CN100390050C - Method of continuously preparing potassium dihydrogen phosphate - Google Patents
Method of continuously preparing potassium dihydrogen phosphate Download PDFInfo
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- CN100390050C CN100390050C CNB2006100107822A CN200610010782A CN100390050C CN 100390050 C CN100390050 C CN 100390050C CN B2006100107822 A CNB2006100107822 A CN B2006100107822A CN 200610010782 A CN200610010782 A CN 200610010782A CN 100390050 C CN100390050 C CN 100390050C
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- 238000000034 method Methods 0.000 title claims abstract description 62
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910000402 monopotassium phosphate Inorganic materials 0.000 title claims abstract description 22
- 235000019796 monopotassium phosphate Nutrition 0.000 title claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 114
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000005406 washing Methods 0.000 claims abstract description 56
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000011259 mixed solution Substances 0.000 claims abstract description 40
- 239000012074 organic phase Substances 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- -1 Tertiary Amine Hydrochloride Chemical class 0.000 claims description 24
- 150000001412 amines Chemical class 0.000 claims description 23
- 241000370738 Chlorion Species 0.000 claims description 22
- 235000019270 ammonium chloride Nutrition 0.000 claims description 21
- 239000006227 byproduct Substances 0.000 claims description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 16
- 239000003350 kerosene Substances 0.000 claims description 16
- 239000011591 potassium Substances 0.000 claims description 16
- 229910052700 potassium Inorganic materials 0.000 claims description 16
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 9
- 238000009713 electroplating Methods 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 42
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001103 potassium chloride Substances 0.000 abstract description 3
- 235000011164 potassium chloride Nutrition 0.000 abstract description 3
- 125000005270 trialkylamine group Chemical group 0.000 abstract 3
- 238000010924 continuous production Methods 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 239000008346 aqueous phase Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000005303 weighing Methods 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 14
- 230000009466 transformation Effects 0.000 description 13
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 6
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 6
- 229910001950 potassium oxide Inorganic materials 0.000 description 6
- 238000004886 process control Methods 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ZRBROGSAUIUIJE-UHFFFAOYSA-N azanium;azane;chloride Chemical compound N.[NH4+].[Cl-] ZRBROGSAUIUIJE-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000006558 Dental Calculus Diseases 0.000 description 1
- PVNJLUVGTFULAE-UHFFFAOYSA-N [NH4+].[Cl-].[K] Chemical group [NH4+].[Cl-].[K] PVNJLUVGTFULAE-UHFFFAOYSA-N 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- INQZXVMNJLSCGI-UHFFFAOYSA-M azanium;potassium;hydrogen phosphate Chemical compound [NH4+].[K+].OP([O-])([O-])=O INQZXVMNJLSCGI-UHFFFAOYSA-M 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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Abstract
The present invention discloses a method for continuously preparing potassium dihydrogen phosphate. The method completely uses wet-process phosphoric acid and potassium chloride as raw materials, and the wet-process phosphoric acid is chemically treated and is prepared into homogeneously mixed solution with the potassium chloride; a composite extraction agent using trialkylamine as a main component is used for extracting chloride ions in the mixed solution to form an organic phase of trialkylamine hydrochloride, free potassium ions in the mixed solution and phosphoric acid are combined into potassium dihydrogen phosphate, and the organic phase of trialkylamine hydrochloride is regenerated by washing and back extraction and is circularly used; in the method, the inorganic aqueous phase solution and the organic phase solution carry out counter-flow reaction in an extraction tower, a washing tower and a back extraction tower, and a circular and continuous production technology is formed by the extraction, the washing and the back extraction; the quality of the prepared potassium dihydrogen phosphate product can reach the quality standards of a potassium dihydrogen phosphate product of an industrial grade in the HG2321-92 standard; the method has the advantages of easy acquirement of inexpensive raw material, low production cost, simple technological flow and continuous production.
Description
Technical field
The present invention relates to the preparation method of potassium primary phosphate, more particularly, the present invention relates to a kind of method of continuously preparing potassium dihydrogen phosphate.
Background technology
At present, the method for manufacture level potassium primary phosphate mainly contains neutralisation, ion exchange method, double decomposition etc. both at home and abroad.Neutralisation at present at home factory account for the overwhelming majority, have that technical maturity is simple, the advantage of reliable product quality, its shortcoming is to consume thermal phosphoric acid and two kinds of raw materials that cost an arm and a leg of potash, production cost is too high.The advantage of ion exchange method is that the quality product of producing is higher, its shortcoming is an ion exchange reaction process complexity, yin, yang ion eluate solution concentration is lower, evaporation load is big, energy consumption is high, should not be used for scale operation, and the ion exchange method one-time investment is bigger, at present domestic have only two station-service this method to produce, wherein Wuhan Inorganic Salts Chemical Industry Factory uses better, is used for manufacture level product.The advantage of double decomposition is to adopt cheap Repone K to replace potassium hydroxide, and to reduce cost, its shortcoming is that the transformation efficiency of potassium only reaches 70%, and byproduct is an ammonium chloride potassium, and quality product does not reach the above product requirement of technical grade, and equipment corrosion is serious simultaneously.In addition, Wang Zhiren invention " association-displacement " method of Shenyang Complex Fertilizer Technology Development Co., comprise association, displacement, form and put, regeneration, finished product is refining, by-product is handled six steps, mainly be to adopt the tertiary amine of carbon atom more than seven as the association agent, after association agent and the phosphoric acid generation association reaction, leave standstill two phase stratification, lower floor's water is drained for the surplus liquid that associates, reaction generates the tertiary amine dihydrogen phosphate, and displacer---Klorvess Liquid leaves standstill two phase stratification to input after replacement(metathesis)reaction, the water of telling removes by filter throw out, displacement liquid after the filter is put reaction usefulness for forming, and organic phase is that Amine from Tertiary Amine Hydrochloride is still stayed in the reactor, treats manipulation of regeneration.Displacement liquid add again association agent and displacer through form put reaction after, leave standstill two phase stratification, lower floor is that water is formed and put liquid, through adsorption treatment, concentrate, crystallisation by cooling, separation obtain the product potassium primary phosphate, after isolating mother liquor carries out aminating reaction, through evaporating, concentrating and drying, by-product goes out vitriolate of tartar and ammonium hydrogen phosphate potassium; Upper organic phase is the Amine from Tertiary Amine Hydrochloride of Amine from Tertiary Amine Hydrochloride after displacement, use regenerator---after the ammoniacal liquor regeneration, leave standstill two phase stratification, upper organic phase recycles for regeneration association agent, lower floor's water is a regenerated liquid, add the hydrochloric acid neutralization, through the evaporation concentration crystallisation by cooling, by-product goes out ammonium chloride product.Replacement(metathesis)reaction is filtered and is obtained throw out, adds salt of wormwood through alkaline hydrolysis, adding yellow soda ash process metathesis by-product salt of wormwood and Sodium Fluoride.By foregoing as can be seen, the technology that this method is produced potassium primary phosphate mainly still is the batch production method, complex manufacturing, and by product is many.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, overcome above-mentioned various preparation methods' limitation, the method for the continuously preparing potassium dihydrogen phosphate that a kind of raw material is cheap and easy to get, technical process is simple, production energy consumption is little, can effectively reduce production costs is provided.
Purpose of the present invention is achieved by following technical proposals.
Except as otherwise noted, the percentage ratio that is adopted among the present invention is weight percentage.
The invention provides a kind of method of continuously preparing potassium dihydrogen phosphate, this method adopts following steps:
(1) extraction
With phosphoric acid by wet process and Repone K is 1: 0.8～1.2 to be mixed with mixed solution in molar ratio, adopt the extraction agent of Compositional type, the mol ratio of chlorion and extraction agent is 1: 1.9～3.0 in the mixed solution, mixed solution and extraction agent are pumped into extraction tower respectively, under 20 ℃～70 ℃ temperature, carry out counter-current extraction, extraction agent constantly extracts the chlorion in the Repone K, becomes the Amine from Tertiary Amine Hydrochloride organic phase; Simultaneously, potassium ion in the Repone K and phosphoric acid constantly are combined into potassium primary phosphate, iron, aluminium, calcium, fluorine foreign ion constantly generate solid precipitation, to filter from the effusive suspension in extraction tower bottom, concentrating filter liquor, crystallization, filtration, drying obtain potassium dihydrogen phosphate product of the present invention;
(2) washing
To effusive Amine from Tertiary Amine Hydrochloride organic phase pump into the washing tower from extraction tower top, also washings is pumped in the washing tower simultaneously, under 20 ℃～70 ℃ temperature, carry out countercurrent washing, Repone K washing lotion after the washing flows out from the washing tower bottom, returns step (1) and is used to prepare described mixed solution;
(3) back extraction
To effusive Amine from Tertiary Amine Hydrochloride organic phase pump into the back extraction tower from washing tower top by pump, simultaneously also strip liquor is pumped in the back extraction tower, in the Amine from Tertiary Amine Hydrochloride organic phase in chlorion and the strip liquor mol ratio of ammonia be 1: 1.1～1.3, under 20～70 ℃ temperature, carry out the continuous countercurrent back extraction; The ammonium chloride solution that is generated flows out from back extraction tower bottom, obtains byproduct ammonium chloride through condensing crystal; Organic phase after the back extraction flows out from back extraction tower top, is regenerating extracting agent, returns step (1) and recycles.
Wherein: the described phosphoric acid by wet process of step (1) is the phosphoric acid by wet process through electroplating effluent recycling and using, wherein P
2O
5Content is 5%～50%, SO
4 2-Content≤0.4%, F
-Content≤0.4%.
The extraction agent of the described Compositional type of step (1), it is composite and make by tertiary amine, tributyl phosphate and the kerosene of commodity N235 by name, wherein, the weight ratio of N235, tributyl phosphate and kerosene is 30%～75%: 2%～9%: 16%～68%.
The described washings of step (2) is 10%～26% Klorvess Liquid.
The described strip liquor of step (3) is the ammonium chloride solution that contains 5%～12% ammonia.
The present invention compared with prior art has following outstanding advantage:
1. to adopt phosphoric acid by wet process and Repone K fully be raw material in the present invention, with extraction, washing, back extraction--three tower continous way preparing phosphoric acid by solvent extraction potassium dihydrogen and side product sodium chloride.With tertiary amine is the main composite Compositional type extraction agent that makes, chlorion in the homogeneous mixed solution that extraction phosphoric acid by wet process and Repone K are mixed with, form the Amine from Tertiary Amine Hydrochloride organic phase, make in the mixing solutions free potassium ion directly and phosphoric acid be combined into potassium primary phosphate; To extract completely the Amine from Tertiary Amine Hydrochloride organic phase washs with washings, carry out back extraction with strip liquor again, chlorion in the Amine from Tertiary Amine Hydrochloride organic phase and the ammonia react in the strip liquor generate ammonium chloride, extraction agent obtains regeneration, constitutes a processing method of being produced potassium primary phosphate by the continous way solvent extraction of extraction, washing, back extraction.
2. raw material is cheap and easy to get, and good quality of product, prepared potassium primary phosphate quality reach industrial phosphoric acid potassium dihydrogen standard in the HG2321-92 standard; Technical process is short, and the mixing solutions of phosphoric acid by wet process and Repone K and extraction agent carry out the counter-current extraction reaction in extraction tower, and a step can obtain potassium dihydrogen phosphate;
3. technology advantages of simple, the mixing solutions of phosphoric acid and Repone K and extraction agent carry out the counter-current extraction reaction in extraction tower, when generating potassium dihydrogen phosphate, also make foreign ions such as the iron brought into by phosphoric acid by wet process, aluminium, calcium, fluorine generate precipitation and separate out, remove after filtration;
4. cyclic production continuously, temperature of reaction is low, reaction process is steady, operation control easily, extraction agent recycles and consumes lowly, raw material availability height, by product have only ammonium chloride a kind of;
5. production cost descends significantly, compares with traditional neutralisation, and raw materials cost of the present invention only is 51% of a neutralisation, detailed being shown in Table 1.
Table 1.
Description of drawings
Fig. 1 is the synoptic diagram of technical process of the present invention.
Embodiment
Below in conjunction with drawings and the specific embodiments, technical process of the present invention and chemical principle are further described.It is emphasized that because length is limit.Embodiment is just to explanation of the present invention, rather than to the qualification of content of the present invention.In implication suitable and any change in the scope, all should think to be included in the scope of claims with claims of the present invention.
As shown in Figure 1, the present invention is a kind of employing extraction, washing, back extraction---the extraction of three tower continous ways prepares the method for potassium primary phosphate and side product sodium chloride, chlorion in the phosphoric acid by wet process of the extraction agent extraction process electroplating effluent recycling and using of Compositional type and the homogeneous mixed solution that Repone K is mixed with, form the Amine from Tertiary Amine Hydrochloride organic phase, make in the mixing solutions free potassium ion directly and phosphoric acid be combined into potassium primary phosphate; To extract completely the Amine from Tertiary Amine Hydrochloride organic phase washs with washings, carry out back extraction with strip liquor again, chlorion in the Amine from Tertiary Amine Hydrochloride organic phase and the ammonia react in the strip liquor generate ammonium chloride, extraction agent obtains regeneration, constitutes a preparation method who produces potassium primary phosphate by the continous way extraction of extraction, washing, back extraction.
It is extraction agent that the present invention adopts the tertiary amine of Compositional type, and its utmost point is insoluble in water, and contained tertiary amine general formula is R in the extraction agent
3N, but can be to Cl
-, SO
4 2-, F
-Extract Deng negatively charged ion.Extraction principal reaction formula is:
R
3N (organic phase)+{ KCl+H
3PO
4(mixed solution water) → [R
3NH] Cl (organic phase)+KH
2PO
4(water)
Because extraction agent can be entrained with small amounts of phosphoric acid in extractive reaction,, the phosphoric acid of carrying secretly is changed into potassium primary phosphate so adopt washing of Klorvess Liquid.
The principal reaction formula of back extraction is:
[R
3NH] Cl (organic phase)+{ NH
3+ NH
4CL} (water) → R
3N (organic phase)+NH
4CL (water)
Embodiment 1
Used phosphoric acid by wet process is the phosphoric acid by wet process through electroplating effluent recycling and using, wherein P
2O
5Content is 6.20%, SO
4 2-Content is 0.36%, F
-Content is 0.34%; Take by weighing phosphoric acid by wet process 2808.00g, taking by weighing content is 96.45% technical grade Repone K 192.00g, and phosphoric acid and Repone K are carried out mixed dissolution, and it is stand-by to obtain mixed solution 3000g; To be that N235, tributyl phosphate and kerosene are composite make extraction agent, and the weight ratio of uncle N235, tributyl phosphate and kerosene is 32%: 3%: 65%, recycles with the 5000g extraction agent, and operation steps and process control condition are as follows:
(1) extraction: the phosphoric acid of mixed solution and the mol ratio of Repone K are 1: 1, and the mol ratio of chlorion and extraction agent is 1: 2 in the mixed solution, and reaction pressure is a normal pressure, and temperature of reaction is 25 ℃, and the mixed solution inlet amount is 400g/h, and the extractant feed amount is 641g/h.
Extraction agent and mixed solution pump into extraction tower respectively through pump and carry out the counter-current extraction reaction with above-mentioned inlet amount, pump into the washing tower washing by pump again from the effusive organic phase in extraction tower top; Effusively from the extraction tower bottom contain sedimentary potassium primary phosphate suspension, after filtration, condensing crystal, drying, obtain potassium dihydrogen phosphate product 304.97g, quality product sees Table 2, and the transformation efficiency of Vanadium Pentoxide in FLAKES is 91.00%, and the transformation efficiency of potassium oxide is 90.21%.
(2) washing: the Klorvess Liquid of preparation 20% is as washings, and reaction pressure is a normal pressure, and temperature of reaction is 25 ℃, and the washings inlet amount is 60g/h.
, pump into washing tower respectively through pump and carry out the countercurrent washing reaction with above-mentioned inlet amount from the effusive organic phase in extraction tower top and washings, pump into the back extraction tower by pump again from the effusive organic phase in washing tower top; Return the preparation mixed solution from the effusive washing lotion in washing tower bottom.
(3) back extraction: the preparation contain 5% ammonia ammonium chloride solution as strip liquor, in the organic phase in the chlorion of Amine from Tertiary Amine Hydrochloride and the strip liquor mol ratio of ammonia be 1: 1.1, reaction pressure is a normal pressure, temperature of reaction is 25 ℃, the strip liquor inlet amount is 124g/h.
, pump into the back extraction tower respectively through pump and carry out the countercurrent reextraction reaction with above-mentioned inlet amount from the effusive organic phase in washing tower top and ammoniated ammonium chloride solution, be the regenerated extraction agent, recycle from the effusive organic phase in back extraction tower top; Effusive solution obtains the ammonium chloride byproduct through condensing crystal from back extraction tower bottom, and quality product sees Table 3.
Embodiment 2
Technical process and operation steps repeat embodiment 1, and process control condition has following difference:
Used phosphoric acid is the phosphoric acid by wet process through electroplating effluent recycling and using, wherein P
2O
5Content is 24.60%, SO
4 2-Content is 0.25%, F
-Content is 0.31%; Take by weighing phosphoric acid by wet process 1325.40g, taking by weighing content is 96.45% technical grade Repone K 390.00g, takes by weighing water 1284.60g, and phosphoric acid, Repone K and water carry out mixed dissolution, and it is stand-by to obtain mixed solution 3000g; To be that N235, tributyl phosphate and kerosene are composite make extraction agent, and the weight ratio of N235, tributyl phosphate and kerosene is 57%: 9%: 34%, recycles with the 5000g extraction agent.
(1) extraction: the phosphoric acid of mixed solution and the mol ratio of Repone K are 1: 1.1, the mol ratio of chlorion and extraction agent is 1: 2.6 in the mixed solution, reaction pressure is a normal pressure, temperature of reaction is 50 ℃, the mixed solution inlet amount is 400g/h, the extractant feed amount is 968g/h, makes potassium dihydrogen phosphate product 571g, and quality product sees Table 2; The transformation efficiency of Vanadium Pentoxide in FLAKES is 91.44%, and the transformation efficiency of potassium oxide is 83.15%.
(2) washing: the Klorvess Liquid of preparation 15% is as washings, and temperature of reaction is 50 ℃, and the washings inlet amount is 70g/h.
(3) back extraction: the preparation contain 8% ammonia ammonium chloride solution as strip liquor, in the organic phase in the chlorion of Amine from Tertiary Amine Hydrochloride and the strip liquor mol ratio of ammonia be 1: 1.2, temperature of reaction is 50 ℃, the strip liquor inlet amount is 172g/h; The solution that goes out the back extraction tower obtains the ammonium chloride byproduct through condensing crystal, and quality product sees Table 3.
Embodiment 3
Technical process and operation steps repeat embodiment 1, and process control condition has following difference:
Used phosphoric acid by wet process is the phosphoric acid by wet process through electroplating effluent recycling and using, wherein P
2O
5Content is 47.09%, SO
4 2-Content is 0.30%, F
-Content is 0.20%; Take by weighing phosphoric acid by wet process 646.20g, taking by weighing content is 96.45% technical grade Repone K 297.90g, takes by weighing water 2055.90g, and phosphoric acid, Repone K and water carry out mixed dissolution, and it is stand-by to obtain mixed solution 3000g; To be that N235, tributyl phosphate and kerosene are composite make extraction agent, and the weight ratio of N235, tributyl phosphate and kerosene is 72%: 6%: 22%, recycles with the 5000g extraction agent.
(1) extraction: the phosphoric acid of mixed solution and the mol ratio of Repone K are 1: 0.9, the mol ratio of chlorion and extraction agent is 1: 3.0 in the mixed solution, temperature of reaction is 65 ℃, the mixed solution inlet amount is 400g/h, extractant feed amount 664g/h makes potassium dihydrogen phosphate product 519.50g, and quality product sees Table 2, the transformation efficiency of Vanadium Pentoxide in FLAKES is 89.12%, and the transformation efficiency of potassium oxide is 99.04%.
(2) washing: the Klorvess Liquid of preparation 12% is as washings, and reaction pressure is a normal pressure, and temperature of reaction is 65 ℃, and the washings inlet amount is 75g/h.
(3) back extraction: preparation contains the ammonium chloride solution of 10% ammonia as strip liquor, in the organic phase in the chlorion of Amine from Tertiary Amine Hydrochloride and the strip liquor mol ratio of ammonia be 1: 1.3, temperature of reaction is 65 ℃, the strip liquor inlet amount is 114g/h, the solution that goes out the back extraction tower obtains the ammonium chloride byproduct through condensing crystal, and quality product sees Table 3.
Embodiment 4
Technical process and operation steps repeat embodiment 1, and process control condition has following difference:
Used phosphoric acid by wet process is the phosphoric acid by wet process through electroplating effluent recycling and using, wherein P
2O
5Content is 35.86%, SO
4 2-Content is 0.20%, F
-Content is 0.20%; Take by weighing phosphoric acid by wet process 969.70g, taking by weighing content is 96.45% technical grade Repone K 567.34g, takes by weighing water 1462.96g, and phosphoric acid, Repone K and water are carried out mixed dissolution, and it is stand-by to obtain mixed solution 3000g; To be that N235, tributyl phosphate and kerosene are composite make extraction agent, and the weight ratio of N235, tributyl phosphate and kerosene is 65%: 8%: 27%, recycles with the 5000g extraction agent.
(1) extraction: the phosphoric acid of mixed solution and the mol ratio of Repone K are 1: 1.5, the mol ratio of chlorion and extraction agent is 1: 2.8 in the mixed solution, temperature of reaction is 40 ℃, the mixed solution inlet amount is 400g/h, the extractant feed amount is 1 326g/h, makes potassium dihydrogen phosphate product 618.16g, and quality product sees Table 2, the transformation efficiency of Vanadium Pentoxide in FLAKES is 92.79%, and the transformation efficiency of potassium oxide is 61.88%.
(2) washing: the Klorvess Liquid of preparation 15% is as washings, and temperature of reaction is 40 ℃, and the washings inlet amount is 70g/h.
(3) back extraction: preparation contains the ammonium chloride solution of 10% ammonia as strip liquor, in the organic phase in the chlorion of Amine from Tertiary Amine Hydrochloride and the strip liquor mol ratio of ammonia be 1: 1.3, temperature of reaction is 40 ℃, the strip liquor inlet amount is 216g/h, the solution that goes out the back extraction tower obtains the ammonium chloride byproduct through condensing crystal, and quality product sees Table 3.
Embodiment 5
Technical process and operation steps repeat embodiment 1, and process control condition has following difference:
Used phosphoric acid by wet process is the phosphoric acid by wet process through electroplating effluent recycling and using, wherein P
2O
5Content is 25.72%, SO
4 2-Content is 0.23%, F
-Content is 0.15%; Take by weighing phosphoric acid by wet process 1014.10g, taking by weighing content is 96.45% technical grade Repone K 227.10g, takes by weighing water 1758.80g, and phosphoric acid, Repone K and water are carried out mixed dissolution, and it is stand-by to obtain mixed solution 3000g; To be that N235, tributyl phosphate and kerosene are composite make extraction agent, and the weight ratio of N235, tributyl phosphate and kerosene is 49%: 4%: 47%, recycles with the 5000g extraction agent.
(1) extraction: the mol ratio of phosphoric acid and Repone K is 1: 0.8 in the mixed solution, the mol ratio of chlorion and extraction agent is 1: 2.5 in the mixed solution, temperature of reaction is 45 ℃, the mixed solution inlet amount is 400g/h, the extractant feed amount is 632g/h, makes potassium dihydrogen phosphate product 396.00g, and quality product sees Table 2, the transformation efficiency of Vanadium Pentoxide in FLAKES is 79.25%, and the transformation efficiency of potassium oxide is 99.04%.
(2) washing: the Klorvess Liquid of preparation 24% is as washings, and temperature of reaction is 45 ℃, and the washings inlet amount is 55g/h.
(3) back extraction: preparation contains the ammonium chloride solution of 12% ammonia as strip liquor, in the organic phase in the chlorion of Amine from Tertiary Amine Hydrochloride and the strip liquor mol ratio of ammonia be 1: 1.2, temperature of reaction is 45 ℃, the strip liquor inlet amount is 67g/h, the solution that goes out the back extraction tower obtains the ammonium chloride byproduct through condensing crystal, and quality product sees Table 3.
Embodiment 6
Technical process and operation steps repeat embodiment 1, and process control condition has following difference:
Used phosphoric acid by wet process is the phosphoric acid by wet process through electroplating effluent recycling and using, wherein P
2O
5Content is 15.50%, SO
4 2-Content is 0.10%, F
-Content is 0.08%; Take by weighing phosphoric acid by wet process 1402.00g, taking by weighing content is 96.45% technical grade Repone K 236.40g, takes by weighing water 1361.6g, and phosphoric acid, Repone K and water carry out mixed dissolution, and it is stand-by to obtain mixed solution 3000g; To be that N235, tributyl phosphate and kerosene are composite make extraction agent, and the weight ratio of N235, tributyl phosphate and kerosene is 41%: 5%: 54%, recycles with the 5000g extraction agent.
(1) extraction: the phosphoric acid of mixed solution and the mol ratio of Repone K are 1: 1, the mol ratio of chlorion and extraction agent is 1: 2.4 in the mixed solution, temperature of reaction is 35 ℃, the mixed solution inlet amount is 400g/h, the extractant feed amount is 758g/h, the potassium dihydrogen phosphate product 385.14g of system, and quality product sees Table 2, the transformation efficiency of Vanadium Pentoxide in FLAKES is 92.49%, and the transformation efficiency of potassium oxide is 92.53%.
(2) washing: the Klorvess Liquid of preparation 20% is as washings, and temperature of reaction is 35 ℃, and the washings inlet amount is 60g/h;
(3) back extraction: preparation contains the ammonium chloride solution of 8% ammonia as strip liquor, in the organic phase in the chlorion of Amine from Tertiary Amine Hydrochloride and the strip liquor mol ratio of ammonia be 1: 1.2, temperature of reaction is 35 ℃, the strip liquor inlet amount is 104g/h, the solution that goes out the back extraction tower obtains the ammonium chloride byproduct through condensing crystal, and quality product sees Table 3.
Table 2.
The testing data of table 2 shows that the potassium dihydrogen phosphate product that obtains reaches the technical grade acceptable end product.
Table 3.
The testing data of table 3 shows that the ammonium chloride product that obtains reaches agricultural level premium grads.
Claims (2)
1. the method for a continuously preparing potassium dihydrogen phosphate, this method adopts the step of following order:
(1) extraction
With phosphoric acid by wet process and Repone K is 1: 0.8～1.2 to be mixed with mixed solution in molar ratio, adopt the extraction agent of Compositional type, the mol ratio of chlorion and extraction agent is 1: 1.9～3.0 in the mixed solution, mixed solution and extraction agent are pumped into extraction tower respectively, under 20 ℃～70 ℃ temperature, carry out counter-current extraction, extraction agent constantly extracts the chlorion in the Repone K, becomes the Amine from Tertiary Amine Hydrochloride organic phase; Simultaneously, potassium ion in the Repone K and phosphoric acid constantly are combined into potassium primary phosphate, iron, aluminium, calcium, fluorine foreign ion constantly generate solid precipitation, to filter from the effusive suspension in extraction tower bottom, concentrating filter liquor, crystallization, filtration, drying obtain potassium dihydrogen phosphate product of the present invention; Described Compositional type extraction agent, it is composite and make by tertiary amine, tributyl phosphate and the kerosene of commodity N235 by name, wherein, the weight ratio of N235, tributyl phosphate and kerosene is 30%～75%: 2%～9%: 16%～68%;
(2) washing
To effusive Amine from Tertiary Amine Hydrochloride organic phase pump into the washing tower from extraction tower top, also washings is pumped in the washing tower simultaneously, under 20 ℃～70 ℃ temperature, carry out countercurrent washing, Repone K washing lotion after the washing, flow out from the washing tower bottom, return step (1) and be used to prepare described mixed solution;
(3) back extraction
To effusive Amine from Tertiary Amine Hydrochloride organic phase pump into the back extraction tower from washing tower top by pump, simultaneously also strip liquor is pumped in the back extraction tower, in the Amine from Tertiary Amine Hydrochloride organic phase in chlorion and the strip liquor mol ratio of ammonia be 1: 1.1～1.3, under 20 ℃～70 ℃ temperature, carry out the continuous countercurrent back extraction; The ammonium chloride solution that is generated flows out from the bottom of back extraction tower, obtains byproduct ammonium chloride through condensing crystal; Organic phase after the back extraction flows out from the top of back extraction tower, is regenerating extracting agent, returns step (1) and recycles.
2. the method for continuously preparing potassium dihydrogen phosphate according to claim 1 is characterized in that described phosphoric acid by wet process is the phosphoric acid by wet process through electroplating effluent recycling and using, wherein P
2O
5Content is 5%～50%, SO
4 2-Content≤0.4%, F
-Content≤0.4%.
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| CN102951623A (en) * | 2012-11-15 | 2013-03-06 | 贵州开磷（集团）有限责任公司 | Production process for monopotassium phosphate |
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| CN101759168B (en) * | 2010-01-08 | 2012-05-30 | 武汉工程大学 | A kind of technique of producing potassium phosphate salt with wet-process phosphoric acid |
| CN101979311A (en) * | 2010-11-15 | 2011-02-23 | 中化重庆涪陵化工有限公司 | Method for producing industrial monopotassium phosphate and nitrogen, phosphorus and potassium compound fertilizer by using wet-process purified phosphoric acid as raw material through extraction |
| CN102424374A (en) * | 2011-09-07 | 2012-04-25 | 湖北三宁化工股份有限公司 | Production method of potassium dihydrogen phosphate |
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| CN106586990B (en) * | 2016-11-09 | 2019-03-19 | 长江师范学院 | With the method for Wet-process Phosphoric Acid Production potassium dihydrogen phosphate |
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| CN113415791B (en) * | 2021-06-25 | 2022-11-29 | 云南云天化红磷化工有限公司 | Device and method for recovering extractant in production of monopotassium phosphate by wet-process phosphoric acid extraction |
| CN114191847B (en) * | 2021-12-12 | 2022-12-30 | 四川鑫瑞源科技发展有限公司 | Extracting agent for producing potassium dihydrogen phosphate by solvent extraction method and preparation method and application thereof |
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