro carbons and volatility very close, cause and be difficult to it to be separated completely, therefore general only as fuel combustion, cause the significant wastage of resource.More typical example is the mixed c 4 cut from refinery catalytic cracking unit and chemical plant ethylene cracker, due to the boiling point of n-butene wherein and iso-butylene and relative volatility closely, n-butene boiling point is-6.250 DEG C, iso-butylene boiling point is-6.896 DEG C, and relative volatility only differs 0.005, therefore be difficult to be separated it with traditional rectificating method.
At present, the utilization ratio of China's carbon four in chemical industry only has about 10%, and the utilization ratio of industrially developed country's carbon four resources such as the U.S., Japan and West Europe has reached 60 ~ 90%, and the utilization ratio level of visible China carbon four also lags far behind developed country.How to make full use of the n-butene in carbon four resource and iso-butylene, separating-purifying goes out highly purified n-butene and iso-butylene, the high value added product such as valeral, amylalcohol be badly in need of in producing country, improves the economic benefit of enterprise, has become the problem of people's extensive concern.
Iso-butylene separation method industrially mainly contains sulfuric acid extraction process, resin hydration evaporation, methyl tertiary butyl ether (MTBE) cracking process and adsorption method of separation.The separating technology of n-butene mainly contains the Kruup Uhde technology of Germany, Japanese auspicious father-in-law's technique, the NPC technology of Japan petroleum chemical company, the IFP isolation technique of France and the UOP isolation technique of the U.S..
Sulfuric acid extraction process is the industrial iso-butylene partition method adopted the earliest, and it utilizes n-butene, iso-butylene and the difference of sulfuric acid reaction speed to realize the object be separated.Iso-butylene and sulfuric acid generation esterification generate the sulfuric acid tert-butyl ester, and the hydrolysis of the sulfuric acid tert-butyl ester generates the trimethyl carbinol, and tert-butyl alcohol dehydration generates iso-butylene, and then through alkali cleaning, washing, compression and the refining iso-butylene obtaining purity and be greater than 99%.
Methyl tertiary butyl ether method is under liquid-phase condition, macropore strong acid ion exchange resin is adopted to make catalyzer, carry out selective reaction containing the C-4-fraction of iso-butylene and methyl alcohol and produce methyl tertiary butyl ether (MTBE), the etherification procedure of iso-butylene and methyl alcohol carries out with electrophilic addition mechanism, then MTBE cracking generation iso-butylene again.
Cation exchange resin is under the effect of Zeo-karb, and iso-butylene catalytic hydration generates the trimethyl carbinol.Okumura etc. have studied a kind of method of the continuous prodution trimethyl carbinol, small-particle ion exchange resin is adopted to be catalyzer, bed resistance is large, flow direction of material is after C-4-fraction mixes with water and flows, upper entering and lower leaving, once by whole reactor, reaction product concentration is little, and isobutene conversion is only 40% ~ 50%.
Dense heteropolyacid hydration method is by adding heteropolyacid catalyst in carbon-4, makes selective isobutene ground hydration produce the trimethyl carbinol, realizes being separated of iso-butylene and n-butene.Due to the complicacy of reaction system itself, one, toray company is only had to achieve the industrialization of heteropolyacid hydration method up to now.
Adsorption method of separation is the difference according to n-butene and pib molecule shape and size, and the difference of adsorptive power realizes the Technology of separation over a molecular sieve.At present, the Parex method of UOP (UOP) and the Aromax method of toray company (Toray) are two large mainstream technologys of adsorption method of separation, and all adopt zeolite molecular sieve as sorbent material.
The auspicious father-in-law's technique of Japan: it is extraction agent distillation technique that Nippon Zeon Co., Ltd. develops with polar solvent.Material carbon four is introduced in extractive distillation column, butene fraction and butane cut is become through separation of extractive distillation, butylene and solvent mixture enter in stripping tower at the bottom of tower, butylene and separated from solvent in stripping tower, butylene steams from tower top and enters rectifying tower, in rectifying tower, be separated n-butene and 2-butylene, then obtain highly purified n-butene product through extracting rectifying.
The Kruup Uhde technology of Germany: this technology extracts using morpholine and N-methylmorpholine mixture as extraction agent, and the advantage of this technology is the selectivity of n-butene high, and solvability is better, the yield of product can reach 95%, and the flow process of the method is simple, number of devices is less, and energy consumption is low.
The NPC technology of Japan petroleum chemical company: 4 column distillation series compositions of Japan petroleum Chemical Co., Ltd. exploitation reclaim n-butene system, wherein front 2 tower serial operations, from tower top except the Trimethylmethane carbon elimination four.Be raw materials recovery n-butene with discharging at the bottom of the tower of front 2 distillation towers.Purity is greater than 99%, and the rate of recovery can reach 96%.But due to normal butane and n-butene relative volatility closely, be only 1.10, therefore need the rectifying tower of 140 polylith theoretical trays, required energy consumption is then higher.
The IFP isolation technique of France: the technical process that IFP adopts a conventional distillation and one-time extractive rectification to combine, can obtain highly purified n-butene product from extraction distillation solvent recovery tower tower top.
UOP isolation technique: Uop Inc. proposes and utilizes physical method for separation mixed c 4, with the technical process of high-purity n-butene.Uop Inc. adopts Sorbutene technique, and with the simulation moving-bed production n-butene of band rotary valve, the purity of n-butene product is greater than 97%, and the rate of recovery can reach 88%.
Summary of the invention
The object of the invention is to propose a kind of technique based on the positive isomery butylene of carbon molecular sieve fractionation by adsorption, carbon molecular sieve through toning hole aligns isomery butylene Molecular Geometries and has high selectivity, utilize non-equilibrium adsorption effect separating mechanism, adopt the absorbing process flow process of band displacement step, make enrichment on the sorbent material of n-butene in fixing adsorption tower, realize the object of outlet enrichment iso-butylene; Replaced by n-butene, obtain the yield of highly purified n-butene and raising iso-butylene, thus realize effective separation of positive isomery butylene in C-4-fraction, the utilization ratio improving resource and the protection realized environment.
The technical solution used in the present invention is as follows:
The technique based on the positive isomery butylene of carbon molecular sieve fractionation by adsorption that the present invention proposes, the carbon molecular sieve adopted is the carbon-supported catalyst of close hydrocarbon, its adsorption separation process has taken into account kinetics of adsorption effect and steric effect simultaneously, material primary aperture controls at 0.5 ~ 0.6nm, and adopt by three towers or multi-tower variable pressure adsorption separating technology, can obtain highly purified n-butene and iso-butylene component, purity can reach 99% ~ 99.5%.Concrete steps are as follows:
(1) carbon molecular sieve through toning hole is packed in each adsorption tower;
(2) positive for unstripped gas isomery butylene gas mixture is pressurizeed through compressor, and feeding the 1st adsorption tower adsorbs under constant pressure, controlling the 1st adsorption tower internal adsorption pressure is 0.3 ~ 1MPa, adsorption temp is 60 ~ 100 DEG C, the direct enrichment iso-butylene in exit of the 1st adsorption tower, its purity is greater than 99%, and n-butene is collected by vacuum pump;
(3) replace and vacuum pumping the n-th adsorption tower, all the other are the 2nd, 3 years old ... n-1 (n >=3) individual adsorption tower then carries out step-down or equal press operation;
(4) when the 1st absorption tower adsorbs completes, the n-th adsorption tower vacuumizes stopping, and the 1st adsorption tower starts all to press the n-th adsorption tower or carry out reduced pressure operation to the 1st adsorption tower, thus improves iso-butylene yield;
(5) the part n-butene adopting n-butene or a upper loop cycle to collect carries out replacement operator to the 1st adsorption tower, iso-butylene residual in 1st adsorption tower is replaced away, displacement gas iso-butylene returns in unstripped gas n-butene and iso-butylene mixed gas, now (n-1)th adsorption tower is carried out to gas product fast pressurization and enters absorption phase;
(6) method utilizing vacuum pump to aspirate carries out vacuum desorption to the 1st adsorption tower, and control desorption pressures is 0 ~ 0.08MPa, and outlet obtains highly purified n-butene, and purity can reach 96%; , the n-butene major part in exit is as product, and a small amount of n-butene has been used for the displacement of next loop cycle;
(7) so far, the 1st adsorption tower completes an absorption-desorption and regeneration process, prepares boosting again and carries out next one circulation.
The present invention is relative to the zeolite adsorbent of Uop Inc., and the sorbent material adopted is the carbon-supported catalyst of close hydrocarbon, and its adsorption separation process has taken into account kinetics of adsorption effect and steric effect simultaneously, and material primary aperture controls at 0.5 ~ 0.6nm.Because carbon molecular sieve is non-polar absorbent material, stronger chemical bond can not be formed with alkene relative to zeolite molecular sieve, so vacuum desorption can realize good regeneration effect, improve the processing efficiency to raw material.
The displacement desorption agent that the absorbing process that the present invention proposes adopts is n-butene, but is not limited to this kind of strippant.
Accompanying drawing explanation
Fig. 1 is that the present invention adjusts hole carbon molecular sieve to be separated three tower pressure-changing process flow figure of positive isomery butylene.
Number in the figure: 1 is the first adsorption tower, 2 is the second adsorption tower, and 3 is the 3rd adsorption tower, and 4 is compressor, and 5 is vacuum pump.
Embodiment
Below by embodiment, the present invention is described in further details.
The present invention adopts three towers or multi-tower variable pressure adsorption technique, by absorption, the cyclical operation process of all pressing (step-down), displacement, desorb, pressurising, realizes enrichment n-butene on sorbent material, the object of the direct enrichment iso-butylene of adsorption column outlet.
To the carbon molecular sieve in hole be adjusted to be packed in adsorption tower, pass into n-butene and iso-butylene mixed gas, the iso-butylene exporting direct enrichment be directly collected; After absorption terminates, adopt n-butene to carry out replacement operator to adsorption tower, the iso-butylene in adsorbent pores is replaced, promote the concentration of n-butene in adsorption tower.Finally carry out vacuum desorption to adsorption tower, the n-butene in exit major part is as product, and a small amount of n-butene has been used for the displacement of next cycle.For ensureing the continuity of product output, three towers or multi-tower variable pressure adsorption technique can be adopted.
In above-mentioned steps, adsorption tower internal pressure controls at 0.3 ~ 1MPa, and temperature controls within the scope of 60 ~ 100 DEG C.
The n-butene purity >96% obtained by above-mentioned processing method, the purity >99% of iso-butylene.
Embodiment 1
Adsorption tower adopts three tower absorption, and positive isomery butylene gas mixture (n-butene 50%, iso-butylene 50%) is sent into through overdraft and is equipped with in the adsorption tower of 156kg/ tower carbon molecular sieve, and be forced into 0.5MPa, in tower, temperature controls at 80 DEG C.Positive isomery butylene gas mixture enters the first adsorption tower 1 and adsorbs, and absorption simultaneously the second adsorption tower 2 is all pressed and finally boosted, and the 3rd adsorption tower 3 is all pressed, bleeds off pressure, replaced and vacuum pumping.When first adsorption tower 1 has adsorbed, the 3rd adsorption tower 3 vacuumizes stopping.First adsorption tower 1 is all pressed the 3rd adsorption tower 3, and the second adsorption tower 2 enters adsorption process simultaneously.All rear first adsorption tower 1 of pressure enters and forward bleeds off pressure, and now carries out gas product to the 3rd adsorption tower 3 and finally boosts.After first adsorption tower 1 bleeds off pressure end, namely enter replacement process and vacuum desorption.Sequential control is: adsorb 300 seconds, and all press 60 seconds, pressurising 240 seconds, forward bleeds off pressure 30 seconds, replaces 180 seconds, vacuum desorption 30 seconds.Cyclical operation like this, after pressure-variable adsorption, the purity of n-butene can reach 96% ~ 97%, and yield is 95.5%; The purity of iso-butylene can reach 99% ~ 99.5%, and yield is 98.8%.
Embodiment 2
Adsorption tower adopts three tower absorption, and positive isomery butylene gas mixture (iso-butylene 99%, n-butene 1%) is sent into through overdraft and is equipped with in the adsorption tower of 310kg/ tower carbon molecular sieve, and be forced into 0.3MPa, in tower, temperature controls at 60 DEG C.Positive isomery butylene gas mixture enters the first adsorption tower 1 and adsorbs, and absorption simultaneously the second adsorption tower 2 is all pressed and finally boosted, and the 3rd adsorption tower 3 is all pressed, bleeds off pressure, replaced and vacuum pumping.When first adsorption tower 1 has adsorbed, the 3rd adsorption tower 3 vacuumizes stopping.First adsorption tower 1 carries out reduced pressure operation, and the second adsorption tower 2 enters adsorption process simultaneously.After step-down, the first adsorption tower 1 enters and forward bleeds off pressure, and now carries out gas product to the 3rd adsorption tower 3 and finally boosts.After first adsorption tower 1 bleeds off pressure end, namely enter replacement process and vacuum desorption.Sequential control is: adsorb 600 seconds, step-down 120 seconds, pressurising 480 seconds, forward bleeds off pressure 60 seconds, replaces 360 seconds, vacuum desorption 60 seconds.Cyclical operation like this, after pressure-variable adsorption, the purity of iso-butylene can reach 99.9% ~ 99.99%, and yield is greater than 98%.
The above-mentioned description to embodiment can understand and apply the invention for the ease of those skilled in the art.Person skilled in the art obviously easily can make various amendment to these embodiments, and the General Principle again illustrated is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement made for the present invention and amendment all should within protection scope of the present invention.
Claims (1)
1. the technique based on the positive isomery butylene of carbon molecular sieve fractionation by adsorption, it is characterized in that the carbon molecular sieve adopted is the carbon-supported catalyst of close hydrocarbon, its adsorption separation process has taken into account kinetics of adsorption effect and steric effect simultaneously, material primary aperture controls at 0.5 ~ 0.6nm, and adopt multi-tower variable pressure adsorption separating technology, obtain highly purified n-butene and iso-butylene component, concrete technology step is as follows:
(1) carbon molecular sieve through toning hole is packed in each adsorption tower as sorbent material;
(2) positive for unstripped gas isomery butylene gas mixture is pressurizeed through compressor, and feeding the 1st adsorption tower adsorbs under constant pressure, controlling the 1st adsorption tower internal adsorption pressure is 0.3 ~ 1MPa, adsorption temp is 60 ~ 100 DEG C, the direct enrichment iso-butylene in exit of the 1st adsorption tower, its purity is greater than 99%, and n-butene is collected by vacuum pump;
(3) replace and vacuum pumping the n-th adsorption tower, all the other are the 2nd, 3 years old ... n-1 (n >=3) individual adsorption tower carries out step-down or equal press operation;
(4) when the 1st absorption tower adsorbs completes, the n-th adsorption tower vacuumizes stopping, and the 1st adsorption tower starts all to press the n-th adsorption tower or carry out reduced pressure operation to the 1st adsorption tower, thus improves iso-butylene yield;
(5) the part n-butene adopting n-butene or a upper loop cycle to collect carries out replacement operator to the 1st adsorption tower, iso-butylene residual in 1st adsorption tower is replaced away, displacement gas iso-butylene returns in unstripped gas n-butene and iso-butylene mixed gas, now (n-1)th adsorption tower is carried out to gas product fast pressurization and enters absorption phase;
(6) method utilizing vacuum pump to aspirate carries out vacuum desorption to the 1st adsorption tower, and control desorption pressures and be greater than 0, be less than 0.08MPa, outlet obtains highly purified n-butene, and purity can reach 96%; The n-butene major part in exit is as product, and a small amount of n-butene has been used for the displacement of next loop cycle;
(7) so far, the 1st adsorption tower completes an absorption-desorption and regeneration process, prepares boosting again and carries out next one circulation.
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