CN105567341A - Wet purification apparatus for coke oven gas - Google Patents

Wet purification apparatus for coke oven gas Download PDF

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Publication number
CN105567341A
CN105567341A CN201510978062.4A CN201510978062A CN105567341A CN 105567341 A CN105567341 A CN 105567341A CN 201510978062 A CN201510978062 A CN 201510978062A CN 105567341 A CN105567341 A CN 105567341A
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CN
China
Prior art keywords
gas
coke
column
thionizer
tower
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510978062.4A
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Chinese (zh)
Inventor
蒲安斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan Aviation Tube Industry Co Ltd
Original Assignee
Sichuan Aviation Tube Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan Aviation Tube Industry Co Ltd filed Critical Sichuan Aviation Tube Industry Co Ltd
Priority to CN201510978062.4A priority Critical patent/CN105567341A/en
Publication of CN105567341A publication Critical patent/CN105567341A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/002Removal of contaminants
    • C10K1/003Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004Sulfur containing contaminants, e.g. hydrogen sulfide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/002Removal of contaminants
    • C10K1/003Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/005Carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/002Removal of contaminants
    • C10K1/003Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/006Hydrogen cyanide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/08Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/08Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/16Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
    • C10K1/18Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids hydrocarbon oils

Abstract

The invention discloses a wet purification apparatus for coke oven gas, comprising a primary cooling column, an electric tar precipitator, a precooling column, an ammonia remover, a desulfurizing column, a final cooling column, and a benzol scrubber that are in successively connection with a coke oven gas pipe. The benzol scrubber is provided with a purified gas outlet, and a regenerating column which provides a desulfurizing liquid is connected to the desulfurizing column. A purification process implemented by the apparatus includes the steps: after cooling, tar removal and ammonia removal, feeding the coke oven gas to the desulfurizing column, sprinkling in the desulfurizing column the desulfurizing liquid from the regenerating column, and after acidic gases in the ammonia-remove coal gas such as H2S, HCN and CO2 are absorbed by the desulfurizing liquid, cooling and removing benzol to obtain purified coal gas. The purified coal gas is directly applicable to urban civil use, metallurgical use and the like, and the desulfurizing rate is up to 98 %.

Description

A kind of Wet purifier of coke-oven gas
Technical field
The present invention is a kind of Wet purifier of coke-oven gas, is specifically related to the purification treatment technology of objectionable impurities in coke-oven gas, belongs to waste gas pollution control and treatment field.
Background technology
Coke-oven gas is the by product produced in process of coking, and China is coking big country, produces 320m by dry coal per ton 3coke-oven gas calculates, and the coke-oven gas of the annual discharge in the whole nation can reach more than 640 billion cubic meters.At present, coke-oven gas is widely used in fuel, the aspects such as industrial chemicals, we know, multiple gases component is contained without in the coke-oven gas of purification, especially containing tar, naphthalene, prussic acid, the organosulfur etc. of hydrogen sulfide and various structures complexity, when using for fuel, particularly coke-oven gas because of its calorific value high, CO content is low, be usually used in city civilian, because the sulphur in coking feed coal proceeds to coal gas mainly with the form of hydrogen sulfide, easily produce sulfurous gas in combustion, not only air is polluted, also larger toxic is had to human body, and to gas line, coal gas relevant device and combustion gas have serious corrosive nature, during for industrial chemicals, can act on iron and steel enterprise's refining steel, but the content of hydrogen sulfide in coke oven then can reduce steel product quality, therefore, coke-oven gas must carry out desulfurization process before use.
Example is treated to desulfurization, existing desulfuration processing method of coke oven gas mainly contains dry desulfurization and wet desulphurization two kinds, dry desulfurization is by the sweetening agent containing ironic hydroxide by coke-oven gas, ironic hydroxide and hydrogen sulfide are reacted and generates iron sulphide or Iron sulfuret, after saturated, sweetening agent is contacted with air, when there being moisture to exist, the sulphidic conversion of iron is become oxide compound by the oxygen in air, and desulfurizer regeneration uses continuously and is generally applicable to gas yield at the less coal chemical enterprise of below 8000/h scale; The doctor solution counter current contact of spraying with tower top after wet desulphurization refers to coal gas feeding thionizer, after hydrogen sulfide in coal gas is absorbed by absorbent solution, discharged by tower top, sweetening agent in absorption liquid and hydrogen sulfide reacting generating compound, sulfur removing pregnant solution contacts with air, oxidizing reaction occurs, and is desulfurization regeneration, the process that elemental sulfur is separated out.
On the basis of existing desulfurization wet processing, patent documentation CN101250440(wet desulfurization system and sulfur removal technology thereof, 2008-08-27) propose a kind of blocking that can effectively eliminate melt flow still that elemental sulfur causes and waste liquid tank, ensure the wet desulfurizing process of the normal running continuously of pipeline and each sweetener, operating environment and the intensity of wet desulfurization system can be alleviated.But along with the enhancing of industrial development and environmental protection consciousness; particularly metallurgical works; there has also been higher requirement to the sulphur content of the coke gas that the rolling of high quality steel uses, therefore, a kind of high-level efficiency, oligosaprobic purification process are the task of top priority processing coke gas at present.
Summary of the invention
The object of the present invention is to provide a kind of Wet purifier of coke-oven gas, the purification process that this device realizes be coke-oven gas through cooling, tar removing, deliver to thionizer except after ammonia, the doctor solution in regenerator column sprays in thionizer, except the H in the coal gas after ammonia 2s, HCN, CO 2be desulfurized after liquid absorbs Deng sour gas, then carry out lowering the temperature, except naphthalene, being purified coal gas, this purification coal gas can be directly used in the uses such as city is civilian, metallurgical industry, and desulfurization degree is up to 98%.
The present invention is achieved through the following technical solutions: a kind of Wet purifier of coke-oven gas, comprise be connected with coke-oven coal tracheae successively first cold tower, electrical tar precipitator, precooling tower, Ammonia removing machine, thionizer, final cooling tower, wash benzene tower, be provided with purification gas exit washing on benzene tower, thionizer is connected with the regenerator column providing doctor solution.
Coke-oven gas produces by process of coking, its temperature is higher, first cold tower adopts air to carry out heat exchange, first cold rear coke-oven gas temperature controls between 85 ~ 120 DEG C, electrical tar precipitator utilizes mechanize clarification or tar and ammonia water separation hopper two kinds of modes to be separated with coal gas by tar, temperature controls after 60 ~ 80 DEG C by precooling tower by coal gas, delivers to thionizer by Ammonia removing machine except after ammonia, sprays by the doctor solution from regenerator column the H removed in coal gas 2s, HCN, CO 2after sour gas, deliver to final cooling tower again to lower the temperature, gas temperature can control below 50 DEG C by final cooling tower, prevent coal gas of high temperature through washing benzene tower except the blocking caused during naphthalene, wash benzene tower and adopt oil wash naphthalene mode, utilize washing oil to wash coal gas and absorb naphthalene wherein, generally the naphthalene amount that contains of coal gas can be down to 0.5g/m 3below, wash benzene tower and can obtain purification coal gas except after naphthalene, and deliver to user by purification gas exit.
This process system desulfuration efficiency is high, and the coal gas after purification reaches town gas standard, and coal gas is after thionizer, and hydrogen sulfide content can drop to 0.02g/m 3, prussic acid can drop to 0.1g/m 3.
In the present invention, the epimere of described thionizer is provided with NaOH washing section, and thionizer top is provided with the gas exit be connected with Ammonia removing machine, and thionizer hypomere is provided with the gas entry be connected with precooling tower, the doctor solution entrance be connected with regenerator column and rich solution and exports.
Coal gas sends into the hypomere of thionizer by gas entry, and the lean solution from regenerator column is sprayed to the hypomere of thionizer by doctor solution entrance, washs, remove the H in coal gas to the coal gas sent into 2s, HCN, CO 2deng sour gas, the coal gas after washing delivers to final cooling tower with after the NaOH solution washing of 5% by the gas exit at thionizer top through NaOH washing section; Washings delivers to regenerator column from rich solution outlet, and regenerator column regenerates washings, separates out sour gas H 2s, HCN, CO 2rear obtained lean solution, then deliver to by doctor solution entrance the desulfurization process that thionizer continues next round coal gas.
The present invention is reasonable in design, the pipeline that connection regenerator column and doctor solution entrance, regenerator column and rich solution export is connected with container for storing liquid, for when system overhaul, with pump, the feed liquid in thionizer and regenerator column is delivered to container for storing liquid, during driving, again the feed liquid in container for storing liquid is delivered to regenerator column, deliver to thionizer after regeneration and start desulfurization process.
Described Ammonia removing machine is the Spray Saturator being provided with the outlet of sulphur ammonium, in actual industrial process, Spray Saturator comes from sulphur ammonium production section, coal gas sends into the Spray Saturator of ammonium sulfate workshop section, spray with the circulating mother liquor containing free acid amount (sulfuric acid) 3.5 ~ 45% in Spray Saturator, circulating mother liquor forms sulphur ammonium after absorbing the ammonia in coal gas, through Spray Saturator except ammonia quantity in the coal gas after ammonia is generally less than 0.05g/m 3.
Gas blower is connected with between described electrical tar precipitator and precooling tower, coal gas after tar removing is sent into precooling tower by gas blower and is lowered the temperature, gas blower can reduce the temperature of coal gas on the one hand, the water content of coal gas can also be reduced on the other hand, can improve the purification efficiency of follow-up coal gas to a certain extent, practical effect is good.
For reducing environmental pollution, improve the purification efficiency of coke-oven gas, described regenerator column is provided with acid gas outlet, the outlet of this acid gas is connected with Cross unit, and the offgas outlet of Cross unit is connected with coke-oven coal tracheae, simultaneously, elemental sulfur in sour gas can also remove by Cross unit, for the production of sulphur, after sulphur recovery, can be used for the field such as medicine, chemical industry, enrich the diversity of derived product.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) the process system desulfuration efficiency that the present invention relates to is high, and the coal gas after purification can be directly used in the uses such as city is civilian, metallurgical industry, and after desulfurizing and purifying, hydrogen sulfide content can drop to 0.02g/m 3, prussic acid can drop to 0.1g/m 3.
(2) the present invention adopts the design of container for storing liquid, for when system overhaul, with pump, the feed liquid in thionizer and regenerator column is delivered to container for storing liquid, during driving, with pump, the feed liquid in container for storing liquid is delivered to regenerator column again, deliver to thionizer after regeneration and start desulfurization process, be convenient to maintenance and the system maintenance of equipment.
(3) coal gas after the present invention utilizes gas blower tar removing is sent into precooling tower and is lowered the temperature, gas blower can reduce the temperature of coal gas on the one hand, can also reduce the water content of coal gas on the other hand, can improve the purification efficiency of follow-up coal gas to a certain extent, practical effect is good.
(4) the present invention by regenerator column to washings resolve after recycle again, the sour gas parsed produces sulphur for reclaiming through Cross unit again, tail gas delivers to the process of coke-oven gas circularly purifying again, the secondary pollution of the environment avoided, and is suitable for extensively promoting the use of.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the embodiment of the present invention 1.
Fig. 2 is the process flow sheet of the embodiment of the present invention 2.
Wherein, 1-coke-oven coal tracheae, 2-purification gas exit, 3-NaOH washing section, 4-gas exit, 5-gas entry, 6-doctor solution entrance, 7-rich solution exports, and 8-sulphur ammonium exports, and 9-acid gas exports, 10-offgas outlet.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment:
Fig. 1 is the process flow sheet of the Wet purifier of the coke-oven gas that the present embodiment relates to, as shown in Figure 1, this device primarily of the first cold tower be connected with coke-oven coal tracheae successively, electrical tar precipitator, precooling tower, Ammonia removing machine, thionizer, final cooling tower, wash benzene tower and form, purification coal gas delivers to user by the purification gas exit washed on benzene tower, the regenerator column that thionizer connects for providing doctor solution to thionizer, for removing the sulfide and prussiate etc. in coal gas.
In actual industrial production, first coke-oven gas delivers to just cold tower by coke-oven coal tracheae 1, through electrical tar precipitator tar removing, precooling tower is cooled to 60 ~ 80 DEG C, Ammonia removing machine is except after ammonia, thionizer hypomere is sent into by gas entry 5, because the doctor solution entrance 6 of thionizer is connected with regenerator column respectively with rich solution outlet 7, therefore, the coal gas sending into thionizer hypomere is washed by doctor solution, the washings formed exports 7 by rich solution again and delivers to regenerator column, after regenerator column regeneration, send into thionizer by doctor solution entrance 6 be again used as doctor solution use, send into the coal gas of thionizer hypomere after doctor solution washing, be stripped of the H in coal gas 2s, HCN, CO 2deng sour gas, and then through the NaOH washing section 3 of thionizer epimere, deliver to final cooling tower with after the NaOH solution washing of 5% by gas exit 4, in the coal gas after thionizer, hydrogen sulfide content is down to 0.02g/m 3, prussic acid is down to 0.1g/m 3, final cooling tower will be cooled to less than 50 DEG C except coal gas, then deliver to and wash benzene tower except naphthalene, and the purification coal gas of acquisition delivers to user by purification gas exit 2 again, and the desulfurizing and purifying rate of system can reach 98%.
In actual mechanical process, for convenience of system maintenance and overhaul of the equipments, the present embodiment exports on the pipeline of 7 at connection regenerator column and doctor solution entrance 6, regenerator column and rich solution and is also connected with container for storing liquid, as shown in Figure 1, before system overhaul, the feed liquid in thionizer and regenerator column is delivered to container for storing liquid and is sealed up for safekeeping by available pump, after having overhauled, again by the feed liquid in container for storing liquid with being pumped to regenerator column, after system is driven, feed liquid is delivered to thionizer and is started desulfurization process after regeneration.
Embodiment 2:
The difference of the present embodiment and embodiment 1 is: as shown in Figure 2, the present embodiment adds gas blower on the basis of embodiment 1, gas blower is arranged between electrical tar precipitator and precooling tower, coal gas after tar removing is sent into precooling tower by gas blower and is carried out cooling process, gas blower can reduce the temperature of coal gas on the one hand, can also reduce the water content of coal gas on the other hand, can improve the subsequent purification efficiency of coal gas to a certain extent, practical effect is good.
As shown in Figure 2, the Ammonia removing machine that the present embodiment relates to is the Spray Saturator being provided with sulphur ammonium outlet 8, in actual industrial process, Spray Saturator comes from sulphur ammonium production section, coal gas sends into the Spray Saturator of ammonium sulfate workshop section, spray with the circulating mother liquor containing free acid amount (sulfuric acid) 3.5 ~ 45% in Spray Saturator, circulating mother liquor forms sulphur ammonium after absorbing the ammonia in coal gas, through Spray Saturator except ammonia quantity in the coal gas after ammonia is generally less than 0.05g/m 3.
As shown in Figure 2, the present embodiment also add Cross unit on the basis of embodiment 1, and the washings of regenerator column to thionizer regenerates, the sour gas H of precipitation 2s, HCN, CO 2send Deng by the acid gas outlet 9 on regenerator column, then through vacuum pumping to Cross unit, the offgas outlet 10 of this Cross unit is connected with coke-oven coal tracheae 1 again.When reality uses, elemental sulfur in sour gas can remove by Cross unit, for the production of sulphur, the field such as medicine, chemical industry is can be used for after sulphur recovery, deviate from the gas tail gas after elemental sulfur and deliver to coke-oven coal tracheae 1 by offgas outlet 10, the temperature of coke-oven gas can be reduced on the one hand, can purify tail gas at this on the other hand, reduce secondary pollution, improve the purification efficiency of coke-oven gas.
The above is only preferred embodiment of the present invention, and not do any pro forma restriction to the present invention, every any simple modification, equivalent variations done above embodiment according to technical spirit of the present invention, all falls within protection scope of the present invention.

Claims (6)

1. the Wet purifier of a coke-oven gas, it is characterized in that: comprise be connected with coke-oven coal tracheae (1) successively first cold tower, electrical tar precipitator, precooling tower, Ammonia removing machine, thionizer, final cooling tower, wash benzene tower, benzene tower is provided with purification gas exit (2) washing, thionizer is connected with the regenerator column providing doctor solution.
2. the Wet purifier of a kind of coke-oven gas according to claim 1, it is characterized in that: the epimere of described thionizer is provided with NaOH washing section (3), thionizer top is provided with the gas exit (4) be connected with final cooling tower, and thionizer hypomere is provided with the gas entry (5) be connected with Ammonia removing machine, the doctor solution entrance (6) be connected with regenerator column and rich solution and exports (7).
3. the Wet purifier of a kind of coke-oven gas according to claim 2, is characterized in that: on the pipeline connecting regenerator column and doctor solution entrance (6), regenerator column and rich solution and export (7), be connected with container for storing liquid.
4. the Wet purifier of a kind of coke-oven gas according to claim 1, is characterized in that: described Ammonia removing machine is for being provided with the Spray Saturator of sulphur ammonium outlet (8).
5. the Wet purifier of a kind of coke-oven gas according to claim 1, is characterized in that: between described electrical tar precipitator and precooling tower, be connected with gas blower.
6. the Wet purifier of a kind of coke-oven gas according to any one of Claims 1 to 5, it is characterized in that: on described regenerator column, be provided with acid gas outlet (9), this acid gas outlet (9) is connected with Cross unit, and the offgas outlet (10) of Cross unit is connected with coke-oven coal tracheae (1).
CN201510978062.4A 2015-12-23 2015-12-23 Wet purification apparatus for coke oven gas Pending CN105567341A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
CN201510978062.4A CN105567341A (en) 2015-12-23 2015-12-23 Wet purification apparatus for coke oven gas

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107511048A (en) * 2017-09-08 2017-12-26 中冶焦耐(大连)工程技术有限公司 A kind of Claus tail gases condensation process technique
CN111662753A (en) * 2020-05-08 2020-09-15 广东韶钢松山股份有限公司 Tandem type coke oven gas final cooling purification equipment and process thereof
CN113604258A (en) * 2021-08-18 2021-11-05 国家电投集团远达环保装备制造有限公司 Coke oven gas desulfurization method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107511048A (en) * 2017-09-08 2017-12-26 中冶焦耐(大连)工程技术有限公司 A kind of Claus tail gases condensation process technique
CN111662753A (en) * 2020-05-08 2020-09-15 广东韶钢松山股份有限公司 Tandem type coke oven gas final cooling purification equipment and process thereof
CN113604258A (en) * 2021-08-18 2021-11-05 国家电投集团远达环保装备制造有限公司 Coke oven gas desulfurization method

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Application publication date: 20160511