CN1724119A - Dechlorination agent and its preparation process - Google Patents
Dechlorination agent and its preparation process Download PDFInfo
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- CN1724119A CN1724119A CN 200510027186 CN200510027186A CN1724119A CN 1724119 A CN1724119 A CN 1724119A CN 200510027186 CN200510027186 CN 200510027186 CN 200510027186 A CN200510027186 A CN 200510027186A CN 1724119 A CN1724119 A CN 1724119A
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- antichlor
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- bentonite
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- alkylammonium salt
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Abstract
An antichlor is proportionally prepared from polyhexenol, bentorite, alkylammonium salt, sodium hydroxide, magnesium hydroxide and copper hydro-oxide through slurry synthesizing reaction, extruding for shaping, baking and calcining. Its advantages are high effect and Cl capacity, and high thermal stability.
Description
Technical field
The present invention relates to the friendly antichlor of novel environmental of high temperature deep removal hydrogen chloride gas, the present invention relates to a kind of antichlor that is used for coal gasification coal gas of high temperature, biomass-making gas and various combustion power generation, chemical industry chlorine-containing gas deep removal hydrogen chloride and preparation method thereof in particular.
Background technology
Can poison deactivation when many expensive catalysts are used in containing the atmosphere of hydrogen chloride, industrially in preparing synthetic gas, coal gas of high temperature, biomass-making gas and various combustion power generation process, need to solve the problem that therefrom removes hydrogen chloride gas.The antichlor kind that occurs is a lot of both at home and abroad, but still have many problems to need to be resolved hurrily, the antichlor of calcium base active component for example, be easy to absorb steam and influence performance and quicken efflorescence, and it is various that alkali metal or alkaline-earth metal are carried on the antichlor preparation process of the organic clay carrier that modification in advance handles, not only introduce the component difficulty, and be difficult to realize optimized load ratio of multiple alkali metal/alkaline-earth metal and load capacity, poor controllability.Present in addition antichlor ubiquity use cost height, poor heat stability, antichlor caused secondary pollution problems after losing efficacy easily.
Summary of the invention
Technical problem to be solved by this invention provides a kind of superior performance, the scope of application is wide and eco-friendly cheap antichlor and preparation method thereof.
The technical solution used in the present invention: a kind of antichlor, its preparation material composition comprises: polyhexene alcohol 5~10wt%, bentonite 30~60wt%, alkylammonium salt 5wt%, NaOH 5~20wt%, magnesium hydroxide 10~40wt% and Kocide SD 5~20wt%.
The preparation method of described antichlor carries out slurries synthetic reaction with the precursor liquid of multivariant oxide with polyhexene alcohol, stratiform bentonite mineral and alkylammonium salt under 40~80 ℃ of temperature; After treating fully reaction, product is squeezed into bar shaped, under 80~100 ℃ of temperature, dries 4h, make described antichlor at 650 ℃ of roasting temperature 10h then.The precursor liquid of described multivariant oxide is the mixed ammonium/alkali solutions of NaOH, magnesium hydroxide and Kocide SD, and alkylammonium salt is a softex kw.
Beneficial effect of the present invention: the crystal structure of natural montmorillonite generally believes to be two layers of silicon-oxy tetrahedron wafer with therebetween alumina octahedral wafer combine formation crystal layer, constitute 2: 1 structures, every layer of lattice arrangement with high-sequential, between layer and the layer is weak molecular link, the ion that the interlayer weak bond closes can be replaced by other ion, but the distance between the while regulating course, these unique natural structures make it have many valuable characteristics such as ion exchangeable, dilatancy, thixotropy, caking property and adsorptivity, are the precursor materials of good preparation antichlor.The present invention is incorporated into multivariant oxide in the bentonite structure, has not only strengthened the skeleton structure of system, has further improved thermal stability, and serviceability temperature reaches 923K, and helps porous, compoundization and the functionalization of material.The present invention has made full use of the interlayer expansiveness of stratiform bentonite uniqueness, good adsorptivity and ion-exchange performance, with polyhexene alcohol is surfactant, add alkylammonium salt, in the performance surperficial multicomponent reactive synergistic while of center, taken into full account the factor of augmentation of heat transfer, mass transfer, acceleration chemical reaction, the dechlorination precision is less than 0.1mg/m
3, utilization rate and chlorosity amount very high (at 823K, tail gas 0.1mg/m
3Breakthrough chlorine content reach 55.3%).The used primary raw material of the present invention is cheapness and abundant mineral and hydroxide, and preparation process is simple, controlled, does not relate to complex apparatus and operation, and cost is very low.Antichlor of the present invention belongs to the compound antichlor of multicomponent, superior performance, and the scope of application is wide, has realized the high temperature deep removal to HCl gas in experiment.Antichlor environmental friendliness of the present invention, behind the absorption reaction hydrogen chloride gas, the oxygen of its composition is substituted by chlorine, and useless antichlor is mainly bentonite and is mingled with the chloride salt that generates behind the dechlorination reaction, even directly abandon, the secondary pollution of chlorion also must not take place.
Description of drawings
Fig. 1 is embodiment one chlorosity amount and temperature relation figure;
Fig. 2 is embodiment one breakthrough curve figure;
Fig. 3 is embodiment dichloro capacity and temperature relation figure;
Fig. 4 is embodiment two breakthrough curve figure;
Fig. 5 is embodiment trichlorine capacity and temperature relation figure;
Fig. 6 is embodiment three breakthrough curve figure.
The specific embodiment
Below by embodiment the present invention is described in further detail: a kind of antichlor, its composition comprises: poly-enol 5~10wt%, bentonite 30~60wt%, alkylammonium salt 5wt%, NaOH 5~20wt%, magnesium hydroxide 10~40wt% and Kocide SD 5~20wt%.
The preparation method of described antichlor carries out slurries synthetic reaction with the precursor liquid of multivariant oxide with polyhexene alcohol, stratiform bentonite mineral and alkylammonium salt under 40~80 ℃ of temperature; After treating fully reaction,, under 80~100 ℃ of temperature, dry 4h, make described antichlor at 650 ℃ of roasting temperature 10h then the product extrusion molding.The precursor liquid of described multivariant oxide is the mixed ammonium/alkali solutions of NaOH, magnesium hydroxide and Kocide SD, and alkylammonium salt is a softex kw.
Performance test:
MgCl in the dechlorination reaction product
2, CuCl
2And NaCl, MgCl
2Fusing point minimum (being 974K), therefore, the MgO that surpasses one of 974K antichlor active constituent when temperature is with ineffective, this will influence the dechlorination performance of antichlor, therefore, the maximum operation (service) temperature of antichlor of the present invention should be less than 974K.The test condition of dechlorination performance is: internal diameter 10mm fixed bed reactors, inlet HCl gas concentration is 1000mg/m
3, air speed is 3000h
-1The antichlor particle is 0.3~0.5mm, to in the dechlorination fixed bed reactors, establish the steel wire of 1~2 layer of aperture during the sample filling less than agent kind particle diameter, online face laying depth is that 200mm, granularity are the porcelain ball of about 10mm, the antichlor bed should load smooth even as far as possible, and nitrogen is adopted in carrier gas, and the pass of chlorosity amount and temperature ties up under the condition of reacting 10h and measures, breakthrough curve is to measure atmospheric operation under 6 the condition at ratio of height to diameter.Performance test shows that the bulk density of antichlor of the present invention is 0.60~0.80g.ml
1, side pressure strength is 90~110N/cm, specific area is 80~100m
2/ g.With 0.1mg/m
3Penetrate as tail gas, test is found to reach 0.1mg/m at 623K, 723K and 823K reaction end gas
3Time of break-through respectively greater than 16.1h, 16.9h and 22.8h, breakthrough chlorine content is successively greater than 48.2%, 50.5% and 55.3%.Breakthrough curve hints that also antichlor of the present invention is saturated needed chronic, just trends towards saturation state later at 80h, and the dechlorination performance is in 573~923K scope, increases with the rising of temperature.
Embodiment one
The compositing formula of antichlor:
Bentonite 50wt%, chemical reagent polyhexene alcohol 5wt%, softex kw 5wt%, Mg (OH)
2(20wt%), Cu (OH)
2(8wt%), NaOH (12wt%).
Performance test:
Bulk density is 0.76g.ml
1, side pressure strength is 103N/cm, the specific area of BET test is 93.356m
2/ g.
The relation of temperature and chlorosity amount is seen shown in Figure 1, and breakthrough curve as shown in Figure 2.
Embodiment two
The compositing formula of antichlor:
Bentonite 55wt%, chemical reagent polyhexene alcohol 5wt%, softex kw 5wt%, Mg (OH)
2(15wt%), Cu (OH)
2(5wt%), NaOH (15wt%).
Performance test:
Bulk density is 0.70g.ml
1, side pressure strength is 95N/cm, the specific area of BET test is 98.267m
2/ g.
The relation of temperature and chlorosity amount is seen shown in Figure 3, and breakthrough curve as shown in Figure 4.
Embodiment three
The compositing formula of antichlor:
Bentonite 40wt%, chemical reagent polyhexene alcohol 8wt%, softex kw 5wt%, Mg (OH)
2(17wt%), Cu (OH)
2(10wt%), NaOH (20wt%).
Performance test:
Bulk density is 0.78g.ml
1, side pressure strength is 108N/cm, the specific area of BET test is 82.305m
2/ g.
The relation of temperature and chlorosity amount is seen shown in Figure 5, and breakthrough curve as shown in Figure 6.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (3)
1. antichlor, its preparation raw material comprises: polyhexene alcohol 5~10wt%, bentonite 30~60wt%, alkylammonium salt 5wt%, NaOH 5~20wt%, magnesium hydroxide 10~40wt% and Kocide SD 5~20wt%.
2. the preparation method of the described antichlor of claim 1 is characterized in that: polyhexene alcohol, stratiform bentonite mineral and alkylammonium salt are carried out the slurries synthetic reaction with the precursor liquid of multivariant oxide under 40~80 ℃ of temperature; After treating fully reaction,, under 80~100 ℃ of temperature, dry 4h, make described antichlor at 650 ℃ of roasting temperature 10h then the product extrusion molding.
3. according to the preparation method of the described antichlor of claim 2, it is characterized in that: be matrix material with the bentonite, polyhexene alcohol is surfactant, and alkylammonium salt is a softex kw, and the precursor liquid of multivariant oxide is the mixed ammonium/alkali solutions of NaOH, magnesium hydroxide and Kocide SD.
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CNB2005100271860A CN1325146C (en) | 2005-06-28 | 2005-06-28 | Dechlorination agent and its preparation process |
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CNB2005100271860A CN1325146C (en) | 2005-06-28 | 2005-06-28 | Dechlorination agent and its preparation process |
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CN1724119A true CN1724119A (en) | 2006-01-25 |
CN1325146C CN1325146C (en) | 2007-07-11 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102485837A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | High-temperature dechlorination agent and preparation method thereof |
CN103406015A (en) * | 2013-08-16 | 2013-11-27 | 云南铜业股份有限公司 | Chlorine-containing smoke absorption and purification device and method |
CN104689787A (en) * | 2013-12-09 | 2015-06-10 | 东营科尔特化工科技有限公司 | Liquefied petroleum gas dechlorination adsorbent and application method thereof |
EP3007806B1 (en) * | 2013-06-13 | 2018-10-03 | Clariant Corporation | Method for reducing halide concentration in gas streams |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5244785A (en) * | 1975-10-07 | 1977-04-08 | Sumitomo Chem Co Ltd | Catalyst for oxidizing chlorinated hydrocarbons |
CN1088388C (en) * | 1996-04-26 | 2002-07-31 | 湖北省化学研究所 | Refined antichlor and method for preparing same |
JPH1099643A (en) * | 1996-09-26 | 1998-04-21 | Kobe Steel Ltd | Molded object for removing hydrogen chloride gas |
CN1060408C (en) * | 1997-09-10 | 2001-01-10 | 中国石油化工总公司 | High performance dechloridizing agent and preparation thereof |
-
2005
- 2005-06-28 CN CNB2005100271860A patent/CN1325146C/en not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102485837A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | High-temperature dechlorination agent and preparation method thereof |
EP3007806B1 (en) * | 2013-06-13 | 2018-10-03 | Clariant Corporation | Method for reducing halide concentration in gas streams |
CN103406015A (en) * | 2013-08-16 | 2013-11-27 | 云南铜业股份有限公司 | Chlorine-containing smoke absorption and purification device and method |
CN103406015B (en) * | 2013-08-16 | 2015-10-28 | 云南铜业股份有限公司 | A kind of chloride smoke absorption, purifier and method |
CN104689787A (en) * | 2013-12-09 | 2015-06-10 | 东营科尔特化工科技有限公司 | Liquefied petroleum gas dechlorination adsorbent and application method thereof |
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CN1325146C (en) | 2007-07-11 |
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