CN100390091C - Method for preparing phosphoric acid and byproduct building brick by using phosphatic ore tailings after phosphate ore dressing - Google Patents
Method for preparing phosphoric acid and byproduct building brick by using phosphatic ore tailings after phosphate ore dressing Download PDFInfo
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- CN100390091C CN100390091C CNB2006100187808A CN200610018780A CN100390091C CN 100390091 C CN100390091 C CN 100390091C CN B2006100187808 A CNB2006100187808 A CN B2006100187808A CN 200610018780 A CN200610018780 A CN 200610018780A CN 100390091 C CN100390091 C CN 100390091C
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- phosphoric acid
- brick
- mine tailing
- ore
- byproduct
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The present invention discloses a method for preparing phosphoric acid and a byproduct building brick by phosphatic tailings after phosphate ore dressing, which is the application of tailings containing more than 6% of P2O5 after phosphate ore dressing. In the present invention, cabosil, coke powder (coal slack powder) and kaolin powder are added into the phosphatic tailings to be uniformly mixed, added with water and aged; the materials are moulded by the production line of a vacuum extruder or a brick press; the materials are soaked with glaze after being dried and are placed into a kiln vehicle to enter a tunnel kiln; phosphorus steam and carbon monoxide are obtained after preheating and heating, the thick phosphoric acid is obtained by the suction of a hydrated tower, and a brick is used a load bearing brick product after being exchanged with heat and cooled. In the present invention, mine and ore dressing waste slag is used for preparing the acid and preparing the brick. The present invention is a three-waste utilization project. P2O5 in the ore is lager than or equal to 6%, and then, the ore can be used. The present situation that the ore of which the P2O5 content is smaller than or equal to 12% is considered to be not used in the past and is not used as storage capacity to be calculated is changed, and phosphatic waste slag becomes available resources.
Description
Technical field
The present invention relates to a kind of method for preparing phosphoric acid and building brick, particularly a kind of employing contains P
2O
5〉=6% flotation of phosphate rock mine tailing or low-grade phosphate ore are directly produced the method for high-concentration phosphoric acid and building brick.
Background technology
The industrialized preparing process of phosphoric acid mainly contains following several: (1) phosphoric acid by wet process: with the sulfuric acid decomposing phosphate rock phosphoric acid of getting made of stones, this method needs a large amount of high-quality Rock Phosphate (72Min BPL) and sulfuric acid, produces a large amount of phosphogypsum slags simultaneously.(2) thermal phosphoric acid: use producing yellow Phosphorus by electric oven, burning absorbs and produces phosphoric acid then, and this method needs a large amount of electric energy and middle higher-grade phosphorus ore lump ore.(3) new kiln method technology: do not see successful Application in this explained hereafter, but report is arranged in the patented method, as: the patent No. of Changsha mining and metallurgy institute is 93111447.0, name is called the patent of invention that a kind of direct reduction Rock Phosphate (72Min BPL) is produced the method for phosphoric acid, grade phosphorus mine stone during this method needs, the utilization ratio of phosphorus has only about 80%; The number of patent application of chemical fertilizer institute of the Ministry of Chemical Industry is 89100292.8, and name is called a kind of method of producing high-concentration phosphoric acid, grade phosphorus mine stone in also needing.
Summary of the invention
The purpose of this invention is to provide a kind of P that utilizes in the phosphorus ore selecting and purchasing process
2O
5〉=6% phosphorus-containing waste slag and mine tailing are raw material, produce high-concentration phosphoric acid and building brick, and the utilization ratio of its phosphorus surpasses 90%, and the mine tailing with behind the flotation of phosphate rock that the wherein warm fragment of brick of firing meets request of national standard is produced the method for phosphoric acid and byproduct building brick.
The object of the present invention is achieved like this: a kind of method of utilizing phosphorous mine tailing behind the flotation of phosphate rock to produce phosphoric acid and byproduct building brick is characterized in that: will phosphorous mine tailing, carbonaceous reducing agent and ground silica obtain compound after mixing, and the P of phosphorous mine tailing wherein
2O
5〉=6%, according to weight ratio be: mine tailing: ground silica=1: 0.6-2; Carbonaceous reducing agent is a coke, and coal or coal gangue are to contain fixation of C content add-on P
2O
5%: C%=1: 0.5-1; Add tackiness agent again and mix through old homogenizing, tackiness agent is selected kaolin or polyvinyl alcohol or methylcellulose gum for use, and its add-on is the 3-10% of compound gross weight, makes plasticity index 〉=6 of material; Vacuum-extruder is extruded or brick pressing machine is pressed into base substrate, soaks glaze 1-3 time again after the drying, sign indicating number go into tunnel kiln car in tunnel furnace through preheating, be warmed up to 1280 ℃-1450 ℃, make the carbonaceous reducing agent of material in the piece and phosphorus ore reaction generation phosphorous vapor P
4And carbon monoxide, make P toward the interior bubbling air of kiln
4Be oxidized to P with CO
2O
5And CO
2, containing P
2O
5High-temperature gas release after interchanger cooling, go into hydrated tower and with recycle acid absorb phosphoric acid, the fragment of brick after reaction finishes is the composition brick product behind cooling heat transferring.
The plug-in glaze slip of adobe after the oven dry is formed by one or more cooperations in kaolin, ground silica, coke, methylcellulose gum, the polyvinyl alcohol.The glaze slip weight ratio is: kaolin: ground silica: coke: methylcellulose gum or polyvinyl alcohol=30-50: 20-30: 20-30: 3-5.
The method of utilizing mine tailing behind the flotation of phosphate rock to produce phosphoric acid and byproduct building brick provided by the present invention is utilized mine and rejects relieving haperacidity, and brickmaking is utilization of three wastes project.P in the ore deposit
2O
5〉=6% can use, and has changed to think P in the past
2O
5≤ 12% just can not utilize, and not as the present situation of calculation of reserves, makes phosphorus-containing waste slag all become useful resources.
Can make full use of liberated heat in phosphorous vapor and the CO oxidizing reaction, reduce fuel consumption, guarantee to burn till the building block energy consumption and be not higher than sintering shale brick energy consumption, its quality standard also meets GB51010, GB13544, the requirement of GB13545.
The present invention can utilize carbon containing bastard coal masonry carbonaceous reducing agent, and it provides Al simultaneously
2O
3And SiO
2Composition.This all is a composition useful among the present invention.Volatile component in the coal gangue is then taken away in the section volatilization back of heating up, and can not enter in the phosphoric acid absorption process, has guaranteed that phosphoric acid quality reaches the GB2091 requirement, reduces the phosphoric acid cost for purification.
Except that fuel, the present invention is industrial residue or mine waste residue with raw material, and good society and economic benefit are arranged.
Embodiment
Principle of work of the present invention is as follows:
The present invention finishes the reduction of phosphorus ore and the oxidizing reaction of phosphorus with the tunnel furnace for principal reaction equipment, absorbs by the smoke absorption tower to make phosphoric acid.The reduction of phosphorus ore as reductive agent, adds ground silica with carbon raw materials such as coke or coal or coal gangues, and kaolin participates in reduction reaction, generates Calucium Silicate powder (CaOSiO
2), tricalcium aluminate (3CaOAl
2O
3), they are the main components that form brick intention.
React as follows:
4Ca
5(PO
4)
3F+50C+16SiO
2+Al
2O
3·2SiO
2→
17(CaO·SiO
2)+3CaO·Al
2O
3+SiF
4↑+50CO↑+3P
4↑
Phosphorous vapor and CO gas that reaction produces are supplied with quantitative O in kiln
2Make it to take place oxidizing reaction:
P
4+5O
2→2P
2O
5+ΔH
2CO+O
2→CO
2+ΔH
The oxidizing reaction liberated heat is used to keep temperature of reaction, can reduce firing rate, with save energy, reduces cost.
In order to prevent to expect carbon in the piece by premature oxidation, the present invention will expect piece dipping 1-3 layer glaze slip, and the atmosphere in the control kiln is weak oxide atmosphere.The glaze slip layer is by ground silica, kaolin, and the coke powder, methylcellulose gum, one or more cooperations in the polyvinyl alcohol etc. form.Can reduce the premature oxidation of coke in temperature-rise period, simultaneously weak oxide atmosphere helps the easy volatile material and overflows, and takes away when heating up 1220 ℃ of sections entering, and reduces the foreign matter content that enters the reduction section flue gas, improves phosphoric acid quality.
Technical process of the present invention is as follows: phosphorus mine tailing, ground silica, coke powder, kaolin, tackiness agent etc. are prepared burden in proportion, it is even to put into the old moisture string that makes in ageing storehouse behind the batch mixing, go into the drying kiln oven dry after using brick pressing machine (solid brick) or vacuum extruder (porous or hollow) moulding then, soak glaze 1-3 layer after the oven dry, tunnel furnace is gone in entrucking again.Pass through preheating, be warmed up to reduction and oxidizing reaction that 1400 ℃ of high temperature section are finished phosphorus, the reacted P that contains
2O
5Gas is in time derived through introducing the hydration tower after the interchanger heat exchange, with recycle acid absorb, cool off, filter finished product phosphoric acid.Receive the phosphoric acid purity height that day with fog is accepted, be directly used in and adjust the use of finished product acid concentration.Gas goes out to receive to reenter behind the day with fog puts into atmosphere after the fluorine recovery tower reclaims fluorine gas.Fragment of brick reaction finishes after the heat exchange cooling to draw off from the kiln tail and is building brick, and its quality meets the concerned countries standard-required.
Working process in the kiln of the present invention is as follows: soaks and shuts wicket after fragment of brick sign indicating number behind the glaze goes into to go into kiln on the kiln car, and all kiln cars parking stall of marching forward, the time in whole kiln is 〉=4 hours, wherein main reaction section time 〉=3 hour.In kiln, be warmed up to 1220 ℃ and cool to 1220 ℃ and set two zero-pressure forces.In preheating, the gas extraction that is warmed up in 1220 ℃ of temperature sections is used for drying kiln oven dry adobe; Gas at 1220 ℃ of-1450 ℃ of-1220 ℃ of temperature sections that heat up is to contain P
2O
5Gas, go into hydration tower system product after in time extracting heat exchange out; Being used for drying kiln oven dry adobe at 1220 ℃ of-60 ℃ of section gases of cooling with freezing air heat exchange extraction uses.In whole process, adopt the PLC automatic control technology, effectively control temperature, pressure, O in the kiln
2, CO, CO
2Concentration.Guarantee to react completely, reach energy saving purposes.
Example:
With Hubei Shennongjia mining company phosphorus milltailings, surrounding area, Yichang kaolin, coke powder, ground silica, chemical analysis sees attached list 1, and according to table 1 proportioning mixture as a result, ratio is a weight ratio: mine tailing: ground silica=1: 1, C%: P
2O
5%=0.5-1: 1. compound requires fineness 〉=120 orders; In compound, mix kaolin, methylcellulose gum, its add-on is the 3-10% of compound, and extrusion moulding requires plasticity 〉=6, and the plasticity requirement is not done in the die mould moulding.Compound put into earlier old back, ageing storehouse with vacuum-extruder (porous, hollow) or forming press (solid) be pressed into meet the building size requirement fragment of brick in 20M/1.9M * 1.5M drying kiln waste heat drying, kiln discharge moisture≤2%, moisture controlled is≤6% after soaking glaze 2 times, sign indicating number goes into to go on 1.5 * 1.5M kiln car 36.98M/1.9 * 1.5M tunnel furnace through preheating, be warmed up to 1400 ℃, material piece total time in kiln is 12 hours. its operational process is controlled automatically with the PLC programming. and residual P in the reacted fragment of brick
2O
5≤ 0.8%, its quality is up to state standards; Phosphoric acid meets the GB2091 standard-required.
The plug-in glaze slip of adobe among the present invention after the oven dry is formed by one or more cooperations in kaolin, ground silica, coke, methylcellulose gum or the polyvinyl alcohol.Concrete weight ratio is: kaolin: ground silica: coke: methylcellulose gum or polyvinyl alcohol=30-50: 20-30: 20-30: 3-5.
Subordinate list one: starting material chemical analysis
| Loss | CaO | MgO | P 2O 5 | SiO 2 | Fe 2O 3 | Al 2O 3 | C | |
| The phosphorus mine tailing | 7.30 | 31.03 | 3.44 | 10.12 | 21.92 | 1.78 | 1.05 | - |
| Coke | - | 4.68 | 3.12 | - | 43.21 | 5.11 | 27.02 | 72.50 |
| Kaolin | 13.66 | 0.22 | 0.81 | - | 43.26 | 2.32 | 35.37 | - |
| Silica | 1.30 | 0.06 | - | - | 94.77 | 1.12 | 3.26 | - |
Claims (3)
1. method of utilizing phosphorous mine tailing behind the flotation of phosphate rock to produce phosphoric acid and byproduct building brick is characterized in that: will phosphorous mine tailing, carbonaceous reducing agent and ground silica obtain compound after mixing, and the P of phosphorous mine tailing wherein
2O
5〉=6%, according to weight ratio be: mine tailing: ground silica=1: 0.6-2; Carbonaceous reducing agent is coke, coal or coal gangue, to contain fixation of C content add-on P
2O
5%: C%=1: 0.5-1; Adding tackiness agent again mixes through old homogenizing, tackiness agent is selected kaolin or polyvinyl alcohol or methylcellulose gum for use, its add-on is the 3-10% of compound gross weight, make plasticity index 〉=6 of material, vacuum-extruder is extruded or brick pressing machine is pressed into base substrate, soaks glaze 1-3 time again after the drying, the sign indicating number go into tunnel kiln car in tunnel furnace through preheating, be warmed up to 1280 ℃-1450 ℃, make carbonaceous reducing agent and phosphorus ore reaction in the material piece generate phosphorous vapor P
4And carbon monoxide, make P toward the interior bubbling air of kiln
4Be oxidized to P with CO
2O
5And CO
2, containing P
2O
5High-temperature gas release after interchanger cooling, go into hydrated tower and with recycle acid absorb phosphoric acid, the fragment of brick after reaction finishes is the composition brick product behind cooling heat transferring.
2. the method for utilizing phosphorous mine tailing behind the flotation of phosphate rock to produce phosphoric acid and byproduct building brick according to claim 1, it is characterized in that: the plug-in glaze slip of the adobe after the oven dry is formed by one or more cooperations in kaolin, ground silica, coke, methylcellulose gum or the polyvinyl alcohol.
3. the method for utilizing phosphorous mine tailing behind the flotation of phosphate rock to produce phosphoric acid and byproduct building brick according to claim 2, it is characterized in that: the glaze slip weight ratio is: kaolin: ground silica: coke: methylcellulose gum or polyvinyl alcohol=30-50: 20-30: 20-30: 3-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100187808A CN100390091C (en) | 2006-04-14 | 2006-04-14 | Method for preparing phosphoric acid and byproduct building brick by using phosphatic ore tailings after phosphate ore dressing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100187808A CN100390091C (en) | 2006-04-14 | 2006-04-14 | Method for preparing phosphoric acid and byproduct building brick by using phosphatic ore tailings after phosphate ore dressing |
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|---|---|
| CN1837129A CN1837129A (en) | 2006-09-27 |
| CN100390091C true CN100390091C (en) | 2008-05-28 |
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Families Citing this family (12)
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|---|---|---|---|---|
| US7910080B2 (en) | 2004-06-04 | 2011-03-22 | Jdcphosphate, Inc. | Phosphorous pentoxide producing methods |
| WO2008043222A1 (en) * | 2006-09-30 | 2008-04-17 | Hubei Sanxin Phosphoric Acid Co. Ltd | Method for directly producing phosphoric acid and several silicate or aluminate byproducts from phosphate ore raw materials |
| CN101125646B (en) * | 2007-09-26 | 2010-12-29 | 云南常青树化工有限公司 | Method for preparing high concentration phosphoric acid by directly reducing low and middle grade phosphorus ore |
| CN102219197B (en) * | 2010-04-14 | 2013-03-06 | 湖北三新磷酸有限公司 | Equipment for preparing phosphoric acid and refractory brick byproduct by using vertical phosphorus acid preparation brick kiln |
| US8734749B2 (en) | 2011-11-29 | 2014-05-27 | Jdcphosphate, Inc. | Phosphorous pentoxide producing methods and phosphate ore feed agglomerates |
| CN104211034B (en) * | 2013-06-04 | 2016-02-10 | 四川玖长科技有限公司 | Be applicable to preprocessing method of raw materials and the raw material pretreatment process system of kiln-process phosphoric acid technique |
| CN104230371B (en) * | 2014-08-15 | 2016-01-27 | 五河鼎顺新型建材有限公司 | A kind of with phosphorus mine tailing aerating hollow brick that is major ingredient and preparation method thereof |
| US9783419B2 (en) | 2014-09-26 | 2017-10-10 | Jdcphosphate, Inc. | Phosphorous pentoxide producing methods and systems with increased agglomerate compression strength |
| CN104291369A (en) * | 2014-09-28 | 2015-01-21 | 青岛康合伟业商贸有限公司 | Method for synthesizing magnesia-alumina spinel at low temperature |
| CN106517120B (en) * | 2016-09-22 | 2018-08-07 | 西南科技大学 | A kind of method of kiln legal system phosphoric acid coproduction aglite |
| US11858811B2 (en) | 2019-06-30 | 2024-01-02 | Novaphos Inc. | Phosphorus production methods and systems and methods for producing a reduction product |
| CN110606722B (en) * | 2019-09-30 | 2022-03-22 | 武汉工程大学 | Building wallboard and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044077A (en) * | 1989-01-14 | 1990-07-25 | 化学工业部化肥工业研究所 | Preparation of phosphorus by frunace |
| CN1096273A (en) * | 1993-06-11 | 1994-12-14 | 冶金工业部长沙矿冶研究院 | Method for producing phosphoric acid by directly reducing phosphate ore |
| CN1172766A (en) * | 1996-08-07 | 1998-02-11 | 熊心诚 | Blast furnace phosphorus preparation technology |
| US20030194559A1 (en) * | 2002-04-12 | 2003-10-16 | Ding Gen Ming | Composition for construction material and its method of making and using the same |
| WO2004106250A1 (en) * | 2003-06-02 | 2004-12-09 | Anton Francois De Jager | A composition for the preparation of a vitrified product |
-
2006
- 2006-04-14 CN CNB2006100187808A patent/CN100390091C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044077A (en) * | 1989-01-14 | 1990-07-25 | 化学工业部化肥工业研究所 | Preparation of phosphorus by frunace |
| CN1096273A (en) * | 1993-06-11 | 1994-12-14 | 冶金工业部长沙矿冶研究院 | Method for producing phosphoric acid by directly reducing phosphate ore |
| CN1172766A (en) * | 1996-08-07 | 1998-02-11 | 熊心诚 | Blast furnace phosphorus preparation technology |
| US20030194559A1 (en) * | 2002-04-12 | 2003-10-16 | Ding Gen Ming | Composition for construction material and its method of making and using the same |
| WO2004106250A1 (en) * | 2003-06-02 | 2004-12-09 | Anton Francois De Jager | A composition for the preparation of a vitrified product |
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| CN1837129A (en) | 2006-09-27 |
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