CN1393278A - Adsorptive process for removing acidic stink gas - Google Patents

Adsorptive process for removing acidic stink gas Download PDF

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Publication number
CN1393278A
CN1393278A CN 01114180 CN01114180A CN1393278A CN 1393278 A CN1393278 A CN 1393278A CN 01114180 CN01114180 CN 01114180 CN 01114180 A CN01114180 A CN 01114180A CN 1393278 A CN1393278 A CN 1393278A
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adsorbent
zone
gas
adsorption bed
hydrogen
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CN1242832C (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 stink gas by adsorption bed features that a rotary adsorption bed in used to remove the acidic harmful gas containing hydrogen sulfide, thiol and thioether, the continuous rotation mode is used for sprinking, washing and so regenerating the liquid-phase regenerating agent, and the regenerating liquid can be treated by the ordinary water-treating equipment. Its advantages are low cost and high effect.

Description

The purification method of acid foul 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 ADSORPTION IN A FIXED BED method, thermopnore absorption method and rotary adsorption bed absorption method.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, just should be with the above adsorption plant of the same type of two covers is set, 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.149P59 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 invention provides 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 carried out spray washing 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 the spray washing formula.
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 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.
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 spray washing form, and regenerative agent can recycle, and changes when wherein alkali content drops to a certain degree.The rotary adsorption bed layer is to horizontally rotate or the rotation form of other modes.The spray washing intensity of the regenerative agent that uses can determine that its consumption can be 0.01~500m according to the renewing zone size 3/ min.
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 spray washing 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 spray washing 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 revolving bed structural representation that the inventive method is used.
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, horizontally 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 a side of rotary adsorption bed 1; The opposite side of rotary adsorption bed 1 makes 4% NaOH regenerative agent 5 regenerated from washing districts 4 as renewing zone 4 with the mode that sprays.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 become Purge gas 6, and purifying rate reaches 100%; Along with the continuous rotation of rotary adsorption bed 1, adsorbed the adsorbent of hydrogen sulfide harmful components, constantly enter in the renewing zone 4, (spraying intensity is 4m at the spray washing of 4% NaOH regenerative agent 5 3/ min) under, because of factors such as chemical reactions, the hydrogen sulfide harmful components that are adsorbed on the adsorbent are got off by desorb, adsorbent has recovered absorption property again, has realized regeneration; Adsorbent after the regeneration in the continuation rotation of rotary adsorption bed 1, is got back to adsorption zone 2, once more pernicious gas 3 is carried out adsorbing and removing.Like this, pernicious gas 3 has obtained continuous adsorbing and removing in the continuous rotation of rotary adsorption bed 1, and simultaneously, the adsorbent that has adsorbed hydrogen sulfide also obtains continuous regeneration because of the spray washing of NaOH regenerative agent 5.Used NaOH regenerative agent 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, diatomite, ion exchange resin and zeolite, purified treatment capacity 20m 3/ min, concentration of emission are the foul gas of hydrogen sulfide 40 μ L/L, methyl mercaptan 0.6 μ L/L, methyl sulfide 2 μ L/L, sulfur dioxide 500 μ L/L, hydrogen fluoride 100 μ L/L, hydrogen chloride 180 μ L/L.
Adsorbent is filled in diameter 5m, on the circular rotary adsorption bed of thick 0.5m, make rotary adsorption bed center on diameter 0.2m the rotating shaft zone, horizontally rotate continuously with the speed of 40 degree/min.The volume ratio of adsorption zone and renewing zone adsorbent is 0.44: 1.Rotary adsorption bed is divided into adsorption zone and renewing zone two parts, makes the pernicious gas that contains above-mentioned harmful components by the gas absorption district, and above-mentioned harmful components are adsorbed agent absorption, and pernicious gas is purified, and purifying rate reaches 100%; In the renewing zone, with 25% NaOH regenerative agent spray washing renewing zone, spraying intensity is 120m 3/ min makes the harmful components that are adsorbed on the adsorbent be got off by desorb, and adsorbent has recovered absorption property again, has realized regeneration; Adsorbent after the regeneration is got back to adsorption zone, once more to purifying in the pernicious gas with the continuation rotation of rotary adsorption bed.Like this, above-mentioned harmful components have obtained continuous adsorbing and removing in the continuous rotation of rotary adsorption bed, and simultaneously, the adsorbent that has adsorbed harmful components also obtains continuous regeneration because of the spray washing of regenerative agent.Used regenerative agent 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.

Claims (9)

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 carried out spray washing regeneration in the renewing zone, the adsorbent after the regeneration continues rotation and gets back to adsorption zone.
2, according to the method for claim 1, the rotation mode that it is characterized in that described rotary adsorption bed is level rotation or other rotation modes continuously.
3,, 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 2.
5,, it is characterized in that described regenerative agent is an alkaline solution according to the method for claim 1.
6,, it is characterized in that described regenerative agent is sodium hydroxide solution, the potassium hydroxide solution of 1~50W% according to the method for claim 1 or 5.
7,, 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.
8,, it is characterized in that in described pernicious gas sulfide hydrogen, mercaptan, thioether, sulfur dioxide, sulfur trioxide, hydrogen fluoride, hydrogen chloride, the hydrogen bromide one or more according to the method for claim 1.
9, according to the method for claim 1 or 8, 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.
10,, 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.
CN 01114180 2001-07-02 2001-07-02 Adsorptive process for removing acidic stink gas Expired - Lifetime CN1242832C (en)

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Cited By (7)

* 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
CN104549138A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Ni-containing molecular sieve adsorbent and preparation method thereof
CN105903308A (en) * 2016-05-23 2016-08-31 天津市环境保护技术开发中心设计所 Organic exhaust gas treatment method and organic exhaust gas treatment system
CN111282380A (en) * 2020-03-26 2020-06-16 河南中白环境科学技术研究院有限公司 Treatment process and treatment device for high-concentration hydrogen sulfide gas
CN111282395A (en) * 2020-03-26 2020-06-16 河南中白环境科学技术研究院有限公司 Low-concentration hydrogen sulfide gas treatment process and treatment device
CN111825150A (en) * 2020-06-11 2020-10-27 上海市政工程设计研究总院(集团)有限公司 In-situ regeneration adsorption deodorization type sewage pressure pipeline ventilating device
CN113230866A (en) * 2021-06-10 2021-08-10 广州市华英防腐设备有限公司 Glass fiber reinforced plastic acid mist purification tower

Cited By (10)

* 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
CN104549138A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Ni-containing molecular sieve adsorbent and preparation method thereof
CN104549138B (en) * 2013-10-28 2017-09-15 中国石油化工股份有限公司 Adsorbent of molecular sieve containing Ni and preparation method thereof
CN105903308A (en) * 2016-05-23 2016-08-31 天津市环境保护技术开发中心设计所 Organic exhaust gas treatment method and organic exhaust gas treatment system
CN105903308B (en) * 2016-05-23 2019-09-03 天津市环境保护技术开发中心设计所 The processing method and its organic waste gas treatment system of organic exhaust gas
CN111282380A (en) * 2020-03-26 2020-06-16 河南中白环境科学技术研究院有限公司 Treatment process and treatment device for high-concentration hydrogen sulfide gas
CN111282395A (en) * 2020-03-26 2020-06-16 河南中白环境科学技术研究院有限公司 Low-concentration hydrogen sulfide gas treatment process and treatment device
CN111825150A (en) * 2020-06-11 2020-10-27 上海市政工程设计研究总院(集团)有限公司 In-situ regeneration adsorption deodorization type sewage pressure pipeline ventilating device
CN113230866A (en) * 2021-06-10 2021-08-10 广州市华英防腐设备有限公司 Glass fiber reinforced plastic acid mist purification tower

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