CN102718373A - Method for treating white mud produced by papermaking and use of the white mud treated by the method in removal of CO2 in tail flue gas from coal-fired boiler - Google Patents

Method for treating white mud produced by papermaking and use of the white mud treated by the method in removal of CO2 in tail flue gas from coal-fired boiler Download PDF

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CN102718373A
CN102718373A CN2011103406278A CN201110340627A CN102718373A CN 102718373 A CN102718373 A CN 102718373A CN 2011103406278 A CN2011103406278 A CN 2011103406278A CN 201110340627 A CN201110340627 A CN 201110340627A CN 102718373 A CN102718373 A CN 102718373A
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paper white
white sludge
sludge
white mud
flue gas
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李英杰
孙荣岳
韩奎华
赵建立
路春美
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Shandong University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

The invention discloses a method for treating white mud produced by papermaking. The method is characterized in that through multistage washing filtration and solar energy drying of white mud produced by papermaking, impurity ions such as Na, K and Cl producing adverse effects on white mud carbonation are removed and the white mud produced by papermaking and treated by the method can be used as a CO2 absorbent. A research result shows that through multistage washing filtration and solar energy drying, the CO2 cyclic-trapping performance of the white mud treated by the method is greatly improved. The method provided by the invention realizes a process route combining recycling application of white mud produced by papermaking, and removal of CO2 discharged by a coal-fired boiler. The method provided by the invention has simple and convenient processes, a small investment, a low cost and good industrial application prospects.

Description

The treatment process of paper white sludge and in removing the coal firing boiler tail flue gas CO 2Application
Technical field
The present invention relates to the treatment process of paper white sludge, and the paper white sludge CO in removing the coal firing boiler tail flue gas after handling 2Application, belong to environmental pollutant controls and clean burning technical field.
Background technology
Combustion of fossil fuel such as coal, oil, Sweet natural gas discharge a large amount of CO 2, caused serious Greenhouse effect, environment for human survival has been constituted very big threat.How to control CO 2Discharge, become the emphasis and the difficult point of countries in the world scholar's research.China is main primary energy source with coal, control coal power station CO 2Instant stage has been arrived in discharging.
CO 2Separation and storing technology are considered to reduce in a short time the main path of carbon emission.The investigator has proposed a variety of CO to the coal-burning power plant 2The separation and collection technology comprises O 2/ CO 2Combustion method, membrane separation process, MEA process, burning chemistry chains method, biosorption process and calcium circulation method etc.This wherein, the calcium circulation method utilizes that reserves are abundant, the calcium sills such as extensive and cheap Wingdale, rhombspar that distribute are as CO 2Absorption agent has reduced the decarburization cost.This method receives the extensive concern of Chinese scholars in recent years.
The calcium circulation method, the calcination/carbonation of calcium-base absorbing agent circulation just captures CO 2Technology.At first high-temperature calcination in calcination reactor of absorption agent, calcining institute energy requirement adopts O by fuel 2/ CO 2Combustion system provides, thereby can obtain high concentration CO 2Air-flow and CaO.Calcining furnace outlet CO 2Concentration can reach more than 95%, CO 2Seal up for safekeeping through behind the cooling de-watering.The CaO that obtains gets into CO in carbonation reactor and the flue gas 2Reaction generates CaCO 3, reach separation of C O 2Purpose.The CaCO that generates in the carbonating stove 3Get into calcining furnace once more, recycle.
Paper white sludge is the waste residue that produces in the alkali recovery process of paper mill, is a kind of common calcium base waste, and discharge capacity is huge.Research shows that every recovery 1t alkali is with the paper white sludge that produces 1250-2200kg at least.At present, most of white clay can't effectively utilize, and generally piles up as industrial refuse, has both polluted environment, must pay huge effluent charge simultaneously.The staple of paper white sludge is CaCO 3, also contain a spot of lime (with Ca (OH) 2Form exists) and elements such as Na, K, Cl.Wherein, CaCO 3Massfraction can reach more than 90%, therefore, in theory, can adopt paper white sludge replacing lime stone etc. as the CO in the high temperature sorbent circularly trapping coal firing boiler tail flue gas 2, the recycling and the coal firing boiler CO of realization paper white sludge 2Remove the process combined route.But through discovering, basic metal such as Na, K and Cl constituent content are higher in the white clay, and the existence of these compositions has seriously reduced white clay circularly trapping CO 2Performance causes white clay to capture CO 2Ability is compared on the low side with Wingdale, and the existence of these elements, also can aggravate the corrosion of reactor drum.Therefore, how from white clay, to separate elements such as Na, K and Cl, capture CO improving white clay circulation calcination/carbonation 2Performance has crucial meaning.
Summary of the invention
To above-mentioned prior art, the invention provides a kind of treatment process of paper white sludge, this technology is carried out multistage washing filtering and solar energy drying to paper white sludge and is handled, and can effectively remove Na, K and Cl etc. in the white clay to capturing CO 2The element that disadvantageous effect is arranged; Thereby improved carbonating transformation efficiency problem of lower in the paper white sludge circulation calcination/carbonation process; The anti-agglutinatting property of absorption agent ability when having strengthened high-temperature calcination, therefore, paper white sludge after treatment can be used for removing the CO of coal firing boiler tail flue gas 2
The present invention realizes through following technical scheme:
A kind of treatment process of paper white sludge, step is following:
(1) paper white sludge and water add the mixed of 4L water according to the 1Kg paper white sludge in the one-level agitated pool, stir 2～4 hours, make that soluble ion fully dissolves in the white clay, and mixed serum gets into grade one filter and filters then, discharges filtered water, must solid materials;
(2) above-mentioned gained solid materials gets into the secondary agitated pool, with the mixed of water according to 1Kg solid materials interpolation 2L water, stirs after 2～4 hours, and mixed serum gets into secondary filter and filters, and discharges filtered water; The filtered water that two-stage filter is discharged can repeatedly be discharged the back in recycle, owing to do not contain heavy metal ion in the white clay, the filtered water of discharge can directly be discharged;
(3) to the solid materials that after secondary filter filters, obtains in the step (2) dry analysis of taking a sample; If the ratio of Na in the paper white sludge, K, Cl element mole number sum and Ca element mole number is greater than 0.5%, then solid materials returns step (2) secondary agitated pool and mixes agitation and filtration with water again; If the ratio of Na in the white clay, K, Cl element mole number sum and Ca element mole number is less than 0.5%, then solid materials gets into moisture eliminator and carries out drying and dewater, and must handle the back paper white sludge, gets into storage silo and stores.
In the said step (3) solid materials is carried out the drying employing solar dryer that dewaters.
A kind of paper white sludge that obtains through above-mentioned treatment process processing, it can be used for removing the CO of coal firing boiler tail flue gas 2, concrete application method is: according to the actual amount demand, paper white sludge is sent in the fluidized bed calcination stove, carried out high-temperature calcination, then the staple CaCO in the paper white sludge 3Decompose and generate CaO and CO 2, after cyclonic separator separated, CaO got in the fluidized-bed carbonating stove, the CO in the flue gas that produces with coal firing boiler 2Carry out carbonation reaction, generate CaCO 3Thereby, make CO in the flue gas that fluidized-bed carbonating fire grate goes out 2Concentration less than 5%, thereby reached the purpose of decarburization, the paper white sludge that obtains after the carbonating then can get into calcining furnace, recycle again.Calcination reaction institute energy requirement is provided by the fuel pure oxygen burning, and paper white sludge decomposes expellant gas CO in the calcining furnace 2Concentration can directly seal up for safekeeping or use greater than 95%.
Temperature of reaction suitable in the said carbonating stove is 650～720 ℃, and temperature of reaction suitable in the calcining furnace is 900～950 ℃.In the reaction process, for guaranteeing enough CO 2Collection efficiency needs the constantly paper white sludge of discharge inactivation, and additional paper white sludge.
The waste residue of the present invention to producing in the alkali recovery process of paper mill---paper white sludge is handled, and utilizes the paper white sludge after handling to remove the CO in the coal firing boiler tail flue gas 2, both realized the recycling of paper white sludge, the CO in again can effective elimination coal firing boiler tail flue gas 2, it has the following advantages:
1. the recycling and the coal firing boiler CO of paper white sludge have been realized 2Remove the process combined route.
2. paper white sludge is carried out multistage washing filtering and drying treatment, the ratio that makes Na in the white clay, K, Cl element mole number sum and Ca element mole number has improved the circularly trapping CO of white clay less than 0.5% 2Performance.
3. removed elements such as the Na in the white clay, K, Cl, can effectively reduce in calcining, the carbonation reaction process these elements, improved the security and the economy of system's operation corrosion on Equipment.
4. whole technological operation is simple and convenient, is easy to realize, it is low to invest little cost, has favorable industrial application prospect.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Wherein, 1, one-level agitated pool; 2, grade one filter; 3, secondary agitated pool; 4, secondary filter; 5, solar dryer; 6, storage silo; 7, fluidized bed calcination stove; 8, fluidized-bed carbonating stove; 9, coal firing boiler; 10, paper white sludge; 11, water; 12, filtered water; 13, the paper white sludge after the processing; 14, calcining back white clay; 15, white clay after the carbonating; 16, remove CO 2After flue gas; 17, high CO 2The concentration flue gas; 18, coal and oxygen; 19, inactivation white clay; 20, cyclonic separator; 21, flue gas.
Fig. 2 is that the pore volume after the 1st calcining of paper white sludge after paper white sludge and the processing distributes and accumulation pore volume figure, wherein, (a) is the pore volume distribution, (b) is the accumulation pore volume.
Fig. 3 is the SEM figure after the 1st calcining of paper white sludge after paper white sludge and the processing, wherein, (a) is the SEM figure of paper white sludge, (b) is the SEM figure of the paper white sludge after the processing.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment handles paper white sludge, and utilizes the paper white sludge after handling to carry out CO in the coal firing boiler tail flue gas 2Remove
Fig. 1 is that the coal firing boiler that reaches according to the invention adopts CO in the paper white sludge circularly removing tail flue gas 2The technical process of method.
The processing mode that paper white sludge is handled is following:
Paper white sludge 10 mixes in one-level agitated pool 1 with water 11, and blending ratio stirs after 2-4 hour for the 1Kg white clay adds 4L water, and mixed serum gets in the grade one filter 2 and filters, and discharges filtered water 12.After fully filtering, the gained solid gets into secondary agitated pool 3 according to the mixed that the 1Kg white clay adds 2L water, stirs 2-4 hour.Mixed serum gets in the secondary filter 4 and fully filters then, discharges filtered water 12.The filtered water 12 that two-stage filter is discharged can be drained after repeatedly recycling.To the white clay behind secondary filter sampling dry analysis, greater than 0.5%, then white clay returns secondary agitated pool 3 and carries out the repetition agitation and filtration like the ratio of Na in the white clay, K, Cl element mole number sum and Ca element mole number; , get into solar dryer 5 and carry out drying and dewater less than 0.5% like the ratio of Na in the white clay, K, Cl element mole number sum and Ca element mole number, the paper white sludge 13 after obtaining handling gets into storage silo 6 and stores for future use.
Utilize the paper white sludge after handling to carry out CO in the coal firing boiler tail flue gas 2The mode that removes following:
According to the actual amount demand, the paper white sludge 13 after the processing gets into fluidized bed calcination stove 7 and carries out high-temperature calcination, the staple CaCO in the paper white sludge 3Decomposition reaction takes place, and generates CaO and CO 2, calcining temperature is 900-950 ℃, calcining institute energy requirement is provided by the fuel pure oxygen burning, so CO in the fluidized bed calcination stove 7 outlet flue gases 2Concentration can reach more than 95%, separates through cyclonic separator 20, discharges high CO 2 Concentration flue gas 17 can directly be sealed up for safekeeping or utilize; White clay 14 gets into fluidized-bed carbonating stove 8 through material-returning device after separating the calcining that obtains, and the flue gas 21 that produces with coal firing boiler 9 carries out gas-solid reaction, absorbs the CO in the flue gas 2, temperature of reaction is 650-720 ℃.Through cyclonic separator 20 gas solid separation, discharge and remove CO 2After flue gas 16, white clay 15 then returns calcining furnace high-temperature calcination once more after the carbonating, realizes the recycle of absorption agent.In the circulating reaction process, constantly discharge inactivation white clay 19, and replenish and handle back white clay 13.
Experimental example
On double-fixed bed reactor drum, certain paper mill white clay that is untreated is measured with the carbonating transformation efficiency of handling back white clay (embodiment preparation), the carbonating transformation efficiency has characterized the capture CO of absorption agent 2Ability.At first high-temperature calcination in calcination reactor of absorption agent, calcination atmosphere are pure N 2, calcining temperature is 850 ℃, calcination time is 10min; Calcine the CaO that obtains then and get into carbonation reactor and CO 2Carry out carbonation reaction, carbonating atmosphere is 15%CO 2And 85%N 2, the carbonating temperature is 700 ℃, the carbonating time is 40min.After calcining and the carbonating, sample is accurately weighed on high-precision electronic balance, through the carbonating transformation efficiency of quality change calculating absorption agent before and after the carbonation reaction, shown in (1).
X N = m N - m cal m 0 A · M CaO M C O 2 - - - ( 1 )
X in the formula NBe the carbonating transformation efficiency; N is the circulating reaction number of times; m 0Be the absorption agent initial weight; m NBe the N time circulating reaction post-absorption agent quality; m CalBe the quality after the absorption agent calcining; M CaOAnd M CO2Be respectively CaO and CO 2Molar mass; A is a CaO content in the absorption agent.
Experiment showed, that paper white sludge has certain circulation calcination/carbonation and captures CO 2Ability, but compare with natural calcium base absorbants such as Wingdale, rhombspars, the carbonating transformation efficiency is on the low side.As shown in table 1, the 1st time cyclic carbon acidifying transformation efficiency only has 0.22.The x-ray fluorescence analysis result shows that the Na that contains in the white clay that is untreated, K, Cl element mole number sum are about 2% with the ratio of Ca element mole number, and the existence of these elements has had a strong impact on the circularly trapping CO of white clay 2Performance.Show that through X-ray diffraction analysis Na, K, these elements of Cl all are that the form with soluble salt exists, and therefore can remove these elements through the method for washing, thereby realize harmful element and CaCO in paper white sludge 3Separation.Through after multistage washing filtering and the drying treatment, Na, K, Cl element obviously reduce, and drop to below 0.5% with the ratio of Ca element mole number.Microtexture to the white clay after handling is carried out ESEM and nitrogen adsorption analysis; Find to handle back burning of lime sludge product specific pore volume and specific surface area and all obviously increase (shown in Fig. 2, Fig. 3 and table 2); Pore texture is flourishing more, cyclic carbon acidifying transformation efficiency be significantly improved (as shown in table 1).This shows, has effectively improved white clay circularly trapping CO through washing filtering and drying treatment 2Ability.
Table 1 be untreated white clay with handle the contrast of back white clay cyclic carbon acidifying transformation efficiency
Figure BDA0000104616390000051
Table 2 white clay that is untreated compares with specific surface area with the specific pore volume of handling after the 1st calcining of back white clay
Figure BDA0000104616390000052

Claims (9)

1. the treatment process of a paper white sludge is characterized in that, step is following:
(1) paper white sludge and water stirred 2～4 hours according to the mixed that the 1Kg paper white sludge adds 4L water, then mixed serum were filtered, and discharged filtered water, got solid materials;
(2) above-mentioned gained solid materials and water stir after 2～4 hours according to the mixed that the 1Kg solid materials adds 2L water, and mixed serum is filtered, and discharge filtered water;
(3) to the solid materials that obtains after filtering in the step (2) dry analysis of taking a sample, if the ratio of Na in the paper white sludge, K, Cl element mole number sum and Ca element mole number greater than 0.5%, then solid materials returns step (2) and mixes agitation and filtration with water again; If the ratio of Na in the white clay, K, Cl element mole number sum and Ca element mole number then carries out drying to solid materials and dewaters less than 0.5%, must handle the back paper white sludge.
2. the treatment process of paper white sludge according to claim 1 is characterized in that: in the said step (3) solid materials is carried out the drying employing solar dryer that dewaters.
3. the treatment process of a paper white sludge according to claim 1 is handled the paper white sludge that obtains.
4. the described paper white sludge of claim 3 CO in removing the coal firing boiler tail flue gas 2Application.
5. application according to claim 4 is characterized in that, concrete applying step is: paper white sludge gets into the calcining of fluidized bed calcination furnace high-temperature, and calcination reaction institute energy requirement is provided the staple CaCO in the white clay by the fuel pure oxygen burning 3Decompose and generate CaO and CO 2, after cyclonic separator separated, CaO got in the fluidized-bed carbonating stove, the CO in the flue gas that produces with coal firing boiler 2Carry out carbonation reaction, fluidized-bed carbonating fire grate goes out CO 2Concentration reaches the purpose of decarburization less than 5% flue gas; Calcining furnace expellant gas CO 2Concentration is greater than 95%, directly seals up for safekeeping or uses.
6. application according to claim 5 is characterized in that: the white clay that obtains after the said carbonating gets into calcining furnace, recycle again.
7. application according to claim 5 is characterized in that: the temperature of reaction of said carbonating stove is 650～720 ℃.
8. application according to claim 5 is characterized in that: the temperature of reaction of said calcining furnace is 900～950 ℃.
9. application according to claim 5 is characterized in that: in the reaction process, for guaranteeing enough CO 2Collection efficiency is constantly discharged the inactivation white clay, and additional paper white sludge.
CN2011103406278A 2011-11-01 2011-11-01 Method for treating white mud produced by papermaking and use of the white mud treated by the method in removal of CO2 in tail flue gas from coal-fired boiler Pending CN102718373A (en)

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Cited By (7)

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CN102921292A (en) * 2012-11-13 2013-02-13 山东大学 Method used to improve carbon dioxide trapping performance of papermaking white mud in fire coal fluidized bed boiler system
CN104971690A (en) * 2015-06-15 2015-10-14 昆明理工大学 Method for preparing high-temperature CO2 calcium-based adsorbent from papermaking white mud
US9610537B2 (en) 2013-12-11 2017-04-04 Industrial Technology Research Institute Loop tower CO2 capture system, carbonator, calciner and operating method thereof
CN107261815A (en) * 2017-08-01 2017-10-20 宜宾纸业股份有限公司 A kind of circulating fluidized bed combustion coal boiler in-furnace desulfurization method
CN110822444A (en) * 2019-11-01 2020-02-21 通玉实业发展(上海)有限公司 Application of white mud in waste incineration treatment and waste incineration treatment method
CN115092950A (en) * 2022-08-01 2022-09-23 中国铝业股份有限公司 Method for recycling papermaking white mud
CN115178075A (en) * 2022-07-20 2022-10-14 合肥中亚环保科技有限公司 Process system for removing carbon dioxide in flue gas of small kiln

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102921292A (en) * 2012-11-13 2013-02-13 山东大学 Method used to improve carbon dioxide trapping performance of papermaking white mud in fire coal fluidized bed boiler system
US9610537B2 (en) 2013-12-11 2017-04-04 Industrial Technology Research Institute Loop tower CO2 capture system, carbonator, calciner and operating method thereof
CN104971690A (en) * 2015-06-15 2015-10-14 昆明理工大学 Method for preparing high-temperature CO2 calcium-based adsorbent from papermaking white mud
CN107261815A (en) * 2017-08-01 2017-10-20 宜宾纸业股份有限公司 A kind of circulating fluidized bed combustion coal boiler in-furnace desulfurization method
CN110822444A (en) * 2019-11-01 2020-02-21 通玉实业发展(上海)有限公司 Application of white mud in waste incineration treatment and waste incineration treatment method
CN115178075A (en) * 2022-07-20 2022-10-14 合肥中亚环保科技有限公司 Process system for removing carbon dioxide in flue gas of small kiln
CN115092950A (en) * 2022-08-01 2022-09-23 中国铝业股份有限公司 Method for recycling papermaking white mud

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