CN1712109A - Catalyzed aqueous vapour reducing method from waste chlorine - Google Patents
Catalyzed aqueous vapour reducing method from waste chlorine Download PDFInfo
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- CN1712109A CN1712109A CN 200510039274 CN200510039274A CN1712109A CN 1712109 A CN1712109 A CN 1712109A CN 200510039274 CN200510039274 CN 200510039274 CN 200510039274 A CN200510039274 A CN 200510039274A CN 1712109 A CN1712109 A CN 1712109A
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Abstract
A catalytic steam reducing process for reclaiming rejected chlorine gas includes such steps as reacting between rejected chlorine gas and steam at 250-350 deg.C under the action of catalyst using activated carbon as its carrier to generate hydrogen chloride gas and O2, absorbing the hydrogen chloride gas by falling film absorber to become industrial hydrochloric acid, and absorbing the residual chlorine gas by lime milk.
Description
The technical field is as follows:
the invention relates to a waste chlorine reduction method, in particular to a waste chlorine catalytic steam reduction method. Belongs to the technical field of waste gas recovery.
Background art:
chlorine is known to be a serious hazard to humans. The eye patch can stimulate eyes, nose, throat and respiratory tract, has obvious stimulation to human body when the concentration is 1-6 mg per cubic meter, and can cause serious poisoning in 30-60 minutes; when the concentration is 120-170 mg per cubic meter, acute pulmonary edema and pneumonia can be caused; when the dose reaches 3000 mg per cubic meter, the respiratory center can be paralyzed rapidly, and 'lightning death' occurs. Chronic poisoning is caused by long-term inhalation of low-concentration chlorine gas, and the main symptoms are rhinitis, chronic bronchitis, emphysema and cirrhosis of liver. People who are chlorine-sensitive can develop dermatitis or eczema when exposed to chlorine. And has harmful effect on plants. The hydrochloric acid generated by the combination of the hydrochloric acid and water in the air has a corrosive effect on metals and buildings. Therefore, the national has already established the industrial enterprise sanitary standard, and the emission of chlorine in the air is regulated to be less than or equal to 1 milligram per cubic meter.
At present, the waste chlorine generated in industrial production is treated by a solvent absorption method, a synthetic furnace method and a lime milk or carbide slag absorption method.
The solvent absorption method is to absorb the waste chlorine by carbon tetrachloride, then to release chlorine after the waste chlorine is resolved by the resolving tower, and finally to return to the reaction system for utilization. The process has the advantages of longer flow, higher investment and more energy consumption, and simultaneously, the carbon tetrachloride can damage the ozone layer of the air.
The synthetic furnace method is also called combustion method. The application of this process is very limited, since it must have sufficient hydrogen and a certain requirement for chlorine concentration.
Although the lime milk or carbide slag absorption method can play a role in absorbing chlorine and is not limited by resources, a large amount of waste water and waste slag are generated while absorbing waste chlorine, and great pressure is caused to the environmental protection construction of enterprises. With the increase of the national requirements for environmental protection and the closing of small chlor-alkali devices with serious energy consumption in many developed countries, the price of chlorine is gradually increased, and enterprises urgently hope to have a new method for changing the current situation.
The invention content is as follows:
the invention aims to overcome the defects and provide the waste chlorine catalytic steam reduction method which has the advantages of shorter process flow, lower investment, less energy consumption, wide application and environmental protection.
The purpose of the invention is realized as follows: a catalytic reduction method of water vapour from waste chlorine is characterized by that the waste chlorine and water vapour are reacted at 250-350 deg.C under the catalysis of catalyst using active carbon as carrier to produce hydrogen chloride gas and oxygen gas, the hydrogen chloride gas is absorbed by falling-film absorber and used as industrial hydrochloric acid, the oxygen gas is directly discharged from top or upper portion of hydrochloric acid storage tank, and the small quantity of unreacted chlorine gas is finally absorbed by lime milk.
The reaction mechanism is as follows: chlorine reacts with steam to generate chlorine chloride and hypochlorous acid, which is rapidly decomposed at high temperature under the catalytic action of acatalyst to generate hydrogen chloride and oxygen. The reaction equation is as follows:
the invention relates to a method for catalyzing steam reduction by using waste chlorine, wherein zinc, vanadium, phosphorus and molybdenum are added into a catalyst taking active carbon as a carrier.
According to the waste chlorine catalytic steam reduction method, the molar ratio of the added zinc, vanadium, phosphorus and molybdenum is 1: 0.01-0.05: 0.08-0.1: 0.005-0.01.
According to the method for catalyzing the steam reduction by the waste chlorine, the added zinc, vanadium, phosphorus and molybdenum are respectively zinc oxide, vanadium pentoxide, phosphoric acid and molybdenum trioxide.
The invention relates to a method for catalyzing water vapor reduction by using waste chlorine, which comprises the following steps: adding zinc oxide, vanadium pentoxide and molybdenum trioxide into water, adding phosphoric acid and oxalic acid into the generated mixture at 60-80 ℃ under stirring, adding activated carbon after the zinc oxide, the vanadium pentoxide and the molybdenum trioxide are completely dissolved to prepare a mixture, heating and concentrating, drying at constant temperature for 120-140 ℃ for 10-14 hours, calcining the prepared mixture in air at 240-260 ℃ for 0.5-1 hour, and calcining at 340-360 ℃ for 3.5-4.5 to obtain the catalyst.
In the method for reducing the waste chlorine by catalyzing the water vapor, the temperature of the reaction of the waste chlorine and the water vapor under the catalysis of the catalyst is preferably 280-310 ℃. The activity of the catalyst can be stabilized in the optimum state in the temperature range, and the repeatability of the reaction result is better.
According to the method for catalyzing the steam reduction by the waste chlorine, the molar ratio of the waste chlorine to the steam is 1: 1.85-2.05. Considering that hydrochloric acid is easily formed by contacting water vapor and hydrogen chloride, the hydrochloric acid has strong corrosion at high temperature, and puts high requirements on the corrosion resistance of equipment. So that the water vapour cannot be in excess. Meanwhile, in order to complete the further reaction, a two-stage series reaction mode is generally adopted so as to meet the requirement of 95% of reaction efficiency.
The steam reduction method adopted by the invention is a brand new process route, and the adopted catalyst can greatly reduce the generation of waste water and waste residue while achieving the purpose of absorbing low-content waste chlorine, thereby reducing the labor intensity of workers and improving the working environment. But also makes full use of waste resources and changes waste into valuable. The single-stage conversion rate of the chlorine gas can reach more than 80 percent. The product hydrochloric acid reaches the standard of refined hydrochloric acid.
The specific implementation mode is as follows:
comprehensive treatment of waste chlorine in chlorothalonil tail gas:
the chlorothalonil project mainly comprises a chlorination working section, an ammonia oxidation working section, three-waste treatment and related auxiliary facilities. The tail gas of the chlorination section mainly comprises chlorine, hydrogen chloride gas and non-condensable gas. The chlorine in the chlorothalonil tail gas is reduced by waste chlorine catalytic steam. The process flow comprises the following steps:
chlorothalonil tail gas (hydrogen chloride, chlorine and non-condensable gas) → three-stage falling film water absorption → high-temperature water vapor reactor (250-350 ℃) → three-stage falling film water absorption → lime milk absorption.
Example 1:
the preparation method of the catalyst taking the active carbon as the carrier comprises the following steps: adding 81.0g of zinc oxide, 4.60g of vanadium pentoxide and 0.72g of molybdenum trioxide into 200 ml of water, adding 7.84g of phosphoric acid and 150g of oxalic acid into the generated mixture at 60-80 ℃ under stirring, adding 300g of activated carbon after the zinc oxide, the vanadium pentoxide and the molybdenum trioxide are completely dissolved to prepare a mixture, heating and concentrating the mixture, drying the mixture at constant temperature of 120-140 ℃ for 10-14 hours, calcining the prepared mixture in the air at 240-260 ℃ for 0.5-1 hour, and calcining the mixture at 340-360 ℃ for 3.5-4.5 to obtain the catalyst.
Example 2:
example 2 differs from example 1 only in the amounts of vanadium pentoxide and molybdenum trioxide added: 2.23g of vanadium pentoxide and 0.72g of molybdenum trioxide. The rest is the same as example 1.
Example 3:
example 3 differs from example 1 only in the amounts of vanadium pentoxide and molybdenum trioxide added: 0.90g of vanadium pentoxide and 0.72g of molybdenum trioxide. The rest is the same as example 1.
Example 4:
example 4 differs from example 1 only in the amounts of vanadium pentoxide and molybdenum trioxide added: 4.60g of vanadium pentoxide and 1.15g of molybdenum trioxide. The rest is the same as example 1.
Example 5:
example 5 differs from example 1 only in the amounts of vanadium pentoxide and molybdenum trioxide added: 4.60g of vanadium pentoxide and 1.44g of molybdenum trioxide. The rest is the same as example 1.
Example 6:
example 6 differs from example 1 only in the amounts of vanadium pentoxide and molybdenum trioxide added: 2.23g of vanadium pentoxide and 1.15g of molybdenum trioxide. The rest is the same as example 1.
Example 7:
example 7 differs from example 1 only in the amounts of vanadium pentoxide and molybdenum trioxide added: 2.23g of vanadium pentoxide and 1.44g of molybdenum trioxide. The rest is the same as example 1.
Example 8:
example 8 differs from example 1 only in the amounts of vanadium pentoxide and molybdenum trioxide added: 0.90g of vanadium pentoxide and 1.15g of molybdenum trioxide. The rest is the same as example 1.
Example 9:
example 9 differs from example 1 only in the amounts of vanadium pentoxide and molybdenum trioxide added: 0.90g of vanadium pentoxide and 1.44g of molybdenum trioxide. The rest is the same as example 1.
Example 10:
example 10 differs from example 1 only in the amounts of vanadium pentoxide and phosphoric acid added: 4.60g of vanadium pentoxide and 8.82g of phosphoric acid. The rest is the same as example 1.
Example 11:
example 11 differs from example 1 only in the amounts of vanadium pentoxide and phosphoric acid added: 2.23g of vanadium pentoxide and 8.82g of phosphoric acid. The rest is the same as example 1.
Example 12:
example 12 differs from example 1 only in the amounts of vanadium pentoxide and phosphoric acid added: 0.90g of vanadium pentoxide and 8.82g of phosphoric acid. The rest is the same as example 1.
Example 13:
example 13 differs from example 1 only in the addition amounts of molybdenum trioxide and phosphoric acid: 0.72g of molybdenum trioxide and 7.84g of phosphoric acid. The rest is the same as example 1.
Example 14:
example 14 differs from example 1 only in the addition amounts of molybdenum trioxide and phosphoric acid: 0.72g of molybdenum trioxide and 8.82g of phosphoric acid. The rest is the same as example 1.
Example 15:
example 15 differs from example 1 only in the addition amounts of molybdenum trioxide and phosphoric acid: 0.72g of molybdenum trioxide and 9.80g of phosphoric acid. The rest is the same as example 1.
Example 16:
example 16 differs from example 1 only in the addition amounts of molybdenum trioxide and phosphoric acid: 1.15g of molybdenum trioxide and 7.84g of phosphoric acid. The rest is the same as example 1.
Example 17:
example 17 differs from example 1 only in the addition amounts of molybdenum trioxide and phosphoric acid: 1.15g of molybdenum trioxide and 8.82g of phosphoric acid. The rest is the same as example 1.
Example 18:
example 18 differs from example 1 only in the addition amounts of molybdenum trioxide and phosphoric acid: 1.15g of molybdenum trioxide and 9.80g of phosphoric acid. The rest is the same as example 1.
Example 19:
example 19 differs from example 1 only in the addition amounts of molybdenum trioxide and phosphoricacid: 1.44g molybdenum trioxide, 7.84g phosphoric acid. The rest is the same as example 1.
Example 20:
example 20 differs from example 1 only in the addition amounts of molybdenum trioxide and phosphoric acid: 1.44g molybdenum trioxide, 8.82g phosphoric acid. The rest is the same as example 1.
Example 21:
example 21 differs from example 1 only in the addition amounts of molybdenum trioxide and phosphoric acid: 1.44g of molybdenum trioxide and 9.80g of phosphoric acid. The rest is the same as example 1.
Example 22:
example 22 differs from example 1 only in the amount of vanadium pentoxide added: 2.23g of vanadium pentoxide. The rest is the same as example 1.
Example 23:
example 23 differs from example 1 only in the amount of vanadium pentoxide added: 0.90g of vanadium pentoxide. The rest is the same as example 1.
The catalyst adopted by the project ensures that the low-content waste chlorine in the tail gas achieves the absorption purpose and simultaneously greatly reduces the generation of waste water and waste residue. The expected target of the project is that the continuous service life of the catalyst reaches 600 hours, the production capacity reaches 20 tons of waste chlorine treated by the project, the single-stage conversion rate of the chlorine reaches 80 percent, and the product hydrochloric acid reaches the standard of refined hydrochloric acid.
Claims (8)
1. A catalytic reduction method of water vapour from waste chlorine is characterized by that the waste chlorine and water vapour are reacted at 250-350 deg.C under the catalysis of catalyst using active carbon as carrier to produce hydrogen chloride gas and oxygen gas, the hydrogen chloride gas is absorbed by falling film absorber and used as industrial hydrochloric acid, the oxygen gas is directly discharged from top or upper portion of hydrochloric acid storage tank, and the small quantity of unreacted chlorine gas is finally absorbed by lime milk.
2. The catalytic steam reduction method of waste chlorine as claimed in claim 1, wherein the catalyst using activated carbon as carrier is added with zinc, vanadium, phosphorus and molybdenum.
3. The catalytic steam reduction method of claim 2, wherein the molar ratio of the added zinc, vanadium, phosphorus and molybdenum is 1: 0.01-0.05: 0.08-0.1: 0.005-0.01.
4. The catalytic steam reduction process of claim 3, wherein the zinc, vanadium, phosphorus and molybdenum are added as zinc oxide, vanadium pentoxide, phosphoric acid and molybdenum trioxide, respectively.
5. The method for catalytic steam reduction of waste chlorine according to claim 4, wherein the preparation method of the catalyst using activated carbon as a carrier comprises: firstly, adding zinc oxide, vanadium pentoxide and molybdenum trioxide into water, adding phosphoric acid and oxalic acid into the generated mixture at 60-80 ℃ under stirring, adding activated carbon after the zinc oxide, the vanadium pentoxide and the molybdenum trioxide are completely dissolved to prepare a mixture, heating and concentrating, drying at constant temperature of 120-140 ℃ for 10-14 hours, calcining the prepared mixture in air at 240-260 ℃ for 0.5-1 hour, and calcining at 340-360 ℃ for 3.5-4.5 to obtain the catalyst.
6. The method of claim 1 to 5, wherein the waste chlorine and the steam are reacted at 280 to 310 ℃ under the catalysis of a catalyst.
7. The method as claimed in any one of claims 1 to 5, wherein the molar ratio of the waste chlorine to the steam is 1: 1.85-2.05.
8. A catalytic steam reduction method of waste chlorine according to claim 7, wherein the molar ratio of the waste chlorine to the steam is 1: 1.85-2.05.
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| CNB2005100392742A CN100434145C (en) | 2005-05-10 | 2005-05-10 | Catalyzed aqueous vapour reducing method from waste chlorine |
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| CNB2005100392742A CN100434145C (en) | 2005-05-10 | 2005-05-10 | Catalyzed aqueous vapour reducing method from waste chlorine |
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| CN100434145C CN100434145C (en) | 2008-11-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531341B (en) * | 2009-03-18 | 2011-02-09 | 寿光市新龙电化有限责任公司 | Device for producing sodium hypochlorite by using waste chlorine water and production method thereof |
| CN101961588B (en) * | 2009-07-23 | 2013-03-27 | 江苏新河农用化工有限公司 | Method for reclaiming chlorine in chlorothalonil chlorinated exhaust |
| CN111298603A (en) * | 2020-03-12 | 2020-06-19 | 江苏维尤纳特精细化工有限公司 | Hydrogen chloride detection processing equipment for chlorothalonil production line and processing technology thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4075313A (en) * | 1974-12-23 | 1978-02-21 | American Gas Association | Process for producing hydrogen and oxygen from water |
| CN2404916Y (en) * | 1999-12-22 | 2000-11-08 | 山东晨鸣纸业集团股份有限公司 | Reactor for preparing bleaching liquid |
| JP2002001065A (en) * | 2000-06-21 | 2002-01-08 | Nkk Corp | Decomposition catalyst and decomposition method for organic chlorine compound |
| JP2002079056A (en) * | 2000-09-06 | 2002-03-19 | Babcock Hitachi Kk | Method for cleaning exhaust gas containing chlorine- containing compound and cleaning catalyst |
| DE10309799A1 (en) * | 2003-03-05 | 2004-09-23 | Sgl Acotec Gmbh | Method and device for producing hydrogen chloride |
-
2005
- 2005-05-10 CN CNB2005100392742A patent/CN100434145C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531341B (en) * | 2009-03-18 | 2011-02-09 | 寿光市新龙电化有限责任公司 | Device for producing sodium hypochlorite by using waste chlorine water and production method thereof |
| CN101961588B (en) * | 2009-07-23 | 2013-03-27 | 江苏新河农用化工有限公司 | Method for reclaiming chlorine in chlorothalonil chlorinated exhaust |
| CN111298603A (en) * | 2020-03-12 | 2020-06-19 | 江苏维尤纳特精细化工有限公司 | Hydrogen chloride detection processing equipment for chlorothalonil production line and processing technology thereof |
| CN111298603B (en) * | 2020-03-12 | 2022-02-15 | 江苏维尤纳特精细化工有限公司 | Hydrogen chloride detection processing equipment for chlorothalonil production line and processing technology thereof |
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| CN100434145C (en) | 2008-11-19 |
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Assignee: JIANGYIN SULI TECHNOLOGY CO.,LTD. Assignor: Jiangyin Suli Fine Chemical Co.,Ltd. Contract fulfillment period: 2008.12.5 to 2014.12.31 Contract record no.: 2008320001157 Denomination of invention: Catalyzed aqueous vapour reducing method from waste chlorine Granted publication date: 20081119 License type: Exclusive license Record date: 20081231 |
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Assignee: JIANGYIN SULI TECHNOLOGY CO.,LTD. Assignor: Jiangyin Suli Fine Chemical Co.,Ltd. Contract record no.: 2008320001157 Date of cancellation: 20120615 |
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Address after: 214444 No. 83, Ding Ding villa, Li Town, Jiangsu, Jiangyin Patentee after: JIANGSU SULI FINE CHEMICAL Co.,Ltd. Address before: 214444 No. 83, Ding Ding villa, Li Town, Jiangsu, Jiangyin Patentee before: Jiangyin Suli Fine Chemical Co.,Ltd. |
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Effective date of registration: 20230620 Address after: 21444 No.7, Runhua Road, Ligang Town, Jiangyin City, Wuxi City, Jiangsu Province Patentee after: JIANGYIN SULI CHEMICAL Co.,Ltd. Address before: 214444 No. 83, Ding Ding villa, Li Town, Jiangsu, Jiangyin Patentee before: JIANGSU SULI FINE CHEMICAL Co.,Ltd. |