CN105197902B - Phosphorus ore containing potassium prepares the circulation clean production method of yellow phosphorus, sylvite, aluminium oxide, molecular sieve, slag cements and architectural shape - Google Patents
Phosphorus ore containing potassium prepares the circulation clean production method of yellow phosphorus, sylvite, aluminium oxide, molecular sieve, slag cements and architectural shape Download PDFInfo
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention relates to the circulation clean production method that a kind of phosphorus ore containing potassium prepares yellow phosphorus, sylvite, aluminium oxide, molecular sieve, slag cements and architectural shape.This method utilizes two lines, route one：Phosphorus ore containing potassium produces high-quality yellow phosphorus with nut coke electrothermal way.Yellow phosphorus water quenched slag, dissolution KAlO2, it is filtered, be passed through CO2, it is settled out Al (OH)3And the first filtrate is made.Al(OH)3Changed through temperature control and Al is made2O3.Route two：By feldspar in powder and Na2CO3It is uniformly mixed, water extraction is used after being calcined with yellow phosphoric tail gas, is passed through CO2It is settled out sial colloid and the second filtrate is made.First, second filtrate is crystallized, is dry, K is made2CO3And Na2CO3。Na2CO3Return route two recycles.Sial colloid and filtrate of the part without precipitation are via its K of adjustment2O、Na2O、SiO2、Al2O3Content, then carry out hydrothermal crystallizing reaction, so as to obtain molecular sieve；The sial colloid being settled out is mixed with yellow phosphorus furnace slag, for preparing slag cements and/or architectural shape.
Description
Technical field
The present invention relates to phosphorous chemical industry field, more particularly to a kind of phosphorus ore containing potassium prepare yellow phosphorus, sylvite, aluminium oxide, molecular sieve,
The circulation clean production method of slag cements and architectural shape.
Background technology
Phosphorus ore containing potassium is a kind of marine deposit phosphorus deposit containing potassium based on terrigenous clastic.Be mainly distributed on Hanyuan County, sichuan Province~
The ground such as Ganluo, Dianchi Lake, Yunnan Province periphery, Yichang.
Hanyuan County, sichuan Province formula phosphorus ore containing potassium, be mainly distributed in Hanyuan ten thousand, city's honor, bucket ditch, the new base aunt in Ganluo, Tian Ba, fiber crops
The areas such as nest ditch.The stratum of phosphorite containing potassium belongs to Bamboo Temple group lower part.The thickness of phosphoric rock series be 40~50 meters, by a set of shallow sea-
Littoral facies deposition rich shale, dolomite it is cementing phosphorous siltstone and clay rock composition, bottom accompany Tephra Deposits rock,
Clay rock and dolomitic lenticular body.Phosphoric rock series bottom is black, Dark grey shale or flour sand, packsand, rich in vanadium, uranium,
Organic matter and Authigenic pyrite, sometimes containing glauconite and phosphorite nodule；Lower part is shale, siltstone and phosphorous siltstone, burning into sand matter
Dolomite；Top is chiltern (predominantly potassium feldspar and quartz) phosphorite and phosphorous flour sand rock stratum；Top is medium bed shape feldspar
Quartzy packsand.The thickness change of phosphoric rock series is larger.Ore body is in stratiform, thickness 5.95~9.51m, P2O5Content for 11%~
23%, averagely containing 18.91%, K2O is 3%~7%.Dianchi Lake area phosphorus ore rock stratum containing potassium preservation is in the top plate on phosphorus ore upper strata or two
In interlayer between layer rock phosphate in powder.And the phosphorus ore containing potassium of Yichang also belongs to mid low grade phosphate rock.
For a long time, the comprehensive utilization of the phosphorus ore containing potassium is all being explored in the ground such as Sichuan, Yunnan, Hubei.Also once attempted to be used for Huang
Phosphorus produces.It is of poor benefits to wait series of problems not succeed but since reaction is complicated, efficiency is low, and stove ore deposit is unstable.Current phosphorus ore containing potassium
The research direction utilized is mainly phosphate fertilizer field.
Publication No. discloses a kind of phosphorus ore containing potassium for the Chinese patent of 104724686 A of CN and prepares yellow phosphorus coproduction potassium phosphate
The method of salt, this method are put into phosphorus ore containing potassium in the electric furnace of production yellow phosphorus, the K in phosphorus ore containing potassium2With furnace gas after O distillations
After the process processing such as effusion cools through circulated sprinkling system, spray-absorption, yellow phosphorus and phosphoric acid potassium salt product are finally obtained.Its
That utilize is the gas phase K escaped with furnace gas2O.Because of the K of its effusion2O limited amounts, Utilization prospects are restricted.
Potassium is the important element of crop growth, contains much contain potassium resource, but mostly shipwreck in the world
It is dissolubility or insoluble.China's potassium resource enriches, but soluble potassium resource is very poor.External soluble potassium resource is enough full
The demand of foot agricultural, therefore, the research that potash fertilizer is produced using the potassium resource of slightly water-soluble is less.China is from twentieth century sixties
From the beginning of beginning to the research using producing potassium fertilizer from potash feldspar, tens of kinds of technical studies are successively carried out, integrating to be divided into：Burn
Connection, high-temperature melting method, hydro-thermal method, blast furnace process method and low-temperature decomposition method.
Sintering process：Make raw material using lime stone and coal, by crushing, in shaft kiln calcination after balling-up, make oxidation therein
Potassium changes into water solubility, this kind of method production cost is low, but energy consumption is big in production process, and the potassium conversion ratio in potassium feldspar is relatively low
(60%~90%), makes its popularization hindered.
High-temperature melting method：The method is on the basis of calcium magnesium phosphate is produced, the potassium feldspar of supplying 25%~30%, high-temperature fusion
(1200~1300 DEG C) are made calcium and magnesium phosphorus potassium complex fertilizer, its product (P containing available phosphorus2O5) 10%~14%, soluble potassium (K2O)
4%~5%, this method production cost is low.
Hydro-thermal method：With KOH solution pressurized treatments potassium feldspar, it is K to make potassium feldspar component2O·Al2O3·SiO2·XH2The boiling of O
Stone class solid phase.Wherein K2O is soluble, can be absorbed by plants, and is not easily runed off, and is a kind of slow release fertilizer, meanwhile, part
SiO2Also become solubility, become the fertilizer of crops.
Blast furnace process method：When producing cement, by lime stone 81.4%~82%, potassium feldspar 14.2%~15.6%, iron ore
The ratio of stone 2.6%~3.2%, fluorite 1.1% and coke 3%, broken rear dispensing is mixed into stove, when temperature of the furnace hearth is up to 1500
DEG C make K2O volatilizees, and is taken out of with high temperature gas flow, while K2O and CO in stove2Effect, generates K2CO3Product, the clinker warp of blast furnace discharge
White cement is made after processing.This method is only limitted to cement plant or phosphate fertilizer plant, as byproduct production potash fertilizer.
Low-temperature decomposition method：Potassium feldspar raw material is crushed to below 6mm by jaw crusher, and mineral are crushed to by Raymond mill
Below 100 meshes, mineral are transported in pond by adhesive tape conveyor and soak 20min with CaO water, then squeeze into temperature-pressure stove through pump
In, temperature control is at 100~200 DEG C in stove.By after a certain period of time, exited into from stove in pond with Na2SO4Mixing immersion,
By techniques such as crystallization, separation of solid and liquid, K is obtained2SO4, the NaOH raw materials of industry.
Yellow phosphorus also known as white phosphorus, industrially prepare the phosphoric acid and phosphate of high-purity with yellow phosphorus.Utilize the inflammable generation of yellow phosphorus
Cigarette (P4O10) and mist (P4O10H is formed with vapor3PO4Deng mist), militarily it is commonly used to smoke shell processed, firebomb.Also
Red phosphorus (red phosphorus), phosphorous sesquisulfide (P can be manufactured with yellow phosphorus4S3), organophosphorus ester, firebomb, detergent, pesticide etc..
Domestic existing yellow phosphorus is mainly produced with electric furnace process, is existed with phosphorus ore, nut coke (semi-coke or anthracite) and silica by proportioning
Produced in electric furnace.Wherein, silica is mainly used for the phosphatic reaction of fluxing agent participation carbon reduction, key reaction SiO2With phosphorus ore
The CaO that stone decomposes generation generates meltable calcium metasilicate (CaSiO3).The hot legal system yellow phosphorus of electric furnace, high energy consumption is of high cost, added value
Low, product is single, seriously polluted.And phosphorus is important biological element, daily life and national economy necessary product.How to drop
Low energy consumption and cost, reduce pollution, improve tail gas, the comprehensive utilization ratio of clinker thermal energy, increase added value is Yellow Phosphorus Industry
The target try hard to gain.In addition, the metallurgy such as yellow phosphorus, calcium carbide, chemical industry tail gas, mostly directly to be arranged outside torch burning, the utilization of resources
Rate is low, and environmental issue protrudes.
The Chinese patent that publication No. is 103466576 A of CN discloses one kind phosphorus ore, potassium feldspar produces phosphoric acid coproduction alkali
The method of property fertilizer.This method comprises the following steps：Rock phosphate in powder, potassium feldspar and coke are subjected to dispensing, grinding, ball processed, blast furnace
Calcining obtains clinker and blast furnace gas, and the water-bath cooling that blast furnace gas first passes through recycles thick phosphorus and mud phosphorus, and the blast furnace gas after water-bath cooling is again
Mud phosphorus is recycled through dedusting；Water absorption phosphorus pentoxide gas prepares phosphoric acid after the thick oxidized burning of phosphorus and mud phosphorus；It is described
Clinker alkaline fertilizer is made through water quenching, drying, grinding.Coproduction alkalescence fertilizer while the technical solution realizes production phosphoric acid
Material, but it cannot produce high-quality yellow phosphorus, and the heat produced in production process is not made full use of, do not meet yellow phosphorus enterprise
Reduce energy consumption, improve tail gas, the demand of comprehensive utilization of slag rate.
The content of the invention
For the deficiency of the prior art, the present invention provides one kind phosphorus ore containing potassium to prepare yellow phosphorus, sylvite, aluminium oxide, molecule
The circulation clean production method of sieve, slag cements and architectural shape, it comprises the following steps：
Phosphorus ore containing potassium adds yellow phosphorus electric furnace with nut coke and contains P to react to be made2Furnace gas, furnace gas regather slightly after being washed
Phosphorus, refine so that high-quality yellow phosphorus is made；Yellow phosphorus furnace slag and dissolution KAlO are removed after water quenched slag leaching2, added after being filtered to it
The CO that yellow phosphoric tail gas boiler and sintering machine tail gas collecting, purifying are obtained2To be settled out Al (OH)3And the first filtrate is obtained, wherein,
Al(OH)3Changed through temperature control and Al is made2O3；
Feldspar in powder and Na2CO3Calcined, kept the temperature and cooled down with yellow phosphoric tail gas after being mixed by proportioning, sintered with water extraction
Material, then adds and collects obtained CO to sintering tail gas clean-up2, so as to isolate sial colloid and obtain the second filtrate；Will
First filtrate concentrates crystallization, drying with the second filtrate, so that K be made2CO3And Na2CO3, obtained Na2CO3Return and grown with potassium
The compounding process of mountain flour recycles；
Sial colloid of the part without precipitation and filtrate through hydrothermal crystallizing to prepare 13X molecular sieves or 4A type molecular sieves,
The sial colloid being settled out is stirred through batch mixing, dried with yellow phosphorus furnace slag, ball milling is so as to obtained slag cements；It is described to be settled out
Sial colloid carry out batch mixing stirring, foaming and pressed compact with the yellow phosphorus furnace slag after ball milling and be molded, so that architectural shape be made.
According to a preferred embodiment, the constituent mass ratio of the phosphorus ore containing potassium is P2O5∶CaO∶SiO2∶K2O (contains Na2O)=1
: (1.19~1.45): (0.42~0.52): (0.07~0.13), SiO in the phosphorus ore component containing potassium2With the ratio of CaO content
For 0.357~0.9, so that it is guaranteed that smoothly slagging tap.
According to a preferred embodiment, the phosphorus ore containing potassium is graininess, and particle diameter is 3~25mm, described
Nut coke further includes semi-coke fourth and anthracite fourth, and its particle diameter is 3~25mm.
According to a preferred embodiment, Al (OH)3For the heat source that temperature control is changed into yellow phosphoric tail gas, its inversion temperature is 400
DEG C~700 DEG C.
According to a preferred embodiment, the feldspar in powder and Na2CO3Proportioning be 1: (0.80~1.2), potassium feldspar
Powder is -200 mesh >=85%.
According to a preferred embodiment, calcining heat is 700 DEG C~1100 DEG C, and calcination time is 0.1~120min；Forge
For imitation frosted glass through 0~4h sealed thermal insulatings, it is 700 DEG C~1100 DEG C to keep temperature；
Cooling device used in cooling procedure is provided with heat recovery system, it is used to the heat of recycling returning to calcining
System circulation utilizes.
According to a preferred embodiment, the method for isolating sa colloid is：Add distillation water extraction, while be passed through Huang
The CO that phosphorus tail gas boiler and sintering machine tail gas collecting, purifying are obtained2, and 10min~40min is leached, then through precipitation, separation
Go out sial colloid and the second filtrate.
According to a preferred embodiment, the method for preparing 4A type molecular sieves is to use NaOH and Na3SiO3Adjust K2O、
Na2O、SiO2、Al2O3Content arrive：K2O+Na2O accounts for 13.9%, SiO2Account for 26.9%, Al2O322.9% is accounted for, remaining is water, so
Hydrothermal crystallizing reaction is carried out under conditions of 90~100 DEG C afterwards, hydrothermal crystallizing is filtered after reaction, filter cake distilled water
Washing to filtrate pH value is 9~10, and 4A type molecular sieves are obtained after it is dried；
The method for preparing 13X molecular sieves is：With NaOH and Na3SiO3Adjust K2O、Na2O、SiO2、Al2O3Content arrive：K2O
+Na2O accounts for 13.8%, SiO2Account for 37.4%, Al2O322.7% is accounted for, remaining is water, is then carried out under conditions of 90~100 DEG C
Hydrothermal crystallizing reacts, and hydrothermal crystallizing is filtered after reaction, and it is 9~10 that filter cake, which is washed with distilled water to filtrate pH value, right
It obtains 13X molecular sieves after being dried.
According to a preferred embodiment, the method for preparing slag cements is：Sial colloid and yellow phosphorus furnace slag are pressed 1: (5
~12) ratio mixes, and through drying, is milled to -200 mesh >=85% so as to obtained slag cements.
According to a preferred embodiment, the method for preparing architectural shape is：By yellow phosphorus furnace slag be milled to -100 mesh >=
After 65% batch mixing stirring is carried out with the sial colloid；
Be optionally added flyash, river sand to the sial colloid, and the yellow phosphorus furnace slag, flyash, river sand with
The mixed proportion of the sial colloid is (5~15): 1, foam through aerating foaming or not aerating, and pressed compact shaping, so as to be made each
Type architectural shape.
This method is also applied for phosphorus ore and potassium feldspar substitution phosphorus ore containing potassium or the Concentrate Pellet of phosphorus ore containing potassium.Potassium feldspar and phosphorus
Ore deposit, nut coke proportioning are：Potassium feldspar: phosphorus ore: nut coke=(1.57~2.5): (7.5~12): (1.45~2.1).The potassium feldspar,
Phosphorus ore and nut coke are graininess or powdery, wherein, particle diameter is 3~25mm.Powdery potassium feldspar includes potassium feldspar original powder and potassium
Feldspar concentrate powder.Powdery phosphorus ore includes：Phosphorus ore original powder, phosphorus concentrate powder and other processing ground phosphate rock.To ensure smoothly to slag tap, phosphorus ore
SiO in component2Content ratio with CaO is 0.357~0.9.When being such as less than aforesaid standards, SiO need to be supplemented2.Powdery coking coal bag
Include：Coking coal powder, semi-coke powder, anthracite powder.During using granular material, binding agent need to be added, at agitated, balling-up, drying and consolidation
Reason.
Potassium phosphorus ore and nut coke will be contained and be sent into the obtained yellow phosphorus of yellow phosphorus electric furnace reaction by proportioning, do not influence the normal production of yellow phosphorus.
Since phosphorus ore containing potassium is actually phosphorus ore and the product of the mutual association of potassium feldspar, its K2The main source of O is potassium feldspar, and potassium
Feldspar fusing point is 1150 ± 20 DEG C, it is consistent with phosphorus ore softening point.After potassium feldspar enters yellow phosphorus electric furnace with phosphorus ore and nut coke, in life
Bed of material potassium feldspar will not melt, and any reaction will not occur.
After phosphorus ore containing potassium enters half crucible zone (temperature is 1150 DEG C~1350 DEG C), potassium feldspar melts.At this moment, due to phosphorus ore
The reduction reaction occurred with carbon is limited, and without enough CaO as precipitation additive, it is anti-that thermal decomposition will not largely occur for potassium feldspar
Should.
It is rapid since phosphate reduces fierceness after potassium feldspar enters melting layer (temperature is 1350 DEG C~1400 DEG C),
Generate substantial amounts of CaO.At this moment substantial amounts of thermal decomposition also occurs under conditions of substantial amounts of CaO is as precipitation additive for potassium feldspar anti-
Should.Part is undecomposed complete potassium feldspar and CaO are when yellow phosphorus electric furnace molten slag layer just stay 2 to 3 is small, when it is with potassium feldspar decomposition
Between it is consistent with temperature.The final resolution ratio of potassium feldspar reaches more than 92%, generates KAlO2And Ca2SiO4。
Key reaction in yellow phosphorus electric furnace is：
Ca3(PO4)2+3SiO2+5C→3CaSiO3+P2↑+5CO↑
Ca3(PO4)2+5C→3CaO+P2↑+5CO↑
KAlSi3O8+6CaO→KAlO2+3Ca2SiO4
KAlO2Extremely stablize in yellow phosphorus electric furnace melting zone, only few part is with K2O gas phases are escaped with furnace gas.For ease of
Clinker is discharged, and slag acidity is controlled 0.8~0.9.Yellow phosphorus furnace slag is slagged tap into water quenching pool or water quenching tower, through solid-liquid point after water quenching
From heel row slag discharging.
Foregoing water quenching liquid is through precipitating, filter, then is passed through CO2So as to be settled out Al (OH)3.The crystallized drying of filtrate, is made
K2CO3And Na2CO3。K2CO3It can continue deep processing as food-grade and high-grade water-soluble level KH2PO4And K2SO4Deng sylvite.Al(OH)3
Changed through temperature control and Al is made2O3.The alternate embodiments thoroughly eliminate traditional potassium feldspar thermal decomposer, greatly reduce potassium
Feldspar thermally decomposes energy consumption and material consumption.Eliminate the additional silica needed for phosphorus production again at the same time, it is revolutionary to give birth to a set of yellow phosphorus
Production device has been modified to electrothermal way production yellow phosphorus and has thermally decomposed the integrated system of potassium feldspar.
The route two of the present invention overcomes the metallurgy such as yellow phosphorus, calcium carbide, chemical industry tail gas, mostly directly to be arranged outside torch burning,
The problem of resource utilization is low, and environmental pollution is serious.By feldspar in powder and Na2CO3It is fast with yellow phosphoric tail gas high temperature after being mixed by proportioning
Speed calcining, keeps the temperature 0~4h, with distillation water extraction, while is passed through CO2, isolate sial colloid and filtrate.
Potassium feldspar thermal decomposition key reaction be：
KAlSi3O8+3Na2CO3→KAlO2+3Na2SiO3+3CO2↑
2KAlO2+3H2O+CO2→2Al(OH)3+K2CO3
Na2SiO3With Al (OH)3For colloidal substance.
Filtrate and the sial colloid isolated are divided into four and utilize path afterwards.Path one：By route one and route two
The filtrate of preparation concentrates crystallization, dry, produces K2CO3And Na2CO3。Na2CO3Two compounding process of return route recycles, K2CO3
It can continue deep processing as food-grade and high-grade water-soluble level KH2PO4And K2SO4Deng sylvite.Path two：A part is without precipitation
Sial colloid and filtrate prepare 13X molecular sieves or 4A type molecular sieves through hydrothermal crystallizing.Path three：Precipitate the sial colloid isolated
Slag cements is prepared with yellow phosphorus furnace slag.Path four：Precipitate the sial colloid isolated and prepare architectural shape with yellow phosphorus furnace slag.
The invention has the advantages that：
1st, can be yellow phosphorus, sylvite, oxidation from single yellow phosphorus product up-gradation using the method for the present invention, yellow phosphorus enterprise
Multiple major products such as aluminium, molecular sieve, slag cements and architectural shape.Comprehensive production cost is greatly reduced, and cost saving effect is grand, has
Very prominent economic benefit and energy-saving effect, are one of important channels of yellow phosphorus enterprise technology and product diversification upgrading.
2nd, in by the use of the CaO that rock phosphate in powder decomposites under the action of carbon as the precipitation additive and yellow phosphorus electric furnace of potassium feldspar
The pyrolytic potassium feldspar of molten state, generates KAlO2.Realize making full use of for molten state yellow phosphorus furnace slag waste heat.
When the 3rd, preparing yellow phosphorus using feldspar in powder, ground phosphate rock (containing phosphorus concentrate), carbon dust, the pelletizing green-ball yellow phosphorus suppressed
Tail gas do heat source be dried with it is rapidly solidified, enrich the comprehensive Utilization Ways of yellow phosphoric tail gas.Additionally it is possible to utilize Huang
The metallurgy such as phosphorus, calcium carbide, chemical industry tail gas do heat source and carry out quick burning, improve resource utilization, while also more environmentally-friendly.
4th, the CO of the purified collection of exhaust gas caused by yellow phosphoric tail gas boiler, the dry, consolidation of pelletizing etc. is utilized2With KAlO2Instead
Should, it is settled out Al (OH)3, reached CO2The purpose of direct emission reduction.
5th, when using the concentrate powder of phosphorus ore containing potassium, the pelletizing green-ball suppressed with yellow phosphoric tail gas do heat source be dried with soon
Speed consolidation.Reach the comprehensive utilization of yellow phosphoric tail gas, reduce the energy consumption in production process.
6th, the present invention can produce K2CO3、KH2PO4And K2SO4Deng sylvite, be conducive to change the poor potassium situation in China, have wide
General market application range.
7th, potassium feldspar sintering process, high-temperature melting method, hydro-thermal method, blast furnace process method and low-temperature decomposition method of the invention and traditional
Prepare K2CO3Yellow phosphorus is prepared with electric furnace process to compare, can substantially reduce energy consumption, material consumption and production cost, improves product profit sky
Between, while reduce environmental pollution.A new utilization ways are have found for phosphorus ore containing potassium.
8th, the disposable consumed resource of the present invention is small, and energy consumption is low, greenhouse gases CO2Discharge capacity is small, and added value of product is high.Contain
Potassium phosphorus ore thermal decomposition filter residue utilization rate reaches 100%, and yellow phosphoric tail gas utilization rate reaches more than 92%, reaches national clean manufacturing mark
Standard, is that one of important channel of circulation clean manufacturing is realized in yellow phosphorus enterprise technology and product diversification upgrading.
Brief description of the drawings
Fig. 1 is the process flow chart of the present invention.
Embodiment
It is described in detail below in conjunction with the accompanying drawings.As shown in Figure 1, the route one in the present invention：Phosphorus ore containing potassium and nut coke are pressed
Proportioning, which is sent into yellow phosphorus electric furnace reaction and is made, contains P2Furnace gas.Furnace gas is washed through aeration tower, thick phosphorus is collected by phosphorus groove, is refined so as to obtained
High-quality yellow phosphorus.Yellow phosphorus water quenched slag, removes yellow phosphorus furnace slag, while dissolution KAlO2, then it is filtered, is added to tail
The CO that gas purification is collected2, it is settled out Al (OH)3。Al(OH)3Changed through temperature control and Al is made2O3, it is stand-by to leach filtrate.Al(OH)3Control
The heat source that temperature is changed is yellow phosphoric tail gas or other fuel, 400 DEG C~700 DEG C of inversion temperature.
Route two：By feldspar in powder and Na2CO3Yellow phosphoric tail gas high temperature quick burning is used after being mixed by proportioning, keeps the temperature 0~4h,
The thermal energy of cooling recycling returns to quick burning process.With water extraction sintering feed, the CO that the purification of quick burning machine is collected is added2, from
And sial colloid is isolated, leaching filtrate is stand-by.
Foregoing leaching filtrate and the sial colloid isolated are divided into four and utilize path, path one：By route one and road
Filtrate prepared by line two concentrates crystallization, dry, to produce K2CO3And Na2CO3。Na2CO3Two compounding process of return route circulation profit
With K2CO3It can continue deep processing as food-grade and high-grade water-soluble level KH2PO4And K2SO4Deng sylvite.Path two：A part without
The sial colloid (containing filtrate) of precipitation prepares 13X molecular sieves or 4A type molecular sieves through hydrothermal crystallizing.The precipitation of path three is isolated
Sial colloid and yellow phosphorus furnace slag prepare slag cements.Path four：The sial colloid isolated is precipitated to build with yellow phosphorus furnace slag preparation
Build section bar.
This method is also applied for phosphorus ore and potassium feldspar substitution phosphorus ore containing potassium or the Concentrate Pellet of phosphorus ore containing potassium.Potassium feldspar and phosphorus
Ore deposit, nut coke proportioning are：Potassium feldspar: phosphorus ore: nut coke=(1.57~2.5): (7.5~12): (1.45~2.1).The potassium feldspar,
Phosphorus ore and nut coke are graininess or powdery, wherein, particle diameter is 3~25mm.Powdery potassium feldspar includes potassium feldspar original powder and potassium
Feldspar concentrate powder.Powdery phosphorus ore includes：Phosphorus ore original powder, phosphorus concentrate powder and other processing ground phosphate rock, phosphorus ore require to include in principle
SiO2It is not less than 0.357 with the content ratio of CaO.As when being less than this standard, SiO can be supplemented2.Powdery coking coal includes：Coking coal powder,
Semi-coke powder, anthracite powder.When preparing yellow phosphorus using granular material, binding agent, agitated, balling-up, drying and consolidation process need to be added.
The CO of addition2Can be boiler, pelletizing it is dry, it is rapidly solidified etc. during the exhaust gas that produces through obtained by collection and purification
The CO arrived2Or the CO that other methods are collected2。CO2It is passed through leaching liquid and is settled out Al (OH)3, thereby realize CO2Direct emission reduction
And comprehensive utilization.
Binding agent is one or both of silicate, sepiolite and montmorillonite and two or more, additive amount for 1%~
15%.The method of foregoing globulation is：The granular material after mixture, homogenizing is suppressed with the ball press that pressure is 4~23MPa
Into the pelletizing of 5~35mm.
Drying and the method consolidated are：With 180 DEG C~400 DEG C, dried through 30~50min；With 500 DEG C~1000 DEG C, warp
10~30min Fast Sinterings.Dry and consolidation heat source is yellow phosphoric tail gas or other fuel, the pelletizing compression strength after consolidation >=
80Kg/cm2, tumbler index >=75%.
Feldspar in powder and Na2CO3Specifically referred to by proportioning mixing：Feldspar in powder and Na2CO3Quality parts ratio be 1:
(0.80~1.2).Feldspar in powder particle diameter is -200 mesh >=80%.
The present invention can be also used for calcium carbide tail gas, blast furnace tail gas, coking tail gas etc. to the method for comprehensive utilization of yellow phosphoric tail gas
Metallurgical, chemical industry tail gas.This addresses the problem the problem of directly to be arranged outside torch burning, resource utilization is low, and environmental pollution is serious.
Quick burning, the method for insulation are：Quick burning temperature is 700 DEG C~1100 DEG C, calcination time for 0.1~
120min.For calcining material through 0~4h sealed thermal insulatings, it is 700 DEG C~1100 DEG C to keep temperature.Cooling device in the present invention is provided with
Heat recovery system, utilizes for recycling heat and returning it into quick burning system circulation.
Described plus distillation water extraction, while it is passed through CO2, filtering to isolate sa colloid step is：Leaching time is
10min~40min.The CO being passed through2Can be the rapidly solidified CO for collecting, purifying2Or the purification CO that other approach obtain2。
The method for preparing 4A type molecular sieves is：With NaOH and Na3SiO3Adjust K2O、Na2O、SiO2、Al2O3Content arrive：
K2O+Na2O accounts for 13.9%, SiO2Account for 26.9%, Al2O322.9% is accounted for, remaining is water.Water is carried out under conditions of 90~100 DEG C
Thermal crystallisation reacts, and hydrothermal crystallizing is filtered after reaction.It is 9~10 that filter cake, which is washed with distilled water to filtrate pH value, to it
4A type molecular sieves are obtained after being dried.
The method for preparing 13X molecular sieves is：With NaOH and Na3SiO3Adjust K2O、Na2O、SiO2、Al2O3Content arrive：K2O
+Na2O accounts for 13.8%, SiO2Account for 37.4%, Al2O322.7% is accounted for, remaining is water.Hydro-thermal is carried out under conditions of 90~100 DEG C
Crystallization, hydrothermal crystallizing are filtered after reaction.Filter cake is washed with distilled water to filtrate pH value as 9~10, to its into
13X molecular sieves are obtained after row is dry.
Preparing slag cements step is：Yellow phosphorus furnace slag and sa colloid are mixed in 5~12: 1 ratio, through drying,
- 200 mesh >=85% are milled to, so as to obtain slag cements.
Preparing architectural shape step is：Yellow phosphorus furnace slag is milled to -100 mesh >=65%.Flyash, natural river sand can be mixed
And add up to 5~15: 1 ratio to be uniformly mixed with sa colloid in yellow phosphorus furnace slag, flyash, river sand, through aerating foaming or not
Aerating is foamed, and then needs pressed compact to be molded according to section bar type, so that various architectural shape be made.
Potassium carbonate coproduction molecular sieve, potassium carbonate coproduction slag cements and potassium carbonate coproduction constructure type can be manufactured separately in the present invention
Material.Also can prepare two or three wherein any.
Embodiment 1
Certain mining firm of phosphorus ore containing potassium provides yellow phosphorus electric furnace 5 for oneself, and capacity is 5 × 20000KVA.Its phosphorus ore containing potassium P2O5Content
For 17%, SiO2Content is 28%, CaO content 35%, CO2Content is 3.9%, K2O content is 5%, Na2O content is micro.
P is made after ore dressing2O5Content is 23%, SiO2Content is 12%, CaO content 32%, CO2Content is 3.9%, K2O content
For 2.9%, Na2The micro concentrate of phosphorus ore containing potassium of O content.
The method according to the invention, with the concentrate balling-up of phosphorus ore containing potassium, using yellow phosphoric tail gas drying, is consolidated into pelletizing and nut coke
Produce yellow phosphorus.Yellow phosphorus electric furnace proportioning is the Concentrate Pellet of phosphorus ore containing potassium: nut coke=1000: 145.Water quenched slag, removes clinker, filter
Liquid is stand-by.The potassium feldspar concentrate K selected with phosphorus ore containing potassium2O content is 14.5%, Na2O content for micro feldspar in powder with
Na2CO3By 1: 0.98 mixture, through 5s high temperature quick burnings, 830 DEG C of calcining heat, 800 DEG C of constant temperature 2h, through leaching, are passed through CO2,
It is settled out Al (OH)3And Na2SiO3Colloid.Leaching liquid mixed with yellow phosphorus furnace slag filtrate after through crystallization, be made K2CO3。Al(OH)3Through
Al is made in temperature control conversion2O3(powder).The Al (OH) filtered out3And Na2SiO3Colloid, is mixed in 1: 10 ratio with yellow phosphorus furnace slag, is dried
Slag cements is made in dry, ball milling.Sial colloid and filtrate of the part without precipitation are used to prepare 4A type molecular sieves.
Realize and produce 50000 t of yellow phosphorus, the Concentrate Pellet of phosphorus ore containing potassium 66,000,000 Nm of gas per year3, potassium feldspar calcining and decomposing utilizes yellow phosphorus
26,300,000 Nm of tail gas3, boiler 10,000,000 Nm of yellow phosphoric tail gas3.4.4 ten thousand t of potassium feldspar concentrate that year processing phosphorus ore containing potassium is selected, year
Produce K2CO32.3 ten thousand t, Al2O31.15 ten thousand t, 420,000 t of slag cements, 1.4 ten thousand t of 4A types molecular sieve.
With potassium feldspar-lime sintering route ratio, mark 1.6 ten thousand t of coal can be saved, 9.5 ten thousand t of lime is saved, saves additional silicon
Stone 7.9 ten thousand t, CO20.74 ten thousand t of direct emission reduction.Yellow phosphoric tail gas utilization rate more than 92%, clinker utilization rate 100%, reaches national clear
Clean production standard.
Embodiment 2
Certain factory's yellow phosphorus electric furnace 1, capacity are 1 × 20000KVA.
The method according to the invention, uses P2O5Content is 20.5%, SiO2Content is 22.2%, CaO content 33.0%,
K2O content is 1.89%, Na2O content is 0.44%, CO2The phosphorus ore containing potassium (15~25mm) that content is 4.0% contains with fixed carbon
The nut coke (3~25mm) of amount 80%, by proportioning phosphorus ore containing potassium: nut coke=1000: 131.5 add yellow phosphorus electric furnace.Water quenched slag,
Clinker is removed, filtrate is stand-by.The potassium feldspar concentrate K selected with phosphorus ore containing potassium2O content is 14.5%, Na2O content is micro potassium
Feldspar powder and Na2CO3By 1: 0.92 mixture, through 5 seconds high temperature quick burnings, 830 DEG C of calcining heat, 800 DEG C of constant temperature 2h, through leaching,
It is passed through CO2, it is settled out Al (OH)3And Na2SiO3Colloid.Leaching liquid mixed with yellow phosphorus furnace slag filtrate after through crystallization, be made K2CO3。
Al(OH)3Changed through temperature control and Al is made2O3(powder).The Al (OH) filtered out3And Na2SiO3Colloid, ratio and Yellow phosphorus furnace in 1: 10
Slag mixes, and slag cements is made in drying, ball milling.Sial colloid and filtrate of the part without precipitation are used to prepare 13X type molecules
Sieve.
10kt/a Yellow Phosphorus Plants can produce yellow phosphorus 10,000 t, K per year2CO30.57kt, Al2O30.27 ten thousand t, slag cements 10
30,000 t of ten thousand t, 13X molecular sieve.The K produced2CO3Can deep processing generate 1.1 ten thousand t KH2PO4。
With potassium feldspar-lime sintering route ratio, mark 0.51 ten thousand t of coal can be saved, 2.2 ten thousand t of lime is saved, saves additional silicon
Stone 1.8 ten thousand t, CO20.22 ten thousand t of direct emission reduction.Yellow phosphoric tail gas utilization rate more than 92%, clinker utilization rate 100%, reaches national clear
Clean production standard.
Embodiment 3
There is yellow phosphorus electric furnace 2 in certain company, and capacity is 2 × 20000KVA.
The method according to the invention, uses P2O5Content is 19.5%, SiO2Content is 22.2%, CaO content 33.0%,
K2O content is 2.2%, Na2O content is 0.10%, CO2The phosphorus ore containing potassium (15~25mm) that content is 4.0% and fixed carbon content
80% nut coke (3~25mm), by proportioning phosphorus ore containing potassium: nut coke=1000: 125.6 add yellow phosphorus electric furnace.Water quenched slag, is removed
Clinker is removed, filtrate is stand-by.The potassium feldspar concentrate K selected with phosphorus ore containing potassium2O content is 15%, Na2O content is 1% potassium feldspar
Powder and Na2CO3By 1: 0.92 mixture, through 5 seconds high temperature quick burnings, 830 DEG C of calcining heat, 800 DEG C of constant temperature 2h, through leaching, are passed through
CO2, it is settled out Al (OH)3And Na2SiO3Colloid.Leaching liquid mixed with yellow phosphorus furnace slag filtrate after through crystallization, be made K2CO3。Al
(OH)3Changed through temperature control and Al is made2O3(powder).The Al (OH) filtered out3And Na2SiO3Colloid, ratio and yellow phosphorus furnace slag in 1: 10
Slag cements is made in mixing, drying, ball milling.Sial colloid and filtrate of the part without precipitation are used to prepare 13X type molecular sieves.
The method according to the invention, 20,000 t/a Yellow Phosphorus Plants can produce yellow phosphorus 20,000 t, K per year2CO31.65 ten thousand t,
Al2O30.56 ten thousand t, 210,000 t of slag cements, 5.6 ten thousand t of 13X molecular sieves.The K produced2CO3Can deep processing generate 3.2 ten thousand t
KH2PO4。
With potassium feldspar-lime sintering route ratio, mark 1.07 ten thousand t of coal can be saved, saves 4.64 ten thousand t of lime, is saved additional
Silica 3.86 ten thousand t, CO20.53 ten thousand t of direct emission reduction.Yellow phosphoric tail gas utilization rate more than 92%, clinker utilization rate 100%, reaches state
Family's clean production standard.
Embodiment 4
Certain company's phosphorizing treatment possesses yellow phosphorus electric furnace 3, and capacity is respectively 35000KVA, 31500KVA and 12500KVA,
Total capacity is 79000KVA.Use P2O5Content is 29.05%, SiO2Content is 14.66%, CaO content 42.03%, CO2Contain
Measure and produce yellow phosphorus for 2.39% phosphorus concentrate pelletizing, additional silica and nut coke.Ton yellow phosphorus consumption of raw materials is phosphorus concentrate pelletizing
8.48t, nut coke 1.46t, additional silica 1.91t, power consumption 14215kwh.Year total dosage of phosphorus concentrate pelletizing be 300,000 t, production yellow phosphorus
35385t, 27.98 ten thousand t of by-product yellow phosphorus furnace slag.
The method according to the invention, uses K2O content is 13.0%, Na2O content be 2.0% potassium feldspar particle (3~
Additional silica 25mm) is replaced, with P2O5Content is 29.05%, SiO2Content is 14.66%, CaO content 42.03%, CO2Contain
Measure the phosphorus concentrate pelletizing for 2.39%, the nut coke (3~25mm) of fixed carbon content 80%.By proportioning phosphorus concentrate pelletizing: nut coke: potassium
Feldspar=1000: add yellow phosphorus electric furnace at 172: 214.Clinker removes clinker, filtrate is stand-by through water quenching.Use K2O content is
13.0%, Na2O content is 2.0% feldspar in powder and Na2CO3By 1: 1.069 mixture, through 5s high temperature quick burnings, calcining temperature
830 DEG C, 800 DEG C of constant temperature 2h of degree, through leaching, is passed through CO2, it is settled out Al (OH)3And Na2SiO3Colloid.Leaching liquid and yellow phosphorus furnace slag
Through crystallization after filtrate mixing, K is made2CO3And Na2CO3, Na2CO3Return to potassium feldspar calcining compounding process.Al(OH)3Turn through temperature control
Change obtained Al2O3(powder).The Al (OH) filtered out3And Na2SiO3Colloid, is mixed in 1: 10 ratio with yellow phosphorus furnace slag, drying, ball milling
Slag cements is made.Sial colloid and filtrate of the part without precipitation are used to prepare 13X molecular sieves.
Realize and produce yellow phosphorus 35007t, phosphorus concentrate pelletizing production 33,000,000 Nm of tail gas per year3, potassium feldspar calcining and decomposing utilizes yellow
27,920,000 Nm of phosphorus tail gas3, boiler 5,000,000 Nm of yellow phosphoric tail gas3.Year processing 110,000 t of potassium feldspar, produces K per year2CO31.76 ten thousand t,
Al2O30.89 ten thousand t, 280,000 t of slag cements, 13X molecular sieves 3.75 ten thousand t, obtained 2827t Na2CO3Make as dispensing circulation
With.
With potassium feldspar-lime sintering route ratio, mark 1.30 ten thousand t of coal is saved, 7.33 ten thousand t of lime is saved, saves additional silica
6.11 ten thousand t, CO2Direct emission reduction 5597t.Yellow phosphoric tail gas utilization rate more than 92%, clinker utilization rate 100%, reaches national cleaning
Production standard.
Embodiment 5
Certain phosphorous chemical industry enterprise group possesses yellow phosphorus electric furnace 8, and capacity is 8 × 20000KVA.Use P2O5Content is 30.0%,
SiO2Content is 16.5%, CaO content 43%, CO2The phosphorus ore, additional silica and nut coke that content is 3.5% produce yellow phosphorus.Ton
Yellow phosphorus consumption of raw materials is phosphorus ore 8.12t, nut coke 1.44t, additional silica 1.45t, power consumption 13373kwh.Year total dosage of phosphorus ore is
66.7 ten thousand t, produce 8.21 ten thousand t of yellow phosphorus, 580,000 t of by-product yellow phosphorus furnace slag.
The method according to the invention, uses K2O content is 15.0%, Na2O content is micro potassium feldspar particle (3~25mm)
Instead of additional silica, with P2O5Content is 30.0%, SiO2Content is 16.5%, CaO content 43%, CO2Content is 3.5%
Phosphorus ore (3~25mm), the nut coke (3~25mm) of fixed carbon content 80%, by proportioning phosphorus ore: nut coke: potassium feldspar=1000:
Add yellow phosphorus electric furnace at 183: 216.Clinker removes clinker, filtrate is stand-by through water quenching.Use K2O content is 15.0%, Na2O content is
Micro feldspar in powder and Na2CO3By 1: 1.011 mixture, through 5s high temperature quick burnings, 830 DEG C of calcining heat, 800 DEG C of constant temperature
2h, through leaching, is passed through CO2, it is settled out Al (OH)3And Na2SiO3Colloid.Leaching liquid mixed with yellow phosphorus furnace slag filtrate after through crystallization,
K is made2CO3, then neutralized with phosphoric acid and produce food-grade and high-grade water-soluble level potassium dihydrogen phosphate.Al(OH)3It is made through temperature control conversion
Al2O3(powder).The Al (OH) filtered out3And Na2SiO3Colloid, is mixed in 1: 10 ratio with yellow phosphorus furnace slag, and ore deposit is made in drying, ball milling
Slag cement.Sial colloid and filtrate of the part without precipitation are used to prepare 4A type molecular sieves.
Produce 8.04 ten thousand t of yellow phosphorus per year, 100,000,000 Nm of yellow phosphoric tail gas is used in power generation3, potassium feldspar calcining and decomposing utilizes yellow phosphoric tail gas 49,400,000
Nm3, boiler 10,000,000 Nm of yellow phosphoric tail gas3, year processing 22.67 ten thousand t of potassium feldspar, produces food-grade and high-grade water-soluble level per year
KH2PO47.88 ten thousand t, Al2O31.88 ten thousand t, 61.7 ten thousand t of slag cements, 4.7 ten thousand t of 4A types molecular sieve.
With potassium feldspar-lime sintering route ratio, mark 2.67 ten thousand t of coal is saved, 15.47 ten thousand t of lime is saved, saves additional silica
12.89 ten thousand t, CO21.27 ten thousand t of direct emission reduction.Yellow phosphoric tail gas utilization rate more than 92%, clinker utilization rate 100%, reaches national clear
Clean production standard.
Present invention is compared with existing potassium feldspar-lime sinter process, its energy-saving and CO2Emission reduction index is such as
Shown in table 1：
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Save mark coal (t) | 15975 | 5180 | 10665 | 13027 | 26661 |
| Save CaO (t) | 95217 | 22027 | 46372 | 73292 | 154691 |
| CO2Direct emission reduction (t) | 7376 | 2223 | 5271 | 5597 | 12734 |
| Save additional silica (t) | 79315 | 18348 | 38628 | 61035 | 128858 |
It should be noted that above-mentioned specific embodiment is exemplary, those skilled in the art can disclose in the present invention
Various solutions are found out under the inspiration of content, and these solutions also belong to disclosure of the invention scope and fall into this hair
Within bright protection domain.It will be understood by those skilled in the art that description of the invention and its attached drawing are illustrative and are not
Form limitations on claims.Protection scope of the present invention is limited by claim and its equivalent.
Claims (7)
1. a kind of phosphorus ore containing potassium prepares the circulation cleaning life of yellow phosphorus, sylvite, aluminium oxide, molecular sieve, slag cements and architectural shape
Production method, it is characterised in that comprise the following steps：
Potassium phosphorus ore will be contained and contain P with nut coke addition yellow phosphorus electric furnace to react to be made2Furnace gas, the constituent mass ratio of the phosphorus ore containing potassium is P2O5：
CaO：SiO2：(K2O+Na2O)=1：(1.19~1.45)：(0.42~0.52)：(0.07~0.13)；When phosphorus ore containing potassium enters half
After crucible zone, potassium feldspar melts；After potassium feldspar enters melting layer, reaction generation KAlO2And Ca2SiO4；Furnace gas washed after again
Collect thick phosphorus, is refined with obtained high-quality yellow phosphorus；Yellow phosphorus furnace slag and dissolution KAlO are removed after water quenched slag leaching2, it is filtered
The CO that yellow phosphoric tail gas boiler and sintering machine tail gas collecting, purifying are obtained is added afterwards2To be settled out Al (OH)3And obtain the first filter
Liquid, wherein, Al (OH)3Changed through temperature control and Al is made2O3；
By feldspar in powder and Na2CO3Calcined, kept the temperature and cooled down with yellow phosphoric tail gas after being mixed by proportioning, sintered with water extraction
Material, then adds and collects obtained CO to sintering tail gas clean-up2, so as to be settled out sial colloid and obtain the second filtrate；Will
First filtrate concentrates crystallization, drying with the second filtrate, so that K be made2CO3And Na2CO3, obtained Na2CO3Return and grown with potassium
The compounding process of mountain flour recycles；
Sial colloid and filtrate of the part without precipitation are via its K of adjustment2O、Na2O、SiO2、Al2O3Content, then carry out
Hydrothermal crystallizing reacts, so as to obtain molecular sieve；The sial colloid being settled out is mixed with yellow phosphorus furnace slag, for preparing slag
Cement and/or architectural shape.
2. the method as described in claim 1, it is characterised in that Al (OH)3Into yellow phosphoric tail gas, it is changed the heat source that temperature control is changed
Temperature is 400 DEG C~700 DEG C.
3. the method as described in claim 1, it is characterised in that the feldspar in powder and Na2CO3Proportioning be 1：(0.80~
1.2), feldspar in powder is -200 mesh >=85%.
4. the method as described in claim 1, it is characterised in that calcining heat is 700 DEG C~1100 DEG C, calcination time 0.1
~120min；For calcining material through 0~4h sealed thermal insulatings, it is 700 DEG C~1100 DEG C to keep temperature；
Cooling device used in cooling procedure is provided with heat recovery system, it is used to the heat of recycling returning to calcination system
Recycle.
5. the method as described in claim 1, it is characterised in that the method for isolating sa colloid is：Add distillation water extraction,
It is passed through the CO that yellow phosphoric tail gas boiler and sintering machine tail gas collecting, purifying are obtained at the same time2, and 10min~40min is leached, Ran Houjing
Precipitation, isolates sial colloid and the second filtrate.
6. the method as described in one of claim 1 to 5, it is characterised in that the method for preparing 4A type molecular sieves is：With NaOH and
Na3SiO3Adjust K2O、Na2O、SiO2、Al2O3Content arrive：K2O+Na2O mass ratioes account for 13.9%, SiO2Mass ratio accounts for
26.9%, Al2O3Mass ratio accounts for 22.9%, remaining is water, and hydrothermal crystallizing reaction, water are then carried out under conditions of 90~100 DEG C
Thermal crystallisation is filtered after reaction, and it is 9~10 that filter cake, which is washed with distilled water to filtrate pH value, is obtained after it is dried
4A type molecular sieves；
The method for preparing 13X molecular sieves is：With NaOH and Na3SiO3Adjust K2O、Na2O、SiO2、Al2O3Content arrive：K2O+
Na2O mass ratioes account for 13.8%, SiO2Mass ratio accounts for 37.4%, Al2O3Mass ratio accounts for 22.7%, remaining is water, then 90~
Hydrothermal crystallizing reaction is carried out under conditions of 100 DEG C, hydrothermal crystallizing is filtered after reaction, and filter cake is washed with distilled water to filter
Liquid pH value is 9~10, and 13X molecular sieves are obtained after it is dried.
7. the method as described in one of claim 1 to 5, it is characterised in that the method for preparing slag cements is：By sial colloid
1 is pressed with yellow phosphorus furnace slag：The ratio of (5~12) mixes, and through drying, is milled to -200 mesh >=85% so as to obtained slag cements.
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|---|---|---|---|---|
| CN102531710A (en) * | 2010-12-08 | 2012-07-04 | 中国科学院过程工程研究所 | Method for producing potassium fertilizer and aluminum oxide by comprehensively using potassium feldspar |
| CN102557050A (en) * | 2011-12-20 | 2012-07-11 | 昆明冶金研究院 | New process for comprehensively utilizing potassium feldspar |
| CN103466576A (en) * | 2013-09-16 | 2013-12-25 | 山东金正大生态工程股份有限公司 | Method for production of phosphoric acid and coproduction of alkaline fertilizer from phosphate ore and potash feldspar |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531710A (en) * | 2010-12-08 | 2012-07-04 | 中国科学院过程工程研究所 | Method for producing potassium fertilizer and aluminum oxide by comprehensively using potassium feldspar |
| CN102557050A (en) * | 2011-12-20 | 2012-07-11 | 昆明冶金研究院 | New process for comprehensively utilizing potassium feldspar |
| CN103466576A (en) * | 2013-09-16 | 2013-12-25 | 山东金正大生态工程股份有限公司 | Method for production of phosphoric acid and coproduction of alkaline fertilizer from phosphate ore and potash feldspar |
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