CN102198937A - Static multistage melting crystallization method for preparing electronic grade phosphoric acid - Google Patents
Static multistage melting crystallization method for preparing electronic grade phosphoric acid Download PDFInfo
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Abstract
The invention provides a static multistage melting crystallization method for preparing electronic grade phosphoric acid. The method comprises the following steps of: adding phosphoric acid liquid serving as a raw material into a crystallization tower at one time, and introducing a cooling/heating medium to a crystallization tower jacket to control the temperature of the phosphoric acid liquid; adding crystal seeds into the crystallization tower at constant temperature when the phosphoric acid liquid is cooled to the temperature of between 15 and 28 DEG C; and performing static melting crystallization operations of two to four stages by the following steps of: cooling and crystallizing the materials, discharging partial mother solution at constant temperature, heating and melting to the constant temperature, continuously performing the operation of next stage at the temperature, and gradually discharging the mother solution for N times in equal mass to gradually improve the purity of the phosphoric acid crystal. Finally, the left crystal in the tower is the product, and the crystal is melted by heating and collected. The method is simple in operation, low in energy consumption and mild in operating conditions; the product has high purity; an 88 to 90 percent electronic grade phosphoric acid liquid product is directly obtained; and the product purity index accords with multiple standards of domestic and foreign users.
Description
Technical field
The invention belongs to the crystallization technique field, particularly multi-stage static fusion-crystallization legal system power backup sub level phosphoric acid.
Background technology
Electronic grade chemicals refers generally to the specialty chemicals supporting with electronic industry, and far above food grade and technical grade, high pure electronic grade phosphoric acid is one of electronic chemical product series product to the requirement of its impurity ion content.Being accompanied by electronic industry production such as international semiconductor chip (IC) and liquid crystal shifts to China on a large scale, etching in China electronic technology industry, particularly semiconducter device and the unicircuit retrofit and cleaning and film-liquid crystal manufacturing process to the demand of electron-level phosphoric acid also in steady-state growth.Raising to metallic impurity ionic concn requirement in the product, the quality of electron-level phosphoric acid also improves thereupon, the market value of product also significantly promotes, and therefore high-quality electron-level phosphoric acid is the electronic chemical product product with high added value, is described as a jewel of fine chemical product industry.
Electron-level phosphoric acid standard both domestic and external is more, but do not form unified electron-level phosphoric acid international standard and industry market standard as yet, present domestic electron-level phosphoric acid target level of product quality generally proposes (seeing the following form) by the final user with reference to domestic and international many standards, though specific requirement is had nothing in common with each other, all higher requirement has been proposed foreign ions such as Ca, Fe, K, Mg, Na, Cr.
Country variant and regional user require the index contrast table to electron-level phosphoric acid
W is a massfraction
The difficulty of phosphoric acid separation and purification techniques mainly is its physico-chemical property, as non-volatility (158 ℃ of 85% phosphoric acid solution boiling points); High viscosity (85% phosphoric acid solution, viscosity 47mPas in the time of 20 ℃ are 50 times of water approximately); Easily produce coarse crystal dirt layer in the crystallization, reduce heat conductivility (0.43W/m ℃ of phosphoric acid coarse crystal thermal conductivity is the 1/100-1/150 of the thermal conductivity of iron, the 1/2-1/3 of glass thermal conductivity); Stronger corrodibility uses general hardware easily to introduce the metallic impurity ion, the production unit material is required high.Simultaneously, the preparation environment of electron-level phosphoric acid product, preparation process water, finished product packing transportation all have high requirement, careless slightlyly all may introduce impurity.
Because require impurity metal ion content few in the electron-level phosphoric acid, separating difficulty is bigger, the PHOSPHORIC ACID TECH.GRADE with food grade phosphoric acid or preliminary purification is that raw material prepares electron-level phosphoric acid usually.Present known method of purification relates to extraction process, ion-exchange-resin process, ion-exchange membrane electrodialysis method (abbreviation electroosmose process), crystallization process etc.Extraction process is to add organic solvent in raw material acid, utilize phosphoric acid organic phase with inorganic mutually in the difference of fusibility, make impurity stay inorganic mutually in, and phosphoric acid enrichment in organic phase, fractionation by distillation goes out electron-level phosphoric acid from organic phase again.The distillation procedure energy consumption is bigger in this method, and separating effect is relatively poor.Ion-exchange-resin process makes the impurity metal ion in the spent ion exchange resin separation phosphate raw material, this method equipment complexity, ion exchange resin needs frequent replacing or could continue to use through manipulation of regeneration, the production cost height, because the phosphoric acid viscosity is bigger, the ion exchange resin treatment ability is lower, is difficult to scale operation.Electroosmose process is comparatively desirable to purified food grade phosphoric acid removal effect, but for Ca, Na ion remaval poor effect, residual concentration has reached 3.81mg/L and 1.7mg/L (Ca, Na ionic concn are respectively 54.86mg/L, 14.2mg/L in the raw material) respectively, is difficult to satisfy customer requirements.Simultaneously, adopt electroosmose process to prepare the electronic-grade high-purity phosphoric acid, the selection of perviousness ion-exchange membrane is crucial, and counter electrode material, concentrating unit material have relatively high expectations, more special.
Crystallization process is used as the primary study method of electron-level phosphoric acid preparation because its energy consumption is low, equipment is simple, running cost is low, pollute little advantage always.Over nearly 20 years, the research for preparing electron-level phosphoric acid with crystallization process is scale to be carried out, and russian patent 2209178 usefulness crystallisation by cooling methods purify thermal phosphoric acid, and product reaches Russia's electronic industry phosphoric acid standard, but some concentration of metal ions can not satisfy the present market requirement up to 6.8mg/L; Japanese Patent 3193614,3237009 and 2000026111 with crystallisation by cooling method and the fusion-crystallization method electron-level phosphoric acid of further purifying, obtain more highly purified phosphoric acid, but this method is very high to the requirement of raw material acid purity respectively; Korean Patent 2003042108 usefulness crystallisation by cooling legal system power backup sub level phosphoric acid, but this method to equipment require highly, energy consumption is big; Chinese patent 200510013714.7 adopts solvent precipitations and extraction process that raw material is carried out pre-treatment, prepares electron-level phosphoric acid through crystallisation by cooling repeatedly.But this complicated operating process relates to multistep unit operations such as precipitation, filtration, extraction and crystallization, and it is high to set up the industrial dustless factory building cost of extensive electron-level phosphoric acid, is unfavorable for that the marketable value of technology realizes.In addition, product very easily produces the dirt layer in the crystallisation by cooling operation, causes the cooling difficulty, has a strong impact on the production cycle.
Chinese patent 200610013611.5 usefulness fusion-crystallization legal system power backup sub level phosphoric acid, produce crystal seed at-45～-35 ℃ of following wall built-ups, be warming up to-2～-10 ℃ then, circulation adds raw material to be made it grow at plane of crystal to begin when thickness reaches 2～4cm to heat up, get rid of liquid mass and be at 10～40% o'clock and stop, productive rate is 12～20%.This method service temperature is extremely low, and energy consumption is big, and need carry out pre-treatment to raw material and remove arsenic, and the operating time is long, the production cost height, and productive rate is low.
Chinese patent 201010100473.0 is used preparing highly-pure phosphoric acid by flow chromatographic crystallization method, employing adds sound field and goes out crystalline substance, to raw materials used purity requirement high (the major impurity ionic concn is all less than 1.7mg/L, and the need micro-pore-film filtration is handled), it is bigger to use difficulty, is not easy to industrialization.
Chinese patent 201010104321.8 adopts liquid membrane crystal legal system power backup sub level phosphoric acid, on 10～20 ℃ wall, add crystal seed and begin cooling simultaneously, by sparger raw material phosphoric acid liquid is added on the wall, raw material is the liquid film state and flows through crystal seed, grow into epitaxial at wall, reach the cooling terminal point and treat for 5～10 ℃ to begin the sweating that heats up after mother liquor is fully got rid of, stop during sweating to 15～29 ℃.This method is a dynamic crystallization operation process, and crystalline mother solution is not discharged immediately.By disposable decrease temperature crystalline---constant temperature discharge opeing---intensification thermal treatment comes refined product.This method has been improved the crystal seed producing method, and service temperature is brought up to the easy to reach interval, twice crystallization yields 20～30%.But Na, Al, Mg, Cr plasma concentration higher (1.79mg/L, 0.94mg/L, 0.49mg/L, 0.37mg/L) can not satisfy the demand that the user upgrades day by day in the electron-level phosphoric acid for preparing with this method, still need further to improve.
Summary of the invention
Weak point at present preparation electron-level phosphoric acid method, the present invention proposes a kind of is raw material with food grade phosphoric acid liquid, adopt multi-stage static (multistage be meant that operation progression is Integer N, N equals 2,3 or 4) fusion-crystallization to prepare the method for electron-level phosphoric acid, may further comprise the steps:
(1) closes the prilling tower bottom valve, mass concentration 83%～91% raw material phosphoric acid liquid body disposable is added in the prilling tower, logical heat-eliminating medium cooling phosphoric acid liquid in the prilling tower chuck, constant temperature adds crystal seed to prilling tower when the phosphoric acid fluid temperature reaches 15～28 ℃, and crystal seed is uniformly dispersed in tower;
(2) first step to the N-1 level fusion-crystallization working method: logical heat-eliminating medium continues cooling in the prilling tower chuck, temperature of charge in the tower is reduced to Tc (if the first step operation of corresponding progression, then be the one-level Tc) back constant temperature 15-60min, open the prilling tower bottom valve, discharge the not crystalline mother solution of constant-quality, discharge the not 1/N of crystalline mother solution total mass during first step operation, the mother liquor that lifting rate after this at different levels and first step operation are discharged is identical in quality, then valve-off; The feeding heating medium is warming up to material melt temperature (if first step operation then is the one-level melt temperature) the back constant temperature 15-60min of corresponding progression in the prilling tower chuck.So far finish this grade operation, under the melt temperature of this grade, proceed the operation of next stage fusion-crystallization then;
The fusion-crystallization operation of (3) N levels then N-1 level operation is carried out, logical heat-eliminating medium continues cooling in the prilling tower chuck, temperature of charge in the tower is reduced to constant temperature 15-60min after the N level Tc, open the prilling tower bottom valve, discharge all remaining not crystalline mother solutions.After this keep valve wide open, rising prilling tower temperature to the N level melt temperature, constant temperature 15-60min makes the liquid of fusing fully discharge from tower bottom.Last crystal is product in the tower, feeds heating medium in the prilling tower chuck and makes crystal melting, and collect.
The used prilling tower of the present invention is the prilling tower that column has chuck, feeds cooling temperature control medium in the chuck, the control temperature of charge.Crystal seed and raw material add from top of tower, and tower bottom has valve, and controlled liq is discharged from tower bottom.
The step of the inventive method (1) is that crystal seed adds, and the phosphoric acid crystal seed adopts the solid crystal seed or crystal added in the supercooled phosphoric acid liquid and is mixed with phosphoric acid suspension.The crystal seed quality that adds is 0.1～5% of a raw material phosphoric acid liquid mass.
The step of the inventive method (2), (3) are multi-stage static fusion-crystallization process, discharge mother liquor step by step, progressively improve phosphoric acid crystalline purity.Every grade of operation comprises: material decrease temperature crystalline-constant temperature-discharge section mother liquor-intensification fusion-constant temperature, under this temperature, proceed the material decrease temperature crystalline-constant temperature-discharge section mother liquor-intensification fusion-constant temperature of next stage then again.
Tcs at different levels refer to decrease temperature crystalline terminal temperatures at different levels, and melt temperatures at different levels refer to intensification end of melting temperature at different levels, and its scope is: first step Tc is 6～23 ℃, and first step melt temperature is 12～28 ℃; Second stage Tc is 11～27 ℃, and second stage melt temperature is 14～29 ℃; Third stage Tc is 12～28 ℃, and third stage melt temperature is 16～29 ℃; Fourth stage Tc is 13～28 ℃, and fourth stage melt temperature is 18～29 ℃.
According to the operation sum of series raw material phosphoric acid liquid bulk concentration difference that reality adopts, certain one-level Tc is higher 0～5 ℃ than previous stage Tc, and certain one-level melt temperature is higher 0～8 ℃ than previous stage melt temperature.
Every grade of crystallization rate of temperature fall is 2～6 ℃/h, and every grade of fusion temperature rise rate is 2～6 ℃/h.
In order to obtain more high-quality product, use the single job products obtained therefrom and do raw material, adopt the inventive method to carry out secondary and the above multi-stage static fusion-crystallization operation of secondary, products obtained therefrom is high-quality electron-level phosphoric acid product.
Show by experiment, two～level Four fusion-crystallization process is selected in a multi-stage static fusion-crystallization operation for use, two～three grades of fusion-crystallization processes are selected in the operation of secondary multi-stage static fusion-crystallization for use, secondary fusion-crystallization process is selected in three multi-stage static fusion-crystallization operations for use, production efficiency is higher, good quality of product.
In addition, phosphoric acid concentration also progressively increases in the mother liquor of Pai Chuing in batches, and foreign metal ionic concn wherein reduces thereupon, and the mother liquor that these can be discharged in batches and sweat classification are reclaimed and made raw material usefulness.
The multi-stage static fusion-crystallization operation productive rate that the raw material phosphoric acid liquid of mass concentration 85% is carried out can reach 30～45% according to the method described above, the secondary multi-stage static fusion-crystallization operation productive rate that carries out again can reach 55～65%, and three multi-stage static fusion-crystallization operation productive rates that carry out again can reach 80～90%.
The present invention adopts multi-stage static fusion-crystallization method to make with extra care the electron-level phosphoric acid product, and the product quality analysis data see the following form, and secondary multi-stage static fusion-crystallization operated products meets above-mentioned country variant and regional user's multiple electron-level phosphoric acid standard.
W is a massfraction
The impurity metal ion content of phosphoric acid product is analyzed with inductively coupled plasma absorption spectrometer (ICP-AES) of generally acknowledging in the industry and inductivity coupled plasma mass spectrometry (ICP-MS) among the present invention.
The present invention is raw material with the food grade phosphoric acid, adopts multi-stage static fusion-crystallization method to obtain the electron-level phosphoric acid product, reaches the electron-level phosphoric acid standard.Present method is simple to operate, and energy consumption is low, the operational condition gentleness, the product purity height, the yield height directly obtains the electron-level phosphoric acid liquid product of concentration at 88-90%, the product purity index meets the standard of multiple users at home and abroad, and good market outlook and industrial value are arranged.
Description of drawings
The temperature of charge operating curve of Fig. 1: embodiment 1 (once static secondary fusion-crystallization);
The temperature of charge operating curve of Fig. 2: embodiment 2 (once static three grades of fusion-crystallizations);
The temperature of charge operating curve of Fig. 3: embodiment 3 (once static level Four fusion-crystallization);
The temperature of charge operating curve of Fig. 4: embodiment 4 (once static secondary fusion-crystallization);
The temperature of charge operating curve of Fig. 5: embodiment 5 (once static level Four fusion-crystallization);
The temperature of charge operating curve of Fig. 6: embodiment 5 (the static secondary fusion-crystallization of secondary);
The temperature of charge operating curve of Fig. 7: embodiment 6 (three static secondary fusion-crystallizations).
Embodiment
Embodiment 1:
Close the prilling tower bottom valve, with raw material food grade phosphoric acid liquid 2400g (impurity metal ion content is as shown in table 1), the disposable prilling tower that places.The prilling tower chuck leads to water coolant, and raw material is cooled to 21.5 ℃, and constant temperature adds solid crystal seed 10g in the feed liquid of prilling tower, and is uniformly dispersed.
Continue to feed heat-eliminating medium, with the speed cooling of 6 ℃/h, crystal evenly grows into crystal column in prilling tower inside.Be cooled to 10 ℃ and reach the one-level Tc, discharge 1/2 not crystalline mother solution 586g behind the constant temperature 30min, the weighing device of mother liquor quality at the bottom of by tower measured.Valve-off afterwards, the prilling tower chuck leads to hot water, speed with 6 ℃/h is warming up to 15 ℃ of one-level melt temperatures, speed with 6 ℃/h behind the constant temperature 15min continues to be cooled to 12 ℃ of secondary crystallization temperature, discharge not crystalline mother solution 584g behind the constant temperature 60min, Open valve is warming up to 22 ℃ of secondary melt temperatures with the speed of 6 ℃/h, and constant temperature 60min fully discharges sweat.
Rising prilling tower temperature is discharged collection with the pure crystal column fusing back in the prilling tower and is once static secondary fusion-crystallization product 1015g.The temperature of charge operating curve of process as shown in Figure 1.The product detected result sees Table 1.
Table 1 raw material phosphoric acid, static secondary fusion-crystallization operated products detected result once
Close the prilling tower bottom valve, with the disposable prilling tower that places of raw material food grade phosphoric acid liquid 2400g (impurity metal ion content is as shown in table 3) of different mass concentration.Raw material is cooled off proper temperature, previously prepared crystal seed is added in the prilling tower feed liquid, and be uniformly dispersed.Begin material decrease temperature crystalline-constant temperature-discharge section mother liquor-intensification fusion step by step-homothermic operation then, concrete parameter sees Table 2.The temperature of charge operating curve of process is shown in Fig. 2,3,4.Raw material and product detected result see Table 3.
A multi-stage static fusion-crystallization of table 2 operating parameters
Table 3 raw material phosphoric acid, a multi-stage static fusion-crystallization operated products detected result
Embodiment 5:
Close the prilling tower bottom valve, with the disposable prilling tower that places of mass concentration 83% raw material food grade phosphoric acid liquid 3000g (impurity metal ion content is as shown in table 4).Raw material is cooled to 15 ℃, previously prepared crystal seed 100g is added in the feed liquid, and be uniformly dispersed.
Continue to feed heat-eliminating medium and begin cooling, with the speed cooling of 4 ℃/h, crystal evenly grows into crystal column in prilling tower inside.Be cooled to 6 ℃ and reach the one-level Tc, discharge 1/4 not crystalline mother solution 450g behind the constant temperature 60min, the weighing device of its quality at the bottom of by tower measured.Valve-off afterwards, after being warming up to 12 ℃ of constant temperature 15min of one-level melt temperature with the speed of 6 ℃/h, continuation is cooled to 11 ℃ of secondary crystallization temperature with the speed of 4 ℃/h, open valve behind the constant temperature 30min and discharge not crystalline mother solution 447g, valve-off is warming up to 14 ℃ of secondary melt temperatures with the speed of 6 ℃/h, speed with 4 ℃/h behind the constant temperature 15min is cooled to 12 ℃ of three grades of Tcs, discharges mother liquor 453g behind the constant temperature 20min.Valve-off is warming up to 16 ℃ of three grades of melt temperatures with 6 ℃/h speed then, and the speed with 4 ℃/h behind the constant temperature 20min is cooled to 13 ℃ of level Four Tcs, discharges all residue mother liquor 450g behind the constant temperature 60min.Open valve is warming up to 18 ℃ of level Four melt temperatures with the speed of 6 ℃/h, and constant temperature 60min fully discharges sweat.
Rising prilling tower temperature is discharged collection with the pure crystal column fusing back in the prilling tower and is once static level Four fusion-crystallization product 931g.
As the static fusion-crystallization raw material of secondary, use crystallization apparatus on a small scale with the said products, adopt the static secondary fusion-crystallization operation of secondary, its method and static level Four similar once.Adding the crystal seed temperature is 23 ℃, crystal seed quality 10g, one-level Tc, melt temperature are respectively 18 ℃, 22 ℃, secondary crystallization temperature, melt temperature are respectively 20 ℃, 28 ℃, rate of temperature fall at different levels are 6 ℃/h, and fusion temperature rise rates at different levels are 4 ℃/h, reach constant temperature 30min after the Tcs at different levels, reach constant temperature 20min after the melt temperatures at different levels, discharge not crystalline mother solution 120g and 122g respectively twice.Be product through the crystal column in the fusion-crystallization post crystallization tower step by step, continue the electron-level phosphoric acid product 603g that elevated temperature promptly obtains the crystal column fusing liquid.
The temperature of charge operating curve of process is shown in Fig. 5,6.Raw material and product detected result see Table 4.
Table 4 raw material phosphoric acid, once with secondary multi-stage static fusion-crystallization operated products detected result
Get the static secondary product 600g (impurity metal ion content is as shown in table 5) of secondary of embodiment 5, the disposable prilling tower that places.Raw material is cooled to 28 ℃, previously prepared crystal seed 5g is added in the feed liquid, and be uniformly dispersed.
Continue to feed heat-eliminating medium, with the speed cooling of 3 ℃/h, crystal evenly grows into crystal column in prilling tower inside.Be cooled to 23 ℃ and reach the one-level Tc, discharge 1/2 not crystalline mother solution 38g behind the constant temperature 20min, the weighing device of its quality at the bottom of by tower measured.Valve-off afterwards, continue to be cooled to 25 ℃ of secondary crystallization temperature after being warming up to 27 ℃ of constant temperature 20min of one-level melt temperature with the speed of 2 ℃/h with the speed of 3 ℃/h, behind the constant temperature 60min, open the prilling tower bottom valve and discharge mother liquor 40g, keep valve wide open, be warming up to 29 ℃ of secondary melt temperatures with 2 ℃/h speed, constant temperature 60min fully discharges sweat.
Rising prilling tower temperature is discharged collection with the pure crystal column fusing back in the prilling tower and is static secondary fusion-crystallization product 508g three times.The temperature of charge operating curve of process as shown in Figure 7.The product detected result sees Table 5.
Three static secondary fusion-crystallization operation raw materials of table 5 and product detected result
The impurity metal ion content of phosphoric acid product is analyzed with inductively coupled plasma absorption spectrometer (ICP-AES) of generally acknowledging in the industry and inductivity coupled plasma mass spectrometry (ICP-MS) among the present invention.
The present invention open and the preparation method and the product that propose, those skilled in the art can be by using for reference this paper content, and appropriate change raw material, processing parameter link realize.Method of the present invention is described by embodiment preferably, person skilled obviously can be in the scope that does not break away from content of the present invention, spirit to the method under this paper and product is changed or suitably change realize the technology of the present invention with combination.Special needs to be pointed out is that all similarly replace and change apparent to those skilled in the art, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (7)
1. the method for the refining electron-level phosphoric acid product of multi-stage static fusion-crystallization method is characterized in that with food grade phosphoric acid liquid be raw material, and step is as follows:
(1) closes the prilling tower bottom valve, mass concentration 83%～91% raw material phosphoric acid liquid body disposable is added in the prilling tower, logical heat-eliminating medium cooling phosphoric acid liquid in the prilling tower chuck, constant temperature adds crystal seed to prilling tower when the phosphoric acid fluid temperature reaches 15～28 ℃, and crystal seed is uniformly dispersed in tower;
(2) first step to the N-1 level fusion-crystallization working method: logical heat-eliminating medium continues cooling in the prilling tower chuck, temperature of charge in the tower is reduced to constant temperature 15-60min after the Tc of corresponding progression, open the prilling tower bottom valve, discharge the not crystalline mother solution of constant-quality, discharge the not 1/N of crystalline mother solution total mass during first step operation, after this mother liquor that lifting rate at different levels and first step operation are discharged is identical in quality, then valve-off; Feed heating medium in the prilling tower chuck and material is warming up to constant temperature 15-60min after the melt temperature of corresponding progression; So far finish this grade operation, under the melt temperature of this grade, proceed the operation of next stage fusion-crystallization then;
The fusion-crystallization operation of (3) N levels then N-1 level operation is carried out, logical heat-eliminating medium continues cooling in the prilling tower chuck, temperature of charge in the tower is reduced to constant temperature 15-60min after the N level Tc, open the prilling tower bottom valve, discharge all remaining not crystalline mother solutions; After this keep valve wide open, rising prilling tower temperature to the N level melt temperature, constant temperature 15-60min makes the liquid of fusing fully discharge from tower bottom; Last crystal is product in the tower, feeds heating medium in the prilling tower chuck and makes crystal melting, and collect;
Wherein: N equals 2,3 or 4.
2. the method for claim 1, it is characterized in that Tcs at different levels, melt temperature scope are: first step Tc is 6～23 ℃, and first step melt temperature is 12～28 ℃; Second stage Tc is 11～27 ℃, and second stage melt temperature is 14～29 ℃; Third stage Tc is 12～28 ℃, and third stage melt temperature is 16～29 ℃; Fourth stage Tc is 13～28 ℃, and fourth stage melt temperature is 18～29 ℃.
3. method as claimed in claim 1 or 2 is characterized in that certain one-level Tc is higher 0～5 ℃ than previous stage Tc, and certain one-level melt temperature is higher 0～8 ℃ than previous stage melt temperature.
4. the method for claim 1 is characterized in that every grade of crystallization rate of temperature fall is 2～6 ℃/h, and every grade of fusion temperature rise rate is 2～6 ℃/h.
5. the method for claim 1 is characterized in that using the single job products obtained therefrom and does raw material, adopts the inventive method to carry out secondary and the above multi-stage static fusion-crystallization operation of secondary.
6. as claim 1 or 5 described methods, it is characterized in that the operation of multi-stage static fusion-crystallization selects two～level Four fusion-crystallization process for use, two～three grades of fusion-crystallization processes are selected in the operation of secondary multi-stage static fusion-crystallization for use, and secondary fusion-crystallization process is selected in three multi-stage static fusion-crystallization operations for use.
7. the method for claim 1 is characterized in that prilling tower is the prilling tower that column has chuck, feeds temperature control medium, the temperature of control tower in the chuck; Crystal seed and raw material add from top of tower, and tower bottom has valve, and controlled liq is discharged from tower bottom.
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| CN102502549A (en) * | 2011-10-27 | 2012-06-20 | 华东理工大学 | Device for continuously separating and purifying phosphoric acid and application thereof in preparation of food-grade phosphoric acid |
| CN103012030A (en) * | 2012-12-31 | 2013-04-03 | 浙江工业大学 | Method for purifying organic mixture by static melt crystallization |
| CN103754848A (en) * | 2013-12-30 | 2014-04-30 | 广西明利化工有限公司 | Method for preparing electronic-grade phosphoric acid by U-shaped pipe static multistage melt crystallization |
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