CN102442657A - Washing technology for refinement of wet-process phosphoric acid by solvent extraction method - Google Patents
Washing technology for refinement of wet-process phosphoric acid by solvent extraction method Download PDFInfo
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Abstract
The invention relates to a washing technology for refinement of wet-process phosphoric acid by a solvent extraction method. The technology comprises: subjecting crude phosphoric acid obtained from a wet process to pretreatment and extraction in order so as to obtain a saturated phase, and taking 400-600g/L of phosphoric acid as mixing acid, with the phase ratio of the mixing acid and the saturated phase maintained at 1:16-25, then adding NH4<+> ions which are of 100-120% of the stoichiometric amount of sulfate radicals in the saturated phase into the mixing acid for dissolving, conducting filtration after dissolving, and washing the saturated phase with washing water obtained from filtration so as to obtain a washed phase and scourage, carrying out subsequent treatment to the washed phase so as to obtain industrial grade 85% phosphoric acid, and subjecting the scourage to heavy metal ion removal and desulphurization treatment in order, thus obtaining colorless or white industrial grade monoammonium phosphate. The technology design of the invention not only can effectively remove corroded nickel, chromium, manganese, molybdenum and other metal ions in a phosphoric acid feed liquid and improve sulfate radical removing effect, but also has high recovery and utilization rate to the scourage, thus boasting powerful economic benefits.
Description
Technical field
The present invention relates to a kind of impurity removal process of phosphoric acid by wet process, relate in particular to a kind of washing process that is used for the refining phosphoric acid by wet process of solvent extration, specifically be applicable to and remove the band look heavy metal ion in the extracted organic phase and recycle consequent wash water.
Background technology
At present, be in the process of PHOSPHORIC ACID TECH.GRADE or food grade phosphoric acid with wet phosphoric acid purifying adopting solvent extration, to carry out pre-treatment to raw phosphoric acid earlier; With extraction agent pretreated phosphoric acid is extracted then, in the extraction process, earlier phosphoric acid (water) after extraction agent (organic phase) and the pre-treatment is contacted; Again by extraction agent with phosphoric acid extraction to organic phase; And the impurity of the overwhelming majority stayed the surplus water of collection, at this moment, the organic phase without washing of load phosphoric acid is called " full have "; In like manner, organic phase load phosphoric acid and the warp washing is called " having washed ".
Owing to receive the restriction of separation factor, in phosphoric acid extraction, have impurity such as a spot of metals ion and sulfate radical and be extracted to satisfy and have; If the direct stripping of carrying out is arranged to satisfying; Then product can not reach the PHOSPHORIC ACID TECH.GRADE standard, therefore need wash full, to reduce foreign matter content wherein; Thereby, and guarantee that the finished product reach the PHOSPHORIC ACID TECH.GRADE standard for the subsequent disposal operation reduces the heavy burdens.
In patent of invention ZL03117850.2, a kind of comprehensive washing process has been proposed, promptly adopt a part of back extraction acid to wash to desulfurization is full, adding in the washing acid of generation behind the barium carbonate has the desulfurization of a carrying out washing to full again, and extraction is again returned in the desulfurization acid that obtains again.The comprehensive washing process of this kind can not effectively wash full, and reason is following:
At first, when utilizing back extraction acid washing to be arranged, can not the impurity (like sulfate radical) that desulfurization is full in having be removed effectively, still have more sulfate radical and remain in and washed, reduce washing effect, increase the burden of subsequent disposal operation desulfurization is full; Secondly; Contact when carrying out the desulfurization washing with full with containing the barium salt washing acid, its objective is and attempt to utilize the method that produces barium sulfate precipitate removing sulfate radical, but the throw out of generation this moment is too thin too much; Can cause phase-splitting difficulty or throw out to remain in the organic phase; Cause the obstruction of extraction equipment in the subsequent step easily, needing increases extra clarification and straining installation, and this has increased production cost.This shows, during the comprehensive washing process among the patent of invention ZL03117850.2 not only can cause more sulfate radical to remain in having washed, reduce washing effect, and can cause throw out too many too thin, need add extra clarification and straining installation.
A kind of washing process has also been proposed in patent of invention ZL200510019734.5; Promptly adopt the phosphoric acid solution that contains sodium salt to wash to full; To reduce the content of metals ion and sulfate radical effectively; After in subsequent disposal, removing remaining sulfate radical, quality product just can reach the industrial phosphoric acid standard, near the phosphoric acid for food standard.But this kind washing process has following shortcoming:
At present domestic phosphoric acid by wet process enterprise mostly adopts the equipment of 316L stainless steel in the leaching of phosphoric acid by wet process and concentration process; This patent also is, thereby in its production process, elements such as the nickel in the 316L stainless steel, chromium, manganese, molybdenum can be corroded and get into the phosphoric acid feed liquid; The various mode of washing that relate in this patent all can not effectively be removed them; This can cause strip liquor to have a little light blue or light green, and product technical grade 85% phosphoric acid that obtains is all the more so, although technical grade 85% phosphoric acid of this moment can be up to state standards; Cause user's misunderstanding easily but " have a little light green ", reduce its price.Therefore the washing process among the patent of invention ZL200510019734.5 can not effectively be removed metals ions such as the nickel that is corroded into, chromium, manganese, molybdenum, thereby causes the light blue or light green of the finished product band, reduces economic benefit.In like manner, also have same problem among the patent of invention ZL03117850.2, its finished product also have light blue or light green, also can be lowered economic benefit.
In addition; To the wash water that washing back among foregoing invention patent ZL03117850.2 and the patent of invention ZL200510019734.5 produces, they all return wash water to extraction workshop section and extract, have seemingly reused wash water apparently; Improved the utilization ratio of wash water; But we think that this is a kind of waste, because after washing, the foreign matter content in the wash water is far below the foreign matter content in the phosphoric acid by wet process; At this time wash water being returned extraction workshop section, to extract again be non-remunerative economically, can not show a candle to it is carried out the phosphoric acid salt that simple removal of impurities and processing just can obtain technical grade.
To sum up can get, washing process of the prior art has following shortcoming:
At first, can not remove metals ions such as the nickel that is corroded in the phosphoric acid feed liquid into, chromium, manganese, molybdenum, cause the light blue or light green of the finished product band, reduce economic benefit.
Secondly, good inadequately to the removal effect of sulfate radical, in still having the sulfate radical of more content to remain in to have washed, increased the burden of follow-up desulfurization process.
Once more, lower to the recovery utilization rate of wash water, economic benefit is relatively poor.
Summary of the invention
The objective of the invention is to overcome metals ions such as nickel that can not removing of existing in the prior art be corroded in the phosphoric acid feed liquid into, chromium, manganese, molybdenum; Removal effect to sulfate radical is good inadequately; Defective and the problem lower to the recovery utilization rate of wash water; Provide a kind of and can effectively remove metals ions such as the nickel that is corroded in the phosphoric acid feed liquid into, chromium, manganese, molybdenum; Can improve removal effect, the washing process that be used for solvent extration refining phosphoric acid by wet process higher to the recovery utilization rate of wash water to sulfate radical.
For realizing above purpose, technical solution of the present invention is:
A kind of washing process that is used for the refining phosphoric acid by wet process of solvent extration, this washing process may further comprise the steps successively:
The first step: full producing of having: the raw phosphoric acid that earlier wet method is made carries out pre-treatment, and that this pre-treatment comprises successively is concentrated, defluorinate, desulfurization, decolouring and filtration step, the filtrating of filtering gained is extracted again, and the organic phase of extraction back gained is fullly to be had;
Second step: the preparation of wash water: the phosphoric acid of getting concentration earlier and be 400 – 600g/L is as complex acid, this complex acid with full have be in a ratio of 1:16 – 25, again with NH
4 +Ion has stoichiometric 100 – 120% of middle sulfate radical to add in the complex acid to dissolve, filter after dissolving finishes by full, and the filtrating of filtration gained is wash water;
The 3rd step: the carrying out of washing: have the four-stage counter-current of carrying out contact to wash with above-mentioned wash water to full earlier; The organic phase that obtains after the washing is and has washed, water is wash water; Strip to having washed again; And wash water carried out subsequent disposal, and the phosphoric acid solution that obtains after the reextraction is back extraction acid, and this back extraction acid is successively through reclaiming extraction agent, concentrate, desulfurization, filtration, concentrating to make technical grade 85% phosphoric acid.
Said the 3rd step with back extraction acid successively through reclaiming extraction agent, concentrate, desulfurization, filtration, concentrating with in the process that makes technical grade 85% phosphoric acid; When being concentrated into 75% phosphoric acid, this 75% phosphoric acid of desirable part returns in said second step and substitutes complex acid to produce the required wash water of next round; Said alternative complex acid is meant: extract part 75% phosphoric acid and allocate, until its H that comprises
3PO
4Concentration be 400 – 600g/L, promptly alternative complex acid; Between being had by to be washed full of complex acid and next round, the extracted amount of said part 75% phosphoric acid compares 1:16 – 25, allotment back H
3PO
4Concentration be that the concentration requirement of 400 – 600g/L is calculated and to be got.
In said the 3rd step wash water being carried out subsequent disposal is meant: earlier wash water is reclaimed extraction agent and handle, the wash water after will handling is again sent in the encloses container, in wash water, adds sulfide then; Adding mass percent concentration in every liter of wash water is the sulfide 60 – 200mL of 1 – 10%; Reheat, and in 90 ℃ of following insulated and stirred of 85 – 3 hours, filter then; Again under 80 ℃ of 60 –, barium carbonate is added in the filtrating by stoichiometric 95 – 100% of sulfate radical in the filtrating; And stirring 1 hour to obtain the desulfurization feed liquid, 1 – 10 ‰ by the desulfurization material liquid volume adds sinking agent, 10 minutes after-filtration of restir then; In filtrating, feeding the ammonia neutralization then is 4.4 – 4.6 until the pH value; 30 minutes after-filtration of insulated and stirred again, filtrating successively through concentrate, crystallisation by cooling, filtration, oven dry to be to obtain the product industrial grade monoammonium phosphate, product is colourless or the white crystals body.
In said the 3rd step wash water being carried out subsequent disposal is meant: earlier wash water is reclaimed extraction agent and handle, the wash water after will handling is again sent in the encloses container, in wash water, adds sulfide then; Add mass percent concentration in every liter of wash water and be 6% sulfide 100mL; Reheat, and in 90 ℃ of following insulated and stirred of 85 – 3 hours, filter then; Again under 80 ℃ of 60 –, barium carbonate is added in the filtrating by sulfate radical stoichiometric 97% in the filtrating; And stir 1 hour to obtain the desulfurization feed liquid, add sinking agent, 10 minutes after-filtration of restir by 5 ‰ of desulfurization material liquid volume then; In filtrating, feeding the ammonia neutralization then is 4.4 – 4.6 until the pH value; 30 minutes after-filtration of insulated and stirred again, filtrating successively through concentrate, crystallisation by cooling, filtration, oven dry to be to obtain the product industrial grade monoammonium phosphate, product is colourless or the white crystals body.
Compared with prior art, beneficial effect of the present invention is:
1, the wash water that adopts of a kind of washing process that is used for the refining phosphoric acid by wet process of solvent extration of the present invention is for being dissolved with NH
4 +The ionic phosphoric acid solution, its manner of formulation is: the phosphoric acid of getting concentration earlier and be 400 – 600g/L is as complex acid, this complex acid with full have be in a ratio of 1:16 – 25, again with NH
4 +Ion has stoichiometric 100 – 120% of middle sulfate radical to add in the complex acid to dissolve, filter after dissolving finishes by full, and the filtrating of filtering gained is wash water, this shows, the staple of the wash water of the present invention's employing is phosphoric acid and NH
4 +Ion (being generally volatile caustic), when with it during to full the washing, metals ion meeting and NH such as full into the nickel of being corroded that contains in having, chromium, manganese, molybdenum
4 +Ionic reaction forms the metal ammino and closes ion, and after forming the metal ammonium complex ion, the association of metals ion such as nickel, chromium, manganese, molybdenum and extraction agent enters into water with regard to being disengaged; Effect no longer includes green exactly in having washed intuitively, but that wash water then becomes is greener, and metals ions such as the nickel of this explanation band look, chromium, manganese, molybdenum have effectively been washed away; What obtain has washed through after stripping; Also do not have green (through detecting, the content of beavy metal impurities such as nickel, chromium, manganese, molybdenum is far below the requirement of GB in the back extraction acid) in the back extraction acid, technical grade 85% phosphoric acid that obtains through subsequent disposal again is except each item index all the National standard; Also no longer include light blue or light green; This misunderstanding that can not cause the client with light blue or jade-green the finished product is prone to guarantee its price, has stronger economic benefit.Therefore the present invention can effectively remove metals ions such as the nickel that is corroded in the phosphoric acid feed liquid into, chromium, manganese, molybdenum, can on product meets the basis of technical grade 85% phosphoric acid national standard, no longer include light blue or light green, has stronger economic benefit.
2, the wash water that adopts of a kind of washing process that is used for the refining phosphoric acid by wet process of solvent extration of the present invention is for being dissolved with NH
4 +The ionic phosphoric acid solution, when washing satisfying with it, NH
4 +Ion can form ammonium sulfate with the full sulfate radical reaction that contains in having; Sulfate radical had stronger removal effect; Through detecting; Sulfate radical content in can having satisfying to less than 0.4g/L, and makes that sulfate radical content greatly reduces the burden of follow-up desulfurization process less than 2g/L in the back extraction acid from about 5g/L washing; In addition, ZL200510019734.5 compares with patent of invention, and it adopts the phosphoric acid solution that contains sodium salt to wash full; What form when sulfate radical is removed is sodium sulfate, and sodium sulfate water-soluble relatively poor is if the full sulfate radical content that has is higher; Then can produce sulfate crystal, not only influence phase-splitting, and be prone to cause the obstruction of extraction equipment; But the present invention is when removing sulfate radical, formation be ammonium sulfate, ammonium sulfate water-soluble far above sodium sulfate; Thereby can guarantee the flowability of wash water neither can influence phase-splitting, can not cause the obstruction of extraction equipment yet.Therefore the present invention can not only improve the removal effect to sulfate radical, and can not influence phase-splitting and stop up extraction equipment.
3, a kind of washing process that is used for the refining phosphoric acid by wet process of solvent extration of the present invention is not it to be returned extraction workshop section extract to the subsequent disposal of wash water again; But to its carry out simple removal of impurities and processing to make the phosphoric acid salt of technical grade; The reason of this design is: after washing; Foreign matter content in the wash water is far below the foreign matter content in the phosphoric acid by wet process, and at this time wash water being returned that extraction workshop section extracts again is non-remunerative economically, can not show a candle to it and makes industrial monoammonium phosphate or other phosphoric acid salt; Thereby improve the recovery utilization rate of wash water, have very strong economic benefit.Therefore the present invention is higher to the recovery utilization rate of wash water, has very strong economic benefit.
4, a kind of washing process that is used for the refining phosphoric acid by wet process of solvent extration of the present invention mainly comprises the subsequent disposal of wash water and removes heavy metal ion and these two steps of desulfurization; To removing the heavy metal ion step: after full being washed, the heavy metal ion such as the nickel of middle band look, chromium, manganese, molybdenum are arranged of satisfying have been advanced in the wash water by effective washing, and the wash water that obtains becomes greener; The direct manufacturing articles industrial monoammonium phosphate if do not remove heavy metal ion such as nickel, chromium, manganese, molybdenum this moment, though product can National standard, the color relation of product be a green; Be prone to cause that client misreads; Its price is far below colourless or white industrial monoammonium phosphate, thereby must from wash water, to remove heavy metal ion such as nickel, chromium, manganese, molybdenum serve as white or colourless with the color of guaranteeing the product industrial monoammonium phosphate, for this reason; When handling wash water, the design adds sulfide solution (sodium sulphite, hydrogen sulfide or five oxidations, two sulphur); Remove heavy metal ion such as nickel, chromium, manganese, molybdenum through sulfide, thereby remove the green in the wash water, when guaranteeing with its manufacture monoammonium phosphate; Product is colourless or white xln, and then guarantees its economic interests; To desulfurized step: the purpose that in wash water, adds barium carbonate is desulfurization, use the barium carbonate desulfurization, and one side can not introduced other foreign ions, can sell as product by reclaim(ed) sulfuric acid barium on the other hand yet; This shows; Through removing these two steps of heavy metal ion and desulfurization; The present invention not only can effectively remove the color and the sulfate ion of wash water to the subsequent disposal of wash water; And can not introduce new impurity, to make the product industrial monoammonium phosphate be content greater than 99%, colourless or white xln.Therefore the present invention can through wash water make content greater than 99%, colourless or white industrial monoammonium phosphate, have strong recovery utilization rate and economic worth.
Embodiment
Below in conjunction with embodiment and embodiment the present invention is done further detailed explanation.
A kind of washing process that is used for the refining phosphoric acid by wet process of solvent extration, this washing process may further comprise the steps successively:
The first step: full producing of having: the raw phosphoric acid that earlier wet method is made carries out pre-treatment, and that this pre-treatment comprises successively is concentrated, defluorinate, desulfurization, decolouring and filtration step, the filtrating of filtering gained is extracted again, and the organic phase of extraction back gained is fullly to be had;
Second step: the preparation of wash water: the phosphoric acid of getting concentration earlier and be 400 – 600g/L is as complex acid, this complex acid with full have be in a ratio of 1:16 – 25, again with NH
4 +Ion has stoichiometric 100 – 120% of middle sulfate radical to add in the complex acid to dissolve, filter after dissolving finishes by full, and the filtrating of filtration gained is wash water;
The 3rd step: the carrying out of washing: have the four-stage counter-current of carrying out contact to wash with above-mentioned wash water to full earlier; The organic phase that obtains after the washing is and has washed, water is wash water; Strip to having washed again; And wash water carried out subsequent disposal, and the phosphoric acid solution that obtains after the reextraction is back extraction acid, and this back extraction acid is successively through reclaiming extraction agent, concentrate, desulfurization, filtration, concentrating to make technical grade 85% phosphoric acid.
Above-mentioned the 3rd step with back extraction acid successively through reclaiming extraction agent, concentrate, desulfurization, filtration, concentrating with in the process that makes technical grade 85% phosphoric acid; When being concentrated into 75% phosphoric acid, this 75% phosphoric acid of desirable part returns in said second step and substitutes complex acid to produce the required wash water of next round; Said alternative complex acid is meant: extract part 75% phosphoric acid and allocate, until its H that comprises
3PO
4Concentration be 400 – 600g/L, promptly alternative complex acid; Between being had by to be washed full of complex acid and next round, the extracted amount of said part 75% phosphoric acid compares 1:16 – 25, allotment back H
3PO
4Concentration be that the concentration requirement of 400 – 600g/L is calculated and to be got.
In above-mentioned the 3rd step wash water being carried out subsequent disposal is meant: earlier wash water is reclaimed extraction agent and handle, the wash water after will handling is again sent in the encloses container, in wash water, adds sulfide then; Adding mass percent concentration in every liter of wash water is the sulfide 60 – 200mL of 1 – 10%; Reheat, and in 90 ℃ of following insulated and stirred of 85 – 3 hours, filter then; Again under 80 ℃ of 60 –, barium carbonate is added in the filtrating by stoichiometric 95 – 100% of sulfate radical in the filtrating; And stirring 1 hour to obtain the desulfurization feed liquid, 1 – 10 ‰ by the desulfurization material liquid volume adds sinking agent, 10 minutes after-filtration of restir then; In filtrating, feeding the ammonia neutralization then is 4.4 – 4.6 until the pH value; 30 minutes after-filtration of insulated and stirred again, filtrating successively through concentrate, crystallisation by cooling, filtration, oven dry to be to obtain the product industrial grade monoammonium phosphate, product is colourless or the white crystals body.
In above-mentioned the 3rd step wash water being carried out subsequent disposal is meant: earlier wash water is reclaimed extraction agent and handle, the wash water after will handling is again sent in the encloses container, in wash water, adds sulfide then; Add mass percent concentration in every liter of wash water and be 6% sulfide 100mL; Reheat, and in 90 ℃ of following insulated and stirred of 85 – 3 hours, filter then; Again under 80 ℃ of 60 –, barium carbonate is added in the filtrating by sulfate radical stoichiometric 97% in the filtrating; And stir 1 hour to obtain the desulfurization feed liquid, add sinking agent, 10 minutes after-filtration of restir by 5 ‰ of desulfurization material liquid volume then; In filtrating, feeding the ammonia neutralization then is 4.4 – 4.6 until the pH value; 30 minutes after-filtration of insulated and stirred again, filtrating successively through concentrate, crystallisation by cooling, filtration, oven dry to be to obtain the product industrial grade monoammonium phosphate, product is colourless or the white crystals body.
Principle of the present invention is explained as follows:
1, about the light green of removing product technical grade 85% phosphoric acid or light blue:
At present domestic phosphoric acid by wet process enterprise mostly adopts the equipment of 316L stainless steel in the leaching of phosphoric acid by wet process and concentration process; The SPA that goes out through this device fabrication all has light green or light blue; This is to cause that owing to heavy metal ion such as the nickel in the 316L stainless steel, chromium, manganese, molybdenum are corroded to get in the phosphoric acid feed liquid if carry out extracting and refining with this phosphoric acid feed liquid, technical grade 85% phosphoric acid that obtains at last all can have a little light green or light blue; Although technical grade 85% phosphoric acid of this moment can be up to state standards; This characteristic causes user's misunderstanding easily but " have a little light green ", is prone to be lowered its price, damages its economic interests.Though the used extraction agent of prior art (like patent of invention ZL03117850.2 and patent of invention ZL200510019734.5) has certain elimination ability to these heavy metal ion; But it is relatively poor to get rid of effect; Be difficult to meet the demands; As long as there is the above-mentioned heavy metal ion of several PPm just to be enough to make product phosphoric acid band light green or light blue after all in the organic phase, thereby the forward mode of washing of stating two patents all can not effectively be removed above-mentioned impurity.For this reason, the present invention proposes a kind of new design: close ion through formation metal ammino and remove heavy metal ion such as nickel, chromium, manganese, molybdenum.
Through experiment showed, at NH
4 +The reaction of heavy metal ion such as ion and nickel, chromium, manganese, molybdenum forms after the metal ammonium complex ion; The association of these metals ions and extraction agent enters into water with regard to being disengaged, effect no longer includes green or blueness exactly in having washed intuitively, through stripping; Back extraction acid does not have green or blueness yet; Pass through aftertreatment again, technical grade 85% phosphoric acid that obtains is each item index National standard all not only, nor shows green or blue again.Simultaneously, it is greener that the wash water that obtains after the washing then becomes, and heavy metal ion such as the nickel of this explanation band look, chromium, manganese, molybdenum are by effective washing.
2, about improving removal effect to sulfate radical:
With containing NH
4 +The ionic phosphoric acid solution substitutes the sodium salt phosphoric acid solution has washing to satisfying, and except removing nickel, chromium, manganese, molybdenum etc. the heavy metal ion, also has following benefit: at first, and NH
4 +Ion combines to form ammonium sulfate with sulfate radical, better to the washing effect of sulfate radical, and the sulfate radical content in can having satisfying extremely less than 0.4g/L, and makes that sulfate radical content greatly reduces the burden of follow-up desulfurization process less than 2g/L in the back extraction acid from about 5g/L washing; Secondly; Because ammonium sulfate is water-soluble better than sodium sulfate; Thereby the present invention washs the good fluidity of the flowability of back wash water than sodium salt phosphoric acid solution washing back wash water, and the sodium salt phosphoric acid solution produces sulfate crystal sometimes at higher full of washing sulfate radical content, not only influences phase-splitting; And be prone to extraction equipment is resulted in blockage, and the present invention washs the back wash water and just can effectively avoid these shortcomings.
3, about improving the recovery utilization rate of wash water:
After washing; Foreign matter content in the wash water is far below the foreign matter content in the phosphoric acid by wet process; At this time wash water being returned extraction workshop section, to extract (like the way among patent of invention ZL03117850.2 and the patent of invention ZL200510019734.5) again be non-remunerative economically; Can not show a candle to it and make industrial monoammonium phosphate, thereby the recovery utilization rate of raising wash water has very strong economic benefit.
Though wash water is made the recovery utilization rate that industrial monoammonium phosphate can improve wash water, have very strong economic benefit, also must there be suitable technology to match, otherwise also be difficult to guarantee its recovering effect.For this reason, the present invention has carried out unique design to the subsequent treatment process of wash water, mainly comprises removing heavy metal ion and these two steps of desulfurization.
Remove the heavy metal ion step: add sulfide solution when wash water is handled; Purpose is to remove heavy metal ion such as nickel, chromium, manganese, molybdenum; Thereby remove the green in the wash water, when making with its manufacture monoammonium phosphate, product is colourless or white xln.
Desulfurized step: in wash water, add barium carbonate and come desulfurization, can not introduce other foreign ions on the one hand, also can sell as product by reclaim(ed) sulfuric acid barium on the other hand, improve recovery utilization rate once more.
With removing the purpose that the heavy metal ion step is arranged in before the desulfurized step is the carrying out for the ease of technological process.
The purpose that the request for utilization (by 1 – 10 ‰ of desulfurization material liquid volume) of the request for utilization (95 – 100%) of the request for utilization of sulfide (1 – 10%, 60 – 200mL), barium carbonate and sinking agent is limited is: usage quantity is difficult to satisfy the reaction requirement very little; Usage quantity is too many, and sulfide is then wasted and is poisonous, and barium carbonate is not only waste, poisonous then, and is prone to increase cost, and sinking agent then is prone to increase cost.
Embodiment 1:
A kind of washing process that is used for the refining phosphoric acid by wet process of solvent extration may further comprise the steps successively:
The first step: full producing of having: the raw phosphoric acid that earlier wet method is made carries out pre-treatment, and that this pre-treatment comprises successively is concentrated, defluorinate, desulfurization, decolouring and filtration step, the filtrating of filtering gained is extracted again, and the organic phase of extraction back gained is fullly to be had;
Second step: the preparation of wash water: the phosphoric acid of getting concentration earlier and be 400g/L is as complex acid, this complex acid with full have be in a ratio of 1:25, again with NH
4 +Ion has middle sulfate radical stoichiometric 100% to add in the complex acid to dissolve, filter after dissolving finishes by full, and the filtrating of filtration gained is wash water;
The 3rd step: the carrying out of washing: have the four-stage counter-current of carrying out contact to wash with above-mentioned wash water to full earlier; The organic phase that obtains after the washing is and has washed, water is wash water; Strip to having washed, and wash water is carried out subsequent disposal, the phosphoric acid solution that obtains after the reextraction is back extraction acid; Through reclaiming extraction agent, concentrate, desulfurization, filtration, concentrating to make technical grade 85% phosphoric acid, quality product sees attached list 1 successively in this back extraction acid; Saidly wash water is carried out subsequent disposal be meant: earlier wash water is reclaimed extraction agent and handle, the wash water after will handling is again sent in the encloses container, in wash water, adds sulfide then; Add mass percent concentration in every liter of wash water and be 10% sulfide 60mL, reheat, and in 90 ℃ of following insulated and stirred of 85 – 3 hours; Filter then, again under 80 ℃ of 60 –, barium carbonate is added in the filtrating, and stir 1 hour to obtain the desulfurization feed liquid by sulfate radical stoichiometric 100% in the filtrating; Add sinking agent by 1 ‰ of desulfurization material liquid volume then, 10 minutes after-filtration of restir, in filtrating, feeding the ammonia neutralization then is 4.4 – 4.6 until the pH value; 30 minutes after-filtration of insulated and stirred again; Filtrating successively through concentrate, crystallisation by cooling, filtration, oven dry to be to obtain the product industrial grade monoammonium phosphate, product is colourless or the white crystals body, monoammonium phosphate content 99.23%; N 11.88%, P
2O
561%.
Above-mentioned the 3rd step with back extraction acid successively through reclaiming extraction agent, concentrate, desulfurization, filtration, concentrating with in the process that makes technical grade 85% phosphoric acid; When being concentrated into 75% phosphoric acid, this 75% phosphoric acid of desirable part returns in said second step and substitutes complex acid to produce the required wash water of next round; Said alternative complex acid is meant: extract part 75% phosphoric acid and allocate, until its H that comprises
3PO
4Concentration be 400 – 600g/L, promptly alternative complex acid; Between being had by to be washed full of complex acid and next round, the extracted amount of said part 75% phosphoric acid compares 1:16 – 25, allotment back H
3PO
4Concentration be that the concentration requirement of 400 – 600g/L is calculated and to be got.
Embodiment 2:
Step is with embodiment 1, and difference is:
Second step: the preparation of wash water: the phosphoric acid of getting concentration earlier and be 500g/L is as complex acid, this complex acid with full have be in a ratio of 1:16, again with NH
4 +Ion has middle sulfate radical stoichiometric 120% to add in the complex acid to dissolve, filter after dissolving finishes by full, and the filtrating of filtration gained is wash water;
The 3rd step: the carrying out of washing: quality product sees attached list 1; Saidly wash water is carried out subsequent disposal be meant: earlier wash water is reclaimed extraction agent and handle, the wash water after will handling is again sent in the encloses container, in wash water, adds sulfide then; Add mass percent concentration in every liter of wash water and be 6% sulfide 100mL, reheat, and in 90 ℃ of following insulated and stirred of 85 – 3 hours; Filter then, again under 80 ℃ of 60 –, barium carbonate is added in the filtrating, and stir 1 hour to obtain the desulfurization feed liquid by sulfate radical stoichiometric 97% in the filtrating; Add sinking agent by 5 ‰ of desulfurization material liquid volume then, 10 minutes after-filtration of restir, in filtrating, feeding the ammonia neutralization then is 4.4 – 4.6 until the pH value; 30 minutes after-filtration of insulated and stirred again; Filtrating successively through concentrate, crystallisation by cooling, filtration, oven dry to be to obtain the product industrial grade monoammonium phosphate, product is colourless or the white crystals body, monoammonium phosphate content 99.33%; N 11.89%, P
2O
561%.
Embodiment 3:
Step is with embodiment 1, and difference is:
Second step: the preparation of wash water: the phosphoric acid of getting concentration earlier and be 600g/L is as complex acid, this complex acid with full have be in a ratio of 1:22, again with NH
4 +Ion has middle sulfate radical stoichiometric 110% to add in the complex acid to dissolve, filter after dissolving finishes by full, and the filtrating of filtration gained is wash water;
The 3rd step: the carrying out of washing: quality product sees attached list 1; Saidly wash water is carried out subsequent disposal be meant: earlier wash water is reclaimed extraction agent and handle, the wash water after will handling is again sent in the encloses container, in wash water, adds sulfide then; Add mass percent concentration in every liter of wash water and be 1% sulfide 200mL, reheat, and in 90 ℃ of following insulated and stirred of 85 – 3 hours; Filter then, again under 80 ℃ of 60 –, barium carbonate is added in the filtrating, and stir 1 hour to obtain the desulfurization feed liquid by sulfate radical stoichiometric 95% in the filtrating; Add sinking agent by 10 ‰ of desulfurization material liquid volume then, 10 minutes after-filtration of restir, in filtrating, feeding the ammonia neutralization then is 4.4 – 4.6 until the pH value; 30 minutes after-filtration of insulated and stirred again; Filtrating successively through concentrate, crystallisation by cooling, filtration, oven dry to be to obtain the product industrial grade monoammonium phosphate, product is colourless or the white crystals body, monoammonium phosphate content 99.4%; N 11.9%, P
2O
561%.
Subordinate list 1
Above-described specific embodiment; The object of the invention, technical scheme and beneficial effect have been carried out further explain, and institute it should be understood that the above is merely specific embodiment of the present invention and oneself; Be not limited to the present invention; All within claim of the present invention, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. one kind is used for the washing process that solvent extration is made with extra care phosphoric acid by wet process, and it is characterized in that: said washing process may further comprise the steps successively:
The first step: full producing of having: the raw phosphoric acid that earlier wet method is made carries out pre-treatment, and that this pre-treatment comprises successively is concentrated, defluorinate, desulfurization, decolouring and filtration step, the filtrating of filtering gained is extracted again, and the organic phase of extraction back gained is fullly to be had;
Second step: the preparation of wash water: the phosphoric acid of getting concentration earlier and be 400 – 600g/L is as complex acid, this complex acid with full have be in a ratio of 1:16 – 25, again with NH
4 +Ion has stoichiometric 100 – 120% of middle sulfate radical to add in the complex acid to dissolve, filter after dissolving finishes by full, and the filtrating of filtration gained is wash water;
The 3rd step: the carrying out of washing: have the four-stage counter-current of carrying out contact to wash with above-mentioned wash water to full earlier; The organic phase that obtains after the washing is and has washed, water is wash water; Strip to having washed again; And wash water carried out subsequent disposal, and the phosphoric acid solution that obtains after the reextraction is back extraction acid, and this back extraction acid is successively through reclaiming extraction agent, concentrate, desulfurization, filtration, concentrating to make technical grade 85% phosphoric acid.
2. a kind of washing process that is used for the refining phosphoric acid by wet process of solvent extration according to claim 1; It is characterized in that: said the 3rd step with back extraction acid successively through reclaiming extraction agent, concentrate, desulfurization, filtration, concentrating with in the process that makes technical grade 85% phosphoric acid; When being concentrated into 75% phosphoric acid, this 75% phosphoric acid of desirable part returns in said second step and substitutes complex acid to produce the required wash water of next round; Said alternative complex acid is meant: extract part 75% phosphoric acid and allocate, until its H that comprises
3PO
4Concentration be 400 – 600g/L, promptly alternative complex acid; Between being had by to be washed full of complex acid and next round, the extracted amount of said part 75% phosphoric acid compares 1:16 – 25, allotment back H
3PO
4Concentration be that the concentration requirement of 400 – 600g/L is calculated and to be got.
3. a kind of washing process that is used for the refining phosphoric acid by wet process of solvent extration according to claim 1 and 2; It is characterized in that: in said the 3rd step wash water is carried out subsequent disposal and be meant: earlier wash water is reclaimed extraction agent and handle, the wash water after will handling is again sent in the encloses container, in wash water, adds sulfide then; Adding mass percent concentration in every liter of wash water is the sulfide 60 – 200mL of 1 – 10%; Reheat, and in 90 ℃ of following insulated and stirred of 85 – 3 hours, filter then; Again under 80 ℃ of 60 –, barium carbonate is added in the filtrating by stoichiometric 95 – 100% of sulfate radical in the filtrating; And stirring 1 hour to obtain the desulfurization feed liquid, 1 – 10 ‰ by the desulfurization material liquid volume adds sinking agent, 10 minutes after-filtration of restir then; In filtrating, feeding the ammonia neutralization then is 4.4 – 4.6 until the pH value; 30 minutes after-filtration of insulated and stirred again, filtrating successively through concentrate, crystallisation by cooling, filtration, oven dry to be to obtain the product industrial grade monoammonium phosphate, product is colourless or the white crystals body.
4. a kind of washing process that is used for the refining phosphoric acid by wet process of solvent extration according to claim 3 is characterized in that: in said the 3rd step wash water is carried out subsequent disposal and be meant: earlier wash water is reclaimed extraction agent and handle, the wash water after will handling is again sent in the encloses container; In wash water, add sulfide then, add mass percent concentration in every liter of wash water and be 6% sulfide 100mL, reheat; And in 90 ℃ of following insulated and stirred of 85 – 3 hours; Filter then, again under 80 ℃ of 60 –, barium carbonate is added in the filtrating, and stir 1 hour to obtain the desulfurization feed liquid by sulfate radical stoichiometric 97% in the filtrating; Add sinking agent by 5 ‰ of desulfurization material liquid volume then; 10 minutes after-filtration of restir, in filtrating, feeding the ammonia neutralization then is 4.4 – 4.6 until the pH value, again 30 minutes after-filtration of insulated and stirred; Filtrating successively through concentrate, crystallisation by cooling, filtration, oven dry to be to obtain the product industrial grade monoammonium phosphate, product is colourless or the white crystals body.
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Cited By (5)
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| CN103233134A (en) * | 2013-05-10 | 2013-08-07 | 桃江瑞龙金属新材料有限责任公司 | Recycling method of organic phase used for extracting scandium |
| CN105776169A (en) * | 2016-04-05 | 2016-07-20 | 瓮福（集团）有限责任公司 | Method for washing phosphoric acid loaded organic solvent with compound washing agent |
| CN109941979A (en) * | 2019-04-30 | 2019-06-28 | 舒爱桦 | A kind of technique of concentrated fertilizer phosphoric acid food grade phosphoric acid |
| CN113548651A (en) * | 2021-09-09 | 2021-10-26 | 中国石油化工股份有限公司 | Method for purifying wet-process phosphoric acid by solvent extraction |
| CN114031057A (en) * | 2021-12-17 | 2022-02-11 | 四川大学 | Method for producing industrial phosphoric acid and co-producing ammonium polyphosphate or solid phosphoric acid by wet-process phosphoric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103233134A (en) * | 2013-05-10 | 2013-08-07 | 桃江瑞龙金属新材料有限责任公司 | Recycling method of organic phase used for extracting scandium |
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| CN105776169A (en) * | 2016-04-05 | 2016-07-20 | 瓮福（集团）有限责任公司 | Method for washing phosphoric acid loaded organic solvent with compound washing agent |
| CN109941979A (en) * | 2019-04-30 | 2019-06-28 | 舒爱桦 | A kind of technique of concentrated fertilizer phosphoric acid food grade phosphoric acid |
| CN113548651A (en) * | 2021-09-09 | 2021-10-26 | 中国石油化工股份有限公司 | Method for purifying wet-process phosphoric acid by solvent extraction |
| CN114031057A (en) * | 2021-12-17 | 2022-02-11 | 四川大学 | Method for producing industrial phosphoric acid and co-producing ammonium polyphosphate or solid phosphoric acid by wet-process phosphoric acid |
| CN114031057B (en) * | 2021-12-17 | 2022-06-21 | 四川大学 | Method for producing industrial phosphoric acid and co-producing ammonium polyphosphate or solid phosphoric acid by wet-process phosphoric acid |
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