CN111617631A - Yellow phosphorus tail gas dephosphorization purification method - Google Patents
Yellow phosphorus tail gas dephosphorization purification method Download PDFInfo
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- CN111617631A CN111617631A CN202010349884.7A CN202010349884A CN111617631A CN 111617631 A CN111617631 A CN 111617631A CN 202010349884 A CN202010349884 A CN 202010349884A CN 111617631 A CN111617631 A CN 111617631A
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- tail gas
- yellow phosphorus
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- phosphorus tail
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/265—Drying gases or vapours by refrigeration (condensation)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
Abstract
The invention provides a method for dephosphorizing yellow phosphorus tail gas, which comprises the following steps: s1: heating the yellow phosphorus tail gas by using a heating system; s2: sending the yellow phosphorus tail gas after temperature rise into a catalytic reaction tower, and carrying out high-temperature catalytic oxidation on total phosphorus components in the yellow phosphorus tail gas under the action of a catalyst to generate yellow phosphorus tail gas containing phosphorus-oxygen compounds; s3: sending the yellow phosphorus tail gas containing the phosphorus-oxygen compound into a cooling absorption tower, cooling, absorbing the phosphorus-oxygen compound, and discharging redundant heat and generated residual acid out of the cooling absorption tower; s4: and (4) conveying the cooled and absorbed tail gas into a demisting and drying device, and performing demisting and drying treatment to obtain dephosphorized tail gas. The invention relates to a method for dephosphorizing yellow phosphorus tail gasThe content of total phosphorus in the tail gas is less than or equal to 1mg/Nm3Other harmful components in the tail gas have no influence on dephosphorization and purification of the method, and the requirement of subsequent processes on heat energy utilization of the tail gas is met.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for purifying yellow phosphorus tail gas through dephosphorization.
Background
Yellow phosphorus is a basic chemical raw material and has wide application. Yellow phosphorus is mainly produced by an electric furnace method, and when one ton of yellow phosphorus is produced, yellow phosphorus tail gas with the standard size of 2500-3000 is produced. The yellow phosphorus tail gas contains about 85 percent of CO and can be used as fuel. Because the harmful impurities in the yellow phosphorus tail gas are more in variety, the difficulty coefficient of purification and separation is larger, and the effective utilization of the yellow phosphorus tail gas is hindered. Particularly, the content of phosphorus and phosphide in the tail gas is high, so that the tail gas can seriously corrode used equipment after being combusted, the utilization of the tail gas is greatly limited, great waste is caused, and the environment is also seriously influenced.
The current yellow phosphorus industry does not allow the combustion emission of yellow phosphorus tail gas after simple treatment, and advocates the comprehensive utilization of energy. The power generation by using the yellow phosphorus tail gas is one of the main directions of the current yellow phosphorus tail gas application, and the key problem is that the total phosphorus in the tail gas needs to be removed. From the power generation project which is implemented at present, the corrosion of a power generation boiler is serious due to the incomplete removal of total phosphorus, and the normal production cannot be realized.
At present, the methods for treating yellow phosphorus tail gas at home and abroad are many and can be divided into an absorption method, a temperature and pressure swing adsorption method and a catalytic oxidation method. Namely, the yellow phosphorus tail gas is mostly purified by simple treatment of water washing and alkali washing, or by Temperature Swing Adsorption (TSA) and Pressure Swing Adsorption (PSA) after water washing and alkali washing, or by low-temperature catalytic oxidation treatment. But the purification effect is not ideal enough, the dephosphorization is not up to the standard due to the complex process, the treatment cost is high, and the requirements are difficult to meet. Therefore, the development of a low-cost new process for dephosphorization and purification treatment of the yellow phosphorus tail gas can promote the development of tail gas utilization in the whole yellow phosphorus industry.
Disclosure of Invention
In view of the above-mentioned deficiencies and problems of the prior art, the present inventionThe invention aims to provide a method for dephosphorizing yellow phosphorus tail gas, which solves the problem of purification application of the yellow phosphorus tail gas and ensures that the total phosphorus content in the purified tail gas reaches 1mg/Nm3The application requirements of the tail gas power generation system are completely met, and the corrosion of combustion to the used equipment is avoided.
In order to achieve the aim, the invention provides a method for dephosphorizing yellow phosphorus tail gas, which comprises the following steps:
s1: heating the yellow phosphorus tail gas by using a heating system;
s2: sending the yellow phosphorus tail gas after temperature rise into a catalytic reaction tower, and carrying out high-temperature catalytic oxidation on total phosphorus components in the yellow phosphorus tail gas under the action of a catalyst to generate yellow phosphorus tail gas containing phosphorus-oxygen compounds;
s3: sending the yellow phosphorus tail gas containing the phosphorus-oxygen compound into a cooling absorption tower, cooling, absorbing the phosphorus-oxygen compound, and discharging redundant heat and generated residual acid out of the cooling absorption tower;
s4: and (4) conveying the cooled and absorbed tail gas into a demisting and drying device, and performing demisting and drying treatment to obtain dephosphorized tail gas.
Further, before the step S1, a step of washing the yellow phosphorus tail gas with water is also included.
Further, in step S1, the heating system is a gas circulation heating system, and preferably, the indirect heat transfer medium of the gas circulation heating system is nitrogen, inert gas or water vapor.
Further, in the step S1, the temperature of the yellow phosphorus tail gas is raised to 400 to 500 ℃, and preferably, the temperature of the yellow phosphorus tail gas is raised to 450 ℃.
Further, in the step S2, the total phosphorus component is P4And/or pH3。
Further, the catalyst in the step S2 has catalytic selectivity only for the total phosphorus component in the yellow phosphorus tail gas, and the catalytic reaction temperature of the catalyst is 400-500 ℃.
Further, the cooling absorption tower in the step S3 further includes sprayingA spraying system for spraying the yellow phosphorus tail gas to cool and absorb the phosphorus oxide, preferably, the spraying liquid of the spraying system is water, Ca (OH)2NaOH or other alkaline solutions.
Further, the demisting drying device is arranged at the rear end of the cooling absorption tower or at the top of the cooling absorption tower.
Further, the defogging drying device is a combination of one or more of a flat-plate defogger, a tubular defogger, a ridge defogger, a cloth bag defogger and a tube bundle defogger.
Further, the total phosphorus content in the dephosphorized tail gas is less than or equal to 1mg/Nm3。
The invention provides a method for dephosphorizing and purifying yellow phosphorus tail gas, which is characterized in that the yellow phosphorus tail gas before combustion is firstly dephosphorized and then is combusted for power generation and used as other fuels.
Compared with the prior art, the invention has the following advantages and effects:
1) the invention utilizes the physical characteristic of phosphorus to temperature, adopts a high-temperature catalytic oxidation process flow, and can more thoroughly convert the total phosphorus in the tail gas into phosphorus oxide compared with other medium-temperature and low-temperature treatment methods.
2) The catalyst adopted by the invention has selectivity, namely, the catalyst is only used for carrying out catalytic oxidation on total phosphorus and is not poisoned by the influence of other components; meanwhile, the catalyst selected by the invention does not need to be regenerated, and the catalyst is used in a one-time filling long-life cycle (3-5 years), so that the consumption is low.
3) The invention utilizes the physical characteristics of phosphorus-oxygen compounds, adopts a process of spray liquid rapid cooling absorption, fully and rapidly absorbs the phosphorus-oxygen compounds, avoids other chemical reactions, and realizes the purpose of rapid separation.
4) If other alkali liquor is sprayed by the spraying system, partial SO removal can be realized2Or other acid gases, to reduce SO in the tail gas2And other acid gas content.
Drawings
FIG. 1 illustrates an exemplary dephosphorization process for yellow phosphorus tail gas according to the present invention;
FIG. 2 shows a dephosphorization purification process of yellow phosphorus tail gas in another embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As an embodiment, the purification process of carrying out high-temperature catalytic oxidation absorption dephosphorization on the yellow phosphorus tail gas utilizes the selective catalytic oxidation characteristic of a catalyst to carry out catalytic oxidation on total phosphorus in the tail gas to form a phosphorus-oxygen compound, and then adopts a liquid spraying mode to rapidly cool the tail gas, realize the absorption of the phosphorus-oxygen compound and realize the dephosphorization purpose.
As shown in fig. 1, the present invention provides a method for dephosphorizing yellow phosphorus tail gas, comprising the following steps:
s1: heating the yellow phosphorus tail gas by using a heating system;
s2: sending the yellow phosphorus tail gas after temperature rise into a catalytic reaction tower, and carrying out high-temperature catalytic oxidation on total phosphorus components in the yellow phosphorus tail gas under the action of a catalyst to generate yellow phosphorus tail gas containing phosphorus-oxygen compounds;
s3: sending the yellow phosphorus tail gas containing the phosphorus-oxygen compound into a cooling absorption tower, cooling, absorbing the phosphorus-oxygen compound, and discharging redundant heat and generated residual acid out of the cooling absorption tower;
s4: and (4) conveying the cooled and absorbed tail gas into a demisting and drying device, and performing demisting and drying treatment to obtain dephosphorized tail gas.
Specifically, in step S1, the yellow phosphorus tail gas is heated and heated by a gas circulation heating system, and an indirect heat transfer medium of the gas circulation heating system is nitrogen, an inert gas, or water vapor. According to the invention, the yellow phosphorus tail gas is heated to 400-500 ℃ by a gas circulation heating system, the physical characteristics of phosphorus to temperature are utilized, and a high-temperature catalytic oxidation process flow is adopted, so that compared with other medium-temperature and low-temperature treatment methods, the total phosphorus in the tail gas can be more thoroughly converted into phosphorus oxide compounds, and further dephosphorization is carried out subsequently. In a preferred embodiment of the present invention, the yellow phosphorus tail gas is heated to about 450 ℃.
Sending the yellow phosphorus tail gas after temperature rise into a catalytic reaction tower, and reacting the total phosphorus component (P) in the yellow phosphorus tail gas under the action of a catalyst4And/or pH3) The catalyst only has catalytic selectivity on total phosphorus components in the yellow phosphorus tail gas, is not influenced by other components in the tail gas, has the catalytic reaction temperature of 400-500 ℃, and can more thoroughly convert the total phosphorus in the tail gas into phosphorus oxide compounds.
Then, sending the yellow phosphorus tail gas containing phosphorus-oxygen compounds into a cooling absorption tower, wherein a spraying system is arranged on the cooling absorption tower, and the spraying liquid of the spraying system is water and Ca (OH)2And NaOH or other alkaline solution is used for spraying the yellow phosphorus tail gas to cool the yellow phosphorus tail gas and absorb the phosphorus oxide compound.
And finally, sending the cooled and absorbed tail gas into a demisting drying device, and performing demisting drying treatment to obtain dephosphorized tail gas. The demisting drying device can be arranged at the rear end of the cooling absorption tower or directly arranged at the top of the cooling absorption tower. The demisting drying device can be a combination of one or more of a flat demister, a tubular demister, a ridge demister, a cloth bag demister or a tube bundle demister, and is determined according to actual requirements.
By the purification method, the total phosphorus content in the dephosphorized tail gas is less than or equal to 1mg/Nm3Thereby realizing the purpose of dephosphorization.
As shown in fig. 2, before the step S1, a step of washing the yellow phosphorus tail gas with water is further included. The method comprises the following steps that raw yellow phosphorus tail gas enters a water washing tower, mechanical impurities and part of strong acid gas in the tail gas are removed by utilizing circulating washing water in the water washing tower, the washed yellow phosphorus tail gas is discharged from the water washing tower, the yellow phosphorus tail gas is heated by a heating system to be heated, the heated yellow phosphorus tail gas is sent to a catalytic reaction tower, and the total phosphorus component in the yellow phosphorus tail gas is subjected to high-temperature catalytic oxidation under the action of a catalyst to generate yellow phosphorus tail gas containing phosphorus oxide compounds; sending the yellow phosphorus tail gas containing the phosphorus-oxygen compound into a cooling absorption tower, cooling, absorbing the phosphorus-oxygen compound, and discharging redundant heat and generated residual acid out of the cooling absorption tower; and (4) conveying the cooled and absorbed tail gas into a demisting and drying device, and performing demisting and drying treatment to obtain dephosphorized tail gas.
The invention utilizes the temperature characteristics of phosphorus and phosphide, aiming at the tail gas generated by a yellow phosphorus electric furnace, simple substance phosphorus and phosphide in the tail gas are oxidized into phosphorus oxide under the action of a catalyst by a thermal state high-temperature catalytic oxidation method, then the temperature of the tail gas is rapidly reduced by a spray tower, and meanwhile, the phosphorus oxide in the tail gas is rapidly absorbed in the contact process of spray liquid and the tail gas, thereby achieving the purpose of removing the total phosphorus in the tail gas. The content of total phosphorus in the tail gas treated by the method is less than 1mg/Nm3Other harmful components in the tail gas have no influence on dephosphorization and purification of the method, and the requirement of subsequent processes on heat energy utilization of the tail gas is met.
Claims (10)
1. A method for dephosphorizing yellow phosphorus tail gas is characterized by comprising the following steps:
s1: heating the yellow phosphorus tail gas by using a heating system;
s2: sending the yellow phosphorus tail gas after temperature rise into a catalytic reaction tower, and carrying out high-temperature catalytic oxidation on total phosphorus components in the yellow phosphorus tail gas under the action of a catalyst to generate yellow phosphorus tail gas containing phosphorus-oxygen compounds;
s3: sending the yellow phosphorus tail gas containing the phosphorus-oxygen compound into a cooling absorption tower, cooling, absorbing the phosphorus-oxygen compound, and discharging redundant heat and generated residual acid out of the cooling absorption tower;
s4: and (4) conveying the cooled and absorbed tail gas into a demisting and drying device, and performing demisting and drying treatment to obtain dephosphorized tail gas.
2. The method for dephosphorization of yellow phosphorus tail gas according to claim 1, further comprising a step of washing said yellow phosphorus tail gas with water before said step S1.
3. The phosphorus removal purification method of claim 1, wherein in step S1, the heating system is a gas circulation heating system, preferably the indirect heat transfer medium of the gas circulation heating system is nitrogen, inert gas or water vapor.
4. The method for dephosphorization and purification of yellow phosphorus tail gas according to claim 1, wherein in step S1, the temperature of the yellow phosphorus tail gas is raised to 400-500 ℃, preferably to 450 ℃.
5. The method for dephosphorization of yellow phosphorus tail gas according to claim 1, wherein in said step S2, said total phosphorus component is P4And/or pH3。
6. The method for dephosphorization of yellow phosphorus tail gas according to claim 1, wherein said catalyst in step S2 has catalytic selectivity only for total phosphorus component in said yellow phosphorus tail gas, and the catalytic reaction temperature of said catalyst is 400-500 ℃.
7. The method for dephosphorization of yellow phosphorus tail gas according to claim 1, wherein said cooling absorption tower of step S3 further comprises a spraying system for spraying said yellow phosphorus tail gas to cool it and absorb said phosphorus-oxygen compounds, preferably, the spraying liquid of said spraying system is water, ca (oh)2NaOH or other alkaline solutions.
8. The phosphorus removal process from phosphorus tail gas as claimed in claim 1, wherein said demister drying apparatus is disposed at the rear end of said cooling tower or at the top of said cooling tower.
9. The dephosphorization purifying method for yellow phosphorus tail gas according to claim 1, wherein said demisting drying device is one or a combination of several forms of a flat plate demister, a tube demister, a ridge demister, a cloth bag demister or a tube bundle demister.
10. The method for dephosphorization purification of yellow phosphorus tail gas according to claim 1, wherein the total phosphorus content in said dephosphorized tail gas is less than or equal to 1mg/Nm3。
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010349884.7A CN111617631A (en) | 2020-04-28 | 2020-04-28 | Yellow phosphorus tail gas dephosphorization purification method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010349884.7A CN111617631A (en) | 2020-04-28 | 2020-04-28 | Yellow phosphorus tail gas dephosphorization purification method |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398658A (en) * | 2002-04-26 | 2003-02-26 | 昆明理工大学 | Catalytic yellow phosphorus tail gas oxidizing and purifying method in fixed bed |
| CN101732962A (en) * | 2008-11-04 | 2010-06-16 | 侯莲香 | Method for purifying exhausting gas of yellow phosphorus by removing phosphine and hydrogen sulfide |
| CN103182316A (en) * | 2011-12-30 | 2013-07-03 | 北京北大先锋科技有限公司 | Catalyst for dephosphorizing yellow phosphorus tail gas and preparation method thereof |
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2020
- 2020-04-28 CN CN202010349884.7A patent/CN111617631A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398658A (en) * | 2002-04-26 | 2003-02-26 | 昆明理工大学 | Catalytic yellow phosphorus tail gas oxidizing and purifying method in fixed bed |
| CN101732962A (en) * | 2008-11-04 | 2010-06-16 | 侯莲香 | Method for purifying exhausting gas of yellow phosphorus by removing phosphine and hydrogen sulfide |
| CN103182316A (en) * | 2011-12-30 | 2013-07-03 | 北京北大先锋科技有限公司 | Catalyst for dephosphorizing yellow phosphorus tail gas and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张怀武等: "《炭素成型工》", 31 October 2013, 北京：冶金工业出版社 * |
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Application publication date: 20200904 |