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CN1837129A - 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 PDF

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Publication number
CN1837129A
CN1837129A CNA2006100187808A CN200610018780A CN1837129A CN 1837129 A CN1837129 A CN 1837129A CN A2006100187808 A CNA2006100187808 A CN A2006100187808A CN 200610018780 A CN200610018780 A CN 200610018780A CN 1837129 A CN1837129 A CN 1837129A
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CN
China
Prior art keywords
phosphoric acid
brick
mine tailing
byproduct
building brick
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Application number
CNA2006100187808A
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Chinese (zh)
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CN100390091C (en
Inventor
张定斌
汤才洲
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HUBEI SANXIN PHOSPHORIC ACID CO Ltd
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HUBEI SANXIN PHOSPHORIC ACID CO Ltd
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Priority to CNB2006100187808A priority Critical patent/CN100390091C/en
Publication of CN1837129A publication Critical patent/CN1837129A/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

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  • Compositions Of Oxide Ceramics (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention discloses a preparing phosphoric acid and by-product building brick method by debris with phosphor after phosphorus ore dressing ore, which comprises the following steps: adding in dinas rock powder, coking carbon powder (coal gangue powder), caoline to mix up; adding in water; ageing the mixture; modeling by vacuum extrusion machine or brick press; dipping after drying; putting mixture in kiln vehicle and entering tunnel oven; getting phosphor vapour and carbon monoxide after preheating and heating-up; getting concentrated phosphoric acid through hydrated tower; getting carrying brick production through heat transferring and cooling. The invention uses the mine and ore dressing fag-end to prepar acid and brick. We can use the ore when the P2O5 is not smaller than 6%.

Description

Utilize phosphorous mine tailing behind the flotation of phosphate rock to produce the method for phosphoric acid and byproduct building brick
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, it is characterized in that: with phosphorous mine tailing and carbonaceous reducing agent, ground silica mixes the back adding and obtains compound, adding bonding agent again mixes through old homogenizing, vacuum-extruder is extruded or brick pressing machine is pressed into base substrate, soak 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 coke 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.
The P of phosphorous mine tailing 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.
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.
The plug-in glaze slip of adobe after the oven dry is by kaolin, ground silica, and coke, methylcellulose gum, one or more cooperations in the polyvinyl alcohol form.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, the phosphorus-containing waste slag that makes all becomes 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:
Phosphorous vapor and CO gas that reaction produces are supplied with quantitative O in kiln 2Make it to take place oxidizing reaction:
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, and to draw off from the kiln tail through heat exchange cooling back be building brick both, 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 by kaolin, ground silica, and coke, one or more cooperations in methylcellulose gum or the polyvinyl alcohol form.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 P2O5 SiO2 Fe2O3 Al2O3 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 (5)

1, a kind of method of utilizing phosphorous mine tailing behind the flotation of phosphate rock to produce phosphoric acid and byproduct building brick, it is characterized in that: with phosphorous mine tailing and carbonaceous reducing agent, ground silica mixes the back adding and obtains compound, adding bonding agent again mixes through old homogenizing, 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 coke 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 is characterized in that: the P of phosphorous mine tailing 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.
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 1, it is characterized in that: tackiness agent is selected kaolin or polyvinyl alcohol or methylcellulose gum for use, its add-on is the 3-10% of compound gross weight, makes plasticity index 〉=6 of material.
4, 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 by kaolin, ground silica, coke, one or more cooperations in methylcellulose gum or the polyvinyl alcohol form.
5, according to claim 1 or the 4 described methods of utilizing phosphorous mine tailing behind the flotation of phosphate rock to produce phosphoric acid and byproduct building brick, 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.
CNB2006100187808A 2006-04-14 2006-04-14 Method for preparing phosphoric acid and byproduct building brick by using phosphatic ore tailings after phosphate ore dressing Expired - Fee Related CN100390091C (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US7910080B2 (en) 2004-06-04 2011-03-22 Jdcphosphate, Inc. Phosphorous pentoxide producing methods
CN102219197A (en) * 2010-04-14 2011-10-19 湖北三新磷酸有限公司 Method and 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
CN104211034A (en) * 2013-06-04 2014-12-17 四川玖长科技有限公司 Raw material pretreatment method and raw material pretreatment process system suitable for kiln method phosphoric acid technology
CN104230371A (en) * 2014-08-15 2014-12-24 五河鼎顺新型建材有限公司 Hollow aerated brick taking phosphate tailing as main ingredient and preparation method of hollow aerated brick
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
US9783419B2 (en) 2014-09-26 2017-10-10 Jdcphosphate, Inc. Phosphorous pentoxide producing methods and systems with increased agglomerate compression strength
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
CN110606722A (en) * 2019-09-30 2019-12-24 武汉工程大学 A kind of building wall board and preparation method thereof
US11858811B2 (en) 2019-06-30 2024-01-02 Novaphos Inc. Phosphorus production methods and systems and methods for producing a reduction product

Family Cites Families (5)

* Cited by examiner, † Cited by third party
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CN1023862C (en) * 1989-01-14 1994-02-23 化学工业部化肥工业研究所 Method for preparing high-concentration phosphoric acid
CN1040199C (en) * 1993-06-11 1998-10-14 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
US7052542B2 (en) * 2002-04-12 2006-05-30 American As Recycle Technique Co., Ltd. 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

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN102219197A (en) * 2010-04-14 2011-10-19 湖北三新磷酸有限公司 Method and equipment for preparing phosphoric acid and refractory brick byproduct by using vertical phosphorus acid preparation brick kiln
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
US10744512B2 (en) 2013-06-04 2020-08-18 Sichuan Ko Chang Technology Co., Ltd. Raw material pre-treatment method and raw material pre-treatment process system suitable for kiln phosphoric acid process
CN104211034A (en) * 2013-06-04 2014-12-17 四川玖长科技有限公司 Raw material pretreatment method and raw material pretreatment process system suitable for kiln method phosphoric acid technology
CN104230371A (en) * 2014-08-15 2014-12-24 五河鼎顺新型建材有限公司 Hollow aerated brick taking phosphate tailing as main ingredient and preparation method of hollow aerated brick
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
CN110606722A (en) * 2019-09-30 2019-12-24 武汉工程大学 A kind of building wall board and preparation method thereof
CN110606722B (en) * 2019-09-30 2022-03-22 武汉工程大学 A kind of building wall panel and preparation method thereof

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