CN101058415A - Method of preparing feedstuff-stage tricalcium phosphate from industrial production sodium hypophosphite waste slag - Google Patents
Method of preparing feedstuff-stage tricalcium phosphate from industrial production sodium hypophosphite waste slag Download PDFInfo
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- CN101058415A CN101058415A CNA2007100575687A CN200710057568A CN101058415A CN 101058415 A CN101058415 A CN 101058415A CN A2007100575687 A CNA2007100575687 A CN A2007100575687A CN 200710057568 A CN200710057568 A CN 200710057568A CN 101058415 A CN101058415 A CN 101058415A
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- tricalcium phosphate
- calcining
- phosphorus
- waste slag
- sodium hypophosphite
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Abstract
The invention discloses a manufacturing method of superior feed-grade tricalcium phosphate through industrial slag of sodium hypophosphite, which comprises the following steps: predrying calcium phosphite as main industrial slag to remove water; adding into sintering furnace to sinter under 650-750 deg. c; cooling; grinding; obtaining the product with 16-18% phosphor without harmful element such as fluorine, arsenic and heavy metal; realizing zero discharge of manufacturing device of tricalcium phosphate.
Description
[technical field] the invention belongs to environmental protection and technical field of three-waste treatment, particularly a kind of phosphorous acid calcium is produced feed-level tricalcium phosphate for main waste residue manufacture method that contains of utilizing the industrial production of sodium hypophosphite discharge.
[background technology] was that main waste residue mainly adopts and stores up or buried processing to containing phosphorous acid calcium in the past, the part waste residue is taken away without the direct as fertilizer sources of any processing by the peasant and is executed in the soil, a large amount of phosphoric can be lost in the water body with rainwater, easily cause environmental pollution, cause the resource significant wastage simultaneously; Monochromatic light Chongqing will contain phosphorus waste liquid and be converted into that to contain phosphorous acid calcium be main waste residue in to the treating processes that contains phosphorus waste liquid, adopt high-temperature processing method that phosphorous acid calcium is converted into tricalcium phosphate again, wherein high-temperature process adopts the fuel heat supply, and temperature requirement 800-1000 ℃, the energy consumption height pollutes heavy; The phosphoric acid that tail gas recycle obtains directly adds pending containing in the phosphorus waste liquid, the waste resource.
[summary of the invention] the objective of the invention is the utilization of industrial production of sodium hypophosphite waste residue resource, solve waste residue because of needs are stacked or buried processing caused problem of environmental pollution, reduce the energy consumption of waste residue processing and the secondary pollution problem that environment is produced simultaneously, a kind of industrial production of sodium hypophosphite is discharged, phosphorus-containing waste slag (hereinafter to be referred as phosphorus-containing waste slag) recycling to contain phosphorous acid calcium is provided, produce the production method of feed-level tricalcium phosphate, this method energy consumption is low, pollute for a short time, meet the cleaner production requirement.
Production method of the present invention may further comprise the steps:
(1), predrying: with phosphorus-containing waste slag through predrying to containing free-water≤0.1%;
(2), pulverize: the phosphorus-containing waste slag after predrying is crushed to granularity≤20mm;
(3), calcining: the phosphorus-containing waste slag after will pulverizing joins in the calcining furnace, and in (preferred 650～750 ℃) calcining more than 650 ℃, calcining makes the tricalcium phosphate work in-process more than 15 minutes (preferred 15～20 minutes);
(4), cooling: will go up step tricalcium phosphate work in-process and be cooled to normal temperature;
(5), pulverize:, be the feed-level tricalcium phosphate finished product cooled tricalcium phosphate work in-process pulverizing, levigate.
It is a disproportionation decomposition course that phosphorous acid calcium changes tricalcium phosphate into, becoming phosphuret-(t)ed hydrogen by 25% phosphoric in theory overflows, be oxidized to the phosphoric acid acid mist under high temperature and the condition that has oxygen to exist, wherein a part of phosphoric acid acid mist generates tricalcium phosphate with a small amount of calcium hydroxide reaction in the waste residue; Part enters the flue gas washing system.The sodium hypophosphite high temperature transformation is that trisodium phosphate and sodium-metaphosphate also are disproportionation decomposition coursees, having 40% phosphoric will become phosphuret-(t)ed hydrogen in theory overflows, under high temperature and the condition that has oxygen to exist, be oxidized to the phosphoric acid acid mist, part is absorbed by the calcium hydroxide in the solid materials in its effusion process, generates tricalcium phosphate; Part enters the flue gas washing system.
Above-mentioned reaction process can be described with following reaction equation:
2H
3PO
4+3Ca(OH)
2＝Ca
3(PO
4)
2+6H
2O
Because the phosphorus-containing waste slag particle is tiny, water content height, even thickness is difficult for disperseing broken, must carry out pre-dried contains on a small quantity phosphorus-containing waste slag or does not contain free-water.
The high temperature tricalcium phosphate work in-process that generate after the calcining furnace calcining, through air cooling, Mechanical Crushing is the feed-level tricalcium phosphate product to desired grade.Phosphorus content is 16～18% (weight), harmful elements such as not fluorine-containing, arsenic and heavy metal, and quality is excellent especially.In order to the half-finished air of cooling tricalcium phosphate, be can be used as secondary air after the product by heating and sent into moisture eliminator and calcining furnace, save a large amount of electric energy.
Described calcination process function is to change tricalcium phosphate under the phosphorous acid calcium high temperature, changes a spot of sodium hypophosphite in the waste residue into trisodium phosphate and sodium-metaphosphate simultaneously, and best calcining temperature is 650～750 ℃.
Described calcination process is relatively low because of calcining temperature, can use electric energy, and characteristics are the calcining temperature may command, and generation is polluted little to environment.
The described flue gas that contains dust and phosphoric acid acid mist of discharging from calcining furnace, qualified discharge after dedusting and wet scrubbing, washings through repeatedly recycle carry dense after, produce PHOSPHORIC ACID TECH.GRADE.
Advantage of the present invention and positively effect:
After adopting production technique of the present invention, needed in the past to store up or the poisonous solid-state waste residue of buried processing changes the feed-level tricalcium phosphate with higher marketable value into, the environmental pollution of having avoided phosphorus-containing waste slag to cause is so have remarkable environmental benefit, social benefit and economic benefit.
The feed-level tricalcium phosphate phosphorus content that adopts the present invention to make is 16～18% (weight), harmful elements such as not fluorine-containing, arsenic and heavy metal, and quality is excellent especially.
From the flue gas that calcining furnace is discharged, contain phosphoric acid acid mist and dust, adopt wet scrubbing technology to reclaim the phosphoric acid acid mist behind the flue gas ash removal, washings through repeatedly recycle carry dense after, produce PHOSPHORIC ACID TECH.GRADE.So the production equipment of tricalcium phosphate can be realized zero release.
[description of drawings]
Fig. 1 adopts the present invention to produce the process flow diagram of feed-level tricalcium phosphate.
[embodiment]
Embodiment 1
As shown in Figure 1: it is tiny to contain phosphorous acid calcium and be main waste residue 1 particle, the water content height, even thickness is difficult for disperseing broken, must carry out predrying 2 handles, phosphorus-containing waste slag is contained on a small quantity or do not contain free-water, pulverize 3 to granularity≤20mm then and add and calcine 4 in the calcining furnace, calcining temperature is 650～750 ℃, and calcination time is 15～20 minutes.The work in-process 5 of the high temperature tricalcium phosphate that draws off in the stove cool off 6 with air 7 in water cooler, be tricalcium phosphate the finished product 10 through pulverizing 9 to required grade again.Cool off half-finished air and be heated the back, cut down the consumption of energy as predrying and secondary air 8 calcining furnace.The flue gas that contains phosphoric acid acid mist and dust 11 of discharging in the calcining furnace adopts 12 washings 13 of wet method water after dedusting, remove the phosphoric acid acid mist after discharging 15 go into atmosphere.Washings through repeatedly recycle carry dense after, produce PHOSPHORIC ACID TECH.GRADE 14.So the tricalcium phosphate production equipment can be realized the pollution substance zero release.
Embodiment 2
With the waste residue that contains phosphorous acid calcium 42% that Tianjin sodium hypophosphite manufacturer production equipment is discharged, the feed-level tricalcium phosphate that adopts production technique of the present invention (specific embodiment is with embodiment 1) to make consists of:
Contain P 16.98%
Ca 34.92％
F does not detect
As does not detect
Pb 0.0029％。
Claims (5)
1, a kind of utilize that industrial production of sodium hypophosphite is discharged, based on contain phosphorous acid calcium, phosphorus-containing waste slag produces the production method of feed-level tricalcium phosphate, it is characterized in that this production method may further comprise the steps:
(1), predrying: with phosphorus-containing waste slag through predrying to containing free-water≤0.1%;
(2), pulverize: the phosphorus-containing waste slag after predrying is crushed to granularity≤20mm;
(3), calcining: the phosphorus-containing waste slag after will pulverizing joins in the calcining furnace, and in calcining more than 650 ℃, calcining made the tricalcium phosphate work in-process more than 15 minutes;
(4), cooling: will go up step tricalcium phosphate work in-process and be cooled to normal temperature;
(5), pulverize:, be the feed-level tricalcium phosphate finished product cooled tricalcium phosphate work in-process pulverizing, levigate.
2, production method according to claim 1 is characterized in that, the flue gas that calcining furnace is discharged, and qualified discharge after dedusting and wet scrubbing, washings reclaim produces PHOSPHORIC ACID TECH.GRADE.
3, production method according to claim 1 and 2, it is characterized in that, described phosphorus-containing waste slag main source is the waste residue that industrial production of sodium hypophosphite discharged, wherein containing phosphorous acid calcium is 42～48%, moisture 47～53%, calcium hydroxide 2～4%, sodium hypophosphite 0.5～1%, other are 0.5～1% years old.
4, according to claim 1 or 2 described production methods, it is characterized in that preferred 650～750 ℃ of the calcining temperature of material in stove, preferred 15～20 minutes of calcination time.
5, according to claim 1 or 2 described production methods, it is characterized in that, with the pyrolytic conversion of phosphorous acid calcium is the calcination process of tricalcium phosphate, the calcining furnace that uses is optional in order to rotary kiln or the tunnel furnace of electric energy as thermal source, material is wanted simultaneously and can constantly be overturn at the furnace high-temperature incinerating, it is heated evenly, sufficient reacting.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100575687A CN101058415A (en) | 2007-06-06 | 2007-06-06 | Method of preparing feedstuff-stage tricalcium phosphate from industrial production sodium hypophosphite waste slag |
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| CNA2007100575687A CN101058415A (en) | 2007-06-06 | 2007-06-06 | Method of preparing feedstuff-stage tricalcium phosphate from industrial production sodium hypophosphite waste slag |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381077B (en) * | 2008-10-17 | 2011-02-09 | 昆明理工大学 | Method for preparing dicalcium phosphate from yellow phosphorus slag |
| CN102616914A (en) * | 2011-01-31 | 2012-08-01 | 浙江新安化工集团股份有限公司 | Treatment method of phosphorus-containing waste from pesticide production and product obtained thereby |
| CN101863515B (en) * | 2009-04-20 | 2012-10-10 | 宝山钢铁股份有限公司 | Purification method of dry-type iron oxide powder solid |
| CN103058156A (en) * | 2011-10-18 | 2013-04-24 | 王军民 | Method for preparing calcium phosphate by utilizing slag charge discharged during sodium hypophosphite preparation |
-
2007
- 2007-06-06 CN CNA2007100575687A patent/CN101058415A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381077B (en) * | 2008-10-17 | 2011-02-09 | 昆明理工大学 | Method for preparing dicalcium phosphate from yellow phosphorus slag |
| CN101863515B (en) * | 2009-04-20 | 2012-10-10 | 宝山钢铁股份有限公司 | Purification method of dry-type iron oxide powder solid |
| CN102616914A (en) * | 2011-01-31 | 2012-08-01 | 浙江新安化工集团股份有限公司 | Treatment method of phosphorus-containing waste from pesticide production and product obtained thereby |
| CN102616914B (en) * | 2011-01-31 | 2015-04-01 | 浙江新安化工集团股份有限公司 | Treatment method of phosphorus-containing waste from pesticide production and product obtained thereby |
| CN103058156A (en) * | 2011-10-18 | 2013-04-24 | 王军民 | Method for preparing calcium phosphate by utilizing slag charge discharged during sodium hypophosphite preparation |
| CN103058156B (en) * | 2011-10-18 | 2014-12-03 | 王军民 | Method for preparing calcium phosphate by utilizing slag charge discharged during sodium hypophosphite preparation |
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Open date: 20071024 |