CN101116807A - Gas dechlorinating agent and its preparing method - Google Patents
Gas dechlorinating agent and its preparing method Download PDFInfo
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- CN101116807A CN101116807A CNA2006100890329A CN200610089032A CN101116807A CN 101116807 A CN101116807 A CN 101116807A CN A2006100890329 A CNA2006100890329 A CN A2006100890329A CN 200610089032 A CN200610089032 A CN 200610089032A CN 101116807 A CN101116807 A CN 101116807A
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Abstract
A gas dechlorinating agent comprises alumina occupying 10-60 percent of mass, modifier occupying 5-60 percent of mass, zeolite occupying 1-15 percent of mass and alkaline earth metal oxide occupying 5-80 percent of mass, wherein the modifier is clay or bentonite. The dechlorination agent can effectively remove the hydrogen chloride in gas, and has higher penetrating chlorine capacity.
Description
Technical field
The present invention is a kind of dechlorinating agent for high-temp gas and preparation method, specifically, is antichlor and the preparation method who removes hydrogen chloride from high-temperature gas.
Background technology
In petroleum refining industry produces, for guaranteeing the performance of oil refining catalyst, keep the normal operation of system, prevent equipment corrosion, removing hydrogen chloride in gas is an important purge segment.In the continuous reformer operation process, the cyclic regeneration of reforming catalyst is very important process, and early stage alkali cleaning, washing workshop section dechlorination effect are not good, cause the equipment corrosion of regenerative system serious, influence the normal operation of device.Thereby the hydrogen chloride that uses solid dechlorinating agent to remove in the reformation regeneration gas is desirable selection, but reformation regeneration gas temperature up to 450～550 ℃, water content is up to 1000ppm, and contains oxygen and carbon compound in addition, and is very high to the requirement of solid dechlorinating agent.The solid dechlorinating agent that generally is used for below 300 ℃ can not meet the demands.In addition, integrated coal gasification combined cycle of developing (IGCC) and coal gasification fuel cell (MCFC) have also 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, easily evaporation and cause electrolytical loss at high temperature, and the hydrogen chloride that contains 10ppm in the gas just makes cell resistance increase, and causes cell voltage to reduce.Therefore, the dechlorination of high-temperature fuel gas is to realize one of key technology of IGCC and MCFC.
US4374654 disclose a kind of from catalytic reforming waste gas adsorbing separation HCl and H
2The method of S, this method make described waste gas pass through activated alumina or molecular sieve bed layer-selective absorption hydrogen chloride wherein at 40～70 ℃, and then will remove the waste gas feeding zinc oxide bed of hydrogen chloride, absorption H wherein
2S.Used molecular sieve is the 4A molecular sieve, and the HCl in the waste gas is at low temperatures by molecular sieve adsorption.
CN92103886.0 discloses a kind of chloride absorbent and preparation method thereof, and this adsorbent is made up of gama-alumina and alkali carbonate or alkaline earth metal carbonate auxiliary agent.The preparation method can adopt any in the pinching bar method of mixing, infusion process, rolling ball method or the pressed disc method moulding.It is stronger that this agent removes the hydrogen chloride ability, and hydrogen chloride impurity content in gas or the liquid hydrocarbon is reduced to 0.5ppm when following, and the saturating chlorosity of the biography of adsorbent reaches as high as 25.2 weight ﹠, but the undeclared probe temperature that penetrates chlorosity.
CN1081936A discloses a kind of adsorbent that removes de-chlorine hydride, comprise activated alumina and alkali metal promoter, alkali metal promoter is at least 5 weight % in the content of alkali metal oxide with respect to aluminium oxide, the micro pore volume that this adsorbent has is distributed as: micro-pore diameter accounts for 0.1 milliliter/gram at least greater than the hole of 750 dusts, hole greater than 40 dusts accounts for 0.35 milliliter/gram at least, and the hole of 100～10000 dusts accounts for 0.16 milliliter/gram at least.This adsorbent with water-soluble alkali organic salt dipping, and makes it decompose being lower than under 500 ℃ the condition in aluminium oxide, sloughs water at 300～550 ℃ and forms and contain alkali-metal alumina adsorbant.
CN1064099A discloses a kind of antichlor, use alkali metal or alkaline earth metal compound to be the dechlorination active component, with the natural inorganic clay, preferred sheep earthenware soil is made antichlor for binding agent, adds expanding agent-ammonium carbonate, carbonic hydroammonium, lignin or sesbania powder during preparation.200 ℃ of following dechlorinations, hydrogen chloride in gas is reduced to below the 0.5ppm.
CN97116288.3 discloses a kind of high performance dechloridizing agent and preparation method thereof, and described antichlor uses sodium carbonate, calcium carbonate and magnesia to be active component, is carrier with inorganic clay, bentonite, kaolin or diatomite.This antichlor adds inorganic binder aluminium colloidal sol or colloid SiO in preparation process
2Or high-temperature cement, and add organic or the macromolecular compound methylcellulose or/and polyethylene glycol, urea, after the extrusion drying in 350～400 ℃ of roastings.This antichlor is under 200～400 ℃, 1000～3000 hours-1 reaction condition, and the chlorosity that penetrates that the chlorine in the gas is reduced to below the 0.1ppm is 30 weight %.
It is active component that above antichlor adopts alkali metal or alkaline earth metal compounds mostly, and degree of purification is all higher, but the dechlorination temperature all is lower than 500 ℃, and its application is restricted.
CN1334139A discloses a kind of dechlorinating agent for high-temp gas and preparation method, uses natural sepiolite, sodium carbonate, calcium carbonate, kaolin and expanding agent to make, and described expanding agent is ammonium carbonate or carboxymethyl cellulose and composition thereof.This antichlor was 650 ℃, reaction velocity 1000～1700 hours
-1Condition under, the gas vent hydrogen cloride concentration is reduced to below the 0.5ppm, penetrate chlorosity and reach 36.7%.
Summary of the invention
The purpose of this invention is to provide a kind of dechlorinating agent for high-temp gas and preparation method, the preparation method is simple for this antichlor, and the chlorosity height under hot conditions can effectively remove the chlorine in the gas.
Gas dechlorinating agent provided by the invention comprises aluminium oxide, 5～50 quality % modifier, the zeolite of 1～25 quality % and the alkaline earth oxide of 20～80 quality % of 10～60 quality %, and described modifier is carclazyte or bentonite.
The present invention adds modifier and zeolite in basic anhydride, and adds expanding agent in the preparation process of antichlor, makes the antichlor that makes have bigger specific area, and chlorosity increases.In addition, the aluminium oxide in the antichlor can make antichlor at high temperature use and keep higher chlorosity and gas purification degree.
The specific embodiment
Antichlor of the present invention adds zeolite and modifier in aluminium oxide and alkaline earth oxide, simultaneously in the antichlor preparation process, add expanding agent, make the antichlor that makes at high temperature have bigger chlorosity, thereby effectively remove the chlorine in the gas, reduce the corrosivity of gas.
Modifier is carclazyte or bentonite in the antichlor of the present invention, is mainly used in the specific area that increases antichlor.Preferred 20～50 quality % of alumina content in the antichlor, preferred 5～25 quality % of modifier content, preferred 5～15 quality % of zeolite content, preferred 30～60 quality % of alkaline earth oxide content.
The preferred gama-alumina of aluminium oxide in the antichlor.The preferred macropore h-type zeolite of zeolite, as Y, β or modenite, more preferably H β.The sodium content of described h-type zeolite is less than 0.5 quality %, preferably less than 0.1 quality %.
The specific surface agent of described antichlor is 60～200 meters
2/ gram, preferred 100～150 meters
2/ gram, pore volume are 0.1～0.4 milliliter/gram.
The preparation method of antichlor provided by the invention, comprise aluminium oxide precursor, alkaline earth oxide or its precursor, zeolite and modifier are mixed into raw material, adding expanding agent again mixes, add the suitable quantity of water extruded moulding then, 450～700 ℃ of roastings, described modifier are carclazyte or bentonite.
The preferred macropore h-type zeolite of described zeolite, more preferably H β, the preferred boehmite of aluminium oxide precursor, the preferred calcium oxide of alkaline earth oxide, precursor preferably calcium hydroxide, calcium carbonate or the calcium bicarbonate of alkaline earth oxide.
Described expanding agent preferable methyl cellulose or urea.The addition of expanding agent is 0.5～10 quality % of raw material, preferred 1～5 quality %.
In the above-mentioned extruded moulding process, in raw material, add expanding agent after, be preferably and add extrusion aid again.The addition of extrusion aid is 0.5～10 quality % of raw material, preferred 1～5 quality %, the preferred sesbania powder of described extrusion aid.Behind described solids mixing, add suitable quantity of water and mix the pinching bar, preferably in water, add peptizing agent, the dosage of peptizing agent is 0.5～15 quality % of solids total amount, preferred 1～10 quality %.Peptizing agent is selected from organic acid or inorganic acid, example hydrochloric acid, nitric acid, acetate or citric acid.Extruded moulding thing dry roasting is promptly got antichlor, preferred 50～130 ℃ of described baking temperature, preferred 580～680 ℃ of sintering temperature.
The preparation method of described h-type zeolite carries out ion-exchange with na-pretreated zeolite at normal temperatures with ammonium salt solution, dry then, roasting.Preferred ammonium chloride of described ammonium salt or ammonium nitrate, baking temperature are 50～130 ℃, and sintering temperature is 300～650 ℃.
Antichlor provided by the invention is suitable for the hydrogen chloride in the high temperature removal industrial gasses, is particularly useful for removing the hydrogen chloride in the reformation regeneration gas.Use the antichlor of the present invention's preparation, the hydrogen chloride in gas impurity content can be reduced to below the 0.5ppm.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
(1) preparation H β zeolite
With the NH of Na type β zeolite with 1 mol
4Cl solution carried out ion-exchange 3 hours, used NH at 95 ℃
4The specific mass of Cl solution and β zeolite is 5: 1,120 ℃ of dryings 2 hours, and 550 ℃ of roastings 4 hours obtain the H β zeolite of Na content less than 0.1 quality %.
(2) preparation antichlor
Get 28 gram boehmites, 10 gram carclazytes, 12 gram H β zeolites, 50 gram calcium hydroxides mixing, adding 2.5 gram methylcellulose (sale of Guangzhou chemical reagents corporation) and 2.5 gram sesbania powder mix, adding nitric acid that 15ml concentration is 36 quality % and 45ml deionized water again mixes and pinches evenly, extruded moulding, 650 ℃ of roastings 4 hours, get antichlor A, it is formed and physical property sees Table 1.
(3) estimate the antichlor performance
With the antichlor porphyrize, getting 150～420 microns the particle internal diameter of packing into was that feeding hydrogen chloride content is the nitrogen of 40-100ppm, and adsorption temp is transferred to setting value in 6 millimeters the quartz glass tube, gas volume air speed 1500 hours
-1Condition under the content of hydrogen chloride in the continuous detecting antichlor bed exit gas, when hydrogen chloride content is higher than 0.5ppm, stop reaction.Analyze the hydrogen chloride content in the antichlor, this value is and penetrates chlorosity.The penetrate chlorosity of antichlor A under each adsorption temp sees Table 2.
Example 2
Method by 1 (1) step of example prepares H β, and the method by (2) step prepares antichlor again, and different is that the boehmite that adds is 40 grams, and composition and the physical property of the antichlor B that makes see Table 1.
The method of pressing 1 (3) step of example is estimated the dechlorination performance of antichlor B, and the penetrate chlorosity of antichlor B under each adsorption temp sees Table 2.
Example 3
Method by 1 (1) step of example prepares H β, and the method by (2) step prepares antichlor again, and different is that the boehmite that adds is 55 grams, and calcium hydroxide is 40 grams, and composition and the physical property of the antichlor C that makes see Table 1.
The method of pressing 1 (3) step of example is estimated the dechlorination performance of antichlor C, and the penetrate chlorosity of antichlor C under each adsorption temp sees Table 2.
Example 4
The method that goes on foot by example 1 (1) prepares H β, and the method by (2) step prepares antichlor again, and different is to add 55 gram boehmites, and 40 restrain calcium hydroxides, and replace carclazytes with 10 gram bentonites, and composition and the physical property of the antichlor D that makes see Table 1.
The method of pressing 1 (3) step of example is estimated the dechlorination performance of antichlor D, and the penetrate chlorosity of antichlor D under each adsorption temp sees Table 2.
Example 5
Method by 1 (1) step of example prepares H β, and the method by (2) step prepares antichlor again, and different is to add 30 gram boehmites, and replaces carclazyte with 10 gram bentonites, and composition and the physical property of the antichlor E that makes see Table 1.
The method of pressing 1 (3) step of example is estimated the dechlorination performance of antichlor E, and the penetrate chlorosity of antichlor E under each adsorption temp sees Table 2.
Example 6
Method by 1 (1) step of example prepares H β, method by (2) step prepares antichlor again, and different is that the boehmite that adds is 55 grams, and calcium hydroxide is 40 grams, and replace methylcellulose with 2.5 gram urea, composition and the physical property of the antichlor F that makes see Table 1.
The method of pressing 1 (3) step of example is estimated the dechlorination performance of antichlor F, and the penetrate chlorosity of antichlor F under each adsorption temp sees Table 2.
Table 1
| Instance number | Numbering | Form quality % | Specific area, rice 2/ gram | Pore volume, milliliter/gram | ||||
| Aluminium oxide | Carclazyte | Bentonite | Hβ | Calcium oxide | ||||
| 1 | A | 25.0 | 12.1 | - | 14.5 | 48.4 | 94 | 0.18 |
| 2 | B | 32.2 | 10.9 | - | 13.1 | 43.8 | 111 | 0.20 |
| 3 | C | 42.9 | 10.6 | - | 12.7 | 33.8 | 148 | 0.21 |
| 4 | D | 42.9 | - | 10.6 | 12.7 | 33.8 | 144 | 0.20 |
| 5 | E | 26.3 | - | 11.9 | 14.2 | 47.6 | 98 | 0.17 |
| 6 | F | 42.9 | 10.6 | - | 12.7 | 33.8 | 142 | 0.20 |
Table 2
Claims (10)
1. gas dechlorinating agent comprises aluminium oxide, 5～50 quality % modifier, the zeolite of 1～25 quality % and the alkaline earth oxide of 20～80 quality % of 10～60 quality %, and described modifier is carclazyte or bentonite.
2. according to the described antichlor of claim 1, it is characterized in that alumina content is 20～50 quality % in the described antichlor, modifier content is 5～25 quality %, and zeolite content is 5～15 quality %, and alkaline earth oxide content is 30～60 quality %.
3. according to the described antichlor of claim 1, it is characterized in that described aluminium oxide is a gama-alumina, described zeolite is the macropore h-type zeolite.
4. according to the described antichlor of claim 1, it is characterized in that described zeolite is H β.
5. according to the described antichlor of claim 1, the specific area that it is characterized in that described antichlor is 60～200 meters
2/ gram, pore volume are 0.1～0.4 milliliter/gram.
6. the preparation method of the described antichlor of claim 1, comprise aluminium oxide precursor, alkaline earth oxide or its precursor, zeolite and modifier are mixed into raw material, adding expanding agent again mixes, add the suitable quantity of water extruded moulding then, 450～700 ℃ of roastings, described modifier are carclazyte or bentonite.
7. according to claims 6 described methods, it is characterized in that described zeolite is H β, the aluminium oxide precursor is a boehmite.
8. according to claims 6 described methods, it is characterized in that alkaline earth oxide is a calcium oxide, the precursor of alkaline earth oxide is calcium hydroxide, calcium carbonate or calcium bicarbonate.
9. according to claims 6 described methods, it is characterized in that expanding agent is methylcellulose or urea.
10. according to claims 6 described methods, the addition that it is characterized in that expanding agent is 0.5～10 quality % of raw material.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101569830B (en) * | 2008-04-29 | 2012-07-18 | 中国石油化工股份有限公司 | Method for dechlorinating gas discharged from continuous reforming regenerator |
| CN102676207A (en) * | 2011-03-10 | 2012-09-19 | 中国石油化工股份有限公司 | Dechlorinating method for catalystic reforming reaction product |
| CN102895988A (en) * | 2011-07-25 | 2013-01-30 | 中国石油天然气股份有限公司 | Preparation method of in-situ crystallization catalyst |
| CN101724435B (en) * | 2008-10-31 | 2014-04-30 | 中国石油化工股份有限公司 | Dechlorination method of oil product or gas |
| CN104307463A (en) * | 2014-11-11 | 2015-01-28 | 东南大学 | Chemically modified calcium-based CO2 adsorbent and preparation method thereof |
| 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 |
| CN108745332A (en) * | 2018-07-03 | 2018-11-06 | 贵州大学 | A kind of method of ardealite and high-sulfur bauxite dechlorination catalyst |
| CN109453754A (en) * | 2017-09-06 | 2019-03-12 | 中国石化扬子石油化工有限公司 | A kind of regeneration method of useless 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 |
| CN110885699A (en) * | 2018-09-07 | 2020-03-17 | 中国石化扬子石油化工有限公司 | Dechlorinating agent with large pore volume and pore diameter as well as preparation method and application thereof |
| CN112973414A (en) * | 2021-02-04 | 2021-06-18 | 西安元创化工科技股份有限公司 | High-temperature gas-phase dechlorinating agent composition and preparation method and application thereof |
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2006
- 2006-07-31 CN CNB2006100890329A patent/CN100509139C/en active Active
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101569830B (en) * | 2008-04-29 | 2012-07-18 | 中国石油化工股份有限公司 | Method for dechlorinating gas discharged from continuous reforming regenerator |
| CN101724435B (en) * | 2008-10-31 | 2014-04-30 | 中国石油化工股份有限公司 | Dechlorination method of oil product or gas |
| CN102676207A (en) * | 2011-03-10 | 2012-09-19 | 中国石油化工股份有限公司 | Dechlorinating method for catalystic reforming reaction product |
| CN102895988A (en) * | 2011-07-25 | 2013-01-30 | 中国石油天然气股份有限公司 | Preparation method of in-situ crystallization catalyst |
| 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 |
| CN104307463B (en) * | 2014-11-11 | 2016-04-13 | 东南大学 | A kind of chemical modification calcium base CO 2adsorbent and preparation method thereof |
| CN104307463A (en) * | 2014-11-11 | 2015-01-28 | 东南大学 | Chemically modified calcium-based CO2 adsorbent and preparation method thereof |
| CN109453754A (en) * | 2017-09-06 | 2019-03-12 | 中国石化扬子石油化工有限公司 | A kind of regeneration method of useless 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 |
| CN108745332A (en) * | 2018-07-03 | 2018-11-06 | 贵州大学 | A kind of method of ardealite and high-sulfur bauxite dechlorination catalyst |
| CN110885699A (en) * | 2018-09-07 | 2020-03-17 | 中国石化扬子石油化工有限公司 | Dechlorinating agent with large pore volume and pore diameter as well as preparation method and application thereof |
| CN110885699B (en) * | 2018-09-07 | 2021-12-24 | 中国石化扬子石油化工有限公司 | Dechlorinating agent with large pore volume and pore diameter as well as preparation method and application thereof |
| CN112973414A (en) * | 2021-02-04 | 2021-06-18 | 西安元创化工科技股份有限公司 | High-temperature gas-phase dechlorinating agent composition and preparation method and application thereof |
| CN112973414B (en) * | 2021-02-04 | 2022-06-28 | 西安元创化工科技股份有限公司 | High-temperature gas-phase dechlorinating agent composition and preparation method and application thereof |
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