CN108744906A - A kind of phosphorus ore slurry wet desulfurization additive - Google Patents
A kind of phosphorus ore slurry wet desulfurization additive Download PDFInfo
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- CN108744906A CN108744906A CN201810612132.8A CN201810612132A CN108744906A CN 108744906 A CN108744906 A CN 108744906A CN 201810612132 A CN201810612132 A CN 201810612132A CN 108744906 A CN108744906 A CN 108744906A
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- China
- Prior art keywords
- ore pulp
- mass percent
- nitrate
- phosphate ore
- phosphorus ore
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 67
- 230000023556 desulfurization Effects 0.000 title claims abstract description 43
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011574 phosphorus Substances 0.000 title claims abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 33
- 239000000654 additive Substances 0.000 title claims abstract description 27
- 239000002002 slurry Substances 0.000 title claims abstract description 24
- 230000000996 additive effect Effects 0.000 title claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 54
- 239000010452 phosphate Substances 0.000 claims abstract description 52
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 20
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 239000001361 adipic acid Substances 0.000 claims description 10
- 235000011037 adipic acid Nutrition 0.000 claims description 10
- 239000001509 sodium citrate Substances 0.000 claims description 10
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000000779 smoke Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 18
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 16
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 14
- 239000003546 flue gas Substances 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229910000165 zinc phosphate Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 235000005979 Citrus limon Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002367 phosphate rock Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 244000248349 Citrus limon Species 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 235000010269 sulphur dioxide Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000036642 wellbeing Effects 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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- 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
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/602—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/70—Organic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/202—Alkali metals
- B01D2255/2027—Sodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2045—Calcium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
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- B01D2255/207—Transition metals
- B01D2255/20738—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20792—Zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/70—Non-metallic catalysts, additives or dopants
- B01D2255/707—Additives or dopants
-
- 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
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- General Chemical & Material Sciences (AREA)
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Abstract
The present invention discloses a kind of phosphorus ore slurry wet desulfurization additive, including nitrate, metal oxide, organic acid and salts substances.The pH value that the additive can slow down reaction system declines, and improves the utilization rate of phosphorus ore, increases the stability of desulphurization system, and then improve SO2Removal rate.Within a certain period of time, additive, which is added in reaction system, handles industrial smoke, and after reacting 120min, the desulfuration efficiency of phosphate ore pulp desulphurization system, to improve the utilization rate of phosphorus ore, achievees the purpose that recycling than improving 5-20% under the conditions of not doping.
Description
Technical field
The present invention relates to a kind of phosphorus ore slurry wet desulfurization additives, belong to prevention and control of air pollution and improvement, more particularly to phosphorus
Chemical industry flue gases purification field.
Background technology
Phosphate rock resource is widely used in industry, agricultural, medicine and other fields, and social development be unable to do without phosphate rock resource.Therefore,
Rational exploitation and utilization phosphate rock resource is of great significance to the sustainable development of phosphorous chemical industry enterprise.China's phosphate rock resource is abundant, phosphorus
Contain a large amount of impurity in mine, mainly there is iron, aluminium, magnesium, calcium, silicon, also manganese, vanadium, iodine, potassium, strontium etc..Sulphur dioxide of phosphor chemical industry economy is imitated
Benefit is good, but environmental pollution is very important, how effectively clean manufacturing and economic well-being of workers and staff to be combined together, and is phosphorous chemical industry enterprise
The very severe problem faced.Currently, administered for sulphur dioxide of phosphor chemical industry flue gas desulfurization, wet process of FGD is and wet using more
Method flue gas desulfurization mainly has limestone-gypsum method, sodium alkali, ammonia process, magnesium processes, Dual alkali, phosphorus ore slurry processes etc..In recent years, phosphatization
There is relatively advanced enterprise's adaptation to local conditions in industrial and commercial bank's industry, using " the phosphate ore pulp catalytic oxidative desulfurization of the patent No. 200610011003.0
Method described in the method for low-concentration sulfur dioxide " creates or sulfuric acid tail gas purifier has been transformed, obtains good fortune
Row effect.
And phosphorus ore slurry wet desulfurization is a kind of more emerging sulfur method, for phosphorous chemical industry enterprise, is had de-
The features such as sulfur feedstock is easy to get, the byproduct of desulfurization can recycle, is easy to operate.But there is also some problems, such as phosphorus for this method
Mine consumption is big, the not first-class factor of phosphorus ore grade causes desulfuration efficiency fluctuation larger so that desulphurization system is unable to stable operation, adds
Some problems existing for acute desulphurization system itself.In recent years, " a kind of Gypsum Wet of the patent No. 201110182586.4
Sulfur-removing additives " prepare sulfur-removing additives using organic acid substance, metal oxide, salts substances etc., which is subtracting
The significant effect of few fouling, raising desulfuration efficiency etc..A kind of " the Gypsum Wet of the patent No. 201410112266.5
Flue gas desulfurization additive " is composed of one or more of organic acid, acylate, inorganic metal salt etc., the additive
The resistance to mass tranfer of desulfurization slurry solid-liquid interface, the pH value of stably desulphurizing slurries can be effectively reduced, and then improves desulfuration efficiency.
The patent No. 201410072548.7 " a kind of Wet Fgd By Limestone With Additives and preparation method thereof ", using adipic acid, lemon
Lemon acid sodium, magnesia etc. prepare a kind of sulfur-removing additives, which has significant desulfurization effect to high-sulfur flue-gas, and
The utilization rate and desulfuration efficiency that desulfurization slurry can be effectively improved have many advantages, such as to reduce energy consumption, prevention desulphurization system fouling.
In existing phosphate ore pulp desulfurization technology, since the ingredient of phosphorus ore itself is more complex, its property of the phosphorus ore of different sources
Also difference, this can cause desulphurization system performance unstable so that phosphorus ore is not fully utilized, and then leads to desulfurization effect
It is undesirable.
Invention content
To overcome the shortcomings of the prior art, the present invention to provide one kind and need not be on a large scale transformed equipment, subtracted
Few desulphurization reaction period, dosage is small and can improve the phosphorus ore slurry wet desulfurization additive of desulfuration efficiency the long period, to reach
Desulfurization effect stablizes preferable purpose.
The technical scheme is that：
A kind of phosphorus ore slurry wet desulfurization additive, including nitrate, metal oxide and organic acid and salts substances, each component
Dosage is：The mass percent of nitrate and phosphate ore pulp is 1 ~ 5%, the mass percent of metal oxide and phosphate ore pulp is 0.5 ~
5%, organic acid and the mass percent of salts substances and phosphate ore pulp are 1 ~ 5%.
The nitrate is at least one of ferric nitrate, calcium nitrate, zinc nitrate.
The metal oxide is at least one of manganese dioxide, di-iron trioxide, zinc oxide.
The organic acid and salts substances are at least one of sodium citrate, citric acid, adipic acid.
Advantages of the present invention is：
（1）The prior art（Additive of the present invention is not added）When pH is below 4, desulfuration efficiency drastically declines, Bu Nengwei
Keep steady fixed desulfurization performance, and the pH run in equipment using additive of the present invention is down to 4 and still had below preferable
Desulfurization effect；
（2）Nitrate provides metal ion to desulfurization system in the present invention, is easy to the O being passed into an acidic solution2Oxidation,
Metal ion again can be SO3 2-It is oxidized to SO4 2-.Metal ion plays good catalysed oxidn to phosphate ore pulp desulfurization, increases
Add the stability of desulphurization system, promotes SO2Oxidation, and then improve desulfuration efficiency；
（3）Metal oxide to desulfurization system while providing transition metal ions in the present invention, additionally it is possible to reach very high
Valence state from S4+In capture electronics, then generate active middle medium, middle medium promotes catalytic oxidation again, moreover it is possible to which buffering is anti-
The pH value of system is answered to decline so that the utilization rate higher of phosphorus ore；
（4）Organic acid and salts substances in the present invention by synergistic effect can effectively reduce in phosphate ore pulp reaction system it is solid-
The resistance to mass tranfer at liquid interface improves the reactivity of phosphate ore pulp, promotes the dissolving of phosphate ore pulp, greatly shortens industrial smoke and slurries
Time of contact, within a certain period of time, desulfuration efficiency higher；In addition, when sodium citrate, citric acid, adipic acid are used in mixed way,
Can form pH buffer systems, the fluctuation of stably desulphurizing system phosphate ore pulp pH value, they between each other can also by act synergistically into
One step strengthens phosphate ore pulp desulfurization effect.
Specific implementation mode
In order to more fairly set out the technology contents of the present invention, illustrated herein in conjunction with specific example.But the present invention's
Protection domain is without being limited thereto.
Embodiment 1
A kind of phosphorus ore slurry wet desulfurization additive, including ferric nitrate, zinc oxide, di-iron trioxide, sodium citrate and adipic acid, respectively
The dosage of component is：The mass percent of ferric nitrate and phosphate ore pulp is 2%, and the mass percent of zinc oxide and phosphate ore pulp is 2%, three
The mass percent for aoxidizing two iron and phosphate ore pulp is 2%, and the mass percent of sodium citrate and phosphate ore pulp is 2%, adipic acid and phosphorus
The mass percent of ore pulp is 2%.It adds it in phosphate ore pulp and mixes, stir evenly.
Desulfurization system inlet flue gas SO2A concentration of 3000mg/m3, ore pulp solid-to-liquid ratio is 5%, and reaction temperature is 25 DEG C.Actual measurement
120min desulfuration efficiencies averagely improve about 13% up to 95% or more, than not doping desulfuration efficiency.
Embodiment 2
A kind of phosphorus ore slurry wet desulfurization additive, including zinc nitrate, manganese dioxide, di-iron trioxide, zinc oxide, sodium citrate and
The dosage of citric acid, each component is：The mass percent of zinc nitrate and phosphate ore pulp is 1%, the quality hundred of manganese dioxide and phosphate ore pulp
Divide than being 2%, the mass percent of di-iron trioxide and phosphate ore pulp is 2%, and the mass percent of zinc oxide and phosphate ore pulp is 1%, lemon
The mass percent of lemon acid sodium and phosphate ore pulp is 2%, and the mass percent of citric acid and phosphate ore pulp is 1%.Add it to phosphorus ore
It mixes, stirs evenly in slurry.
Desulfurization system inlet flue gas SO2A concentration of 3000mg/m3, ore pulp solid-to-liquid ratio is 5%, and reaction temperature is 25 DEG C.Actual measurement
120min desulfuration efficiencies averagely improve about 12% up to 94% or more, than not doping desulfuration efficiency.As pH=2.7, desulfurization effect
Rate 78%；Under the conditions of same pH, not doping desulfuration efficiency is 62%.
Embodiment 3
A kind of phosphorus ore slurry wet desulfurization additive, including zinc nitrate, calcium nitrate, manganese dioxide, zinc oxide and sodium citrate, each group
Point dosage be：The mass percent of zinc nitrate and phosphate ore pulp is 4%, and the mass percent of calcium nitrate and phosphate ore pulp is 1%, dioxy
The mass percent for changing manganese and phosphate ore pulp is 0.5%, and the mass percent of zinc oxide and phosphate ore pulp is 0.5%, sodium citrate and phosphorus
The mass percent of ore pulp is 3%.It adds it in phosphate ore pulp and mixes, stir evenly.
Desulfurization system inlet flue gas SO2A concentration of 3000mg/m3, ore pulp solid-to-liquid ratio is 5%, and reaction temperature is 25 DEG C.Actual measurement
120min desulfuration efficiencies averagely improve about 11% up to 92% or more, than not doping desulfuration efficiency.
Embodiment 4
A kind of phosphorus ore slurry wet desulfurization additive, including calcium nitrate, manganese dioxide, di-iron trioxide and adipic acid, each component
Dosage is：The mass percent of calcium nitrate and phosphate ore pulp is 3%, and the mass percent of manganese dioxide and phosphate ore pulp is 2%, three oxidations
The mass percent of two iron and phosphate ore pulp is 1%, and the mass percent of adipic acid and phosphate ore pulp is 1%.Add it to phosphate ore pulp
Middle mixing, stirs evenly.
Desulfurization system inlet flue gas SO2A concentration of 3000mg/m3, ore pulp solid-to-liquid ratio is 5%, and reaction temperature is 25 DEG C.Actual measurement
120min desulfuration efficiencies averagely improve about 14% up to 93% or more, than not doping desulfuration efficiency.
Embodiment 5
A kind of phosphorus ore slurry wet desulfurization additive, including ferric nitrate, zinc nitrate, di-iron trioxide and citric acid, the use of each component
Amount is：The mass percent of ferric nitrate and phosphate ore pulp is 2%, and the mass percent of zinc nitrate and phosphate ore pulp is 2%, di-iron trioxide
Mass percent with phosphate ore pulp is 5%, and the mass percent of citric acid and phosphate ore pulp is 2%.It adds it in phosphate ore pulp and mixes
It closes, stirs evenly.
Desulfurization system inlet flue gas SO2A concentration of 3000mg/m3, ore pulp solid-to-liquid ratio is 5%, and reaction temperature is 25 DEG C.Actual measurement
120min desulfuration efficiencies averagely improve about 15% up to 95% or more, than not doping desulfuration efficiency.
Embodiment 6
A kind of phosphorus ore slurry wet desulfurization additive, including ferric nitrate, calcium nitrate, zinc oxide, sodium citrate, citric acid and oneself two
The dosage of acid, each component is：The mass percent of ferric nitrate and phosphate ore pulp is 3%, and the mass percent of calcium nitrate and phosphate ore pulp is
1%, the mass percent of zinc oxide and phosphate ore pulp is 2%, and the mass percent of sodium citrate and phosphate ore pulp is 1%, citric acid and phosphorus
The mass percent of ore pulp is 2%, and the mass percent of adipic acid and phosphate ore pulp is 2%.It adds it in phosphate ore pulp and mixes, stir
It mixes uniformly.
Desulfurization system inlet flue gas SO2A concentration of 3000mg/m3, ore pulp solid-to-liquid ratio is 5%, and reaction temperature is 25 DEG C.Actual measurement
120min desulfuration efficiencies averagely improve about 17% up to 96% or more, than not doping desulfuration efficiency.
Embodiment 7
A kind of phosphorus ore slurry wet desulfurization additive, including ferric nitrate, calcium nitrate, zinc nitrate, manganese dioxide, citric acid and oneself two
The dosage of acid, each component is：The mass percent of ferric nitrate and phosphate ore pulp is 3%, and the mass percent of calcium nitrate and phosphate ore pulp is
1%, the mass percent of zinc nitrate and phosphate ore pulp is 1%, and the mass percent of manganese dioxide and phosphate ore pulp is 0.5%, citric acid with
The mass percent of phosphate ore pulp is 2%, and the mass percent of adipic acid and phosphate ore pulp is 2%.It adds it in phosphate ore pulp and mixes,
It stirs evenly.
Desulfurization system inlet flue gas SO2A concentration of 3000mg/m3, ore pulp solid-to-liquid ratio is 5%, and reaction temperature is 25 DEG C.Actual measurement
120min desulfuration efficiencies averagely improve about 16% up to 97% or more, than not doping desulfuration efficiency.
It is sub that the foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, all the present invention's
Within spirit and principle, any modification, equivalent substitution, improvement and etc. done should be included within the scope of the present invention.
Claims (4)
1. a kind of phosphorus ore slurry wet desulfurization additive, including nitrate, metal oxide and organic acid and salts substances, each component
Dosage be：The mass percent of nitrate and phosphate ore pulp is 1 ~ 5%, and the mass percent of metal oxide and phosphate ore pulp is 0.5
~ 5%, organic acid and the mass percent of salts substances and phosphate ore pulp are 1 ~ 5%.
2. phosphorus ore slurry wet desulfurization additive according to claim 1, which is characterized in that the nitrate includes nitric acid
At least one of iron, calcium nitrate, zinc nitrate.
3. phosphorus ore slurry wet desulfurization additive according to claim 1, which is characterized in that the metal oxide includes two
At least one of manganese oxide, di-iron trioxide, zinc oxide.
4. phosphorus ore slurry wet desulfurization additive according to claim 1, which is characterized in that the organic acid and salts substances
Including at least one of sodium citrate, citric acid, adipic acid.
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