CN101816889A - Desulphurization process by combining printing and dyeing wastewater - Google Patents

Desulphurization process by combining printing and dyeing wastewater Download PDF

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Publication number
CN101816889A
CN101816889A CN200910155739A CN200910155739A CN101816889A CN 101816889 A CN101816889 A CN 101816889A CN 200910155739 A CN200910155739 A CN 200910155739A CN 200910155739 A CN200910155739 A CN 200910155739A CN 101816889 A CN101816889 A CN 101816889A
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China
Prior art keywords
waste water
dyeing waste
desulphurization
sulfur removal
carbide slag
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Pending
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CN200910155739A
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Chinese (zh)
Inventor
莫建松
李泽清
吴忠标
程常杰
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Zhejiang Tianlan Environmental Protection Technology Co Ltd
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Zhejiang Tianlan Environmental Protection Technology Co Ltd
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Priority to CN200910155739A priority Critical patent/CN101816889A/en
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Abstract

The invention discloses a desulphurization process by combining printing and dyeing wastewater. Carbide slag, lime or lime stone serving as a desulphurizer is adopted to desulphurize fume by a wet method; and the water adopted in the pulping process for preparing desulphurization pulp from the desulphurizer is the printing and dyeing wastewater, wherein the mass content of solids in the desulphurization pulp is 8 to 15 percent, the pH value of the desulphurization system is 5.2 to 6.0, and the liquid-air ratio is 8 to 12L/m<3>. In the desulphurization process, the mixed pulp of the carbide slag and the printing and dyeing wastewater serves as the desulphurizer to treat the fume by the wet method; the discharging amount of the printing and dyeing wastewater is greatly reduced; the COD removing rate in the high-concentration wastewater of which the concentration is over 10,000mg/L is over 80 percent; the colour removing rate is over 90 percent; and the discharging amount of the wastewater is reduced by over 30 percent.

Description

The sulfur removal technology that combines with dyeing waste water
Technical field
The invention belongs to water pollution control and Air Pollution Control field, be specifically related to utilize the sulfur removal technology of desulfurizing agent and dyeing waste water mixing complementary characteristic.
Background technology
Along with the fast development of textile industry, textile industry has become one of maximum door of China's discharging industrial wastewater, and wherein the discharge capacity of dyeing waste water has occupied 80% of textile waste.About 300-400 ten thousand m of whole nation dyeing waste water discharge capacity 3/ day, wherein Zhejiang, Jiangsu, Guangdong, Shandong, Fu Jianwu economize output and account for 80% of total amount.Characteristics such as dyeing waste water has the organic components complexity, concentration is big, hard-degraded substance is many, the water yield is big, alkalescence is big, COD is high, strong contaminative.
Before the eighties, the biodegradability of China's dyeing waste water is higher, COD CrConcentration is everlasting below the 800mg/L, adopts traditional biology and materialization joint processing system, and water outlet can reach discharge standard.But recent two decades comes, and along with the improvement of development in science and technology and dyeing and printing process, very big variation has taken place dyeing waste water water quality, the COD in some technology dyeing waste water CrConcentration is up to more than the 10000mg/L even higher, and the kind and the content of difficult degradation, toxic organic compound significantly increase.Traditional treatment method of printing and dying wastewater, it is simple to have equipment as methods such as absorption, suspension, flocculation, filtration, coagulations, the advantage of easy and simple to handle and technical maturity, but this class processing method is normally transferred to solid phase or gas phase with organic matter from liquid phase, not only do not eliminate organic pollution and chemical agent consumption fully, and cause refuse to pile up and secondary pollution; Bioanalysis can only be removed the BOD in the dyeing waste water, and particularly the removal effect of poisonous hardly degraded organic substance is not obvious for COD, and processing cost is higher.Single processing method can not satisfy the requirement of current dyeing waste water development.Therefore must carry out preliminary treatment to dyeing waste water, reduce intractability.A lot of enterprises also reduce COD in the dyeing waste water greatly being devoted to seek by a kind of low-cost pre-treating process to dyeing waste water Cr, pH and colourity, improve the treatment effect of dyeing waste water.
The pH of dyeing waste water is higher, and the pH value can absorb neutralization reaction with sulfur in smoke preferably generally 8 to 12, absorbs the SO in the flue gas 2Deng sour gas.Dyeing waste water pH in absorbing the flue gas process reduces gradually, and organic matter such as original deliquescent terephthalic acid (TPA) is separated out gradually with the solid suspension form and existed in the waste water.Because the basicity that contains of waste water is not very high, the desulfurization capacity of dyeing waste water unit volume is less, causes the waste water water yield of printing and dyeing enterprise not satisfy the whole boiler smoke SO of absorption 2Demand, and dyeing waste water can not get the processing of essence.
Because characteristics such as the high pH value of dyeing waste water, high content of organics, difficult degradation, enter the oxygen content that natural water can reduce natural water greatly after the dyeing waste water discharging, the nondegradable organic substance of poisonous and harmful is enriched in the senior organism gradually, sharply destroy the ecological balance of natural water, make natural water worsen the harm ecological environment.At present the treatment technology intractability at dyeing waste water is big, cost is high, thereby makes and seek one to techniques of Dyeing Wastewater Treatment efficient height, and the technology way that cost is low becomes extremely urgent current.
Carbide slag is a product of producing polyvinyl chloride with calcium carbide, and main component is a calcium hydroxide, wherein also contains micro constitutents such as silicate, chloride, sulphur, phosphorus, aluminium, ferro element.Carbide slag is a kind of discarded solid pollutant, and one ton of polyvinyl chloride of every production will produce 2.8～3.0 tons carbide slag.Along with the development of PVC industry, a large amount of carbide slag discarded object of the annual generation of domestic polyvinyl chloride industry; Carbide slag does not have the actual industrial purposes, can only pile up or landfill, has occupied valuable land resource.And carbide slag runs into rainwater or underground water is dissolved into alkaline aqua calcis, makes soil salinization of soil contaminated land resource and groundwater resources.
Domestic wet desulphurization company has researched and developed a kind of technology that carbide slag is used for wet desulphurization, make strong basicity slurries and acid boiler smoke haptoreaction with carbide slag by certain technology, to react the calcium sulphate dihydrate that the calcium sulfite oxidation that generates becomes to have industrial use again, realize the purpose that the treatment of wastes with processes of wastes against one another is turned waste into wealth, solved the difficult problem of carbide slag pollution and smoke pollution simultaneously.
Wet process of FGD mainly is to utilize in the slurries the not only OH of stripping of calcium hydroxide -SO in ion and the flue gas 2Neutralization reaction takes place, and absorbs the SO in the flue gas 2, the OH in the slurries -Ion concentration is big more then abundant more with smoke absorption, and desulfuration efficiency is high more.Because the main component calcium hydroxide of carbide slag is a kind of material hard to tolerate, the saturation solubility in water has only 22.8mmol/L, with the smoke reaction process in, the OH that consumes rapidly -Ion can not in time be replenished, thus cause need be bigger liquid-gas ratio satisfy and absorb requirement, and need bigger tower still volume to satisfy the complete dissolution time of carbide slag, increased the investment and the operating cost of wet desulfurization system.
Summary of the invention
The invention provides a kind of wet fuel gas desulfurizing technology, improve wet desulphurization efficient, reduce wet desulfurizing process liquid-gas ratio, avoid fouling, reduce to have reduced investment outlay and operating cost since the tower still volume, can also reduce pH value, colourity and the COD content of discharging dyeing waste water greatly.
A kind of sulfur removal technology that combines with dyeing waste water utilizes carbide slag work, lime or lime stone for desulfurizing agent carries out wet desulphurization to flue gas, utilizes the change slurry process water of desulfurizing agent preparation desulfurization slurry to adopt dyeing waste water; The mass content of solid is 8～15% in the desulfurization slurry, and the pH value of desulphurization system is 5.2～6.0, and liquid-gas ratio is 8～12L/m 3
The mass content of solid is 10% in the described desulfurization slurry.
The present invention most preferably uses carbide slag as desulfurizing agent, utilizes the complementary characteristic of boiler smoke, carbide slag and dyeing waste water to handle three kinds of pollutants simultaneously.It is 10% desulfurization slurry that carbide slag and dyeing waste water are made into the mass fraction of solids optimum, and the adding of carbide slag has increased the desulfurization capacity of mixed serum, has satisfied the needs of flue gas desulfurization.If the waste water water yield of printing and dyeing enterprise is bigger, can dyeing waste water and carbide slag be made into the slurries of mass fraction of solids about 10% according to the different operating modes of boiler smoke, also the desulfurization capacity of mixed serum can be brought up to 5～100g SO 2/ L.
In desulphurization system, the pH value of desulphurization system is controlled at 5.2～6.0 in the absorption tower, and the difficult oxidation of organic compounds of the macromolecule in the dyeing waste water can be separated out under acid condition on a small quantity, reduces the inhibition to oxidation.
Utilize dyeing waste water to replace the fresh water (FW) slurry to reduce the consumption of sulfur removal technology to fresh water (FW).Only under the not enough situation of the dyeing waste water water yield and to the cooling flushing of equipment, need use fresh water (FW) in system's running, significantly reduce operating cost.
And carbide slag has improved absorption efficiency and the gypsum quality of slurries to flue gas with combining of dyeing waste water.Contain certain density Na in the dyeing waste water +Ion is because the solubility of NaOH is much larger than Ca (OH) 2Solubility, the OH in mixed serum -The concentration of ion is because Na +Ion must add also can be greater than saturated Ca (OH) 2OH in the solution -Concentration, can make OH in the mixed serum -OH in the pure carbide slag slurry of the concentration ratio of ion -The concentration of ion is big 3～8 times.Acidic flue gas is more abundant, efficient is higher thereby the slurries that make unit volume utilize the slurries ratio of dyeing waste water preparation to prepare with common process water absorb.Avoided causing fouling in the absorption tower for the pH of guaranteed efficiency is too high in the pure carbide slag wet desulfurization system, under same efficiency, reduced the demand of liquid-gas ratio, saved equipment investment, operating cost.
A kind of sulfur removal technology that combines with dyeing waste water of optimization, to smoke reaction after desulfurizing agent carry out oxidation processes, the desulfurizing agent rotational flow separation after the oxidation, top stream returns desulfurizing tower and recycles, the underflow Separation of Solid and Liquid.
Utilization blasts the mode of oxidizing gas and carries out oxidation processes in desulfurizing agent, embodiment is simple, economical and effective.Described oxidizing gas selects for use air the most economical.The air quantity of the oxidizing gas that blasts is 5～10m 3/ m 3H.
Carbide slag and SO 2Reacted calcium sulfite oxidizing and crystallizing in oxidizing process, generate a large amount of calcium sulphate crystal particles, pigment in the dyeing waste water is also oxidized to fade, Al that contains in the carbide slag and the salt of Fe can be brought into play the mixed flocculation effect in the desulfurization slurry environment simultaneously, make the organic substance granule flocculation in the dyeing waste water grow up, condense into the organic matter bulky grain of free settling,, filter with gypsum and to slag tap finally by the underflow Separation of Solid and Liquid behind the eddy flow.Most organic in the dyeing waste water also is cured and enters gypsum and be used to produce cement.Enter the dyeing waste water in the desulphurization system because system volatilizees and gypsum is taken out of, wastewater flow rate significantly reduces than the original dyeing waste water water yield, and the pH value of discharge waste water is 5.5～7.5, reduced the cost of waste water subsequent treatment, if dyeing waste water water shortage filtrate can also further be reduced discharge capacity by continuing to serve as slurry, reduce follow-up processing cost.
Wet fuel gas desulfurizing technology of the present invention, mixed serum with desulfurizing agent and dyeing waste water carries out the discharge capacity that wet treatment method reduces dyeing waste water in a large number as desulfurization slurry to flue gas, to COD at the COD of the high-concentration waste water more than 10000mg/L clearance more than 80%, chroma removal rate is more than 90%, and the discharging of the waste water water yield reduces more than 30%.
Description of drawings
Fig. 1 is a process chart of the present invention.
The specific embodiment
As shown in Figure 1, the desulfurization slurry of the 10% solid masses content that dyeing waste water and carbide slag are mixed with is stored in the serum storage tank 1 standby, when dyeing waste water is not enough, replenish a small amount of fresh water (FW) 13, desulfurization slurry by slush pump 2 squeeze in the absorption tower 4 with the absorption tower in slurries form desulfurization slurry.Slurries are sent to spraying layer by circulating pump 3 and spray desulfurization in the absorption tower 4, and flue gas enters absorption tower 4 from gas approach 7, fall into the process of 4 bottoms, absorption tower the slurries droplet from nozzle constantly and the SO in the flue gas at slurries 2Reaction generates calcium sulfite, along with OH in the droplet -Continuous consumption, calcium hydroxide is constantly stripping also, in this process dyeing waste water originally with Na +Ion has promoted OH -Continuous stripping, guaranteed that droplet is to SO 2High-absorbility.Flue gas after the processing is discharged from exhanst gas outlet 8.
Oxidation fan 5 is constantly sent into air in the absorption tower 4, and serum density is not higher than 1.15 in the absorption tower 4, and the oxidation air quantity is controlled at 5～10m 3/ m 3H, the calcium sulfite that generates constantly is oxidized to the calcium sulphate dihydrate crystal by airborne oxygen, simultaneously easily the organic matter of oxidation is also oxidized in the dyeing waste water, in the calcium sulphate dihydrate crystal of generation and the carbide slag with a small amount of Al and the salt of Fe in the absorption tower, finish flocculation of suspended organic matter granule and absorption to the difficult degradation in the dyeing waste water.
Desulfurization slurry in the absorption tower 4 is sent into rotational flow station 9 through gypsum excavationg pump 6 gypsum is separated with calcium sulfite, also enter band filter 10 with gypsum from the underflow of rotational flow station 9 through flocculation and adsorbed organic matter and dewater and separate, the vacuum degree control of being with filter 10 is between 0.04～0.07MPa.The calcium sulfite of top stream and calcium hydroxide enter absorption tower 4 and proceed the oxidation absorption.The organic matter that enters the dehydration of band filter 10 with gypsum is used to manufacture of cement, and is burned and do not solidify and can produce secondary pollution.Do filtrate after dehydration branch two to, stream part 11 being used to slurries recycle, stream parts 12 is disposed to wastewater disposal basin and enters advanced treating, the water yield of this moment and COD reduce greatly.
Application examples 1
Certain the 2 * 75t/h of printing and dyeing mill coal-burning boiler adopts dyeing waste water carbide slag/gypsum wet sulfur removal technology, and the COD content of dyeing waste water is 31000mg/L, and colourity is 4600 times, and original pH value is 12.65; Exhaust gas volumn 270000m 3/ h, absorption tower import SO 2Concentration 3100mg/Nm 3, liquid-gas ratio is 5L/m 3, the pH value is controlled at 5.6, and desulfuration efficiency is 98.5%, and desulfurated plaster purity is greater than 90%, and dyeing waste water colourity is removed fully, and wastewater discharge is 48% of a former dyeing waste water, and the COD clearance is 82%.
Application examples 2
Certain printing and dyeing enterprise 1 * 410t/h coal-burning boiler adopts dyeing waste water, carbide slag/gypsum wet sulfur removal technology, and the COD content of dyeing waste water is 18000mg/L, and colourity is 3200 times, and original pH value is 12.37; Exhaust gas volumn is 630000m 3/ h, absorption tower import SO 2Concentration 2800mg/Nm 3, liquid-gas ratio is 6L/m 3, the pH value is controlled at 5.5, and desulfuration efficiency is 97.9%, and desulfurated plaster purity is greater than 90%, and dyeing waste water colourity is removed fully, and wastewater discharge is 39% of a former dyeing waste water, and the COD clearance is 85%.
Application examples 3
Printing and dyeing enterprise waste water is taked dyeing waste water, carbide slag/gypsum wet sulfur removal technology near near certain the 1 * 220t/h of power plant coal-burning boiler utilization, and dyeing waste water COD content is 12000mg/L, and colourity is 4160 times, and original pH value is 11.88; Exhaust gas volumn is 310000m 3/ h, absorption tower import SO 2Concentration 4100mg/Nm 3, liquid-gas ratio is 6L/m 3, the pH value is controlled at 5.7, and desulfuration efficiency is 99.2%, and desulfurated plaster purity is greater than 90%, and dyeing waste water colourity is removed fully, and wastewater discharge is 43% of a former dyeing waste water, and the COD clearance is 87%.

Claims (7)

1. a sulfur removal technology that combines with dyeing waste water utilizes carbide slag, lime or lime stone as desulfurizing agent flue gas to be carried out wet desulphurization, it is characterized in that: utilize the change slurry process water of desulfurizing agent preparation desulfurization slurry to adopt dyeing waste water; The mass content of solid is 8～15% in the desulfurization slurry, and the pH value of desulphurization system is 5.2～6.0, and liquid-gas ratio is 8～12L/m 3
2. sulfur removal technology as claimed in claim 1 is characterized in that: the mass content of solid is 10% in the described desulfurization slurry.
3. sulfur removal technology as claimed in claim 1 is characterized in that: described desulfurizing agent is a carbide slag.
4. sulfur removal technology as claimed in claim 1 is characterized in that: to smoke reaction after desulfurizing agent carry out oxidation processes, the desulfurizing agent rotational flow separation after the oxidation, top stream returns desulfurizing tower and recycles, the underflow Separation of Solid and Liquid.
5. sulfur removal technology as claimed in claim 4 is characterized in that: to smoke reaction after desulfurizing agent in blast oxidizing gas and carry out oxidation processes.
6. sulfur removal technology as claimed in claim 5 is characterized in that: described oxidizing gas is an air.
7. sulfur removal technology as claimed in claim 5 is characterized in that: the air quantity of the oxidizing gas that blasts is 5～10m 3/ m 3H.
CN200910155739A 2009-12-25 2009-12-25 Desulphurization process by combining printing and dyeing wastewater Pending CN101816889A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102115248A (en) * 2011-04-07 2011-07-06 常州大学 Method for treating anionic dye-containing waste water
CN102814117A (en) * 2012-09-14 2012-12-12 重庆理工大学 Garbage leaching liquor biochemical treatment effluent method for garbage incinerator tail gas treatment
CN104548914A (en) * 2014-11-07 2015-04-29 浙江理工大学 Method for comprehensively treating sulfur dioxide and printing and dyeing wastewater
CN110523255A (en) * 2019-09-16 2019-12-03 德蓝水技术股份有限公司 A kind of alkali decrement waste water flue gases purification
CN111575075A (en) * 2020-05-20 2020-08-25 中国华能集团有限公司 Method for desulfurizing and decarbonizing methane by combining solid waste and waste alkali liquor

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102115248A (en) * 2011-04-07 2011-07-06 常州大学 Method for treating anionic dye-containing waste water
CN102115248B (en) * 2011-04-07 2012-05-30 常州大学 Method for treating anionic dye-containing waste water
CN102814117A (en) * 2012-09-14 2012-12-12 重庆理工大学 Garbage leaching liquor biochemical treatment effluent method for garbage incinerator tail gas treatment
CN102814117B (en) * 2012-09-14 2015-04-22 重庆理工大学 Method for garbage leaching liquor biochemical treatment effluent to be used in garbage incinerator tail gas treatment
CN104548914A (en) * 2014-11-07 2015-04-29 浙江理工大学 Method for comprehensively treating sulfur dioxide and printing and dyeing wastewater
CN110523255A (en) * 2019-09-16 2019-12-03 德蓝水技术股份有限公司 A kind of alkali decrement waste water flue gases purification
CN111575075A (en) * 2020-05-20 2020-08-25 中国华能集团有限公司 Method for desulfurizing and decarbonizing methane by combining solid waste and waste alkali liquor

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