CN102502498A - Method for separating and recovering chlorine and oxygen of hydrogen chloride oxidation gas mixture by use of PSA (Pressure Swing Adsorption) technology - Google Patents
Method for separating and recovering chlorine and oxygen of hydrogen chloride oxidation gas mixture by use of PSA (Pressure Swing Adsorption) technology Download PDFInfo
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Abstract
The invention relates to a method for separating and recovering chlorine and oxygen of a hydrogen chloride oxidation gas mixture by use of a PSA (Pressure Swing Adsorption) technology and belongs to the technical field of gas separation. The method aims at a gas mixture generated by catalytic oxidation of hydrogen chloride and comprises the following steps of: firstly absorbing unreacted hydrogen chloride with water, dehydrating through concentrated sulfuric acid, and introducing a residual gas mixture into a PSA device so as to be separated, wherein the PSA device comprises at least two absorbing tower units, adsorbents filled in the absorbing tower units are at least one of silica gel and active carbon, and the volume proportion of the active carbon is 0-50%; chlorine with the purity of more than 99.2% is obtained after adsorption, pressure equalizing, flushing and desorption steps are carried out on the gas mixture, adsorption tail gas is oxygen with the purity of more than 99.5%, and the recovery rates of chlorine and oxygen are more than 98.5%. The method for separating and recovering the chlorine and oxygen of the hydrogen chloride oxidation gas mixture by the PSA technology, disclosed by the invention, is especially suitable for separation recovery of the chlorine and oxygen of the hydrogen chloride oxidation gas mixture, and has the advantages of simple process, high recovery rates and purities of chlorine and oxygen, and excellent economical and environmental-friendly benefits.
Description
Technical field
The present invention relates to the method that chemical field separates chlorine and oxygen, be specifically related to a kind of pressure swing adsorption process (PSA) selective separation and method that reclaims chlorine and oxygen from the chloration hydro-oxidation mixed gas, utilized.
Background technology
Along with the development of Chinese national economy, many chloride industry have become the important component part of national economy, and its development has driven the heavy demand to chlorine, and the imbalance between supply and demand of the in great demand and undersupply of chlorine has just appearred in some areas; Most chlorine all obtains from chlorine industry in the industry; The simple scale that enlarges chlorine industry that relies on can cause the chlor-alkali balanced contradiction again; Along with the operation of project begun newly and the continuous release of production capacity, when satisfying the demand of chlorine, caustic soda is excessive; China is that minority needs a large amount of import chlorine productss, but exports the country of caustic soda simultaneously; In general organic chlorination, a chlorine atom replaces a Wasserstoffatoms effectively to be used, and another chlorine atom combines this Wasserstoffatoms to generate so-called byproduct hydrogen chloride, and such 50% chlorine is with the form output of byproduct hydrogen chloride.The processing of by-product hydrogen chloride is a difficult problem always, and use and by-product become a pair of contradiction again like this, use manyly more, and the by-product amount is also just big more, and contradiction is serious more.Urethane MDI/TDI, PTFE, Mannheim proeess produce production processes such as vitriolate of tartar, methane chloride, propylene oxide, and by-product hydrogen chloride that all can be a large amount of in the production process of Mono Chloro Acetic Acid, clorafin, dimethylphosphite.Whenever obtain 1 ton of title product in the production of Mannheim proeess vitriolate of tartar, will increase by 0.4 ton of by-product HCl.In the production of dimethylphosphite, this value is 0.66 ton in theory.Refrigeration agent production is with hydrogen fluoride and trichloromethane substitution reaction, and producing 100000 tons of devices per year just has 6～70,000 tons/year by-product HCl.The main raw material of urethane is MDI ('-diphenylmethane diisocyanate) and TDI (tolylene diisocyanate).Urethane and basic material thereof have become after polyvinyl chloride, and another consumes the more Chemicals of chlorine.World's polyurethane products ultimate production reached 1,700 ten thousand tons in 2010, and Chinese urethane output 2009 is close on 4000000 tons.Global TDI had 2,300,000 tons production capacity in 2010,190.9 ten thousand tons of demands, and the production capacity of MDI will reach 4,880,000 tons, and demand has 418.8 ten thousand tons.The production capacity that China expects MDI in 2017 will reach 1,400,000 tons.When chlorine demand and usage quantity increased day by day, the output of by-product hydrogen chloride also increased year by year.Surpass 1,000 ten thousand tons/year as far back as America and Europe in 1999, and the demand gap of chlorine just continues to increase.Also the have an appointment by-product hydrogen chloride of 60,000 t/a of the MDI device of 100,000 t/a.Also the have an appointment by-product hydrogen chloride of 8.39 ten thousand t/a of the TDI device of 100,000 t/a.Therefore, need badly and find a kind of economic and practical hydrogenchloride preparing chlorine gas technology, realize the closed cycle and the zero release of chlorine element,, solved the problems such as chlor-alkali balance that many areas exist again both for by-product hydrogen chloride finds a way out.
The method of hydrogenchloride preparing chlorine gas mainly contains electrolytic process, an inorganic oxidizer direct oxidation method and air/oxygen catalytic oxidation (being the Deacon process).Conventional electrolysis preparing chlorine gas energy consumption is too high, and the shortcoming of an inorganic oxidizer direct oxidation method is the equipment more complicated, and product separation difficulty, energy consumption are too high.The Deacon process is under the condition of the oxide compound of Cu, Ru, Cr etc. or oxide catalyst existence, directly hydrogen chloride gas is oxidized to chlorine at 300～550 ℃ of oxygen of high temperature.It is generally acknowledged that the Deacon process is following:
2HCL+1/2O
2→CL
2+H
2O ΔH＝-13.8kcal/mol
This technology is because problems such as the conventional catalyst activity is low, the life-span is short and the reactor design difficulty is big, subsequent product gas purification energy consumption height restrict large-scale industrialization always.At present domesticly developed catalyst for catalytic oxidation and designed the fluidized-bed reactor relatively more suitable, realized the maximum difficult problem of industrialization of catalytic oxidation of hydrogen chloride for preparing chlorine gas Technology is how to reduce the separating energy consumption of subsequent product gas catalytic oxidation process.Because can not aerobic and water in the photochemical system, so, in the TDI production process in the various feed composition oxygen level all be controlled within the scope of quite strictness with water-content.At present, the TDI industry is generally 0 with the quality index of chlorine
2≤100ppm; H
2O≤100ppm.
Hydrogenchloride contains chlorine, hydrogenchloride, oxygen G&W through catalytic oxidation in the reacted gas mixture.Mixed gas is through the water absorbing hydrogen chloride, remove water through the vitriol oil again after, have only chlorine and oxygen in the gas mixture basically.Separate chlorine and oxygen domestic method at present and mainly contain pressure swing adsorption process, condensation method, cryogenic rectification method, absorption-desorption method and membrane separation process etc.The pressure swing adsorption process ultimate principle be utilize different adsorbates under certain temperature, different pressures condition in the separation between each adsorbate that is achieved of the difference of the rate of adsorption on the solid adsorbent, adsorptive power, adsorptive capacity; This technology has that technology is simple, investment and process cost is low, level of automation is high, product purity is high, stop characteristics such as car is convenient, energy consumption is low, since the eighties in 20th century, has been successfully applied to numerous areas such as making oxygen by air separation and system nitrogen, synthetic ammonia relief gas hydrogen recovery, natural gas conditioning, coke(oven)gas decarburization, oil refinery dry gas olefin recovery, coal mine gas methane recovery.In pressure swing adsorption technique process commonly used, the unitary cyclical operation process of each adsorption tower generally comprise absorption (A), the equal pressure drop of one or many (ED), along put (P) or contraryly put (D), slow rinse (C), vacuumize (V), the equal voltage rise of one or many (ER), whole pressurising steps such as (FR).
Chinese patent document CN90110412.4 discloses a kind of concentrating means of chlorine, and this method adopts pressure swing adsorption to carry the gas mixture of carbonic acid gas that contains 5～15% chlorine (or nitrogen) and helium dense to 55～83%.CN200680005928.2 discloses a kind of method for preparing chlorine, and the method that this method utilizes condensation method and membrane separation process to combine reclaims the chlorine in the hydrogenchloride catalyzed oxidation gas mixture, and the product purity of chlorine gas feeding is greater than 95 (wt) %.Chinese patent 201010194714.2 discloses a kind of method that reduces oxygen content in the circulating chlorine gas, and it adopts the pyrochemistry reduction method to reduce the oxygen level in the circulating chlorine gas.U.S. Pat 33995387 (A) discloses a kind of with CCl
4Be the method that the absorption-desorption method of absorption agent is produced liquid chlorine, US5308383 discloses a kind of with C
7F
3H
4-nCl
n(n=1～3) are that the chlorine of absorption agent absorbs reuse method.Chinese patent CN200510025910.6 discloses a kind of separating and purifying method that contains chlorine and hydrogenchloride mix waste gas, and this method adopts absorption process to obtain the product purity of chlorine gas feeding can reach 99%.Chinese patent 200780018846.6 through hydrogenchloride and oxygen in the thermal response of using the catalyzer condition and/or pass through the method for the non-thermal activation prepared in reaction chlorine of hydrogenchloride and oxygen; The gaseous mixture cooling that wherein a) generates in will reacting is so that the salt acid condensation; This gaseous mixture is at least by title product chlorine G&W, unreacted hydrogen chloride and oxygen and other accessory constituent, and for example carbonic acid gas and nitrogen and optional phosgene are formed; B) the liquid hydrochloric acid of resulting separation from remaining gaseous mixture; C) remove remaining residual water in the separated gaseous mixture, particularly, it is characterized in that d through with vitriol oil washing) pass through gas-permeable; Remove oxygen and optional other accessory constituent, particularly carbonic acid gas and/or nitrogen and/or phosgene from resulting chlorine-containing gas mixture.Preferably use film according to molecular sieve principle operation to carry out, this gas-permeable preferably uses so-called carbon film to carry out.Known carbon film is made up of pyrolytic polymer, for example is selected from the pyrolytic polymer of group: resol, furfuryl alcohol, Mierocrystalline cellulose, polyacrylonitrile and gather phthalimide.
In above-mentioned each patented process, the product purity of chlorine gas feeding that pressure swing adsorption process obtains is not high, can not satisfy Chemical Manufacture with purity of chlorine gas feeding greater than 99% requirement.Though adopt condensation method, absorption process, low-temperature distillation method, membrane separation process and coupled method thereof can reach purity requirement, but energy consumption is high, complex process, is unfavorable for national energy-saving and emission-reduction, implementation of sustainable development.
Under the electrolysis situation, hydrogenchloride at first changes into aqueous hydrochloric acid, is electrolyzed to produce chlorine and hydrogen then, and chlorine obtains with spissated form.Deacon (Deacon) in that another kind is more energy-conservation than electrolysis process is made in the chlorine method, and hydrogenchloride is changed into chlorine, oxygen, water, and only can obtain cl content is rare chlorine logistics of 10～50% (volumes).This rare chlorine logistics must be passed through aftertreatment and obtain with spissated form, and this is because Chemical Manufacture requires purity to be higher than 99% high purity dry chlorine gas.The Shell-Deacon method of HCL oxidation (The Chemical Engineer, (1963) 224-232) is used CCL through absorption-desorption method
4Isolate chlorine as absorption agent.In the absorption tower, under about 0.15MPa and about 11 ℃ tower top temperature, be 27～48% (also to contain N from chlorine content
2, O
2And CO
2) feeding gas in wash out chlorine.The process that from absorption liquid, discharges chlorine is to be that about 65.5 ℃, pressure carry out in desorption tower under the condition of about 1.1MPa in tower top temperature, the chlorine that discharges add depress, quilt is purified through partial condensation in the water condenser that install at the top.Uncooled chlorine and other gaseous fractions that still are present in wherein turn back to the absorption tower.EP-A0518553 has described first with separating chlorine with Vacuum Pressure Swing Adsorption (Vaculmm pressure swing adsorption) behind the low-temperature distillation tower.With feed gas compression and earlier with no chlorine exit gas cooling, be passed into condensation or low-temperature distillation tower then, the form that part chlorine can neat liquid in this tower is from the bottom discharge of tower.Remaining chlorine-containing gas leaves tower through cat head, gets into Vacuum Pressure Swing Adsorption (VPSA) tower then.In adsorption tower, about 0.4～1.1MPa and 0～150 ℃, preferred at room temperature the hocket absorption extraction of chlorine and residual gas.Through the Vacuum Pressure Swing Adsorption of 1～60 kPa of continuous application, obtained the chlorine of high density from adsorption tower, after the chlorine desorb of absorption, these adsorption towers can be reused for charging.Spendable absorption agent is synthetic or natural zeolite or nonzeolite porous oxide, preferred carbon back absorption agent, for example gac and carbonaceous molecular sieve.Yet it all is highly purified chlorine that this method is not suitable for from feed gas, because the gas phase that exists in the adsorption tower still contains all gas component of gas stream, therefore, not only chlorine is absorbed, and other gaseous fractions also are partially absorbed simultaneously.When adopting vacuum, these components get into from the chlorine logistics that adsorption tower is discharged with the chlorine of absorption.Have only and be only pure from the chlorine that condensation/the low ternperature separation process section obtains.Yet; Owing to limited cooling temperature technically and economically, so the amount of chlorine only is a limited part, this depends on the chlorine gas concentration in the feed gas; In order all to be pure chlorine from VPSA, isolated chlorine must pass through further purification step.Therefore, the shortcoming that adds condensation/low-temperature distillation step before the VPSA is, chloride feed gas stream must be compressed to high chlorine condensing pressure (0.5～1MPa), and must be cooled to corresponding chlorine condensing temperature.Chinese invention patent ZL200410048809.8 disclosed a kind of from gaseous mixture selective separation and the method that reclaims chlorine; This method is at first carried out Vacuum Pressure Swing Adsorption (VPSA) with the chlorine-containing gas logistics; To be compressed to 0.5～1MPa from the chlorine-containing gas of Vacuum Pressure Swing Adsorption (VPSA); Carry out low-temperature distillation then, isolate pure chlorine, the overhead product of distillation tower is turned back in the feed gas stream of Vacuum Pressure Swing Adsorption (VPSA) as the bottom product of distillation tower.
The objective of the invention is to improve the above-mentioned method of isolating highly purified chlorine from the chlorine-containing gas logistics; And be optimized aspect energy-saving and emission-reduction, the consumption reduction, present method can be carried out with minimum device, through the transformation fractionation by adsorption; Oxygen in the absorption tail gas also purifies to more than 99.5%; Basically do not have chlorine, the chlorine content in the stripping gas reaches more than 99.2%, and chlorine content inspecting standard adopts GB5138-2006.The two recovery can reach more than 98.5%.Oxygen after the purification can return the hydrogenchloride catalytic oxidation unit as the oxygen source utilization, really realizes the maximum using of resource.
Summary of the invention
Mainly contain chlorine, intact hydrogenchloride, the oxygen G&W of unreacted in the gas mixture that produces behind the hydrogenchloride catalyzed oxidation.Before this gas mixture gets into pressure-swing absorption apparatus, need carry out pre-treatment to remove hydrogenchloride and the water in the gas mixture, the mode that specifically removes is: at first utilize hydrogenchloride characteristic soluble in water, gas mixture is absorbed through water remove de-chlorine hydride; Then with gas mixture through the drying tower of the vitriol oil is housed, the water-content in the gas mixture is reduced to below the 200ppm.T1 bottom side mouth gets into gaseous mixture from the absorption tower; Bubble column spray in T1 top injects an amount of water on the absorption tower simultaneously; In absorption tower T1 bottom packed tower and top bubble column, the hydrogen chloride water in the gaseous mixture that rises is carried out blended absorbent; Absorption tower T1 bottom connects salt acid circulating pump P1 to be returned the packed tower top and forms closed circuit, the hydrochloric acid that makes blended absorbent in filler again with the gaseous mixture that rises in the hydrogen chloride absorption enrichment that circulates, when concentration of hydrochloric acid reach set index after; Beginning is by absorption tower T1 bottom extraction hydrochloric acid, and still unabsorbed hydrogen chloride rises in the bubble column of top and all absorbs.Gaseous mixture gets into from concentrated sulfuric acid drying tower T2 bottom side mouth; Simultaneously soak the full concentrated sulfuric acid at inner-tower filling material, the moisture content in the gaseous mixture of rising carries out blended absorbent with the concentrated sulfuric acid, and the moisture content in the gaseous mixture rises to tower top and all absorbed; The concentrated sulfuric acid is diluted gradually; After the sulfuric acid concentration dilution reached the setting index, beginning refilled an amount of concentrated sulfuric acid by drying tower T2 bottom extraction dilute sulfuric acid.
Through behind the aforementioned pretreatment unit, only contain chlorine and oxygen in the gas mixture basically, through the mode of transformation absorption the two is carried out Separation and Recovery again.Pressure-swing absorption apparatus of the present invention comprises at least two adsorption tower unit, and each adsorption tower unit obtains product chlorine through adsorbing, all press, wash, vacuumize steps such as regeneration successively, and wherein absorption tail gas is a product oxygen.The key of pressure swing adsorption process is sorbent material; At least a as in silica gel and the gac of the sorbent material that the present invention uses; Content according to chlorine and oxygen in the material mixed gas of front end hydrogenchloride catalyzed oxidation technology generation is different, and the filling ratio of gac is 0～50% (weight ratio), when using silica gel and gac at the same time; Its type of feed is that gac places the adsorption tower lower end, and silica gel places the adsorption tower upper end.The arrangement that can rationally increase and decrease each step and respectively go on foot preface according to adsorbents adsorb characteristic, purity of product gas and yield requirement etc. is to reach continuous, the energy consumption minimized purpose of technology.Pressure swing adsorption technique process of the present invention is made up of at least 2 adsorption tower unit, and each adsorption tower unit all need pass through aforementioned each cyclical operation process.Concrete technological process is following:
Transformation absorption employing 4-1-2 flow process, device is made up of four adsorption towers, an equalizer tank and a vacuum pump, and the chloration hydro-oxidation gas mixture removes device and drying installation processing through hydrogenchloride before getting into transformation absorption.In four adsorption towers; Wherein adsorption tower is in the different steps of absorption; An adsorption tower is in and vacuumizes regenerative process; Nine steps such as in addition two adsorption towers are in and all press and along letting slip journey, and in whole sepn process, technological process has experienced that absorption, twice equal pressure drop are pressed, suitablely put, replace, vacuumized, twice equal voltage rise pressure and product oxygen boost.
The detailed process of each step is following:
A. adsorption process
The virgin gas that contains chlorine and oxygen is after heat exchange, and homo(io)thermism directly gets into from the bottom of adsorption tower in certain value back, and wherein chlorine is adsorbed onto on the special-purpose sorbent material entirely, and the oxygen that is not adsorbed etc. can be smoothly through the adsorbent bed battery limit (BL) of seeing off.
B. all process is pressed in pressure drop
This process is along the absorption direction; The gas of adsorption tower is pressed through all pressing the adsorption tower of pressing with another equal voltage rise to carry out equal pressure drop; This process is with being difficult for adsorbed components oxygen in the adsorption tower all to another adsorption tower; Reduce the pressure of adsorption tower on the one hand gradually, satisfy the condition of adsorption tower desorption and regeneration, reclaim a spot of chlorine in the interior dead space of adsorption tower on the other hand.
According to the actually operating pressure condition, it all presses number of times can be once, also can be twice even more times.Originally be stated as twice.
C. along putting decompression process
After accomplishing pressure equalizing; Along the absorption direction, the pressure of adsorption tower is reduced gradually, the chlorine that be adsorbed on the sorbent material this moment begins desorb again; The chlorine of separating sucking-off is full of whole adsorption tower dead space gradually, makes the purity of chlorine gas feeding that stops and be adsorbed reach required value as far as possible.
Enter the mouth through turning back to the native system virgin gas after pressurizeing along the gas that contains part chlorine of emitting.
D. replacement process
Along after letting slip journey, adsorption tower is replaced with a spot of chlorine along the direction of absorption again, a spot of replacement of oxygen in the adsorption tower headspace is gone out adsorption tower, improve chlorine gas concentration in the adsorption tower.
If the chlorine gas concentration that requires is not high especially, also can replaces, and, reclaim chlorine wherein directly to the adsorption tower desorb of regenerating.
Displacement gas also returns the feed(raw material)inlet compressor, and recovery capable of circulation is chlorine wherein.
E. vacuum desorption process
After pressure and displacement are forward put in completion; Gaseous fraction in the adsorption tower mainly is a chlorine; Gas concentration is more than 99%, and adopt the mode that vacuumizes this moment, makes the chlorine of adsorption tower internal adsorption under vacuum state, be able to desorb; Separate the product chlorine of gas for reclaiming of sucking-off, through seeing the battery limit (BL) off after the surge tank buffering.
F. all process is pressed in voltage rise
All voltage rise is pressed with all the pressure drop pressure is corresponding; The pressure of adsorption tower gradually raises on the one hand; Prepare for absorption next time, reclaim a spot of chlorine in another adsorption tower step-down process on the other hand, device can be once all to press according to the pressure condition of virgin gas still; Also twice even more times, this narration is all compressed into line description by twice.
G. the product oxygen process of finally boosting
Accomplish in the vacuum regeneration process, and, pressure surge does not take place, need adsorption column pressure be risen to adsorptive pressure with the oxygen of separating for adsorption tower can be switched in the process of adsorbing reposefully next time through after all pressing.This process not only makes adsorption tower boost; For absorption next time is prepared; Simultaneously also with respect to the process that adsorption tower is exported a flushing at position; A small amount of chlorine of the sorbent material internal adsorption of adsorption tower outlet position is moved to the adsorption tower inlet end, and oxygen purity arrives requirement when guaranteeing next time fractionation by adsorption.
Adsorption tower has just been accomplished complete " adsorption-regeneration " circulation after this process, gets ready for absorption next time again.Four adsorption towers said process that hockets reaches the purpose of continous-stable oxygen separation and chlorine.The characteristic of transformation absorption is many adsorption towers, can all press can be once also twice even repeatedly all press from two to more than ten adsorption towers in the sepn process.Absorption can series adsorption, also can non-series adsorption.
Description of drawings
Fig. 1 is the synoptic diagram of feed gas preprocessing, transformation absorption process.
Code name explanation among the figure: P1-salt acid circulating pump, T1-absorption tower, T2-vitriol oil drying tower, P2-vacuum pump, V1-equalizer tank, four adsorption towers of T3a～T3d-.
Compared with prior art, the present invention has the following advantages:
The present invention can effectively reclaim chlorine in the chloration hydro-oxidation gas mixture and oxygen separation, and wherein the adsorption tower exit end obtains highly purified oxygen, vacuumizes and obtains highly purified chlorine.The product gas oxygen that is obtained can return hydrogenchloride catalytic oxidation unit device and utilize, and it is synthetic that product gas chlorine can directly be used for phosgene.Below embodiment through embodiment the present invention is further specified, but context of the present invention not only is confined to following specific embodiment.
Embodiment
Under the normal temperature and pressure, chlorine and oxygen get into the series adsorption tower through the air glass rotameter with 7: 3 ratio at the bottom of adsorption tower.This virgin gas is chlorine and the remaining oxygen of oxidation behind the chloration hydro-oxidation, and it consists of: 70% chlorine, and 30% oxygen, pressure are 0.3MPa, water cut is below the 200ppm.To the component characteristic of virgin gas, can select certain specific sorbent material, wherein chlorine is fully adsorbed, obtain purity greater than 99.5% oxygen, adsorbent amount of chlorine is higher, through the mode that vacuumizes, the purer chlorine of reentrying.
Main operating parameters
Transformation absorption adsorptive pressure :～0.3MPa
Product oxygen pressure: 0.25MPa (than the low 0.05MPa of raw gas pressure)
Product chlorine gas pressure: normal pressure
Transformation adsorption operations temperature: 60～100 ℃
Transformation adsorption-desorption pressure :-0.07MPa
The process design parameter of device
The virgin gas condition
Form:
Chlorine content: 70%
Oxygen content: 30%
Water-content :≤200ppm
Flow: 2500Nm
3/ h
Pressure: 0.3MPa
Reclaim the oxygen requirement
Reclaim oxygen content: >=99.5%
Unit capacity regulation range: 30～110%
Reclaim oxygen pressure: >=0.25MPa
Oxygen temperature: 60 ℃
Oxygen recovery rate: 98.5%
Number during design operation: annual operate continuously
Reclaim the chlorine requirement
Reclaim chlorine content: >=99.2%
Unit capacity regulation range: 30～110%
Reclaim chlorine gas pressure: 0.02MPa (normal pressure)
Chlorine temperature: 60 ℃
The chlorine recovery: 99.0%
Number during design operation: annual operate continuously
Table 1PSA sorbent material
Below, with reference to accompanying drawing the preferred embodiments of the present invention are described particularly.The following example only is used for further explain the inventive method.The top the spirit and scope of the present invention that disclose do not receive the restriction of these embodiment.
Embodiment 1
This example is four tower pressure swing adsorption processs of chloration hydro-oxidation mixed gas separation recovery chlorine and oxygen, and virgin gas composition (removing device and drying installation processing through hydrogenchloride) and flow are as shown in table 2.
Table 2 chloration hydro-oxidation gas mixture is through pretreated composition and flow
This routine pressure swing adsorption system is made up of 4 adsorption towers, 1 vacuum pump and corresponding program-controlled valve, pipeline.Wherein 1 adsorption tower is in adsorbed state, and 1 is in and vacuumizes reproduced state, and all the other two are in equal pressure condition, and this routine process using is all pressed for 1 time.Adsorptive pressure is gauge pressure 0.3MPa, and adsorption temp is a normal temperature.
Material mixed gas (is essentially chlorine and oxygen) after pre-treatment the entering pressure swing adsorption system carries out Separation and Recovery; Chlorine is adsorbed agent and is adsorbed in the bed; And oxygen is not adsorbed basically, directly passes bed, can obtain highly purified oxygen at the adsorption tower exit end.After adsorption step is accomplished, carry out equal pressure drop, rapid along strideing, for improving the product purity of chlorine gas feeding, increase displacement step, displacement gas is a chlorine, and the replacement of oxygen of dead space in the tower is gone out, and the gas mixture that displaces returns in the virgin gas to guarantee product gas yield.Vacuumize step at last again and obtain highly purified chlorine.Purity of product gas and yield are as shown in table 3.
Table 3 purity of product gas and yield
Embodiment 2
This example is four tower pressure swing adsorption processs of chloration hydro-oxidation mixed gas separation recovery chlorine and oxygen, and virgin gas composition (removing device and drying installation processing through hydrogenchloride) and flow are as shown in table 4.
Table 4 chloration hydro-oxidation gas mixture is through pretreated composition and flow
This routine pressure swing adsorption system is identical with embodiment 1.Wherein 1 adsorption tower is in adsorbed state, and 1 is in and vacuumizes reproduced state, and all the other two are in equal pressure condition, and this routine process using is all pressed for 2 times.Adsorptive pressure is gauge pressure 0.5MPa, and adsorption temp is a normal temperature.
This routine pressure swing adsorption technique flow process is except that all pressing the number of times and routine 1 basically identical.Products obtained therefrom gas purity and yield are as shown in table 5.
Table 5 purity of product gas and yield
Although in above illustrating, describe the present invention in detail, should be understood that described details only is used to illustrate, those skilled in the art can make change to it in not deviating from spirit that claim of the present invention limits and scope.
Claims (8)
1. method that adopts chlorine and oxygen in the pressure swing adsorption Separation and Recovery chlorination hydroxide gas mixture, it is characterized in that comprising three steps, step 1: material mixed gas absorbs through water removes the intact hydrogenchloride of unreacted; Step 2: gas mixture gets into vitriol oil drying tower and removes the water that catalyzed reaction produces; Step 3: after preceding two step pre-treatment, gas mixture is sent to Vacuum Pressure Swing Adsorption VPSA system again and is carried out chlorine and oxygen separation.
2. a kind of method that adopts chlorine and oxygen in the pressure swing adsorption Separation and Recovery chlorination hydroxide gaseous mixture according to claim 1; It is characterized in that said step 1 process is: T1 bottom side mouth gets into gaseous mixture from the absorption tower; Bubble column spray in T1 top injects an amount of water on the absorption tower simultaneously; In absorption tower T1 bottom packed tower and top bubble column, the hydrogen chloride water in the gaseous mixture that rises is carried out blended absorbent; Absorption tower T1 bottom connects salt acid circulating pump P1 to be returned the packed tower top and forms closed circuit, the hydrochloric acid that makes blended absorbent in filler again with the gaseous mixture that rises in the hydrogen chloride absorption enrichment that circulates, when concentration of hydrochloric acid reach set index after; Beginning is by absorption tower T1 bottom extraction hydrochloric acid, and still unabsorbed hydrogen chloride rises in the bubble column of top and all absorbs.
3. a kind of method that adopts chlorine and oxygen in the pressure swing adsorption Separation and Recovery chlorination hydroxide gaseous mixture according to claim 1; It is characterized in that said step 2 process is: gaseous mixture gets into from concentrated sulfuric acid drying tower T2 bottom side mouth; Simultaneously soak the full concentrated sulfuric acid at inner-tower filling material, the moisture content in the gaseous mixture of rising carries out blended absorbent with the concentrated sulfuric acid, and the moisture content in the gaseous mixture rises to tower top and all absorbed; The concentrated sulfuric acid is diluted gradually; After the sulfuric acid concentration dilution reached the setting index, beginning refilled an amount of concentrated sulfuric acid by drying tower T2 bottom extraction dilute sulfuric acid.
4. a kind of method that adopts chlorine and oxygen in the pressure swing adsorption Separation and Recovery chlorination hydroxide gas mixture according to claim 1; It is characterized in that said step 3 Vacuum Pressure Swing Adsorption VPSA system is made up of at least two adsorption tower unit; Adopt the sorbent material of same way as filling equal amts in each adsorption tower; Virgin gas obtains high purity product chlorine after adsorbing, all press, replace, vacuumizing desorption procedure, in absorption tail gas, obtain highly purified oxygen simultaneously.
5. a kind of method that adopts chlorine and oxygen in the pressure swing adsorption Separation and Recovery chlorination hydroxide gas mixture according to claim 4; It is characterized in that said sorbent material is at least a in silica gel and the gac; Gac volume ratio 0～50%; When using silica gel and gac at the same time, its type of feed is that gac places the adsorption tower lower end, and silica gel places the adsorption tower upper end.
6. a kind of method that adopts chlorine and oxygen in the pressure swing adsorption Separation and Recovery chlorination hydroxide gas mixture according to claim 5, it is characterized in that: the adsorptive pressure of each adsorption tower is gauge pressure 0.1～1.0MPa in the adsorption process, adsorption temp is a normal temperature.
7. a kind of method that adopts chlorine and oxygen in the pressure swing adsorption Separation and Recovery chlorination hydroxide gas mixture according to claim 6; It is characterized in that: before the vacuum desorption step, increase flushing operation to improve the purity of chlorine gas feeding in the stripping gas, purge gas is a product gas chlorine.
8. a kind of method that adopts chlorine and oxygen in the pressure swing adsorption Separation and Recovery chlorination hydroxide gas mixture according to claim 7; It is characterized in that transformation absorption employing 4-1-2 flow process; (form by T3a～T3d), an equalizer tank (V1) and a vacuum pump (P2) by four adsorption towers for device; In four adsorption towers, wherein adsorption tower is in the different steps of absorption, and an adsorption tower is in and vacuumizes regenerative process; Two adsorption towers are in and all press and the suitable journey of letting slip in addition; In whole sepn process, technological process experienced the equal pressure drop of absorption, twice press, along nine steps such as putting, replace, vacuumize, twice equal voltage rise pressure and product oxygen boost, the detailed process of each step is following:
(i) adsorption process: the virgin gas that contains chlorine and oxygen is after heat exchange; Homo(io)thermism directly gets into from the bottom of adsorption tower in certain value back; Wherein chlorine is adsorbed onto on the special-purpose sorbent material entirely, and the oxygen that is not adsorbed etc. can be smoothly through the adsorbent bed battery limit (BL) of seeing off;
(ii) all process is pressed in pressure drop: this process is along the absorption direction; The gas of adsorption tower is pressed through all pressing the adsorption tower of pressing with another equal voltage rise to carry out equal pressure drop; This process is with being difficult for adsorbed components oxygen in the adsorption tower all to another adsorption tower; Reduce the pressure of adsorption tower on the one hand gradually, satisfy the condition of adsorption tower desorption and regeneration, reclaim a spot of chlorine in the interior dead space of adsorption tower on the other hand; According to the actually operating pressure condition, it all presses number of times can be once, also can be twice even more times;
(iii) along putting decompression process: after accomplishing pressure equalizing; Again along the absorption direction; The pressure of adsorption tower is reduced gradually; The chlorine that be adsorbed on the sorbent material this moment begins desorb, and the chlorine of separating sucking-off is full of whole adsorption tower dead space gradually, makes the purity of chlorine gas feeding that stops and be adsorbed reach required value as far as possible; Enter the mouth through turning back to the native system virgin gas after pressurizeing along the gas that contains part chlorine of emitting;
(iv) replacement process: along after letting slip journey; Adsorption tower is replaced with a spot of chlorine along the direction of absorption again, a spot of replacement of oxygen in the adsorption tower headspace is gone out adsorption tower, improve chlorine gas concentration in the adsorption tower; Displacement gas also returns the feed(raw material)inlet compressor, and recovery capable of circulation is chlorine wherein;
(v) vacuum desorption process: accomplish forward put press and displacement after; Gaseous fraction in the adsorption tower mainly is a chlorine; Concentration is more than 99%, and adopt the mode that vacuumizes this moment, makes the chlorine of adsorption tower internal adsorption under vacuum state, be able to desorb; Separate the product chlorine of gas for reclaiming of sucking-off, through seeing the battery limit (BL) off after the surge tank buffering;
(vi) all process is pressed in voltage rise: all voltage rise is pressed and is pressed corresponding with equal pressure drop; The pressure of adsorption tower gradually raises on the one hand; For absorption next time is prepared; Reclaim a spot of chlorine in another adsorption tower step-down process on the other hand, device can be once all to press according to the pressure condition of virgin gas still, also twice even more times;
(the vii) product oxygen process of finally boosting: accomplish in the vacuum regeneration process; And through after all pressing; For adsorption tower can be switched in the process of adsorbing reposefully next time pressure surge not taking place, need adsorption column pressure be risen to adsorptive pressure with the oxygen of separating; This process not only makes adsorption tower boost; For absorption next time is prepared; Simultaneously also with respect to the process that adsorption tower is exported a flushing at position; A small amount of chlorine of the sorbent material internal adsorption of adsorption tower outlet position is moved to the adsorption tower inlet end, and oxygen purity arrives requirement when guaranteeing next time fractionation by adsorption.
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