CN100402418C - Hydrochloric acid process of producing feed level calcium diphosphate and gypsum coproduct - Google Patents
Hydrochloric acid process of producing feed level calcium diphosphate and gypsum coproduct Download PDFInfo
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- CN100402418C CN100402418C CNB2004100812212A CN200410081221A CN100402418C CN 100402418 C CN100402418 C CN 100402418C CN B2004100812212 A CNB2004100812212 A CN B2004100812212A CN 200410081221 A CN200410081221 A CN 200410081221A CN 100402418 C CN100402418 C CN 100402418C
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Abstract
The present invention belongs to a method for producing feed calcium hydrogen phosphate and a gypsum coproduct by a hydrochloric acid method. The method comprises steps of acid hydrolysis, settlement separation, filtration, primary section neutralization, secondary section neutralization, feed calcium hydrogen phosphate preparation, calcium water purification and concentration, gypsum synthesis, hydrochloric acid recovery and gypsum product preparation. The method adopts ground phosphorite and sulfuric acid as raw materials, acid hydrolysis is carried out on the ground phosphorite by the hydrochloric acid, and the hydrochloric acid is recovered for circular use; the dissolution of fluorine in the acid hydrolysis process is controlled, the precipitating separation of the fluorine is prompted, and meanwhile, a process step of calcium water purification is added. The present invention has the characteristics that the quality of the feed calcium hydrogen phosphate is good, the P2O5 yield reaches 90%, the gypsum of food grade and medical application grade has wide purposes and high utility value, the calcium water of waste liquid is effectively used, the environmental pollution is reduced, the comprehensive benefit can be improved by more than 30% than that of the background art, etc. The present invention overcomes the defects of the background art of high production cost, poor product quality, no effective use of the calcium water, environmental pollution, large hydrochloric acid consumption, high cost of a main product and a byproduct, weak market competitiveness of ammonium chloride, etc.
Description
Technical field
The invention belongs in the Chemical Manufacture a kind of method that adopts the salt acid system to produce calcium hydrogen phosphate fodder and coproduction gypsum.
Background technology
The production method of conventional wet method calcium hydrogen phosphate fodder comprises sulfuric acid process and two kinds of operational paths of salt acid system, based on the former.Production cost is low though sulfuric acid process has, main raw material sulfuric acid is easy to get, can carry out characteristics such as large-scale industrial production; But there is defluorinate and intractability is big, processing cost is high to a large amount of phosphogypsum slags (calcium product of raising per ton will produce 2.5 tons of phosphogypsums) of producing in producing, the gained secondary calcium phosphate causes the product phosphorus content on the low side because of containing a small amount of calcium sulfate, and can not utilize low grade rock phosphate to make disadvantages such as raw material.Though and the traditional salt acid system has the calcium hydrogen phosphate fodder good product quality of production and stablize, production process is easy to control, can adopt low grade rock phosphate to make raw material and the three wastes are handled advantages such as easier; But have hydrochloric acid consumption and production cost height, the difficulty that from acid hydrolysis solution, removes slag, defluorinate handle the phosphorus loss big, to the processing of a large amount of calcium water of by-product and the outlet defectives such as better solution of failing always.To this, the patent documentation that be 94109345 at application number, name is called " hydrochloric acid or nitric acid circulation method decomposing rock phosphate with hydrogen " disclose a kind of at first adopt hydrochloric acid or nitric acid decomposing rock phosphate with hydrogen after, separate earlier sour insoluble impurity, again with sulfuric acid reaction to reclaim hydrochloric acid or nitric acid and to be reused for decomposing rock phosphate with hydrogen; Separate after filtration and can get phosphoric acid and comparatively purified white calcium sulfate.Though this technology is by recycle decomposing phosphate rock by chlorhydric acid powder and avoid producing characteristics such as waste material phosphogypsum, because the first evaporates hydrogenchloride and reclaims through cooling by be heated to 120～200 ℃ in the synthetic gypsum process; Its two, acid hydrolysis solution does not fully purify, its gypsum still is a rubble cream, can only do industrial; Its three, the problem that removes slag in the phosphoric acid by wet process hydrogen calcium does not obtain the solution on the industrial significance yet.Thereby this technology exists that hydrochloric acid is recycled the energy consumption height, by-product gypsum is of poor quality, purposes is restricted, defectives such as many, the of poor quality and instability of the phosphoric acid impurity of being produced.Loss problem at phosphorus in the quality of the processing of by product calcium water and calcium hydrogen phosphate fodder and the defluorinate, the patent No. be ZL99118228 patent documentation, disclose name and be called " method that the hydrochloric acid legal system is made calcium hydrophosphate fodder and by-product lime carbonate and ammonium chloride ", this method is the extraction liquid that at first generates phosphorous and calcium chloride by hydrochloric acid and ground phosphate rock reaction, adopt chemical precipitation method that extraction liquid is purified then, the extraction liquid after will purifying again is at ammonia and volatile salt or CO
2Effect under, calcium hydrophosphate fodder and lime carbonate and ammonium chloride are produced in reaction successively.P in the calcium phosphate that this method is produced
2O
5Yield can reach more than 85% and by-product technical grade lime carbonate and ammonium chloride, thereby improved the quality and the P of calcium hydrogen phosphate fodder
2O
5Yield; Solved simultaneously the problem of outlet of a large amount of calcium water of former technology institute by-product technically.But this method exists: one, hydrochloric acid can not recycle as raw material, and its consumption is big, production cost is than the sulfuric acid process height; Two, used CO
2With ammonia and ammonium chloride be respectively again raw material and the byproduct that the connection alkaline process is produced soda ash, the ammonium chloride of this invention coproduction its product cost by comparison is too high, extremely uneconomical economically.Thereby this method exists again and connection alkaline process production soda ash is contended over raw materials hydrochloric acid, CO
2Disadvantages such as big and hydrochloric acid can not be recycled with the consumption of ammonia, and major and minor products production cost is all high, the byproduct ammonium chloride market competitiveness is extremely weak.
Summary of the invention
The objective of the invention is to, defective at the background technology existence, design a kind of salt acid system and produce the method for calcium hydrogen phosphate fodder coproduction gypsum, improve calcium hydrogen phosphate fodder quality and co-production of high-quality gypsum to reach, realize that hydrochloric acid low temperature reclaims and recycle, reduce production costs, improve comprehensive utilization ratio and production efficiency, effectively solve calcium water outlet, overcome purpose such as environmental pollution.
Solution of the present invention is the advantage during comprehensive salt acid system and sulfuric acid process calcium hydrogen phosphate fodder are produced, on raw material route, adopt ground phosphate rock and sulfuric acid as raw material, and adopting salt acid system technology from technological operations such as acidolysis, purifications, make extraction agent and reclaim its recycle with hydrochloric acid; Reduce the fluorine stripping quantity by in the acidolysis process, slowly adding hydrochloric acid, then sedimentation concentrated solution and the Na after one section neutralizing treatment of adding in acid hydrolysis solution
2S rises slip acidity and impels the fluorine precipitation to separate out back, eliminating system; Be used for the phosphate rock-sulfuric acid powder to adding sulfuric acid synthetic gypsum, recovery dilute hydrochloric acid after purifying at the calcium water after three sections neutralizations, sedimentation, the filtration operation, concentrating again and returning; Thereby realize its goal of the invention.Therefore, the inventive method comprises:
A, acidolysis and settlement separate: adopt after two sections neutralizing treatment calcium water or/and clear water ground phosphate rock is made into after weight percent concentration is 50～70% ore pulp, CaO amount mol ratio is that 95～105% hydrochloric acid, reaction are after 30～90 minutes in slowly adding by ground phosphate rock under stirring condition, add one section sedimentation concentrated solution and sodium sulfide solution after the neutralizing treatment successively, mixed the back stirring reaction 2～10 minutes, and added weight percent concentration again and be 0.5～1.5% flocculation agent polyacrylamide solution, leave standstill with settlement separate acid hydrolysis solution after mixing; The sodium sulphite that is added is that the polyacrylamide solution that 0.03～0.1% of ground phosphate rock weight adds is counted 0.01～0.025% of ground phosphate rock weight with its solid content;
B, filtration: will be through settlement separate acid hydrolysis solution supernatant liquid suction neutralizing treatment groove, lower floor's concentrated solution is then sent into filter and is filtered, and is 30～60% of breeze gross weight with calcium water washing acid sludge, the calcium water consumption after two sections neutralizing treatment; Filtrate and washings are also imported the neutralizing treatment groove;
C, one section neutralization: the slow adding under whipped state of supernatant liquid, filtrate and the washings of input neutralizing treatment groove is 5～20% milk of lime in the CaO weight percent concentration, carry out one section neutralizing treatment after 1.0～1.5 hours, standing sedimentation, two sections neutralizing wells of the supernatant liquid suction after the sedimentation, lower floor's concentrated solution return the A step and continue reaction; Neutralizer pH value 1.5～2.3, neutralizing treatment temperature are no more than 60 ℃;
D, two sections neutralizations: the clear liquid in the neutralizing well is 5～20% milk of lime, had been no more than under 60 ℃ of temperature neutralizing treatment 1～2 hour slowly adding under the whipped state in the CaO weight percent concentration, to slip pH value be 3.5～5.0 only, standing sedimentation;
E, produce calcium hydrogen phosphate fodder: supernatant liquid suction calcium tank that will be after D handles, lower floor's concentrated solution are after filtration, its filtrate also imports the calcium tank; Behind the distilled water wash that filter cake returns via F, be dried to water ratio and be lower than 5%, promptly get the calcium hydrogen phosphate fodder product;
F, purify and concentrate calcium water: will be under stirring condition through clear liquid that E obtains and filtrate, add milk of lime successively and carry out three sections neutralizing treatment to pH8～10, add flocculation agent polyacrylamide solution to feed liquid and only play alumen ustum, with impurity such as sedimentation magnesium hydroxides, the CaCl to the calcium water of the calcium water evaporation concentration after will filtering gained then and purifying
2Weight percent concentration be 12～20% must purify spissated calcium water; The water that distills out is used for the washing to filter cake and gypsum of E and H step respectively, and filter residue uses it for anything else in addition;
G, gypsum synthesize: will be concentrated in calcium water and the washings input gypsum synthesizer behind H washing gypsum by the F gained, slowly the adding sulfuric acid reaction is after 30～120 minutes under whipped state, and growing the grain was not less than 0.5 hour under stirring at a slow speed, with synthetic gypsum; The vitriolic add-on with calcium water in the mol ratio of calcium ion amount be 90～100%, its adding speed is no more than 90 ℃ with the temperature of reaction of slip and is as the criterion;
H, reclaim hydrochloric acid and produce gypsum product; The slip that synthetic gypsum reacts after finishing is sent into the filter filtration, its filtrate dilute hydrochloric acid returns the A step and is used for the phosphate rock-sulfuric acid powder, the gained gypsum promptly gets the high-quality gypsum that meets medical treatment and food use standard via F gained distilled water wash, centrifuge dehydration, drying treatment; It is synthetic that washings returns G participation gypsum again.
The above-mentioned hydrochloric acid that slowly adds in acidolysis, its adding speed is to guarantee that the phosphorus fluorine in the feed liquid is than being as the criterion after the acidolysis in 50～80 scopes.And slowly adding milk of lime described in one section neutralization and the two sections N-process, its adding speed so that feed liquid neutralization reaction temperature be no more than 60 ℃ and be as the criterion; And described standing sedimentation, its settling time is 5～20 minutes.Acidolysis and settlement separate in the molecular weight of the flocculation agent polyacrylamide that adds be 5～70,000.
The present invention has the production technique advanced person, combines the advantage of traditional salt acid system and sulfuric acid process feed grade calcium phosphate production method, further remove fluorine, iron, aluminium impurity by the acid hydrolysis solution after removing slag being carried out a neutralizing treatment, its calcium hydrogen phosphate fodder quality is good after the secondary neutralizing treatment again; Adopt a sedimentation concentrated solution returning charge after the neutralizing treatment, make the phosphorus loss after once neutralizing obtain regeneration, P again
2O
5Yield is up to 90%, and coproduction (by product) gypsum is food, medical grade high-quality gypsum, and purposes is wide, utility value is high, and waste liquid calcium water is utilized effectively, and has reduced environmental pollution; Its overall economic efficiency can improve more than 30 percentage points than background technology, characteristics such as also more conventional sulfuric acid process raising about 20%.
Embodiment:
A. acidolysis and settlement separate: at first will adopt P in the solid content 60%, ground phosphate rock of calcium water (or/and clear water) allotment after the secondary neutralizing treatment
2O
5Content is 33% ore pulp 2m
3Add in the acidolysis groove of belt stirrer, under agitation with 14m
3It is 125g/L hydrochloric acid 7.3m that the flow of/h adds concentration
3(the dilute hydrochloric acid 6.3m that present embodiment is reclaimed by H
3And 1m
3The technical hydrochloric acid of concentration 20% is made into), reaction is after 60 minutes, the sedimentation concentrated solution 1.5m that one section neutralization is obtained
3And the sodium sulfide solution 50Kg of concentration 2% adds, stirring reaction 5 minutes, adds concentration 0.5%, molecular weight then and be the aqueous solution 50Kg of 60,000 polyacrylamide, mixes the back, standing sedimentation separates acid hydrolysis solution;
B. filter: supernatant liquid suction neutralizing well, the lower floor's concentrated solution after sedimentation is handled put into the band filter and filtered, the calcium water 400Kg washing that filter residue produces with two sections neutralizations, and filtrate and washings are also imported neutralizing well, the filter residue discharging;
C. one section neutralization: will import supernatant liquid, filtrate and the washings of neutralizing well, and under whipped state, open the milk of lime volume pump, with 1.6m
3The flow of/h is with the milk of lime 0.8m of 150gCaO/L
3Spray into and carry out one section neutralizing treatment in the feed liquid, neutralizing treatment after 70 minutes, put into the subsider sedimentation 30 minutes, two sections neutralizing wells of supernatant liquid suction, lower floor's concentrated solution return the A step; Material liquid pH 1.8 after 52 ℃ of neutralizing treatment temperature, the neutralizing treatment;
D. two sections neutralizations: open two sections neutralizing well agitators, with in two sections of suction and clear liquid place under the whipped state, open grey newborn volume pump, with 2.6m
3The flow of/h is with the milk of lime 1.3m of 150gCao/L
3Spray in the feed liquid, carry out two sections neutralizing treatment after 70 minutes, sedimentation is stand-by; Material liquid pH 4.2 after 58 ℃ of neutralizing treatment temperature, the neutralizing treatment;
E. produce calcium hydrogen phosphate fodder: will send into calcium tank, lower floor's concentrated solution through the supernatant liquid after the D. sedimentation is handled and deliver to that whizzer filters, filtrate is also put into the calcium tank; Behind the distilled water wash that filter cake returns via F, drying treatment is to water ratio 3.5%, obtains 1364Kg calcium hydrogen phosphate fodder product, this product contains after measured: P
2O
540.5%, F 0.10%, Ca 25.7%, water ratio 3.5%;
F. calcium water purifies, concentrates: supernatant liquid that will obtain from step e and filtrate are after adding milk of lime that concentration is 150gCaO/L successively, the pH value of feed liquid is transferred to 8.5 under the whipped state, add weight percent concentration and be the about 100L of 0.5% flocculation agent and play about 10 minutes of alumen ustum, sedimentation to feed liquid, supernatant liquid is put into calcium pond, lower floor's concentrate pump and is gone into that the sheet frame pressure filter filters, its filtrate is also put into the calcium pond, in the calcium pond, after the preheater preheating, enter two and imitate countercurrent evaporation device control two 110 ℃ of temperature of effect, vacuum tightness 0.06MPa, be concentrated into CaCl
2Weight percent concentration be 14.5% (to distill out 3.8m approximately
3Water), through get thickening-purification technology calcium water in preheater with after rare calcium water heat exchange cooling, filter cake uses it for anything else; Distilled water is respectively applied for the washing to filter cake and gypsum of E and H step;
G. gypsum is synthetic: will purify spissated calcium water through F and put into dense calcium pond and the about 2.3m of washings behind H washing gypsum
3Mix, turn on agitator is with 1.0m
3The flow adding concentration of/h is 98% sulfuric acid 900Kg, and building-up reactions was put into the slip storage tank with slip after 50 minutes, and growing the grain is 1 hour under stirring at a slow speed; 78 ℃ of synthesis reaction temperatures;
H. reclaim hydrochloric acid and produce gypsum: above-mentioned gypsum synthetic material stock pump is gone into the press filtration of sheet frame pressure filter, got the about 6.3m of filtrate
3Dilute hydrochloric acid put into the hydrochloric acid storage tank and return and be used for A step phosphate rock-sulfuric acid powder; Be pressed into then by F gained distilled water wash gypsum, the about 2.3m of its washings
3It is synthetic to return G participation gypsum, and the filter cake after the washing gets product β-gypsum 1350Kg after drying; This gypsum contains CaSO
495.67%, F 0.003%, heavy metal (in Pb) 2.0ppm.
Claims (4)
1. a salt acid system is produced the method for calcium hydrogen phosphate fodder coproduction gypsum, it is characterized in that this method comprises:
A, acidolysis and settlement separate: adopt after two sections neutralizing treatment calcium water or/and clear water ground phosphate rock is made into after weight percent concentration is 50～70% ore pulp, CaO amount mol ratio is 1: 0.95～1.05 hydrochloric acid in slowly adding by ground phosphate rock under stirring condition, react after 30～90 minutes, add one section sedimentation concentrated solution and sodium sulfide solution after the neutralizing treatment successively, mixed the back stirring reaction 2～10 minutes, add weight percent concentration again and be 0.5～1.5% flocculation agent polyacrylamide solution, leave standstill after mixing with settlement separate acid hydrolysis solution; The sodium sulphite that is added is 0.03～0.1% of ground phosphate rock weight, and the polyacrylamide solution that adds is counted 0.01～0.025% of ground phosphate rock weight with its solid content;
B, filtration: will be through settlement separate acid hydrolysis solution supernatant liquid suction neutralizing treatment groove, lower floor's concentrated solution is then sent into filter and is filtered, and with the calcium water washing acid sludge after two sections neutralizing treatment, the calcium water consumption is 30～60% of a breeze gross weight; Filtrate and washings are also imported the neutralizing treatment groove;
C, one section neutralization: the slow adding under whipped state of supernatant liquid, filtrate and the washings of input neutralizing treatment groove is 5～20% milk of lime in the CaO weight percent concentration, carry out one section neutralizing treatment after 1.0～1.5 hours, standing sedimentation, two sections neutralizing wells of supernatant liquid suction after the sedimentation, lower floor's concentrated solution return the A step and continue reaction; Neutralizer pH value 1.5～2.3, neutralizing treatment temperature are no more than 60 ℃;
D, two sections neutralizations: it is 5～20% milk of lime that the clear liquid in the neutralizing well is slowly added in the CaO weight percent concentration under whipped state, is being no more than under 60 ℃ of temperature neutralizing treatment 1～2 hour, to slip pH value be 3.5～5.0 only, standing sedimentation;
E, produce calcium hydrogen phosphate fodder: supernatant liquid suction calcium tank that will be after D handles, lower floor's concentrated solution after filtration, its filtrate is also imported the calcium tank; Behind the distilled water wash that filter cake returns via F, be dried to water ratio and be lower than 5%, promptly get the calcium hydrogen phosphate fodder product;
F, purify and concentrate calcium water: will be under stirring condition through clear liquid that E obtains and filtrate, add milk of lime successively and carry out three sections neutralizing treatment to pH8～10, add flocculation agent polyacrylamide solution to feed liquid and only play alumen ustum, with impurity such as sedimentation magnesium hydroxides, the CaCl to the calcium water of the calcium water evaporation concentration after will filtering gained then and purifying
2Weight percent concentration be 12～20%, must purify spissated calcium water; The water that distills out is used for the washing to filter cake and gypsum of E and H step respectively, and filter residue uses it for anything else in addition;
G, gypsum synthesize: will be concentrated in calcium water and the washings input gypsum synthesizer behind H washing gypsum by the F gained, slowly the adding sulfuric acid reaction is after 30～120 minutes under whipped state, and growing the grain was not less than 0.5 hour under stirring at a slow speed, with synthetic gypsum; The vitriolic add-on with calcium water in the mol ratio of calcium ion amount be 0.90～1.00: 1, its adding speed is no more than 90 ℃ with the temperature of reaction of slip and is as the criterion;
H, reclaim hydrochloric acid and produce gypsum product; The slip that synthetic gypsum reacts after finishing is sent into the filter filtration, its filtrate dilute hydrochloric acid returns the A step and is used for the phosphate rock-sulfuric acid powder, gained rubble cream promptly gets the high-quality gypsum that meets medical treatment and food use standard via F gained distilled water wash, centrifuge dehydration, drying treatment; It is synthetic that washings returns G participation gypsum again.
2. produce the method for feed phosphorus hydrogen calcium coproduction gypsum by the described salt acid system of claim 1; It is characterized in that the described hydrochloric acid that in acidolysis, slowly adds, its adding speed so that after the acidolysis phosphorus fluorine in the feed liquid than in 50～80 scopes.
3. produce the method for feed phosphorus hydrogen calcium coproduction gypsum by the described salt acid system of claim 1; It is characterized in that slowly adding milk of lime described in one section neutralization and the two sections N-process, its adding speed is so that the neutralization reaction temperature of feed liquid is no more than 60 ℃ is as the criterion; And described standing sedimentation, its settling time is 5～20 minutes.
4. produce the method for feed phosphorus hydrogen calcium coproduction gypsum by the described salt acid system of claim 1; It is characterized in that acidolysis and settlement separate in the molecular weight of the flocculation agent polyacrylamide that adds be 5～70,000.
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| CNB2004100812212A CN100402418C (en) | 2004-11-12 | 2004-11-12 | Hydrochloric acid process of producing feed level calcium diphosphate and gypsum coproduct |
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| CN100402418C true CN100402418C (en) | 2008-07-16 |
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| CN101168852B (en) * | 2007-08-31 | 2011-10-26 | 武善东 | Mass production method for calcium sulfate whisker |
| CN102502553A (en) * | 2011-09-30 | 2012-06-20 | 瓮福（集团）有限责任公司 | Method for preparing feed grade calcium hydrogen phosphate from waste water of phosphate fertilizer plant |
| CN102583290A (en) * | 2012-02-18 | 2012-07-18 | 张黔生 | Low-grade phosphorite mineral dressing technology and method for producing by-product high-purity gypsum powder |
| CN103496685B (en) * | 2013-10-14 | 2015-09-09 | 四川省化工设计院 | The method of continuous seepage calcium hydrophosphate fodder |
| CN105692575B (en) * | 2016-01-27 | 2018-02-09 | 贵州省冶金化工研究所 | A kind of Application way of rock phosphate in powder |
| CN106115641A (en) * | 2016-05-23 | 2016-11-16 | 禄丰天宝磷化工有限公司 | A kind of remove the technique of impurity in calcium hydrogen phosphate |
| CN106044733A (en) * | 2016-06-05 | 2016-10-26 | 禄丰天宝磷化工有限公司 | Novel method for removing arsenic in phosphorite-produced calcium hydrophosphate |
| CN106044732B (en) * | 2016-06-05 | 2018-06-08 | 禄丰天宝磷化工有限公司 | A kind of method that double phosphate rock-sulfuric acids make calcium monohydrogen phosphate |
| CN106186601B (en) * | 2016-07-26 | 2019-02-26 | 四川高绿平环境科技有限公司 | A kind of processing method of sludge |
| CN109836177B (en) * | 2017-11-27 | 2022-04-15 | 川恒生态科技有限公司 | Method for producing calcium phosphate salt and high-purity gypsum by using hydrochloric acid and phosphorite |
| CN111017894B (en) * | 2019-12-31 | 2022-05-10 | 云南力达一矿物技术有限公司 | Method for preparing clean phosphoric acid and high-purity gypsum by decomposing ground phosphate rock with hydrochloric acid |
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