CN1250486C - Process for preparing K fertilizer from non-soluble potassium ore and waste ammonia-soda solution - Google Patents
Process for preparing K fertilizer from non-soluble potassium ore and waste ammonia-soda solution Download PDFInfo
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- CN1250486C CN1250486C CN 01100594 CN01100594A CN1250486C CN 1250486 C CN1250486 C CN 1250486C CN 01100594 CN01100594 CN 01100594 CN 01100594 A CN01100594 A CN 01100594A CN 1250486 C CN1250486 C CN 1250486C
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- potash fertilizer
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Abstract
The present invention relates to a technologic method for preparing soluble potassium chloride (a potash fertilizer) from insoluble potassium ore. The present invention is characterized in that potash feldspar is used as raw material, and a transforming agent is waste slag and waste liquid of soda; a mixture ratio of the potash feldspar to caustic slag to calcium mother liquid is 1: 1 to 3: 0.7, spent lye is added as a leaching agent, and a liquid to solid ratio of the spent lye to roasted clinker is 1: 0.8 to 1; the potash feldspar is crashed and milled and then mixed with ingredients to produce raw slurry which is roasted and leached; after leaching, slurry liquid is processed through conventional chemical processes, such as filtration, evaporation, crystallization, dryness, etc. to be generated into the potassium chloride (potash fertilizer), regenerated salt and calcium chloride, and residues can be made into various kinds of building material. The technology of the present invention opens up a new path for national potash fertilizer industry and sweeps obstacles for the survival and development of ammonia alkali industry; besides, the technologic process has no three wastes.
Description
The present invention solves the technology novel method of extracting Repone K (potash fertilizer) from insoluble potassium ore (potassium felspar sand, nepheline, glaukonine etc.).Its transforming agent is the waste liquid and the waste residue of discharging during solvay soda process soda ash is produced.
China's soluble potassium salt is in great shortage, potash fertilizer is wanted a large amount of imports (about 5,000,000 tons of annual import), though Qinghai Chaerhan salt lakes has and abundant contain potassium bittern and can develop, but because physical environment is abominable, lack of water, the scarce energy are difficult to a large amount of exploitations and utilize, and add and have inconvenient traffic, far away, it is not low that product is transported to the east cost yet.But the insoluble potassium ore resources of China is very abundant, the each province that almost spreads all over the country, and only capital, North China, area, Tianjin standing stock just have tens tons.How economically its extraction to be changed into solubility potash fertilizer, be that agricultural science and technology department is first when the research topic of considering after liberation, and implemented as torch plan.
After liberation, the whole nation successively has dozens of chemical industry institute, institute all to carry out this important function for of research, the lime carbonate (CaCO of the wherein representative sodium-chlor that Shanghai Hua Yuan is arranged (NaCl) roasting method, Shanxi Hua Yuan and mine, Lianyun Harbour institute
3) vapor phase process (NaCl method) of method, the emerging potash fertilizer pilot plant in Guangdong.Calcium chloride (the CaCl that Rome Leah research is abroad arranged
2) roasting method, also have other multiple physical method.These chemical methods are single transforming agent, promptly with NaCl or CaCO
3Or CaCl
2And the NaCl method is because low, the easy dross of material of roasting fusing point, caking make the baking operation difficulty, and easy mistake is burnt till vitreum and made leaching effective ingredient difficulty, so yield is low, it is big to consume, and the technology of being sorry and economic pass.CaCO
3The method transformation efficiency is low, the separation and Extraction difficulty.CaCl
2Method raw material costliness, basic mistake not economic pass.And waste lye and alkaline residue are the three wastes, have caused serious public hazards, do not charge basically, and its main chemical compositions just in time are NaCl, CaCl
2And CaCO
3Mixture.And its component proportions basicly stable (referring to new slag liquid of discharging), alkaline residue contains NaCl 5～8%, CaCl
210～16%, CaCO
355～65%, other 10～20% waste lye contains CaCl
290～100 grams per liters, NaCl 45～50 grams per liters.The prescription of this three wastes mixture has great advantage technically and economically as the transforming agent of extracting potassium from potash feldspar, we can say and has found the good opportunity that turns waste into wealth.
This technology also is and can carries out coproduction with existing alkali factory salt, calcium workshop than the technology advantage economically of transforming agents such as single use NaCl, (salt, calcium are produced decades, technical maturity) except that producing KCl, but calcium chloride that also production added value is high and refine salt (or Cardia Salt), add effective utilization of residue, comprehensive cost just can reduce greatly like this, is to achieve many things at one stroke, this just can overcome defectives such as the potassium ore treatment capacity is big, energy consumption height, the heel of can standing firm economically.
It is that the big potash feldspar ore that grade is higher has been found in area, county, Pinggu, Beijing in recent years that this technology also has prior basic substance, and exploitation and traffic (nearly highway, railway) are all very convenient, and this ore deposit point has passed through the test and the evaluation of National Geology department.
This technological process (seeing schema 1) is that potassium felspar sand pulverizing and jevigating (100～200 order) and alkaline residue (moisture about 50%) and mother liquor of calcium (are contained CaCl
2About 42%), by potassium felspar sand: alkaline residue: mother liquor of calcium=1: 1～in stirred pot stir at 3: 0.7, make charge pulp, enter roasting kiln (wet method) again and carry out drying and roasting, maturing temperature is 600～900 ℃ of high temperature section, kept about 60～80 minutes, grog enters the spiral leacher after the roasting after fragmentation, add through clarifying waste liquid clear liquid as leaching agent by liquid-solid ratio 1: 0.8～1, the leaching liquid pulp stirs in stirred pot after 20～30 minutes and enters the press filtration washing procedure, when press filtration during to liquid content 20% left and right sides, wash with the waste liquid clear liquid, washings returns spiral leaching system to reclaim sylvite more fully.The filtrate that elder generation's press filtration goes out enters evaporization process.Deslagging Cl after the press filtration
-Content should be controlled at below 1%, stores up deslagging and can do building materials.The leaching filtered liquid, through evaporation concentration, separate out crude salt earlier, make the refine salt product through centrifugation, washing, filtration, drying, the mother liquor of separating out crude salt makes the Repone K product through crystallisation by cooling, centrifugation, thick potassium washing with after filtering, and the mother liquor of carrying behind the potassium claims mother liquor of calcium (CaCl
242%), most of retrieval system batching, a part enter system calcium chloride operation, make the calcium chloride product after heat exchange heats up, clarifies separation, the evaporation of lifting film, insulation sedimentation.
This technology roasting apparatus turns round long kiln for the most desirable with wet method, the level of automation height, and it is low to consume energy, but needs to solve afterbody knot mud collar problem.Labour intensity such as other tunnel furnace, vertical furnace are big, and level of automation is low, and need oven dry earlier, complex technical process with shaft kiln.
The key of this technology is (to contain CaCl as leaching agent with the clear liquid of waste soda ash solution
290 grams per liters, NaCl 45 grams per liters) be to reclaim heat energy (about 90～100 ℃ of waste lye) on the one hand, reclaim wherein a large amount of CaCl simultaneously
2And NaCl, this technology can coproduction CaCl
2Promptly be this with the material source of NaCl.Leaching temperature should be controlled at about 80 ℃, influences the filter cloth life-span during too high press filtration, crosses that low to reclaim heat energy few.
The mechanism of this technology roasting reaction is inquired into
Potassium felspar sand chemistry analysis of components: (%)
| K 2O | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | Cl - | H 2O |
| 13.17 | 55.10 | 17.44 | 8.58 | 7.33 | 0.44 | 0.35 | 1.06 |
The alkaline residue Chemical Composition is analyzed (%)
| CaCO 3 | CaO | CaCl 2 | NaCl | SiO 2 | Mg(OH) 2 | Al 2O 3 | Fe 2O 3 | CaSO 4 |
| 51.83 | 7.27 | 20.00 | 5.30 | 6.50 | 3.04 | 1.21 | 1.10 | 1.81 |
The reaction mechanism of potassium felspar sand and alkaline residue and calcium liquid is roughly as follows according to pertinent data record and contriver's understanding:
Above-mentioned K
+With C
++, Na
+Replacement(metathesis)reaction enough excessive N a must be arranged
+, Ca
++Reaction just can reach higher transformation efficiency, Cl
-The carrying out of enough concentration ability driving a reactions must be arranged, so a large amount of mother liquor of calcium of necessary adding, excessive mother liquor of calcium recycles, and wherein a part participates in reacting, and major part is just participated CaCl in the mother liquor of calcium as impellent
2With the K in the potassium felspar sand
2The ratio of O is about 8: 1, and this has only utilization of waste material to realize, if use single transforming agent, spend money on expensive CaCl
2Transforming agent is that very difficult realization is industrialized.Add CaCl
2Be the principal element that improves transformation efficiency, because CaCl
2In Ca
++Be easy to potassium felspar sand in sieve and silica-sesquioxide form firm ca aluminosilicate (CaOAl
2OSiO
2Thereby) displace KCl, and the ca aluminosilicate basic chemical ingredients of making cement and building materials just.Because of in the batching CaCO being arranged
3Participate in reaction, not only make the replacement(metathesis)reaction acceleration.And CaCO
3Decompose effusion CO in high temperature section
2Make the loose porous of roasting grog, do not lump, plasticity, good fluidity can normally move baking operation, and non-nodulating, do not burn till vitreum, and (because fusing point height) also is convenient to leaching and proposed effective ingredient.This is that this technology can realize normal industrialized basis.This also is to extract soluble potassium salt (potash fertilizer) from insoluble potassium ore in decades.Though study in many ways and but fail to realize industrialization, and can realize technology, economic two basic reasons that reach a standard as transforming agent with soda ash, waste liquid, waste residue.
China is maximum in the world agriculture country, and potash fertilizer production is a weakest ring in nitrogen, phosphorus, the potassium three big fertilizer, and China is maximum in the world potash fertilizer importer, and there is abundant insoluble potassium ore resources in China, effectively extracting potash fertilizer from insoluble potassium ore, should be developing direction.This technology has been opened a new breakthrough mouth for this reason.The soda ash of solvay soda process is simultaneously produced, and the discharging of waste lye, alkaline residue always is exactly the big problem that restricts the survival and development of soda industry.Waste liquid, alkaline residue are commonly called as " white sea ", " white suffering from ", when current environmental protection has been state basic policy, solve the alkaline residue emission problem, have also become the matter of great urgency.
The raw material preparation and the roasting part of this processing method forebody, the equipment that is adopted is current cement manufacture plant.Latter half of leaching separation, evaporation concentration, crystallization, drying etc. also all are chemical unit equipment, especially CaCl commonly used
2, NaCl, KCl production technique and equipment all be comparative maturity, also be comparative maturity so form the condition of large-scale industrial production.This also provides objectively advantageous conditions for the successful implementation of this processing method.
Because this technology is raw materials used for the insoluble potassium ore of no big purposes and waste lye, waste soda residue, so raw materials cost is cheap, and except that production potash fertilizer (KCl), but high added value such as co-product calcium chloride, refine salt Chemicals also.See and be the good raw material of system building materials from the Chemical Composition of residue, now down with the chemical constitution of residue row:
Grog leaching, washing back residue Chemical Composition (%)
| CaO | SiO 2 | Fe 2O 3 | Al 2O 3 | MgO | K 2O | Cl - | SO4 ＝ |
| 20-25 | 40-50 | 7-10 | 10-15 | 0.5-1 | 2-3％ | ＜1 | ＜1 |
Above-listed residue main chemical compositions is a silicate, wherein objectionable constituent MgO and Cl
-Equal size is all lower, so be the good raw material of system cement and other building materials.
Description of drawings:
Accompanying drawing 1 is the schematic flow sheet of this processing method.
Illustrate: alkaline residue in this technical process and mother liquor of calcium all derive from the production of solvay soda process soda ash, the calcined soda waste residue liquid that ammonia still is discharged (being called for short " waste ammonia-soda solution " or " waste liquid "), contain about 5% solids in the waste liquid, and most of loss of waste liquid clear liquid in discharging is stored up (or filtration), remaining solids is exactly that alkaline residue (contains H
2O about 50～70%).Leach because this technology roasting grog is the clear liquid with waste liquid, (seeing schema 1) and alkaline residue (through stacking) after the clarification can be as batchings, and the mother liquor of calcium that circular batching is used also is by CaCl in the waste liquid
2Replenish, just can reach material balance.Therefore, in essence, in fact the used batching of this technology is exactly the waste residue liquid that ammonia still was discharged during solvay soda process soda ash was produced.Alkali factory custom claims " waste ammonia-soda solution " or " waste liquid ".
Because the rear section of this technology, the extraction of Repone K, calcium chloride, sodium-chlor is existing comparatively proven technique with refining, thus this technology only the instance data of roasting part is tabulated in after.From example, when potassium felspar sand: alkaline residue: transformation efficiency can reach 87.33% when mother liquor of calcium was 1: 1.6～2.5: 0.7, and grog KCl is more than 8%.Fixedly the intensification transformation efficiency is high slightly but difference is little, and the condition of heating up can satisfy the roasting of the high rotary kiln of level of automation continuously.Fixedly intensification can should be not less than 60 minutes for well with reference to 600～900 ℃ of, roasting time high temperature section as vertical furnace, and potassium felspar sand and alkaline residue ratio of components are that 1: 2 o'clock grog porous is crisp, are convenient to leach effective constituent.The two proportioning less than 1 because of CaCO
3Content is low to make roasting grog poor performance, is unfavorable for leaching and separates.
Optimum implementation example: (with reference to technical process Fig. 1) ratio of components: potassium felspar sand: alkaline residue (50%H
2O): mother liquor of calcium (42%CaCl
2)=1: 2.4: 0.7,600～900 ℃ of maturing temperatures, 60 minutes time, grog contains solvable K
2O 4.98%, total K
2O 5.89%, transformation efficiency 83.53%, and 80 ℃ of leaching temperatures, leaching, press filtration, washing total efficiency are more than 90%.Liquid-solid ratio with the waste lye leaching is 1: 0.8～1, and centrifugation is carried NaCl and kept 100 ℃ of temperature, proposes the crude salt washing of NaCl, and adding water is 50% of crude salt amount, stirs 10 minutes, keeps carrying out more than 80 ℃ centrifugation.Carry 120～135 ℃ of the evaporation concentration controlled temperature of NaCl, put forward 30 ℃ of the crystallisation by cooling temperature of potassium, it is 60% of thick potassium that thick potassium washing adds water, keeps 29～31 ℃ of temperature, stirs 10 minutes.Carry CaCl
2The climbing-film evaporation controlled temperature of process is 150～155 ℃, and the falling film evaporation temperature is controlled at 170 ℃.Through preliminary material balance, 8 tons of potassium felspar sands are joined 16 tons of alkaline residues and 16 tons of waste lyes, can produce 1 ton 90% Repone K, and 0.5 ton of 96% refine salt of 1.2 ton 70% calcium chloride can be made about 12 tons of the residue of building materials, engineering soil.
Roasting test data list one
| The examination number | Proportioning (weight) | Roasting time (branch) | Maturing temperature (℃) | Heating mode | Solvable K2O (%) | Total K2O (%) | Transformation efficiency (%) | Grog contains KCl (%) | Roasting grog character observation | ||
| Potassium felspar sand | Alkaline residue (wetting) | Calcium halogen (CaCl 2) | |||||||||
| 1 | 1 | 1.2 | 0.78 | 45 | 900 | Fixing | 5.76 | 6.91 | 83.48 | 9.12 | Heavily fortified point is choked |
| 60 | 600-900 | Continuously | 5.44 | 6.81 | 79.88 | 8.65 | Hard | ||||
| 2 | 1 | 1.6 | 0.7 | 45 | 900 | Fixing | 5.37 | 6.71 | 80.03 | 8.54 | Porous is crisp |
| 60 | 600-900 | Continuously | 5.27 | 6.60 | 79.80 | 8.34 | Porous is crisp | ||||
| 3 | 1 | 1.6 | 0.74 | 45 | 900 | Fixing | 5.59 | 6.80 | 82.21 | 8.89 | Porous |
| 60 | 600-900 | Continuously | 5.63 | 6.87 | 81.95 | 8.35 | Hard slightly | ||||
| 4 | 1 | 2.4 | 0.7 | 45 | 900 | Fixing | 5.24 | 6.00 | 87.33 | 8.33 | Porous is crisp |
| 60 | 600-900 | Continuously | 4.92 | 5.89 | 83.53 | 7.82 | Porous is crisp | ||||
| 5 | 1 | 2.5 | 0.68 | 45 | 900 | Fixing | 5.31 | 6.89 | 82.80 | 8.44 | Porous is crisp |
| 60 | 600-900 | Continuously | 5.10 | 6.45 | 79.07 | 8.11 | Porous is crisp | ||||
| 6 | 1 | 2.75 | 0.62 | 45 | 900 | Fixing | 5.30 | 6.45 | 82.92 | 8.43 | Porous is crisp |
| 60 | 600-900 | Continuously | 5.19 | 6.39 | 80.13 | 8.12 | Porous is crisp | ||||
| 7 | 1 | 2 | 0.74 | 45 | 900 | Fixing | 5.50 | 6.34 | 86.75 | 8.75 | Porous |
| 60 | 600-900 | Increase progressively | 5.14 | 6.48 | 79.20 | 8.17 | Hard slightly | ||||
| 8 | 1 | 3 | 0.58 | 45 | 900 | Fixing | 4.90 | 6.33 | 76.92 | 7.79 | Porous is crisp |
| 60 | 600-900 | Increase progressively | 4.86 | 6.33 | 76.77 | 7.72 | Porous is crisp | ||||
| 9 | 1 | 3 | 0.55 | 45 | 900 | Fixing | 4.97 | 6.21 | 80.03 | 7.90 | Porous is crisp |
| 60 | 600-900 | Increase progressively | 4.81 | 6.08 | 79.11 | 7.65 | Loose | ||||
| 10 | 1 | 2.7 | 0.7 | 45 | 900 | Fixing | 5.10 | 6.23 | 81.86 | 8.11 | Porous is crisp |
| 60 | 600-900 | Increase progressively | 5.10 | 6.23 | 81.86 | 8.11 | Loose | ||||
Claims (1)
1. use insoluble potassium ore for one kind, the Process of waste ammonia-soda solution system potash fertilizer, to be the mother liquor of calcium potassium felspar sand being worn into the alkaline residue of 100～200 orders and water content 50% and contain calcium chloride 42% be mixed into charge pulp with 1: 1～3: 0.7 butt weight ratio for it, carry out roasting through wet process rotary kiln or dry back in dry-process rotory kiln or shaft kiln again, the temperature of high temperature section kept 60～80 minutes from 600～900 ℃, grog after the roasting leaches with the clear liquor of waste ammonia-soda solution, the solid-to-liquid ratio of leaching agent and roasting grog is 1: 0.8～1, leaching liquid is through filtering, evaporation, crystallization, drying process obtains potash fertilizer, the Chemicals of sodium-chlor and calcium chloride, the bits behind the filtration washing can be as building materials raw material and engineering soil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01100594 CN1250486C (en) | 2001-01-17 | 2001-01-17 | Process for preparing K fertilizer from non-soluble potassium ore and waste ammonia-soda solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01100594 CN1250486C (en) | 2001-01-17 | 2001-01-17 | Process for preparing K fertilizer from non-soluble potassium ore and waste ammonia-soda solution |
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| Publication Number | Publication Date |
|---|---|
| CN1298848A CN1298848A (en) | 2001-06-13 |
| CN1250486C true CN1250486C (en) | 2006-04-12 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381247B (en) * | 2008-08-29 | 2010-12-15 | 东莞市大众农业科技有限公司 | Sulphate-potassium magnesium fertilizer and preparation method thereof |
| CN101880179B (en) * | 2010-05-28 | 2012-06-27 | 华南理工大学 | Method for preparing potash fertilizer and building material products from white alkali-making mud |
| CN102583450B (en) * | 2012-02-27 | 2013-11-27 | 青海中航资源有限公司 | Removing method of high undissolved substances and low-grade solid potassium ore undissolved substances |
| CN103664242B (en) * | 2013-09-18 | 2015-07-22 | 薛彦辉 | Caustic sludge treatment method |
| CN103693659B (en) * | 2013-11-11 | 2015-06-10 | 四川大学 | Method for concurrent production of potassium chloride and mineralization fixation of CO2 |
| CN104529633B (en) * | 2014-12-22 | 2018-01-16 | 山东省海洋化工科学研究院 | A kind of Chemical Mixed Fertilizer prepared using salt manufacturing, alkaline discarded object and preparation method thereof |
| CN106702139B (en) * | 2015-07-28 | 2018-05-22 | 中国科学院过程工程研究所 | A kind of method that sylvite is extracted from water-insoluble potassium bearing rock |
| CN113735138B (en) * | 2021-09-18 | 2023-08-22 | 青海中迪跃科技有限公司 | Ammonia distillation wastewater treatment method |
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