CN109331636A - A kind of preprocess method of desulfurizing agent carbide slag - Google Patents

A kind of preprocess method of desulfurizing agent carbide slag Download PDF

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Publication number
CN109331636A
CN109331636A CN201811404329.9A CN201811404329A CN109331636A CN 109331636 A CN109331636 A CN 109331636A CN 201811404329 A CN201811404329 A CN 201811404329A CN 109331636 A CN109331636 A CN 109331636A
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CN
China
Prior art keywords
carbide slag
desulfurizing agent
filtrate
slurries
desulfurization
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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
CN201811404329.9A
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Chinese (zh)
Inventor
毛焱明
张进萍
张绍波
阚中华
邹玲玲
常万彬
庞济林
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YIBIN HAIFENG HERUI CO Ltd
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YIBIN HAIFENG HERUI CO Ltd
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Publication date
Application filed by YIBIN HAIFENG HERUI CO Ltd filed Critical YIBIN HAIFENG HERUI CO Ltd
Priority to CN201811404329.9A priority Critical patent/CN109331636A/en
Publication of CN109331636A publication Critical patent/CN109331636A/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/80Semi-solid phase processes, i.e. by using slurries
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/50Sulfur oxides
    • B01D53/501Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases

Abstract

The invention discloses a kind of preprocess methods of desulfurizing agent carbide slag, and carbide slag slurries are carried out separation of solid and liquid removing carbide slag filtrate and obtain carbide slag filter cake, carbide slag filter cake is configured to desulfurizing agent carbide slag slurries using desulfurized gypsum filtrate.Carbide slag slurries are separated by solid-liquid separation by the present invention, removing 90% or more sulfide, phosphide etc. in carbide slag influences the reducing substances of gypsum crystal shapes and sizes, the sulfur dioxide removal effect of resulting desulfurizing agent carbide slag slurries greatly improves, the oxidation efficiency of calcium sulfite is improved simultaneously, and oxidation efficiency can achieve 85% or more;The dehydration rate of desulfurization slurry is improved, the moisture content of resulting desulfurized gypsum is reduced to 20% by 50% or so and is sold hereinafter, can be used as product, turned waste into wealth, and brings economic benefit for enterprise;Carbide slag filtrate and desulfurized gypsum filtrate realize resource comprehensive and recycle simultaneously, meet today's society and promote industry clean manufacturing, the requirement of developing crcycle economy.

Description

A kind of preprocess method of desulfurizing agent carbide slag
Technical field
The present invention relates to the recovery and utilization technology of waste residue in a kind of production of acetylene from calcium carbide, especially a kind of carbide slag is located in advance The method of reason.
Background technique
Carbide produces polyvinyl chloride (PVC), process occurs for the acetylene of chlorovinyl alcohol (PVA) device, and generation is a large amount of secondary The key reaction of product carbide slag slurries, hydrolysis is: CaC+2H2O=C2H2+Ca(OH)2, it can be seen that carbide slag from reaction equation The main ingredient of slurry is Ca (OH)2, produce the C of an equivalent2H2The carbide slag of identical equivalent will be generated.Under normal circumstances, wet The carbide slag slurries solid content being discharged in formula generator is 5%~15%, and water content is 85%~95%, is in liquid (suspension) State, at aqueous about 40% solid slag, i.e., wet carbide slag after filters pressing.Since wet carbide slag quantity is larger, transportation cost Higher, the wet carbide slag generated at present is most of to be handled using stacking on the spot or by the way of filling.Preciousness is not only taken up in this way Land resource, and large effect is also produced to air, surface water and groundwater.
Since the main component of carbide slag is calcium hydroxide, lime can be replaced to make desulfurizing agent de- for power-plant flue gas Sulphur, product can aerating oxidation be further made desulfurized gypsum realize resource utilization.Calcium hydroxide and fuel sulphur oxide Reaction are as follows:
Ca(OH)2+SO2=CaSO3·1/2H2O+1/2H2O
CaSO3·1/2H2O+3/2H2O+1/2O2=CaSO4·2H2O
CaSO3·1/2H2O+1/2H2O+SO2=Ca (HSO3)2
CaSO3·1/2H2O+3/2H2O+1/2O2=CaSO4·2H2O
Contain many impurity, such as sulfide, phosphide and the substance SiO for easily forming colloidal attitude in carbide slag slurries2And Iron, magnesium, oxide of aluminium etc., these impurity will affect the shapes and sizes of gypsum crystal, they can preferentially in conjunction with oxygen and It is oxidized;In addition, the metal oxide in carbide slag may wrap up calcium sulfite, contact of the calcium sulfite with oxygen is influenced, These factors will lead to that the calcium sulfite reactivity formed after desulfurization is poor, and the difficulty that oxidation process is completed in desulfurizing tower is larger, Reduce oxidation rate.Bigger tower reactor volume and oxidized input air are thus needed, this adds increased investment cost and operating costs.Cause This, carbide slag desulfurization oxidation technology is flue gas desulfurization technique urgent problem to be solved.
It is de- that the Chinese invention application of Publication No. CN106582246A discloses a kind of carbide slag wet flue gas desulfurization simultaneously Nitre technique is that flue gas to be clean is passed through absorbing reaction device, and flue gas comes into full contact with absorbing liquid in the reactor, in flue gas NOx、SO2It is absorbed after-purification discharge, the absorbing liquid is the slurry being configured to by carbide slag, potassium permanganate and chloric strong oxidant Liquid.Chloric strong oxidant is dissolved in water and generates ClO-、ClO2-Etc. strong oxidizing properties ion, NO can be aoxidized, generate NO3-、Cl-Deng production Object, absorbent are dissolved in water in alkalescent, hydrolyze the OH of generation-With SO2Reaction generates SO3 2-And SO4 2-Ion, to remove flue gas In NOx and SO2.This method removes SO by the way that potassium permanganate and chloric strong oxidant are added in carbide slag slurries2, improve The cost of investment of flue gas desulfurization.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preprocess methods of desulfurizing agent carbide slag, and this method is not The reducing substances in carbide slag sweetening process can be only effectively removed, and solve that coal-burning boiler desulphurization cost is high to ask Topic.
The technical solution adopted by the present invention to solve the technical problems is: a kind of pretreatment side of desulfurizing agent carbide slag Method, carbide slag slurries be separated by solid-liquid separation removes carbide slag filtrate and obtains carbide slag filter cake, using desulfurized gypsum filtrate by carbide slag Filter cake is configured to desulfurizing agent carbide slag slurries.
Preferably, the solid content of the desulfurizing agent carbide slag slurries is 10~20%.
Preferably, the carbide slag filter cake moisture content is 10~20%.
Preferably, the desulfurized gypsum filtrate comes from means of flue gas desulfurization of power plant, i.e. carbide slag is used for power plant as desulfurizing agent Flue gas desulfurization obtains desulfurization slurry after generating the further aerating oxidation of product, then carries out being separated by solid-liquid separation up to desulfurized gypsum and taking off Sulphur gypsum filtrate.
Preferably, the desulfurized gypsum moisture content is 10~20%, can be used as the additive of manufacture of cement.
Preferably, the carbide slag filtrate returns to acetylene generation process and reacts instead of water with calcium carbide.
Preferably, the separation of solid and liquid selects plate and frame type filter-press to carry out filters pressing.
The beneficial effects of the present invention are: carbide slag slurries are separated by solid-liquid separation by the present invention, remove 90% or more in carbide slag Sulfide, phosphide etc. influence the reducing substances of gypsum crystal shapes and sizes, resulting desulfurizing agent carbide slag slurries Sulfur dioxide removal effect greatly improves, while improving the oxidation efficiency of calcium sulfite, oxidation efficiency can achieve 85% with On;The dehydration rate of desulfurization slurry is improved, the moisture content of resulting desulfurized gypsum is reduced to 20% hereinafter, can make by 50% or so It is sold, is turned waste into wealth for product, bring economic benefit for enterprise;Carbide slag filtrate and desulfurized gypsum filtrate are realized simultaneously Resource comprehensive recycles, and meets today's society and promotes industry clean manufacturing, the requirement of developing crcycle economy.
Detailed description of the invention
Fig. 1 is the process flow chart of the embodiment of the present invention;
Fig. 2 is the schematic device of the embodiment of the present invention;
In the figure, it is marked as 1- polyvinyl chloride carbide slag slurries conveyance conduit, 2- plate and frame type filter-press, 3- conveyor belt, 4- are electric Rock ballast starch preparing tank, 5- blender, 6- carbide slag slurries delivery pump, 7- carbide slag slurries conveyance conduit, 8- carbide slag slurries reflux line, 9- carbide slag slurries conveyance conduit, 10- oxidation air pipeline, 11- power-plant flue gas pipeline, 12- flue gas after desulfurization pipeline, 13- desulfurization Tower, 14- desulfurization slurry delivery pump, 15- desulfurization slurry conveyance conduit, 16- vacuum bag filter, 17- desulfurized gypsum filtrate are defeated Send pipeline, 18- desulfurized gypsum filtrate tank, 19- desulfurized gypsum filtrate delivery pump, 20- desulfurized gypsum filtrate conveyance conduit, 21- de- Sulphur gypsum conveyance conduit, 22- chimney, 24- desulfurized gypsum storage tank.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.
As shown in Figure 1 and Figure 2, the preprocess method of a kind of desulfurizing agent carbide slag of the invention, carbide slag slurries are consolidated Liquid is separated off carbide slag filtrate and obtains carbide slag filter cake, and the carbide slag filter cake moisture content is 10~20%;Using desulfurization stone Carbide slag filter cake is configured to desulfurizing agent carbide slag slurries by cream filtrate.The solid content of the desulfurizing agent carbide slag slurries be 10~ 20%.
Carbide slag slurries reproducibilities soluble matter such as 90% or more sulfide, phosphide after being separated by solid-liquid separation just is trapped in calcium carbide In slag filtrate, carbide slag filtrate returns to acetylene generation process and water is replaced to react with calcium carbide.The major function of acetylene generator is Calcium carbide and water haptoreaction are generated into acetylene and carbide slag slurries, reaction equation are as follows:
CaC2(calcium carbide)+2H2O (water) → C2H2+Ca(OH)2, carbide slag slurries are Ca (OH)2Slurries, carbide slag slurries pressure Carbide slag filtrate after filter returns to acetylene generator and water is replaced to react with calcium carbide, and sulfide and phosphatization are contained in carbide slag filtrate Object part can be taken away with acetylene gas, and sulfide and phosphide remove in subsequent acetylene cleaning device in acetylene gas, therefore calcium carbide Slag filtrate can be back to use PVC plant acetylene generator completely, without will affect acetylene quality.
The desulfurized gypsum filtrate comes from means of flue gas desulfurization of power plant, i.e. carbide slag is de- for power-plant flue gas as desulfurizing agent Sulphur obtains desulfurization slurry after generating the further aerating oxidation of product, then carries out being separated by solid-liquid separation up to desulfurized gypsum and desulfurized gypsum Filtrate;Main component is water in desulfurized gypsum filtrate water, and containing a small amount of calcium sulfate and calcium sulfite, the desulfurized gypsum is aqueous Rate is 10~20%, can be used as the additive of manufacture of cement.
The separation of solid and liquid selects plate and frame type filter-press to carry out filters pressing.
Embodiment:
As shown in Figure 1 and Figure 2, the carbide slag slurries that process occurs from polyvinyl chloride calcium carbide are passed through into polyvinyl chloride carbide slag Slurry conveyance conduit 1 is sent to plate and frame type filter-press 2 and carries out filters pressing separation of solid and liquid, and the filter cake main component after filters pressing is Ca (OH)2, contain Water rate is 10~20%, is sent to carbide slag slurries preparing tank 4 by conveyor belt 3, then uses desulfurized gypsum filtrate delivery pump 19 Desulfurized gypsum filtrate is added into carbide slag slurries preparing tank 4 by desulfurized gypsum filtrate conveyance conduit 20, while using blender 5 It is stirred, is configured to the desulfurizing agent carbide slag slurries that solid content is 10~20%, then by carbide slag slurries delivery pump 6 through calcium carbide Slurry conveyance conduit 7 is transported to desulfurizing tower 13, carries out to the power plant's sulfur-containing smoke gas for entering desulfurizing tower 13 by power-plant flue gas pipeline 11 Desulfurization, the SO 2 from fume after desulfurization is up to standard, enters chimney 22 through flue gas after desulfurization pipeline 12 and discharges.Carbide slag slurries delivery pump 6 outlets are connect through carbide slag slurries reflux line 8 with carbide slag slurries preparing tank 4, form reflux.
In desulfurizing tower 13 desulfurizing agent carbide slag slurries reacted with sulfur dioxide generate calcium sulfite, calcium sulfite with come from oxygen The air haptoreaction for changing air pipeline 10 generates calcium sulfate, and the desulfurization slurry containing a large amount of calcium sulfate is through desulfurization in desulfurizing tower 13 Slurry feeding pump 14 is sent to vacuum bag filter 16 by desulfurization slurry conveyance conduit 15, using negative pressure of vacuum by desulfurization slurry into Row is separated by solid-liquid separation, and the desulfurized gypsum that moisture content is 10~20% after separation is sent to desulfurized gypsum storage through desulfurized gypsum conveyance conduit 21 Tank 24 is sold after being collected as product, and desulfurized gypsum filtrate is sent to desulfurized gypsum through desulfurized gypsum filtrate conveyance conduit 17 and filters Flow container 18 is collected spare.
Through detecting, the average moisture content of filter cake is 15% after the progress filters pressing separation of solid and liquid of plate and frame type filter-press 2, then using de- Sulphur gypsum filtrate is configured to the desulfurizing agent that solid content is 20% and carries out the resulting desulfurization slurry of desulfurization to flue gas with carbide slag slurries, Dehydration difficulty substantially reduces, then be separated by solid-liquid separation resulting desulfurized gypsum moisture content and be reduced to 15% left side by current 50% or so It is right.

Claims (7)

1. a kind of preprocess method of desulfurizing agent carbide slag, which is characterized in that carry out carbide slag slurries to be separated by solid-liquid separation removing electricity Rock ballast filtrate obtains carbide slag filter cake, and carbide slag filter cake is configured to desulfurizing agent carbide slag slurries using desulfurized gypsum filtrate.
2. a kind of preprocess method of desulfurizing agent carbide slag according to claim 1, which is characterized in that the desulfurization The solid content of agent carbide slag slurries is 10~20%.
3. a kind of preprocess method of desulfurizing agent carbide slag according to claim 1, which is characterized in that the calcium carbide Slag filter cake moisture content is 10~20%.
4. a kind of preprocess method of desulfurizing agent carbide slag according to claim 1, which is characterized in that the desulfurization Gypsum filtrate comes from means of flue gas desulfurization of power plant, i.e. carbide slag is used for means of flue gas desulfurization of power plant as desulfurizing agent, generates product and further exposes Desulfurization slurry is obtained after gas oxidation, then carries out being separated by solid-liquid separation up to desulfurized gypsum and desulfurized gypsum filtrate.
5. a kind of preprocess method of desulfurizing agent carbide slag according to claim 4, which is characterized in that the desulfurization stone Cream moisture content is 10~20%, can be used as the additive of manufacture of cement.
6. a kind of preprocess method of desulfurizing agent carbide slag according to claim 1, which is characterized in that the calcium carbide Slag filtrate returns to acetylene generation process and water is replaced to react with calcium carbide.
7. a kind of preprocess method of desulfurizing agent carbide slag according to claim 1, which is characterized in that the solid-liquid Separation selects plate and frame type filter-press to carry out filters pressing.
CN201811404329.9A 2018-11-23 2018-11-23 A kind of preprocess method of desulfurizing agent carbide slag Pending CN109331636A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1986458A (en) * 2006-12-12 2007-06-27 梁永洪 Carbide residue and waste water treating process
CN101318100A (en) * 2008-07-21 2008-12-10 北京博奇电力科技有限公司 Wet process of FGD with acetylene sludge as absorbing agent
CN101670223A (en) * 2009-09-18 2010-03-17 山东泰山建能机械集团有限公司 Method and device for desulfurizing flue gas
CN101797466A (en) * 2009-10-14 2010-08-11 中国科学院过程工程研究所 Wet flue gas desulphurizing method utilizing carbide slag slurry and device thereof
CN201643976U (en) * 2010-04-08 2010-11-24 北京至清时光环保工程技术有限公司 Double-loop vertical jet wet-method desulfurization device used for preparing desulfurizing agent by utilizing carbide slag
CN207493633U (en) * 2017-09-21 2018-06-15 中国联合工程有限公司 A kind of carbide slag slurry prepares transhipment stocking system

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1986458A (en) * 2006-12-12 2007-06-27 梁永洪 Carbide residue and waste water treating process
CN101318100A (en) * 2008-07-21 2008-12-10 北京博奇电力科技有限公司 Wet process of FGD with acetylene sludge as absorbing agent
CN101670223A (en) * 2009-09-18 2010-03-17 山东泰山建能机械集团有限公司 Method and device for desulfurizing flue gas
CN101797466A (en) * 2009-10-14 2010-08-11 中国科学院过程工程研究所 Wet flue gas desulphurizing method utilizing carbide slag slurry and device thereof
CN201643976U (en) * 2010-04-08 2010-11-24 北京至清时光环保工程技术有限公司 Double-loop vertical jet wet-method desulfurization device used for preparing desulfurizing agent by utilizing carbide slag
CN207493633U (en) * 2017-09-21 2018-06-15 中国联合工程有限公司 A kind of carbide slag slurry prepares transhipment stocking system

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