CN108147441A - Utilize the new process of potash feldspar ore production potassium carbonate, sodium carbonate and aluminium oxide - Google Patents
Utilize the new process of potash feldspar ore production potassium carbonate, sodium carbonate and aluminium oxide Download PDFInfo
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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Abstract
Using the new process of potash feldspar ore production potassium carbonate, sodium carbonate and aluminium oxide, it is sintered using pre-desiliconizing soda lime and dissolves out aluminium, potassium and sodium resource that carbon divides in the method synthetical recovery potash feldspar ore for carrying aluminum evaporation Crystallization Separation potassium, sodium.This technique has the following advantages：Technical solution is reasonable, produces active calcium silicate, white carbon, sodium carbonate, potassium carbonate and aluminium oxide.The CO2 gases that this technique carbonization decomposable process is generated using sintering, cost of material is extremely low, reduces greenhouse gas emission.Because pre-desiliconizing raw material amount reduces about 35% during sintering, the silico-calcium quantity of slag few 30% or so；Desiliconization slag carries out raw-meal ingredient without additional soda ash；The wash water of detergent active calcium silicates can be used for the washing of desiliconization slag, reduce process water consumption and wastewater flow rate；The product form of abundant silicon, output added value high white carbon and active calcium silicate；It is regenerated by the causticization of sodium carbonate, realizes alkali self-sufficiency and the cyclic balance of entire technique.
Description
Technical field
The present invention relates to non-ferrous metallurgy technology field more particularly to a kind of utilization potash feldspar ore production potassium carbonate, carbon
The new process of sour sodium and aluminium oxide.
Background technology
China's water-soluble potassium resource is extremely poor, and the main place of production is Qinghai.The water-insoluble potassium resource in China is very much, especially
Its potash feldspar ore reserves is extremely abundant, is mainly distributed on Yunnan, Guizhou, Sichuan, Hunan, Hubei, Henan, Anhui, Jiangxi, Shandong
With the l9 provinces and regions such as Xinjiang, Heilungkiang, Shanxi, Shaanxi, Guangdong, Zhejiang, Hebei, the Inner Mongol, nearly 10,000,000,000 tons of total amount, oneself surveys at present
The potassium feldspar mineral resources with extraction value is leant out up to more than 40.Wherein l9 have reserves report, and reserves amount to up to more than 78.66
It hundred million tons, is calculated with potassium oxide average grade 10.21%, potassium oxide reserves are up to more than 8.03 hundred million tons.
The research that sylvite is produced using potassium feldspar starts from the beginning of this century, and Neuman B.Z have done potassium feldspar thermal decomposition preliminary
Research, hereafter, many scholars do a lot of work in succession.Before nineteen seventies, the optimization of process conditions is focused on
With the selection of auxiliary agent in thermal decomposition method, such as：Tomula S., Sanda Iupan, Dasgupta A. and Dyson Peter et al.
Successively have studied the process conditions for thermally decomposing potassium feldspar for auxiliary agent with CaO (or CaCO3) and CaCl2 (or MgCl2)：NagiS.、
E.Saxena, D.Datar and Venkatesham Y. utilize CaO or CaCO3 pyrolytic potassium feldspars；1956, E.Saxena
With M.Y.Bakr et al. by the use of gypsum and CaO (or CaCO3) as auxiliary agent, thermal decomposition potassium feldspar generates K2SO4.But various sides
Method is not that temperature is excessively high, energy consumption is big, is exactly that process route is miscellaneous, and equipment requirement is also excessively high, because without industrial value,
So technology is difficult to promote.After nineteen seventies, the external research report that sylvite is produced about the potassium length right side is less.I
State has begun to extracting potassium from potash feldspar research from nineteen fifties, in chemical fertilizer, ceramics, White Carbon black and molecular sieve etc.
Achieve many achievements.Both at home and abroad to successively having carried out kinds of processes research using Potassic Fertilizer Production from Potash Feldspar, integrating can be divided into：
Blast furnace process method, autoclave method open wide leaching and closing constant temperature method, thermal decomposition water seaoning, acid decomposition, sintering process, low-temperature decomposition
Method etc..
(1) blast furnace process method
Potassium feldspar, lime stone, from marble, fluorite and coke etc., after crusher in crushing, dispensing enters stove in proportion.Burner hearth
Temperature is up to 1500 DEG C, and the CO2 effects in the K2O and stove evaporated generate K2CO3.Existing for vapor and a large amount of CO2
In the case of, the K2CO3 of generation is partially converted into KHCO3.The slag of blast furnace discharge, through water quenching post-processing into white cement.This method exists
Wenxi, southwestern Shansi county potash fertilizer plant is successful, is the first of China's comprehensive utilization.But by 1987, which was forced calcium and magnesium phosphorus of changing the line of production
Fertilizer, utilizing for potassium feldspar are interrupted, and main cause is as follows：
1. basicity is excessively high.Excessively high basicity (>1.1) it is unnecessary to reduction reaction, the fusing point liter of furnace charge can be made instead
Height, viscosity increase, is unfavorable for the diffusion of reduction reaction.
2. furnace charge fluctuation is big.In operation of blast furnace, furnace charge fluctuation is big, causes in stove and scabs, blast wandering, thus must
Must higher furnace temperature could maintain, so reducing the economic benefit of production.
3. slagging overfrequency.Slagging interval is only 15~30 minutes to Wenxi County's potash fertilizer plant small furnace twice, is dropped in burner hearth
Potassium feldspar do not obtain fully restore be released, reduce reduction rate.
Since the method energy consumption is excessively high (temperature of the furnace hearth is up to 1500 DEG C or so), the reduction rate of potassium is relatively low (70% or so), raw
The white cement index of output is undesirable (whiteness is inadequate, intensity is difficult to improve), thus economic benefit does not increase, and is forced calcium and magnesium of changing the line of production
Phosphate fertilizer.
(2) autoclave method
The various leaching agents such as method CaCl2, Ca (OH) 2, CaO+NaCl, CaO+CaCl2 200~500 DEG C, 0.3~
Decomposing of potassium feldspar prepares sylvite under 6.1Mpa.Nineteen fifty, Jumei Yamasa 2 autoclave method decomposing of potassium feldspar of Ca (OH).1968
Year, under 110~230 DEG C, 2.0Mpa, with KOH decomposition 1~6h of potassium feldspar, soluble potassium salt is made in Edward.It is 1994, blue
Meter perfume (or spice) et al. also studied a variety of leaching agents such as Ca (OH) 2 decomposing of potassium feldspar under 150~300 DEG C, 4.05MPa, it is believed that Ca
(OH) 2 pairs of orthoclases and microcline have apparent extraction rate.The method is since pressure is too high, and investment of production is big, thus skill so far
Art is difficult to industrialize.
(3) leaching and closing constant temperature method are opened wide
Katherine S Riggs etc. have studied two kinds of potassium being fully ground using leaching and closing constant temperature technique is opened wide
Dissolubility of the feldspar (KFR) in four kinds of local acid soils.In unlimited leaching system, by 3：1 ratio by 166g each
Soil is crossed sand with pickling and is mixed respectively, is subsequently poured into 20cm depths, and internal diameter is in the cylinder of 3.75cm；0 and 600mg is pressed respectively
(K) ratio of/kg mixes the soil/sand of potassium feldspar and potassium chloride respectively with surface layer (referring to ground between subsurface 5cm) 5cm.
Soil column is leached 49 days with distilled water by the flow velocity of 14mL/h.After leaching, soil is placed 5 days to discharge extra water
Amount.In constant-temperature enclosed system, by MKFR (potassium feldspar comes from Malawi) and SLKFR (potassium feldspar comes from Sri Lanka) respectively
It adds in Malawi and Sri Lanka soil；It is being added to respectively by the ratio of 0,200mg (K)/kg, 600mg (K)/kg simultaneously
In 80g soil, laboratory sample constant temperature 49 days at 90% soil moisture and 25 DEG C.
By contrast experiment, in unlimited leaching system and closing constant temperature system, potassium nutrition all increases in soil, potassium feldspar
Solubility be significantly increased；Anne Kjersti Bakken and J.G.Wang et al. also have similar document report.Method master
To achieve the purpose that crop yield using slowly available potassium, which makees fertilizer without three industrial wastes, but since the method utilizes potassium feldspar
Period it is very very long, and the utilization rate of potassium feldspar is not also high, and to be industrialized also needs one section of extremely very long distance.
(4) water seaoning is thermally decomposed
Using potassium feldspar the water-soluble sylvite of pyrolysis generation can occur at 600-1200 DEG C with auxiliary agent for the method, then
Sylvite is detached by water extraction.Usual auxiliaries have fluoride, CaO or CaCO3 or CaCO3 and CaSO4.1954,
Sanda Lupan make auxiliary agent using CaCl2 and CaCO3, and at 800~850 DEG C, 2.5h, yield 85% are reacted with potassium feldspar.
1975, A.Dasgupta utilized the method, is decomposed at 900 DEG C, and product is in HNO3 and obtained compound fertilizer.In addition, it can incite somebody to action
Potassium feldspar is mixed with excessive salt with coal dust, is added water balling-up, is calcined at 900~950 DEG C, the KCl generated with water extraction.
1979, M.Y.Bakr using CaCO3 and CaSO4 1000 DEG C similarly hereinafter potassium feldspar react 5h, obtained water-soluble potassium
Salt and aluminium salt.Work as potassium feldspar：CaSO4·2H20：CaCO3=1：2：When 2 (mass ratio), maximum resolution ratio 80%.In recent years, Qiu
Dragon meeting and Wang Lisheng et al. have carried out a large amount of research to the method.They using potassium feldspar and apatites mixed ore deposit (K2O7.5%,
P2O510.25%), ardealite (main K-feldspar, quartz and dihydrate gypsum) is first removed into moisture content with wet underwater welding phosphoric acid
Afterwards, it adds in CaC03 and adds in a small amount of additive, 2-3h is thermally decomposed at 900-950 DEG C, with water extraction sylvite (K2SO4), potassium
Resolution ratio reaches 90-93%.Through analysis, residue composition is close with clinker, using the method, can be used directly using cement is made
Ardealite largely discarded particularly when phosphorus ore is with potassium feldspar symbiosis, further produces potash fertilizer as raw material in phosphoric acid industry,
Reach Optimizing Flow, reduce three wastes discharge amount, comprehensively utilize the purpose of resource.But from the point of view of comprehensive utilization, there is no fully profits
With resource, leaching slag is only utilized cement processed, has walked traditional Potassic Fertilizer Production from Potash Feldspar and the old road using residue, and flow relates to
And it is wide, development difficulty is increased, energy consumption is also the largest weakness, sad economic pass.
(5) acid decomposition
With fluorine-containing aqueous acid decomposing of potassium feldspar, water-soluble sylvite is generated.Yang Bo is decomposed with mixture of sulfuric phosphoric acid in phosphorus potassium ore deposit
Potassium feldspar, resolution ratio is up to 50% or so；Jiangxi Huang carrys out method and also reports, and ore deposit is mixed with sulfuric acid decomposition potassium feldspar rock phosphate in powder and fluorite, with
In ammonium hydrogen carbonate and free acid, One-step production NITROGEN IN LOW CONCENTRATION phosphorus potassium complex fertilizer.Acid decomposition can save energy consumption, can be at low temperature
Decomposing of potassium feldspar, but potassium resolution ratio is low, and the method can cause environmental pollution and equipment heavy corrosion, and technology is difficult to promote.
(6) sintering process
Sintering process is mainly calcined using compound additive and potassium feldspar, reduces reaction temperature.Han Xiaozhao, Yan Fulin et al. are done
Many research work.Han Xiaozhao etc. carries potassium feldspar using the different auxiliary agents such as (NH4) 2SO4, H2SO4, NaCl, LH
Potassium research show that LH is best auxiliary agent, and system research and optimizes the process conditions that the auxiliary agent carries potassium, obtains mass ratio (LH：
K [AlSi3O8]) it is 0.809：During l, 30min is roasted at 800 DEG C or so, Potassium leaching rate may be up to more than 98%.Although the method has
Certain saving grace (100~200 DEG C lower than the temperature of traditional cofiring connection), but energy consumption is still difficult to reach a standard, moreover, burning
Solid state fermentation after knot is also an extremely complex process, and processing is not good at, and can bring secondary pollution.
(7) low-temperature decomposition method
From 1989, the effort of 6 years is passed through by Changsha chemical mine design and research institute, successfully develop in auxiliary agent and
The new process of low-temperature decomposing of potassium feldspar potash fertilizer and by-product aluminium salt and silicon series of products in the presence of sulfuric acid.It is long that nineteen ninety-five completes potassium
The expanding test of stone comprehensive utilization.Method K2O yields are up to 70%, A12O3 yields up to 65%.The characteristics of technique is comprehensive profit
Use potassium feldspar.In addition to potassium-ammonium sulfate is produced, aluminium hydroxide, aluminium oxide, aluminium polychloride and sodium metasilicate, White Carbon black are also produced
Deng.The method, to equipment heavy corrosion, causes equipment investment big due to containing fluoride in production, and caused by environmental pollution
It is self-evident, technically has breakthrough hope less, also sad environmental protection is closed.
(8) experiment progress of the potassium feldspar in terms of molecular sieve, White Carbon black
Tao Hong, horse great writing, Zhang Xuemei et al. are utilized respectively each 13x molecular sieves of potassium feldspar system, zeolite molecular sieve.Tao Hong et al.
It is 1 in mass ratio with the potassium feldspar and sodium carbonate of 120 mesh：1.0~1.4 are matched, and at 750~800 DEG C, roast 1~2h,
By (11~16) Na2OA12O3, (10~15) SiO2, (200~320) H2O proportioning (molar ratio) add in crystal seed, and stirring is equal
It is even, water, sodium hydroxide, sodium metasilicate and aluminium hydroxide are mixed, homogeneous gel is stirred into, is aged at room temperature spare for 24 hours.Reaction
Object presses M2O (M=Na, K)/SiO2=1~1.5, the proportioning (molar ratio) of H2O/M2O=35~60, by clinker, water and hydroxide
Sodium is uniformly mixed, and is aged at room temperature for 24 hours, and 13x molecular sieves are synthesized in 90~100 DEG C of hydrothermal synthesis methods.Zhang Xuemei is long using potassium
A series of additives such as stone and sodium hydroxide are roasted, and experimental result measures product and L-type, D type molecular sieve kissings after roasting
It closes.Qi Hong is refined et al. to be reacted using potassium feldspar with soda ash, and ageing plastic simultaneously adds in crystal seed, using hydro-thermal method synthetic zeolite molecule
Sieve.To filter the mother liquor of gained in separation process after synthesis of molecular sieve as raw material, therefrom separation and Extraction potassium carbonate and White Carbon black.With
Although upper various methods are reacted using potassium feldspar with various auxiliary agents synthesizes molecular sieve, from experimental products such as carbon blacks, comprehensively utilize
The elements such as potassium, aluminium, silicon in potassium feldspar, but technological process is numerous and diverse, and thermal energy consumption is very serious, each Product recycling gets up to compare
Trouble, will realize industrialization, difficulty is bigger.
China begins to explore from the fifties develops and uses potassium feldspar resource, also develops many extracting potassium from potash feldspar works so far
Skill, each technique have its distinctive feature.But large-scale industrial production up to the present, is had no always.To find out its cause, traditional work
More or less all there are such or such shortcomings for skill.
Invention content
The present invention is big for high energy consumption, the quantity of slag existing for blast furnace process method, sintering process for deficiency existing for more than technology
And the problems such as pollution environment, there are leaching condition is harsh, mass flow is big, to equipment material requirement for low-temperature decomposition method, acid system etc.
High drawback proposes the novel environment-friendly process that a kind of environmental-friendly potash feldspar ore economical rationality utilizes, and reduces energy consumption and waste residue amount,
While synthetical recovery aluminium, potassium and sodium, the product form of silicon is enriched, reduces the construction materials such as the silico-calcium quantity of slag and by-product cement.
New process uses wet method pre-desiliconizing-soda lime stone sintering process synthetical recovery aluminium, potassium and sodium from potassium feldspar, and product is oxidation
Aluminium, potassium carbonate and sodium carbonate, and by-product active calcium silicate, white carbon, residue are calcium silicate slag, available for Building woods such as production cement
Material.
The purpose of the present invention is what is be achieved through the following technical solutions.
Utilize the technique of potash feldspar ore production potassium carbonate, sodium carbonate and aluminium oxide, which is characterized in that include the following steps：
(1) potash feldspar ore is crushed, ball milling；
(2) by the potash feldspar ore pre-desiliconizing after step (1) ball milling, desilication filter cake and desiliconization filtrate are obtained, desilication filter cake is washed
Filter cake wash water and desiliconization slag are obtained after washing；
(3) ball milling after matching the desiliconization slag of step (2) and lime stone by a certain percentage, then sintering obtain being sintered ripe
Material；
(4) sintered clinker of step (3) with aqueous slkali is dissolved out, obtains crude sodium aluminate solution and dissolution slag；
(5) the crude sodium aluminate solution of step (4) is subjected to desiliconization processing, obtains refined aluminium acid sodium solution and calcium silicate slag；
(6) the refined aluminium acid sodium solution of step (5) is subjected to carbonization decomposition, obtains aluminium hydroxide and carbon mother liquid；
(7) aluminium hydroxide of step (6) is calcined to obtain alumina product；
(8) the carbon mother liquid evaporative crystallization of step (7) is obtained into sodium carbonate and potassium carbonate product.
Further, the pre-desiliconizing described in step (2) is to be blended in the potash feldspar ore after step (1) ball milling with lye
Leach reaction is carried out under high temperature.After pre-desiliconizing, alumina silica ratio is increased to about 0.8 from about 0.2, and the raw material amount into sintering reduces, from
And reduce energy consumption.
Further, the pre-desiliconizing described in step (2) is to be blended in the potash feldspar ore after step (1) ball milling with lye
Leach reaction is carried out under high temperature, the lye is sodium hydroxide and the mixed alkali liquor of potassium hydroxide, and total alkali concn is calculated as with R2O
170-320g/l, R are Na and K, and naoh concentration is calculated as 165-250g/l with Na2O, and concentration of potassium hydroxide is calculated as 5- with K2O
70g/l；Liquid-solid ratio 2:1-6:1,120-260 DEG C of extraction temperature, pressure 0.5-2.5Mpa, extraction time 1-4h.Leach lye
It is middle to be incorporated low potassium composition, on the one hand it is to be leached for potassium in inhibition potash feldspar ore, potassium is avoided to be dispersed to leachate in pre-desiliconizing,
Potassium is made to be enriched in desiliconization slag, so as to realize the centralized and unified recycling of potassium element in follow-up sintering-dissolution fluid；On the other hand it is pre-
Lye used in desiliconization, can use the sodium carbonate causticization by step (8) to obtain regeneration lye, and regeneration lye is practical containing low
The potassium composition of concentration.
Further, the potassium feldspar rock ore particle degree after step (1) ball milling accounts for more than 80% below 200 mesh.
Further, step (9) is further included, the desiliconization filtrate of step (2) is added in into Ca (OH) 2 solution causticization, causticization item
Part is：Calcium silicon ratio (molar ratio) n (CaO)/n (SiO2)=0.5-1.0,80-100 DEG C of temperature, time 1-20h, slurry after causticization
It filters, return to step (2) uses after filtrate, that is, causticized alkali liquor adjusting component, and filter cake is washed with water to neutral left and right, in 800-
Byproduct active calcium silicate is obtained after 1000 DEG C of roastings；Wash the desilication filter cake that the wash water after filter cake is used for washing step (2).
Further, step (10) is further included, the filter cake wash water of step (2) is carbonized and is decomposed, obtains byproduct white carbon
With liquid after carbon point, the rear liquid of carbon point enters step (8) and carbon mother liquid together evaporative crystallization.
Further, the proportioning of step (3) lime stone and desiliconization slag is：Lime stone in terms of CaO, desiliconization slag in terms of SiO2,
Molar ratio n (CaO)/n (SiO2)=1.9-2.1；1150-1300 DEG C of sintering temperature, sintering time 20-80min.
Further, step (4) leaching condition is, the sintered clinker of step (3) is levigate to 60 mesh hereinafter, liquid-solid ratio 2:
1-6:1,50-80 DEG C of temperature, time 10-60min.It is separated by filtration, after dissolving out slag pulping and washing, dries sample presentation.At this point, aluminium dissolves out
Rate is more than 86%, and potassium, sodium dissolution rate are more than 92%.Dissolution wash heat can be as the raw material of the building materials such as production cement, wash water tune after washing
It can return to after being made into point and do the use of clinker dissolution fluid.
Further, the desiliconization described in step (5) be two sections of desiliconizations, middle pressure-off silicon strip part：Pressure is 0.6-1.0Mpa, temperature
120-200 DEG C, time 1-4h of degree, calcium oxide addition 0-1g/L；Atmospheric silicon removing condition：80-100 DEG C of temperature, time 2-10h,
Calcium oxide addition 1-5g/L；Calcium silicate slag return to step (3) and desiliconization slag, lime stone proportioning ball milling after two sections of desiliconizations.Middle pressure
It is more than 3000 with siliceous modulus after atmospheric silicon removing.
Further, CO2 step (2) sintering generated decomposes for carbonization in step (6) and step (10).
The invention has the advantages that：Products scheme is reasonable, produces active calcium silicate, white carbon, sodium carbonate, carbon
Sour potassium and aluminium oxide.The method of industrial production potassium carbonate is mainly electrolysis and ion-exchange, using high purity potassium chloride as
Raw material, converts it into potassium carbonate, and production cost is higher.Industrial production white carbon is mainly using two sections of acid adding methods of sulfuric acid, base
This raw material is sodium silicate water glass and sulfuric acid.This technique uses the CO2 gases of sintering stage discharge, and cost of material is extremely low.During sintering
Because pre-desiliconizing raw material amount reduces about 35%, calcium silicate slag (cement slurry, added value the are low) amount few 30% or so of output；Desiliconization slag
Because containing however, residual base, technological parameter of the alkali than 1 or so when can meet sintering carries out raw-meal ingredient without additional soda ash；Washing is lived
Property calcium silicates wash water can be used for the washing of desiliconization slag, reduce process water consumption and wastewater flow rate；The product form of abundant silicon, output
Added value high white carbon and active calcium silicate；When potash feldspar ore is leached at high temperature using the low potassium mixed alkali liquor pre-desiliconizing of high sodium
The sodium of the alkali number of loss, i.e. desiliconization slag liquid content loss, by entering wash water after washing, and is converted into follow-up sodium carbonate product,
It can be regenerated again by the realization of the causticization of sodium carbonate, return to the alkali number of pre-desiliconizing process supplement loss, realize the alkali of entire technique certainly
It gives and cyclic balance；Be carbonized the CO2 that decomposable process is generated using sintering, reduces greenhouse gas emission.
Description of the drawings
Attached drawing is the principle process flow chart of the method for the present invention.
Specific embodiment
Further explanation is made to the present invention below in conjunction with attached drawing.
Potash feldspar ore is milled to below 200 mesh of granularity after broken, two pairs of rollers and accounts for more than 80%.Pressurization carries out pre-desiliconizing
Processing, pressure 0.5-2.5Mpa, 120-260 DEG C of temperature, liquid-solid ratio 2:1-6:1, time 1-4h, total alkali R2O concentration 170-
320g/l, wherein Na2O concentration 165-250g/l, K2O concentration 5-70g/l.After filtering, with the wash water after detergent active calcium silicates
It is washed, silicon removal efficiency is counted as 20-50% using desiliconization slag at this time.
Desiliconization slag according to alkali than n [(Na2O)+(K2O)]/n [(Al2O3)+(Fe2O3)]=0.9-1.1, calcium than n (CaO)/
N (SiO2)=1.9-2.1,1150-1300 DEG C of temperature of control, the condition of time 20-80min are sintered.Sintered clinker carries out
Dissolution, dissolving-out process parameter：It is levigate to 60 mesh hereinafter, liquid-solid ratio 2:1-6:1,50-80 DEG C of temperature, time 10-60min, filtering
Separation after dissolving out slag pulping and washing, dries sample presentation.At this point, aluminium dissolution rate is more than 86%, potassium, sodium dissolution rate are more than 92%.Dissolution
Wash heat after wash water adjusting component can return to and do the use of sintered clinker dissolution fluid as the raw material of the production building materials such as cement after washing.
Pressure and two sections of desiliconizations of normal pressure in dissolution fluid warp, middle pressure-off silicon strip part：Pressure is 0.6-1.0Mpa, temperature 120-200
DEG C, time 1-4h, calcium oxide addition 0-1g/L；Atmospheric silicon removing condition：80-100 DEG C, time 2-10h, calcium oxide addition 1-
5g/L.Siliceous modulus is more than 3000 after middle pressure and atmospheric silicon removing.Burning is passed through into liquid after two sections of desiliconizations, that is, refined aluminium acid sodium solution
The CO2 generated during knot, aluminium hydroxide calcining prepared by carbon point obtain meeting nonferrous metallurgy professional standard YS/T274-1998 metallurgy
Grade aluminum oxide.The difference of solubility is utilized after carbon point containing potassium, sodium solution, crystallization process is evaporated, obtains the carbon for meeting national standard
Sour sodium and potassium carbonate product.
Desiliconization filtrate prepares active silicic acid calcium product, and calcium silicon is than being n (CaO)/n (SiO2)=0.5-1.0, temperature 80-100
DEG C, time 1-20h, after synthesizing slurry filtration, product is washed to neutrality left and right, and active calcium silicate is obtained after 800-1000 DEG C of roasting
Product.Circulating leaching potash feldspar ore is can return to after filtrate, that is, causticized alkali liquor adjusting component.
Using the wash water of detergent active calcium silicates, desiliconization slag is washed, makes the concentration enrichment of potassium, sodium and silicon, is passed through sintering
When the CO2 gases that generate, by-product white carbon black product, while be mixed into potassium, sodium solution carbonating and main flow carbon mother liquid
The evaporative crystallization separation and Extraction process of potassium, sodium.The highly basic lost in desiliconization process can pass through the causticization of partial sodium carbonate product
Regeneration, while by-product light calcium carbonate product.
The method of the present invention is further described with following nonlimiting examples, to help to understand the present invention's
Content and its advantage, and not as limiting the scope of the present invention, protection scope of the present invention is determined by claims.
Embodiment 1
Potash feldspar ore is milled to granularity to account for 90% below 200 mesh after broken, two pairs of rollers.Pressurization carries out pre-desiliconizing, control
Leach stirring linear velocity 1.7m/s, 170 DEG C of temperature, liquid-solid ratio 3:1, time 3h, total alkali R2O concentration 250g/l, wherein Na2O are dense
Spend 200g/l, K2O concentration 50g/l.It is washed after filtering with the wash water after detergent active calcium silicates, the removal efficiency of slag meter silicon is at this time
42.5%.For desiliconization slag according to alkali than 1, calcium ratio is 2, is sintered under 1300 DEG C of temperature of control, time 0.5h.Clinker is levigate to 60
Mesh is hereinafter, liquid-solid ratio 2:1, temperature 70 C carries out Clinker digestion under time 20min, filters, after dissolving out slag pulping and washing, drying
Sample presentation.At this point, aluminium dissolution rate 86.5%, potassium, sodium dissolution rate 92.4%.
After the two sections of desiliconizations of sintered clinker dissolution fluid, carbon point prepares aluminium hydroxide, production metallurgy grade aluminum oxide after calcining.Carbon point
Mother liquid evaporation crystallization production meets the sodium carbonate of national standard and potassium carbonate product.
Desiliconization liquid prepares active silicic acid calcium product in 95 DEG C of temperature, time 3h, n (CaO)/n (SiO2)=0.9, synthesis material
After slurry filtering, cleaning product to neutrality left and right obtains active silicic acid calcium product after 900 DEG C of roastings.
Embodiment 2
Potash feldspar ore is milled to granularity to account for 95% below 200 mesh after broken, two pairs of rollers.Pressurization carries out desiliconization experiment, control
System leaches stirring linear velocity 1.6m/s, 180 DEG C of temperature, liquid-solid ratio 4:1, time 3h, total alkali R2O concentration 220g/l, wherein Na2O
Concentration 200g/l, K2O concentration 20g/l.It is washed after filtering with the wash water after detergent active calcium silicates, at this time the removal efficiency of slag meter silicon
It is 38.6%.According to alkali than 1.05, calcium is sintered desiliconization slag than 1.95 under 1250 DEG C of temperature of control, time 0.5h.Clinker grinding mill
Carefully to 60 mesh hereinafter, in liquid-solid ratio 3：1,80 DEG C of temperature carries out Clinker digestion under time 40min, filters, and dissolves out slag pulping and washing
Afterwards, sample presentation is dried.At this point, aluminium dissolution rate 87.3%, potassium, sodium dissolution rate 93.5%.
After the two sections of desiliconizations of sintered clinker dissolution fluid, carbon point prepares aluminium hydroxide, production metallurgy grade aluminum oxide after calcining.Carbon point
Mother liquid evaporation crystallization production meets the sodium carbonate of national standard and potassium carbonate product.
Desiliconization liquid prepares active silicic acid calcium product in 95 DEG C of temperature, time 5h, n (CaO)/n (SiO2)=1.0, synthesis material
After slurry filtering, cleaning product to neutrality left and right obtains active silicic acid calcium product after 900 DEG C of roastings.
Embodiment 3
Potash feldspar ore is milled to granularity to account for 85% below 200 mesh after broken, two pairs of rollers.Pressurization carries out desiliconization experiment, control
System leaches stirring linear velocity 1.6m/s, 190 DEG C of temperature, liquid-solid ratio 2:1, time 4h, total alkali R2O concentration 240g/l, wherein Na2O
Concentration 200g/l, K2O concentration 40g/l.It is washed after filtering with the wash water after detergent active calcium silicates, at this time the removal efficiency of slag meter silicon
It is 46.6%.According to alkali than 0.95, calcium is sintered desiliconization slag than 1.9 under 1230 DEG C of temperature of control, time 0.5h.Clinker grinding mill
Carefully to 60 mesh hereinafter, in liquid-solid ratio 3：1,80 DEG C of temperature carries out Clinker digestion under time 40min, filters, after dissolving out slurry,
Dry sample presentation.At this point, aluminium dissolution rate 88.1%, potassium, sodium dissolution rate 94.5%.
After the two sections of desiliconizations of sintered clinker dissolution fluid, carbon point prepares aluminium hydroxide, production metallurgy grade aluminum oxide after calcining.Carbon point
Mother liquid evaporation crystallization production meets the sodium carbonate of national standard and potassium carbonate product.
Desiliconization liquid prepares active silicic acid calcium product in 90 DEG C of temperature, time 5h, n (CaO)/n (SiO2)=0.7, synthesis material
After slurry filtering, cleaning product to neutrality left and right obtains active silicic acid calcium product after 900 DEG C of roastings.
Embodiment 4
Potash feldspar ore is milled to granularity to account for 96% below 200 mesh after broken, two pairs of rollers.Pressurization carries out desiliconization experiment, control
System leaches stirring linear velocity 1.7m/s, 240 DEG C of temperature, liquid-solid ratio 3:1, time 3h, total alkali R2O concentration 300g/l, wherein Na2O
Concentration 250g/l, K2O concentration 50g/l.It is washed after filtering with the wash water after detergent active calcium silicates, at this time the removal efficiency of slag meter silicon
It is 39.6%.For desiliconization slag according to alkali than 1.1, calcium ratio is 2, is sintered under 1250 DEG C of temperature of control, time 0.5h.Clinker is levigate
To 60 mesh hereinafter, in liquid-solid ratio 6：1,80 DEG C of temperature carries out Clinker digestion under time 40min, filters, and dissolves out slag pulping and washing
Afterwards, sample presentation is dried.At this point, aluminium dissolution rate 86.3%, potassium, sodium dissolution rate 96.5%.
After the two sections of desiliconizations of sintered clinker dissolution fluid, carbon point prepares aluminium hydroxide, production metallurgy grade aluminum oxide after calcining.Carbon point
Mother liquid evaporation crystallization production meets the sodium carbonate of national standard and potassium carbonate product.
Desiliconization liquid prepares active silicic acid calcium product in 90 DEG C of temperature, time 16h, n (CaO)/n (SiO2)=0.6, synthesis material
After slurry filtering, cleaning product to neutrality left and right obtains active silicic acid calcium product after 900 DEG C of roastings.
Embodiment 5
Potash feldspar ore is milled to granularity to account for 87% below 200 mesh after broken, two pairs of rollers.Pressurization carries out desiliconization experiment, control
System leaches stirring linear velocity 1.5m/s, 220 DEG C of temperature, liquid-solid ratio 3:1, time 4h, total alkali R2O concentration 300g/l, wherein Na2O
Concentration 300g/l, K2O concentration 0g/l.It is washed after filtering with the wash water after detergent active calcium silicates, at this time the removal efficiency of slag meter silicon
It is 39.5%.According to alkali than 1, calcium is sintered desiliconization slag than 2.1 under 1200 DEG C of temperature of control, time 0.5h.Clinker is levigate extremely
60 mesh are hereinafter, in liquid-solid ratio 3：1,80 DEG C of temperature carries out Clinker digestion under time 10min, filters, after dissolving out slag pulping and washing,
Dry sample presentation.At this point, aluminium dissolution rate 87.2%, potassium, sodium dissolution rate 95.3%.
After the two sections of desiliconizations of sintered clinker dissolution fluid, carbon point prepares aluminium hydroxide, production metallurgy grade aluminum oxide after calcining.Carbon point
Mother liquid evaporation crystallization production meets the sodium carbonate of national standard and potassium carbonate product.
Desiliconization liquid prepares active silicic acid calcium product in 95 DEG C of temperature, time 5h, n (CaO)/n (SiO2)=0.9, synthesis material
After slurry filtering, cleaning product to neutrality left and right obtains active silicic acid calcium product after 900 DEG C of roastings.
Embodiment 6
Potash feldspar ore is milled to granularity to account for 96% below 200 mesh after broken, two pairs of rollers.Pressurization carries out desiliconization experiment, control
System leaches stirring linear velocity 1.7m/s, 130 DEG C of temperature, liquid-solid ratio 5:1, time 4h, total alkali R2O concentration 320g/l, wherein Na2O
Concentration 270g/l, K2O concentration 50g/l.It is washed after filtering with the wash water after detergent active calcium silicates, at this time the removal efficiency of slag meter silicon
It is 41.6%.According to alkali than 1.05, calcium is sintered desiliconization slag than 2.05 under 1150 DEG C of temperature of control, time 0.5h.Clinker grinding mill
Carefully to 60 mesh hereinafter, in liquid-solid ratio 3：1,80 DEG C of temperature carries out Clinker digestion under time 40min, filters, and dissolves out slag pulping and washing
Afterwards, sample presentation is dried.At this point, aluminium dissolution rate 88.6%, potassium, sodium dissolution rate 97.5%.
After the two sections of desiliconizations of sintered clinker dissolution fluid, carbon point prepares aluminium hydroxide, production metallurgy grade aluminum oxide after calcining.Carbon point
Mother liquid evaporation crystallization production meets the sodium carbonate of national standard and potassium carbonate product.
Desiliconization liquid prepares active silicic acid calcium product in 95 DEG C of temperature, time 20hn (CaO)/n (SiO2)=0.9, synthesis material
After slurry filtering, cleaning product to neutrality left and right obtains active silicic acid calcium product after 900 DEG C of roastings.
Embodiment 7
Potash feldspar ore is milled to granularity to account for 86% below 200 mesh after broken, two pairs of rollers.Pressurization carries out desiliconization experiment, control
System leaches stirring linear velocity 1.7m/s, 150 DEG C of temperature, liquid-solid ratio 6:1, time 4h, total alkali R2O concentration 280g/l, wherein Na2O
Concentration 270g/l, K2O concentration 10g/l.It is washed after filtering with the wash water after detergent active calcium silicates, at this time the removal efficiency of slag meter silicon
It is 44.6%.According to alkali than 1, calcium is sintered desiliconization slag than 2 under 1180 DEG C of temperature of control, time 0.5h.Clinker is levigate to 60
Mesh is hereinafter, in liquid-solid ratio 3：1, temperature 50 C carries out Clinker digestion under time 30min, filters, and after dissolving out slag pulping and washing, dries
Dry sample presentation.At this point, aluminium dissolution rate 87.6%, potassium, sodium dissolution rate 95.5%.
After the two sections of desiliconizations of sintered clinker dissolution fluid, carbon point prepares aluminium hydroxide, production metallurgy grade aluminum oxide after calcining.Carbon point
Mother liquid evaporation crystallization production meets the sodium carbonate of national standard and potassium carbonate product.
Desiliconization liquid prepares active silicic acid calcium product in 95 DEG C of temperature, and time 10h, n (CaO)/n (SiO2)=1 synthesize slurry
After filtering, cleaning product to neutrality left and right obtains active silicic acid calcium product after 900 DEG C of roastings.
Claims (10)
1. utilize the technique of potash feldspar ore production potassium carbonate, sodium carbonate and aluminium oxide, which is characterized in that include the following steps：
(1) potash feldspar ore is crushed, ball milling；
(2) by the potash feldspar ore pre-desiliconizing after step (1) ball milling, desilication filter cake and desiliconization filtrate are obtained, after desilication filter cake washing
Obtain filter cake wash water and desiliconization slag；
(3) ball milling after matching the desiliconization slag of step (2) and lime stone by a certain percentage, then sintering obtain sintered clinker；
(4) sintered clinker of step (3) with aqueous slkali is dissolved out, obtains crude sodium aluminate solution and dissolution slag；
(5) the crude sodium aluminate solution of step (4) is subjected to desiliconization processing, obtains refined aluminium acid sodium solution and calcium silicate slag；
(6) the refined aluminium acid sodium solution of step (5) is subjected to carbonization decomposition, obtains aluminium hydroxide and carbon mother liquid；
(7) aluminium hydroxide of step (6) is calcined to obtain alumina product；
(8) the carbon mother liquid evaporative crystallization of step (7) is obtained into sodium carbonate and potassium carbonate product.
2. technique according to claim 1, which is characterized in that the pre-desiliconizing described in step (2) is by step (1) ball milling
Potash feldspar ore afterwards is mixed with lye carries out Leach reaction at high temperature.
3. technique according to claim 2, which is characterized in that the lye is sodium hydroxide and the mixed base of potassium hydroxide
Liquid, total alkali concn are calculated as 170-320g/l with R2O, and R is Na and K, and naoh concentration is calculated as 165-250g/l, hydrogen-oxygen with Na2O
Change potassium concn and 5-70g/l is calculated as with K2O；Liquid-solid ratio 2:1-6:1,120-260 DEG C of extraction temperature, pressure 0.5-2.5Mpa, leaching
Go out time 1-4h.
4. technique according to claim 1, which is characterized in that potash feldspar ore granularity after step (1) ball milling 200 mesh with
Under account for more than 80%.
5. technique according to claim 1, which is characterized in that further include step (9), the desiliconization filtrate of step (2) is added
Enter 2 solution causticizations of Ca (OH), causticization condition is：Calcium silicon is than n (CaO)/n (SiO2)=0.5-1.0,80-100 DEG C of temperature, time
1-20h, slurry filtration after causticization, return to step (2) uses after filtrate adjusting component, and filter cake is washed with water to neutrality left and right, washes
It washs rear filter cake and obtains byproduct active calcium silicate after 800-1000 DEG C of roasting；It washs the wash water after filter cake and is used for washing step
(2) desilication filter cake.
6. technique according to claim 1, which is characterized in that step (10) is further included, by the filter cake wash water carbon of step (2)
Change and decompose, obtain liquid and byproduct white carbon after carbon point, liquid enters step (8) and carbon mother liquid together evaporative crystallization after carbon point.
7. technique according to claim 1, which is characterized in that the proportioning of step (3) lime stone and desiliconization slag is：Lime stone
In terms of CaO, desiliconization slag is in terms of SiO2, molar ratio n (CaO)/n (SiO2)=1.9-2.1；1150-1300 DEG C of sintering temperature, sintering
Time 20-80min.
8. technique according to claim 1, which is characterized in that step (4) leaching condition is, the sintering of step (3) is ripe
Expect levigate to 60 mesh hereinafter, liquid-solid ratio 2:1-6:1,50-80 DEG C of temperature, time 10-60min；Conduct after dissolution slag is washed with water
The raw material of cement is produced, return to step (4) dissolves out sintered clinker as lye after wash water adjusting component.
9. technique according to claim 1, which is characterized in that desiliconization described in step (5) is two sections of desiliconizations, middle pressure-off silicon
Condition：Pressure is 0.6-1.0Mpa, 120-200 DEG C of temperature, time 1-4h, calcium oxide addition 0-1g/L；Atmospheric silicon removing condition：
80-100 DEG C of temperature, time 2-10h, calcium oxide addition 1-5g/L；Calcium silicate slag return to step (3) and desiliconization after two sections of desiliconizations
Slag, lime stone proportioning raw material ball milling.
10. technique according to claim 6, which is characterized in that the CO2 for generating step (2) sintering for step (6) and
Carbonization is decomposed in step (10).
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|---|---|---|---|---|
| CN109319792A (en) * | 2018-11-08 | 2019-02-12 | 渤海大学 | A kind of method that high added value comprehensively utilizes silicon, aluminium, potassium in potash feldspar ore |
| CN113620754A (en) * | 2021-08-27 | 2021-11-09 | 长春市祯盛检测技术有限公司 | Method for preparing mineral organic fertilizer from insoluble potassium-rich rock and comprehensively utilizing mineral organic fertilizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109319792A (en) * | 2018-11-08 | 2019-02-12 | 渤海大学 | A kind of method that high added value comprehensively utilizes silicon, aluminium, potassium in potash feldspar ore |
| CN113620754A (en) * | 2021-08-27 | 2021-11-09 | 长春市祯盛检测技术有限公司 | Method for preparing mineral organic fertilizer from insoluble potassium-rich rock and comprehensively utilizing mineral organic fertilizer |
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