CN1350878A - Process for removing acidic gas by adsorption - Google Patents

Process for removing acidic gas by adsorption Download PDF

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Publication number
CN1350878A
CN1350878A CN 00123152 CN00123152A CN1350878A CN 1350878 A CN1350878 A CN 1350878A CN 00123152 CN00123152 CN 00123152 CN 00123152 A CN00123152 A CN 00123152A CN 1350878 A CN1350878 A CN 1350878A
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adsorbent
gas
adsorption bed
zone
rotary adsorption
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CN 00123152
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CN1132661C (en
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王玉亭
曾向东
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

A process for removing acidic harmful gas by rotary adsorption bed is disclosed, which features its continuous rotation mode for liquid-phase regeneration instead of gas-phase regeneration. It is suitable to purify the gas containing hydrogen sulfide, thiol and thioether. Its advantages include less investment to equipment and low operation cost.

Description

A kind of purification method of sour gas adsorbing and removing
The present invention relates to the purification method that a kind of gas absorption removes, particularly the gas continuous adsorption remove, the method for adsorbent cyclic regeneration.
Various industrial deodorization devices, living facilities etc. all often produce pernicious gas, particularly contain the gas of hydrogen sulfide, methyl mercaptan, methyl sulfide sulfides, can produce toxic action to environment.For the purification of this class pernicious gas, normally adopt methods such as adsorbing and removing, burning, washing, catalytic oxidation.
Adsorbing and removing is a kind of method of effective purifying harmful gas wherein, the kinds of processes form is arranged, as " the up-to-date trend of foul smell countermeasure technology " (day), J.Odor Research and Eng.Vol.28 No.2 P27,1997, mention ADSORPTION IN A FIXED BED method, thermopnore absorption method and rotary adsorption bed absorption method among the CN 2175637.Said method though in various degree clean-up effect is all arranged, all has defective in various degree in actual use.The ADSORPTION IN A FIXED BED method adopts and makes pernicious gas gas reach the method that purifies purpose by fixing adsorption bed, harmful substance because of being adsorbed to remove, its shortcoming is when adsorbent need be regenerated, this adsorption plant is shut down, just can carry out the regeneration or the replacing of adsorbent, as guarantee that purification process can carry out continuously, the above adsorption plant of the same type of two covers just should be set simultaneously, absorption/regeneration (replacing) process of adsorbent hockets, improved equipment investment, regenerative process is loaded down with trivial details, regeneration expense height.
The thermopnore absorption method adopts and makes adsorbent be the state of circulating between adsorption zone and renewing zone, in adsorption zone, the adsorbent that is flow regime contacts with the pernicious gas of big air quantity, harmful components are adsorbed and remove and reach the purification purpose, when the adsorbent stream of having adsorbed harmful components during through the renewing zone, make the method desorb that the desorption gas of little air quantity contacts with adsorbent and obtain regeneration, the little air quantity stripping gas that contains harmful components further carries out purified treatment again.This method can realize the regeneration of adsorbent in continuous purification run, but because adsorbent is in flow regime all the time, the wear rate height of adsorbent, consumption is big, operation easier is big and stripping gas also needs to handle with other gas processing method again, and the problem that its equipment investment is big, the regeneration expense is high is very outstanding.
The characteristics of rotary adsorption bed absorption method are that adsorbent is fixed on the rotary adsorption bed, described in " industrial coating " (day) NO.149 P59 and CN215637, rotary adsorption bed is in rotation status, be divided into adsorption zone and renewing zone two parts, the pernicious gas of big air quantity passes through rotary adsorption bed through adsorption zone, harmful components are removed because of adsorbing and removing, reach the purification purpose, when the adsorbent that has adsorbed harmful components moves to the renewing zone with rotary adsorption bed, make the air-breathing renewing zone of passing through of pyrolysis of little air quantity, adsorbent in the renewing zone obtains regeneration because of desorb, and the little air quantity stripping gas that contains harmful components further carries out purified treatment again.Although this method is fixed on the rotary adsorption bed because of adsorbent, reduced the attrition of adsorbent, operation control also obtains simplifying, but the same problem that needs further to handle stripping gas that exists, promptly need to handle the gas treatment facility of little air quantity, high concentration harmful components, equipment investment and the high problem of regeneration expense still exist.Therefore, need after-treatment, equipment investment and the regeneration expense of a kind of undesirable gas of exploitation low, easy and simple to handle, particularly can be used in the purification process technique of sulfide hydrogen sulfides foul gas.
The purpose of this invention is to provide a kind of after-treatment, equipment investment and regeneration expense cleaning harmful gas treatment process low, easy and simple to handle of eliminating gas.
Pernicious gas treatment process provided by the invention is: adopt rotary adsorption bed to carry out the absorption of pernicious gas, bed is divided into adsorption zone and renewing zone, pernicious gas passes through adsorption zone, rotation along with bed, the adsorbent that has adsorbed pernicious gas rotates to the renewing zone, use the liquid phase regenerative agent that the adsorbent that has adsorbed harmful gas is soaked regeneration in the renewing zone, the adsorbent after the regeneration rotates again gets back to adsorption zone, continues pernicious gas is adsorbed.
Method of the present invention can be handled various pernicious gases, foul gas as sulfide hydrogen, mercaptan, thioether sulfides, contain the sour gas of sulfur dioxide, sulfur trioxide, hydrogen fluoride, hydrogen chloride, hydrogen bromide etc., the inventive method is specially adapted to the processing of low concentration gases containing stench sulphureous gases.
The adsorbent that is applicable to the inventive method can be the material that active carbon, zeolite, diatomite particle, ion exchange resin etc. have adsorptivity, also can be according to the dissimilar adsorbent of the different choice of the difference of handled gas and regenerative agent kind or the combination of different adsorbents.
The regenerative agent that is applicable to the inventive method is an alkaline solution, can select a kind of in NaOH, potassium hydroxide or other alkaline solutions, perhaps several alkaline solutions is used in combination.Regeneration is an immersion type.
In the inventive method, the object component of processing can be class single kind or multiple; The volume ratio of handling tolerance and adsorbent consumption is: 0.5~32: 1; The total concentration of handling harmful components can reach 800 μ L/L, as: hydrogen sulfide 0~100 μ L/L, mercaptan 0~20 μ L/L, thioether 0~10 μ L/L, oxysulfide 0~800 μ L/L, hydrogen halides class 0~200 μ L/L etc.
The rotation mode of rotary adsorption bed can be continous way, and the adsorption zone in the rotary adsorption bed layer and the volume of renewing zone can be the same or different, and available ratio is 0.3~5: 1.The continuous rotary speed of rotary adsorption bed is 0.6~60 degree/min.The regenerative agent that uses is 1~50% alkali lye (as NaOH or potassium hydroxide); The mode of regeneration can adopt regenerative agent to soak form, and regenerative agent concentration should be changed after dropping to below 1%.The rotary adsorption bed layer is vertical rotation form.The volume of the regenerative agent that uses can determine that its consumption can be 0.01~500m according to the renewing zone size 3/ time.
Among the present invention, the processing of pernicious gas is carried out continuously by the rotary adsorption bed that is in rotation status.Pernicious gas is by rotary adsorption bed, and harmful components reach the purification purpose because of the suction-operated of adsorbent is removed.Along with the rotation of rotary adsorption bed, the adsorbent that has adsorbed harmful components is rotated the liquid renewing zone, and under the immersion of regenerative agent, harmful components are by physics or chemical reaction, and desorb is got off from adsorbent, makes adsorbent obtain regeneration.Adsorbent after the regeneration is rotated further with rotary adsorption bed, gets back to the gas absorption district again, once more pernicious gas is carried out adsorbing and removing.So go round and begin again, pernicious gas removes because of harmful components are adsorbed and obtains continuous purification, and adsorbent also obtains cyclic regeneration because of the immersion of regenerative agent.Contain the regenerated liquid that is removed composition, after simple neutralisation treatment, can introduce in the water processing establishment that generally uses at present and handle, do not need to set up again the regenerated liquid treatment facility, also having overcome existing gas phase regeneration need carry out the deficiency of purified treatment to the regeneration desorption gas, thereby has reduced equipment investment and operating cost.
In a word, the inventive method can be carried out the continuous adsorption and the regeneration of pernicious gas, regenerated liquid can utilize the water processing establishment that generally uses at present to handle, the after-treatment of undesirable gas, saved the equipment investment and the operating cost of gas after-treatment, the inventive method is simple to operate, and regenerative agent is easy to obtain, the regeneration expense is low, goes for multiple low concentration unwanted gas cleaning and handles.
Fig. 1 is the present invention program's a revolving bed operation chart.
Further specify the solution of the present invention and effect below by embodiment and accompanying drawing.
Embodiment 1
The rotary adsorption bed that use is made of acticarbon, purified treatment concentration of emission are 50 μ L/L, capacity 0.8m 3The sulfureted hydrogen foul gas of/min.
Adsorbent is filled in diameter 1m, on the circular rotary adsorption bed 1 of thick 0.1m, make rotary adsorption bed center on diameter 0.2m the rotating shaft zone, vertically rotate (as shown in drawings) continuously with the speed of 6 degree/min.As adsorption zone 2, hydrogen sulfide containing pernicious gas 3 is passed through on the top of rotary adsorption bed; The bottom of rotary adsorption bed is immersed in 1m as renewing zone 4 3In 4% the sodium hydroxide solution.The volume ratio of adsorbent is 3: 1 in adsorption zone 2 and the renewing zone 4.In adsorption zone 2, the hydrogen sulfide harmful components that pernicious gas 3 contains are adsorbed agent absorption and remove, and pernicious gas 3 is cleaned, and becomes Purge gas 5, and purifying rate reaches 100%.In renewing zone 4, continuous rotation along with rotary adsorption bed, the adsorbent that has adsorbed the hydrogen sulfide harmful components constantly enters in the sodium hydroxide solution soak 6, under the immersion of sodium hydroxide solution, because of factors such as chemical reactions, the hydrogen sulfide harmful components that are adsorbed on the adsorbent are got off by desorb, and adsorbent has recovered absorption property again, has realized regeneration; Adsorbent after the regeneration in the continuation rotation of rotary adsorption bed, is got back to the gas absorption district, once more the hydrogen sulfide pernicious gas is carried out adsorbing and removing.Like this, the hydrogen sulfide pernicious gas has obtained continuous adsorbing and removing in the continuous rotation of rotary adsorption bed, and simultaneously, the adsorbent that has adsorbed hydrogen sulfide also obtains continuous regeneration because of the immersion of sodium hydroxide solution.Used sodium hydroxide solution becomes regenerated liquid 7, mainly contains the not NaOH and the regeneration product SO of complete reaction 4 2-, S 2O 3 2-, SO 3 2-, through after the neutralisation treatment, can be introduced in the water processing establishment that generally adopts at present and handle, the double purification that does not need to carry out gas is handled.
Embodiment 2
Use is formed the rotary adsorption bed that adsorbent constitutes by active carbon and diatomite, and the purified treatment concentration of emission is hydrogen sulfide 10 μ L/L, methyl mercaptan 4 μ L/L, methyl sulfide 1.6 μ L/L, capacity 10m 3The foul gas of/min.
Adsorbent is filled in diameter 3m, on the circular rotary adsorption bed of thick 0.2m, make rotary adsorption bed center on diameter 0.2m the rotating shaft zone, be rotated with the speed of 1 degree/min.The volume ratio of adsorption zone and renewing zone adsorbent is 0.7: 1.The top of rotary adsorption bed as the gas absorption district, passes through the pernicious gas that contains above-mentioned harmful components, and harmful components are adsorbed agent absorption and remove, and pernicious gas is purified, and purifying rate reaches 100%; The bottom of rotary adsorption bed layer as the liquid renewing zone, is immersed in 5m 3In 20% the sodium hydroxide solution.Along with the continuous rotation of rotary adsorption bed, the adsorbent that has adsorbed the hydrogen sulfide harmful components constantly enters in the sodium hydroxide solution soak, and the immersion by sodium hydroxide solution makes adsorbent realize regeneration; Adsorbent after the regeneration in the continuation rotation of rotary adsorption bed, is got back to the gas absorption district again, once more the hydrogen sulfide pernicious gas is carried out adsorbing and removing.Like this, the hydrogen sulfide pernicious gas has obtained continuous adsorbing and removing in the continuous rotation of rotary adsorption bed, and simultaneously, the adsorbent that has adsorbed hydrogen sulfide also obtains continuous regeneration because of the immersion of sodium hydroxide solution.Used sodium hydroxide solution mainly contains the not NaOH and the regeneration product SO of complete reaction 4 2-, S 2O 3 2-, SO 3 2-, through after the neutralisation treatment, can be introduced in the water processing establishment that generally adopts at present and handle, the double purification that does not need to carry out gas is handled.
Embodiment 3
Use is formed the rotary adsorption bed that adsorbent constitutes by active carbon and diatomite, and the purified treatment concentration of emission is hydrogen sulfide 50 μ L/L, methyl mercaptan 20 μ L/L, tolerance 20m 3The sour gas of/min.
Adsorbent is filled in diameter 6m, on the circular rotary adsorption bed of thick 1m, make rotary adsorption bed center on diameter 0.2m the rotating shaft zone, be rotated with the speed of 60 degree/min.The volume ratio of adsorption zone and renewing zone adsorbent is 1: 1.The top of rotary adsorption bed as the gas absorption district, passes through the pernicious gas that contains above-mentioned harmful components, and harmful components are adsorbed agent absorption and remove, and pernicious gas is purified, and purifying rate reaches 100%; The bottom of rotary adsorption bed layer as the liquid renewing zone, is immersed in 30m 3In 40% the sodium hydroxide solution.Along with the continuous rotation of rotary adsorption bed, the adsorbent that has adsorbed the hydrogen sulfide harmful components constantly enters in the sodium hydroxide solution soak, and the immersion by sodium hydroxide solution makes adsorbent realize regeneration; Adsorbent after the regeneration in the continuation rotation of rotary adsorption bed, is got back to the gas absorption district again, once more the hydrogen sulfide pernicious gas is carried out adsorbing and removing.Like this, the hydrogen sulfide pernicious gas has obtained continuous adsorbing and removing in the continuous rotation of rotary adsorption bed, and simultaneously, the adsorbent that has adsorbed hydrogen sulfide also obtains continuous regeneration because of the immersion of sodium hydroxide solution.Used sodium hydroxide solution mainly contains the not NaOH and the regeneration product SO of complete reaction 4 2-, SO 3 2-, through after the neutralisation treatment, can be introduced in the water processing establishment that generally adopts at present and handle, the double purification that does not need to carry out gas is handled.

Claims (10)

1, the purification method that removes of a kind of rotary adsorption bed gas absorption, the rotary adsorption bed layer is divided into adsorption zone and renewing zone, pernicious gas passes through adsorption zone, rotation along with bed, the adsorbent that has adsorbed pernicious gas forwards the renewing zone to bed, use the liquid phase regenerative agent that the adsorbent that has adsorbed harmful gas is soaked regeneration in the renewing zone, the adsorbent after the regeneration continues rotation and gets back to adsorption zone.
2,, it is characterized in that described pernicious gas is a deleterious acidic gas, one or more in sulfide hydrogen, mercaptan, thioether, sulfur dioxide, sulfur trioxide, hydrogen fluoride, hydrogen chloride, the hydrogen bromide according to the method for claim 1.
3,, it is characterized in that described adsorbent is selected from active carbon, zeolite, diatomite particle, ion exchange resin according to the method for claim 1.
4,, it is characterized in that described regenerative agent is an alkaline solution according to the method for claim 1.
5,, it is characterized in that described rotary adsorption bed is vertical rotation according to the method for claim 1 or 4.
6,, it is characterized in that the rotation mode of described rotary adsorption bed is rotation continuously according to the method for claim 1.
7,, it is characterized in that rotary adsorption bed adopts the continuous rotation of 0.6~60 degree/min according to the method for claim 1 or 6.
8, according to the method for claim 1 or 2, the concentration that it is characterized in that handled harmful components is: hydrogen sulfide 0~50 μ L/L, mercaptan 0~10 μ L/L, thioether 0~5 μ L/L, sulfur dioxide 0~800 μ L/L, sulfur trioxide 0~600 μ L/L, hydrogen fluoride 0~200 μ L/L, hydrogen chloride 0~200 μ L/L, hydrogen bromide concentration 0~200 μ L/L.
9,, it is characterized in that the adsorption zone in the rotary adsorption bed layer and the volume ratio of renewing zone are 0.3~5: 1 according to the method for claim 1.
10,, it is characterized in that described regenerative agent is NaOH, the potassium hydroxide solution of 1~50W% according to the method for claim 1 or 4.
CN 00123152 2000-10-26 2000-10-26 Process for removing acidic gas by adsorption Expired - Lifetime CN1132661C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102527298A (en) * 2011-12-15 2012-07-04 昆明理工大学 Circular ring type continuous feed fixed bed reactor
CN108273353A (en) * 2018-01-08 2018-07-13 深圳市玖品空气净化科技有限公司 A kind of organic waste gas treatment equipment with adsorbent reactivation function

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102527298A (en) * 2011-12-15 2012-07-04 昆明理工大学 Circular ring type continuous feed fixed bed reactor
CN102527298B (en) * 2011-12-15 2014-09-03 昆明理工大学 Circular ring type continuous feed fixed bed reactor
CN108273353A (en) * 2018-01-08 2018-07-13 深圳市玖品空气净化科技有限公司 A kind of organic waste gas treatment equipment with adsorbent reactivation function

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Granted publication date: 20031231