A kind of from method that potassium rich rock-lime hydro-thermal legal system is got potash fertilizer
Technical field
The present invention relates to a kind of from method that potassium rich rock-lime hydro-thermal legal system is got potash fertilizer.
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 2.5%2 simultaneously
#Auxiliary agent reacts 3h down at 900 ℃, and 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.
Goal 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) with potassium rich rock and lime pulverizing to 2cm;
(2) according to potassium rich rock: lime is 1: 0.8~1 ratio, potassium rich rock below the 2cm and lime fragment be delivered to carry out wet ball grinding in the ball mill, during wet pulverization, Gu: liquid=1: 0.75~1.20, 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 remove by filter slag, the extracting solution that will contain KOH is sent into vaporizer and is concentrated, and makes the intact Ca (OH) of unreacted
2Recrement is separated out, and carries out the second time then and filters, and removes recrement, obtains KOH solution;
(6) use the KOH solution that obtains to produce potash fertilizer.
In aforesaid method of the present invention, using the KOH solution that obtains to produce the step of potash fertilizer can be by feeding CO in the KOH concentrated 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 and lime are pulverized.
Use the extraction yield average out to 62.10% of method of the present invention potassium in 8 tests.
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) 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.
(4) 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.
(5) 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, and the aspect is single with regard to the stripping operation of potassium in addition, promptly can be considered silico-calcium potassium and mixes fertile production technique, itself be invention and innovation, it is particularly suitable for China's southern area, and this mixing fertilizer benefits to farm crop, and production cost is also lower.
Embodiment
Embodiment
Raw material
Potassium rich rock: pick up from Miyun County South Mountain, Beijing, its chemical constitution (%):
SiO
2TiO
2Al
2O (Fe
2O
3+ FeO) MnO
2CaO MgO K
2O Na
2O P
2O
5Loss on ignition adds up to
3
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%, market is bought.
(1) potassium rich rock meal 5.000g and lime meal 5.000g are inserted 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, add a little water again, make solid: liquid=1: 3;
(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,, adopt excessive water, obtain 100ml in the test and contain the potassium extracting solution for soluble potassium in the reaction product is as far as possible all extracted;
(4) will carry potassium liquid dilution 20 * 10=200 doubly (two-stage dilution), and measure potassium, na concn in the liquid sample with flare photometer, measurement result is converted into K
2O and Na
2O concentration is respectively 3960mg/l and 32mg/l, its Na
2O/K
2The O concentration ratio is 0.0081, and is very favourable to producing pure sylvite later on.
(5) potassium rich rock contains K
2O 12.79%, 5 gram powder sample can contain K
2O 639.5mg, extracting solution is amounted to K
2O concentration 3960mg/l, then 100ml contains K
2O 396.0mg, therefore, the extraction yield of potassium is 396.0 ÷, 639.5 * 100%=61.92% in the potassium rich rock.
(6) carry slag behind the potassium air-dry after, through X ray powder crystal diffraction analysis, main thing is hydrosilicate 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
2), 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.