CN103357242A - Method for purifying and removing chlorides contained in chlorine-containing industrial mixed gas and recovering light hydrocarbon - Google Patents
Method for purifying and removing chlorides contained in chlorine-containing industrial mixed gas and recovering light hydrocarbon Download PDFInfo
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- CN103357242A CN103357242A CN2013102762113A CN201310276211A CN103357242A CN 103357242 A CN103357242 A CN 103357242A CN 2013102762113 A CN2013102762113 A CN 2013102762113A CN 201310276211 A CN201310276211 A CN 201310276211A CN 103357242 A CN103357242 A CN 103357242A
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Abstract
The invention discloses a method for purifying and removing chlorides contained in a chlorine-containing industrial mixed gas and recovering light hydrocarbon, and the method comprises a pressure-swing adsorption and/or temperature swing adsorption method. An adsorptive separation system which comprises two or more than two adsorption towers filled with adsorbents and a series of program control valves absorbs and fine removes the chlorine-containing industrial mixed gas; a tail gas is respectively subjected to the following steps of: adsorption, reverse release, normal-temperature evacuation or heating flushing and filling increase in the adsorption towers under the action of the program control valves; the adsorption towers is operated according to a sequence circulating and time sequence alternating mode; the outlets positioned on the upper ends of the adsorption towers control the total content of the chlorides to be less than 5 ppm, so that a purified gas or other target product gases are obtained after the chlorides are purified and removed. The method disclosed by the invention can be used for fine purifying and removing various organic chlorides, chlorine hydride and chlorine which are contained in a dichloroethane synthetic tail gas synthesized by directly chloridizing a refining and chemical dry gas and dilute ethylene or other chlorine-containing industrial mixed gases and recovering the light hydrocarbon or the other target product gases.
Description
Technical field
The present invention relates to the method that a kind of purification removes the chloride in the chloride industrial mist and reclaims lighter hydrocarbons, especially a kind of purification removes the chloride in the dichloroethanes synthesis tail gas and reclaims the method for lighter hydrocarbons.
Background technology
In the chloride industrial mist, generally contain and comprise chloromethanes, chloroethanes, the chlorides such as hydrogen chloride, take the dichloroethanes synthesis tail gas as example: in the synthetic dichloroethanes technique of the rare ethene of oil refinery dry gas and chlorine direct chlorination, because carrying part ethane and a small amount of methane in the rare ethene that participates in chlorination reaction, the light hydrocarbon components such as propane, when reacting the generation dichloroethanes with chlorine, can produce a small amount of monochloro methane, carrene, chloroform, monochlorethane, trichloroethanes, the chlorides such as hydrogen chloride, enter in the synthesis tail gas of dichloroethanes, not because not transforming fully of the ethene in the dry gas, therefore also contain a large amount of unreacted ethene in the tail gas, ethane, the light hydrocarbon gases such as methane can be used as industrial chemicals or fuel utilizes again, if burning disposal can cause huge waste, and directly discharging is not only wasted serious, the various chlorides that contain in the gaseous mixture also will produce startling exhaust emission, so these contain muriatic gaseous mixture and should again utilize.But the existence of organic chloride and hydrogen chloride affects the again utilization of hydrocarbon gas in the tail gas, such as ethylene cracking material the time since muriatic existence meeting the cracking furnace zone is corroded, for preventing from corroding pyrolysis furnace, enter generally that chloride is controlled in the 5ppm in the tail gas of pyrolysis furnace; Acting as a fuel can will produce the dioxin noxious material during burning because contain various chlorides in the tail gas when using, and causes environmental pollution; Therefore, this class tail gas must could utilize after removing various chlorides again through meticulous, generally chloride total content in the tail gas should be controlled in the 5ppm.
At present, purification removes that muriatic method mainly contains charcoal absorption in the chloride industrial mist, vacuum desorption or steam malleation desorption technique, membrane separation process, transformation or Temp .-changing adsorption etc. if remove merely hydrogen chloride, generally adopt alkali cleaning to add the again method of drying of washing.
Chinese patent ZL200410040545 discloses a kind of pressure swing absorption process that reclaims vinyl chloride and acetylene from gaseous mixture, can from the gaseous mixture that contains vinyl chloride and acetylene, purify and reclaim vinyl chloride and acetylene, but the method can only be applicable to the gaseous mixture of vinyl-chloride-containing and acetylene, do not provide the solution of the gaseous mixture that relates to multiple organic chloride and hydrogen chloride, and the content of vinyl chloride reaches 12.9ppm in the discharging gas after purifying, and muriatic residual quantity is still too large; Simultaneously this technique be with vinyl chloride with acetylene as in addition concentration and recovery utilization of gas product, its purpose mainly is to recycle a large amount of vinyl chloride and acetylene gas in the tail gas, be not as target product gas with other gas component in the mist, and vinyl chloride, the acetylene rate of recovery are lower, if purified gas directly discharges, because content of vinylchloride is high can't be up to standard, this technique can not be applicable to the meticulous chloride that removes in the industrial mist.
Chinese patent ZL200510022156 discloses the pressure-variation adsorption separation recovering method of a kind of vinyl-chloride-containing and acetylene gas mixture, can reclaim the vinyl chloride in the gaseous mixture and acetylene respectively, and the adaptability to vinyl chloride in the mixed tail gas and acetylene content increases, but also just for vinyl chloride, do not relate to separating of more other organic chloride and hydrogen chloride, this process goal gas specific aim is too strong simultaneously, is take concentration and recovery vinyl chloride or acetylene as purpose, does not have universality.
Chloride that comprising of can the rare vinyl chlorination process of purified treatment dry gas producing, monochloro methane, carrene, chloroform, chloroethanes, trichloroethanes, hydrogen chloride etc. were multiple and the method for chlorine are not provided in the above invention.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of fine purifying and removes multiple organic chloride and hydrogen chloride in dichloroethanes synthesis tail gas or other the chloride industrial mist, reclaims the adsorption separating method that comprises ethane, ethene, methane or other target product gas.
For solving the problems of the technologies described above, the present invention includes the method for pressure-variable adsorption and/or Temp .-changing adsorption, by the two or more silica gel that are filled with, active carbon, adsorption tower and a series of sequencing valve of one or more the adsorbent combinations in activated alumina or the carbon molecular sieve form adsorption separation system, chloride industrial mist is adsorbed essence to be taken off, under the programme-control valve action, tail gas passes through respectively following step in each adsorption tower: absorption, inverse put, the normal temperature flushing of finding time or heat up, fill liter, adsorption tower operates by above sequential loop and sequential interlace mode; Adsorption tower upper end control of export chloride total content reaches＜5ppm, be purified the purified gas or other target product gas that remove behind the chloride, export inverse put, find time by the adsorption tower lower end, or by heat temperature raising the chloride desorb of adsorbing on the adsorbent is got off, adsorbent is regenerated, chloride content in the stripping gas is higher can further be recycled, and also directly high temperature incineration reclaims hydrochloric acid.
Described chloride industrial mist can be the dichloroethanes synthesis tail gas that contains chlorides such as comprising monochloro methane, carrene, chloroform, monochlorethane, dichloroethanes, trichloroethanes, hydrogen chloride and chlorine, described purification removes purified gas or other target product gas behind the chloride, refer to contain the purified gas that comprises ethane, ethene and methane, the target product gas that perhaps contains propylene perhaps contains the target product gas of nitrogen.
The present invention adopts pressure-variable adsorption or Temp .-changing adsorption to depend primarily in the dichloroethanes synthesis tail gas or other contains the size of organic chloride molecular weight in the muriatic industrial gaseous mixture, and whether contain the inorganic chlorines such as hydrogen chloride, in specific implementation process according in the dichloroethanes synthesis tail gas or other contain in the muriatic industrial gaseous mixture various muriatic compositions and determine suction type, this has carried out respectively in an embodiment correspondence and has enumerated.
The inventor finds, organic chloride total amount＜4.5% in dichloroethanes synthesis tail gas or other chloride industrial mist, and chloroform, dichloroethanes and above chloride content thereof＜2%, and when inorganic chlorine comprises hydrogen chloride, chlorine content＜2%, adopt the mode of pressure-variable adsorption, comprise the steps:
1. absorption: chloride industrial mist enters adsorption tower from adsorbing tower bottom, under normal temperature and adsorptive pressure 0.05～0.5MPa, adsorbent in the tower adsorbs chloride, the control adsorption tower exports chloride total content＜5ppm in the purified gas, the target product gas after purifying from the adsorption tower recovered overhead;
2. inverse put: after absorption finishes, from the reverse normal pressure that is depressured in adsorption tower bottom;
3. find time: inverse put is to normal pressure, by the vavuum pump that is connected with adsorption tower bottom to the adsorption tower desorb of finding time, find time the middle and later periods, backflow is with the gaseous mixture of a small amount of purified gas or nitrogen or purified gas and nitrogen, capacity of returns is 8～20% of purified gas total amount, adsorption tower washed find time, evacuation pressure 0.075～0.085MPa is regenerated adsorbent;
4. pressurising: after finding time to finish, with another absorption cat head gas product that is in adsorption step this adsorption tower is carried out pressurising and boost, prepare to adsorb next time.
As scheme more specifically, operating process of the present invention comprises: unstripped gas enters the adsorption separation system that is comprised of all the people present's adsorption tower by tower 1 bottom, chloride is adsorbed on the adsorbent, and adsorbent is one or more the adsorbent combinations in silica gel, active carbon, activated alumina or the carbon molecular sieve; Remove muriatic purified product gas and discharge adsorption separation system by tower 1 top, after purifying in the gas product chloride total content reach＜during the control index of 5ppm, unstripped gas switches to tower 2, tower 1 stops into unstripped gas, then tower 1 is in the adsorption tower 3 that boosts with another and enters all and to press, tower 1 step-down, tower 3 boosts, after tower 1 equal pressure drop finishes, from the reverse normal pressure that is depressured to of unstripped gas arrival end, after tower 1 reverse step-down finishes, the desorb of finding time, evacuation pressure 0.075～0.085MPa, backflow is with the gaseous mixture of a small amount of purified gas or nitrogen or purified gas and nitrogen, capacity of returns is 8～20% of purified gas total amount, adsorption tower washed find time, after the desorb of finding time finishes, all press with another adsorption tower 3 that is in equal pressure drop, tower 1 boosts, tower 3 step-downs, tower 1,3 all press to finish after, tower 1 is finished final pressurising and is boosted to adsorptive pressure, treat next adsorption cycle, so tower 1 is finished whole absorbing process, tower 2,3,4 circulate with this, carry out the adsorption separation process of 4 adsorption towers, unstripped gas enters adsorption separation system continuously, and the gas product after the purification is discharged adsorption separation system continuously.
The inventor finds, organic chloride total amount 〉=4.5% in dichloroethanes synthesis tail gas or other chloride industrial mist, or chloroform, dichloroethanes and above chloride content 〉=2% thereof, or the inorganic Temp .-changing adsorption separating technology that adopts when comprising hydrogen chloride, chlorine content 〉=2%; Use at least 3 adsorption towers, comprise the steps:
1. absorption: chloride industrial mist enters adsorption tower from adsorbing tower bottom, under 20～40 ℃ of temperature and pressure 0.05～0.5MPa condition, adsorbent in the tower adsorbs chloride, the control adsorption tower exports chloride total content＜5ppm in the purified gas, the target product gas after purifying from the adsorption tower recovered overhead;
2. inverse put: after absorption finishes, from the reverse normal pressure that is depressured in adsorption tower bottom;
3. intensification desorb: inverse put is to normal pressure, be warming up to 100～180 ℃ of the desorption temperatures of setting in the adsorption tower external heat, and keep this temperature to finish to desorb, a small amount of purified gas or nitrogen or purified gas and nitrogen mixture reflux, capacity of returns is 5～30% of purified gas total amount, adsorption tower is washed, adsorbent is regenerated;
4. adsorption tower cold blowing: after adsorption tower intensification desorption and regeneration finishes, comprise that with regeneration gas purified gas or nitrogen or purified gas and nitrogen mixture cold blowing to temperature are lower than 40 ℃;
5. pressurising: adsorption tower is cooled to after temperature is lower than 40 ℃, this adsorption tower is pressurized to adsorptive pressure, pending next time absorption with the purified gas of the absorption cat head that is in adsorption step another this moment.
As scheme more specifically, operating process of the present invention comprises: unstripped gas enters the adsorption separation system that is comprised of three adsorption towers by tower 1 bottom, chloride is adsorbed on the adsorbent, and adsorbent is one or more the adsorbent combinations in silica gel, active carbon, activated alumina or the carbon molecular sieve; Remove muriatic purified product gas and discharge adsorption separation system by tower 1 top, after purifying in the gas product chloride total content reach＜during the control index of 5ppm, unstripped gas switches to tower 2, tower 1 stops into unstripped gas, then tower 1 carries out the heat temperature raising desorb, be heated to 150～180 ℃ of design temperatures, and keep this temperature to finish to desorb, stripping gas is discharged by tower 1 bottom, backflow is with the gaseous mixture of a small amount of purified gas or nitrogen or purified gas and nitrogen, capacity of returns is 5～30% of purified gas total amount, tower 1 is washed, and purge cooling, after purging cools to 20～40 ℃, tower 1 is carried out final pressurising boost to adsorptive pressure, treat next adsorption cycle, so tower 1 is finished whole absorbing process, tower 2,3 circulate with this, carry out the adsorption separation process of 3 adsorption towers, unstripped gas enters adsorption separation system continuously, and the gas product after the purification is discharged adsorption separation system continuously.
Inventor's discovery, one or more in use silica gel, active carbon, carbon molecular sieve and the activated alumina are compound can realize that as adsorbent this enumerates respectively in an embodiment to muriatic effective absorption.
Adopt method of the present invention, can purify the various organic chlorides that remove in the synthetic dichloroethanes synthesis tail gas of the rare ethene direct chlorination of refinery dry gas or other the chloride industrial mist, comprise monochloro methane, carrene, chloroform, monochlorethane, dichloroethanes, trichloroethanes, and hydrogen chloride and chlorine, be no more than 5ppm through muriatic total content in the industrial mist of the chloride after the smart dechlorination purification, reach smart dechlorination, reclaim the purpose that ethene, ethane, methane or other target product gas bag are drawn together propylene, nitrogen; Because the chloride industrial mist that the present invention is directed to different chloride kinds and content has provided respectively the method for Temp .-changing adsorption and pressure-variable adsorption, high and low mist can both reach and remove purpose to chloride content, and accommodation is wider.
Pressure-variable adsorption of the present invention separates, Temp .-changing adsorption isolation of purified chlorine-containing compound industry gaseous mixture system controls each sequencing valve switch by the computer follow procedure, carry out the continuous circulation operation, to chloride dichloroethanes synthesis tail gas and other industrial gaseous mixture, adsorption cleaning afterchlorinate thing total content all can be removed to below the 5ppm, organic chloride and hydrogen chloride removal efficiency can reach 100%, reclaim the light hydrocarbon gas such as ethane a large amount of in the tail gas, ethene, methane, reached the purpose of comprehensive utilization dichloroethanes synthesis tail gas or other industrial gaseous mixture; If be used for purifying the chloride that removes the high altitude discharge gas of producing methane chloride, then can reclaim nitrogen wherein, nitrogen content of recovery reaches the standard of purity nitrogen, and rate of recovery of nitrogen surpasses 87%.
The present invention will be further described below in conjunction with drawings and Examples, unless mark separately, the data of the listed percentage of specification of the present invention all are weight percentage.
Description of drawings
Fig. 1 is that the attached process flow diagram of pressure is inhaled in change of the present invention;
Fig. 2 is temperature swing adsorption process schematic flow sheet of the present invention.
The specific embodiment
Embodiment 1:
Referring to Fig. 1, comprise in the flow process of the present invention: unstripped gas enters the adsorption separation system that is comprised of all the people present's adsorption tower by tower 1 bottom, chloride is adsorbed on the adsorbent, remove muriatic purified product gas and discharge adsorption separation system by tower 1 top, when chloride content reaches the control index in the gas product after purify, unstripped gas switches to tower 2, tower 1 stops into unstripped gas, then tower 1 is in the adsorption tower 3 that boosts with another and enters all and to press, tower 1 step-down, tower 3 boosts, after tower 1 equal pressure drop finishes, from the reverse normal pressure that is depressured to of unstripped gas arrival end, after tower 1 reverse step-down finishes, the desorb of finding time, find time after desorb finishes, all press with another adsorption tower 3 that is in equal pressure drop, tower 1 boosts, tower 3 step-downs, tower 1,3 all press to finish after, tower 1 is finished final pressurising and is boosted to adsorptive pressure, treats next adsorption cycle, and so tower 1 is finished whole absorbing process, tower 2,3,4 circulate with this, carry out the adsorption separation process of 4 adsorption towers, unstripped gas enters adsorption separation system continuously, and the gas product after the purification is discharged adsorption separation system continuously.
The chloride industrial mist composition of the present embodiment sees Table 1:
The chloride industrial mist of table 1 forms (V%)
The present embodiment comprises the steps:
1. absorption: chloride industrial mist enters the adsorption tower that complete silica gel is loaded from adsorbing tower bottom, under normal temperature and adsorptive pressure 0.3MPa, adsorbent in the tower adsorbs chloride, the control adsorption tower exports chloride total content＜5ppm in the purified gas, the target product gas after purifying from the adsorption tower recovered overhead;
2. inverse put: after absorption finishes, from the reverse normal pressure that is depressured in adsorption tower bottom;
3. find time: inverse put, is found time the middle and later periods to the adsorption tower desorb of finding time by the vavuum pump that is connected with adsorption tower bottom to normal pressure, backflow accounts for the purified gas of purified gas total amount 8%, adsorption tower washed find time, evacuation pressure 0.075～0.085MPa is regenerated adsorbent;
4. pressurising: after finding time to finish, with another absorption cat head gas product that is in adsorption step this adsorption tower is carried out pressurising and boost, prepare to adsorb next time.
Through adsorption separation process, obtain test result as shown in table 2.
The chloride industrial mist pressure-variable adsorption test result of table 2
Can be seen by table 2, with this understanding, chloride industrial mist separates through pressure-variable adsorption, and the rear gas product of purification can reach the chloride total content and drop to below the 5ppm, total organic chloride removal efficiency reaches 99.996%, and methane, ethane recovery can reach respectively 64%, 62.7%.
Embodiment 2:
Referring to Fig. 1, this example dichloroethanes synthesis tail gas (unstripped gas) composition sees Table 3:
Table 3 dichloroethanes synthesis tail gas (unstripped gas) forms
The present embodiment comprises the steps:
1. absorption: the dichloroethanes synthesis tail gas enters admission space by silica gel from adsorbing tower bottom: active carbon is the adsorption separation system of the composite adsorption bed of 5:1, under normal temperature and adsorptive pressure 0.08MPa, adsorbent in the tower adsorbs chloride, the control adsorption tower exports chloride total content＜5ppm in the purified gas, the target product gas after purifying from the adsorption tower recovered overhead;
2. inverse put: after absorption finishes, from the reverse normal pressure that is depressured in adsorption tower bottom;
3. find time: inverse put is to normal pressure, by the vavuum pump that is connected with adsorption tower bottom to the adsorption tower desorb of finding time, find time the middle and later periods, backflow is washed adsorption tower with a small amount of nitrogen (account for purified gas total amount 15%) and is found time, evacuation pressure 0.075～0.085MPa is regenerated adsorbent;
4. pressurising: after finding time to finish, with another absorption cat head gas product that is in adsorption step this adsorption tower is carried out pressurising and boost, prepare to adsorb next time.
Through adsorbing separation, obtain following test result, as shown in table 4.With this understanding, can reach the chloride total content that purifies in the rear gas product drops to below the 5ppm.
Table 4 dichloroethanes synthesis tail gas pressure-variable adsorption test result
Can be seen by table 4, under these process conditions, the dichloroethanes synthesis tail gas has removed whole organic chlorides, butter through the gas product after purifying, and ethane, Recovery rate of ethylene all can reach about 70%.
Embodiment 3:
Referring to Fig. 1, the present embodiment purifies the high altitude discharge gas of producing methane chloride and removes, and its composition sees Table 5:
The high altitude discharge gas that table 5 is produced methane chloride forms (V%)
The present embodiment comprises the steps:
1. absorption: synthesis tail gas enters admission space by silica gel from adsorbing tower bottom: aluminium oxide is the adsorption separation system of the composite adsorption bed of 4:3, under normal temperature and adsorptive pressure 0.45MPa, adsorbent in the tower adsorbs chloride, the control adsorption tower exports chloride total content＜5ppm in the purified gas, the target product gas after purifying from the adsorption tower recovered overhead;
2. inverse put: after absorption finishes, from the reverse normal pressure that is depressured in adsorption tower bottom;
3. find time: inverse put is to normal pressure, by the vavuum pump that is connected with adsorption tower bottom to the adsorption tower desorb of finding time, find time the middle and later periods, backflow is washed adsorption tower with the gaseous mixture of a small amount of purified gas and nitrogen (account for purified gas total amount 18%) and is found time, evacuation pressure 0.075～0.085MPa is regenerated adsorbent;
4. pressurising: after finding time to finish, with another absorption cat head gas product that is in adsorption step this adsorption tower is carried out pressurising and boost, prepare to adsorb next time.
Through adsorbing separation, obtain following test result as shown in table 6.With this understanding, can reach the chloride total content that purifies in the rear gas product drops to below the 5ppm.
Table 6 is produced the high altitude discharge gas pressure-variable adsorption test result of methane chloride
Can be seen by table 6, under these process conditions, produce the high altitude discharge gas of methane chloride through the gas product after purifying, remove whole organic chlorides, the butter in the unstripped gas, rate of recovery of nitrogen 87.91%.
Embodiment 4:
Referring to Fig. 2, flow process of the present invention comprises: unstripped gas enters the adsorption separation system that is comprised of three adsorption towers by tower 1 bottom, chloride is adsorbed on the adsorbent, remove muriatic purified product gas and discharge adsorption separation system by tower 1 top, when chloride content reaches the control index in the gas product after purify, unstripped gas switches to tower 2, tower 1 stops into unstripped gas, then tower 1 carries out the heat temperature raising desorb, be heated to design temperature after, and keep this temperature to finish to desorb, stripping gas is discharged by tower 1 bottom, desorb is washed 1 with a certain amount of purified gas after finishing, and purges cooling, after purging cools to 20～40 ℃, tower 1 is carried out final pressurising boost to adsorptive pressure, treat next adsorption cycle, so tower 1 is finished whole absorbing process, tower 2,3, circulate with this, carry out the adsorption separation process of 3 adsorption towers, unstripped gas enters adsorption separation system continuously, and the gas product after the purification is discharged adsorption separation system continuously.
The chloride industrial mist of this example (unstripped gas) composition sees Table 7:
The chloride industrial mist of table 7 (unstripped gas) forms
The present embodiment comprises the steps:
(1) absorption: chloride industrial mist is from adsorbing the adsorption tower that tower bottom enters whole filling active carbons, under 35 ℃ of temperature and pressure 0.2MPa condition, adsorbent in the tower adsorbs chloride, the control adsorption tower exports chloride total content＜5ppm in the purified gas, the target product gas after purifying from the adsorption tower recovered overhead;
(2) inverse put: after absorption finishes, from the reverse normal pressure that is depressured in adsorption tower bottom;
(3) intensification desorb: inverse put is warming up to 155 ℃ of the desorption temperatures of setting in the adsorption tower external heat to normal pressure, and keeps this temperature to finish to desorb, a small amount of purified gas refluxes, capacity of returns is 5% of purified gas total amount, and adsorption tower is washed, and adsorbent is regenerated;
(4) adsorption tower cold blowing: after adsorption tower intensification desorption and regeneration finished, regeneration gas employing purified gas or nitrogen or purified gas and nitrogen mixture cold blowing to temperature were lower than 40 ℃;
(5) pressurising: adsorption tower is cooled to after temperature is lower than 40 ℃, this adsorption tower is pressurized to adsorptive pressure, pending next time absorption with the purified gas of the absorption cat head that is in adsorption step another this moment.
Through adsorbing separation, obtain test result as shown in table 8.The chloride total content that can reach in the dichloroethanes synthesis tail gas with this understanding, is removed to below the 5ppm.
Table 8 contains industrial gaseous mixture Temp .-changing adsorption test result
Can be seen by table 8, under these process conditions, chloride industrial gaseous mixture has removed whole organic chlorides, the butter in the unstripped gas through the gas product after purifying, and Recovery rate of ethylene reaches about 80%, and ethane recovery can reach about 77%.
Embodiment 5:
Referring to Fig. 2, dichloroethanes synthesis tail gas (unstripped gas) composition sees Table 9:
Table 9 dichloroethanes synthesis tail gas (unstripped gas) forms
The present embodiment comprises the steps:
(1) absorption: the dichloroethanes synthesis tail gas enters admission space by silica gel from adsorbing tower bottom: carbon molecular sieve: activated alumina is the adsorption separation system of the composite adsorption bed of 1:8:1, under normal temperature and pressure 0.45MPa condition, adsorbent in the tower adsorbs chloride, the control adsorption tower exports chloride total content＜5ppm in the purified gas, the target product gas after purifying from the adsorption tower recovered overhead;
(2) inverse put: after absorption finishes, from the reverse normal pressure that is depressured in adsorption tower bottom;
(3) intensification desorb: inverse put is warming up to 170 ℃ of the desorption temperatures of setting in the adsorption tower external heat to normal pressure, and keeps this temperature to finish to desorb, a small amount of nitrogen refluxes, capacity of returns is 15% of purified gas total amount, and adsorption tower is washed, and adsorbent is regenerated;
(4) adsorption tower cold blowing: after adsorption tower intensification desorption and regeneration finished, regeneration gas comprised that purified gas or nitrogen or purified gas and nitrogen mixture cold blowing to temperature are lower than 25 ℃;
(5) pressurising: adsorption tower is cooled to after temperature is lower than 25 ℃, this adsorption tower is pressurized to adsorptive pressure, pending next time absorption with the purified gas of the absorption cat head that is in adsorption step another this moment.
Through adsorbing separation, obtain following test result as shown in table 10.The chloride total content that can reach in the dichloroethanes synthesis tail gas with this understanding, is removed to below the 5ppm.
Table 10 dichloroethanes synthesis tail gas compound adsorbent Temp .-changing adsorption result
Can be seen by table 10, under these process conditions, the dichloroethanes synthesis tail gas has removed whole organic chlorides, the butter in the unstripped gas through the gas product after purifying, and Recovery rate of ethylene surpasses 80%, and ethane recovery can reach about 75%.
Embodiment 6:
Referring to Fig. 2, the present embodiment adsorbs propylene high-temperature chlorination waste gas, and its composition sees Table 11:
Table 11 propylene high-temperature chlorination waste gas forms (V%)
The present embodiment comprises the steps:
(1) absorption: propylene high-temperature chlorination waste gas enters admission space by silica gel from adsorbing tower bottom: active carbon: activated alumina is the adsorption separation system of the composite adsorption bed of 3:6:1, under normal temperature and pressure 0.05MPa condition, adsorbent in the tower adsorbs chloride, the control adsorption tower exports chloride total content＜5ppm in the purified gas, the target product gas after purifying from the adsorption tower recovered overhead;
(2) inverse put: after absorption finishes, from the reverse normal pressure that is depressured in adsorption tower bottom;
(3) intensification desorb: inverse put is to normal pressure, be warming up to 180 ℃ of the desorption temperatures of setting in the adsorption tower external heat, and keep this temperature to finish to desorb, a small amount of purified gas and nitrogen mixture reflux, capacity of returns is 28% of purified gas total amount, adsorption tower is washed, adsorbent is regenerated;
(4) adsorption tower cold blowing: after adsorption tower intensification desorption and regeneration finished, regeneration gas comprised that purified gas or nitrogen or purified gas and nitrogen mixture cold blowing to temperature are 20 ℃;
(5) pressurising: it is 20 ℃ that adsorption tower is cooled to temperature, this adsorption tower is pressurized to adsorptive pressure, pending next time absorption with the purified gas of the absorption cat head that is in adsorption step another this moment.
Through adsorbing separation, obtain following test result as shown in table 12.The chloride total content that with this understanding, can reach propylene high-temperature chlorination waste gas is removed to below the 5ppm.
Table 12 propylene high-temperature chlorination waste gas Temp .-changing adsorption test result
Can be seen by table 12, under these process conditions, propylene high-temperature chlorination waste gas has removed the whole butters in the unstripped gas through the gas product after purifying, and the organic chloride removal efficiency reaches 99.998%, the propylene rate of recovery 86.10%.
Claims (6)
1. a purification removes chloride in the chloride industrial mist and reclaims the method for lighter hydrocarbons, it is characterized in that comprising the method for pressure-variable adsorption and/or Temp .-changing adsorption, by the two or more silica gel that are filled with, active carbon, adsorption tower and a series of sequencing valve of one or more the adsorbent combinations in activated alumina or the carbon molecular sieve form adsorption separation system, chloride industrial mist is adsorbed essence to be taken off, under the programme-control valve action, tail gas passes through respectively following step in each adsorption tower: absorption, inverse put, the normal temperature flushing of finding time or heat up, fill liter, adsorption tower operates by above sequential loop and sequential interlace mode; Adsorption tower upper end control of export chloride total content reaches＜5ppm, is purified the purified gas or other target product gas that remove behind the chloride; Export inverse put, find time or by heat temperature raising, the chloride desorb of adsorbing on the adsorbent is got off by the adsorption tower lower end, adsorbent is regenerated.
2. remove chloride in the chloride industrial mist according to purification claimed in claim 1 and reclaim the method for lighter hydrocarbons, it is characterized in that described chloride industrial mist can be to contain to comprise monochloro methane, carrene, chloroform, monochlorethane, dichloroethanes, trichloroethanes, the dichloroethanes synthesis tail gas of the chlorides such as hydrogen chloride and chlorine, described purification removes purified gas or other target product gas behind the chloride, refer to contain and comprise ethane, the purified gas of ethene and methane, the target product gas that perhaps contains propylene perhaps contains the target product gas of nitrogen.
3. remove chloride in the chloride industrial mist according to purification claimed in claim 1 and reclaim the method for lighter hydrocarbons, it is characterized in that organic chloride total amount＜4.5% in dichloroethanes synthesis tail gas or other chloride industrial mist, and chloroform, dichloroethanes and above chloride content thereof＜2%, and when inorganic chlorine comprises hydrogen chloride, chlorine content＜2%, adopt the mode of pressure-variable adsorption, use at least 4 adsorption towers, comprise the steps:
(1) absorption: chloride industrial mist enters adsorption tower from adsorbing tower bottom, under normal temperature and adsorptive pressure 0.05～0.5MPa, adsorbent in the tower adsorbs chloride, the control adsorption tower exports chloride total content＜5ppm in the purified gas, the target product gas after purifying from the adsorption tower recovered overhead;
(2) inverse put: after absorption finishes, from the reverse normal pressure that is depressured in adsorption tower bottom;
(3) find time: inverse put is to normal pressure, by the vavuum pump that is connected with adsorption tower bottom to the adsorption tower desorb of finding time, find time the middle and later periods, backflow is with a small amount of purified gas or nitrogen or purified gas and nitrogen mixture, capacity of returns is 8～20% of purified gas total amount, adsorption tower washed find time, evacuation pressure 0.075～0.085MPa is regenerated adsorbent;
(4) pressurising: after finding time to finish, with another absorption cat head gas product that is in adsorption step this adsorption tower is carried out pressurising and boost, prepare to adsorb next time.
4. remove chloride in the chloride industrial mist according to purification claimed in claim 3 and reclaim the method for lighter hydrocarbons, it is characterized in that operating process of the present invention comprises: unstripped gas enters the adsorption separation system that is comprised of all the people present's adsorption tower by tower 1 bottom, chloride is adsorbed on the adsorbent, and adsorbent is one or more the adsorbent combinations in silica gel, active carbon, activated alumina or the carbon molecular sieve; Remove muriatic purified product gas and discharge adsorption separation system by tower 1 top, after purifying in the gas product chloride total content reach＜during the control index of 5ppm, unstripped gas switches to tower 2, tower 1 stops into unstripped gas, then tower 1 is in the adsorption tower 3 that boosts with another and enters all and to press, tower 1 step-down, tower 3 boosts, after tower 1 equal pressure drop finishes, from the reverse normal pressure that is depressured to of unstripped gas arrival end, after tower 1 reverse step-down finishes, the desorb of finding time, evacuation pressure 0.075～0.085MPa, backflow is with a small amount of purified gas or nitrogen or purified gas and nitrogen mixture, capacity of returns is 8～20% of purified gas total amount, adsorption tower washed find time, after the desorb of finding time finishes, all press with another adsorption tower 3 that is in equal pressure drop, tower 1 boosts, tower 3 step-downs, tower 1,3 all press to finish after, tower 1 is finished final pressurising and is boosted to adsorptive pressure, treat next adsorption cycle, so tower 1 is finished whole absorbing process, tower 2,3,4 circulate with this, carry out the adsorption separation process of 4 adsorption towers, unstripped gas enters adsorption separation system continuously, and the gas product after the purification is discharged adsorption separation system continuously.
5. remove chloride in the chloride industrial mist according to purification claimed in claim 1 and reclaim the method for lighter hydrocarbons, it is characterized in that containing organic chloride total amount 〉=4.5% in the muriatic industrial gaseous mixture when dichloroethanes synthesis tail gas or other, or chloroform, dichloroethanes and above chloride content 〉=2% thereof, or inorganic chlorine adopts the Temp .-changing adsorption separating technology when comprising hydrogen chloride, chlorine content 〉=2%; Use at least 3 adsorption towers, comprise the steps:
(1) absorption: chloride industrial mist enters adsorption tower from adsorbing tower bottom, under 20～40 ℃ of temperature and pressure 0.05～0.5MPa condition, adsorbent in the tower adsorbs chloride, control adsorption tower upper end exports chloride total content＜5ppm in the purified gas, the target product gas after purifying from the adsorption tower recovered overhead;
(2) inverse put: after absorption finishes, from the reverse normal pressure that is depressured in adsorption tower bottom;
(3) intensification desorb: inverse put is to normal pressure, be warming up to 100～180 ℃ of the desorption temperatures of setting in the adsorption tower external heat, a small amount of purified gas or nitrogen or purified gas and nitrogen mixture reflux, capacity of returns is 5～30% of purified gas total amount, adsorption tower is washed, adsorbent is regenerated;
(4) adsorption tower cold blowing: after adsorption tower intensification desorption and regeneration finished, regeneration gas comprised that purified gas or nitrogen or purified gas and nitrogen mixture cold blowing to temperature are lower than 40 ℃;
(5) pressurising: adsorption tower is cooled to after temperature is lower than 40 ℃, this adsorption tower is pressurized to adsorptive pressure, pending next time absorption with the purified gas of the absorption cat head that is in adsorption step another this moment.
6. remove chloride in the chloride industrial mist according to purification claimed in claim 5 and reclaim the method for lighter hydrocarbons, it is characterized in that operating process of the present invention comprises: unstripped gas enters the adsorption separation system that is comprised of three adsorption towers by tower 1 bottom, chloride is adsorbed on the adsorbent, and adsorbent is one or more the adsorbent combinations in silica gel, active carbon, activated alumina or the carbon molecular sieve; Remove muriatic purified product gas and discharge adsorption separation system by tower 1 top, after purifying in the gas product chloride total content reach＜during the control index of 5ppm, unstripped gas switches to tower 2, tower 1 stops into unstripped gas, then tower 1 carries out the heat temperature raising desorb, be heated to 150～180 ℃ of design temperatures, and keep this temperature to finish to desorb, stripping gas is discharged by tower 1 bottom, 5～30% purified gas take capacity of returns as the purified gas total amount or nitrogen or purified gas and nitrogen mixture wash tower 1, and purging cooling, after purging cools to 20～40 ℃, tower 1 is carried out final pressurising boost to adsorptive pressure, treat next adsorption cycle, so tower 1 is finished whole absorbing process, tower 2,3 circulate with this, carry out the adsorption separation process of 3 adsorption towers, unstripped gas enters adsorption separation system continuously, and the gas product after the purification is discharged adsorption separation system continuously.
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