CN1209323C - Process for preparing K fertilizer (K salt) from K-enriched rock and lime by hydrothermal method - Google Patents
Process for preparing K fertilizer (K salt) from K-enriched rock and lime by hydrothermal method Download PDFInfo
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- CN1209323C CN1209323C CN 01100475 CN01100475A CN1209323C CN 1209323 C CN1209323 C CN 1209323C CN 01100475 CN01100475 CN 01100475 CN 01100475 A CN01100475 A CN 01100475A CN 1209323 C CN1209323 C CN 1209323C
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- potassium
- lime
- gypsum
- rich rock
- koh
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- 239000011435 rock Substances 0.000 title claims abstract description 37
- 239000003337 fertilizer Substances 0.000 title claims abstract description 24
- 235000008733 Citrus aurantifolia Nutrition 0.000 title claims abstract description 14
- 235000011941 Tilia x europaea Nutrition 0.000 title claims abstract description 14
- 239000004571 lime Substances 0.000 title claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 150000003839 salts Chemical class 0.000 title 1
- 239000011591 potassium Substances 0.000 claims abstract description 86
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 86
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000010440 gypsum Substances 0.000 claims abstract description 15
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000000498 ball milling Methods 0.000 claims abstract 4
- 238000003756 stirring Methods 0.000 claims abstract 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 33
- 229940072033 potash Drugs 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 19
- 235000015320 potassium carbonate Nutrition 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002893 slag Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 238000011160 research Methods 0.000 description 9
- 239000004576 sand Substances 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910052900 illite Inorganic materials 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002050 diffraction method Methods 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- YMKIRWHSXOBLCF-UHFFFAOYSA-N [Mg].[P].[Ca] Chemical compound [Mg].[P].[Ca] YMKIRWHSXOBLCF-UHFFFAOYSA-N 0.000 description 1
- LFZAXBDWELNSEE-UHFFFAOYSA-N [S].[K] Chemical compound [S].[K] LFZAXBDWELNSEE-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- JEWHCPOELGJVCB-UHFFFAOYSA-N aluminum;calcium;oxido-[oxido(oxo)silyl]oxy-oxosilane;potassium;sodium;tridecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.[Na].[Al].[K].[Ca].[O-][Si](=O)O[Si]([O-])=O JEWHCPOELGJVCB-UHFFFAOYSA-N 0.000 description 1
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 244000013123 dwarf bean Species 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- -1 glaukonine Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001743 phillipsite Inorganic materials 0.000 description 1
- ZDHURYWHEBEGHO-UHFFFAOYSA-N potassiopotassium Chemical compound [K].[K] ZDHURYWHEBEGHO-UHFFFAOYSA-N 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Fertilizers (AREA)
Abstract
本发明提供了一种从富钾岩石制取钾肥的方法，包括：将富钾岩石、石灰及石膏粉碎至2cm以下；按照富钾岩石∶石灰∶石膏之间1∶0.8～1∶0.2～0.25的比例，将2cm以下的富钾岩石、石灰、石膏碎块输送至球磨机中进行湿法球磨，湿法粉碎时，固∶液比为1∶0.75～1.20，通过湿法球磨将物料磨细至200目以下；将磨好的物料输送至贮料器中，调整水分，使固液比在1∶1～3，并进行搅拌混合；将物料转移至高压反应釜中，通入高压蒸气，在130-250℃进行水热反应，恒温5至24小时，得到KOH；使用得到的KOH制取钾盐。The invention provides a method for producing potassium fertilizer from potassium-rich rocks, comprising: crushing potassium-rich rocks, lime and gypsum to below 2 cm; The ratio of potassium-rich rock, lime, and gypsum below 2cm is transported to the ball mill for wet ball milling. During wet crushing, the solid:liquid ratio is 1:0.75～1.20, and the material is ground to fineness by wet ball milling. Under 200 mesh; transport the ground material to the storage container, adjust the water content so that the solid-liquid ratio is 1:1~3, and stir and mix; transfer the material to a high-pressure reaction kettle, feed high-pressure steam, and Carry out hydrothermal reaction at 130-250°C and keep the temperature constant for 5 to 24 hours to obtain KOH; use the obtained KOH to prepare potassium salt.
Description
Technical field
The present invention relates to a kind ofly produce the method for potash fertilizer from potassium rich rock-lime-gypsum hydrothermal method.
Background technology
Potassium rich rock (insoluble potassium ore deposit) is meant the special rock of mainly being made up of spontaneous high potassium silicate mineral of a class.In this rocks, potassium-bearing mineral is mainly potassium felspar sand, illite, glaukonine, mica mineral etc., K on the chemical ingredients
2O content is higher, generally at 8%-16%.China is containing very abundant potassium rich rock resource, and widely distributes.According to the door expert of Ministry of Geology and Mineral Resources estimation, national potassium rich rock reserves are amounted to K
2O is about more than 5,000,000,000 tons.
China is a country that the soluble potassium salt resource extremely lacks, in order to solve agricultural potash fertilizer wretched insufficiency problem, developing jointly the soluble potassium salt mine in Cha Erhan salt lake, Qinghai with Israel, annual also from a large amount of KCl of external import, and plan and surrounding countries (as Thailand etc.) develop jointly local soluble potassium salt mine, but still can not deal with problems fully.Succeed if utilize potassium rich rock to produce potash fertilizer, and can put into production in a large number, certainly will make huge contribution for the sustainable and healthy development of China's agricultural.
Therefore external industrially developed country (as Canada, France, Germany, Russia, the U.S. etc.) soluble potassium salt aboundresources utilizes insoluble potassium ore deposit to produce potash fertilizer research and carries out lessly relatively.The research that China utilizes potassium rich rock to carry potassium starts from the fifties phase not, and the research-and-development activity over past ten years is paid close attention to by people day by day.Conclusion is got up, and utilizing potassium rich rock to produce potash fertilizer at present both at home and abroad has three kinds of approach, i.e. calcination method or sintering process, hydrothermal chemistry method, microbiological degradation method.
1. calcination method or sintering process
This method is studied often, and principle is that potassium rich rock and other batching are calcined under hot conditions, makes its structure deteriorate, and potassium and other element form soluble potassium salt, reach and put forward the potassium purpose.In all multi-methods, alkali fusion is occupied an leading position.Alkali fusion is meant feldspathoid and alkali (NaOH, Na
2CO
3) or/and CaCO
3Congruent melting at high temperature, the slag water retting dissolves the potassium metaaluminate that, and can make K through carburizing reagent
2CO
3And Al (OH)
3, reaction can be expressed as:
Mining design research institute of the Ministry of Chemical Industry adopts potassium felspar sand: Wingdale=1: 2.61,1330 ℃ of following fusions, back leaching that grog is levigate contains potassium solution and produces K
2CO
3, recrement is used to make cement.People such as China University of Geosciences's horse great writing adopt rich potassium volcanics breeze: Na
2CO
3=1: 1.1～1.4 800-830 ℃ of calcining 1.5-2 hour, and leaching liquid is used to make K
2CO
3, recrement is used for synthetic zeolite.The Wang Li of chemical engineering institute of Sichuan University gives birth to report, adopts potassium felspar sand: gypsum: Wingdale=1: 0.39: 3, mix the 2.5%2# auxiliary agent simultaneously, and react 3h down at 900 ℃, the potassium solubility rate can reach 93%.Sichuan has the people to adopt green bean rock: Wingdale: NaCl=1: 1: 0.6,800-820 ℃ of calcining, the grog dipping extracted KCl.Feng County, Jiangsu Province potash fertilizer plant adopts salt-roast-process to extract KCl, and smelting temperature is up to 1900 ℃.Somebody's report mixes the back at 700 ℃ of roasting 1h with potassium bearing rock with Wingdale, calcium oxide, the transformation efficiency of potassium can reach 66%; Potassium felspar sand, Wingdale, rhombspar, fluorite, coke mixture can extract K 1500 ℃ of smeltings
2CO
3Rich potassium shale: phosphatic rock: rhombspar: coke=1: 0.2: 0.72: 0.45 1200-1300 ℃ of fusion, can make fused(calcium magnesium phosphorus)potash fertilizer.Units such as cement mill, coloured glaze river, Beijing once allocated potassium rich rock in manufacture of cement, under 1300-1500 ℃ of high temperature, can obtain containing K
2CO
3And K
2SO
4The kiln ash, can obtain kiln ash potash fertilizer by method of trapping.USSR (Union of Soviet Socialist Republics) once utilized nepheline to carry potassium, but mainly was for producing aluminum oxide, by-product sylvite.
2. hydrothermal chemistry method
Principle is Chemicals such as employing soda acid, decomposes potassium rich rock in solution, and it is molten from the purpose of coming out to reach potassium ion.It can be subdivided into acid system and alkaline process again.
Acid system
The potassium rich rock and the acid-respons that contain illite, hydromica can make that most of potassium discharges in the rock, but acid (except for hydrofluoric acid) is difficult to stripping to the potassium in the potassium felspar sand lattice.The data report is arranged, illite is pulverized the back at 800-850 ℃ of roasting 2h, use 30%H then
2SO
4Solution was pressed liquid-solid ratio 3: 1, leached under 70-80 ℃ of condition, can make K
2SO
4Tianjin designing institute of the Ministry of Chemical Industry and Wuan, Hebei province fertilizer plant adopt the pressurization acid pasting, carry potassium in illite.Changsha chemical mine design and research institute adopts H
2SO
4And auxiliary agent (may be fluorochemical), decomposing of potassium feldspar under 100 ℃ of conditions, to extract potassium, auxiliary agent is recycled after reclaiming.The data report is arranged, and the someone adopts strong acid leaching method, at H
2SO
4Exist down, utilize hydrofluoric acid with the potassium stripping in the feldspar, to produce sylvite.
Alkaline process
The alkaline process Potassium process is studied seldom.Japan NaOH-Ca (OH) when once the someone adopted 100-400 ℃
2Potassium in the mixed solution high pressure extraction potassium felspar sand.Cherman finds that in the time of 150-200 ℃, KOH solution and Switzerland Opalinus area shale react, can generate phillipsite, make on the one hand that potassium obtains activation in the shale, the aspect is unlikely the leaching by water institute again because potassium ion is in the cavity of zeolite and the passage in addition, can make a kind of long-acting potash fertilizer.According to Chinese science newspaper report on January 24th, 1994, employings such as professor Yan Yongjie of East China University of Science pressurization lime method is proposed potassium research to the two kinds of potassium felspar sands in Hunan Province and Jiangsu Province, but details is not reported.
3. microbiological degradation method
Units such as Institute of Geomechanics of Chinese Academy of Geological Sciences to be to be activator through the K-907 of nuclear radiation mutagenesis screening bacterial strain, make that structure potassium changes the soluble potassium that plant can absorb in glaukonine, the illite.Ecological the research that silicate bacteria is dissociated potassium in the potassium felspar sand of having carried out is jointly used in Liaoning Institute of Micro-biology and Chinese Academy of Sciences Shenyang.Hebei Academy of Sciences Institute of Micro-biology works out biological potassium fertilizer " huge microorganism potassium ".The Chinese Academy of Agricultural Sciences also carried out the research of biological system potash fertilizer.
Summary of the invention
The purpose of this invention is to provide a kind of cut down the consumption of energy and cost produce the novel method of potash fertilizer from potassium rich rock.
The present inventor has since nineteen ninety-six carried out in potassium rich rock the research of extracting potassium, carries both at home and abroad on the empirical basis of potassium using for reference, created a kind of under half wet condition the lime hydrothermal method put forward the potassium novel process.Be reflected under the static conditions and carry out, can reduce energy consumption greatly, obtained KOH, K
2CO
3And K
2SO
4Goods.If slag can obtain further rationally utilizing, then can reduce cost greatly, will start a new way for solving China's potash fertilizer wretched insufficiency problem.
The invention provides and a kind ofly produce the method for potash fertilizer, comprising from potassium rich rock:
(1) potassium rich rock, lime and terra alba are broken to below the 2cm;
(2) according to potassium rich rock: lime: 1: 0.8～1: 0.2～0.25 ratio between the gypsum, potassium rich rock below the 2cm, lime, gypsum fragment be delivered to carry out wet ball grinding in the ball mill, during wet pulverization, Gu: liquor ratio is 1: 0.75～1.20, and is by wet ball grinding that material is levigate to 200 orders;
(3) will grind good mass transport to bank, adjust moisture, and make solid-to-liquid ratio 1: 1～3, and mix;
(4) material is transferred in the autoclave, feeds high compressed steam, at 130-250 ℃, preferably carry out hydro-thermal reaction at 170-190 ℃, constant temperature 5 to 24 hours preferred 7 to 12 hours, obtains containing the extracting solution of KOH;
(5) open reactor, take out reactant and filter, slag can fully utilize, and the extracting solution that will contain KOH is sent into vaporizer.KOH solution is concentrated in vaporizer then, also has the intact Ca (OH) of unreacted simultaneously
2And CaSO
4Recrement is separated out.Carry out the second time then and filter,, can obtain the higher KOH solution of concentration to remove recrement.
(6) use the KOH that obtains to produce potash fertilizer.
In aforesaid method of the present invention, using the KOH obtain to produce the step of potash fertilizer can be by feeding CO in KOH solution
2Gas (or adds H
2SO
4), again through evaporative crystallization, can make K
2CO
3(or K
2SO
4) product.
In aforesaid method of the present invention, can be undertaken by adopting jaw crusher the step that potassium rich rock, lime and gypsum are pulverized.
By method of the present invention, the extraction yield average out to 75.14% of the extraction yield of potassium potassium in 9 tests in the potassium rich rock.
Method of the present invention has following characteristics:
(1) Japanese scholar adopts NaOH-Ca (OH)
2Potassium in the mixed solution high pressure extraction potassium felspar sand, though can obtain higher potassium solubility rate, because of containing a large amount of Na in the reaction rear filtrate
+,, need carry out Na in order to obtain the sylvite goods
+K
+Separate, more loaded down with trivial details on the technology, and the cost height.Need not contain Na in my technology
+Material, employing be to contain Ca
2+Material can make the separation purification process obtain simplifying, and easily obtains purer potash fertilizer goods.
(2) this process using wet ball grinding can merge fine grinding and batch mixing two procedures, makes several materials that participate in reaction reach sufficient mixing in abrasive material, can also receive dustproof preferably effect simultaneously.
(3) in the prescription because the existence of gypsum is arranged, excited Ca (OH) greatly
2Activity, the solubility rate of potassium is improved reaches 13%.
(4) consumption of water is of crucial importance in the prescription, and hypervolia or very few is all unfavorable to producing.The amount ratio of this process water lower (solid-to-liquid ratio 1: 1～3), one side has guaranteed the result of extraction of potassium, the aspect can make the inventory of participating in reaction increase in the reactor of same volume in addition, has improved the material treatment capacity, has just enlarged industrial scale.
(5) when carrying out large-scale commercial production, can adopt the horizontal high-pressure reactor, because of material has reached sufficient mixing after fine grinding, thereby in still, not needing restir, the stripping reaction can be carried out under static conditions, and is easy to operate, energy consumption is low, and production cost is reduced greatly.
(6) when carrying out this process study, I am placed on focus on the stripping operation of potassium in the potassium rich rock, the sylvite of back is produced operation (from filtering workshop section) on the one hand has the technology of comparative maturity to use for reference, the innovation composition is little, the aspect is single with regard to the stripping operation of potassium in addition, promptly can be considered silico-calcium sulphur potassium and mix fertile production technique, itself be invention and innovation, it is particularly suitable for China's southern area, this mixing is fertile to benefit to farm crop, and production cost is also lower.
Embodiment
Raw material
Potassium rich rock: pick up from Miyun County South Mountain, Beijing, its chemical constitution (%):
SiO
2TiO
2Al
2O
3(Fe
2O
3+ FeO) MnO
2CaO MgO K
2O Na
2O P
2O
5Loss on ignition adds up to
63.09 0.71 15.69 4.41 0.02 0.15 0.37 12.79 0.22 0.04 1.93 99.42
X ray powder crystal diffraction analysis points out that this potassium rich rock mineral composition is based on potassium felspar sand, and other is a quartz etc.
Lime: CaO content 97%, purchase in market.
Gypsum: purchase in market.
(1) with potassium rich rock meal 5.000g, lime meal 4.000g, semi-hydrated gypsum powder 1.000g inserts in the agate mortar, add about 10ml water, fully grind, raw meal particle size is reached below 200 orders, and uniform mixing, then material is transferred in the plastic ware, adds a little water again, make solid: liquid :=1: 1.5;
(2) plastic ware that will fill sample is inserted in the autoclave, at 190 ℃ of constant temperature 7h;
(3) after the autoclave cooling, take out plastic ware, reaction product is moved into strainer, filter, obtain 103ml in the test and contain the potassium extracting solution;
(4) with 20 * 10=200 times of dilution of extracting solution (two-stage dilution), measure potassium, na concn in the liquid sample with flare photometer, measurement result is converted into K
2O and Na
2O concentration is respectively 4740mg/l and 36mg/l, its Na
2O/K
2The O concentration ratio is 0.0076;
(5) 5 gram potassium rich rock breezes contain K
2O 639.5mg, extracting solution is amounted to K
2O concentration 4740mg/l, then 103ml contains K
2O 488.2mg, therefore, the extraction yield of potassium is 488.2 ÷, 639.5 * 100%=76.34% in the potassium rich rock;
(6) carry slag behind the potassium air-dry after, be weighed as 10.1g, through X ray powder crystal diffraction analysis, main thing is calcium silicate hydrate mutually.
The potassium solution of carrying that test of many times is obtained mixes, and evaporation concentration in vaporizer removes by filter because of concentrating the throw out of separating out and (is mainly the intact Ca (OH) of unreacted
2And CaSO
4), the clear liquid that obtains is fed CO
2Gas (or adds H
2SO
4), can make K through evaporative crystallization again
2CO
3(or K
2SO
4) product.The product thing is confirmed by X ray powder crystal diffraction analysis mutually.
According to Japanese scholar's distant mountain one youth's research report, calcium silicate hydrate can be used as the heavy metal sorbing material, and I utilize CuSO
4Solution has carried out qualitative test, confirms to truly have the characteristic of this respect.Scoriaceous comprehensive utilization remains further to be furtherd investigate.
Used instrument in the experiment
(1) flame photometer HG-3 type, instrument for environmental protection factory in Beijing makes;
(2) X-ray diffractometer Y-3 type, Dandong instrument plant makes.
Claims (3)
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|---|---|---|---|
| CN 01100475 CN1209323C (en) | 2001-01-15 | 2001-01-15 | Process for preparing K fertilizer (K salt) from K-enriched rock and lime by hydrothermal method |
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308265C (en) * | 2002-12-19 | 2007-04-04 | 中国科学院地质与地球物理研究所 | Method for preparing potash manure (kali salt) from potassium-rich rock using hydrothermal chemical reaction |
| CN1323056C (en) * | 2004-04-30 | 2007-06-27 | 河南省科学院地理研究所 | Process for producing amorphous silicon-kalium fertilizer |
| CN101450875A (en) * | 2007-12-05 | 2009-06-10 | 中国科学院地质与地球物理研究所 | Method for preparing multielement micropore mineral fertilizer from silicate rock through hydrothermal chemical reaction |
| CN102267817B (en) * | 2010-06-02 | 2013-08-28 | 中国科学院地质与地球物理研究所 | Method for producing silicon-potassium-calcium microporous mineral fertilizer |
| CN106866207A (en) | 2013-05-06 | 2017-06-20 | 麻省理工学院 | With the alkali metal ion source of moderate ion release rate and forming method |
| EP4071115A1 (en) * | 2017-01-18 | 2022-10-12 | Massachusetts Institute Of Technology | Potassium-releasing material |
| CN111534704B (en) * | 2020-06-28 | 2022-06-07 | 山西省岩矿测试应用研究所(山西省贵金属及珠宝玉石检测中心) | Method for synergistically extracting potassium and rubidium from potassium-containing rock |
| CN119735468B (en) * | 2024-12-17 | 2025-08-22 | 中国石油大学(华东) | Production method of potassium humate fertilizer by continuous high-pressure hydrothermal method using potassium feldspar |
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