CN112844006A - Yellow phosphorus tail gas purification method - Google Patents
Yellow phosphorus tail gas purification method Download PDFInfo
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- CN112844006A CN112844006A CN202011581406.5A CN202011581406A CN112844006A CN 112844006 A CN112844006 A CN 112844006A CN 202011581406 A CN202011581406 A CN 202011581406A CN 112844006 A CN112844006 A CN 112844006A
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- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000000746 purification Methods 0.000 title claims description 24
- 239000007789 gas Substances 0.000 claims abstract description 186
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 54
- 239000011574 phosphorus Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000005406 washing Methods 0.000 claims abstract description 44
- 238000001914 filtration Methods 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000012528 membrane Substances 0.000 claims abstract description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000428 dust Substances 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000446 fuel Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004280 Sodium formate Substances 0.000 claims abstract description 4
- 235000019253 formic acid Nutrition 0.000 claims abstract description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 4
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 239000011737 fluorine Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000002815 homogeneous catalyst Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 125000001741 organic sulfur group Chemical group 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000003860 storage Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- B01D53/75—Multi-step processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
- B01D50/60—Combinations of devices covered by groups B01D46/00 and B01D47/00
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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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01D53/8603—Removing sulfur compounds
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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
- B01D53/8659—Removing halogens or halogen compounds
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- 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
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- 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
- B01D53/8678—Removing components of undefined structure
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2251/10—Oxidants
- B01D2251/106—Peroxides
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Abstract
The invention discloses a method for purifying yellow phosphorus tail gas, which comprises the following steps: s1, removing dust particles in the yellow phosphorus tail gas by using a metal membrane filtering device to obtain dust-removing tail gas; s2, sequentially carrying out normal-temperature water washing and low-temperature water washing on the dedusting tail gas to cool the dedusting tail gas to 10-20 ℃ so as to obtain cooling tail gas and crude phosphorus; s3, oxidizing the cooled tail gas by using hydrogen peroxide to obtain oxidized tail gas; s4, absorbing the oxidized tail gas by using a copper sulfate solution to obtain an absorbed tail gas; and S5, adopting liquid caustic soda to reabsorb the absorbed tail gas to obtain the purified tail gas. The advantages are that: the method has low treatment cost, and the purified tail gas can reach high quality index, and can completely meet the requirements of using as the raw material of carbon-product such as formic acid, sodium formate and the like or generating steam as boiler fuel to generate power. Solves the problem of treatment of the yellow phosphorus tail gas which is not solved properly in the field.
Description
Technical Field
The invention relates to the technical field of yellow phosphorus production, in particular to a method for treating byproducts in a yellow phosphorus production process.
Background
The purification of the yellow phosphorus tail gas is always an industrial problem, the industry generally adopts a water washing and alkali washing technology for treatment, but the phosphorus content in the yellow phosphorus tail gas is relatively high, so that the primarily purified yellow phosphorus tail gas cannot be directly used for boiler combustion and chemical production, and can only be used as a common fuel in some limited fields. In order to use the yellow phosphorus tail gas for producing chemicals, deep purification is added after water washing and alkali washing in the industry to further remove the contents of sulfur, phosphorus, fluorine and other impurities in the yellow phosphorus tail gas, but the purification cost of the yellow phosphorus tail gas can be greatly increased, and the profitability of producing the chemicals by using the yellow phosphorus tail gas is influenced.
Chinese patent with publication number CN104096462B discloses a method for purifying yellow phosphorus tail gas into fuel gas or feed gas by using techniques of cyclone, copper sulfate solution absorption, etc. The method has the biggest problem that the content of sulfur, phosphorus, fluorine and acid gas in the treated yellow phosphorus tail gas is high, and the yellow phosphorus tail gas is difficult to be used as raw material gas.
Chinese patent with publication number CN101530722B discloses a method for purifying yellow phosphorus tail gas by water washing and wet tube type electric precipitation. The method is only a pretreatment technology of the yellow phosphorus tail gas, and the yellow phosphorus tail gas must be further purified to realize high-value utilization of the yellow phosphorus tail gas.
The Chinese patent with the publication number of CN103182244B discloses a method for realizing deep purification of yellow phosphorus tail gas and producing oxamide products, wherein the primary purification comprises the steps of four-stage water washing, primary alkali washing, catalytic oxidation process and the like, and the deep purification comprises the steps of primary adsorption, deoxidation, pressure swing adsorption, dehydrogenation and the like. The method has the biggest problem that the yellow phosphorus tail gas purification cost is high, and the profitability of the oxamide product is greatly influenced.
The above patent technologies mainly have two problems: on the one hand, the yellow phosphorus tail gas has poor purification effect and cannot be directly used for producing chemicals. On the other hand, the purification cost of the yellow phosphorus tail gas is increased after the yellow phosphorus tail gas is treated by advanced purification technologies such as pretreatment, oxidation, temperature and pressure swing adsorption and the like, and the profitability of the produced chemicals is greatly influenced. The invention is characterized in that on the premise of economy, the purification effect of the yellow phosphorus tail gas can reach higher requirements, so that the yellow phosphorus tail gas can be used for steam power generation and the production of partial chemicals, and is particularly suitable for synthetic products without catalysts.
Disclosure of Invention
The invention provides a method for purifying yellow phosphorus tail gas, which aims to solve the problems that the yellow phosphorus tail gas is difficult to be properly treated or the treatment cost is too high and the economic benefit is low in the prior art.
The technical scheme adopted by the invention is as follows: the yellow phosphorus tail gas purification method comprises the following steps:
s1, removing dust particles in the yellow phosphorus tail gas by using a metal membrane filtering device to obtain dust-removing tail gas;
s2, sequentially carrying out normal-temperature water washing and low-temperature water washing on the dedusting tail gas to cool the dedusting tail gas to 10-20 ℃ so as to obtain cooling tail gas and crude phosphorus;
s3, oxidizing the cooled tail gas by using hydrogen peroxide to obtain oxidized tail gas;
s4, absorbing the oxidized tail gas by using a copper sulfate solution to obtain an absorbed tail gas;
and S5, adopting liquid caustic soda to reabsorb the absorbed tail gas to obtain the purified tail gas.
As the main innovation point of the invention, the combination of metal membrane filtration and primary normal-temperature water washing replaces the traditional four-stage water washing process and the subsequent process, so that the production process can be greatly simplified, the four-stage water washing process is simplified into the primary water washing, the circulation amount of phosphorus-containing wastewater and the water and electricity consumption are greatly reduced, meanwhile, the quality of crude phosphorus is greatly improved after the new process is adopted, the crude phosphorus refining process (comprising the refining processes of rinsing, multi-stage sedimentation and the like) is further simplified, the production amount of phosphorus sludge can be greatly reduced, the miniaturization and the industrialization of the continuous phosphorus steaming technology are promoted, the method for treating the phosphorus sludge by using a rotary pot in the traditional process is replaced, and the field environment of the yellow phosphorus smelting industry is greatly improved.
As a further improvement of the invention, the traditional deep purification process (such as temperature swing adsorption, pressure swing adsorption, catalytic oxidation and the like) is replaced by the combined process of primary low-temperature water washing, hydrogen peroxide oxidation, copper sulfate absorption and liquid caustic soda absorption, so that the investment and operation cost can be greatly reduced.
As a further improvement of the invention, the metal membrane filtering device comprises a metal filtering membrane, and the metal filtering membrane is a net membrane which is woven by metal wires and has uniform through holes and the dust removal efficiency on the yellow phosphorus tail gas is more than or equal to 99.9%. Further, in order to ensure continuous production of the yellow phosphorus device, the metal membrane filtration device can adopt a one-start-one-standby design. Furthermore, in order to ensure the stability of the furnace pressure of the yellow phosphorus furnace, a buffer tank can be arranged behind the gas guide pipe of the yellow phosphorus furnace, and meanwhile, the valve control is increased through the measure that the outlet of the buffer tank is reduced in diameter, so that the switching of two groups of filtering devices is realized. Further, in order to ensure the ash discharge safety, the metal membrane filtering device periodically discharges ash into the intermediate ash storage tank, then replaces and recovers a small amount of yellow phosphorus and carbon monoxide gas in the ash storage tank through nitrogen, and finally periodically discharges the ash according to the material level of the intermediate ash storage tank.
As a further improvement of the invention, the normal-temperature water washing end point is that the dust content of the dedusting tail gas is less than or equal to 1mg/Nm3. Partial yellow phosphorus in the tail gas can be recovered through normal-temperature water washing, the temperature of the yellow phosphorus tail gas at about 200 ℃ is reduced to 50-60 ℃, and the consumption of low-temperature water in the subsequent water washing process can be reduced.
As a further improvement of the invention, the low-temperature water washing end point is that the content of elemental phosphorus in the tail gas is less than or equal to 5mg/Nm3And the temperature of the tail gas is 10-20 ℃. The yellow phosphorus in the tail gas can be further recovered through low-temperature water washing. Crude phosphorus from normal temperature water washing and low temperature water washing can enter a phosphorus receiving groove to be collected and butted with the traditional production process.
As a further improvement of the invention, the equipment adopted by the normal-temperature water washing is an empty tower; the equipment adopted by the low-temperature water washing is a sieve plate tower.
As a further improvement of the invention, the oxidation end point of step S3 is that the total content of organic sulfur and organic phosphorus in the tail gas is less than or equal to 5mg/Nm3。
As a further improvement of the present invention, step S3 is catalyzed by a homogeneous catalyst. More preferably, the homogeneous catalyst is selected from one or more of ferrous chloride, ferrous sulfate and ferrous nitrate.
As a further improvement of the invention, the hydrogen peroxide temperature is 50-90 ℃, and a feed process after preheating can be adopted.
As a further improvement of the invention, the equipment adopted in the step S3 is a combined tower, the upper half section of the combined tower is a foam tower, and the lower half section of the combined tower is a packed tower.
As a further improvement of the invention, the absorption end point of the step S4 is that the content of the simple substance phosphorus in the tail gas is less than or equal to 1mg/Nm3Organic sulfur content less than or equal to 1mg/Nm3The content of organic phosphorus is less than or equal to 1mg/Nm3。
As a further improvement of the present invention, the apparatus used in step S4 is an empty tower.
As a further improvement of the invention, the absorption end point of the step S5 is that the content of acid gas in the tail gas is less than or equal to 1mg/Nm3The total sulfur content is less than or equal to 3mg/Nm3The total phosphorus content is less than or equal to 3mg/Nm3The total fluorine content is less than or equal to 3mg/Nm3。
Experiments show that the purified tail gas obtained by the method has higher quality index and can be used as a production raw material of carbon products (formic acid, sodium formate and the like) (see the embodiment part).
The invention also discloses a carbon product production method, which is characterized in that the purified tail gas prepared by the yellow phosphorus tail gas purification method is used as a production raw material.
The invention has the beneficial effects that: the method has low treatment cost, and the purified tail gas can reach the acid gas content of less than or equal to 1mg/Nm3The total sulfur content is less than or equal to 3mg/Nm3The total phosphorus content is less than or equal to 3mg/Nm3The total fluorine content is less than or equal to 3mg/Nm3The high-quality index of the fuel can completely meet the requirements of using the fuel as a raw material of carbon products such as formic acid, sodium formate and the like or generating power by using the fuel as boiler fuel to generate steam. The method solves the problem of treatment of the yellow phosphorus tail gas which is expected to be solved but not solved in the field all the time, and simultaneously greatly simplifies the treatment process of a crude phosphorus refining unit, improves the technical level of a sludge phosphorus treatment unit and further improves the environment of on-site sludge phosphorus treatment by implementing the process.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
The first embodiment is as follows:
the following method is adopted for purifying the yellow phosphorus tail gas of the first batch:
(1) the acid gas content, the total sulfur content, the total phosphorus content and the total fluorine content of the yellow phosphorus tail gas to be purified of the first batch are measured before treatment, and the results are shown in table 1.
(2) And removing dust particles in the yellow phosphorus tail gas by adopting a metal membrane filtering device behind the gas guide pipe of the yellow phosphorus furnace, wherein the metal membrane filtering device comprises a metal filtering membrane, and the metal filtering membrane is a net membrane which is woven by stainless steel wires and has uniform through holes and the dust removal efficiency of the metal filtering membrane on the yellow phosphorus tail gas is more than or equal to 99.9%. In order to ensure the continuous production of the yellow phosphorus device, the metal membrane filtering device adopts a primary-secondary design. A buffer tank is arranged behind the air guide pipe of the yellow phosphorus furnace, and valve control is increased by means of reducing the outlet diameter of the buffer tank, so that switching of the two groups of filtering devices is realized. The metal film filtering device periodically discharges ash into the intermediate ash storage tank, then a small amount of yellow phosphorus and carbon monoxide gas in the ash storage tank is replaced and recovered by nitrogen, and finally the ash is periodically discharged according to the material level of the intermediate ash storage tank.
(3) The generated dedusting tail gas enters an empty tower for normal temperature water washing, the temperature of the tail gas at a discharge port is measured to be reduced to 54 ℃, and the dust content of the tail gas is 0.79mg/Nm3. The tail gas after being washed by normal temperature water enters a sieve plate tower for low temperature water washing, the temperature of the tail gas at a discharge port is measured to be 17.4 ℃, and the content of elemental phosphorus in the tail gas is 4.28mg/Nm3. Crude phosphorus from normal temperature water washing and low temperature water washing can enter a phosphorus receiving groove to be collected and butted with the traditional production process.
(4) Introducing the cooled tail gas into a combined tower consisting of an upper half section of foam tower and a lower half section of packed tower, carrying out catalytic oxidation on the cooled tail gas and hydrogen peroxide which is preheated to 73 ℃ and then introduced into the combined tower under the catalysis of a homogeneous catalyst ferrous chloride, and measuring that the total content of organic sulfur and organic phosphorus in the tail gas at a discharge port is 4.80mg/Nm3。
(5) Introducing the oxidized tail gas into an empty tower, fully absorbing the oxidized tail gas by adopting a copper sulfate solution, and measuring that the content of elemental phosphorus in the tail gas at a gas outlet is 0.73mg/Nm3Organic sulfur content is less than or equal to 0.89mg/Nm3The content of organic phosphorus was 0.67mg/Nm3。
(6) And introducing the absorbed tail gas into the absorption tower again, and fully absorbing the absorbed tail gas by adopting liquid alkali to obtain the purified tail gas. The content of acid gas, the content of total sulfur, the content of total phosphorus and the content of total fluorine in the purified tail gas are sampled and detected, and the results are shown in table 1.
Example two:
and (3) purifying the yellow phosphorus tail gas of the second batch by adopting the following method:
(1) the acid gas content, total sulfur content, total phosphorus content and total fluorine content of the second batch of yellow phosphorus tail gas to be purified are measured before treatment, and the results are shown in table 1.
(2) And removing dust particles in the yellow phosphorus tail gas by adopting a metal membrane filtering device behind the gas guide pipe of the yellow phosphorus furnace, wherein the metal membrane filtering device comprises a metal filtering membrane, and the metal filtering membrane is a net membrane which is woven by stainless steel wires and has uniform through holes and the dust removal efficiency of the metal filtering membrane on the yellow phosphorus tail gas is more than or equal to 99.9%. In order to ensure the continuous production of the yellow phosphorus device, the metal membrane filtering device adopts a primary-secondary design. A buffer tank is arranged behind the air guide pipe of the yellow phosphorus furnace, and valve control is increased by means of reducing the outlet diameter of the buffer tank, so that switching of the two groups of filtering devices is realized. The metal film filtering device periodically discharges ash into the intermediate ash storage tank, then a small amount of yellow phosphorus and carbon monoxide gas in the ash storage tank is replaced and recovered by nitrogen, and finally the ash is periodically discharged according to the material level of the intermediate ash storage tank.
(3) The generated dedusting tail gas enters an empty tower for normal temperature water washing, the temperature of the tail gas at a discharge port is measured to be reduced to 56 ℃, and the dust content of the tail gas is 0.84mg/Nm3. The tail gas after normal temperature water washing enters a sieve plate tower for low temperature water washing, the temperature of the tail gas at a discharge port is measured to be 18.1 ℃, and the content of elemental phosphorus in the tail gas is 4.16mg/Nm3. Crude phosphorus from normal temperature water washing and low temperature water washing can enter a phosphorus receiving groove to be collected and butted with the traditional production process.
(4) Introducing the cooled tail gas into a combined tower consisting of an upper half section of foam tower and a lower half section of packed tower, carrying out catalytic oxidation on the cooled tail gas and hydrogen peroxide which is preheated to 90 ℃ and then introduced into the combined tower under the catalysis of a homogeneous catalyst ferrous chloride, and measuring that the total content of organic sulfur and organic phosphorus in the tail gas at a discharge port is 4.52mg/Nm3。
(5) Introducing the oxidized tail gas into an empty tower, fully absorbing the oxidized tail gas by adopting a copper sulfate solution, and measuring that the content of elemental phosphorus in the tail gas at a gas outlet is 0.76mg/Nm3Organic sulfur content is less than or equal to 0.73mg/Nm3The organic phosphorus content was 0.81mg/Nm3。
(6) And introducing the absorbed tail gas into the absorption tower again, and fully absorbing the absorbed tail gas by adopting liquid alkali to obtain the purified tail gas. The content of acid gas, the content of total sulfur, the content of total phosphorus and the content of total fluorine in the purified tail gas are sampled and detected, and the results are shown in table 1.
Example three:
the purification of the yellow phosphorus tail gas of the third batch is carried out by adopting the following method:
(1) the acid gas content, the total sulfur content, the total phosphorus content and the total fluorine content of the yellow phosphorus tail gas to be purified of the third batch are measured before treatment, and the results are shown in table 1.
(2) And removing dust particles in the yellow phosphorus tail gas by adopting a metal membrane filtering device behind the gas guide pipe of the yellow phosphorus furnace, wherein the metal membrane filtering device comprises a metal filtering membrane, and the metal filtering membrane is a net membrane which is woven by stainless steel wires and has uniform through holes and the dust removal efficiency of the metal filtering membrane on the yellow phosphorus tail gas is more than or equal to 99.9%. In order to ensure the continuous production of the yellow phosphorus device, the metal membrane filtering device adopts a primary-secondary design. A buffer tank is arranged behind the air guide pipe of the yellow phosphorus furnace, and valve control is increased by means of reducing the outlet diameter of the buffer tank, so that switching of the two groups of filtering devices is realized. The metal film filtering device periodically discharges ash into the intermediate ash storage tank, then a small amount of yellow phosphorus and carbon monoxide gas in the ash storage tank is replaced and recovered by nitrogen, and finally the ash is periodically discharged according to the material level of the intermediate ash storage tank.
(3) The generated dedusting tail gas enters an empty tower for normal temperature water washing, the temperature of the tail gas at a discharge port is measured to be reduced to 53 ℃, and the dust content of the tail gas is 0.76mg/Nm3. The tail gas after being washed by normal temperature water enters a sieve plate tower for low temperature water washing, the temperature of the tail gas at a discharge port is measured to be 17.3 ℃, and the content of elemental phosphorus in the tail gas is 4.09mg/Nm3. Crude phosphorus from normal temperature water washing and low temperature water washing can enter a phosphorus receiving groove to be collected and butted with the traditional production process.
(4) Introducing the cooled tail gas into a combined tower consisting of an upper half section foam tower and a lower half section packed tower, carrying out catalytic oxidation on the cooled tail gas and hydrogen peroxide which is preheated to 64 ℃ and then introduced into the combined tower under the catalysis of a homogeneous catalyst ferrous chloride, and measuring that the total content of organic sulfur and organic phosphorus in the tail gas at a discharge port is 4.31mg/Nm3。
(5) Introducing the oxidized tail gas into an empty tower, fully absorbing the oxidized tail gas by adopting a copper sulfate solution, and measuring that the content of elemental phosphorus in the tail gas at a gas outlet is 0.81mg/Nm3Organic sulfur content is less than or equal to 0.86mg/Nm3The content of organic phosphorus was 0.72mg/Nm3。
(6) And introducing the absorbed tail gas into the absorption tower again, and fully absorbing the absorbed tail gas by adopting liquid alkali to obtain the purified tail gas. The content of acid gas, the content of total sulfur, the content of total phosphorus and the content of total fluorine in the purified tail gas are sampled and detected, and the results are shown in table 1.
TABLE 1 yellow phosphorus Tail gas detection results before and after purification
| Example 1 | Example 2 | Example 3 | |
| Acid gas content (g/Nm) before purification3) | 52 | 57 | 60 |
| Total sulfur content (g/Nm) before purging3) | 3.68 | 3.53 | 3.50 |
| Total phosphorus content (g/Nm) before purification3) | 0.96 | 0.84 | 0.87 |
| Total fluorine content (g/Nm) before purging3) | 0.94 | 1.15 | 0.91 |
| Purified acid gasContent (mg/Nm)3) | 0.75 | 0.83 | 0.74 |
| Total sulfur content (mg/Nm) after purification3) | 1.59 | 1.61 | 1.54 |
| Total phosphorus content (mg/Nm) after purification3) | 0.63 | 0.46 | 0.51 |
| Total fluorine content (mg/Nm) after purification3) | 2.23 | 2.30 | 2.17 |
Claims (16)
1. The yellow phosphorus tail gas purification method comprises the following steps:
s1, removing dust particles in the yellow phosphorus tail gas by using a metal membrane filtering device to obtain dust-removing tail gas;
s2, sequentially carrying out normal-temperature water washing and low-temperature water washing on the dedusting tail gas to cool the dedusting tail gas to 10-20 ℃ so as to obtain cooling tail gas and crude phosphorus;
s3, oxidizing the cooled tail gas by using hydrogen peroxide to obtain oxidized tail gas;
s4, absorbing the oxidized tail gas by using a copper sulfate solution to obtain an absorbed tail gas;
and S5, adopting liquid caustic soda to reabsorb the absorbed tail gas to obtain the purified tail gas.
2. The method for purifying the yellow phosphorus tail gas according to claim 1, wherein the method comprises the following steps: the metal membrane filtering device comprises a metal filtering membrane, and the metal filtering membrane is a net membrane which is woven by metal wires, has uniform through holes and has the dust removal efficiency of yellow phosphorus tail gas more than or equal to 99.9%.
3. The method for purifying the yellow phosphorus tail gas according to claim 1, wherein the method comprises the following steps: the dust content of the dedusting tail gas is less than or equal to 1mg/Nm at the normal-temperature water washing end point3。
4. The method for purifying the yellow phosphorus tail gas according to claim 1, wherein the method comprises the following steps: the low-temperature water washing end point is that the content of elemental phosphorus in the tail gas is less than or equal to 5mg/Nm3And the temperature of the tail gas is 10-20 ℃.
5. The method for purifying the yellow phosphorus tail gas according to claim 1, wherein the method comprises the following steps: the equipment adopted by the normal-temperature water washing is an empty tower; the equipment adopted by the low-temperature water washing is a sieve plate tower.
6. The method for purifying the yellow phosphorus tail gas according to claim 1, wherein the method comprises the following steps: the oxidation end point of the step S3 is that the total content of organic sulfur and organic phosphorus in the tail gas is less than or equal to 5mg/Nm3。
7. The method for purifying the yellow phosphorus tail gas according to claim 1, wherein the method comprises the following steps: step S3 is catalyzed and oxidized by a homogeneous catalyst.
8. The method for purifying the yellow phosphorus tail gas according to claim 7, wherein the method comprises the following steps: the homogeneous catalyst is selected from one or more of ferrous chloride, ferrous sulfate and ferrous nitrate.
9. The method for purifying the yellow phosphorus tail gas according to claim 1, wherein the method comprises the following steps: the temperature of the hydrogen peroxide is 50-90 ℃.
10. The method for purifying the yellow phosphorus tail gas according to claim 1, wherein the method comprises the following steps: the equipment adopted in the step S3 is a combined tower, the upper half section of the combined tower is a foam tower, and the lower half section of the combined tower is a packed tower.
11. The method for purifying the yellow phosphorus tail gas according to claim 1, wherein the method comprises the following steps: the absorption end point of the step S4 is that the content of the simple substance phosphorus in the tail gas is less than or equal to 1mg/Nm3Organic sulfur content less than or equal to 1mg/Nm3The content of organic phosphorus is less than or equal to 1mg/Nm3。
12. The method for purifying the yellow phosphorus tail gas according to claim 1, wherein the method comprises the following steps: the equipment used in step S4 is an empty tower.
13. The method for purifying the yellow phosphorus tail gas according to claim 1, wherein the method comprises the following steps: the absorption end point of the step S5 is that the content of the acid gas in the tail gas is less than or equal to 1mg/Nm3The total sulfur content is less than or equal to 3mg/Nm3The total phosphorus content is less than or equal to 3mg/Nm3The total fluorine content is less than or equal to 3mg/Nm3。
14. The method for purifying yellow phosphorus tail gas according to any one of claims 1 to 13, characterized in that: and generating steam power by using the purified tail gas as a production raw material of a carbon-product or as boiler fuel.
15. The method for purifying the yellow phosphorus tail gas according to claim 14, wherein: the carbon-one product is formic acid or sodium formate.
16. A method of producing a carbon product, comprising: the raw material for production comprises the purified tail gas prepared by the method for purifying the yellow phosphorus tail gas as claimed in any one of claims 1 to 13.
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