CN116510497A - Method and system for removing sulfur, phosphorus and nitrogen oxides in yellow phosphorus tail gas boiler by using phosphorus ore powder - Google Patents
Method and system for removing sulfur, phosphorus and nitrogen oxides in yellow phosphorus tail gas boiler by using phosphorus ore powder Download PDFInfo
- Publication number
- CN116510497A CN116510497A CN202310757914.1A CN202310757914A CN116510497A CN 116510497 A CN116510497 A CN 116510497A CN 202310757914 A CN202310757914 A CN 202310757914A CN 116510497 A CN116510497 A CN 116510497A
- Authority
- CN
- China
- Prior art keywords
- content
- flue gas
- desulfurization
- phosphorus
- denitrification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007789 gas Substances 0.000 title claims abstract description 115
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 84
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000011574 phosphorus Substances 0.000 title claims abstract description 82
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 75
- 239000000843 powder Substances 0.000 title claims abstract description 72
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001392 phosphorus oxide Inorganic materials 0.000 title claims abstract description 16
- 239000011593 sulfur Substances 0.000 title claims abstract description 16
- 229910052815 sulfur oxide Inorganic materials 0.000 title claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000003546 flue gas Substances 0.000 claims abstract description 116
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 102
- 230000023556 desulfurization Effects 0.000 claims abstract description 102
- 239000002367 phosphate rock Substances 0.000 claims abstract description 54
- 239000002893 slag Substances 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 238000001354 calcination Methods 0.000 claims abstract description 35
- 238000002485 combustion reaction Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002002 slurry Substances 0.000 claims abstract description 25
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 40
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 17
- GFIKIVSYJDVOOZ-UHFFFAOYSA-L calcium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Ca+2].[O-]P([O-])(F)=O GFIKIVSYJDVOOZ-UHFFFAOYSA-L 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 28
- 239000000779 smoke Substances 0.000 description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 235000011010 calcium phosphates Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 239000013064 chemical raw material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- -1 phosphorus-oxygen-calcium compounds Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
Classifications
-
- 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
- B01D53/81—Solid phase processes
- B01D53/83—Solid phase processes with moving reactants
-
- 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
-
- 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
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
-
- 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
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to the technical field of phosphorus chemical industry and environmental protection, in particular to a method and a system for removing sulfur, phosphorus and nitrogen oxides in yellow phosphorus tail gas boilers by using phosphorus ore powder. The method comprises the following steps: (1) Carrying out combustion reaction on yellow phosphorus tail gas and oxygen-containing gas to obtain high-temperature flue gas; (2) Under the thermal action of the combustion reaction, the phosphorite powder is fluidized and is subjected to calcination reaction, and the obtained calcination reaction product is mixed with P in the high-temperature flue gas 2 O 5 Dephosphorizing, and performing heat exchange on the obtained high Wen Tuolin flue gas to obtain low Wen Tuolin flue gas; (3) Mixing dephosphorized slag obtained by dephosphorization treatment with simple substance phosphorus-containing slurry to obtain a desulfurization and denitrification agent; (4) And (3) contacting the desulfurization and denitrification agent with low Wen Tuolin flue gas and performing wet desulfurization and denitrification treatment to obtain desulfurization and denitrification flue gas. The method realizes the removal of sulfur, phosphorus and nitrogen oxides in the yellow phosphorus tail gas while recovering the reaction heat of the yellow phosphorus tail gas.
Description
Technical Field
The invention relates to the technical field of phosphorus chemical industry and environmental protection, in particular to a method for removing sulfur, phosphorus and nitrogen oxides in a yellow phosphorus tail gas boiler by using phosphorus ore powder, and a system for removing sulfur, phosphorus and nitrogen oxides in the yellow phosphorus tail gas boiler by using the phosphorus ore powder.
Background
Yellow phosphorus is an important chemical raw material and is indispensable in electronic grade chemicals, medicines, pesticides, extractants, military industry, battery materials and other industries. At present, the energy consumption per 1 ton of yellow phosphorus produced by an electric furnace method is up to 3.2 tons of standard coal, and the byproduct of the phosphorus furnace tail gas 2800-3200m with the CO content of 85-90 vol% 3 Is a high-quality chemical raw material and fuel gas, but because of the yellow phosphorus tail gas purification technology and small single phosphorus furnace gas quantity, the cost competitiveness as the chemical raw material gas is weak, and the large-scale utilization is difficult to obtain; however, if the yellow phosphorus tail gas is used as the fuel of the boiler gas, if the deep purification treatment is not carried out, the yellow phosphorus tail gas contains elemental phosphorus and phosphine gas, and P is generated after the yellow phosphorus tail gas is burnt with air 2 O 5 ，P 2 O 5 The phosphoric acid is produced by combining with water, and the phosphoric acid adheres to the wall of the boiler tube to cause severe equipment corrosion; and the deep purification cost is high, and the gas is not economical. Therefore, the low cost solution of yellow phosphorus tail gas boiler corrosion is yellow phosphorus tail gas utilizationOne of the key technologies. The yellow phosphorus tail gas also contains hydrogen sulfide and COS, and forms SO after oxidation and combustion 2 Generates NO after high-temperature combustion x In order to improve the heat utilization rate of the yellow phosphorus tail gas boiler as much as possible, the outlet temperature of a general economizer is lower than 160 ℃, and the ultra-low standard emission of the boiler is still another challenge facing the yellow phosphorus tail gas boiler.
Therefore, a new corrosion-resistant yellow phosphorus tail gas boiler and a method for purifying boiler flue gas thereof are needed.
Disclosure of Invention
The invention aims to solve the problems that equipment is damaged due to corrosion of phosphoric acid generated by the existing yellow phosphorus tail gas serving as fuel of a gas boiler to the wall of the boiler and the large-scale of the yellow phosphorus tail gas boiler is realized.
In order to achieve the above purpose, the first aspect of the present invention provides a method for removing sulfur, phosphorus and nitrogen oxides in a yellow phosphorus tail gas boiler by using phosphorus ore powder, the method comprising the following steps:
(1) Carrying out combustion reaction on yellow phosphorus tail gas and oxygen-containing gas to obtain high-temperature flue gas;
(2) Under the thermal action of the combustion reaction, the phosphorite powder is fluidized and is subjected to calcination reaction, and the obtained calcination reaction product is mixed with P in the high-temperature flue gas 2 O 5 Dephosphorizing, and performing heat exchange on the obtained high Wen Tuolin flue gas to obtain low Wen Tuolin flue gas;
(3) Mixing dephosphorized slag obtained by dephosphorization treatment with simple substance phosphorus-containing slurry to obtain a desulfurization and denitrification agent;
(4) And (3) contacting the desulfurization and denitrification agent with low Wen Tuolin flue gas and performing wet desulfurization and denitrification treatment to obtain desulfurization and denitrification flue gas.
In the present invention, the dephosphorized slag further contains mineral ash, unless otherwise specified.
Preferably, in the step (1), the content of CO in the yellow phosphorus tail gas is 85-90 vol%, and N 2 The content is 2-4 vol%, P 4 The content is 300-700 mg/Nm 3 ，PH 3 The content is 500-9000 mg/Nm 3 ，H 2 S content is 800-6000 mg/Nm 3 COS content of 200-5000 mg/Nm 3 。
Preferably, in the step (2), the CO content in the low Wen Tuolin flue gas is 0-0.5 volume percent, and P 2 O 5 The content is less than or equal to 5mg/Nm 3 ，SO 2 The content is 1000-20000 mg/Nm 3 ，NO x The content is 150-600 mg/Nm 3 X is selected from 1-2.5.
Preferably, in the step (4), P in the desulfurization and denitrification flue gas 2 O 5 The content is less than or equal to 5mg/Nm 3 ，SO 2 The content is less than or equal to 35mg/Nm 3 ，NO x The content is less than or equal to 50mg/Nm 3 X is selected from 1-2.5.
The second aspect of the invention provides a system for removing sulfur, phosphorus and nitrogen oxides in a yellow phosphorus tail gas boiler by using phosphorus ore powder, which comprises: the fluidized bed gas boiler and the desulfurization and denitrification tower are connected in sequence;
the fluidized bed gas boiler is used for carrying out combustion reaction on yellow phosphorus tail gas and oxygen-containing gas to obtain high-temperature flue gas; under the thermal action of the combustion reaction, the phosphorite powder is fluidized and is subjected to calcination reaction, and the obtained calcination reaction product is mixed with P in the high-temperature flue gas 2 O 5 Dephosphorization treatment is carried out to obtain dephosphorized slag, and the obtained high Wen Tuolin flue gas is subjected to heat exchange to obtain low Wen Tuolin flue gas;
the desulfurization and denitrification tower is used for mixing the dephosphorization slag with the slurry containing the elemental phosphorus, and the obtained desulfurization and denitrification agent is contacted with the low Wen Tuolin flue gas and subjected to wet desulfurization and denitrification treatment to obtain the desulfurization and denitrification flue gas.
Compared with the prior art, the invention has the following advantages:
(1) The method provided by the invention adopts the phosphate rock powder as the dephosphorizing agent, and the phosphate rock powder and yellow phosphorus tail gas are firstly mixed in a gas boilerDephosphorization treatment is carried out under the condition of warm combustion, and elemental phosphorus and PH contained in yellow phosphorus tail gas are removed 3 The dephosphorized slag is obtained, the dephosphorized slag is mixed with simple substance phosphorus-containing slurry to be used as a desulfurization and denitrification agent for wet desulfurization and denitrification treatment, the wet desulfurization and denitrification treatment is carried out on low Wen Tuolin flue gas after the combustion heat of yellow phosphorus tail gas is recovered, and NO in the flue gas of a gas boiler is further removed x 、SO 2 The method comprises the steps of carrying out a first treatment on the surface of the The method realizes the removal of sulfur, phosphorus and nitrogen oxides in the yellow phosphorus tail gas, namely P in the desulfurization and denitrification flue gas, while recovering the reaction heat of the yellow phosphorus tail gas 2 O 5 The content is less than or equal to 5mg/Nm 3 ，SO 2 The content is less than or equal to 35mg/Nm 3 ，NO x The content is less than or equal to 50mg/Nm 3 X is selected from 1-2.5;
(2) The method provided by the invention avoids the phosphoric acid corrosion generated by taking yellow phosphorus tail gas as boiler gas, and prolongs the operation period of gas boiler equipment;
(3) The method provided by the invention realizes the low-temperature integrated desulfurization and denitrification of the gas-fired boiler, and absorbs SO 2 、NO x The prepared sulfuric acid and nitric acid can be used as raw materials for producing chemical fertilizers after decomposing phosphorite, the purification process of entering the yellow phosphorus tail gas boiler is simplified, the dephosphorization slag and the simple substance phosphorus-containing slurry are mixed to form a desulfurization and denitrification agent, the low-temperature integrated desulfurization and denitrification of the smoke of the yellow phosphorus tail gas boiler are realized, and the low-cost efficient utilization and the green desulfurization and denitrification of the yellow phosphorus tail gas are facilitated.
Drawings
Fig. 1 is a schematic structural diagram of a system for removing sulfur, phosphorus and nitrogen oxides in a yellow phosphorus tail gas boiler by using phosphorus ore powder.
Description of the reference numerals
I. A fluidized bed gas boiler; II. A desulfurization and denitrification tower; III, a screening unit; IV, a crushing unit;
1. yellow phosphorus tail gas; 2. phosphate rock powder; 3. dephosphorizing slag; 4. low Wen Tuolin smoke; 5. fine powder slag;
6. large particle slag; 7. a slurry containing elemental phosphorus; 8. a slurry; 9. desulfurization and denitrification flue gas.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a dephosphorization purification method for a yellow phosphorus tail gas flue gas boiler, which comprises the following steps:
(1) Carrying out combustion reaction on yellow phosphorus tail gas and oxygen-containing gas to obtain high-temperature flue gas;
(2) Under the thermal action of the combustion reaction, the phosphorite powder is fluidized and is subjected to calcination reaction, and the obtained calcination reaction product is mixed with P in the high-temperature flue gas 2 O 5 Dephosphorizing, and performing heat exchange on the obtained high Wen Tuolin flue gas to obtain low Wen Tuolin flue gas;
(3) Mixing dephosphorized slag obtained by dephosphorization treatment with simple substance phosphorus-containing slurry to obtain a desulfurization and denitrification agent;
(4) And (3) contacting the desulfurization and denitrification agent with low Wen Tuolin flue gas and performing wet desulfurization and denitrification treatment to obtain desulfurization and denitrification flue gas.
The inventors of the present invention studied and found that: under the thermal action of the combustion reaction of the yellow phosphorus tail gas and the oxygen-containing gas, the phosphorus ore powder is in a fluidized state in a fluidized bed and is subjected to calcination reaction, and a small amount of elemental phosphorus (P) is entrained in the yellow phosphorus tail gas 4 ) And pH (potential of Hydrogen) 3 P produced by combustion 2 O 5 ，P 2 O 5 React with the water carried in the tail gas to generate phosphoric acid, H 2 S and COS formation of SO 2 The method comprises the steps of carrying out a first treatment on the surface of the Phosphoric acid preferentially forms phosphorus-oxygen-calcium compounds (e.g., calcium phosphate, white phosphorus calcium stone, etc.) with the calcination products (e.g., calcium oxide) of carbonates (e.g., dolomite, limestone) in the ground phosphate rock in a fluidized bed to yield phosphorus slag and low Wen Tuolin flue gas, i.e., the purpose of using ground phosphate rock in a furnace is to dephosphorize, causing P in the low Wen Tuolin flue gas 2 O 5 The content is less than or equal to 5mg/Nm 3 Avoiding the corrosion of high-temperature phosphoric acid to boiler materials, while SO 2 Since the reaction rate is much lower than that of phosphoric acid with calcined product, only small amount of SO is available 2 Reacted with the calcined product, and the vast majority of the calcined product is discharged to a desulfurization and denitrification tower along with low-temperature dephosphorization flue gas, the temperature is 120-160 ℃, and the SO in the flue gas is reduced by Wen Tuolin at the moment 2 The content is 1000-20000 mg/Nm 3 ，NO x The content is 150-600 mg/Nm 3 (x is selected from 1-2.5); further desulfurizing and denitrating the flue gas exhausted by the economizer and the air preheater by using phosphorite-containing slurry SO as to lead SO in the desulfurizing and denitrating flue gas 2 The content is less than or equal to 35mg/Nm 3 ，NO x The content is less than or equal to 50mg/Nm 3 (x is selected from 1-2.5). The method mainly solves the problem of corrosion of yellow phosphorus tail gas to the gas boiler, and realizes SO 2 、NO x The method has the advantages of ultra-low emission, simple flow, low cost, no solid waste emission, and good ecological and economic benefits.
In the invention, the yellow phosphorus tail gas contains N besides CO 2 、H 2 S、P 4 、PH 3 COS, etc., COS content refers to the organic sulfur content.
In some embodiments of the present invention, preferably, in step (1), the content of CO in the yellow phosphorus tail gas is 85-90% by volume, N 2 The content is 2-4 vol%, P 4 The content is 300-700 mg/Nm 3 ，PH 3 The content is 500-9000 mg/Nm 3 ，H 2 S content is 800-6000 mg/Nm 3 COS content of 200-5000 mg/Nm 3 。
In the invention, under the condition of no special condition, SO in yellow phosphorus tail gas, low Wen Tuolin smoke and desulfurization and denitrification smoke 2 Content and NO x The content (x is selected from 1-2.5) adopts HJ 1045-2019 to fix the technical requirement of a portable ultraviolet absorption method measuring instrument for pollution source smoke (sulfur dioxide and nitrogen oxide) and a detection method, P 2 O 5 After three-stage absorption of content sampling, the content is measured by an inductively coupled plasma emission spectrometer (ICP-AES method), and 75mL (1+3) HNO is arranged in a first-stage absorption tube 3 The second stage absorber tube was filled with 50mL (1+3) HNO 3 Third stage absorber tubing 75And mL of distilled water.
In the present invention, the oxygen-containing gas includes, but is not limited to, air, oxygen, and the like.
In some embodiments of the invention, preferably, in step (1), the temperature of the combustion reaction is any value in the range of 800-1050 ℃, e.g., 800 ℃, 850 ℃, 900 ℃, 1000 ℃, 1050 ℃, and any two numbers, preferably 850-900 ℃.
In the present invention, in step (1), the combustion reaction is aimed at converting CO in the yellow phosphorus tail gas into CO 2 ，P 4 And pH (potential of Hydrogen) 3 Conversion to P 2 O 5 ，H 2 S and COS conversion to SO 2 ，N 2 Conversion to NO x (x is selected from 1-2.5) to obtain a catalyst containing CO and CO 2 、P 2 O 5 、SO 2 、NO x Is a high temperature flue gas.
In some embodiments of the invention, preferably, in step (1), the temperature of the high temperature flue gas is any value in the range of 800-1050 ℃, e.g., 800 ℃, 850 ℃, 900 ℃, 1000 ℃, 1050 ℃, and any two numbers, preferably 850-900 ℃.
In some embodiments of the present invention, preferably, in step (2), the catalyst is used in an amount of (CaO weight percent to 1.315 XP 2 O 5 The mass ratio of the phosphate rock powder to the yellow phosphorus tail gas calculated by P is 3.5-6:1, for example, 3.5:1, 4:1, 4.5:1, 5:1, 6:1, and any value in the range of any two values, preferably 4-5:1, more preferably 4.5:1. The mass ratio in the range is satisfied, so that the dephosphorization agent not only has better dephosphorization effect, but also has lower energy consumption.
In the present invention, the content of (CaO weight percent is 1.315 xP) 2 O 5 The mass of the ground phosphate rock in weight percent refers to the mass of carbonate in CaO in the ground phosphate rock; wherein, the CaO weight percent refers to the total mass of CaO in the phosphorite powder, 1.315 xP 2 O 5 The weight percent refers to the mass of calcium fluorophosphate in terms of CaO in the ground phosphate rock.
In the invention, the yellow phosphorus is added into the furnace through the electric furnace method, the phosphorite is block ore, screening is needed before the furnace is added, the screened powder ore is mainly piled up, a small amount of the powder ore is added into the furnace after being formed into balls, and the screened phosphorite powder can be directly used as a dephosphorizing agent of a gas boiler. Preferably, the average particle size of the ground phosphate rock is less than or equal to 6mm. The smaller the particle size, the faster the dephosphorization reaction, but the external circulation amount and fly ash are increased; the particle size is too large, so that the mass transfer and reaction efficiency is reduced, and the abrasion of the boiler is increased.
In some embodiments of the present invention, preferably, the ground phosphate rock contains calcium fluorophosphate and carbonate; further preferably, in the phosphorus ore powder, P 2 O 5 The calculated calcium fluophosphate content is 5-35 wt percent, calculated as CO 2 The content of carbonate is 2.5-15wt%; more preferably, in the phosphate rock powder, P is 2 O 5 The calculated calcium fluophosphate content is 15-20 wt percent, calculated as CO 2 The calculated carbonate content is 6-15wt%.
In some embodiments of the invention, the powder phosphate has a Fe content of 0.2-1.1 wt% and a Mn content of 0.05-0.2 wt%, and Fe and Mn in the dephosphorized slag after calcination and dephosphorization of the powder phosphate are taken into water to form Fe 3+ And Mn of 2+ Can obviously catalyze SO 2 Absorbing and converting into sulfuric acid, and then reacting with calcium fluorophosphate to generate calcium sulfate dihydrate, thereby realizing high-efficiency desulfurization.
In some embodiments of the present invention, preferably, in step (2), the calcining process includes: and (3) carrying out the calcination reaction on carbonate in the phosphate rock powder to obtain the calcination reaction product, wherein the calcination reaction product comprises calcium oxide.
In the present invention, the dephosphorization treatment means that the calcination reaction product and P in high-temperature flue gas are treated 2 O 5 Dephosphorization treatment is performed to obtain phosphocalcic compounds, wherein the phosphocalcic compounds include, but are not limited to, calcium phosphate, white brushite and the like.
In the present invention, the temperature of the calcination reaction is provided by the heat of the yellow phosphorus tail gas combustion reaction, unless otherwise specified. Preferably, the temperature of the calcination reaction is in the range of 800-1050 ℃, e.g., 800 ℃, 850 ℃, 900 ℃, 1000 ℃, 1050 ℃, and any value in the range of any two values, preferably 850-900 ℃.
In one specific embodiment of the invention, the elemental phosphorus and phosphine gas contained in the yellow phosphorus tail gas react with air to produce P after combustion 2 O 5 ，P 2 O 5 And then the phosphate is combined with water to produce phosphoric acid, and the phosphoric acid is further reacted with a calcination reaction product (calcium oxide) obtained by the calcination reaction of carbonate (dolomite and limestone) in the phosphate rock powder at high temperature to obtain phosphorus-oxygen-calcium compounds such as calcium phosphate, white phosphorus calcium stone and the like, thereby achieving the purpose of dephosphorization.
In some embodiments of the present invention, preferably, in step (2), the heat exchange process includes: and carrying out heat exchange on the high-temperature dephosphorization flue gas and water to obtain the low Wen Tuolin flue gas and steam. In the invention, the low Wen Tuolin flue gas mainly contains CO and SO 2 、NO x (x is selected from 1-2.5) and trace amount of P 2 O 5 。
In some embodiments of the invention, the low Wen Tuolin flue gas outlet temperature is preferably any value in the range of 120-160 ℃, e.g., 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, and any two values.
In the present invention, the dephosphorization treatment aims at removing P in the high-temperature flue gas 2 O 5 . Preferably, the CO content in the low Wen Tuolin flue gas is 0-0.5 volume percent, P 2 O 5 The content is less than or equal to 5mg/Nm 3 ，SO 2 The content is 1000-20000 mg/Nm 3 ，NO x The content is 150-600 mg/Nm 3 X is selected from 1-2.5.
In some embodiments of the present invention, preferably, in step (3), the elemental phosphorus content of the desulfurization and denitrification agent is 1-5wt%, for example, 1 wt%, 2wt%, 3wt%, 4wt%, 5wt%, and any value in the range of any two values. In the invention, when the content of elemental phosphorus in the desulfurization and denitrification agent is higher, the denitrification effect is better.
In the invention, the dosage ratio of the dephosphorization slag to the slurry containing the elemental phosphorus has a wider selection range, so long as the content of the elemental phosphorus in the desulfurization and denitrification agent meets the limit.
In some embodiments of the invention, the slurry containing the elemental phosphorus is provided by byproduct phosphorus mud produced by yellow phosphorus, and the slurry containing the elemental phosphorus with the elemental phosphorus content of 1-5wt% is obtained after the slurry is mixed with dephosphorization slag and mineral ash. In the present invention, the elemental phosphorus includes, but is not limited to, sludge phosphorus, yellow phosphorus, and the like.
In the invention, in the step (4), the wet desulfurization and denitrification treatment is carried out, and the elemental phosphorus in the slurry containing the elemental phosphorus is used as an oxidant to oxidize NO in the low Wen Tuolin flue gas into NO dissolved in water 2 、N 2 O 3 、N 2 O 5 At the same time NO 2 、N 2 O 3 、N 2 O 5 Further absorption to HNO 3 ，SO 2 Oxidative conversion to H 2 SO 4 And separating by a high-efficiency gas-liquid separator, and exhausting the desulfurization and denitration flue gas.
In some embodiments of the invention, the solids content of the desulfurization and denitrification agent is preferably 5-35 wt%, for example, 5-wt%, 10wt%, 15wt%, 20 wt%, 25wt%, 35wt%, and any value in the range of any two values, preferably 10-25 wt%.
In some embodiments of the present invention, it is preferred that the particles in the desulfurization and denitrification agent have a particle size of 0.15 to mm and a particle ratio of 70% or more, and the maximum particle size of the particles in the desulfurization and denitrification agent is 1 to mm.
In the invention, the wet desulfurization and denitrification treatment aims to further remove SO in low Wen Tuolin flue gas 2 And NO x . Preferably, P in the desulfurization and denitrification flue gas 2 O 5 The content is less than or equal to 5mg/Nm 3 ，SO 2 The content is less than or equal to 35mg/Nm 3 ，NO x The content is less than or equal to 50mg/Nm 3 X is selected from 1-2.5.
In some embodiments of the present invention, it is preferable that the dephosphorized and desulphurized slag is sieved and crushed before the mixing so that the ratio of ore fines having a particle size of 0.15 to mm in the dephosphorized slag is not less than 70% and the maximum particle size is not more than 1 mm.
In the invention, the slurry obtained by the wet desulfurization and denitrification treatment contains phosphoric acid (sulfuric acid reacts with calcium phosphate in phosphorite to generate calcium sulfate solid and phosphoric acid) and nitric acid, so that the slurry can be used as raw materials for subsequent fertilizer processing.
The second aspect of the present invention provides a system for removing sulfur, phosphorus and nitrogen oxides from yellow phosphorus tail gas boiler by using phosphorus ore powder, the structure schematic diagram is shown in fig. 1, and as can be known from fig. 1, the system comprises: a fluidized bed gas boiler I and a desulfurization and denitrification tower II which are connected in sequence;
the fluidized bed gas boiler I is used for carrying out combustion reaction on the yellow phosphorus tail gas 1 and oxygen-containing gas to obtain high-temperature flue gas; under the thermal action of the combustion reaction, the phosphorite powder 2 is fluidized and is subjected to calcination reaction, and the obtained calcination reaction product is mixed with P in the high-temperature flue gas 2 O 5 Dephosphorization treatment is carried out to obtain dephosphorization slag 3, and the obtained high Wen Tuolin flue gas is subjected to heat exchange to obtain low Wen Tuolin flue gas 4;
the desulfurization and denitrification tower II is used for mixing the dephosphorization slag 3 with the slurry 7 containing the elemental phosphorus, contacting the obtained desulfurization and denitrification agent with the low Wen Tuolin flue gas 4, and carrying out wet desulfurization and denitrification treatment to obtain a slurry 8 and desulfurization and denitrification flue gas 9.
According to the invention, preferably, as shown in fig. 1, the system further comprises: a screening unit III and a crushing unit IV; the screening unit III is connected with the fluidized bed gas boiler I and the desulfurization and denitrification tower II and is used for screening the dephosphorization slag 3, the obtained fine powder slag 5 enters the desulfurization and denitrification tower II, and the obtained large particle slag 6 enters the crushing unit IV and then enters the desulfurization and denitrification tower II after being crushed.
According to a particularly preferred embodiment of the invention, a method for removing sulfur, phosphorus and nitrogen oxides in a yellow phosphorus tail gas boiler by using phosphorus ore powder is characterized by comprising the following steps:
(1) Carrying out combustion reaction on yellow phosphorus tail gas and oxygen-containing gas to obtain high-temperature flue gas;
(2) Under the heat of the combustion reaction, the powdered rock phosphate is made into a formCarrying out a calcination reaction in a fluidized state to obtain a calcination reaction product, and mixing the calcination reaction product with P in the high-temperature flue gas 2 O 5 Dephosphorizing, and performing heat exchange on the obtained high Wen Tuolin flue gas to obtain low Wen Tuolin flue gas;
(3) Mixing dephosphorized slag obtained by dephosphorization treatment with simple substance phosphorus-containing slurry to obtain a desulfurization and denitrification agent;
(4) The desulfurization and denitrification agent is contacted with the low Wen Tuolin flue gas and subjected to wet desulfurization and denitrification treatment to obtain desulfurization and denitrification flue gas;
wherein the content of CO in the yellow phosphorus tail gas is 85-90 vol%, and N 2 The content is 2-4 vol%, P 4 The content is 300-700 mg/Nm 3 ，PH 3 The content is 500-9000 mg/Nm 3 ，H 2 S content is 800-6000 mg/Nm 3 COS content of 200-5000 mg/Nm 3 ；
Wherein, (CaO weight percent 1.315 xP) 2 O 5 The mass ratio of the phosphate rock powder to the yellow phosphorus tail gas calculated by P is 3.5-6:1, a step of;
wherein, P is used in the phosphorite powder 2 O 5 The calculated calcium fluophosphate content is 5-35 wt percent, calculated as CO 2 The calculated carbonate content is 2.5-15wt%, the Fe content is 0.2-1.1 wt%, the Mn content is 0.05-0.2 wt%;
wherein, the content of elemental phosphorus in the desulfurization and denitrification agent is 1-5wt percent, and the solid content is 5-35 wt percent;
wherein the particle size of the particles in the desulfurization and denitrification agent is less than or equal to 0.15 and the particle ratio of mm is more than or equal to 70 percent, and the maximum particle size of the particles in the desulfurization and denitrification agent is less than or equal to 1mm;
wherein, P in the desulfurization and denitrification flue gas 2 O 5 The content is less than or equal to 5mg/Nm 3 ，SO 2 The content is less than or equal to 35mg/Nm 3 ，NO x The content is less than or equal to 50mg/Nm 3 X is selected from 1-2.5.
The present invention will be described in detail by examples.
Example 1
The system for removing sulfur, phosphorus and nitrogen oxides in the yellow phosphorus tail gas boiler by the phosphorus ore powder is shown in fig. 1, and the system comprises: the fluidized bed gas boiler I, the desulfurization and denitrification tower II, the screening unit III and the crushing unit IV are connected in sequence;
the screening unit III is connected with the fluidized bed gas boiler I and the desulfurization and denitrification tower II; the crushing unit IV is connected with the screening unit III and the desulfurization and denitrification tower II.
The method for removing sulfur, phosphorus and nitrogen oxides in the yellow phosphorus tail gas boiler by using the phosphorus ore powder is carried out in the system, and comprises the following steps:
(1) The yellow phosphorus tail gas and oxygen are subjected to combustion reaction (the temperature is 850 ℃) to obtain high-temperature flue gas (the temperature is 850 ℃);
wherein the content of CO in the yellow phosphorus tail gas is 88% by volume, N 2 The content is 2 vol%, P 4 The content is 500mg/Nm 3 ，PH 3 The content is 4000 mg/Nm 3 ，H 2 S content of 3000 mg/Nm 3 COS content of 3000 mg/Nm 3 ；
(2) Under the thermal action of the combustion reaction, the phosphorite powder is fluidized and is subjected to calcination reaction (the temperature is 850 ℃), and the obtained calcination reaction product is mixed with P in the high-temperature flue gas 2 O 5 Dephosphorization treatment is carried out to obtain dephosphorized slag and high-temperature dephosphorized flue gas, and the high-temperature dephosphorized flue gas is subjected to heat exchange to obtain low Wen Tuolin flue gas with the temperature of 140 ℃;
wherein (CaO weight percent to 1.315 xP) 2 O 5 The mass ratio of the phosphate rock powder to the yellow phosphorus tail gas calculated by phosphorus is 4.5:1;
wherein, P is used in the phosphorite powder 2 O 5 The calculated calcium fluorophosphate content was 20 wt% in terms of CO 2 The calculated carbonate content is 6wt%; mn content is 0.05 wt%; the Fe content is 0.3 wt%;
the CO content in the low Wen Tuolin flue gas is 0.3 volume percent, P 2 O 5 The content was 4mg/Nm 3 ，SO 2 The content is 7800 mg/Nm 3 NO content of 200 mg/Nm 3 ；
(3) Sieving and crushing the dephosphorized slag to make the ratio of ore powder with the particle size less than or equal to 0.15 and mm in the dephosphorized slag be 70 percent and the maximum particle size be 1mm, and then mixing the ore powder with the slurry containing elemental phosphorus to obtain the desulfurization and denitrification agent;
wherein, the content of elemental phosphorus in the desulfurization and denitrification agent is 1 wt percent, and the solid content is 20 wt percent;
(4) And (3) contacting the desulfurization and denitrification agent with the low Wen Tuolin flue gas and performing wet desulfurization and denitrification treatment to obtain desulfurization and denitrification flue gas S1 and slurry, wherein the slurry is used as a raw material for a phosphate fertilizer device or phosphorite flotation.
Wherein P in the desulfurization and denitration flue gas S1 2 O 5 The content was 4mg/Nm 3 ，SO 2 The content is 30mg/Nm 3 NO content of 40 mg/Nm 3 。
Example 2
The system according to example 1;
the procedure of example 1 was followed, except,
in the step (1), the content of CO in the yellow phosphorus tail gas is 88 percent by volume, N 2 The content is 3 volume percent, P 4 The content is 400mg/Nm 3 ，PH 3 The content is 4500 mg/Nm 3 ，H 2 S content is 3500 mg/Nm 3 COS content of 3000 mg/Nm 3 ；
In the step (2), the weight percentage of CaO is (CaO) to 1.315 xP 2 O 5 The mass ratio of the phosphate rock powder to the yellow phosphorus tail gas calculated by phosphorus is 3.5:1, dephosphorized slag and high-temperature dephosphorized flue gas are obtained, and the high-temperature dephosphorized flue gas is subjected to heat exchange to obtain low Wen Tuolin flue gas with the temperature of 160 ℃;
wherein, P is used in the phosphorite powder 2 O 5 The calculated calcium fluorophosphate content was 25. 25wt% in terms of CO 2 The calculated carbonate content is 8wt%; mn content is 0.06 wt%; fe content is 0.5wt%;
wherein the CO content in the low Wen Tuolin flue gas is 0.3 volume percent, P 2 O 5 The content was 4mg/Nm 3 ，SO 2 The content is 8200 mg/Nm 3 NO content of 400mg/Nm 3 ；
In the step (3), the dephosphorization slag is screened and crushed, so that the proportion of mineral powder with the particle size less than or equal to 0.15mm in the dephosphorization slag is 75%, and the maximum particle size is 1mm;
wherein, the content of elemental phosphorus in the desulfurization and denitrification agent is 2wt percent, and the solid content is 25wt percent;
in the step (4), desulfurization and denitration flue gas S2 is obtained;
wherein P in the desulfurization and denitration flue gas S2 2 O 5 The content is 5mg/Nm 3 ，SO 2 The content was 25mg/Nm 3 NO content of 50mg/Nm 3 。
Example 3
The system according to example 1;
the procedure of example 1 was followed, except,
in the step (1), the content of CO in the yellow phosphorus tail gas is 88 percent by volume, N 2 The content is 3 volume percent, P 4 The content is 500mg/Nm 3 ，PH 3 The content is 5000 mg/Nm 3 ，H 2 S content of 4000 mg/Nm 3 COS content of 3500 mg/Nm 3 ；
In the step (2), the weight percentage of CaO is (CaO) to 1.315 xP 2 O 5 The mass ratio of the phosphate rock powder to the yellow phosphorus tail gas calculated by phosphorus is 6:1, dephosphorized slag and high-temperature dephosphorized smoke are obtained, and the high-temperature dephosphorized smoke is subjected to heat exchange to obtain low Wen Tuolin smoke with the temperature of 120 ℃;
wherein, P is used in the phosphorite powder 2 O 5 The calculated calcium fluorophosphate content was 25. 25wt% in terms of CO 2 The calculated carbonate content was 2.5wt%; mn content is 0.07 to wt percent; fe content is 0.7wt%;
wherein the CO content in the low Wen Tuolin flue gas is 0.4 volume percent, P 2 O 5 The content is 3mg/Nm 3 ，SO 2 The content is 9000 mg/Nm 3 NO content of 450mg/Nm 3 ；
In the step (3), the dephosphorization slag is screened and crushed, so that the proportion of mineral powder with the particle size less than or equal to 0.15mm in the dephosphorization slag is 70%, and the maximum particle size is 1mm;
the content of elemental phosphorus in the desulfurization and denitrification agent is 3wt percent, and the solid content is 30wt percent;
in the step (4), desulfurization and denitration flue gas S3 is obtained;
wherein P in the desulfurization and denitration flue gas S3 2 O 5 The content is 3mg/Nm 3 ，SO 2 The content is 20mg/Nm 3 NO content of 35mg/Nm 3 。
Example 4
The system according to example 1;
the procedure of example 1 was followed, except,
in the step (1), the CO content in the yellow phosphorus tail gas is 90% by volume, N 2 The content is 3 volume percent, P 4 The content was 600mg/Nm 3 ，PH 3 The content is 6000 mg/Nm 3 ，H 2 S content of 5000 mg/Nm 3 COS content of 4000 mg/Nm 3 ；
In the step (2), the weight percentage of CaO is (CaO) to 1.315 xP 2 O 5 The mass ratio of the phosphate rock powder to the yellow phosphorus tail gas calculated by phosphorus is 4:1, dephosphorized slag and high-temperature dephosphorized smoke are obtained, and the high-temperature dephosphorized smoke is subjected to heat exchange to obtain low Wen Tuolin smoke with the temperature of 160 ℃;
wherein, P is used in the phosphorite powder 2 O 5 The calculated calcium fluorophosphate content was 30wt% in terms of CO 2 The content of carbonate is 9wt%; mn content is 0.08 wt%; fe content is 0.9wt%;
wherein the CO content in the low Wen Tuolin flue gas is 0.3 volume percent, P 2 O 5 The content is 5mg/Nm 3 ，SO 2 The content was 12000 mg/Nm 3 NO content of 500mg/Nm 3 ；
In the step (3), the dephosphorization slag is screened and crushed, so that the proportion of mineral powder with the particle size less than or equal to 0.15mm in the dephosphorization slag is 70%, and the maximum particle size is 1mm;
wherein, the content of elemental phosphorus in the desulfurization and denitrification agent is 4wt percent, and the solid content is 30wt percent;
in the step (4), desulfurization and denitration flue gas S4 is obtained;
wherein P in the desulfurization and denitration flue gas S4 2 O 5 The content is 5mg/Nm 3 ，SO 2 The content was 34mg/Nm 3 NO content of 47mg/Nm 3 。
Example 5
The system according to example 1;
the procedure of example 1 was followed, except,
in the step (1), the CO content in the yellow phosphorus tail gas is 90% by volume, N 2 The content is 4 vol%, P 4 The content is 700 mg/Nm 3 ，PH 3 The content is 7000 mg/Nm 3 ，H 2 S content is 6000 mg/Nm 3 COS content of 5000 mg/Nm 3 ；
In the step (2), the weight percentage of CaO is (CaO) to 1.315 xP 2 O 5 The mass ratio of the phosphate rock powder to the yellow phosphorus tail gas calculated by phosphorus is 5:1, dephosphorized slag and high-temperature dephosphorized smoke are obtained, and the high-temperature dephosphorized smoke is subjected to heat exchange to obtain low Wen Tuolin smoke with the temperature of 140 ℃;
wherein, P is used in the phosphate rock powder 2 O 5 The calculated calcium fluorophosphate content was 35wt% as CO 2 The content of carbonate is 10wt%; mn content is 0.1 wt%; fe content is 1.0 wt%;
wherein the CO content in the low Wen Tuolin flue gas is 0.3 volume percent, P 2 O 5 The content is 5mg/Nm 3 ，SO 2 The content is 14000 mg/Nm 3 NO content of 600mg/Nm 3 ；
In the step (3), the dephosphorization slag is screened and crushed, so that the proportion of mineral powder with the particle size less than or equal to 0.15mm in the dephosphorization slag is 70%, and the maximum particle size is 1mm;
wherein, the content of elemental phosphorus in the desulfurization and denitrification agent is 4.8 weight percent, and the solid content is 32 weight percent;
in the step (4), desulfurization and denitration flue gas S5 is obtained;
wherein P in the desulfurization and denitration flue gas S5 2 O 5 The content is 5mg/Nm 3 ，SO 2 The content is 30mg/Nm 3 NO content of 45mg/Nm 3 。
Example 6
The system according to example 1;
the procedure of example 1 was followed, except,
in the step (1), the CO content in the yellow phosphorus tail gas is 90% by volume, N 2 The content is 4 vol%, P 4 The content is 700 mg/Nm 3 ，PH 3 The content is 8000 mg/Nm 3 ，H 2 S content is 6000 mg/Nm 3 COS content of 5000 mg/Nm 3 ；
In the step (2), the weight percentage of CaO is (CaO) to 1.315 xP 2 O 5 The mass ratio of the phosphate rock powder to the yellow phosphorus tail gas calculated by phosphorus is 5:1, dephosphorized slag and high-temperature dephosphorized smoke are obtained, and the high-temperature dephosphorized smoke is subjected to heat exchange to obtain low Wen Tuolin smoke with the temperature of 140 ℃;
wherein, P is used in the phosphorite powder 2 O 5 The calculated calcium fluorophosphate content was 35wt% as CO 2 The content of carbonate is 12wt%; mn content is 0.1 wt%; fe content is 1.1 wt%;
the CO content in the low Wen Tuolin flue gas is 0.3 volume percent, P 2 O 5 The content is 5mg/Nm 3 ，SO 2 The content is 16600 mg/Nm 3 NO content of 600mg/Nm 3 ；
In the step (3), the dephosphorization slag is screened and crushed, so that the proportion of mineral powder with the particle size less than or equal to 0.15mm in the dephosphorization slag is 70%, and the maximum particle size is 1mm;
wherein, the content of simple substance phosphorus in the desulfurization and denitrification agent is 5wt percent, and the solid content is 35wt percent;
in the step (4), desulfurization and denitration flue gas S6 is obtained;
wherein P in the desulfurization and denitration flue gas S6 2 O 5 The content is 5mg/Nm 3 ，SO 2 The content is 30mg/Nm 3 NO content of 48mg/Nm 3 。
Example 7
The system according to example 1;
the procedure of example 1 was followed, except,
in the step (1), the CO content in the yellow phosphorus tail gas is 90% by volume, N 2 The content is 2 vol%, P 4 The content is 300 mg/Nm 3 ，PH 3 The content is 500mg/Nm 3 ，H 2 S content of 800 mg/Nm 3 COS content of 200 mg/Nm 3 ；
In the step (2), the weight percentage of CaO is (CaO) to 1.315 xP 2 O 5 The mass ratio of the phosphate rock powder calculated by weight percent to the yellow phosphorus tail gas calculated by phosphorus is 6:1, and the phosphorus ore powder is obtainedDephosphorization slag and high-temperature dephosphorization flue gas, and carrying out heat exchange on the high-temperature dephosphorization flue gas to obtain low Wen Tuolin flue gas with the temperature of 150 ℃;
wherein, P is used in the phosphorite powder 2 O 5 The calculated calcium fluorophosphate content was 15wt% as CO 2 The calculated carbonate content is 15wt%; mn content is 0.2 wt%; fe content is 0.2 wt%;
the CO content in the low Wen Tuolin flue gas is 0 volume percent, P 2 O 5 The content is 1mg/Nm 3 ，SO 2 At a content of 1720, mg/Nm 3 NO content of 150 mg/Nm 3 ；
In the step (3), the dephosphorization slag is screened and crushed, so that the proportion of mineral powder with the particle size less than or equal to 0.15mm in the dephosphorization slag is 70%, and the maximum particle size is 1mm;
wherein, the content of elemental phosphorus in the desulfurization and denitrification agent is 1 wt percent, and the solid content is 10 percent by weight;
in the step (4), desulfurization and denitration flue gas S7 is obtained;
wherein P in the desulfurization and denitration flue gas S7 2 O 5 The content is 0mg/Nm 3 ，SO 2 The content is 0mg/Nm 3 NO content of 0mg/Nm 3 。
Comparative example
The existing yellow phosphorus tail gas dephosphorization technology mainly adopts a temperature-swing pressure-swing adsorption method (CN 1128000C) and a liquid-phase catalytic oxidation method (CN 101045195A), needs a heating reaction and adsorption, has high cost, and has the byproducts of phosphoric acid and elemental sulfur, which are difficult to further utilize and generate secondary pollution. Compared with the prior art, the method has low cost and simple operation, and the reacted slurry can be used as the raw material of wet phosphoric acid without secondary pollution.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The method for removing sulfur, phosphorus and nitrogen oxides in the yellow phosphorus tail gas boiler by using the phosphorus ore powder is characterized by comprising the following steps of:
(1) Carrying out combustion reaction on yellow phosphorus tail gas and oxygen-containing gas to obtain high-temperature flue gas;
(2) Under the thermal action of the combustion reaction, the phosphorite powder is fluidized and is subjected to calcination reaction, and the obtained calcination reaction product is mixed with P in the high-temperature flue gas 2 O 5 Dephosphorizing, and performing heat exchange on the obtained high Wen Tuolin flue gas to obtain low Wen Tuolin flue gas;
(3) Mixing dephosphorized slag obtained by dephosphorization treatment with simple substance phosphorus-containing slurry to obtain a desulfurization and denitrification agent;
(4) And (3) contacting the desulfurization and denitrification agent with low Wen Tuolin flue gas and performing wet desulfurization and denitrification treatment to obtain desulfurization and denitrification flue gas.
2. The method according to claim 1, wherein in the step (1), the content of CO in the yellow phosphorus tail gas is 85-90% by volume, and N 2 The content is 2-4 vol%, P 4 The content is 300-700 mg/Nm 3 ，PH 3 The content is 500-9000 mg/Nm 3 ，H 2 S content is 800-6000 mg/Nm 3 COS content of 200-5000 mg/Nm 3 。
3. The method of claim 1, wherein the temperatures of the combustion reaction, high temperature flue gas, and calcination reaction are each independently 800-1050 ℃;
and/or (CaO weight percent to 1.315 XP) 2 O 5 The mass ratio of the phosphate rock powder to the yellow phosphorus tail gas calculated by P is 3.5-6:1, a step of;
and/or the average particle size of the ground phosphate rock is less than or equal to 6 mm;
and/or the ground phosphate rock contains calcium fluorophosphate and carbonate;
and/or, P is used in the phosphate rock powder 2 O 5 The calculated calcium fluophosphate content is 5-35 wt percent, calculated as CO 2 Calculated carbonateThe content is 2.5-15wt%;
and/or the content of Fe in the phosphorite powder is 0.2-1.1 wt%, and the content of Mn is 0.05-0.2 wt%.
4. A method according to claim 3, wherein the temperatures of the combustion reaction, high temperature flue gas and calcination reaction are each independently 850-900 ℃;
and/or (CaO weight percent to 1.315 XP) 2 O 5 The mass ratio of the phosphate rock powder to the yellow phosphorus tail gas calculated by P is 4-5:1, a step of;
and/or, P is used in the phosphate rock powder 2 O 5 The calculated calcium fluophosphate content is 15-20 wt percent, calculated as CO 2 The content of carbonate is 6-15wt%.
5. A method according to claim 3, wherein in step (2), the calcination reaction comprises: carrying out the calcination reaction on carbonate in the phosphate rock powder;
and/or, the heat exchange process comprises the following steps: heat exchanging is carried out on the high-temperature dephosphorization flue gas and water to obtain low Wen Tuolin flue gas and steam;
and/or the outlet temperature of the low Wen Tuolin flue gas is 120-160 ℃;
and/or the CO content in the low Wen Tuolin flue gas is 0-0.5 volume percent, P 2 O 5 The content is less than or equal to 5mg/Nm 3 ，SO 2 The content is 1000-20000 mg/Nm 3 ，NO x The content is 150-600 mg/Nm 3 X is selected from 1-2.5.
6. The method of claim 1, wherein in the step (3), the content of elemental phosphorus in the desulfurization and denitrification agent is 1-5 wt%;
and/or the solid content in the desulfurization and denitrification agent is 5-35 wt%;
and/or the particle ratio of the particle size of the particles in the desulfurization and denitrification agent is not more than 0.15 and mm is not less than 70%, and the maximum particle size of the particles in the desulfurization and denitrification agent is not more than 1 mm.
7. The method of any one of claims 1-6, wherein in step (4), P in the desulfurization and denitrification flue gas 2 O 5 The content is less than or equal to 5mg/Nm 3 ，SO 2 The content is less than or equal to 35mg/Nm 3 ，NO x The content is less than or equal to 50mg/Nm 3 X is selected from 1-2.5.
8. The method according to any one of claims 1 to 6, wherein in step (3), the dephosphorized slag is screened and crushed before the mixing so that the ratio of ore powder having a particle size of 0.15 to mm in the dephosphorized slag is not less than 70% and the maximum particle size is not more than 1 mm.
9. A system for removing sulfur, phosphorus and nitrogen oxides in a yellow phosphorus tail gas boiler by using phosphorus ore powder, which is characterized by comprising: the fluidized bed gas boiler and the desulfurization and denitrification tower are connected in sequence;
the fluidized bed gas boiler is used for carrying out combustion reaction on yellow phosphorus tail gas and oxygen-containing gas to obtain high-temperature flue gas; under the thermal action of the combustion reaction, the phosphorite powder is fluidized and is subjected to calcination reaction, and the obtained calcination reaction product is mixed with P in the high-temperature flue gas 2 O 5 Dephosphorization treatment is carried out to obtain dephosphorized slag, and the obtained high Wen Tuolin flue gas is subjected to heat exchange to obtain low Wen Tuolin flue gas;
the desulfurization and denitrification tower is used for mixing the dephosphorization slag with the slurry containing the elemental phosphorus, and the obtained desulfurization and denitrification agent is contacted with the low Wen Tuolin flue gas and subjected to wet desulfurization and denitrification treatment to obtain the desulfurization and denitrification flue gas.
10. The system of claim 9, wherein the system further comprises: a screening unit and a crushing unit;
the sieving unit is connected with the fluidized bed gas boiler and the desulfurization and denitrification tower and is used for sieving the dephosphorization slag, the obtained fine powder slag enters the desulfurization and denitrification tower, and the obtained large particle slag enters the crushing unit and then enters the desulfurization and denitrification tower after being crushed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310757914.1A CN116510497A (en) | 2023-06-26 | 2023-06-26 | Method and system for removing sulfur, phosphorus and nitrogen oxides in yellow phosphorus tail gas boiler by using phosphorus ore powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310757914.1A CN116510497A (en) | 2023-06-26 | 2023-06-26 | Method and system for removing sulfur, phosphorus and nitrogen oxides in yellow phosphorus tail gas boiler by using phosphorus ore powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116510497A true CN116510497A (en) | 2023-08-01 |
Family
ID=87390542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310757914.1A Pending CN116510497A (en) | 2023-06-26 | 2023-06-26 | Method and system for removing sulfur, phosphorus and nitrogen oxides in yellow phosphorus tail gas boiler by using phosphorus ore powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116510497A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2001223A1 (en) * | 1988-10-21 | 1990-04-21 | Shih-Ger Chang | Process for the removal of acid forming gases from exhaust gases |
| JP2004188408A (en) * | 2002-10-16 | 2004-07-08 | Sumitomo Heavy Ind Ltd | Combustion equipment and operation method of combustion equipment |
| JP2015116512A (en) * | 2013-12-16 | 2015-06-25 | 三菱日立パワーシステムズ株式会社 | Adsorbent for removing arsenic or phosphorus from flue gas and flue gas purification method using the same |
| CN105536493A (en) * | 2015-12-28 | 2016-05-04 | 昆明理工大学 | Method for removing SO2 and NOX from flue gas of coal-fired boiler by virtue of phosphoric ore pulp and phosphorus sludge |
| CN108050850A (en) * | 2017-11-02 | 2018-05-18 | 武汉东晟捷能科技有限公司 | A kind of yellow phosphoric tail gas boiler flue gas purification system and purification method |
| JP2019034301A (en) * | 2017-08-10 | 2019-03-07 | 日立造船株式会社 | Phosphorus recovery method and phosphorus recovery apparatus |
| CN109675426A (en) * | 2018-12-06 | 2019-04-26 | 昆明理工大学 | It is a kind of using ground phosphate rock and mud phosphorus to the system and method for flue gas desulfurization and denitrification and by-product nitrophosphate fertilizer |
| CN110813081A (en) * | 2019-11-04 | 2020-02-21 | 北京敬科科技发展有限公司 | Purification process of yellow phosphorus tail gas for combustion power generation |
| CN111097269A (en) * | 2019-12-31 | 2020-05-05 | 东华大学 | Method and device for simultaneously removing SOx and NOx in flue gas and producing compound fertilizer |
-
2023
- 2023-06-26 CN CN202310757914.1A patent/CN116510497A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2001223A1 (en) * | 1988-10-21 | 1990-04-21 | Shih-Ger Chang | Process for the removal of acid forming gases from exhaust gases |
| JP2004188408A (en) * | 2002-10-16 | 2004-07-08 | Sumitomo Heavy Ind Ltd | Combustion equipment and operation method of combustion equipment |
| JP2015116512A (en) * | 2013-12-16 | 2015-06-25 | 三菱日立パワーシステムズ株式会社 | Adsorbent for removing arsenic or phosphorus from flue gas and flue gas purification method using the same |
| CN105536493A (en) * | 2015-12-28 | 2016-05-04 | 昆明理工大学 | Method for removing SO2 and NOX from flue gas of coal-fired boiler by virtue of phosphoric ore pulp and phosphorus sludge |
| JP2019034301A (en) * | 2017-08-10 | 2019-03-07 | 日立造船株式会社 | Phosphorus recovery method and phosphorus recovery apparatus |
| CN108050850A (en) * | 2017-11-02 | 2018-05-18 | 武汉东晟捷能科技有限公司 | A kind of yellow phosphoric tail gas boiler flue gas purification system and purification method |
| CN109675426A (en) * | 2018-12-06 | 2019-04-26 | 昆明理工大学 | It is a kind of using ground phosphate rock and mud phosphorus to the system and method for flue gas desulfurization and denitrification and by-product nitrophosphate fertilizer |
| CN110813081A (en) * | 2019-11-04 | 2020-02-21 | 北京敬科科技发展有限公司 | Purification process of yellow phosphorus tail gas for combustion power generation |
| CN111097269A (en) * | 2019-12-31 | 2020-05-05 | 东华大学 | Method and device for simultaneously removing SOx and NOx in flue gas and producing compound fertilizer |
Non-Patent Citations (3)
| Title |
|---|
| 张洁: "黄磷尾气在循环流化床锅炉中的掺烧使用", 磷肥与复肥, vol. 32, no. 3 * |
| 湖南化工研究所: "钙镁磷肥生产分析方法", vol. 1, 石油化学工业出版社, pages: 103 - 104 * |
| 王磊;王重华;宁平;蒋明;覃扬颂;: "流化床燃烧黄磷尾气过程中Ca(OH)_2的固磷作用", 中南大学学报(自然科学版), vol. 1, no. 02, pages 216 - 104 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100453148C (en) | Method for absorbing sulfur dioxide in flue gas with smelting iron and smelting steel slag as absorbing agents | |
| CN109809456B (en) | System and method for co-producing calcium oxide and sulfur by coal gasification and gypsum calcination | |
| CN107456865A (en) | The method of flue gas desulfurization and denitrification | |
| CN102091517A (en) | Integrated absorption solution for simultaneous desulfuration, denitration and mercury removal and preparation method and application thereof | |
| CN109928415B (en) | System and method for recovering calcium carbonate and sulfur by calcining gypsum | |
| CN103566728B (en) | For the equipment of flue gas desulfuration and denitrification | |
| CN101244811A (en) | Method for improving SO2 concentration in acid making technique with decomposition of calcium sulphate | |
| HU202422B (en) | Method for removing gaseous sulfur compounds from flue gas of boilers | |
| CN107812441A (en) | Flue gas dry desulfurizing method of denitration based on red mud | |
| CN113041838A (en) | Method for cooperatively removing low-concentration sulfur dioxide and mercury in smelting flue gas | |
| CN103332750A (en) | Manganese oxide ore selective reduction method | |
| CN109592647B (en) | Process for preparing sulfur and recovering desulfurizing/nitre agent by sulfur/nitrate iron-carbon reduction | |
| CN107398171A (en) | A kind of method that acid gas in flue gas is removed using metal tailings | |
| CN116510497A (en) | Method and system for removing sulfur, phosphorus and nitrogen oxides in yellow phosphorus tail gas boiler by using phosphorus ore powder | |
| CN112341291B (en) | Device and method for preparing calcium-silicon-potassium phosphate fertilizer and hydrochloric acid by utilizing phosphorite | |
| CN111453702B (en) | Method for recovering sulfur in industrial byproduct calcium sulfide slag by fixed bed | |
| CN103566727B (en) | Method for desulfurization and denitrification of flue gas | |
| CN109499344B (en) | Calcium/magnesium-based wet desulphurization and calcium sulfite/magnesium sulfite resource utilization system and process | |
| CN203525549U (en) | Equipment used for flue gas desulfurization and denitrification | |
| CN1285415A (en) | On-line desulfuration method for agglutination process | |
| CN103599683B (en) | Desulphurization and denitrification device for flue gas | |
| CN116571075B (en) | Method and device for removing phosphorus in yellow phosphorus tail gas boiler by using gangue powder | |
| CN108525513B (en) | Removing agent for simultaneous desulfurization and denitrification and preparation method thereof | |
| CN113117494A (en) | Integrated method for flue gas desulfurization and denitrification and cementing material production | |
| Qian et al. | Enhanced absorption of SO2 from phosphogypsum decomposition by phosphate slurry for phosphoric acid production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |