CN1623648A - Modified calcium adsorbent for purifying incinerated smoke and preparation process thereof - Google Patents
Modified calcium adsorbent for purifying incinerated smoke and preparation process thereof Download PDFInfo
- Publication number
- CN1623648A CN1623648A CN 200410086708 CN200410086708A CN1623648A CN 1623648 A CN1623648 A CN 1623648A CN 200410086708 CN200410086708 CN 200410086708 CN 200410086708 A CN200410086708 A CN 200410086708A CN 1623648 A CN1623648 A CN 1623648A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- sodium salt
- modified calcium
- flue gas
- calcium carbonate
- 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.)
- Granted
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 28
- 150000001669 calcium Chemical class 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000000779 smoke Substances 0.000 title description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 5
- 239000003607 modifier Substances 0.000 claims abstract description 4
- 239000003546 flue gas Substances 0.000 claims description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 9
- 159000000000 sodium salts Chemical class 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 4
- 239000010813 municipal solid waste Substances 0.000 abstract description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 abstract 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000003517 fume Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000009938 salting Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000002906 medical waste Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
An modified Ca-base adsorbent for cleaning the fume of garbage incinerator by removing the acidic gas, heavy metal, dioxin, etc from it is prepared from industrial light calcium carbonate (CaCO3) and Na salt as modifier through proportionally immersing the powder of light calcium carbonate in the solution of Na salt, heating while stirring, and calcining.
Description
Technical field
The invention belongs to waste incineration secondary pollution control technology field, particularly towards the Ca-base adsorbent and the technology of preparing thereof of life, medical waste and incineration of industry peril waste flue gas pollutant dry cleaning.
Technical background
According to the physical form of adsorbent and product, life, medical waste and incineration of industry peril waste flue gases purification can be divided into three kinds of wet type, half dry type and dry types.Wet method basic agent commonly used mainly is a NaOH solution, but the caustic soda price is more expensive, and wet method produces the further processing of sewage needs that contains materials such as heavy metal.The used medicament of semidry method is a lime white, though price is comparatively cheap, and pulping system complexity, slip conveying circuit easy break-down.Dry method directly adopts the pressed powder adsorbent, and advantage is to have overcome problems such as stopping up corrosion, does not need water and reheat system, small investment, and operating cost is low, and is easy to operate easy to control, and shortcoming is that treatment effeciency is low, and the adsorbent utilization rate is low.
For heavy metal and dioxin pollution thing, the most frequently used method is that active carbon sprays into absorption method, i.e. dry method.But consider that active carbon costs an arm and a leg and large usage quantity, therefore be necessary that the adsorbent of developing efficient cheapness substitutes active carbon.In order to improve dry process efficient, people adopt two kinds of methods: the one, transform flue gas purification system, and make adsorbent fully contact with pollutant in the flue gas; The 2nd, adopt the method for adding modifier that original adsorbent is carried out modification, common additive mainly contains silane coupler, shitosan etc.The main purpose of organics additive is the water imbibition that changes the powder granule surface, thereby removes the organic pollution in the water, and for air pollutants, this type of method of modifying also is not suitable for.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned modified adsorbent, a kind of novel modified calcium-based adsorbent that is used for incineration flue gas and preparation method thereof is proposed, promptly adopt class reserves abundant, cheap, Ca-base adsorbent with advantages such as flourishing pore structures is as matrix, utilize alkali metal soln under the high-temperature calcination condition, to carry out modification as additive, to obtain highly active modified calcium-based adsorbent series, have the absorption property suitable even more excellent, can comprehensively remove the sour gas in the flue gas of refuse burning with active carbon, heavy metal and dioxin pollution thing etc.
The modified calcium-based adsorbent that is used for incineration flue gas that the present invention proposes is characterized in that, with CaCO
3For the industrial products precipitated calcium carbonate of main component is a matrix, with the sodium salt modifier, the powder that both mixed calcinings form, wherein the ratio of calcium carbonate and sodium salt is 100: 10-100: 25.
The preparation method of the modified calcium-based adsorbent that is used for incineration flue gas that the present invention proposes is characterized in that, may further comprise the steps:
1) the precipitated calcium carbonate powder is soaked or dipped in 40-80 ℃ the 10%-25% sodium salt solution 24 hours-72 hours, obtains the emulsus mixed liquor;
2) then the emulsus mixed liquor that obtains was calcined 1-2 hour in 850-950 ℃ of Muffle furnace, ground the 100-200 mesh sieve and form, pack stand-by.
Above-mentioned sodium salt can be selected NaCl, Na for use
2CO
3, Na
2Among the S any one.
The mechanism of modification of adsorbent of the present invention and effect:
The CaO that the present invention can make calcining generate has bigger interior hole dimension, thereby the final conversion ratio of CaO is improved; Generated CaO/Na
x(R is Cl to R, CO
3, S) eutectic layer plays " catalytic action " to gas reaction.
Compare with precipitated calcium carbonate, industrial products CaO, utilize the absorption property of the serial calcium base modified adsorbent that the present invention obtains to improve greatly.The modified calcium-based adsorbent method of modifying that is used for garbage-incineration smoke purifying of the present invention's exploitation is simple, easy to operate, can produce in batches; And can comprehensively remove sour gas, heavy metal and dioxin pollution thing etc. in the flue gas of refuse burning.
The specific embodiment
Embodiment 1
(1) preparation of modified calcium-based adsorbent: adding concentration is 10% NaCl salting liquid in the 100g precipitated calcium carbonate, is heated to 40 ℃, soaks 72h, constantly stirs, and leaves standstill, then in 900 ℃ of following heating and calcining 1.5h.Ground 100 mesh sieves, packed stand-by.
(2) the Ca-base adsorbent MC1 after the above-mentioned activation is used among the processing of flue gas of refuse burning:
Carry out gas cleaning field experiment at certain municipal solid waste incinerator, get MC1 and spray in the cleaning system with 10g/min speed.
Flue gas before purifying: HCl concentration is 1625mg/Nm
3
Purify the back flue gas: HCl concentration is 15mg/Nm
3
Clearance is:
Embodiment 2
(1) preparation of modified calcium-based adsorbent: adding concentration is 15% Na in the 100g precipitated calcium carbonate
2CO
3Salting liquid is heated to 60 ℃, soaks 48h, and batch (-type) stirs, and leaves standstill, and in 850 ℃ of following heating and calcining 2h, grinds 200 mesh sieves then, packs stand-by.
(2) the Ca-base adsorbent MC2 after the above-mentioned activation is used among the processing of flue gas of refuse burning:
Carry out tail gas clean-up field experiment in certain medical refuse burning factory, get MC2 and spray in the cleaning system with 10g/min speed.
Flue gas before purifying: Hg concentration is 0.050mg/Nm
3, Cd concentration is 1.095mg/Nm
3, Pb concentration is 76.7mg/Nm
3
Purify the back flue gas: Hg concentration is 1.05e-4mg/Nm
3, clearance is 99.8%; Cd concentration is 2.14e-2mg/Nm
3, clearance is 98.0%; Pb concentration is 0.2774mg/Nm
3, clearance is 99.6%.
Embodiment 3
(1) preparation of modified calcium-based adsorbent: adding concentration is 20% Na in the 100g precipitated calcium carbonate
2The S salting liquid is heated to 80 ℃, soaks 24h, constantly stirs, and leaves standstill, then in 950 ℃ of following heating and calcining 1h.Ground 200 mesh sieves, packed stand-by.
(2) the Ca-base adsorbent MC3 after the above-mentioned activation is used among the processing of flue gas of refuse burning:
Carry out tail gas clean-up field experiment in certain medical refuse burning factory, get MC3 and add in the cleaning system with 10g/min speed.
Flue gas before purifying: dioxin pollution substrate concentration 25.1ng/Nm
3
Purify the back flue gas: dioxin pollution substrate concentration 0.0573ng/Nm
3, clearance is 99.7%.
Claims (4)
1, a kind of modified calcium-based adsorbent that is used for incineration flue gas is characterized in that, with CaCO
3For the industrial products precipitated calcium carbonate of main component is a matrix, with the sodium salt modifier, the powder that both mixed calcinings form, wherein the ratio of calcium carbonate and sodium salt is 100: 10-100: 25.
2, modified calcium-based adsorbent as claimed in claim 1 is characterized in that, described sodium salt is selected NaCl, Na for use
2CO
3, Na
2Among the S any one.
3, a kind of preparation method who is used for the modified calcium-based adsorbent of incineration flue gas is characterized in that, may further comprise the steps:
1) the precipitated calcium carbonate powder is soaked or dipped in 40-80 ℃ the 10%-25% sodium salt solution 24 hours-72 hours, obtains the emulsus mixed liquor;
2) then the emulsus mixed liquor that obtains was calcined 1-2 hour in 850-950 ℃ of Muffle furnace, ground the 100-200 mesh sieve and form, pack stand-by.
4, preparation method as claimed in claim 3 is characterized in that, said sodium salt is selected NaCl, Na for use
2CO
3, Na
2Among the S any one.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB200410086708XA CN100435930C (en) | 2004-10-29 | 2004-10-29 | Modified calcium adsorbent for purifying incinerated smoke and preparation process thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB200410086708XA CN100435930C (en) | 2004-10-29 | 2004-10-29 | Modified calcium adsorbent for purifying incinerated smoke and preparation process thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1623648A true CN1623648A (en) | 2005-06-08 |
CN100435930C CN100435930C (en) | 2008-11-26 |
Family
ID=34766037
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB200410086708XA Expired - Fee Related CN100435930C (en) | 2004-10-29 | 2004-10-29 | Modified calcium adsorbent for purifying incinerated smoke and preparation process thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN100435930C (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102631886A (en) * | 2012-04-01 | 2012-08-15 | 东南大学 | Waste incineration additive with function of capturing heavy metals and preparation method thereof |
CN101310853B (en) * | 2008-02-15 | 2012-09-12 | 郜洪文 | Calcium adsorbing material and its preparation method |
CN101780393B (en) * | 2009-01-15 | 2013-01-23 | 财团法人工业技术研究院 | Adsorbent, regenerating-recycling method and recycling equipment thereof |
CN101679077B (en) * | 2007-06-15 | 2013-05-08 | Omya发展股份公司 | Surface-reacted calcium carbonate in combination with hydrophobic adsorbent for water treatment |
CN103752258A (en) * | 2014-01-09 | 2014-04-30 | 苏州英斯迪尼工贸有限公司 | Harmful gas adsorbate and preparation method thereof |
CN104174353A (en) * | 2014-08-22 | 2014-12-03 | 南京信息工程大学 | Calcium-based adsorbing agent for removing CO2 and SO2 simultaneously, as well as modification method and application of adsorbing agent |
CN105195083A (en) * | 2015-09-14 | 2015-12-30 | 贺州学院 | Method for modifying ground calcium carbonate with sodium chloride to prepare heavy metal adsorbent |
CN105618004A (en) * | 2016-03-28 | 2016-06-01 | 贺州学院 | Preparation method of calcium carbonate-based chelate sorbent |
CN107115838A (en) * | 2017-06-29 | 2017-09-01 | 安徽天顺环保设备股份有限公司 | A kind of low-temperature plasma modified flue gas removes cadmium Ca-base adsorbent and preparation method |
CN109046227A (en) * | 2018-08-28 | 2018-12-21 | 黄志伟 | A kind of natural mineral matter air purifying composition and preparation method thereof |
CN109847689A (en) * | 2019-01-09 | 2019-06-07 | 西安热工研究院有限公司 | It is a kind of for removing the adsorbent and preparation method thereof of sulfur trioxide in flue gas, heavy metal simultaneously |
WO2019205765A1 (en) * | 2018-04-27 | 2019-10-31 | 福州大学 | Preparation method for chlorine adsorbing material for waste incineration and use thereof |
CN114367269A (en) * | 2022-03-02 | 2022-04-19 | 四川大学 | Flue gas pollutant adsorbent and preparation method thereof |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0699151B2 (en) * | 1989-08-23 | 1994-12-07 | 工業技術院長 | Lipophilic modified basic calcium carbonate and method for producing the same |
US5779464A (en) * | 1996-01-10 | 1998-07-14 | The Ohio State University Research Foundation | Calcium carbonate sorbent and methods of making and using same |
-
2004
- 2004-10-29 CN CNB200410086708XA patent/CN100435930C/en not_active Expired - Fee Related
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101679077B (en) * | 2007-06-15 | 2013-05-08 | Omya发展股份公司 | Surface-reacted calcium carbonate in combination with hydrophobic adsorbent for water treatment |
CN101310853B (en) * | 2008-02-15 | 2012-09-12 | 郜洪文 | Calcium adsorbing material and its preparation method |
CN101780393B (en) * | 2009-01-15 | 2013-01-23 | 财团法人工业技术研究院 | Adsorbent, regenerating-recycling method and recycling equipment thereof |
CN102631886A (en) * | 2012-04-01 | 2012-08-15 | 东南大学 | Waste incineration additive with function of capturing heavy metals and preparation method thereof |
CN102631886B (en) * | 2012-04-01 | 2013-10-23 | 东南大学 | Waste incineration additive with function of capturing heavy metals and preparation method thereof |
CN103752258A (en) * | 2014-01-09 | 2014-04-30 | 苏州英斯迪尼工贸有限公司 | Harmful gas adsorbate and preparation method thereof |
CN104174353B (en) * | 2014-08-22 | 2016-01-06 | 南京信息工程大学 | One removes CO simultaneously 2and SO 2ca-base adsorbent and method of modifying thereof and application |
CN104174353A (en) * | 2014-08-22 | 2014-12-03 | 南京信息工程大学 | Calcium-based adsorbing agent for removing CO2 and SO2 simultaneously, as well as modification method and application of adsorbing agent |
CN105195083A (en) * | 2015-09-14 | 2015-12-30 | 贺州学院 | Method for modifying ground calcium carbonate with sodium chloride to prepare heavy metal adsorbent |
CN105618004A (en) * | 2016-03-28 | 2016-06-01 | 贺州学院 | Preparation method of calcium carbonate-based chelate sorbent |
CN107115838A (en) * | 2017-06-29 | 2017-09-01 | 安徽天顺环保设备股份有限公司 | A kind of low-temperature plasma modified flue gas removes cadmium Ca-base adsorbent and preparation method |
WO2019205765A1 (en) * | 2018-04-27 | 2019-10-31 | 福州大学 | Preparation method for chlorine adsorbing material for waste incineration and use thereof |
US11896955B2 (en) | 2018-04-27 | 2024-02-13 | Fuzhou University | Method for preparing chlorine adsorption material for use in waste incineration and application of chlorine adsorption material |
CN109046227A (en) * | 2018-08-28 | 2018-12-21 | 黄志伟 | A kind of natural mineral matter air purifying composition and preparation method thereof |
CN109847689A (en) * | 2019-01-09 | 2019-06-07 | 西安热工研究院有限公司 | It is a kind of for removing the adsorbent and preparation method thereof of sulfur trioxide in flue gas, heavy metal simultaneously |
CN114367269A (en) * | 2022-03-02 | 2022-04-19 | 四川大学 | Flue gas pollutant adsorbent and preparation method thereof |
CN114367269B (en) * | 2022-03-02 | 2023-02-28 | 四川大学 | Flue gas pollutant adsorbent and preparation method thereof |
Also Published As
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