CN109173669A - A method of purification yellow phosphoric tail gas - Google Patents
A method of purification yellow phosphoric tail gas Download PDFInfo
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- CN109173669A CN109173669A CN201811184445.4A CN201811184445A CN109173669A CN 109173669 A CN109173669 A CN 109173669A CN 201811184445 A CN201811184445 A CN 201811184445A CN 109173669 A CN109173669 A CN 109173669A
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- mud
- tail gas
- phosphorus
- phosphoric tail
- yellow phosphoric
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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
- 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
- B01D53/46—Removing components of defined structure
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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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen 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
- B01D53/77—Liquid phase processes
- B01D53/79—Injecting reactants
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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
- B01D2257/40—Nitrogen compounds
- B01D2257/408—Cyanides, e.g. hydrogen cyanide (HCH)
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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
- B01D2257/553—Compounds comprising hydrogen, e.g. silanes
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- Environmental & Geological Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
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- Industrial Gases (AREA)
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Abstract
The present invention provides a kind of methods for purifying yellow phosphoric tail gas, belong to technical field of waste gas treatment, the present invention mixes mud phosphorus with water, obtains mud Emulphors turbid;It is successively passed through oxygen and yellow phosphoric tail gas to be processed into the mud Emulphors turbid, carries out oxidation reaction.The ozone that the present invention induces generation using mud phosphorus and oxygen in the liquid phase cooperates with the Fe contained inside mud Emulphors turbid as oxidant3+Catalysis oxidation, by H2S oxidation is converted into sulfate ion, PH3It is converted into PO4 3‑, HCN is converted into N2And CO2.Operation of the present invention method is simple;Using waste mud phosphorus as H in yellow phosphoric tail gas2S、PH3It is economic and environment-friendly with the absorbent of HCN;The reaction product sulphur simple substance and its sulfate of generation, phosphate are recyclable, without secondary pollution, and to the purification efficiency of yellow phosphoric tail gas height.The present invention is to H2S and PH3Removal efficiency up to 95% or more, HCN purification efficiency up to 90% or more.
Description
Technical field
The present invention relates to technical field of waste gas treatment, in particular to a kind of method for the method for purifying yellow phosphoric tail gas.
Background technique
Phosphorous chemical industry is the important industry in the provinces such as cloud, expensive, river, Hubei Province, and Yunnan accounts for national 50% or more output phosphor.Yellow phosphorus
It being generated in production process along with a large amount of complicated components, poisonous and hazardous gas, every production 1t yellow phosphorus about generates 2500~
3000Nm3Tail gas, wherein 400~1000mg/Nm containing HCN3, PH3750~1200mg/Nm3, H2800~8000mg/Nm of S3
Complicated Deng, yellow phosphoric tail gas ingredient and its property, purified treatment difficulty is big, it is difficult to which processing and recycling are discharged, not only with combustion system
Sulphur in gas, carbon resource waste are caused, and seriously pollutes atmospheric environment.Analysis shows the resource utilization of yellow phosphoric tail gas is
Yellow phosphorus industry enhances the competitiveness, thoroughly gets rid of the fundamental way of high pollution, high energy consumption cap.
Currently, there are many method of processing yellow phosphoric tail gas both at home and abroad, absorption process, alternating temperature pressure swing adsorption method and catalysis oxygen can be divided into
Change method.Wherein alternating temperature pressure swing adsorption method develops a series of high-selectivity catalyst, and regeneration is simple;Each order reaction is mutually held in the mouth
It connects, heat energy utilization is preferable;Purification gas has not only reached carbonylation synthesis requirement, and is stripped of toxic gas HCN.But technology
It is at high cost, trivial operations, and need to consider catalyst life problem.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of method for purifying yellow phosphoric tail gas, method behaviour provided by the invention
It is high to make simple, at low cost and removal efficiency.
The present invention provides a kind of methods for purifying yellow phosphoric tail gas, comprising the following steps:
Mud phosphorus is mixed with water, obtains mud Emulphors turbid;
It is successively passed through oxygen and yellow phosphoric tail gas to be processed into the mud Emulphors turbid, carries out oxidation reaction;
The mud phosphorus is the mud phosphorus generated during producing yellow phosphorus;Phosphorus content is 4%~40% in the mud phosphorus, the mud
Fe in phosphorus3+Mass content be 0.83%;
The yellow phosphoric tail gas is the tail gas generated during producing yellow phosphorus.
Preferably, the solid content of the mud Emulphors turbid is 5~50wt%.
Preferably, the intake of the oxygen is so that the oxygen content in mud Emulphors turbid is 5~30%.
Preferably, the content of hydrogen sulfide is 2000~6000mg/m in the yellow phosphoric tail gas to be processed3, the content of hydrogen cyanide
For 300~800mg/m3, the content of hydrogen phosphide is 700~1000mg/m3。
Preferably, the rate that the yellow phosphoric tail gas to be processed is passed through is 0.2~1.0L/min.
Preferably, the mud Emulphors turbid and the volume ratio of yellow phosphoric tail gas to be processed are 2:5.
Preferably, the temperature of the oxidation reaction is 25 DEG C~70 DEG C, and the pH value of the oxidation reaction is 3.5~7.
Preferably, the device of the purification yellow phosphoric tail gas includes sequentially connected cooler, deduster, absorbing reaction and tail
The lower end air inlet of gas caustic scrubber, the absorbing reaction device is connected with air pump, the upper end feed inlet of the absorbing reaction device
Successively it is connected with head tank and high-pressure pump.
Advantageous effects: the present invention provides it is a kind of purify yellow phosphoric tail gas method, comprising the following steps: by mud phosphorus with
Water mixing, obtains mud Emulphors turbid;It is successively passed through oxygen and yellow phosphoric tail gas to be processed into the mud Emulphors turbid, is aoxidized
Reaction;The mud phosphorus is the mud phosphorus generated during producing yellow phosphorus;Phosphorus content is 4%~40% in the mud phosphorus, the mud phosphorus
Middle Fe3+Mass content be 0.83%;The yellow phosphoric tail gas is the tail gas generated during producing yellow phosphorus.The present invention utilizes mud phosphorus
The ozone of generation is induced in the liquid phase with oxygen as oxidant, cooperates with the Fe contained inside mud Emulphors turbid3+Catalysis oxidation, will
H2S oxidation is converted into sulfate ion, PH3It is converted into PO4 3-, HCN is converted into N2And CO2.Operation of the present invention method is simple;It utilizes
Waste mud phosphorus is as H in yellow phosphoric tail gas2S、PH3It is economic and environment-friendly with the absorbent of HCN;The reaction product sulphur simple substance of generation and its
Sulfate, phosphate are recyclable, without secondary pollution, and to the purification efficiency of yellow phosphoric tail gas height.Experimental data shows this hair
It is bright to H2S and PH3Removal efficiency up to 95% or more, HCN purification efficiency up to 90% or more.
Detailed description of the invention
Fig. 1 is the device figure of the method for purification yellow phosphoric tail gas provided by the invention;
1- cooler, 2- deduster, 3- air pump, 4- absorbing reaction device, 5- tail gas alkaline cleaning device, 6- high-pressure pump, 7- are high-order
Slot.
Specific embodiment
The present invention provides a kind of methods for purifying yellow phosphoric tail gas, comprising the following steps:
Mud phosphorus is mixed with water, obtains mud Emulphors turbid;
It is successively passed through oxygen and yellow phosphoric tail gas to be processed into the mud Emulphors turbid, carries out oxidation reaction;
The mud phosphorus is the mud phosphorus generated during producing yellow phosphorus;Phosphorus content is 4%~40% in the mud phosphorus, the mud
Fe in phosphorus3+Mass content be 0.83%;
The yellow phosphoric tail gas is the tail gas generated during producing yellow phosphorus.
The present invention mixes mud phosphorus with water, obtains mud Emulphors turbid.
In the present invention, phosphorus content is preferably 10%~40% in the mud phosphorus, and more preferably 20%~40%.
In the present invention, Fe in the mud phosphorus3+Content be preferably 0.5%~0.9%, more preferably 0.7%~
0.9%.
In the present invention, the solid content of the mud Emulphors turbid is preferably 5~50wt%, more preferably 10~40wt%,
Most preferably 20~30wt%.
After obtaining mud Emulphors turbid, the present invention is successively passed through oxygen and yellow phosphorus tail to be processed into the mud Emulphors turbid
Gas, the yellow phosphoric tail gas to be processed are the tail gas generated during producing yellow phosphorus.
In the present invention, the oxygen is preferably passed through in the form of air.
In the present invention, the intake of the oxygen is so that the oxygen content in mud Emulphors turbid is preferably 5~30%, more
Preferably 10~20%, most preferably 15%.In the present invention, the oxygen content in the mud Emulphors turbid passes through flue gas analyzer
Measurement.
In the present invention, the content of hydrogen sulfide is preferably 2000~6000mg/m in the gas to be processed3, more preferably
3000~5000mg/m3;The content of hydrogen cyanide is preferably 300~800mg/m3, more preferably 400~700mg/m3, most preferably
500~600mg/m3;The content of hydrogen phosphide is preferably 700~1000mg/m3, more preferably 800~900mg/m3, most preferably
850~880mg/m3。
In the present invention, the rate that the yellow phosphoric tail gas to be processed is passed through is preferably 0.2~1.0L/min, more preferably
0.5~0.8L/min.
In the present invention, the mud Emulphors turbid and the volume ratio of yellow phosphoric tail gas to be processed are preferably 2:5.
The present invention induces the ozone generated using mud phosphorus and oxygen as oxidant, and mud Emulphors turbid the inside is cooperateed with to contain
Fe3+Catalysis oxidation, by H2S oxidation is converted into sulfate ion, PH3It is converted into PO4 3-, HCN is converted into N2And CO2。
In the present invention, the yellow phosphoric tail gas to be located further preferably successively includes cooling and dedusting before being passed through.
The present invention is not particularly limited cooling method, selects cooling means well known to those skilled in the art.
The present invention is not particularly limited the method for dedusting, selects dust removal method well known to those skilled in the art.
In the present invention, the temperature of the oxidation reaction is preferably 25 DEG C~70 DEG C, more preferably 30~50 DEG C;The oxygen
The pH value for changing reaction is preferably 3.5~7, and more preferably 5~6.
In the present invention, the mud Emulphors turbid of the failure obtained after the oxidation reaction can be further recycled.
In the present invention, the device of the purification yellow phosphoric tail gas includes sequentially connected cooler, deduster, absorbing reaction
Be connected with the lower end air inlet of tail gas alkaline cleaning device, the absorbing reaction device with air pump, the upper end of the absorbing reaction device into
Material mouth is successively connected with head tank and high-pressure pump.The device of the purification yellow phosphoric tail gas is specifically as shown in Figure 1.
In the present invention, the concrete operations of the purification yellow phosphoric tail gas are as follows: air is blasted absorbing reaction by air pump 3
Device 4 is sufficiently reacted with the elemental phosphorous and oxygen in mud Emulphors turbid generates ozone, the yellow phosphoric tail gas to be processed in self-discharging in future source
Enter in absorbing reaction device 4 after cooling, 2 dedusting of deduster through cooler 1 and carries out oxidation reaction, the gas warp crossed through absorbing reaction
It is emptied after tail gas alkaline cleaning device 5 is dry, mud Emulphors turbid is housed, bottom is by there is the pipeline of control valve inside the absorbing reaction device 4
Go to next workshop to be recycled the transhipment of the emulsion of failure, mud Emulphors turbid after high-pressure pump 6 throws head tank 7 into successively
Supplement fresh slurry enters absorbing reaction device 4, and the mode that heat exchange can be used in the cooler 1 utilizes its thermal energy to reduce energy
Waste.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
It is 45%, Fe through phosphorus content in detection mud phosphorus using the mud phosphorus 0.5g of Yunnan Province's Yellow Phosphorous Plant3+Content is
0.83%, it is configured to 40mL emulsion, is placed in absorbing reaction device and is passed through air, is passed through after air that oxygen content is in mud phosphorus
20%, it then passes to containing H2S、PH3(H in gas is simulated with the simulation gas of HCN2S gas concentration is 1100mg/m3、PH3Gas
Concentration is 800mg/m3, HCN gas concentration be 600mg/m3), airflow rate 0.3L/min reacts 350min, absorbing reaction device
Temperature control is at 40 DEG C, experimental result H2S removal efficiency is 98%, PH3The time that removal efficiency is 87%, HCN removal efficiency is 83%
Sustainable 270min.
Embodiment 2
It is 45%, Fe through phosphorus content in detection mud phosphorus using the mud phosphorus 0.7g of Yunnan Province's Yellow Phosphorous Plant3+Content is
0.83%, mud phosphorus is configured to 40mL emulsion, is placed in absorbing reaction device and is passed through air, is passed through after oxygen that oxygen contains in mud phosphorus
Amount is 20%, is then passed to containing H2S、PH3(H in gas is simulated with the simulation gas of HCN2S gas concentration is 1100mg/m3、PH3
Gas concentration is 800mg/m3, HCN gas concentration be 600mg/m3), airflow rate 0.3L/min reacts 350min, absorbs anti-
Answer the control of device temperature at 60 DEG C, experimental result H2S removal efficiency is 99%, PH3Removal efficiency is 96%, HCN removal efficiency is 93%
Time sustainable 300min.
Embodiment 3
It is 45%, Fe through phosphorus content in detection mud phosphorus using the mud phosphorus 0.5g of Yunnan Province's Yellow Phosphorous Plant3+Content is
0.83%, mud phosphorus is configured to 40mL emulsion, is placed in absorbing reaction device and is passed through air, is passed through after air oxygen matter in mud phosphorus
Measuring content is 15%, it then passes to containing H2S、PH3(H in gas is simulated with the simulation gas of HCN2S gas concentration is 1100mg/
m3、PH3Gas concentration is 800mg/m3, HCN gas concentration be 600mg/m3), airflow rate 0.7L/min reacts 350min,
The control of absorbing reaction device temperature is at 70 DEG C, experimental result H2S removal efficiency is 94%, PH3Removal efficiency is 83%, HCN removal efficiency is
79% time sustainable 250min.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of method for purifying yellow phosphoric tail gas, comprising the following steps:
Mud phosphorus is mixed with water, obtains mud Emulphors turbid;
It is successively passed through oxygen and yellow phosphoric tail gas to be processed into the mud Emulphors turbid, carries out oxidation reaction;
The mud phosphorus is the mud phosphorus generated during producing yellow phosphorus;Phosphorus content is 4%~40% in the mud phosphorus, in the mud phosphorus
Fe3+Mass content be 0.83%;
The yellow phosphoric tail gas is the tail gas generated during producing yellow phosphorus.
2. the method according to claim 1, wherein the solid content of the mud Emulphors turbid is 5~50wt%.
3. the method according to claim 1, wherein the intake of the oxygen is so that in mud Emulphors turbid
Oxygen content is 5~30%.
4. the method according to claim 1, wherein the content of hydrogen sulfide is in the yellow phosphoric tail gas to be processed
2000~6000mg/m3, the content of hydrogen cyanide is 300~800mg/m3, the content of hydrogen phosphide is 700~1000mg/m3。
5. according to method described in claim 1, which is characterized in that the rate that the yellow phosphoric tail gas to be processed is passed through be 0.2~
1.0L/min。
6. according to claim 1, method described in 4 or 5, which is characterized in that the mud Emulphors turbid and yellow phosphoric tail gas to be processed
Volume ratio be 2:5.
7. the method according to claim 1, wherein the temperature of the oxidation reaction be 25 DEG C~70 DEG C, it is described
The pH value of oxidation reaction is 3.5~7.
8. the method according to claim 1, wherein the device of the purification yellow phosphoric tail gas includes sequentially connected
The lower end air inlet of cooler, deduster, absorbing reaction device and tail gas alkaline cleaning device, the absorbing reaction device is connected with air pump
It connects, the upper end feed inlet of the absorbing reaction device is successively connected with head tank and high-pressure pump.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110102180A (en) * | 2019-06-21 | 2019-08-09 | 云南民族大学 | A kind of method of mud Emulphors turbid liquid phase catalytic oxidation simultaneous SO_2 and NO removal |
CN110304608A (en) * | 2019-07-02 | 2019-10-08 | 昆明理工大学 | A kind of method that ozone phosphoric acid byproduct is produced in the liquid phase oxidation of mud phosphorus |
CN111992028A (en) * | 2020-08-19 | 2020-11-27 | 昆明理工大学 | Additive for enhancing hydrogen sulfide removal of yellow phosphorus slurry and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101024140A (en) * | 2007-01-15 | 2007-08-29 | 左建国 | Method for purifying phosphor tail-gas |
CN104307365A (en) * | 2014-10-17 | 2015-01-28 | 陕西华陆化工环保有限公司 | Cleaning method of hydrogen sulfide gas |
CN108568202A (en) * | 2017-03-09 | 2018-09-25 | 云南民族大学 | A kind of method of mud phosphorus removing nitrogen oxides |
-
2018
- 2018-10-11 CN CN201811184445.4A patent/CN109173669B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101024140A (en) * | 2007-01-15 | 2007-08-29 | 左建国 | Method for purifying phosphor tail-gas |
CN104307365A (en) * | 2014-10-17 | 2015-01-28 | 陕西华陆化工环保有限公司 | Cleaning method of hydrogen sulfide gas |
CN108568202A (en) * | 2017-03-09 | 2018-09-25 | 云南民族大学 | A kind of method of mud phosphorus removing nitrogen oxides |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110102180A (en) * | 2019-06-21 | 2019-08-09 | 云南民族大学 | A kind of method of mud Emulphors turbid liquid phase catalytic oxidation simultaneous SO_2 and NO removal |
CN110304608A (en) * | 2019-07-02 | 2019-10-08 | 昆明理工大学 | A kind of method that ozone phosphoric acid byproduct is produced in the liquid phase oxidation of mud phosphorus |
CN110304608B (en) * | 2019-07-02 | 2023-04-07 | 昆明理工大学 | Method for preparing ozone and by-product phosphoric acid by liquid-phase oxidation of phosphorus sludge |
CN111992028A (en) * | 2020-08-19 | 2020-11-27 | 昆明理工大学 | Additive for enhancing hydrogen sulfide removal of yellow phosphorus slurry and application thereof |
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