CN107008126A - It is a kind of while removing the method for reducing atmosphere sulfureous in flue gas hydrogen and heavy metal - Google Patents
It is a kind of while removing the method for reducing atmosphere sulfureous in flue gas hydrogen and heavy metal Download PDFInfo
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- CN107008126A CN107008126A CN201710285218.XA CN201710285218A CN107008126A CN 107008126 A CN107008126 A CN 107008126A CN 201710285218 A CN201710285218 A CN 201710285218A CN 107008126 A CN107008126 A CN 107008126A
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- flue gas
- aso
- absorbing liquid
- heavy metal
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- 239000003546 flue gas Substances 0.000 title claims abstract description 45
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 7
- 239000001257 hydrogen Substances 0.000 title claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 30
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 19
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 15
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 15
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 4
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 15
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 14
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 229910019668 (NH4)OH Inorganic materials 0.000 claims description 8
- 239000000428 dust Substances 0.000 claims description 8
- 229910052958 orpiment Inorganic materials 0.000 claims description 7
- 239000003463 adsorbent Substances 0.000 claims description 6
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 229910017251 AsO4 Inorganic materials 0.000 claims description 4
- 125000001870 arsonato group Chemical group O=[As]([O-])([O-])[*] 0.000 claims description 4
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 claims description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 2
- 229940000489 arsenate Drugs 0.000 claims description 2
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 claims description 2
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 239000002671 adjuvant Substances 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 2
- 238000005189 flocculation Methods 0.000 abstract description 2
- 230000016615 flocculation Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000006096 absorbing agent Substances 0.000 abstract 1
- 230000023556 desulfurization Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000005864 Sulphur Substances 0.000 description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- -1 flue gas Compound Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005111 flow chemistry technique Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002912 waste gas 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
- B01D53/75—Multi-step processes
-
- 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
-
- 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
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
Abstract
The invention discloses a kind of while remove the method for reducing atmosphere sulfureous in flue gas hydrogen and heavy metal, so that ammoniacal liquor is as main absorber and adds a small amount of ferrous sulfate as adjuvant and is configured to absorbing liquid, absorption contains H2S and heavy metallic oxide flue gas.H2S gases and ammoniacal liquor reaction generation ammonium sulfide, ammonium sulfide generate sulfide precipitation to reach while removing H with the heavy metallic oxide reaction in flue gas again2Iron in S and heavy metal purpose, ferrous sulfate can generate difficulty soluble salt with arsenic, and the hydroxide of iron has the characteristic of powerful absorption and flocculation ability, can aid in removing the heavy metal in flue gas.Present invention process is simple, easy to operate, invests small, and desulfurization removing heavy-metal efficiency high, with preferable prospects for commercial application.
Description
Technical field
The present invention relates to a kind of while the method for removing reducing atmosphere sulfureous in flue gas hydrogen and heavy metal, belongs to gas cleaning
Technical field.
Background technology
Existing phosphorus production method is usually electric furnace process, and 2500 ~ 2800Nm can be produced by often producing 1 ton of yellow phosphorus3Huang
Phosphorus tail gas.The main component of yellow phosphoric tail gas is the CO that volume fraction is 87 ~ 92%, and inorganic sulfur is contained simultaneously（S、H2S、SO2）, it is organic
Sulphur（COS、CS2）、PH3、SiF、P4、HF、CH4、CO2、O2、N2, HCN, heavy metal（Hg, As etc.）With the impurity such as dust, wherein heavy
The main form with metal oxide of metal is present.In existing yellow phosphoric tail gas, the content of sulphur is 0.8 ~ 8.0%g/m3, phosphorus contains
Measure as 0.5 ~ 1.5%g/m3, the fuel value of yellow phosphoric tail gas is 10.5 ~ 11MJ/m3.It is dirty in Current resource shortage, energy shortage, environment
Dye is serious, production cost it is increasingly increased in the case of, yellow phosphoric tail gas deep purifying and comprehensive utilization be the emission reduction of yellow phosphorus industry energy conservation,
One of clean manufacturing, the important channel of comprehensive utilization of resources.Some enterprises carry out yellow phosphoric tail gas to light torch emptying, not only make
Dust, the sour gas produced after into the wasting of resources, and burning can cause the atmosphere pollution such as haze, acid rain.Some will be unnet
The yellow phosphoric tail gas of change is used as fuel, and thermal source needed for for polymerizeing kiln in phosphate production system, preliminary purification yellow phosphoric tail gas is made
Producing saturated vapor for fuel is used for heat energy power-generating, although has given play to certain effect, still there is the wasting of resources；Main flow
Processing scheme is that the yellow phosphoric tail gas after purification is used as into the chemical industry of carbon one, and tail gas passes through deep purifying, remove sulphur therein, phosphorus, arsenic,
The impurity such as fluorine, and the CO of high-purity can be made through concentrate, it is subsequently used for producing multi-chemical, the preferable recycling of this method
Yellow phosphoric tail gas.
Substantially there are four kinds of purification techniques the country according to development level：（1）Washing process：Washing is directly to be washed with water
Wash, remove mechanical admixture and the SiF such as dust4, part H can also be removed2S, HF, washing also have cooling effect, remove part
P4；（2）Wash alkali cleaning：After washing, into caustic wash tower, caustic wash tower is a kind of packed tower for being filled with magnet ring to tail gas, in alkali cleaning
Washed in tower with mass concentration for 8 ~ 15% NaOH solution, remove the H in tail gas2S、HF、CO2Deng acidic materials, but alkali
PH can not be removed by washing3；The desulfuration efficiency of alkali cleaning is 95 ~ 99% or so, and defluorinate efficiency is also up to 99%, takes off CO2Efficiency it is left 50%
It is right, it is seen then that the purification efficiency of caustic wash tower is at a relatively high, but alkali cleaning effect fluctuation is larger；Washing and alkali washing process, available for tail gas
Less demanding occasion, such as fuel gas；（3）Using the pressure swing adsorption method Recovery Purifying yellow phosphoric tail gas that relents, Huang can be removed
Phosphorus, sulphur, CO in phosphorus tail gas2Deng impurity, purification CO purpose is reached；The key of the technique is that can temp.-changing adsorption dephosphorization real
Existing, the fine or not key of dephosphorization effect is adsorbent, because elemental phosphorous is aerosol, is difficult to be adsorbed；The technique is needed according to tail
Impurity content in gas selects to be worth in flow, commercial Application to have consultations with；（4）Higher occasion is being required to purified gas, to carry
The high removal effect to phosphorus, sulphur in tail gas, catalysis oxidation is carried out with catalyst；The advanced water-filling of tail gas is washed, alkali cleaning operation, Ran Houjing
Cross after a dehydrating demisting device, send into injection type proportional controller, air is added according to a certain percentage so that oxysome is accumulated in tail gas
Content about 1% or so, preheated device is heated to 100 ~ 110 DEG C, in fixed bed catalyst so that the impurity such as phosphorus, sulphur is by oxygen
Change, wherein phosphorus is oxidized generation P2O3And P2O5, and hydrogen sulfide is then oxidized generation S, these oxides are easily by catalyst carrier table
Face is adsorbed, so that tail gas is further purified；One advantage of this technique is can be the hydrogen sulfide overflowed by alkali cleaning fluctuation
Deng oxidation of impurities, it is ensured that the tail gas stablized.
The treatment technology of yellow phosphoric tail gas has been mature on the whole, but energy-saving and emission-reduction, reduces investment, optimize technique is still important
Research contents.It is directed to heavy metal in yellow phosphoric tail gas and handles the processing of mercury and arsenic in rare report, yellow phosphoric tail gas also very
It is few studied, although the content of heavy metal is relatively low in yellow phosphoric tail gas, but the influence to whole production technology is larger.Heavy metal
In the presence of catalyst poisoning can be made, the service life of catalyst is reduced；Direct exhaust emission environment, destroys the ecological balance.
The content of the invention
It is an object of the invention to provide a kind of while the method for reducing atmosphere sulfureous in flue gas hydrogen and heavy metal is removed, with ammonia
Water is absorbent and adds a small amount of adjuvant ferrous sulfate, and absorption contains H2S and heavy metallic oxide（HgO、PbO、CdO、
As2O3Deng）Flue gas.H in flue gas2S gases and ammoniacal liquor reaction generation ammonium sulfide, ammonium sulfide again with the heavy metal oxidation in flue gas
Thing reaction generation sulfide precipitation（HgS、PbS、CdS、As2S3Deng）Reach while removing H2S and heavy metal purpose.Sulfuric acid is sub-
Iron in iron can generate difficulty soluble salt with arsenic, while the hydroxide of iron has powerful absorption and flocculation ability, can aid in removing
Heavy metal in flue gas.Absorbing liquid pH value is controlled by adding ammoniacal liquor in absorption process, reaction terminates that ammonium sulfide solution production is made
Product.
It is a kind of while remove the method for reducing atmosphere sulfureous in flue gas hydrogen and heavy metal, specifically include following steps：
（1）Absorbing liquid is prepared, the main composition of absorbing liquid is ammoniacal liquor matter in ammoniacal liquor and a small amount of ferrous sulfate adjuvant, absorbing liquid
It is 4 ~ 12% to measure fraction, and ferrous sulfate mass fraction is 0.01 ~ 0.5%；
（2）Less than 60 DEG C are cooled to after flue gas removing dust, washing, is contacted with absorbing liquid, H in flue gas2S gases react with ammoniacal liquor gives birth to
Into ammonium sulfide, ammonium sulfide again with the heavy metallic oxide in flue gas（HgO、PbO、CdO、As2O3Deng）Reaction generation sulfide precipitation
（HgS、PbS、CdS、As2S3Deng）, specific course of reaction is as follows：
H2S + 2NH3·H2O = (NH4)2S + 2H2O
(NH4)2S + PbO + H2O → PbS↓ + 2(NH4)OH
(NH4)2S + HgO + H2O → HgS↓ + 2(NH4)OH
(NH4)2S + CdO + H2O → CdS↓ + 2(NH4)OH
4(NH4)2S + As2O3 + 3H2O → As2S3↓ + 3(NH4)OH + (NH4)HS；
（3）The Fe of ferrous sulfate in absorbing liquid2+Ferrous hydroxide can be hydrolyzed to, ferrous hydroxide is further oxidized to hydrogen-oxygen
Change iron and the heavy metal formed in colloid, adsorbent solution；Fe3+It can also be sunk with the arsenic generation arsenate and arsenite in solution
Form sediment, course of reaction is as follows：
Fe2+ + 2H2O → 2H+ + Fe(OH)2
Fe(OH)2 + O2 + H2O → Fe(OH)3
4Fe2+ + O2 + 2H2O → 4Fe3+ + 4OH-
As2O3 + H2O → H3AsO3
H3AsO3 + O2 → H3AsO4
H3AsO3 ↔ 3H+ + AsO3 3-
H3AsO4 ↔ 3H+ + AsO4 3-
3Fe3+ + AsO4 3- → FeAsO4↓
Fe3+ + AsO3 3- → FeAsO3↓；
（4）The pH value of solution can be reduced gradually in course of reaction, and control ph is between 6 ~ 10 by way of adding absorbing liquid
To reach optimal assimilation effect；
（5）React the heavy metal terminated in rear solution to precipitate substantially completely, gone out by Filter Press main in precipitation, absorbing liquid
There is material for ammonium sulfide, ammonium sulfide mass fraction is 10 ~ 20%, and this ammonium sulfide solution can be sold as product.
Advantages of the present invention：
1st, hydrogen sulfide gas is changed into ammonium sulfide by adding ammoniacal liquor, then sulphur is generated with the heavy metallic oxide reaction in flue gas
Compound precipitate, absorption process is to consume the sulphur and heavy metal in flue gas, absorbing liquid more simply play one connection and
Transformation, less to the consumption of absorbing liquid, last absorbing liquid has primarily formed ammonium sulfide solution, the market of ammonium sulfide solution
Price is apparently higher than the price of ammoniacal liquor, and certain economic benefit can be brought again by being sold as product；
2nd, the present invention combines the constituent of yellow phosphoric tail gas, with the treatment of wastes with processes of wastes against one another, energy-saving and emission-reduction, resource reclaim, minimum investment, simple
The thinking of operation is innovated, and the heavy metal in flue gas is removed with the hydrogen sulfide gas in reducing atmosphere flue gas, passes through generation
Metal sulfide reaches while the final goal of removing；
3rd, present invention process is simple, easy to operate, invest small, is environmental protection, the new approaches of the waste gas utilization of resources.
Embodiment
With reference to specific embodiment, the invention will be further described, is carried out in fact lower premised on inventive technique scheme
Apply, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
The exhaust gas volumn of pending flue gas is 500m3Contain H in/h, flue gas2S：500mg/m3、Hg：1.5mg/m3、Pb：1.2mg/m3、
Cd：1.7mg/m3、As：3.8mg/m3、O2：0.5%, wherein, Hg, Pb, Cd, As respectively in the form of an oxide HgO, PbO, CdO,
As2O3It is present in flue gas.
It is the absorbing liquid that 4%, ferrous sulfate mass fraction is 0.01% to prepare ammoniacal liquor mass fraction；Flue gas removing dust, washing
After be cooled to 50 DEG C, be passed through in spray column with absorbing liquid counter current contacting, H in flue gas2S gases and ammoniacal liquor reaction generation ammonium sulfide,
Ammonium sulfide again with HgO, PbO, CdO, As in flue gas2O3Deng heavy metallic oxide reaction generation HgS, PbS, CdS, As2S3Deng sulphur
Compound is precipitated；The Fe of ferrous sulfate in absorbing liquid2+Ferrous hydroxide is hydrolyzed to, ferrous hydroxide is further oxidized to hydroxide
Iron simultaneously forms colloid, the heavy metal in adsorbent solution；Fe3+Ferric arsenate and arsenious acid molysite deposition can also be generated with arsenic；Absorbed
Absorbing liquid is added in journey controls solution ph to be 6, and the heavy metal after the completion of reaction in solution is precipitated completely, through filter press mistake substantially
It is 10% that ammonium sulfide mass fraction in sediment and ammonium sulfide solution, solution is obtained after filter, is finally sold as product.
By handling, H in exiting flue gas2S≤50mg/m3、Hg≤0.1mg/m3、Pb≤0.1mg/m3、Cd≤0.3mg/m3、
Arsenic≤0.3mg/m3。
Embodiment 2
The exhaust gas volumn of pending flue gas is 2000m3Contain H in/h, flue gas2S：600mg/m3、Hg：0.9mg/m3、Pb：2.3mg/m3、
Cd：0.7mg/m3、As：2.8mg/m3、O2：0.5%, wherein, Hg, Pb, Cd, As respectively in the form of an oxide HgO, PbO, CdO,
As2O3It is present in flue gas.
It is the absorbing liquid that 8%, ferrous sulfate mass fraction is 0.08% to prepare ammoniacal liquor mass fraction；Flue gas removing dust, washing
After be cooled to 60 DEG C, be passed through in spray column with absorbing liquid counter current contacting, H in flue gas2S gases and ammoniacal liquor reaction generation ammonium sulfide,
Ammonium sulfide again with HgO, PbO, CdO, As in flue gas2O3Deng heavy metallic oxide reaction generation HgS, PbS, CdS, As2S3Deng sulphur
Compound is precipitated；The Fe of ferrous sulfate in absorbing liquid2+Ferrous hydroxide is hydrolyzed to, ferrous hydroxide is further oxidized to hydroxide
Iron simultaneously forms colloid, the heavy metal in adsorbent solution；Fe3+Ferric arsenate and arsenious acid molysite deposition can also be generated with arsenic；Absorbed
Absorbing liquid is added in journey controls solution ph to be 8, and the heavy metal after the completion of reaction in solution is precipitated completely, through filter press mistake substantially
It is 15% that ammonium sulfide mass fraction in sediment and ammonium sulfide solution, solution is obtained after filter, is finally sold as product.
By handling, H in exiting flue gas2S≤50mg/m3、Hg≤0.1mg/m3、Pb≤0.1mg/m3、Cd≤0.3mg/m3、
Arsenic≤0.3mg/m3。
Embodiment 3
The exhaust gas volumn of pending flue gas is 800m3Contain H in/h, flue gas2S：400mg/m3, Hg：0.5mg/m3, Pb：0.8mg/m3,
Cd：1.1mg/m3, As：3.2mg/m3, O2：0.5%；Wherein, Hg, Pb, Cd, As respectively in the form of an oxide HgO, PbO, CdO,
As2O3It is present in flue gas.
It is the absorbing liquid that 12%, ferrous sulfate mass fraction is 0.5% to prepare ammoniacal liquor mass fraction；Flue gas removing dust, washing
After be cooled to 35 DEG C, be passed through in spray column with absorbing liquid counter current contacting, H in flue gas2S gases and ammoniacal liquor reaction generation ammonium sulfide,
Ammonium sulfide again with HgO, PbO, CdO, As in flue gas2O3Deng heavy metallic oxide reaction generation HgS, PbS, CdS, As2S3Deng sulphur
Compound is precipitated；The Fe of ferrous sulfate in absorbing liquid2+Ferrous hydroxide is hydrolyzed to, ferrous hydroxide is further oxidized to hydroxide
Iron simultaneously forms colloid, the heavy metal in adsorbent solution；Fe3+Ferric arsenate and arsenious acid molysite deposition can also be generated with arsenic；Absorbed
Absorbing liquid is added in journey controls solution ph to be 10, and the heavy metal after the completion of reaction in solution is precipitated completely, through filter press substantially
It is 20% that ammonium sulfide mass fraction in sediment and ammonium sulfide solution, solution is obtained after filtering, is finally sold as product.
By handling, H in exiting flue gas2S≤50mg/m3、Hg≤0.1mg/m3、Pb≤0.1mg/m3、Cd≤0.3mg/m3、
Arsenic≤0.3mg/m3。
Claims (3)
1. it is a kind of while the method for removing reducing atmosphere sulfureous in flue gas hydrogen and heavy metal, comprises the following steps：
（1）Prepare and contain ammoniacal liquor and ferrous sulfate in absorbing liquid, absorbing liquid；
（2）Less than 60 DEG C are cooled to after flue gas removing dust, washing, is contacted with absorbing liquid, H in flue gas2S gases react with ammoniacal liquor gives birth to
Into ammonium sulfide, ammonium sulfide generates sulfide precipitation with the heavy metallic oxide reaction in flue gas again, and reaction equation is as follows：
H2S + 2NH3·H2O = (NH4)2S + 2H2O
(NH4)2S + PbO + H2O → PbS↓ + 2(NH4)OH
(NH4)2S + HgO + H2O → HgS↓ + 2(NH4)OH
(NH4)2S + CdO + H2O → CdS↓ + 2(NH4)OH
4(NH4)2S + As2O3 + 3H2O → As2S3↓ + 3(NH4)OH + (NH4)HS；
（3）The Fe of ferrous sulfate in absorbing liquid2+Ferrous hydroxide is hydrolyzed to, ferrous hydroxide is further oxidized to iron hydroxide
And the heavy metal formed in colloid, adsorbent solution；Fe3+It can also be precipitated with the arsenic generation arsenate and arsenite in solution, instead
Answer formula as follows：
Fe2+ + 2H2O → 2H+ + Fe(OH)2
Fe(OH)2 + O2 + H2O → Fe(OH)3
4Fe2+ + O2 + 2H2O → 4Fe3+ + 4OH-
As2O3 + H2O → H3AsO3
H3AsO3 + O2 → H3AsO4
H3AsO3 ↔ 3H+ + AsO3 3-
H3AsO4 ↔ 3H+ + AsO4 3-
3Fe3+ + AsO4 3- → FeAsO4↓
Fe3+ + AsO3 3- → FeAsO3↓；
（4）It is 6 ~ 10 that solution ph is controlled in course of reaction；
（5）Reaction is filtered after terminating, and obtains sediment and ammonium sulfide solution.
2. according to the method described in claim 1, it is characterised in that ammoniacal liquor mass fraction is 4 ~ 12%, ferrous sulfate in absorbing liquid
Mass fraction is 0.01 ~ 0.5%.
3. according to the method described in claim 1, it is characterised in that step（4）PH value of solution is controlled by adding absorbing liquid.
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