CN112408429A - Process for refining primary saline water and preparing by-product slow-release compound fertilizer - Google Patents
Process for refining primary saline water and preparing by-product slow-release compound fertilizer Download PDFInfo
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- CN112408429A CN112408429A CN202011335218.4A CN202011335218A CN112408429A CN 112408429 A CN112408429 A CN 112408429A CN 202011335218 A CN202011335218 A CN 202011335218A CN 112408429 A CN112408429 A CN 112408429A
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 40
- 150000001875 compounds Chemical class 0.000 title claims abstract description 26
- 238000007670 refining Methods 0.000 title claims abstract description 19
- 239000006227 byproduct Substances 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title description 2
- 239000011780 sodium chloride Substances 0.000 title description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 57
- 239000012267 brine Substances 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 37
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000011575 calcium Substances 0.000 claims abstract description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011777 magnesium Substances 0.000 claims abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- 239000001103 potassium chloride Substances 0.000 claims abstract description 18
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 40
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011591 potassium Substances 0.000 abstract description 11
- 229910052700 potassium Inorganic materials 0.000 abstract description 11
- 239000010703 silicon Substances 0.000 abstract description 11
- 229910052710 silicon Inorganic materials 0.000 abstract description 11
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 8
- 239000000460 chlorine Substances 0.000 abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 abstract description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract 1
- 229940072033 potash Drugs 0.000 abstract 1
- 235000015320 potassium carbonate Nutrition 0.000 abstract 1
- 238000013268 sustained release Methods 0.000 abstract 1
- 239000012730 sustained-release form Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 description 31
- 239000000203 mixture Substances 0.000 description 11
- 235000015097 nutrients Nutrition 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002002 slurry Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RJKFOVLPORLFTN-LEKSSAKUSA-N Progesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 RJKFOVLPORLFTN-LEKSSAKUSA-N 0.000 description 2
- 238000009874 alkali refining Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000011361 granulated particle Substances 0.000 description 1
- -1 pharmacy Substances 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229960003387 progesterone Drugs 0.000 description 1
- 239000000186 progesterone Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
- C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
-
- 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
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
-
- 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
Abstract
The invention discloses a process for refining primary brine and producing a byproduct slow-release compound fertilizer with high efficiency and economy, which comprises the following steps: adjusting the pH value of the crude brine to 10-12, and then mixing the crude brine with H3PO4Mixing the solution until the pH value is 9-11, and carrying out solid-liquid separation; the solute of the crude brine is industrial potassium chloride. The method is simple, the content of calcium and magnesium ions in the primary brine in the ionic membrane electrolytic potash process is effectively reduced by optimizing the primary brine refining process, and the by-product sustained-release compound fertilizer rich in calcium, magnesium, potassium, silicon and chlorine is obtained.
Description
Technical Field
The invention belongs to the field of chlor-alkali industry, and particularly relates to a process for refining primary brine and producing a byproduct slow-release compound fertilizer.
Background
The potassium hydroxide has a chemical formula of KOH, is white powder or flaky solid, has strong basicity and corrosivity, is very easy to absorb moisture in air to deliquesce, and absorbs carbon dioxide to form potassium carbonate. The potassium hydroxide can be used for producing potassium salt, soap, dye, medicine and desiccant, and preparing progesterone, vanillin, cosmetics, etc., and can be widely applied in the fields of agriculture, daily chemicals, pharmacy, dye, medicine, etc.
In the current industrial production process of potassium hydroxide, the potassium chloride raw material contains a large amount of impurities such as soil, calcium, magnesium and the like, and the brine refining process needs to be carried out twice on the potassium chloride raw material. Wherein, the primary brine refining mainly comprises the steps of precipitating and separating mud and most of calcium and magnesium ions in raw materials, and if the content of the calcium and magnesium ions is too high, the load of a resin tower in the secondary brine refining process is too high, the resin dosage is increased, and the regeneration cost is increased. The traditional two-alkali refining method has no obvious effect on removing calcium and magnesium ions, and the obtained salt mud can only be directly discarded, so that the resource waste is caused, and the treatment cost of solid waste is increased.
In fact, the salt slurry produced in the primary brine refining process contains a large amount of calcium, magnesium, potassium, silicon, chlorine and the like, and is expected to be used as a raw material of an active fertilizer. However, the traditional primary brine refining process does not consider the fertilizer effect of the salt slurry, so that the obtained salt slurry is uneven in distribution of all components, high in calcium and magnesium content, single in fertilizer elements, poor in fertilizer efficiency and release performance and not suitable for being directly used as a fertilizer.
Disclosure of Invention
The invention aims to provide an efficient and economic process for refining primary brine and producing a byproduct of a slow-release compound fertilizer, which can be used for refining the primary brine with low calcium and magnesium content and producing the byproduct of the slow-release compound fertilizer rich in calcium, magnesium, potassium, silicon and chlorine, and can slowly release fertilizer efficiency and be fully absorbed by plants.
In order to more fully and effectively utilize the salt mud in the process of industrially producing potassium hydroxide, the inventor has surprisingly found through a large number of experimental studies that the content of calcium and magnesium impurities in primary brine can be greatly reduced by accurately controlling the technological parameters such as pH, temperature, retention time and the like in the primary brine refining process, and a slow-release compound fertilizer which is rich in calcium, magnesium, potassium, silicon and chlorine and can effectively control the fertilizer efficiency release speed as a byproduct can be obtained, so that the elements such as calcium, magnesium, phosphorus, potassium, chlorine, silicon and the like in the compound fertilizer are gradually released and are fully absorbed by plants.
In order to achieve the above object, the present invention provides a primary brine purificationThe process of producing slow released composite fertilizer as side product includes the following steps: adjusting the pH value of the crude brine to 10-12, and then mixing the crude brine with H3PO4Mixing the solution until the pH value is 9-11, and carrying out solid-liquid separation;
the solute of the crude brine is industrial potassium chloride.
The industrial potassium chloride provided by the invention is industrial potassium chloride with quality grades such as product properties, net content and the like meeting the national standard GB/T7118-.
In the specific embodiment of the invention, the concentration of the crude brine is 280-350 g/L, and preferably 300-330 g/L.
In the specific embodiment of the invention, KOH or KOH solution is adopted to adjust the pH value of the crude brine to 10-12; further, KOH solution with the mass fraction of 30-48% is adopted to adjust the pH value of the crude brine to 10-12.
Said H3PO4The mass fraction of the solution is 5-20%.
In the present embodiment, with H3PO4And after the solutions are mixed, standing the generated solid-liquid mixed system for natural sedimentation for 10-25 s, and then carrying out solid-liquid separation.
In the present embodiment, the compound is represented by formula II3PO4Before the solution is mixed, the temperature of a solution system is 50-90 ℃, and preferably 60-80 ℃;
further, with H3PO4After the solution mixing is completed, the solution system is cooled and settled.
According to the above method, the solid is subjected to solid-liquid separation, and then granulated and dried, and further, the granulated particles have a particle diameter of 2 to 5 mm.
The moisture content of the solid of the invention before granulation is 25-45%, preferably 30-40%.
The invention also provides a slow-release compound fertilizer, which comprises the solid obtained by the method.
The compound fertilizer comprises the following components in parts by weight: 15-20 parts of potassium chloride, 10-20 parts of magnesium, 3-10 parts of calcium, 3-8 parts of phosphorus and 15-20 parts of silicon dioxide.
The invention also provides a slow-release compound fertilizer prepared from the solid obtained by the method.
When the salt mud prepared by the method for refining primary brine is used for preparing the fertilizer, the salt mud prepared by the method can be directly granulated and dried to prepare a fertilizer product; the salt slurry prepared by the invention can be mixed with other components or subjected to processes such as further fermentation to prepare compound fertilizer products and the like, and the salt slurry prepared by the invention is used in the preparation process and belongs to the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) the calcium and magnesium content of the primary brine obtained by the method is low, and the quality of the primary brine is greatly improved compared with the traditional two-alkali refining process.
(2) The salt mud byproduct of the method is rich in calcium, magnesium, potassium, silicon and chlorine, all components are uniformly distributed, the salt mud can be directly used as a fertilizer, the salt mud fertilizer has good slow release property, inorganic substances after the fertilizer is applied can be slowly dissolved in soil, the release rate of fertilizer efficiency can be effectively controlled, plants can be fully absorbed, and the fertilizer is prevented from being lost too fast.
(3) The method is simple to operate, can realize the efficient utilization of resources in the industrial production process of the potassium hydroxide, and is economic and environment-friendly.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. Other embodiments, which can be obtained by one skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The dechlorinated brine used in the embodiment of the invention is potassium chloride electrolysis outlet light brine which is dechlorinated and is KCl solution containing about 160 g/L.
Example 1
(1) Heating the dechlorinated salt water solution in the water mixing bucket to 60 ℃, pumping into a salt dissolving pool, mixing and dissolving with solid industrial-grade potassium chloride raw materials, and preparing into 300g/L crude salt water.
(2) The crude brine was passed through a baffle to a crude brine storage tank, to which was added a 30% KOH solution to adjust the pH to 10.
(3) The solution with the PH value of 10 in the step (2) is pumped into 300m3In the clarifying tank, the flow rate is 30m3S, 5% H addition3PO4Adjusting the pH value of the solution to 9 to generate a solid-liquid mixture.
(4) Naturally cooling and settling the solid-liquid mixture in a clarifying barrel, reducing the temperature to 20 ℃, and controlling the retention time of the solid-liquid mixture in the clarifying barrel to be 10 s.
(5) And filtering the supernatant in the clarifying barrel by a Gole filter, and delivering primary brine of the filtrate to secondary brine refining.
(6) And (3) sending the sediment at the middle lower part of the clarifying barrel and the solid intercepted by the Goll filter, namely the salt mud into a plate frame for filter pressing, performing filter pressing until the water content is 30% to obtain a filter cake, and directly granulating the filter cake to obtain solid particles with the particle size of 2-5 mm.
(7) And drying the solid particles to obtain the compound fertilizer rich in calcium, magnesium, phosphorus, potassium and silicon.
Example 2
(1) Heating the dechlorinated salt water solution in the water mixing bucket to 60 ℃, pumping into a salt dissolving pool, mixing and dissolving with solid industrial-grade potassium chloride raw materials, and preparing into 300g/L crude salt water.
(2) The crude brine was passed through a baffle to a crude brine storage tank, to which was added a 30% KOH solution to adjust the pH to 10.
(3) The solution with the PH value of 10 in the step (2) is pumped into 300m3In the clarifying tank, the flow rate is 30m3S, 5% H addition3PO4Adjusting the pH value of the solution to 9 to generate a solid-liquid mixture.
(4) Naturally cooling and settling the solid-liquid mixture in a clarifying barrel, reducing the temperature to 40 ℃, and controlling the retention time of the solid-liquid mixture in the clarifying barrel to be 10 s.
(5) And filtering the supernatant in the clarifying barrel by a Gole filter, and delivering primary brine of the filtrate to secondary brine refining.
(6) And (3) sending the sediment at the middle lower part of the clarifying barrel and the solid intercepted by the Goll filter, namely the salt mud into a plate frame for filter pressing, performing filter pressing until the water content is 30% to obtain a filter cake, and directly granulating the filter cake to obtain solid particles with the particle size of 2-5 mm.
(7) And drying the solid particles to obtain the compound fertilizer rich in calcium, magnesium, phosphorus, potassium and silicon.
Example 3
(1) Heating the dechlorinated salt water solution in the water mixing bucket to 80 ℃, pumping into a salt dissolving pool, mixing and dissolving with solid industrial-grade potassium chloride raw materials, and preparing into crude salt water of 330 g/L.
(2) The crude brine was passed through a baffle to a crude brine storage tank, to which was added a 48% KOH solution to adjust the pH to 10.
(3) The solution with the PH value of 10 in the step (2) is pumped into 300m3In the clarifying tank, the flow rate is 30m3S, 20% H addition3PO4Adjusting the pH value of the solution to 9 to generate a solid-liquid mixture.
(4) Naturally cooling and settling the solid-liquid mixture in a clarifying barrel, reducing the temperature to 40 ℃, and controlling the retention time of the solid-liquid mixture in the clarifying barrel to be 25 s.
(5) And filtering the supernatant in the clarifying barrel by a Gole filter, and delivering primary brine of the filtrate to secondary brine refining.
(6) And (3) sending the sediment at the middle lower part of the clarifying barrel and the solid intercepted by the Goll filter, namely the salt mud into a plate frame for filter pressing, performing filter pressing until the water content is 40% to obtain a filter cake, and directly granulating the filter cake to obtain solid particles with the particle size of 2-5 mm.
(7) And drying the solid particles to obtain the compound fertilizer rich in calcium, magnesium, phosphorus, potassium and silicon.
Comparative example 1 conventional primary brine purification method
(1) Heating the dechlorinated salt water solution in the water mixing bucket to 60 ℃, pumping into a salt dissolving pool, mixing and dissolving with solid industrial-grade potassium chloride raw materials, and preparing into 300g/L crude salt water.
(2) The crude brine was passed through a baffle to a crude brine storage tank, to which was added a 30% KOH solution to adjust the pH to 10.
(3) The solution with the PH value of 10 in the step (2) is pumped into 300m3Adding 1mol/LK into the clarifying tank2CO3The solution was brought to a pH of 10.5 to form a solid-liquid mixture.
(4) And naturally cooling and settling the solid-liquid mixture in a clarifying barrel.
(5) And filtering the supernatant in the clarifying barrel by a Gole filter, and delivering primary brine of the filtrate to secondary brine refining.
(6) And (3) sending the sediment at the middle lower part of the clarifying barrel and the solid intercepted by the Goll filter, namely the salt mud into a plate frame for filter pressing, performing filter pressing until the water content is 30% to obtain a filter cake, and directly granulating the filter cake to obtain solid particles with the particle size of 2-5 mm.
(7) And drying the solid particles to obtain the salt mud particles.
The calcium and magnesium ion content of the primary refined brine obtained in examples 1 to 3 and comparative example 1 was measured, and the measurement results are shown in table 1.
TABLE 1 content of calcium and magnesium ions in the first refined brine
| Item | Calcium magnesium ion |
| Example 1 | 0.62ppm |
| Example 2 | 0.58ppm |
| Example 3 | 0.39ppm |
| Comparative example 1 | 1.55ppm |
As can be seen from table 1, the content of calcium and magnesium ions in the primary refined brine obtained in examples 1 to 3 was 0.39 to 0.62ppm, calcium and magnesium ions in the potassium chloride raw material could be effectively removed, primary refinement of the crude brine could be achieved, and the effect was better than that of the conventional method.
The content of the components of the salty mud obtained in examples 1 to 3 and comparative example 1 was measured, and the measurement results are shown in table 2.
TABLE 2 content of salty mud component
As shown in Table 2, the salty mud obtained in examples 1 to 3 had a KCl content of 16.2 to 20.1%, a Mg content of 12.5 to 16.8%, a Ca content of 3.2 to 4.6%, a P content of 3.4 to 4.1%, and SiO2The content is 15.3% -19.2%, and the content of P in the salt mud obtained in the comparative example 1 is only 0.2%, so that the salt mud obtained by the method is more balanced in fertilizer elements and rich in calcium, magnesium, phosphorus, potassium, chlorine and silicon.
The compound fertilizer obtained in example 2 was subjected to the measurement of the nutrient release rate at 25 ℃ according to the national standard of slow release fertilizers GB/T23348-2009, and the measurement results are shown in Table 3.
TABLE 3 determination of nutrient Release Rate
| Time (d) | Total nutrient Release Rate (%) |
| 0-1 | 8 |
| 1-10 | 32 |
| 10-30 | 38 |
| 30-60 | 13 |
TABLE 4 determination of nutrient release rate of comparative example 1
| Time (d) | Total nutrient Release Rate (%) |
| 0-1 | 14 |
| 1-10 | 47 |
| 10-30 | 37 |
| 30-60 | 1 |
From tables 3 and 4, it can be seen that the compound fertilizer obtained in example 2 has a total nutrient release rate of 8% in 0-1 d, 32% in 1-10 d, 38% in 10-30 d, and 13% in 30-60 d, whereas the compound fertilizer obtained in comparative example 1 has a nutrient release rate of 61% in 10d, and is substantially completely released in 30 days, so that the compound fertilizer obtained by the method of the present invention has a slow total nutrient release rate, can prevent the fertilizer from being lost too fast, and can be fully absorbed by plants.
In conclusion, the method effectively reduces the content of calcium and magnesium in the primary brine, can produce a byproduct of the slow-release compound fertilizer rich in calcium, magnesium, potassium, silicon and chlorine, has uniformly distributed element components, contains 15-20% of potassium chloride, 10-20% of magnesium, 3-10% of calcium, 3-8% of phosphorus and 15-20% of silicon dioxide, has balanced fertilizer property and slow nutrient release rate.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The process for refining the primary brine and preparing the byproduct slow-release compound fertilizer is characterized by comprising the following steps of: adjusting the pH value of the crude brine to 10-12, and then mixing the crude brine with H3PO4Mixing the solution until the pH value is 9-11, and carrying out solid-liquid separation;
the solute of the crude brine is industrial potassium chloride.
2. The process according to claim 1, wherein the concentration of the crude brine is 280 to 350g/L, preferably 300 to 330 g/L.
3. The process of claim 1, wherein the pH of the crude brine is adjusted to 10 to 12 by KOH or a KOH solution; further, KOH solution with the mass fraction of 30-48% is adopted to adjust the pH value of the crude brine to 10-12.
4. According to the rightThe process of claim 1, wherein H is3PO4The mass fraction of the solution is 5-20%.
5. The process of claim 1, wherein H is3PO4And after the solutions are mixed, standing the generated solid-liquid mixed system for natural sedimentation for 10-25 s, and then carrying out solid-liquid separation.
6. The process of claim 1 wherein H is3PO4Before the solution is mixed, the temperature of a solution system is 50-90 ℃, and preferably 60-80 ℃;
further, with H3PO4After the solution mixing is completed, the solution system is cooled and settled.
7. The process according to any one of claims 1 to 6, wherein the solid-liquid separation is followed by granulating and drying of the solid matter, and further wherein the particle diameter of the granules obtained after the granulation is 2 to 5 mm.
8. A slow-release compound fertilizer comprising the solid obtained by the method according to any one of claims 1 to 7.
9. The process of claim 8, wherein the compound fertilizer comprises the following components in parts by weight: 15-20 parts of potassium chloride, 10-20 parts of magnesium, 3-10 parts of calcium, 3-8 parts of phosphorus and 15-20 parts of silicon dioxide.
10. A slow-release compound fertilizer characterized by being produced from the solid obtained by the method according to any one of claims 1 to 9.
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