CN102674279B - Method for producing phosphoric acid by hemihydrate technique - Google Patents

Method for producing phosphoric acid by hemihydrate technique Download PDF

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CN102674279B
CN102674279B CN201210188545.0A CN201210188545A CN102674279B CN 102674279 B CN102674279 B CN 102674279B CN 201210188545 A CN201210188545 A CN 201210188545A CN 102674279 B CN102674279 B CN 102674279B
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phosphoric acid
slip
crystallizer tank
groove
tank
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CN102674279A (en
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李进
王佳才
李顺方
赵鹏
唐晓林
吴生平
赵东
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GUIZHOU CHANHEN CHEMICAL CO., LTD.
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GUIZHOU CHUANHENG CHEMICAL CO Ltd
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Abstract

The invention discloses a method for producing phosphoric acid by a hemihydrate technique, belonging to the field of phosphoric acid production by a wet process. The invention aims to provide a method for producing phosphoric acid by a hemihydrate technique, which can enhance the phosphorus yield. The method comprises the following steps: a. pre-reaction: controlling sulfuric acid in a return slurry of a crystallization tank and CaO added into ground phosphorite in a mol ratio of (0.4-0.6):1; b. entering a decomposing tank for further reaction; c. entering the crystallization tank to react with a solution formed by thoroughly mixing a phosphoric acid solution and sulfuric acid to form crystals, and controlling the mass ratio of the sulfate group in the slurry acid liquor to the acid liquor at 1.5-2.0%; d. entering a grain growing tank to promote crystal growth; and e. filtering to obtain the finished phosphoric acid product. The method disclosed by the invention has the advantage of more optimized and reasonable process, is simpler and more stable to operate and control, and can obtain high phosphorus yield.

Description

The method of half water explained hereafter phosphoric acid
Technical field
The invention belongs to Wet-process Phosphoric Acid Production field, be specifically related to a kind of method of half water explained hereafter phosphoric acid.
Background technology
Wet Processes of Phosphoric Acid is the process of manufacturing phosphoric acid with mineral acid (being mainly sulfuric acid) decomposing phosphate rock, with sulfuric acid, reacts generate crystal of calcium sulfate and phosphoric acid solution with phosphorus ore, then carry out liquid-solid separation, obtains phosphoric acid.
From current known references and data, show, except not yet having industrialized unit without water law flow process, other flow processs all have industrialized unit build up and put into operation, in various flow processs, adopt the device of two water laws to account for 85%; And with regard to current research, in the production of phosphoric acid by wet process, direct that phosphoric acid concentration is greater than 40% (with P 2o 5meter) flow process only have half water law flow process and half water two Water flow-paths.Half water two water law flow processs, double water law flow process mutually, flow process is relatively long, and energy consumption is higher.
The differentiation of wet method phosphoric acid manufacture process is to carry out with the difference of crystal of calcium sulfate in reaction slurry, with the terra alba (CaSO generating 4.2H 2o), calcium sulphate hemihydrate (CaSO 4.0.5H 2o) and anhydrous calciumsulphate (CaSO 4) be divided into two water laws (DH method), half water law (HH method), without flow processs such as water law (AH method), half water-bis-water law (HDH) He Ershui-half water laws (DHH).
Current half water thing method wet method phosphoric acid manufacture process mainly contains three kinds of many oars double flute hemihydrate process of single-blade double flute hemihydrate process that Occidental Petroleum Corporation has, the research and development of Norway Nuo Sike-Hai Deluo company and the hemihydrate process of N.K.K-Lu Musi square groove.
The single-blade double flute hemihydrate process of Occidental Petroleum Corporation is that reactive moieties is completed respectively in premix groove, dissolving tank and crystallizer tank, returning to light phosphoric acid and ground phosphate rock joins and in premix groove, carries out premix reaction, the overflow of premix slip is entered in dissolving tank, and with from crystallizer tank overflow and come slip carry out solubilizing reaction; In dissolving tank, reaction slurry is sent crystallizer tank to by dissolving tank bottom transferpump, sulfuric acid is added in crystallizer tank simultaneously, thereby completes the crystallisation process of slip; Slurry is sent to filtering separation after by a process tank.
Many oars double flute half water logistics of Norway Nuo Sike-Hai Deluo company is that reactive moieties is completed respectively in two decomposers and a process tank, ground phosphate rock and cooled through vacuum flashing, from the slip of second decomposer, in first decomposer, complete the decomposition reaction of first stage, then overflow in second decomposer; Sulfuric acid and return to light phosphoric acid and join in second decomposer simultaneously, continued the decomposition reaction process of subordinate phase, a slip part in second decomposer is recycled to first decomposer after vacuum flashing is cooling, and another part overflow is entered process tank and sent to filtering separation;
The hemihydrate process of N.K.K-Lu Musi square groove is that reaction process is concentrated in a square cell body and completed, and be set to respectively pre-confounding and resolver by the form of sequestered partition, ground phosphate rock, return to light phosphoric acid, sulfuric acid and the slip that comes from resolver circulation together joins pre-confounding, complete premix reaction, a resolver slip part is recycled to pre-confounding, and a part is sent to filtering separation.
These three kinds of flow processs mainly have the following disadvantages:
(1) the required four-stage subregion of half water thing method wet-process phosphoric acid reaction is not obvious, is unfavorable for the abundant reaction of phosphorus ore and growing up of calcium sulphate hemihydrate crystallization, thereby makes to decompose and washing effect variation P in phosphogypsum 2o 5content reaches more than 1.5～2%, and overall phosphorus yield is low, generally can only reach 89～92%.
(2) sulfuric acid directly adds in reactive tank, easily forms the partial over saturation of sulfuric acid at sulfuric acid acid adding place, easily forms more tiny calcium sulphate hemihydrate crystallization, and back segment filtering separation and washing effect are poor, affect overall phosphorus yield.
(3) in order to improve phosphorus yield as far as possible, generally adopt wet-process deslagging, be not easy to transhipment conveying and the recycle in later stage of phosphogypsum.
(4) in order to produce 42 set～45%P 2o 5the phosphoric acid of concentration, returns acid amount little, and reaction slurry solid content is controlled at 38% left and right, and phosphoric acid is large, is unfavorable for filtering separation and washing.
(5) in reaction slurry liquid phase, sulfate concentration is controlled at 2.0～3.5wt%, and sulfuric acid consumption is high, and production cost is high.
(6) temperature of reaction control is substantially at 98～103 ℃, and equipment material and equipment anticorrosion require high, and equipment corrosion is serious.
Therefore, now need improve existing half water phosphoric acid process, to overcome above-mentioned defect.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of the half water explained hereafter phosphoric acid that improves phosphorus yield.
The technical solution adopted for the present invention to solve the technical problems is: the method for half water explained hereafter phosphoric acid, comprises the steps:
A, ground phosphate rock and the overfall from crystallizer tank carry out pre-reaction in premix groove, and the sulfuric acid of controlling in overfall is 0.4～0.6 ︰ 1 with adding the mol ratio of the CaO in ground phosphate rock;
Slip after b, pre-reaction enters continuously decomposer and further reacts;
The slip of c, decomposer enters crystallizer tank more continuously, and meanwhile, phosphoric acid solution and sulfuric acid add crystallizer tank continuously after fully mixing, and both react formation crystallization; Wherein, in crystallization control groove, the sulfate radical quality in slip acid solution and the mass ratio of acid solution are 1.5～2.0%;
The slip of d, crystallizer tank enters continuously growing the grain groove and promotes crystal further to grow up, and meanwhile, the slip of crystallizer tank also enters premix groove as the overfall described in step a;
E, the slip in growing the grain groove is delivered to band filter continuously carry out coarse filtration, filtration and washing, the liquid of filtration is finished product phosphoric acid.
Wherein, in aforesaid method step e, slip coarse filtration obtains coarse filtration filtrate, obtains calcium sulphate hemihydrate after filtration, and calcium sulphate hemihydrate obtains wash filtrate through washing; Coarse filtration filtrate, wash filtrate and appropriate finished product phosphoric acid form the phosphoric acid solution described in step c.
Further, in described phosphoric acid solution, quality=50～60 ︰ 8～12 ︰ 30～40 of the Zhi Liang ︰ finished product phosphoric acid of the Zhi Liang ︰ coarse filtration filtrate of wash filtrate.
Further, in crystallizer tank, the liquid-solid ratio of slip is 2.5～3 ︰ 1.
Wherein, in aforesaid method, the slip of crystallizer tank is sent into continuously flasher and is carried out forced cooling, and cooling rear portion enters premix groove as overfall, and another part returns to crystallizer tank.
Wherein, in aforesaid method, the slurry temperature in premix groove, decomposer and crystallizer tank is controlled between 90～97 ℃.
Wherein, in aforesaid method, premix groove is connected by foot passage with decomposer, and decomposer is connected by top overflow port with crystallizer tank, and crystallizer tank is connected by foot passage with growing the grain groove.
Wherein, the washing described in aforesaid method step e is three stage countercurrent washings.
Wherein, ground phosphate rock described in aforesaid method is by weight containing Vanadium Pentoxide in FLAKES 25～40%.
Further, described ground phosphate rock is by weight containing Vanadium Pentoxide in FLAKES 30～35%.
Beneficial effect of the present invention is: first, the negative sulfuric acid condition of premix groove and decomposer is only by returning the sulfuric acid content of slurry and returning slurry amount size and control, in premix reactive tank, control 40～60% and the sulfuric acid reaction of CaO in concentrate and generate half water phosphogypsum, all the other CaO of 40～60% are dissolved in slip, not only controlled negative sulfuric acid condition, a large amount of reaction crystal seeds is provided simultaneously, the crystallization of double water phosphogypsum has larger improvement.The present invention only returns slurry and does not directly add phosphoric acid or sulfuric acid in premix groove, make the negative sulfuric acid condition of premix groove and decomposer more stable, can not produce the parcel because adding sulfuric acid to form, thereby improve the rate of decomposition of phosphorus ore, the rate of decomposition of phosphorus ore reaches more than 98%, and the insoluble phosphorus in gypsum is (with P 2o 5meter) can be low to moderate below 0.4%.
In addition, the present invention just adds the nitration mixture of sulfuric acid and phosphoric acid in crystallizer tank, and to be that sulfuric acid is unique add some crystallizer tank, in production operation, can recently automatically regulate by controlling suitable sour ore deposit, reduce technology controlling and process point.In other inventions, have in premix groove, to fill into sulfuric acid and phosphoric acid and return acid, but weak point in other inventions is embodied in sulfuric acid, add a little at least 2, controlling factor increases and brings unstable.The mode that in the present invention, anti-slurry is the negative sulfuric acid condition of unique control, negative sulfuric acid conditional stability of the present invention, make the crystallization effect of calcium sulfate good, therefore, according to the crystallization effect of half water phosphogypsum, determine sulfate radical span of control 1.5～2.0% in this technique, lower than other technic index sulfate radical span of control 2.0～2.5%.Product phosphoric acid per ton (P2O5 meter) can be saved sulfuric acid 12.5～25kg.Meanwhile, in the 3rd reactive tank material, add the nitration mixture of sulfuric acid and phosphoric acid to be conducive to improve the liquid-solid ratio of crystallizer tank, be conducive to obtain thick, uniform glomerocryst at crystallizer tank, be conducive to the washing of filtering separation operation.
Moreover the required four-stage subregion of the present invention's half water thing method wet-process phosphoric acid reaction is obvious, has increased growing the grain groove after crystallizer tank, growing the grain groove not only extends the crystalline growth time and is beneficial to filtration washing, can dispel the heat and remove the heat because of the further growth of crystallization simultaneously.Can realize water-soluble phosphorus in phosphogypsum (with P 2o 5meter) between 0.2～0.4%, washing rate can reach more than 98%.Thereby the total recovery that realizes phosphorus is greater than 96%(total recovery=rate of decomposition * washing rate, refers to the phosphorus in phosphorus ore, through the percentage ratio that can fully reclaim after processing).Meanwhile, good strainability and washing effect, be conducive to the water balance of system, and provide condition to the later use of phosphogypsum.
The present invention is by increasing the step of the outer low level flash cooling of groove, can be convenient stablize half water temperature of reaction, control the negative sulfuric acid index of premix reactive tank simultaneously, crystal seed is provided, promote the optimization of crystallization.
The present invention has adopted first acid filtering all to return, and finished product phosphoric acid solid content and its clarity of assurance are had to active effect.
The present invention has adopted decomposition reaction and the Tc control that temperature is lower, described decomposition reaction temperature is at 90～97 ℃, low compared with 98～103 ℃ described in other techniques, be conducive to reduce the corrosion of process device, reduce the foam layer height that temperature is conducive to reduce reactive tank simultaneously, reduce defoamer or do not use defoamer, improving the throughput of reactive tank.
Just because of production method of the present invention, possess above feature, therefore technical process of the present invention is optimized more, and rationally, operation is controlled more and simplified and stablize, thereby can obtain higher phosphorus yield.The present invention is stronger to the adaptability of reaction raw materials, and the cleaned system obstruction cycle is long, and production efficiency is high, can effectively raise the service ability of device, thereby obtains good technology controlling and process index and economic and technical norms.
Accompanying drawing explanation
Fig. 1 is the process schematic representation of the present invention's half water explained hereafter phosphoric acid;
In figure, be labeled as: the 1st, premix groove, the 2nd, decomposer, the 3rd, crystallizer tank, the 4th, growing the grain groove, the 5th, liquid seal trough, the 6th, pump, the 7th, flasher, the 8th, nitration mixture groove, the 9th, band filter, the 91st, initial filter district, the 92nd, filtrating area, 93 Shi Yixi districts, 94 Shi Erxi districts, 95 Shi Sanxi districts.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described.
As shown in Figure 1, the method for half water explained hereafter phosphoric acid, comprises the steps:
A, ground phosphate rock and the overfall from crystallizer tank 3 carry out pre-reaction in premix groove 1, and the sulfuric acid of controlling in overfall is 0.4～0.6 ︰ 1 with adding the mol ratio of the CaO in ground phosphate rock;
Slip after b, pre-reaction enters continuously decomposer 2 and further reacts;
The slip of c, decomposer 2 enters crystallizer tank 3 more continuously, and meanwhile, phosphoric acid solution and sulfuric acid add crystallizer tank 3 continuously after fully mixing, and both react formation crystallization; Wherein, the sulfate radical quality in the interior slip acid solution of crystallization control groove 3 and the mass ratio of acid solution are 1.5～2.0%;
The slip of d, crystallizer tank 3 enters continuously growing the grain groove 4 and promotes crystal further to grow up, and meanwhile, the slip of crystallizer tank 3 also enters premix groove 1 as the overfall described in step a;
E, the slip in growing the grain groove 4 is delivered to band filter 9 continuously carry out coarse filtration, filtration and washing, the liquid of filtration is finished product phosphoric acid.
Preferably, in aforesaid method step e, slip coarse filtration obtains coarse filtration filtrate, obtains calcium sulphate hemihydrate after filtration, and calcium sulphate hemihydrate obtains wash filtrate through washing; Coarse filtration filtrate, wash filtrate and appropriate finished product phosphoric acid form the phosphoric acid solution described in step c.
Further, in order to make technological operation of the present invention simple and stable more, in described phosphoric acid solution, quality=50～60 ︰ 8～12 ︰ 30～40 of the Zhi Liang ︰ finished product phosphoric acid of the Zhi Liang ︰ coarse filtration filtrate of wash filtrate.
In like manner, in order to make technological operation of the present invention simple and stable more, the liquid-solid ratio of crystallizer tank 3 interior slips is 2.5～3 ︰ 1.
Preferably, in aforesaid method, in order better to control the temperature of premix groove 1 and crystallizer tank 3, the slip of crystallizer tank 3 is sent into continuously flasher 7 and is carried out forced cooling, and cooling rear portion enters premix groove 1 as overfall, and another part returns to crystallizer tank 3.
Preferably, in aforesaid method, the slurry temperature in premix groove 1, decomposer 2 and crystallizer tank 3 is controlled between 90～97 ℃.
Preferably, in aforesaid method, premix groove 1 is connected by foot passage with decomposer 2, and decomposer 2 is connected by top overflow port with crystallizer tank 3, and crystallizer tank 3 is connected by foot passage with growing the grain groove 4.Arrange like this and can effectively prevent slip short circuit, guarantee the reaction times in each stage.
Preferably, more abundant in order to wash, and water saving, be convenient to the control to the water yield, the washing described in aforesaid method step e is three stage countercurrents washings.
When slip is delivered to band filter 9 and is carried out coarse filtration, filtration and washing, first through initial filter district 91, carry out coarse filtration, initial filter stage slurry cloth does not form uniform filter cake, has a small amount of gypsum to wear filter in acid solution, acid solution is more mixed, therefore coarse filtration filtrate is delivered to the liquid seal trough 5 of dress wash filtrate.After coarse filtration, enter filtrating area 92, filtrating area 92 is owing to having formed uniform filter cake, and acid solution is limpid, therefore as finished product phosphoric acid.After filtration, carry out three stage countercurrent washings, clear water adds San Xi district 95, squeezes into Er Xi district 94 after entering liquid seal trough 5 after washing again, enters another liquid seal trough 5, then send into Yi Xi district 93 after same washing, finally enters the liquid seal trough 5 of dress coarse filtration filtrate.Coarse filtration filtrate, wash filtrate and appropriate finished product phosphoric acid and sulfuric acid enter nitration mixture groove 8, finally enter continuously crystallizer tank 3.
Preferably, ground phosphate rock described in aforesaid method is by weight containing Vanadium Pentoxide in FLAKES 25～40%.
Further, described ground phosphate rock is by weight containing Vanadium Pentoxide in FLAKES 30～35%.
Below by producing 150ktP per year 2o 5the enforcement of half water law phosphoric acid production device is further described the specific embodiment of the invention in fact, but does not therefore limit the present invention among the scope described in embodiment.
Embodiment mono-:
The method is carried out according to the following steps: phosphorus ore and overfall premix, phosphorus ore decomposition, crystallization and return slurry, growing the grain filtration washing and return acid.
Produce by phosphorus ore index situation as follows:
P 2O 5％ CaO％ MgO％ H 2O％ Fe 2O 3 Al 2O 3 Acid non-soluble substance %
33.05 48.21 0.76 12.97 0.46 0.47 5.6
1, phosphorus ore and the overfall premix from crystallizer tank 3
Ground phosphate rock is thrown ore deposit amount and is entered continuously premix groove 1 with 80t/h, from crystallizer tank 3 through the cooled slip of flasher 7 with 1000m 3/ h enters, and carries out premix reaction in premix groove 1, and temperature of reaction is at 90 ℃, and in premix groove, index situation is as follows:
Figure BDA00001744343500051
Overfall index situation is as follows:
Figure BDA00001744343500061
2, phosphorus ore decomposes
Half water material slurry overflow is further carried out decomposition reaction to decomposer 2,90 ℃ of temperature of reaction.
3, crystallization and return slurry
Slip again overflow, to crystallizer tank 3, adds this groove from the acid of returning of filtrating area after nitration mixture groove 8 fully mixes with sulfuric acid, return acid amount for 135m 3/ h, sulphuric acid is 30.8m 3/ h.Temperature of reaction is at 94 ℃, SO 4 2-1.5%.Slip in crystallizer tank 3 is after flash distillation cooling, by 1000m 3/ h enters premix reactive tank 1 and controls CaO index as returning slurry, and part enters crystallizer tank 3.Material is entered to cooling effect.
4, growing the grain and filtration
Crystallizer tank 3 slips to growing the grain groove 4, carry out liquid-solid separation by being pumped into band filter 9 through overflow.Through three countercurrent washings, gained one is washed acid solution, initial filter acid solution enters a liquid seal trough 5, through pump 6, deliver to the nitration mixture groove 8 on crystallizer tank 3 tops, simultaneously the finished acid of filtrating area liquid seal trough 5 part is delivered to finished acid storage tank with pump 6, after the nitration mixture groove 8 that another part is delivered to crystallizer tank 3 tops fully mixes with sulfuric acid, a washing filtrate, initial filter acid solution, carries out crystallizer tank.Filter cake is delivered to ardealite storage yard through Pi Yunji.
Phosphoric acid day output is (with P 2o 5meter) 530t, finished product phosphoric acid product, phosphogypsum, rate of decomposition, washing rate, total recovery index are as follows.
Figure BDA00001744343500062
Embodiment bis-:
The method is carried out according to the following steps: phosphorus ore and overfall premix, phosphorus ore decomposition, crystallization and return slurry, growing the grain filtration washing and return acid.
Produce by phosphorus ore index situation as follows:
P 2O 5％ CaO％ MgO％ H 2O％ Fe 2O 3 Al 2O 3 Acid non-soluble substance %
32.5 47.6 1.40 13.4 0.8 0.5 5.4
1, phosphorus ore and overfall premix
Ground phosphate rock is thrown ore deposit amount for 85t/h, 1150m 3the overfall amount of/h is carried out pre-reaction in premix groove 1, and temperature of reaction is at 95 ℃, and in premix groove 1, index situation is as follows:
P 2O 5％ CaO％ Slip ratio Filtrate acid Solid content
Heavy Proportion ％
43.35 1.01 1.762 1.486 34.38
Overfall index situation is as follows:
Figure BDA00001744343500071
2, phosphorus ore decomposes
Half water material slurry overflow is further carried out decomposition reaction to decomposer 2,95 ℃ of temperature of reaction.
3, crystallization and return slurry
Slip again overflow, to crystallizer tank 3, adds this groove with sulfuric acid from the acid of returning of filtrating area after dark acid tank 8 fully mixes, and returns acid amount for 156m 3/ h,, sulphuric acid is 33.5m 3/ h.Temperature of reaction is at 97 ℃, SO 4 2-1.78%.Slip in crystallizer tank 3 is after flasher 7 coolings, by 1150m 3/ h enters premix reactive tank 1 as overfall and controls CaO index, and part enters crystallizer tank 3, and material is entered to cooling effect.
4, growing the grain and filtration
Crystallizer tank 3 slips, through overflow to the four reactive tank growing the grain grooves 4, are delivered to band filter 9 by pump 6 and are carried out liquid-solid separation.Through three countercurrent washings, gained one is washed acid solution liquid, initial filter acid solution enters a liquid seal trough 5, through pump 6, deliver to the nitration mixture groove 8 on crystallizer tank 3 tops, simultaneously the finished acid of filtrating area liquid seal trough 5 part is delivered to finished acid storage tank with pump 6, and another part delivers to that the nitration mixture groove 8 on crystallizer tank 3 tops is washed acid with sulfuric acid, one, first acid filtering is carried out crystallizer tank 3 after fully mixing.Filter cake is delivered to ardealite storage yard through Pi Yunji.
Phosphoric acid day output is (with P 2o 5meter) 552t, finished product phosphoric acid product, phosphogypsum, rate of decomposition, washing rate, total recovery index are as follows.
Figure BDA00001744343500072
Example three:
The method is carried out according to the following steps: phosphorus ore and overfall premix, phosphorus ore decomposition, crystallization and return slurry, growing the grain filtration washing and return acid.
Produce by phosphorus ore index situation as follows:
P 2O 5％ CaO％ MgO％ H 2O％ Fe 2O 3 Al 2O 3 Acid non-soluble substance %
34.36 48.23 1.17 12.95 0.46 0.81 6.4
1, ground phosphate rock is thrown ore deposit amount for 78t/h, 1000m 3the overfall amount of/h is carried out pre-reaction in premix groove 1, and temperature of reaction is at 97 ℃, and in premix groove 1, index situation is as follows:
Figure BDA00001744343500081
Overfall index situation is as follows:
Figure BDA00001744343500082
2, phosphorus ore decomposes
Half water material slurry overflow is further carried out decomposition reaction to decomposer 2,97 ℃ of temperature of reaction.
3, crystallization and return slurry
Slip is overflow to the three reactive tank crystallizer tanks 3 again, from the acid of returning of filtrating area, add this groove with sulfuric acid after mixing tank fully mixes, and return acid amount for 146m 3/ h,, sulphuric acid is 32m 3/ h., temperature of reaction is at 98 ℃, SO 4 2-2.0wt%.Slip in the 3rd reactive tank crystallizer tank 3 is after flasher 7 coolings, by 1000m 3/ h enters premix groove 1 and controls CaO index as returning slurry, and part enters crystallizer tank 3, and material is entered to cooling effect.
4, growing the grain and filtration
Crystallizer tank 3 slips to growing the grain groove 4, carry out liquid-solid separation by being pumped into band filter 9 through overflow.Through three countercurrent washings, gained one is washed acid solution, initial filter acid solution enters same liquid seal trough 5, delivers to the nitration mixture groove 8 on crystallizer tank 3 tops through pump 6, and a finished acid part for filtrating area liquid seal trough 5 is by pump delivery to finished acid storage tank simultaneously, and finished acid amount is 37m 3/ h another part delivers to that the nitration mixture groove 8 on crystallizer tank 3 tops is washed acid solution with sulfuric acid, one, initial filter acid solution is carried out crystallizer tank 3 after fully mixing.Filter cake is delivered to ardealite storage yard through Pi Yunji.
Phosphoric acid day output is (with P 2o 5t meter) 540t, finished product phosphoric acid product, phosphogypsum, rate of decomposition, washing rate, total recovery index are as follows.
Known by embodiment and background technology contrast, technical process of the present invention is optimized more, and rationally, it is stable that simplification is more controlled in operation, by the design to operational path and the strict control to important parameter, the total yield of phosphorus reached more than 96%.

Claims (7)

1. the method for half water explained hereafter phosphoric acid, is characterized in that comprising the steps:
A, ground phosphate rock and the overfall from crystallizer tank carry out pre-reaction in premix groove, and the sulfuric acid of controlling in overfall is 0.4～0.6 ︰ 1 with adding the mol ratio of the CaO in ground phosphate rock;
Slip after b, pre-reaction enters continuously decomposer and further reacts;
The slip of c, decomposer enters crystallizer tank more continuously, and meanwhile, phosphoric acid solution and sulfuric acid add crystallizer tank continuously after fully mixing, and both react formation crystallization; Wherein, in crystallization control groove, the sulfate radical quality in slip acid solution and the mass ratio of acid solution are 1.5～2.0%;
Slurry temperature in premix groove, decomposer and crystallizer tank is controlled between 90～97 ℃;
The slip of d, crystallizer tank enters continuously growing the grain groove and promotes crystal further to grow up, and meanwhile, the slip of crystallizer tank also enters premix groove as the overfall described in step a; The slip of crystallizer tank is sent into continuously flasher and is carried out forced cooling, and cooling rear portion enters premix groove as overfall, and another part returns to crystallizer tank;
E, the slip in growing the grain groove is delivered to band filter continuously carry out coarse filtration, filtration and washing, the liquid of filtration is finished product phosphoric acid; Slip coarse filtration obtains coarse filtration filtrate, obtains calcium sulphate hemihydrate after filtration, and calcium sulphate hemihydrate obtains wash filtrate through washing; Coarse filtration filtrate, wash filtrate and appropriate finished product phosphoric acid form the phosphoric acid solution described in step c.
2. the method for half water explained hereafter phosphoric acid according to claim 1, is characterized in that: in described phosphoric acid solution, and quality=50～60 ︰ 8～12 ︰ 30～40 of the matter amount ︰ finished product phosphoric acid of the matter amount ︰ coarse filtration filtrate of wash filtrate.
3. the method for half water explained hereafter phosphoric acid according to claim 2, is characterized in that: in crystallizer tank, the liquid-solid ratio of slip is 2.5～3 ︰ 1.
4. according to the method for half water explained hereafter phosphoric acid described in any one in claims 1 to 3, it is characterized in that: premix groove is connected by foot passage with decomposer, decomposer is connected by top overflow port with crystallizer tank, and crystallizer tank is connected by foot passage with growing the grain groove.
5. according to the method for half water explained hereafter phosphoric acid described in any one in claims 1 to 3, it is characterized in that: the washing described in step e is three stage countercurrent washings.
6. according to the method for half water explained hereafter phosphoric acid described in any one in claims 1 to 3, it is characterized in that: described ground phosphate rock is by weight containing Vanadium Pentoxide in FLAKES 25～40%.
7. the method for half water explained hereafter phosphoric acid according to claim 6, is characterized in that: described ground phosphate rock is by weight containing Vanadium Pentoxide in FLAKES 30～35%.
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CN103449391A (en) * 2013-08-30 2013-12-18 云南三环中化化肥有限公司 Method for adding sulfuric acid into reaction system during wet-process production of phosphoric acid
CN103466578B (en) * 2013-09-12 2015-05-06 瓮福（集团）有限责任公司 Sulfuric acid adding method for reducing degree of supersaturation of calcium sulfate in wet method phosphoric acid extraction tank
WO2017120100A1 (en) * 2016-01-08 2017-07-13 Floworks International Llc Mixing tee assembly and process
CN105731406B (en) * 2016-01-13 2018-04-03 中国五环工程有限公司 Half water law Wet Processes of Phosphoric Acid and system
CN107840317B (en) * 2017-10-30 2019-12-03 安徽六国化工股份有限公司 A kind of-half water wet method phosphoric acid manufacture process of two water of one-step method
CN109748252A (en) * 2019-03-19 2019-05-14 济南大学 A method of half water phosphoric acid by wet process is prepared using the controllable acidolysis of mid low grade phosphate rock
CN110451470A (en) * 2019-09-20 2019-11-15 瓮福达州化工有限责任公司 Countercurrent washing system and method in a kind of wet method phosphoric acid manufacture process
CN112551495A (en) * 2020-12-28 2021-03-26 中国科学院过程工程研究所 Optimization method and optimization device for phosphoric acid production process
CN116768171B (en) * 2023-06-28 2024-07-02 昆明川金诺化工股份有限公司 Process for producing high-quality semi-aqueous wet-process phosphoric acid

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63144107A (en) * 1986-12-08 1988-06-16 Mitsui Toatsu Chem Inc Filtration of highly concentrated phosphoric acid-hemihydrate slurry
CN1176011C (en) * 2002-12-25 2004-11-17 云南红磷化工有限责任公司 Production process of semiwater-diaquo phosphoric acid

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