CN1114480C - Dechlorinating agent for high-temp gas and its preparing process - Google Patents
Dechlorinating agent for high-temp gas and its preparing process Download PDFInfo
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- CN1114480C CN1114480C CN 01126381 CN01126381A CN1114480C CN 1114480 C CN1114480 C CN 1114480C CN 01126381 CN01126381 CN 01126381 CN 01126381 A CN01126381 A CN 01126381A CN 1114480 C CN1114480 C CN 1114480C
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- dechlorinating agent
- temperature
- antichlor
- gas
- temperature gas
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Abstract
The present invention provides a dechlorinating agent for high-temperature gas and a preparation method thereof. The dechlorinating agent for high-temperature gas of the present invention uses natural sepiolite and compound of alkali metal with alkaline earth metal as active components, wherein the natural sepiolite is used as both an active component and a dechlorinating agent carrier. Inorganic or organic binder and hole expanding binder are added into the dechlorinating agent to effectively improve the reaction capacity of the active component and the stability of the dechlorinating agent. The dechlorinating agent of the present invention is used to dechlorinate high-temperature gas, and at the temperature of 650DEG C, the dechlorinating agent can dechlorinate the content of hydrogen chloride in high-temperature gas to less than 0.5 ppm and the content of chlorine to 36%. The dechlorinating agent for high-temperature gas is characterized by good purification degree, high chlorine content, easy manufacture and low cost, and can be widely used in hydrogen chloride elimination of high-temperature fuel gas and high-temperature gas.
Description
Technical field
The present invention relates to a kind of gas dechlorinating agent, specifically, relate to a kind of composition that removes hydrogen chloride in high-temperature fuel gas or other industrial gasses.
Background technology
In Chemical Manufacture, be the normal operation or the minimizing equipment corrosion that guarantee system, removing hydrogen chloride in gas often is a very important purge segment.Integrated coal gasification combined cycle of developing (IGCC) and coal gasification fuel cell (MCFC) have then proposed the requirement of upgrading to the hydrogen chloride that removes under the hot conditions in the combustion gas.Hydrogen chloride in the high-temperature gas is very big to the corrosion harmfulness of equipment, even also influences the operate as normal of system.For example, to the MCFC system, the chlorination Hydrogen Energy in the combustion gas and electrolyte form low-boiling compound, and easily evaporation and cause electrolytical loss at high temperature contains 0.0001% hydrogen chloride cell resistance is increased in the gas, cause cell voltage to reduce.Therefore, the dechlorination of high-temperature fuel gas is to realize one of key technology of IGCC and MCFC.
At present, existing many dechlorination technology are published.Adopting aluminium oxide as U.S. Pat 4639259 is the alkaline-earth metal antichlor of carrier, the weight content of alkaline-earth metal is 0.5-45%, this antichlor can be reduced to 1ppm with hydrogen chloride at normal temperatures, and breakthrough chlorine content is 20% (weight of the adsorbed chlorine of antichlor/antichlor weight).U.S. Pat 3935295 used antichlors are made by zinc oxide and alkaline-earth metal, and the chlorosity amount is 10-35% when being lower than 500 ℃.Chinese patent CN1064099A discloses a kind of alkali metal and alkaline-earth metal of using and has been the dechlorination active component, is the antichlor of binding agent with the natural inorganic clay, and when reaction temperature was lower than 280 ℃, hydrogen chloride in gas can be reduced to below the 0.5ppm.Chinese patent CN1079415A has disclosed a kind of use gama-alumina and alkalies and alkaline earth carbonate, hydrogen chloride in gas content can be reduced to below the 0.5ppm, penetrates the hydrogen chloride adsorbance and can reach 25% antichlor.Chinese patent CN1178133A then uses sodium carbonate, calcium carbonate and magnesia to be active component, is carrier with the natural inorganic clay, is being lower than 480 ℃, 1000-3000hr
-1Under the reaction velocity condition, the chlorine in the gas can be reduced to below the 0.1ppm, the weight chlorosity is 30% antichlor.
It is active component that above antichlor adopts alkali metal and alkaline earth metal compounds mostly, and degree of purification is all higher, yet generally uses being lower than under 500 ℃ the condition, thereby is restricted in the commercial Application of high temperature dechlorination.
Summary of the invention
One of technical issues that need to address of the present invention provide a kind of high performance dechloridizing agent that is applicable to high-temperature fuel gas or other industrial gasses, the defective that is restricted with the antichlor commercial Application at high temperature that overcomes prior art, and have the advantage that degree of purification is good, chlorosity is high and cost is low.
Two of the technical issues that need to address of the present invention are to provide the preparation method of described antichlor.
High-temperature dechlorinating agent of the present invention uses natural sepiolite, alkali metal and alkaline earth metal compounds to be active component, and sepiolite wherein both can be used as the antichlor carrier simultaneously as active component.Also add inorganic or organic binder bond and expanding agent in the antichlor, with the respond of effective raising active constituent and the stability of antichlor.
The component and the weight percent content of antichlor of the present invention comprise:
Sepiolite 10-65%
Sodium carbonate 5-55%
Sodium acid carbonate 0-40%
Calcium carbonate 10-55%
Calcium hydroxide 10-50%
Calcium oxide 0-35%
Kaolin 2-15%
Expanding agent 1-20%
Said sepiolite is a kind of natural crystal, also is called hydrated magnesium silicate, and main component is Mg
8(H
2O)
4(Si
6O
15)
2(OH)
4.8H
2O;
Said kaolin is in the present invention as binding agent, and its chemical name is the water aluminosilicate, main component: AL
4(OH)
8(Si
4O
10);
Said expanding agent is ammonium carbonate or carboxymethyl cellulose and composition thereof.
The preparation of above-mentioned antichlor comprises the steps:
The water insoluble solid thing was all through grinding 80 mesh sieves in the raw material, with the water dissolvable raw material blending after add the suitable quantity of water extruded moulding, the finished product high-temperature dechlorinating agent is made in the drying roasting again, sintering temperature is 350～800 ℃, roasting time 1～8 hour.
Antichlor of the present invention is carried out the dechlorination test of high-temperature gas, and its result shows, the hydrogen chloride content in the high-temperature gas can be taken off to 0.5ppm in the time of 650 ℃, and chlorosity reaches 36%.
By above-mentioned disclosed technical scheme as seen, antichlor of the present invention is on the basis of active component adopting alkali metal and alkaline-earth metal, introduce natural sepiolite, not only can be used as the dechlorination active component but also had the effect of antichlor carrier concurrently, and improved high-temperature dechlorinating agent effectively and the stability of antichlor has been increased greatly the adsorption activity of chlorine.This high-temperature dechlorinating agent has the advantages that degree of purification is good, chlorosity is high, preparation is simple and cost is low.This high-temperature dechlorinating agent can be widely used in removing hydrogen chloride in high-temperature fuel gas and the high-temperature gas.
The specific embodiment
By the following examples the concrete embodiment of the present invention is narrated, but embodiment does not limit protection scope of the present invention.
Embodiment 1
20 kilograms of sepiolites, 55 kilograms of sodium carbonate, 10 kilograms of calcium hydroxides, 13 kilograms of kaolin and 2 kilograms of carboxymethyl celluloses at the grinding machine for grinding extruded moulding, 700 ℃ of roasting temperatures 4 hours, are promptly obtained antichlor of the present invention.
Resulting antichlor is carried out the dechlorination test, and the dechlorination reaction condition is: gas feed hydrogen cloride concentration 1000-1500ppm, reaction velocity 1500-2000hr
-1, 600 ℃ of reaction temperatures.This antichlor can make the hydrogen chloride content of exit gas reduce to below the 0.5ppm, penetrates chlorosity 35.7%.
Import and export hydrogen cloride concentration detection employing silver nitrate volumetric method in the gas, solid dechlorinating agent chlorosity amount is according to the assay method analysis of chlorine in the coal.
Embodiment 2
60 kilograms of sepiolites, 25 kilograms of calcium carbonate, 10 kilograms of sodium carbonate, 3 kilograms of carboxymethyl celluloses, 2 kilograms of kaolin at the grinding machine for grinding extruded moulding, were promptly obtained antichlor of the present invention in 2 hours at 750 ℃ of roasting temperatures.
Resulting antichlor is carried out the dechlorination test, and the dechlorination reaction condition is: high-temperature gas import hydrogen chloride content is 1300-1500ppm, reaction velocity 1500-1800hr
-1, 650 ℃ of dechlorination reaction temperature.The chlorosity that penetrates when hydrogen cloride concentration is lower than 0.5ppm in the exit gas is 28.1%.
The analyzing detecting method of hydrogen cloride concentration and chlorosity is with embodiment 1.
Embodiment 3
After 20 kilograms of sepiolites, 42 kilograms of sodium carbonate, 30 kilograms of calcium carbonate, 2 kilograms of kaolin, 3 kilograms of ammonium carbonates and 3 kilograms of carboxymethyl celluloses are ground extruded moulding, place 750 ℃ of roasting temperatures promptly to obtain antichlor of the present invention in 2 hours.
Resulting antichlor is carried out the dechlorination test, and the dechlorination reaction condition is: high-temperature gas import hydrogen chloride content is 1500-1800ppm, reaction velocity 1000-1700hr
-1, 650 ℃ of dechlorination temperature.The gas vent hydrogen cloride concentration is during less than 0.5ppm, and penetrating chlorosity is 36.7%.
The analyzing detecting method of hydrogen cloride concentration and chlorosity is with embodiment 1.
Embodiment 4
15 kilograms of sepiolites, 25 kilograms of calcium hydroxides, 50 kilograms of sodium carbonate, 5 kilograms of carboxymethyl celluloses, 5 kilograms of kaolin are ground and mix the water extruded moulding, and sintering temperature is 680 ℃, and roasting 5 hours promptly obtains antichlor of the present invention.
The dechlorination reaction condition is: 660 ℃ of temperature, air speed 1200-2000hr
-1Hydrogen chloride in gas concentration is reduced to 0.5ppm by 1700ppm after dechlorination absorption, and the chlorosity that penetrates of antichlor is 31.0%.
The analyzing detecting method of hydrogen cloride concentration and chlorosity is with embodiment 1.
Embodiment 5
35 kilograms of sepiolites, 20 kilograms of calcium oxide, 5 kilograms of sodium carbonate, 10 kilograms of sodium acid carbonates, 10 kilograms of kaolin, 5 kilograms of carboxymethyl celluloses and 15 kilograms of ammonium carbonates are ground mix the water extruded moulding, sintering temperature is 750 ℃, roasting 4 hours.
At 600 ℃, 2500hr
-1Chlorosity amount under the dechlorination reaction condition is 29.3%.Hydrogen cloride concentration in the high-temperature gas can be reduced to below the 0.5ppm by 2000-2300ppm.
The analyzing detecting method of hydrogen cloride concentration and chlorosity is with embodiment 1.
Claims (3)
1. a dechlorinating agent for high-temp gas is characterized in that, the component and the weight percent content of this antichlor comprise:
Sepiolite 10-65%
Sodium carbonate 5-55%
Sodium acid carbonate 0-40%
Calcium carbonate 10-55%
Calcium hydroxide 10-50%
Calcium oxide 0-35%
Kaolin 2-15%
Expanding agent 1-20%;
Said expanding agent is ammonium carbonate or carboxymethyl cellulose and composition thereof.
2. the preparation method of antichlor as claimed in claim 1 is characterized in that comprising the steps:
In the raw material water insoluble solid thing all after grinding with the water dissolvable raw material blending, drying and roasting is made the finished product high-temperature dechlorinating agent, wherein sintering temperature is 350～800 ℃, roasting time 1～8 hour.
3. the preparation method of antichlor as claimed in claim 2 is characterized in that, in the raw material water insoluble solid thing all after grinding 80 mesh sieves with the water dissolvable raw material blending.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01126381 CN1114480C (en) | 2001-07-31 | 2001-07-31 | Dechlorinating agent for high-temp gas and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01126381 CN1114480C (en) | 2001-07-31 | 2001-07-31 | Dechlorinating agent for high-temp gas and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1334139A CN1334139A (en) | 2002-02-06 |
| CN1114480C true CN1114480C (en) | 2003-07-16 |
Family
ID=4666400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01126381 Expired - Fee Related CN1114480C (en) | 2001-07-31 | 2001-07-31 | Dechlorinating agent for high-temp gas and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1114480C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446854C (en) * | 2003-05-16 | 2008-12-31 | 中国科学院成都有机化学研究所 | Catalyst for preparing carbon nanotube and its prepn |
| CN100464837C (en) * | 2006-07-14 | 2009-03-04 | 华东理工大学 | Chloride absorbent |
| CN101274211B (en) * | 2008-05-23 | 2011-03-30 | 北京三聚环保新材料股份有限公司 | High-temperature dechlorinating agent and preparing method thereof |
| CN104774654B (en) * | 2015-03-18 | 2017-12-01 | 华北理工大学 | A kind of application method of blast furnace gas antichlor |
| CN110624382A (en) * | 2018-06-25 | 2019-12-31 | 沈阳三聚凯特催化剂有限公司 | High-temperature flue gas dechlorinating agent and preparation method thereof |
| CN112940794A (en) * | 2021-02-23 | 2021-06-11 | 湖北华特尔净化科技股份有限公司 | Anti-toxin protective agent for blast furnace gas and preparation method thereof |
-
2001
- 2001-07-31 CN CN 01126381 patent/CN1114480C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1334139A (en) | 2002-02-06 |
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Granted publication date: 20030716 Termination date: 20110731 |