CN112745160A - Novel process for preparing NPK compound fertilizer by using phosphogypsum and potassium feldspar - Google Patents
Novel process for preparing NPK compound fertilizer by using phosphogypsum and potassium feldspar Download PDFInfo
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- CN112745160A CN112745160A CN202110079015.1A CN202110079015A CN112745160A CN 112745160 A CN112745160 A CN 112745160A CN 202110079015 A CN202110079015 A CN 202110079015A CN 112745160 A CN112745160 A CN 112745160A
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- filtrate
- phosphogypsum
- leaching
- compound fertilizer
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 32
- 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 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000002386 leaching Methods 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 7
- 239000011707 mineral Substances 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000011777 magnesium Substances 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 239000013589 supplement Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011591 potassium Substances 0.000 abstract description 12
- 239000011737 fluorine Substances 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000001502 supplementing effect Effects 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 4
- 229910004014 SiF4 Inorganic materials 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 3
- 229910003638 H2SiF6 Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 241000185686 Apocynum venetum Species 0.000 description 1
- 208000019025 Hypokalemia Diseases 0.000 description 1
- 229910018965 MCl2 Inorganic materials 0.000 description 1
- 229910004074 SiF6 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
- JAQXDZTWVWLKGC-UHFFFAOYSA-N [O-2].[Al+3].[Fe+2] Chemical compound [O-2].[Al+3].[Fe+2] JAQXDZTWVWLKGC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 229940104869 fluorosilicate Drugs 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052651 microcline Inorganic materials 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229910052652 orthoclase Inorganic materials 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 208000007645 potassium deficiency Diseases 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 229910052654 sanidine Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
本发明涉及一种利用磷石膏与钾长石制备NPK复合肥的新工艺，其特征在于包括以下步骤：（1）酸浸：将研磨后的磷石膏、钾长石与盐酸进行混合配料，进行浸出反应后固液分离，得到浸出渣和浸出液；（2）循环酸浸：将浸出液补酸后再循环处理下一批矿物，待重复步骤（1）数次后固液分离，得到滤渣和富集了P、K的滤液；（3）滤液净化：将步骤（2）所得滤液依次进行硫酸除钙，氨水中和除铝、铁、镁等杂质后得到精制的滤液；（4）NPK复合肥的制备；将步骤（3）所得滤液补磷后进行蒸发浓缩，制备出低（无）氯高浓度NPK复合肥。本发明利用了磷石膏中的氟处理钾长石，无需外加氟化物，获得了可溶性钾，实现了磷石膏与钾长石的无害化与高值化利用。
The invention relates to a new process for preparing NPK compound fertilizer by using phosphogypsum and potassium feldspar, which is characterized by comprising the following steps: (1) acid leaching: mixing and batching the ground phosphogypsum, potassium feldspar and hydrochloric acid, and carrying out After the leaching reaction, solid-liquid separation is obtained to obtain leaching residue and leaching solution; (2) Circulating acid leaching: the leaching solution is acidified and then recycled to process the next batch of minerals. The filtrate of P and K is collected; (3) Purification of the filtrate: the filtrate obtained in step (2) is sequentially subjected to sulfuric acid decalcification, and ammonia water is neutralized to remove impurities such as aluminum, iron, and magnesium to obtain a refined filtrate; (4) NPK compound fertilizer The filtrate obtained in step (3) is supplemented with phosphorus and then evaporated and concentrated to prepare low (no) chlorine and high concentration NPK compound fertilizer. The invention utilizes the fluorine in the phosphogypsum to treat the potassium feldspar without adding fluoride to obtain soluble potassium, and realizes the harmless and high-value utilization of the phosphogypsum and the potassium feldspar.
Description
Technical Field
The invention relates to the field of inorganic chemical industry, in particular to a novel process for preparing an NPK compound fertilizer by using phosphogypsum and potassium feldspar.
Background
The phosphogypsum is solid waste discharged in the wet-process phosphoric acid production, and 4-5 t of phosphogypsum is generated every 1t of phosphoric acid production. The main component of the phosphogypsum is CaSO4 ·2H2And O, the pH value is 1.5-4.5, the phosphogypsum is acidic, and the phosphogypsum usually contains undecomposed phosphorite, phosphoric acid, calcium fluoride, iron-aluminum oxide, acid insoluble substances, organic substances and other impurities which are not washed clean and is slightly soluble in water. With the rapid development of the phosphate fertilizer industry in China, the discharge amount of the phosphogypsum is in a greatly increasing trend year by year. The discharge of the phosphogypsum not only pollutes the environment, but also occupies a large amount of land, enterprises also need to invest a large amount of slag yard construction capital and operation management cost, the comprehensive utilization of the phosphogypsum is listed as a resource key project by the nation, the comprehensive utilization and harmless treatment of the phosphogypsum are well done to become an important task of the phosphorus chemical industry, and the method has important significance for saving natural resources, protecting the ecological environment, building a conservation-oriented society, developing the recycling economy and realizing the sustainable development of the industry. Currently, phosphorus chemical industry enterprises in China face double pressure of resources and environment, and sustainable development is seriously challenged; the industrial chain is not perfect, the product structure is not rich, and the added value of the product is low. At present, an effective technology is lacked for high-value utilization of phosphogypsum, and reasonable connection of upstream and downstream industries is realized.
The phosphate fertilizer and the potash fertilizer are used as nutrient element fertilizers of crops and play an extremely important role in the life metabolic process of the crops. In China, the yield of potash fertilizer and compound fertilizerAnd the dosage is insufficient, the proportion of nitrogen, phosphorus and potassium in the applied fertilizer is seriously imbalanced, and the phenomena of more nitrogen, less phosphorus and potassium deficiency are serious. The extraction of potassium mainly comes from soluble sylvite deposits, but China is seriously poor and the distribution is very uneven. According to statistics, the storage capacity of the water-soluble potassium salt in the world of 2012 is converted into K2The O accounts for 95.52 hundred million tons, the Chinese accounts for 2.1 hundred million tons, accounts for about 2.2 percent of the total storage capacity of the world, is mainly distributed in the Qinghai Kerr salt lake and the Xinjiang Apocynum venetum salt lake, and is inconvenient to develop and utilize. The water-insoluble potassium-containing ore beds in China are abundant, the reserves exceed 200 hundred million tons, and the potassium feldspar is mostly distributed in middle and eastern agriculture developed areas in the form of potassium feldspar. At present, the demand of potassium is large in China, the domestic market gap is huge, and a large amount of potassium fertilizer is imported every year. If the non-soluble potassium resource with huge reserves, such as potassium feldspar, can be changed into soluble potassium, the method has great significance. Therefore, how to develop the non-soluble potassium phosphate feldspar efficiently and economically is a difficult task for modern chemical engineering technologists.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a novel process for preparing an NPK compound fertilizer by using phosphogypsum and potassium feldspar.
The purpose of the invention is realized by the following technical scheme:
a new process for preparing NPK compound fertilizer by using phosphogypsum and potassium feldspar comprises the following steps:
(1) acid leaching: mixing the ground phosphogypsum, potassium feldspar and hydrochloric acid, blending, carrying out leaching reaction at 50-100 ℃, and carrying out solid-liquid separation after 2-10 hours to obtain leaching residue and leaching liquid.
(2) And (3) circulating acid leaching: and (3) supplementing acid to the leachate obtained in the step (1), then recycling the next batch of minerals, and after repeating the step (1) for a plurality of times, carrying out solid-liquid separation to obtain filter residue and P, K-enriched filtrate.
(3) Purifying the filtrate: and (3) sequentially removing calcium from the filtrate obtained in the step (2) by using sulfuric acid, and neutralizing with ammonia water to remove impurities such as aluminum, iron, magnesium and the like to obtain a refined filtrate.
(4) Preparing an NPK compound fertilizer; and (4) supplementing phosphorus to the filtrate obtained in the step (3), and then carrying out evaporation concentration to prepare the low (no) chlorine high-concentration NPK compound fertilizer.
P in the phosphogypsum2O55-20wt% of the total weight of the composition, and 0.5-5 wt% of the total weight of the composition.
K in the potassium feldspar2The content of O is 7-15 wt%.
The concentration of the hydrochloric acid used in the step (1) is 10-37%, and the dosage is 2: 1-6: 1 of liquid-solid ratio (hydrochloric acid volume (mL): phosphogypsum + potassium feldspar (g)).
The recycling time of the pickle liquor in the step (2) is 2-8 times, preferably 3-5 times.
The calcium sulfate removal conditions in the step (3) are as follows: according to n (Ca)2+): n(SO4 2-) =1: (0.8-1.2) adding 50-98% sulfuric acid solution at the reaction temperature of 30-90 ℃, the stirring speed of 400-1000 rpm and the reaction time of 0.5-3 h.
And (3) adjusting the pH value of the solution by using an ammonia water solution to perform fractional precipitation and impurity removal, slowly adjusting the pH value to 3.5, precipitating and removing iron, precipitating and removing aluminum when the pH value is 6.5, and precipitating and removing magnesium when the pH value is 9.
The phosphorus supplement agent in the step (4) is one or more of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate, and the addition amount of the phosphorus supplement agent is N + P in the obtained low-chlorine high-concentration NPK compound fertilizer or chlorine-free high-concentration NPK compound fertilizer2O5+K2The proportion of O is more than or equal to 40 percent (mass).
The principle of the invention is as follows: since potassium feldspar has a stable structure and does not generally react with other acids except hydrofluoric acid, hydrofluoric acid or fluoride salt (such as calcium fluoride) and other acids (such as sulfuric acid, phosphoric acid and hydrochloric acid) are required to be added in the process of decomposing the potassium feldspar by acid. The method utilizes the reaction of hydrochloric acid and fluorine in the phosphogypsum to generate hydrogen fluoride to decompose potassium feldspar in the phosphorus and potassium associated ore, and fluorosilicate formed by the reaction further participates in the decomposition of the potassium feldspar in the phosphorus and potassium associated ore. Assuming that the fluorine in phosphogypsum exists in the form of fluoride MF2 and the leaching agent is hydrochloric acid, the main chemical reactions involved include:
MF2 + 2HCl =MCl2 + 2HF↑ (1)
12HF + KAlSi3O8 + 4HCl = KCl + AlCl3 + 3SiF4 ↑ + 8H2O (2)
4HF + SiO2 =SiF4 ↑+2H2O (3)
2HF + SiF4 = H2SiF6 (4)
3SiF4 + 2H2O = 2H2SiF6 + SiO2↓(5)
H2SiF6 =2HF↑+ SiF4 ↑ (6)
compared with the prior art, the invention has the advantages that:
(1) the method can decompose the potassium feldspar by utilizing the fluorine in the phosphogypsum without additionally adding fluorine resources, has low decomposition temperature, and can recycle the acid and the fluorine in the system.
(2) The lixiviant hydrochloric acid used in the invention has wide sources, is an industrial byproduct, and solves the problem of the outlet of the byproduct hydrochloric acid.
(3) The process of the invention does not relate to high temperature and high pressure, and a plurality of production devices can refer to inorganic chemical industries such as wet-process phosphoric acid, soda chemical industry and the like, so the process of the invention is easy to implement.
(4) It can be used for treating potassium feldspar, and can also be used for treating various potassium-containing ores such as clay and nepheline.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
Example 1
(1) Acid leaching: 60g of ground phosphogypsum, 20g of potassium feldspar and 320mL of hydrochloric acid solution (the mass concentration is 22.5%) are mixed and proportioned. And (3) carrying out leaching reaction on the prepared feed liquid at 90 ℃, and carrying out solid-liquid separation after 4 hours to obtain leaching residues and leaching liquid.
(2) And (3) circulating acid leaching: and (3) supplementing acid to the leachate obtained in the step (1) and then recycling the next batch of minerals according to the addition amount of hydrochloric acid and the liquid-solid ratio in the step (1), and carrying out solid-liquid separation after repeating the step (1) for 3 times to obtain filter residue and the filtrate enriched with P, K.
(3) Purifying the filtrate: the filtrate obtained in the step (2) is processed according to the formula of n (Ca)2+): n(SO4 2-) Adding a sulfuric acid solution with the mass concentration of 85% in a ratio of 1:1, carrying out calcium removal reaction at 50 ℃ under the stirring condition of 500 revolutions per minute, and carrying out solid-liquid separation after 2 hours of reaction. Adding ammonia water into the obtained filtrate to slowly adjust the pH value to 3.5 to generate white precipitate, continuously adding ammonia water into the filtrate after filtration and separation to adjust the pH value to 6.5 to generate white precipitate, adding ammonia water into the filtrate after filtration and separation again to adjust the pH value to 9 to generate white precipitate, and performing filtration and separation to obtain filter residue and purified filtrate.
(4) Preparing an NPK compound fertilizer: adding 3g of ammonium dihydrogen phosphate serving as a phosphorus supplement agent into the purified filtrate obtained in the step (3), then performing evaporation concentration at 100 ℃ until the solid content in the filtrate is more than 500g/L, preparing the NPK compound fertilizer, and detecting N, P in the compound fertilizer2O5、K2The contents of O and Cl are respectively 16.8%, 35.1%, 5.9% and 9.4%, which meet the national standard and belong to low-chlorine high-concentration NPK compound fertilizer.
Example 2
(1) Acid leaching: and mixing 50g of ground phosphogypsum, 30g of potassium feldspar and 160mL of hydrochloric acid solution (the mass concentration is 37 percent). And (3) carrying out leaching reaction on the prepared feed liquid at 70 ℃, and carrying out solid-liquid separation after 6 hours to obtain leaching residues and leaching liquid.
(2) And (3) circulating acid leaching: and (3) supplementing acid to the leachate obtained in the step (1) and then recycling the next batch of minerals according to the addition amount of hydrochloric acid and the liquid-solid ratio in the step (1), and carrying out solid-liquid separation after repeating the step (1) for 5 times to obtain filter residue and the filtrate enriched with P, K.
(3) Purification of the filtrate: the filtrate obtained in the step (2) is processed according to the formula of n (Ca)2+): n(SO4 2-) Adding a 65% sulfuric acid solution in a ratio of 1:1.2, carrying out calcium removal reaction at 30 ℃ under the stirring condition of 800 revolutions per minute, and carrying out solid-liquid separation after reaction for 0.5 h. Adding ammonia water into the obtained filtrate to slowly adjust the pH value to 3.5 to generate white precipitate, continuously adding ammonia water into the filtrate after filtration and separation to adjust the pH value to 6.5 to generate white precipitate, adding ammonia water into the filtrate after filtration and separation again to adjust the pH value to 9 to generate white precipitate, and performing filtration and separation to obtain filter residue and purified filtrate.
(4) Preparing an NPK compound fertilizer: adding 5g of phosphoric acid serving as a phosphorus supplement agent into the purified filtrate obtained in the step (3), and then performing evaporation concentration at 100 ℃ until the solid content in the filtrate is more than 500g/L to prepare the NPK compound fertilizer, wherein detection shows that N, P in the compound fertilizer2O5、K2The contents of O and Cl are respectively 19.8%, 30.4%, 3.9% and 12.4%, which meet the national standard and belong to low-chlorine high-concentration NPK compound fertilizer.
Example 3
(1) Acid leaching: 40g of ground phosphogypsum, 40g of potassium feldspar and 160mL of hydrochloric acid solution (the mass concentration is 10%) are mixed and proportioned. And (3) carrying out leaching reaction on the prepared feed liquid at 100 ℃, and carrying out solid-liquid separation after 2 hours to obtain leaching residues and leaching liquid.
(2) And (3) circulating acid leaching: and (3) supplementing acid to the leachate obtained in the step (1) and then recycling the next batch of minerals according to the addition amount of hydrochloric acid and the liquid-solid ratio in the step (1), and carrying out solid-liquid separation after repeating the step (1) for 2 times to obtain filter residue and the filtrate enriched with P, K.
(3) Purifying the filtrate: the filtrate obtained in the step (2) is processed according to the formula of n (Ca)2+): n(SO4 2-) Adding 50% sulfuric acid solution at a ratio of 1:0.8, performing calcium removal reaction at 60 ℃ under a stirring condition of 400 r/min, and performing solid-liquid separation after 3h of reaction. Adding ammonia water into the filtrate to slowly adjust pH to 3.5 to generate white precipitate, filtering, adding ammonia water into the filtrate to adjust pH to 6.5 to generate white precipitate, filtering, adding ammonia water into the filtrate to adjust pH to 9 to generate white precipitate, filtering, separating to obtain filter residue and purifyingAnd (4) liquid.
(4) Preparing an NPK compound fertilizer: adding 5g of phosphoric acid serving as a phosphorus supplement agent into the purified filtrate obtained in the step (3), and then performing evaporation concentration at 100 ℃ until the solid content in the filtrate is more than 500g/L to prepare the NPK compound fertilizer, wherein detection shows that N, P in the compound fertilizer2O5、K2The contents of O and Cl are respectively 23.4%, 33.4%, 4.9% and 10.5%, which meet the national standard and belong to low-chlorine high-concentration NPK compound fertilizer.
Example 4
(1) Acid leaching: and mixing 30g of ground phosphogypsum, 50g of potassium feldspar and 480mL of hydrochloric acid solution (the mass concentration is 25 percent). And (3) carrying out leaching reaction on the prepared feed liquid at 50 ℃, and carrying out solid-liquid separation after 10 hours to obtain leaching residues and leaching liquid.
(2) Leaching liquor is circularly leached: and (3) supplementing acid to the leachate obtained in the step (1) and then recycling the next batch of minerals according to the addition amount of hydrochloric acid and the liquid-solid ratio in the step (1), and carrying out solid-liquid separation after repeating the step (1) for 8 times to obtain filter residue and the filtrate enriched with P, K.
(3) Purifying the filtrate: the filtrate obtained in the step (2) is processed according to the formula of n (Ca)2+): n(SO4 2-) Adding a sulfuric acid solution with the mass concentration of 98% in a ratio of 1:1, carrying out calcium removal reaction at 90 ℃ under the stirring condition of 1000 revolutions per minute, and carrying out solid-liquid separation after 2 hours of reaction. Adding ammonia water into the obtained filtrate to slowly adjust the pH value to 3.5 to generate white precipitate, continuously adding ammonia water into the filtrate after filtration and separation to adjust the pH value to 6.5 to generate white precipitate, adding ammonia water into the filtrate after filtration and separation again to adjust the pH value to 9 to generate white precipitate, and performing filtration and separation to obtain filter residue and purified filtrate.
(4) Preparing an NPK compound fertilizer: adding 8g of diammonium hydrogen phosphate serving as a phosphorus supplement agent into the purified filtrate obtained in the step (3), then performing evaporation concentration at 100 ℃ until the solid content in the filtrate is more than 500g/L, preparing the NPK compound fertilizer, and detecting N, P in the compound fertilizer2O5、K2The contents of O and Cl are respectively 15.4%, 26.4%, 2.9% and 7.5%, which meet the national standard and belong to low-chlorine high-concentration NPK compound fertilizer.
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