CN1283548C - Method for comprehensively utilizing phosphate fertilizer by-product - Google Patents
Method for comprehensively utilizing phosphate fertilizer by-product Download PDFInfo
- Publication number
- CN1283548C CN1283548C CN 200310104113 CN200310104113A CN1283548C CN 1283548 C CN1283548 C CN 1283548C CN 200310104113 CN200310104113 CN 200310104113 CN 200310104113 A CN200310104113 A CN 200310104113A CN 1283548 C CN1283548 C CN 1283548C
- Authority
- CN
- China
- Prior art keywords
- ammonium
- phosphate fertilizer
- hydrogen fluoride
- ammonia
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Fertilizers (AREA)
Abstract
The present invention discloses a method for comprehensively utilizing byproducts of phosphate fertilizer. In the method, 3% to 14% of ammonium fluoride solution is used for absorbing byproduct tail gas containing fluorine produced phosphate fertilizer, and ammonium fluosilicate solution with the (NH4)2SiF6 content of 8% to 32% is obtained. Iron dust or molysite is added in the other byproduct fluorosilicic acid produced by ammonium fluosilicate and/or phosphate fertilizer, and phosphorus in fluorosilicic acid is removed. Liquid ammonia or ammonia water or ammonia bicarbonate is added, silicon dioxide precipitates are removed through filtration and washing, ammonium fluoride solution is partially returned to a phosphate fertilizer absorption system, and solid ammonium bifluoride is obtained through concentration and dryness. The solid ammonium bifluoride reacts with sulphuric acid at high temperatures, ghydrofluoric acid is obtained by purifying and absorbing generated hydrogen fluoride gas, or anhyrous hydrogen fluoride is obtained through purification and condensation, the mixture of ammonium sulfate and ammonium bisulfate is mixed with ammonium bicarbonate or gasified liquid ammonia in a mixer, and fertilizer grade ammonium sulphate products are obtained after aging and pulverization.
Description
Technical field
The present invention relates to the method for utilizing of phosphate fertilizer by product, more particularly, the present invention is to be raw material with phosphate fertilizer by-product fluosilicic acid or fluorinated tail gas, produces the method for hydrofluoric acid, anhydrous hydrogen fluoride and producing ammonium sulfate byproduct.
Background technology
In the prior art, the producer that great majority are produced hydrofluoric acid and anhydrous hydrogen fluoride all adopts " fluorite method ".Its technical process is: fluorite concentrate powder and sulfuric acid measure through measuring apparatus, add continuously in the screw feeder, outside sending into behind mixing in the thermal response stove.The HF gas that produces is derived by feed end, removes wherein section H in topping still
2SO
4And dust.Absorb the hydrofluoric acid that obtains different size with graphite condenser and bubble-plate column condensation then, or make anhydrous hydrogen fluoride through degassing tower, rectifying tower, condenser.The waste gas that degassing tower comes out is discharged by squirt pump after demist.The CaSO that produces
4With unreacted H
2SO
4And CaF
2, discharge with spiral from the other end of stove, with lime powder or milk of lime neutralizing treatment, be reprocessed into material of construction.
The producer that also has utilizes the fluorine in the Rock Phosphate (72Min BPL) to produce hydrofluoric acid.The processing method of having researched and developed at present mainly contains: (1) directly utilizes the Rock Phosphate (72Min BPL) method; (2) calcium superphosphate method; (3) IMC method; (4) Buss method; (5) vitriol oil method.But realized " vitriol oil method " of having only Switzerland Kvaerner AG Technology company to adopt of industrial-scale production." vitriol oil method " is to utilize 93%～99% the vitriol oil to make the silicofluoric acid dehydration, then with the mixture decompression separation.Distilled HF gas sulfuric acid absorption, the postheating desorb gets pure HF gas, the treated hydrofluoric acid that obtains.
Silicofluoric acid is the byproduct produced of phosphoric acid by wet process and general calcium normally.One ton of phosphoric acid by wet process (100%P of every production
2O
5) about 0.06 ton of silicofluoric acid (100%H of by-product
2S
1F
6), one ton of general calcium (100%P of every production
2O
5) about 0.06 ton of silicofluoric acid (100%H of by-product
2S
1F
6).2002, domestic phosphoric acid by wet process (100%P
2O
5) output is about 3,200,000 tons, general calcium (100%P
2O
5) output is about 3,700,000 tons.Calculate with this, 2002, national phosphate fertilizer industry by-product fluosilicic acid (100%H
2SiF
6) about 41.4 ten thousand tons.
By product silicofluoric acid in the production of phosphate fertilizer is very valuable resource, but fails so far to be fully used, and major cause is it to be carried out deep processing have technical difficulty.Up to now, the whole world has only Switzerland Kvaerner AG Technology company to adopt " vitriol oil method " to produce the technology realization industrial-scale production (7000 tons/year) of hydrofluoric acid.Promptly with the vitriol oil silicofluoric acid dehydration is decomposed, hydrofluoric acid is produced in underpressure distillation then, hydrofluoric acid is processed into various fluorine chemical products again.But this method technical process is long, the equipment material requires height, investment is big, causes final production cost height, and product is lacked competitiveness on market.Therefore, fully do not apply so far.
At present, the method for domestic phosphate fertilizer industry processing by-product fluosilicic acid generally is to be processed into Sodium Silicofluoride.But because the market of Sodium Silicofluoride is limited, domestic needs approximately has only 30,000 tons/year, adds upper outlet, and aggregate demand also is no more than 4.5 ten thousand tons/year, can not digest about 400,000 tons/year by-product fluosilicic acid.For solving the deep processing problem of phosphate fertilizer by-product fluosilicic acid, country has introduced several covers production aluminum fluorides and sodium aluminum fluoride device in " eight or five " and the enforcement period of the ninth five-year plan.But all there is same problem: the one, production cost is higher; The 2nd, quality product can not satisfy market demands.So these install the Sodium Silicofluoride of all having changed the line of production.Therefore, the precious resources of phosphate fertilizer industry by product---silicofluoric acid not only can not get effective utilization, has also become the principal pollutant of phosphate fertilizer industry, has seriously restricted the development of phosphate fertilizer industry.
Summary of the invention
The method that provides a kind of phosphate fertilizer byproduct comprehensive to utilize is provided at the deficiencies in the prior art.This method is raw material production hydrofluoric acid and anhydrous hydrogen fluoride and producing ammonium sulfate byproduct with phosphate fertilizer by product silicofluoric acid or fluorinated tail gas.Thereby make the by product in the production of phosphate fertilizer obtain effectively to utilize.
Purpose of the present invention is achieved by following technical proposals.
Except as otherwise noted, the percentage ratio that is adopted among the present invention is weight percentage.
The invention provides the method that a kind of phosphate fertilizer byproduct comprehensive utilizes, this method may further comprise the steps:
(1) absorbs the by product fluorinated tail gas of production of phosphate fertilizer with 3%～14% ammonium fluoride solution, obtain (NH
4)
2SiF
6Content is 8%～32% ammonium fluosilicate solution;
(2) in above-mentioned steps (1) gains or another by product H of production of phosphate fertilizer
2SiF
6Content is to add iron filings or molysite in 6%～26% the silicofluoric acid, to remove phosphorus wherein;
(3) liquefied ammonia or the NH of adding after gasification
3Content is 10%～21% ammoniacal liquor or ammonium hydrogencarbonate;
(4) filter, wash, remove precipitation of silica; The fertile absorption system of ammonium fluoride solution part rephosphorization through concentrated, dry, obtains solid ammonium hydrogen fluoride;
(5) ammonia vapor that contains that concentrate to produce absorbs the back retrieval system through silicofluoric acid, or sends to phosphate fertilizer system absorption fluorinated tail gas after condensation, or delivers to other and reclaim with ammonia device;
(6) solid ammonium hydrogen fluoride with H
2SO
4Content is that 93%～99% sulfuric acid at high temperature reacts, and the hydrogen fluoride gas of generation obtains hydrofluoric acid through purifying, absorbing, or through purify, condensation obtains anhydrous hydrogen fluoride; The mixture of ammonium sulfate and monoammonium sulfate again with bicarbonate of ammonia or the liquefied ammonia after gasification, in a mixing tank, mix, after slaking, pulverizing, obtain the fertilizer grade ammonium sulfate product.
Wherein, in step (2), the addition of iron filings or molysite is 100%～250% of a theoretical amount.In the aminating reaction process of step (3), PH＞8 of control solution.Adding the vitriolic amount in step (6) is 100%～150% of theoretical amount, temperature＜180 of solid ammonium hydrogen fluoride and sulfuric acid generation decomposition reaction ℃, and employing liquefied ammonia vaporizes the condensation hydrogen fluoride gas.
Method of comprehensive utilization provided by the present invention, its main chemical reactions principle is as follows:
(1)
(2)
Or
(3)
(4)
(5)
(6)
Or
Compared with prior art, the present invention has following beneficial effect:
1. processing technology routine is reasonable in design, and the equipment material requires low, is easy to suitability for industrialized production;
2. fully utilize the silicofluoric acid or the fluorinated tail gas of phosphate fertilizer industry by-product, to the protection environment, utilize resources synthetically, the economic benefit of increase phosphoric acid by wet process industry all will play important effect;
3. product fluorine total recovery height (greater than 80%) generally need not be further purified and get final product industrial application;
4. project investment is few, and raw materials cost (behind the by-products recoveries) is lower than 1500 yuan of/ton products;
5. steam consumption is lower than 9 tons of/ton products.
Description of drawings
Fig. 1 is the process flow sheet of fluorite method in the prior art;
Fig. 2 is the process flow sheet of vitriol oil method in the prior art;
Fig. 3 is a process flow sheet of the present invention.
Embodiment
By specific embodiment given below, can further be well understood to the present invention.But they are not limitation of the invention.
Embodiment 1
Ammonium fluoride solution with 10% absorbs the by product fluorinated tail gas of production of phosphate fertilizer, obtains (NH
4)
2SiF
6Content is 22% ammonium fluosilicate solution.In described ammonium fluosilicate solution or another by product H of production of phosphate fertilizer
2SiF
6Content is to add iron filings or molysite (addition be theoretical amount 150%) in 18% the silicofluoric acid.Ammonium fluoride solution pH is 8.5 behind the control aminating reaction.Filter, wash (twice) to remove silica gel.The whole vacuum concentration of ammonium fluoride solution (85 ℃) are to moisture＜4%, and drying obtains solid hydrogen fluoride ammonia.Solid hydrogen fluoride ammonia (98%) reacts with the vitriol oil (dosage be theoretical amount 135%) down at high temperature (140 ℃), and the HF gas of generation is made anhydrous hydrogen fluoride and hydrofluoric acid through condensation or absorption.Ammonium sulfate mixes in a mixing tank with bicarbonate of ammonia with the mixture of monoammonium sulfate again, after slaking, pulverizing, obtains the fertilizer grade ammonium sulfate product.
Quality product and consumption are respectively:
1. hydrofluoric acid (40%) quality:
(1) hydrogen fluoride (HF) content (%) 〉=40;
(2) silicofluoric acid (H
2SiF
6, %)≤0.02;
(3) non-volatile acid is (with H
2SO
4Meter, %)≤0.02;
(4)P
2O
5(PPM)≤100；
(5)N(PPM)≤500。
Consume in (t/t40% hydrofluoric acid):
(1) silicofluoric acid (100%H
2SiF
6) 0.555;
(2) sulfuric acid (98%) 0.740
(3) ammoniacal liquor (17%) 1.667
(4) ferric sulfate 0.009
Fluorine yield: 86.49%
2. anhydrous hydrogen fluoride
(1) hydrogen fluoride (HF) content (%) 〉=99.98;
(2) moisture content (%)≤0.01;
(3) silicofluoric acid (H
2SiF
6, %)≤0.006;
(4) sulfurous gas (%)≤0.001
(5) non-volatile acid is (with H
2SO
4Meter, %)≤0.003;
(6)P
2O
5(PPM)≤100；
(7)N(PPM)≤500。
Consume in (t/t100% hydrofluoric acid):
(1) silicofluoric acid (100%H
2SiF
6) 1.402;
(2) sulfuric acid (98%) 1.849
(3) ammoniacal liquor (17%) 4.167
(4) ferric sulfate 0.022
Fluorine yield: 85.59%
3. fertilizer grade ammonium sulfate
(1) nitrogen (N) content is (in butt, %) 〉=21.0;
(2) moisture (H
2O, %)≤0.5;
(3) free acid (H
2SO
4, %)≤0.08.
Embodiment 2
Except the ammonia vapor that contains that concentrate to produce absorbs the back retrieval system through silicofluoric acid, or send to phosphate fertilizer system absorption fluorinated tail gas after condensation, or deliver to other and reclaim with ammonia device, other processes are with embodiment 1.
Embodiment 3
Except with in 17% the ammoniacal liquor and 18% silicofluoric acid (P
2O
5Content is 0.05%) solution, add iron filings or molysite (addition be theoretical amount 200%) simultaneously.Ammonium fluoride solution PH is 9.0 behind the control aminating reaction.Filter, wash (twice) to remove silica gel.The whole vacuum concentration of ammonium fluoride solution (under 85 ℃) are to moisture＜4%, and drying obtains solid hydrogen fluoride ammonia.Solid hydrogen fluoride ammonia high temperature (180 ℃) down with the vitriol oil (93%, dosage be theoretical amount 100%) react; The mixture of ammonium sulfate and monoammonium sulfate mixes with liquefied ammonia after gasification again.Other process is identical with embodiment 1.
Embodiment 4
Repeat embodiment 1, following difference is arranged: the ammonium fluoride solution of adding 3% obtains (NH
4)
2SiF
6Content is 7% ammonium fluosilicate solution; At H
2SiF
6Content is to add iron filings or molysite in 6% the silicofluoric acid, and its addition is 100% of a theoretical amount; Add NH then
3Content is 10% ammoniacal liquor.The PH of control solution is 8.1.Solid hydrogen fluoride ammonia high temperature (160 ℃) down with the vitriol oil (95%, dosage be theoretical amount 100%) react; The mixture of ammonium sulfate and monoammonium sulfate mixes with liquefied ammonia after gasification again.
Embodiment 5
Repeat embodiment 1, following difference is arranged: the ammonium fluoride solution of adding 14% obtains (NH
4)
2SiF
6Content is 32% ammonium fluosilicate solution; At H
2SiF
6Content is to add iron filings or molysite (addition be theoretical amount 250%) in 26% the silicofluoric acid to remove phosphorus wherein; Add NH then
3Content is 21% ammoniacal liquor, and the PH of control solution is 10.Solid hydrogen fluoride ammonia reacts with the vitriol oil (dosage be theoretical amount 100%) down at high temperature (120 ℃); The mixture of ammonium sulfate and monoammonium sulfate mixes with liquefied ammonia after gasification again.
Embodiment 6
Repeat embodiment 1, following difference is arranged: the ammonium fluoride solution of adding 6% obtains (NH
4)
2SiF
6Content is 14% ammonium fluosilicate solution; At H
2SiF
6Content is to add iron filings or molysite (addition be theoretical amount 150%) in 12% the silicofluoric acid to remove phosphorus wherein; Add NH then
3Content is 17% ammoniacal liquor, and the PH of control solution is 8.5.Solid hydrogen fluoride ammonia reacts with the vitriol oil (dosage be theoretical amount 100%) down at high temperature (140 ℃); The mixture of ammonium sulfate and monoammonium sulfate mixes with liquefied ammonia after gasification again.
Embodiment 7
Repeat embodiment 1, following difference is arranged: the ammonium fluoride solution of adding 6% obtains (NH
4)
2SiF
6Content is 14% ammonium fluosilicate solution; At H
2SiF
6Content is to add molysite or molysite (addition be theoretical amount 150%) in 12% the silicofluoric acid to remove phosphorus wherein; Add NH then
3Content is 17% liquefied ammonia, and the PH of control solution is 8.5.Solid hydrogen fluoride ammonia reacts with the vitriol oil (dosage be theoretical amount 150%) down at high temperature (140 ℃); The mixture of ammonium sulfate and monoammonium sulfate mixes with liquefied ammonia after gasification again.
Embodiment 8
Repeat embodiment 1, following difference is arranged: the ammonium fluoride solution with 6% absorbs the by product fluorinated tail gas of production of phosphate fertilizer, obtains (NH
4)
2SiF
6Content is 14% ammonium fluosilicate solution; At H
2SiF
6Content is to add iron filings or molysite (addition be theoretical amount 150%) in 12% the silicofluoric acid to remove phosphorus wherein; Add the liquefied ammonia after vaporization then, the PH of control solution is 8.5.Solid hydrogen fluoride ammonia reacts with the vitriol oil (dosage be theoretical amount 150%) down at high temperature (140 ℃); Ammonium sulfate mixes with bicarbonate of ammonia with the mixture of monoammonium sulfate again.
Embodiment 9
Repeat embodiment 1, following difference is arranged: the ammonium fluoride solution with 10% absorbs the by product fluorinated tail gas of production of phosphate fertilizer, obtains (NH
4)
2SiF
6Content is 22% ammonium fluosilicate solution; At H
2SiF
6Content is to add iron filings or molysite (addition be theoretical amount 150%) in 18% the silicofluoric acid to remove phosphorus wherein; Add the liquefied ammonia after vaporization then, the PH of control solution is 8.5.Solid hydrogen fluoride ammonia reacts with the vitriol oil (dosage be theoretical amount 150%) down at high temperature (140 ℃); Ammonium sulfate mixes with bicarbonate of ammonia with the mixture of monoammonium sulfate again.
Quality product among the embodiment 2～9 sees the following form:
| Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | ||
| Hydrofluoric acid | Hydrogen fluoride (HF, %) | 40.7 | 40.4 | 41.2 | 40.8 | 41.2 | 40.0 | 40.1 | 40.6 |
| Silicofluoric acid (H 2SiF 6，％) | 0.018 | 0.015 | 0.020 | 0.012 | 0.018 | 0.017 | 0.018 | 0.020 | |
| Non-volatile acid is (with H 2SO 4Meter, %) | 0.016 | 0.020 | 0.017 | 0.014 | 0.014 | 0.017 | 0.016 | 0.017 | |
| P 2O 5(PPM) | 35 | 87 | 73 | 26 | 25 | 37 | 40 | 58 | |
| N(PPM) | 115 | 184 | 216 | 92 | 92 | 118 | 109 | 175 | |
| Anhydrous hydrogen fluoride | Hydrogen oxide (HF, %) | 99.98 | 99.68 | 99.70 | 99.98 | 99.98 | 99.98 | 99.76 | 99.59 |
| Moisture content (%) | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | |
| Silicofluoric acid (H 2SiF 6，％) | 0.005 | 0.004 | 0.006 | 0.004 | 0.005 | 0.005 | 0.005 | 0.006 | |
| Sulfurous gas (%) | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 | |
| Non-volatile acid is (with H 2SO 4Meter, %) | 0.003 | 0.003 | 0.003 | 0.003 | 0.003 | 0.003 | 0.003 | 0.003 | |
| P 2O 5(PPM) | 74 | 86 | 98 | 62 | 63 | 76 | 79 | 84 | |
| N(PPM) | 425 | 496 | 458 | 394 | 387 | 435 | 456 | 472 | |
| Ammonium sulfate | Nitrogen (N) content is (in butt, %) | ≥21.0 | ≥21.0 | ≥21.0 | ≥21.0 | ≥21.0 | ≥21.0 | ≥21.0 | ≥21.0 |
| Moisture (H 2O，％) | ≤0.5 | ≤0.5 | ≤0.5 | ≤0.5 | ≤0.5 | ≤0.5 | ≤0.5 | ≤0.5 | |
| Free acid (H 2SO 4，％) | ≤0.08 | ≤0.08 | ≤0.08 | ≤0.08 | ≤0.08 | ≤0.08 | ≤0.08 | ≤0.08 | |
Claims (4)
1. the method utilized of a phosphate fertilizer byproduct comprehensive is characterized in that adopting following steps:
(1) absorbs the by product fluorinated tail gas of production of phosphate fertilizer with 3%～14% ammonium fluoride solution, obtain (NH
4)
2SiF
6Content is 8%～32% ammonium fluosilicate solution;
(2) in above-mentioned steps (1) gains or another by product H of production of phosphate fertilizer
2SiF
6Content is to add iron filings or molysite in 6%～26% the silicofluoric acid, to remove phosphorus wherein;
(3) liquefied ammonia or the NH of adding after gasification
3Content is 10%～21% ammoniacal liquor or ammonium hydrogencarbonate;
(4) filter, wash, remove precipitation of silica; Ammonium fluoride solution partly returns step (1), and all the other ammonium fluoride solutions obtain solid ammonium hydrogen fluoride through concentrated, dry;
(5) ammonia vapor that contains that concentrate to produce absorbs the back retrieval system through silicofluoric acid, or sends to step (1) absorption fluorinated tail gas after condensation, or delivers to other and reclaim with ammonia device;
(6) solid ammonium hydrogen fluoride with H
2SO
4Content is sulfuric acid reaction under 120 ℃～180 ℃ of 93%～99%, and the hydrogen fluoride gas of generation obtains hydrofluoric acid through purifying, absorbing, or obtains anhydrous hydrogen fluoride through purification, condensation; The mixture of ammonium sulfate and monoammonium sulfate again with bicarbonate of ammonia or the liquefied ammonia after gasification, in a mixing tank, mix, after slaking, pulverizing, obtain the fertilizer grade ammonium sulfate product.
2. the method that phosphate fertilizer byproduct comprehensive according to claim 1 utilizes, wherein the addition at iron filings described in the step (2) or molysite is 100%～250% of a theoretical amount.
3. the method that phosphate fertilizer byproduct comprehensive according to claim 1 utilizes wherein in step (3), is controlled PH＞8 of solution.
4. the method that phosphate fertilizer byproduct comprehensive according to claim 1 utilizes, wherein adding the vitriolic amount in step (6) is 100%～150% of theoretical amount, temperature＜180 of solid ammonium hydrogen fluoride and sulfuric acid generation decomposition reaction ℃ adopt liquefied ammonia to vaporize the condensation hydrogen fluoride gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310104113 CN1283548C (en) | 2003-12-22 | 2003-12-22 | Method for comprehensively utilizing phosphate fertilizer by-product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310104113 CN1283548C (en) | 2003-12-22 | 2003-12-22 | Method for comprehensively utilizing phosphate fertilizer by-product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1554570A CN1554570A (en) | 2004-12-15 |
| CN1283548C true CN1283548C (en) | 2006-11-08 |
Family
ID=34333438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310104113 Expired - Fee Related CN1283548C (en) | 2003-12-22 | 2003-12-22 | Method for comprehensively utilizing phosphate fertilizer by-product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1283548C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102951611A (en) * | 2012-12-24 | 2013-03-06 | 贵州省化工研究院 | Method for preparing anhydrous hydrogen fluoride by utilizing fluorine-containing waste liquid or fluorosilicic acid in phosphate fertilizer enterprises |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121503B (en) * | 2006-08-09 | 2012-06-06 | 贵州省化工研究院 | Liquid phase acid hydrolysis method for ammonium fluoride |
| CN101786607B (en) * | 2010-02-11 | 2011-08-17 | 浙江中宁硅业有限公司 | Method for preparing hydrogen fluoride from byproduct generated in the process of producing silane |
| CN102001628B (en) * | 2010-04-13 | 2012-10-03 | 衢州市鼎盛化工科技有限公司 | Method for preparing hydrogen fluoride by taking ammonium bisulfate and fluorine ammonium salt as raw materials |
| CN101850978B (en) * | 2010-06-06 | 2012-04-25 | 程建方 | Method for preparing ammonium fluosilicate by utilizing tail gas containing fluorine in phosphatic fertilizer production |
| CN101973568B (en) * | 2010-09-20 | 2013-04-24 | 云南云天化国际化工股份有限公司 | Comprehensive utilization method of gypsum containing fluorine and fluosilicic acid as byproduct of phosphatic fertilizer |
| CN102674367B (en) * | 2012-06-07 | 2014-01-15 | 瓮福（集团）有限责任公司 | Method for preparing ammonium fluorosilicate by utilizing fluorine-containing white slime in anhydrous hydrogen fluoride production |
| CN102689877B (en) * | 2012-06-28 | 2013-10-23 | 贵州开磷（集团）有限责任公司 | Preparation method of hydrogen fluoride |
| CN102976336B (en) * | 2012-12-24 | 2015-07-15 | 贵州省化工研究院 | Method for preparing ammonium fluosilicate solids from fluorosilicone compounds |
| CN103754824A (en) * | 2013-07-31 | 2014-04-30 | 山东博丰利众化工有限公司 | Method for preparing hydrogen fluoride by using phosphorus fertilizer by-product fluosilicic acid |
| CN103663475B (en) * | 2013-12-20 | 2016-03-02 | 瓮福（集团）有限责任公司 | Ammonia introducing method for precipitation reaction of white carbon black |
| CN104370277A (en) * | 2014-10-27 | 2015-02-25 | 瓮福（集团）有限责任公司 | Method for recycling fluorine from phosphorus-containing fluorine slag and cogenerating calcium superphosphate |
| CN108002392B (en) * | 2017-11-20 | 2019-11-19 | 湖北六国化工股份有限公司 | The method for preparing ammonium fluosilicate co-producing white carbon black using phosphoric acid plant fluorinated tail gas |
-
2003
- 2003-12-22 CN CN 200310104113 patent/CN1283548C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102951611A (en) * | 2012-12-24 | 2013-03-06 | 贵州省化工研究院 | Method for preparing anhydrous hydrogen fluoride by utilizing fluorine-containing waste liquid or fluorosilicic acid in phosphate fertilizer enterprises |
| CN102951611B (en) * | 2012-12-24 | 2017-03-15 | 贵州省化工研究院 | The method that a kind of fluorine-containing waste liquid of phosphatic fertilizer company or hexafluosilicic acid prepare anhydrous hydrogen fluoride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1554570A (en) | 2004-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1283548C (en) | Method for comprehensively utilizing phosphate fertilizer by-product | |
| CN103785263B (en) | A kind of method that ammonia vent gas treatment reclaims | |
| CN101291875B (en) | Process for production of silicon tetrafluoride, and apparatus for the process | |
| CN1030305C (en) | Process for production of phosphoric acid and hydrogen fluoride from phosphate rock and fluosilicic acid | |
| CN107720800A (en) | Recycle the method and system of carbon dioxide | |
| CN105314599B (en) | A kind of method that anhydrous hydrogen fluoride and white carbon are produced using fluosilicic acid | |
| CN103803561A (en) | Method for recycling fluorine-containing waste gas in phosphorus chemical industry production | |
| CN107055477A (en) | The method and its device of hydrogen fluoride are prepared by fluosilicic acid | |
| CN101134588A (en) | Method for producing aluminun fluoride | |
| CN101134590B (en) | Method for producing aluminun fluoride with combined production of white carbon black and ammonia sulfate | |
| CN103043684A (en) | Method for producing ammonium hydrogen fluoride by recovering fluorine in wet process phosphoric acid tail gas | |
| CN108163812B (en) | Preparation method of hydrogen fluoride and preparation method of hydrofluoric acid | |
| CN103663499B (en) | The method of Potassium monofluoride co-production of ultrafine white carbon black is prepared with phosphate fertilizer by-product ammonium silicofluoride | |
| CN1872799A (en) | Associated production method by using condensed phosphoric acid to produce diammonium phosphate, and by using condensed acidic feed pulp to produce phosphor ammonium or/and compound fertilizer | |
| CN103588220B (en) | A kind of ammonium chloride decomposes soda acid joint process and the system of preparing ammonia and hydrochloric acid | |
| CN1248965C (en) | Process for preparing ammonium hydrogen fluoride | |
| CN102431984A (en) | Method and device for producing monoammonium phosphate from waste ammonia water | |
| CN105347321B (en) | The method that phosphorus ammonium is produced using low-grade low concentration raffinate | |
| CN115010091B (en) | Impurity removal method for hydrogen fluoride, purification method for hydrogen fluoride and purification device for hydrogen fluoride | |
| CN207943871U (en) | A kind of fluosilicic acid produces the production system of anhydrous hydrogen chloride | |
| CN105819415A (en) | Phosphorus ore all-resource utilization production method preparing feed calcium hydrophosphate with hydrochloric acid | |
| CN104788304B (en) | The method that mineral acid acidified formates prepare high-pure anhydrous formic acid | |
| CN102976337B (en) | Rotary kiln is adopted to prepare the method for silicon tetrafluoride | |
| CN104478514B (en) | A kind of utilization gas cleaning accessory substance prepares the thermo-compression evaporation technique of chemical fertilizer | |
| CN101134591B (en) | Method for preparing aluminun fluoride and waterless magnesium sulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061108 Termination date: 20101222 |