CN105536492B - A kind of method that ammonium fluoride waste water prepares phosphate ore pulp desulfurizing agent - Google Patents
A kind of method that ammonium fluoride waste water prepares phosphate ore pulp desulfurizing agent Download PDFInfo
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- CN105536492B CN105536492B CN201510986141.XA CN201510986141A CN105536492B CN 105536492 B CN105536492 B CN 105536492B CN 201510986141 A CN201510986141 A CN 201510986141A CN 105536492 B CN105536492 B CN 105536492B
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- sulfur dioxide
- waste water
- ore pulp
- ammonium fluoride
- absorbent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/12—Methods and means for introducing reactants
- B01D2259/126—Semi-solid reactants, e.g. slurries
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
Flue gas largely containing low-concentration sulfur dioxide is generated in industrial process, phosphate ore pulp desulfurization has apparent technical advantage in phosphorous chemical industry manufacturing enterprise and obtains promoting and application.It is influenced by exhaust gas volumn fluctuation and the variation of sulfur dioxide in flue gas concentration, phosphate ore pulp is not sufficiently stable the absorption efficiency of sulfur dioxide.The present invention prepares desulfurization absorbent using the ammonium fluoride waste water and ground phosphate rock discharged in phosphorous chemical industry enterprise, to absorb the low-concentration sulfur dioxide in flue gas.Pretreated ammonium fluoride waste water and levigate phosphorus ore are mixed to prepare the desulfurization absorbent that solid content is 15~50%, pH value is 8.0~9.0；The control of absorption process liquid-gas ratio is 4~12 L/m3；When loop slurry pH value begins lower than 4.0,50% absorption slurry is discarded, and adds the freshly prepd phosphate ore pulp absorbing liquid of equivalent again to circulating slot.The absorbent desulfuration efficiency of preparation is stablized, and sulfur dioxide flue gas concentration and tolerance fluctuation have not significant impact sulfur dioxide absorption efficiency.This method treatment of wastes with processes of wastes against one another has many characteristics, such as that process facility is simple, operation operating cost is low, raw material is cheap and easy to get.
Description
Technical field
The present invention relates to a kind of preparation methods of phosphate ore pulp in phosphate ore pulp sulfur dioxide absorption technology, and it is net to belong to industrial waste gas
Change absorbent preparation technical field.
Background technique
Flue gas largely containing low-concentration sulfur dioxide is generated in industrial process.Currently, China's low-concentration sulfur dioxide is controlled
Reason technology mainly has Limestone-gypsum Wet Flue Gas Desulfurization Process, the ammonia process of desulfurization, activated carbon adsorption desulfurization, phosphate ore pulp desulfurization etc..In ground phosphate rock
In addition to containing P elements, also contain 0.9~1.5% Fe2O3, 0.4~0.6% MnO2And other components.Phosphate ore pulp sweetening process
In, transition metal element Fe, Mn and trace rare-earth element can be used as the catalyst of desulfurization in ore pulp, by two in liquid-phase system
Sulfur oxide catalysis oxidation is sulfuric acid.Phosphate ore pulp desulfurization technology has apparent advantage in the flue gas desulfurization of phosphorous chemical industry manufacturing enterprise；But
It is influenced by exhaust gas volumn fluctuation and the variation of sulfur dioxide in flue gas concentration, phosphate ore pulp is very unstable to the absorption efficiency of sulfur dioxide
It is fixed.As atmosphere pollutants emission standards are increasingly strict, the existing phosphate ore pulp desulfurization technology of inevitable requirement, which has, adapts to tolerance wave
Dynamic and fluctuation of concentration ability.For this purpose, the desulfurization absorption that the process condition of optimization absorption process, preparation absorption efficiency are stable
Agent etc. becomes the emphasis of researcher's concern.
Summary of the invention
The present invention is intended to provide a kind of preparation method of phosphate ore pulp desulfurizing agent, specific using the fluorine discharged in phosphorous chemical industry enterprise
Change ammonium waste water and ground phosphate rock prepares desulfurization absorbent, to absorb the low-concentration sulfur dioxide in flue gas.This method treatment of wastes with processes of wastes against one another,
Have many characteristics, such as that process facility is simple, operation operating cost is low, raw material is cheap and easy to get.
The present invention using transition metal ions iron ion in the ammonia complexing phosphate ore pulp in ammonium fluoride waste water, iron after complexing from
Son, which can steadily be present in, to be absorbed in slurries, is avoided iron ion and is generated sediment and iron concentration in liquid phase is caused obviously to drop
It is low；Iron ion after complexing as catalyst, in liquid-phase system steadily by sulfur dioxide catalysis oxidation be sulfuric acid.
The method of the invention includes following main operational steps:
(1) by P2O5Content is that 10~30% phosphorus ores are levigate to 150~200 mesh, the sieving of 85% miberal powder；
(2) by ammonium fluoride waste water filtering, solid impurity is removed, adjusts ammonia density 0.5~4.0%, it is spare as solvent；
(3) pretreated ammonium fluoride waste water is mixed with levigate phosphorus ore, desulfurization absorbent is made after being sufficiently stirred,
Absorbent solid content is 15~50%, and pH value is 8.0~9.0.
(4) the ore pulp absorbent prepared is delivered to circulating slot, and send through circulating pump pressurization to spray absorber, and absorbent exists
With sulfur dioxide counter current contacting in absorption tower, the liquid-gas ratio of absorption process is 4~12L/m3, maintain absorption cycle liquid pH value not low
In 4.0, absorption efficiency can be stablized 95% or more.
(5) it after absorption operation carries out a period of time, when absorbent slurry pH begins lower than 4.0, is followed in 50% ratio is discarded
Annular groove absorption mother liquor, and freshly prepd absorbent is supplemented, to maintain higher desulfuration efficiency.Using phosphate ore pulp prepared by the present invention
Absorbent, absorbent out-of-service time can maintain nearly 3 hours；Under the same terms, traditional phosphate ore pulp absorbent out-of-service time is about
30 minutes.
The present invention has following technical advantage:
(1) treatment of wastes with processes of wastes against one another of the present invention avoids environmental impact issues caused by the discharge of phosphorous chemical industry enterprise fluoride waste, together
When have many characteristics, such as that desulfuration efficiency is high, process facility is simple, easy to operate.
(2) compared with traditional phosphate ore pulp desulfurization technology, the absorbent desulfurization duration prepared by the present invention is long, desulfuration efficiency
Stablize, sulfur dioxide flue gas concentration and tolerance fluctuate the influence fluctuated to sulfur dioxide absorption efficiency and is greatly reduced.
(3) the later absorbent of absorption saturation can be used as raw material and be back to phosphoric acid production, to wet method phosphoric acid manufacture process
It has no adverse effects.
Detailed description of the invention
Fig. 1 ammonium fluoride waste water prepares phosphate ore pulp desulfurizing agent and is used for the process flow of flue gas desulfurization.
Specific embodiment
It elaborates below in conjunction with attached drawing 1 to the embodiment of the present invention.The present embodiment is being with technical solution of the present invention
Under the premise of implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to
Following embodiments.
Case study on implementation 1
The method that ammonium fluoride waste water prepares phosphate ore pulp desulfurizing agent described in the implementation case includes ammonium fluoride waste water filtering and ammonia
Concentration adjustment, phosphorus ore is levigate and slurrying etc. must step, which is successfully applied to Yiliang, Yunnan phosphorous chemical industry manufacturing enterprise.Fluorine
Change ammonium waste water and contain ammonia 0.5~0.8%, through the solid matter in precipitating removal waste water, the storage of gained filtrate is spare；Phosphorus ore is levigate
To 150 mesh, the sieving of 85% material；Spare filtrate containing ammonia will be stored and prepare the phosphate ore pulp desulfurizing agent that solid content is 50%, slurries pH
Value about 8.3.Absorption tower diameter is 3.5m, a height of 14m；Exhaust gas volumn to be processed is 35000m3/ h, sulfur dioxide concentration are
1800~2000mg/m3, oxygen content 6.2%.Phosphate ore pulp desulfurizing agent prepared by the present invention is taken out from serum recycle slot, through following
Ring is pumped to absorption tower and carries out two-stage spray, and is in counter current contacting with flue gas to be processed；The internal circulating load of absorbent is 250m3/h。
It is added at one time after new ore pulp continuous operation 30 hours, absorbs slurry pH value and drop to 3.6, export sulfur dioxide in tail gas concentration
Start above 90mg/m3；It draws, is sent to phosphorous chemical industry enterprise phosphoric acid production workshop as former at this point, absorbing slurry in circulating slot 50%
Material；And then the freshly prepd phosphate ore pulp desulfurizing agent of equivalent is added in circulating slot to maintain 95% or more desulfurization effect.Later period
Continuous operation operating process in, maintain 95% or more desulfurization effect when, use the absorbent out-of-service time prepared by the present invention for
3.5 hour；Under the same terms, traditional phosphate ore pulp absorbent out-of-service time is about 30 minutes.
Case study on implementation 2
It is identical with embodiment 1 that ammonium fluoride waste water described in the implementation case prepares the step of phosphate ore pulp desulfurizing agent, the reality
Case application is applied in Yunnan company 3000Nm3/ h sulfuric acid tail gas administers pilot scale plant.Absorption tower diameter is 1.2m, a height of 10m.
Sulfur dioxide concentration is 600~800mg/m in sulfuric acid tail gas amount to be processed3, oxygen content 4.8%；Absorption process liquid-gas ratio is
5L/m3, empty tower gas velocity 1.5m/s.Used phosphate ore pulp is levigate to 200 mesh, the sieving of 85% material；Used ammonium fluoride is useless
Water contains ammonia 0.6~1.0%, after the solid matter in precipitating removal waste water, adjusts in filtrate ammonia density to 4.0%, and with the storage
Standby liquid prepares the phosphate ore pulp absorbent that solid contents is 40%, and slurry pH value is about 8.8.The new ore pulp being added at one time is continuous
After desulfurization operation 120 hours, absorbs slurry pH value and drop to 4.0, outlet sulfur dioxide in tail gas concentration starts above 50mg/
m3；It is drawn at this point, absorbing slurry in circulating slot 50%, and adds the freshly prepd phosphate ore pulp desulfurizing agent of equivalent again to remain stable
Desulfurization effect.In the continuous operation operating process in later period, when maintaining 95% or more desulfurization effect, using suction prepared by the present invention
The agent out-of-service time is received up to 10 hours.
Claims (2)
1. a kind of method that ammonium fluoride waste water prepares phosphate ore pulp desulfurizing agent, it is characterised in that: using what is discharged in phosphorous chemical industry enterprise
Ammonium fluoride waste water and ground phosphate rock prepare desulfurization absorbent, absorb the low-concentration sulfur dioxide in flue gas；The absorbent desulfurization of preparation
Stabilised efficiency, sulfur dioxide flue gas concentration and tolerance fluctuation have not significant impact desulfuration efficiency；
The desulfurization absorbent is prepared using following methods: by ammonium fluoride waste water filtering, being removed solid impurity, is adjusted ammonia density
0.5~4.0%, it is spare as solvent；Phosphorus ore is levigate to 150~200 mesh, the sieving of 85% miberal powder；By pretreated ammonium fluoride
Waste water is mixed with levigate phosphorus ore, and desulfurization absorbent is made after being sufficiently stirred, and absorbent solid content is 15~50%, and pH value is
8.0~9.0.
2. the method that a kind of ammonium fluoride waste water according to claim 1 prepares phosphate ore pulp desulfurizing agent, it is characterised in that: absorb
The liquid-gas ratio of process phosphate ore pulp internal circulating load and exhaust gas volumn to be processed is 4~12L/m3；When loop slurry pH value begins lower than 4.0,
It draws 50% absorption to starch to phosphorous chemical industry enterprise phosphoric acid production workshop as a raw material for production, and adds the freshly prepd phosphorus ore of equivalent again
Absorbing liquid is starched to circulating slot；During continuous operation, when sulfur dioxide in flue gas concentration to be processed is 2000mg/m3When, it absorbs
Agent can stablize the desulfuration efficiency of 95% or more maintenance in 3 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510986141.XA CN105536492B (en) | 2015-12-25 | 2015-12-25 | A kind of method that ammonium fluoride waste water prepares phosphate ore pulp desulfurizing agent |
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| CN201510986141.XA CN105536492B (en) | 2015-12-25 | 2015-12-25 | A kind of method that ammonium fluoride waste water prepares phosphate ore pulp desulfurizing agent |
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| CN105536492B true CN105536492B (en) | 2019-03-08 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106345288B (en) * | 2016-08-24 | 2019-04-26 | 湖北祥云(集团)化工股份有限公司 | A kind of method and system using phosphate ore pulp processing sulfur-containing smoke gas |
| CN112717668B (en) * | 2020-12-11 | 2023-01-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Efficient and stable complexing denitration agent and preparation method thereof |
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| CN1304328A (en) * | 1999-05-17 | 2001-07-18 | 三菱重工业株式会社 | Method for flue gas desulfurization and flue gas desulfurization system |
| CN101130153A (en) * | 2007-08-14 | 2008-02-27 | 湖南大学 | Double -circulation dust settling and desulfurating tower with vertical screen deck |
| CN101745309A (en) * | 2010-03-12 | 2010-06-23 | 史汉祥 | Flue gas desulfurization (FGD) and comprehensive utilization method for flyash pudding blast furnace slag |
| CN101759166A (en) * | 2009-12-31 | 2010-06-30 | 四川龙蟒钛业股份有限公司 | Method for pre-treating phosphorite by using acidic waste water in the production process of titanium pigment |
| CN102674277A (en) * | 2012-05-25 | 2012-09-19 | 四川龙蟒钛业股份有限公司 | Method for pre-treating phosphorus rock by mixture of titanium dioxide waste acid and fluorine-containing waste water |
| CN105056747A (en) * | 2015-08-18 | 2015-11-18 | 昆明尔康科技有限公司 | Process and device for removing SO2 from exhaust gas generated by sulfuric acid production in phosphate chemical enterprise |
-
2015
- 2015-12-25 CN CN201510986141.XA patent/CN105536492B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304328A (en) * | 1999-05-17 | 2001-07-18 | 三菱重工业株式会社 | Method for flue gas desulfurization and flue gas desulfurization system |
| CN101130153A (en) * | 2007-08-14 | 2008-02-27 | 湖南大学 | Double -circulation dust settling and desulfurating tower with vertical screen deck |
| CN101759166A (en) * | 2009-12-31 | 2010-06-30 | 四川龙蟒钛业股份有限公司 | Method for pre-treating phosphorite by using acidic waste water in the production process of titanium pigment |
| CN101745309A (en) * | 2010-03-12 | 2010-06-23 | 史汉祥 | Flue gas desulfurization (FGD) and comprehensive utilization method for flyash pudding blast furnace slag |
| CN102674277A (en) * | 2012-05-25 | 2012-09-19 | 四川龙蟒钛业股份有限公司 | Method for pre-treating phosphorus rock by mixture of titanium dioxide waste acid and fluorine-containing waste water |
| CN105056747A (en) * | 2015-08-18 | 2015-11-18 | 昆明尔康科技有限公司 | Process and device for removing SO2 from exhaust gas generated by sulfuric acid production in phosphate chemical enterprise |
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