CN1060408C - High performance dechloridizing agent and preparation thereof - Google Patents
High performance dechloridizing agent and preparation thereof Download PDFInfo
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- CN1060408C CN1060408C CN97116288A CN97116288A CN1060408C CN 1060408 C CN1060408 C CN 1060408C CN 97116288 A CN97116288 A CN 97116288A CN 97116288 A CN97116288 A CN 97116288A CN 1060408 C CN1060408 C CN 1060408C
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- antichlor
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- chlorine
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Abstract
The present invention relates to a dechloridizing agent with high performance for removing chlorine hydride from chemical raw material gas, which is characterized in that after being mixed, crushed, squeezed into strips and dried by air, 10 to 45 wt% of Na2CO3, 5 to 40 wt% of CaCO3, 5 to 35 wt% of MgO, 10 to 40 wt% of carrier, 1 to 5 wt% of inorganic adhesive and 2 to 8 wt% of organic compound or macromolecular compound are dried for 2 hours at 100 to 120 DEG C and calcined for 1 to 3 hours at 350 to 400 DEG C for preparing the dechloridizing agent with high performance. The provided dechloridizing agent has the advantages of high chlorine content, good purification degree (outlet chlorine content is smaller than 0.1 ppm), large strength, water resistance, high import resistance, obvious rapidness performance and wide active temperature ranges, and is widely applied to chlorine removal in all kinds of gas.
Description
The present invention relates to refined antichlor and preparation thereof that chlorine-containing gas removes chlorine.
In synthetic ammonia and petrochemical industry are produced, use many energy-conservation, new catalysts efficiently, improved the technical merit of whole production technology significantly, obtained remarkable economic efficiency.Yet these new catalysts are very responsive to the poisonous substance in the unstripped gas, require that the related impurities in the unstrpped gas is carried out essence and take off processing, and dechlorination is exactly one of them important step.Chlorine is mainly derived from fresh water (FW), steam, air and raw material hydrocarbon as one of common poisons.Chlorine often exists with the chlorohydrocarbon form in the oil product such as light oil and naphtha, and content is at 3～60ppm; Chlorine in other industrial chemicals generally exists with the inorganic chlorine form, and content is between 1～100ppm.Because chlorine has very high animal migration, often causes the downstream catalyst poisoning and deactivation, causes equipment and pipeline corrosion, has a strong impact on ordinary production, it is very necessary therefore the chlorine in the unstripped gas being removed to below the 0.1ppm.Organochlorine in the various raw material hydrocarbon is to be converted into inorganic chlorine by chemical reaction (as Co-Mo or Ni-Mo hydrogenation), utilizes antichlor to remove then.Research to antichlor has both at home and abroad dropped into more strength, and the system that has related to has CuO-ZnO system, CaO-Zn system, Na-Al
2O
3System, CaO-Al
2O
3, K
2O-Fe
2O
3Deng, but the antichlor degree of purification of being reported is all not high, exports chlorosity content greater than 0.5ppm, the chlorosity of former granularity also not high (20%), and water resistance is undesirable.Though patent CN1064099A reports the chlorosity of former granularity greater than 20%, can not use more than 280 ℃, degree of purification＜0.5ppm, and CN1114238A is the one-component system, degree of purification only＜1ppm, commercial Application is subjected to certain limitation.
The object of the invention provides a kind of high performance dechloridizing agent and preparation method.This antichlor has that degree of purification is good, chlorosity is high, intensity and good, active wide temperature region of water resistance and the low characteristics of cost.
The present invention seeks to realize by following method: with calcium compound, sodium compound and magnesium compound is active constituent, with bentonite, diatomite or kaolin is carrier, cooperate an amount of inorganic adhesive, organic and macromolecular compound and water mixed grind aftershaping, the drying roasting forms refined antichlor then.Active component content in this antichlor is respectively Na
2CO
3Be 10～45% (weight), CaCO
3Be that 5～40% (weight), MgO are 5～35% (weight), carrier is 10～40% (weight), be the plasticity and the pore structure of powder when improving moulding in addition, introduce organic and macromolecular compound, comprise polyethylene glycol, methylcellulose, urea, its composite content reaches 2～8% (weight), be to increase the intensity of antichlor, has also added the inorganic adhesive of 1～5% (weight) such as aluminium colloidal sol, colloid SiO
2Or a kind of in the high-temperature cement, its preparation method is that aforementioned sodium, calcium, magnesium compound and carrier and additive are added water-wet, mixed grind, be squeezed into the bar of 4-6 * 6～10mm immediately with banded extruder, in 100～120 ℃ of oven dry 2 hours, promptly obtained the final products antichlor in 1～3 hour in 350～400 ℃ of roasting temperatures again after air-dry a few hours at room temperature.Product packing density 0.6～0.9Kg/L, side pressure strength＞50N.cm
-1, pore volume 0.5～0.6ml/g, average pore size～800 .The antichlor active testing carries out in glass reactor.Test condition is reaction tube diameter 10mm or 30mm, and the antichlor granularity is 0.45～0.9mm or former granularity, volume 1.5ml or 30ml, and reaction temperature is a normal temperature to 480 ℃, air speed 1000～3000h
-1, normal pressure, unstripped gas is the N that joins chlorine
2Or H
2-N
2Gaseous mixture, (represent by the suction chlorine dose during the middle chlorine of working off one's feeling vent one's spleen＞0.1ppm) to penetrate for chlorosity.
The chlorine that antichlor of the present invention can be used in technical process such as synthetic ammonia, methyl alcohol, hydrogen manufacturing and other unstripped gas removes.The effect that the present invention reached is that novel antichlor has chlorosity and degree of purification height (during outlet chlorine＜0.1ppm, chlorosity reaches 30%), and resistance to water and intensity are good, and preparation technology is simple, and cost is low.Can be widely used in removing of chlorine in all gases.
Accompanying drawing and explanation thereof
Fig. 1 is the chlorosity of antichlor sample A, B, C.
Fig. 2 is the chlorosity of antichlor sample D, F, E.
Fig. 3 is the intensity of antichlor sample F, E, D.
Fig. 4 is the chlorosity of antichlor sample G, H, I.
Fig. 5 is Mg (weight) the content % of antichlor sample G, H, I and the relation of intensity.
Fig. 6 is the chlorosity of antichlor sample J, K, L.
Fig. 7 is the Na of antichlor sample
2CO
3(wt%) content and chlorosity relation curve.
Fig. 8 is the Na of antichlor sample
2CO
3(wt%) content and strength relationship curve.
Fig. 9 is the CaCO of antichlor sample
3(Wt%) content and chlorosity relation curve.
Figure 10 is antichlor sample CaCO
3(wt%) content and strength relationship curve.
Figure 11 is MgO (wt%) content and the chlorosity relation curve of antichlor sample.
Figure 12 is MgO (wt%) content and the strength relationship curve of antichlor sample.
Figure 13 is the kaolin (wt%) and strength relationship curve of antichlor sample.
Figure 14 is the kaolin (wt%) and chlorosity relation curve of antichlor sample.
Sintering temperature and chlorosity relation curve when Figure 15 is the preparation antichlor.
Figure 16 is a patented product antichlor of the present invention (w), and domestic sample (R) compares with external sample (S) dechlorination effect.
Among the figure: T-temperature P (N.cm-1)-intensity
CI%-chlorosity Y-kaolin
Percentage is got CaCO by weight
325%, MgO25%, kaolin 15% are respectively three parts, sneak into 30% NaOH, NaHCO respectively
3And Na
2CO
3, in every duplicate samples, add mixing behind 3% the methylcellulose again, with 2% colloid SiO
2With the abundant mixed grind of water, extruded moulding, at room temperature air-dry, 100 ℃ of oven dry 2 hours, obtain sample A, B, C after 2 hours 350 ℃ of roastings.Survey its chlorosity and the results are shown in Figure 1, visible load Na
2CO
3Antichlor chlorosity is the highest under the same conditions.
Percentage is got Na by weight
2CO
330%, MgO20%, kaolin 18% are respectively three parts, sneak into 25% Ca (OH) respectively
2, CaO and CaCO
3, respectively add in addition 5% high mixing cement and mix.With the soluble in water and above-mentioned sample mixed grind of 2% polyethylene glycol, at room temperature air-dry, 110 ℃ of oven dry 2 hours, made sample D, E, F in 1 hour 350 ℃ of following roastings, survey its chlorosity, intensity results is seen Fig. 2, and is shown in Figure 3, as seen Ca (OH) under the same conditions
2Chlorosity slightly is better than CaCO
3And CaO, but intensity is with CaCO
3Best.
Embodiment 3
Percentage is got Na by weight
2CO
330%, CaCO
325%, kaolin 15% is respectively three parts, sneaks into 25% MgO, Mg (OH) respectively
2, MgCO
3, the high-temperature cement of interpolation 3% and 2% urea in every duplicate samples fully add the water mixed grind behind the mixing again, and is at room temperature air-dry, 120 ℃ of oven dry 2 hours, made sample G, H, I in 3 hours in 400 ℃ of roastings again.Survey its chlorosity and intensity, the results are shown in Figure 4, Fig. 5, the combination property of visible MgO is better than Mg (OH)
2And MgCO
3
Embodiment 4
Percentage is got Na by weight
2CO
330%, MgO25%, CaCO
3Each three parts in 25% sample mixes 15% bentonite, diatomite and kaolin respectively, and each adds 2% urea mixing, introduces 3% aluminium colloidal sol and water mixed grind again, makes sample J, K, L by embodiment 1 method.Survey its chlorosity such as Fig. 6, it is best as seen to contain kaolin sample chlorosity.
Percentage is got CaCO by weight
320%, MgO15% is each five parts, adds 2% methylcellulose in every part, and 3% polyethylene glycol adds 10%, 20%, 30%, 40% and 50% Na respectively in five duplicate samples
2CO
3, surplus is a kaolin, adds 3% colloid SiO behind the mixing
2With the water mixed grind, make five in sample by embodiment 2 methods, measure its chlorosity and intensity, result such as Fig. 7, Fig. 8 take all factors into consideration, Na
2CO
3Content is best with 25～40%.
Embodiment 6
Percentage is got Na by weight
2CO
330%, MgO18% is each five parts, adds CaCO respectively in five duplicate samples
315%, 20%, 25%, 30%, 35%, add 1% high-temperature cement, 3% methylcellulose, 4% polyethylene glycol and 1% urea, surplus is a kaolin, obtains five samples by embodiment 3 methods, measures its chlorosity and intensity, the results are shown in Figure 9, Figure 10, take all factors into consideration chlorosity and intensity, CaCO
3Content is preferably 20～35%.
Embodiment 7
Percentage is got Na by weight
2CO
330%, CaCO
320% each six parts, mix respectively, then to wherein adding MgO0%, 5%, 10%, 15%, 20%, 25% respectively, every duplicate samples adds 3% methylcellulose, 3% polyethylene glycol and 1% urea in addition, surplus is a kaolin, mixes the back with 2% colloid SiO
2Carry out mixed grind with water, make six parts in sample, survey its chlorosity and intensity respectively by preceding method, result such as Figure 11, Figure 12, visible MgO content is preferably at 10～20% o'clock, antichlor combination property the best.
Embodiment 8
Take by weighing Na
2CO
390g, CaCO
3Be divided into six parts behind the abundant mixing of 120g, MgO60g, add 10%, 15%, 20%, 25%, 30%, 35% kaolin by weight percentage respectively, every part is all added 1% aluminium colloidal sol, 4% polyethylene glycol, 3% methylcellulose and 1% urea, add the water mixed grind, make sample by embodiment 3 methods, its intensity and chlorosity are seen Figure 13, Figure 14, can reach a conclusion by figure, kaolin content with 15～25% for well.
Embodiment 9
Percentage is got Na by weight
2CO
335%, CaCO
330%, MgO15%, kaolin 20%, every part of aluminium colloidal sol, 2% polyethylene glycol, 3% methylcellulose and 2% urea that adds total amount 2%, add suitable quantity of water and carry out mixed grind, make sample by embodiment 2 technologies, wherein sintering temperature is respectively 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 500 ℃, constant temperature time 2 hours, and this group sample chlorosity is seen Figure 15, as seen 350 ℃～400 ℃ scope calcinings, chlorosity＞25%.
6 tons of refined antichlors, product .4X6-10mm, packing density 0.6～0.9Kg/L, side pressure strength＞0.5N.cm have been produced as a trial according to the prescription of embodiment 9
-1, pore volume 0.52ml/g, average pore size～800 .This sample and domestic and international market are sold antichlor and have been carried out dechlorination relatively, the results are shown in Figure 16, and visible this sample under the same conditions has higher chlorosity.
Embodiment 11
Antichlor of the present invention has carried out burying the sample experiment in the commercial plant of 300,000 tons of synthetic ammonia, move sample analysis after three months, and average chlorosity reaches 22%, and is identical substantially with little test result.
Application result shows that novel antichlor of the present invention has chlorosity and degree of purification height (during outlet chlorine＜0.1ppm, chlorosity reaches 30%), and resistance to water and intensity are good, and preparation technology is simple, the characteristics that cost is low.Can be widely used in removing of chlorine in all gases.
Claims (2)
1. an antichlor is characterized in that adopting Na
2CO
3, CaCO
3With MgO be active component, be carrier with inorganic clay or bentonite, kaolin or diatomite, and add inorganic adhesive aluminium colloidal sol or colloid SiO
2Or high-temperature cement, and add organic or the macromolecular compound methylcellulose or/and polyethylene glycol, urea, the weight percentage of each component of this antichlor is respectively Na
2CO
310～40% (weight), CaCO
35～40% (weight), MgO 5～35% (weight), carrier 10～40% (weight), inorganic adhesive 1～5% (weight), organic or macromolecular compound 2～8% (weight).
2. the preparation method of antichlor according to claim 1 is characterized in that adopting Na
2CO
3, CaCO
3With MgO be active component, carry out compositely, be carrier with inorganic clay or bentonite, kaolin or diatomite, add inorganic adhesive aluminium colloidal sol or colloid SiO
2Or high-temperature cement, and add organic or the macromolecular compound methylcellulose or/and polyethylene glycol, urea, through mixed grind, extruded moulding, air-dry back made 350 ℃～400 ℃ roastings in 100 ℃～120 ℃ oven dry 2 hours in 1～3 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116288A CN1060408C (en) | 1997-09-10 | 1997-09-10 | High performance dechloridizing agent and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116288A CN1060408C (en) | 1997-09-10 | 1997-09-10 | High performance dechloridizing agent and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1178133A CN1178133A (en) | 1998-04-08 |
| CN1060408C true CN1060408C (en) | 2001-01-10 |
Family
ID=5173743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97116288A Expired - Lifetime CN1060408C (en) | 1997-09-10 | 1997-09-10 | High performance dechloridizing agent and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1060408C (en) |
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| CN1325146C (en) * | 2005-06-28 | 2007-07-11 | 上海电力学院 | Dechlorination agent and its preparation process |
| CN100453147C (en) * | 2005-12-07 | 2009-01-21 | 西北化工研究院 | Antichlor for catalytic reforming regenerated gas and preparation method |
| CN101269294B (en) * | 2008-05-20 | 2013-09-11 | 北京三聚环保新材料股份有限公司 | Zincium-calcium dechlorinating agent at normal temperature and preparing method thereof |
| CN101773768A (en) * | 2010-03-16 | 2010-07-14 | 长春惠工净化工业有限公司 | Dechlorinating agent used for removing HCl from gas by dry method and preparation method thereof |
| CN101804298B (en) * | 2010-04-10 | 2013-03-27 | 太原理工大学 | Method for preparing chlorine arresting agent |
| 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 |
| CN102649702B (en) * | 2011-02-25 | 2014-08-13 | 中国石油化工股份有限公司 | Method for improving stability of ethylene glycol catalyst synthesized by hydrogenation of oxalate |
| CN102205237A (en) * | 2011-04-01 | 2011-10-05 | 昆山市精细化工研究所有限公司 | Magnesium or zinc series purification catalyst and preparation method thereof |
| PL414675A1 (en) * | 2013-03-13 | 2017-06-19 | Novinda Corporation | Multi-component substance for removal mercury |
| CN103386244B (en) * | 2013-08-02 | 2015-08-12 | 广州博能能源科技有限公司 | Antichlor and preparation method thereof |
| KR101847319B1 (en) | 2013-12-17 | 2018-04-09 | 미쓰이 가가쿠 가부시키가이샤 | MOLDED BODY, METHOD FOR PRODUCING SAME, CATALYST FOR α-OLEFIN DIMERIZATION, AND METHOD FOR PRODUCING α-OLEFIN DIMER |
| WO2016108559A1 (en) | 2014-12-30 | 2016-07-07 | Cj 4Dplex Co., Ltd. | Motion chair and motion chair control system |
| CN106334516B (en) * | 2016-10-12 | 2019-05-21 | 中国石油大学(北京) | A kind of antichlor and preparation method thereof |
| CN108786927A (en) * | 2017-04-27 | 2018-11-13 | 沈阳三聚凯特催化剂有限公司 | A kind of preparation method of dechlorination agent carrier and the liquid phase antichlor comprising it |
| CN109382388B (en) * | 2017-08-07 | 2022-05-13 | 中国石化扬子石油化工有限公司 | Method for preparing fresh dechlorinating agent from waste dechlorinating agent |
| CN110548479A (en) * | 2019-10-03 | 2019-12-10 | 武汉禾谷环保有限公司 | High-strength liquid-phase dechlorinating agent and preparation method and application 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 |
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|---|---|---|---|---|
| JPS56144620A (en) * | 1980-04-11 | 1981-11-11 | Hitachi Ltd | Filter for car mounting |
| JPS57209234A (en) * | 1981-06-17 | 1982-12-22 | San Aroo Kagaku Kk | Purifying method of vinyl chloride |
| CN1064099A (en) * | 1992-03-21 | 1992-09-02 | 南京化工学院 | Dechlorinating agent |
| CN1147977A (en) * | 1996-04-26 | 1997-04-23 | 湖北省化学研究所 | Refined antichlor and method for preparing same |
-
1997
- 1997-09-10 CN CN97116288A patent/CN1060408C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56144620A (en) * | 1980-04-11 | 1981-11-11 | Hitachi Ltd | Filter for car mounting |
| JPS57209234A (en) * | 1981-06-17 | 1982-12-22 | San Aroo Kagaku Kk | Purifying method of vinyl chloride |
| CN1064099A (en) * | 1992-03-21 | 1992-09-02 | 南京化工学院 | Dechlorinating agent |
| CN1147977A (en) * | 1996-04-26 | 1997-04-23 | 湖北省化学研究所 | Refined antichlor and method for preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1178133A (en) | 1998-04-08 |
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Owner name: CHINA PETROCHEMICAL CORPORATION; HUBEI PROV. CHEMI Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; HUBEI PROV. CHEMICAL RESEARCH INST. |
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Patentee after: China Petrochemical Group Corp. Patentee after: Hubei Research Institute of Chemistry Patentee before: China Petrochemical Corporation Patentee before: Hubei Research Institute of Chemistry |
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