Method of producing phosphoric acid

专利摘要:
The invention relates to a process for the production of phosphoric acid obtained by the sulfuric acid decomposition of natural phosphates, followed by solvent extraction with tributyl phosphate and treatment with an activated carbon and oxidant and can be used in the production of industrial, feed and food phosphates. The aim of the invention is to reduce the content of impurities in the product, which give color to the product, and to simplify the process. Phosphoric acid is obtained by treating non-calcined phosphates with sulfuric acid, separating the calcium sulfate precipitate by filtration, processing the filtered aqueous solution of phosphoric acid with activated carbon at 50 ° C for 2 hours in an amount of 0.4% by weight of P 2 O 5 , and phosphoric acid is extracted by liquid from purified solution of tributyl phosphate, registraktsiey aqueous, aqueous strip liquor concentration up to 55 - 62% P 2 O 5, by treatment with a concentrated solution of hydrogen peroxide for 15 minutes at 110 - 130 ° C followed by treatment with ASSET ovannym charcoal at the same temperature. Phosphoric acid is obtained with an organic carbon content of less than 70 PPM / P 2 O 5 and a chromaticity of less than 10 units. APHA. 2 tab.
公开号:SU1526579A3
申请号:SU803006999
申请日:1980-11-19
公开日:1989-11-30
发明作者:Винан Луи
申请人:Рон-Пуленк Эндюстри (Фирма)；
IPC主号:

专利说明:

The invention relates to a method for producing phosphoric acid obtained by the sulfuric acid decomposition of natural phosphates, followed by solvent extraction and treatment with oxidizing agents and adsorbents, and can be used in the production of industrial, feed and food phosphates.
The aim of the invention is to reduce the content of impurities in the product.
imparting color to the product, and simplifying the method.
Natural phosphates contain organic impurities and other impurities, causing the color of the phosphoric acid solution. In addition, during ore processing, organic substances are introduced as flotators, antifoaming agents, crystal formation modifiers, phosphoric acid extractants. At the floor
cm
chenin of food (feed) phosphates. phosphoric acid must be purified from DT impurities, in particular of organic origin, and discolored. In the examples, the color of the solutions is given in Apha units according to the standards of the American Society for Testing Materials 2100-71 and in the units of El TBP (TBP).
The invention is illustrated by the following examples.
Example 1. Phosphoric acid having the following characteristics is obtained by a known method of sulfuric acid treatment of uncalcined calcium calcium phosphate (fluoride):% 40
Organic matter, ppm C / PjOj 2450 Color index (E1 TBR) 10, n calcium sulfate precipitate, which is separated by filtration.
This acid is processed to discolor with activated carbon in the form of powder and granules.
Phosphoric acid is first heated with stirring for hours at the presence of 0.40% of the mass of powdered activated carbon of Aktibon C of the Norit Company (Hollandi), BET: 1052.
After filtration, the acid has a color index (E1 TBP) of 3.2 and an organic carbon content of 1700 ppm / P205. The resulting acid is continuously fed into the column with a nozzle of granular activated carbon (quality CAL company PITTSBURG Chemical Campaign USA with a specific surface according to BET: UOOm / g) at a rate of 12 l / h (column section 78 cm, the height of the coal layer 220 cm, weight of activated coal 7.5 kg), and the column is insulated at 85-90 ° C. The column thus made can be used to process 800 kg before collecting the acid with a color index (E1 TBP) 0.10. The resulting sulfuric acid contains 1000 ppm of organic carbon / P505.
The resulting acid is heated to 50 ° C in a battery of eight mixer-settlers, then subjected to countercurrent extraction with three
0
five
0
five
0
five
butyl phosphate with an organic phase / water ratio equal to 9. The organic phase is washed in a battery of seven mixer-settlers with a small volume of water with an aqueous phase / organic ratio equal to 1/18 and, moreover, at the 5th stage 50% soda solution is added at the rate of 30 g of NaCH per kilogram of PjOj, applied for extraction; then, the countercurrent is stripped with water at 65 ° C in a battery consisting of five mixer-settlers with an organic phase / water ratio equal to 6. Purified phosphoric acid is taken from the battery, which has:
% 21.5
Coloring, Apha 9 and concentrate it to a content of 62% under atmospheric pressure in two stages with countercurrent heating through the wall, including the first stage, operating at and intended to bring the concentration to 38% PjOj-, and the second stage, operating at 150 ° C and designed for final concentration.
The acid obtained after being kept at 150 ° C for 1.5 hours has a color of 420 Apha and contains 250 ppm of organic carbon / P 0.
Then the resulting acid is subjected to final discoloration according to several options:
a) a part of the acid is decolorized with 5 g of HjO / iL at the rate of 100% per kg of acid for 15 minutes (66 Apha color is obtained), then with 0.5% Aktibon activated carbon, calculated with 2 hours at 120 ° C. The resulting acid has a color of 5.5 Apha and contains 70 ppm of organic carbon per P2 Oj,
b)
acid with the content of PjOj- 68%
process 5 g. at the rate of 100% at 130 ° C for 15 minutes per kg of acid. The resulting acid has a color of 180 Apha. After dilution to a PjO 5 content of 62% and treatment for 2 hours at IZO C with 5 g of activated carbon Aktibon, an acid with a color of 7 Apha is obtained.
5 and 65 ppm of organic carbon on
pjOs;
c) phosphoric acid purified by extraction with content
515
21.5% is concentrated to 55% at a final temperature of 130 ° C, and then maintained at this temperature for 2 hours in order to develop color. The color is 180 LrBa and the content is 260 ppm.
The acid produced is heated for 15 minutes at 130 ° C using 5 g per 100% per kg of acid. Color is 37 Apha. Then stirring is performed with 0.5 activated Lk tibon carbon for 2 hours at 90 ° C. A 3 Apha color is obtained, the content is 100 ppm. This acid is re-colored to 14 Apha after concentration to 60% at atmospheric pressure (maximum temperature 155 ° C). The re-acid is stained only up to 8 Apha, if it is concentrated under reduced pressure to a content of 60% so as not to exceed a temperature of 110 ° C, i.e. the temperature is kept below the temperature at which the 55% acid was obtained. An acid that can be used for food purposes is: to contain no more than 70 ppm of Cdr and have a color of less than 10 Apha,
Example 1 comparative The initial phosphoric acid of example 1 with a P2.05 content of 0% prior to pre-bleaching according to the present invention is subjected to extrusion with tributyl phosphate according to example 1. Under these conditions, continuous industrial extraction is impossible due to the long period of time required for phase separation in batteries of the settling mixers. On the other hand, after a very long separation time, there is a third blackish fraction at the interface,
Example 2 and comparative example 2 In these examples, in laboratory conditions, the rates of settling of acids obtained from non-cured phosphate (fluoride) are periodically compared. The initial phosphoric acid obtained by the sulfuric acid decomposition of the raw material contains;
Pj05, by weight AO Organic carbon, ppm / P tOs 2250
0
0
five
0
five
10.6
Color indicator, E 1 TVR
Experiments on the extraction of the original phosphoric acid.
600 ml of this acid are contacted at 50 ° C with 600 ml of tributyl phosphate as an extractant in a 12.5 cm diameter glass cylinder with a height of 24 cm. The phases are mixed for 3 minutes using a Rainiery mixer equipped with a centripetal turbine 5.5 cm, rotating 5 at a speed of 800 rpm and a fluid depth immersed by 2/3. The stirrer is stopped and the settling is monitored as a function of time, which is calculated relative to the limiting interface surface. The results are shown in Table 1,
Take part of the specified source acid and process it in example 1, first powdered, and then granular activated carbon. A pre-bleached acid is obtained with a color index of E 1 TBP of 0.03, containing 650 ppm. The pre-bleached acid is extracted in the same way using tributyl phosphate and the delamination ability of the phases is performed by this method. The results are shown in Table 1,
Table 1
Acid used
J1 setting
Raw acid from uncalcined ore (fluoride) E1 TBP 10.6 2250 ppm C / P, 05 40%
The original acid from the ore, pre-discolored using activated carbon to E1 TBP: 0.03 650 ppm C / P Oj10% after 3 minutes 30% after 6 minutes 35% after 20 minutes
25% in 1 min 70% in 1.5 min 100% in
2 min 10 s
In the unbleached pre-acid, blackish gelatinous flakes appear that accumulate on the top of the surface; 1 the interface remains, and the solvent is painted a dark brown color.
These experiments indicate the effect of the pre-bleaching according to the present invention on the ability of the phases to settle in the case of using pure solvents. The difference in the ability to settle and the content of gelatinous substances increases with the use of solvents recycled after reextraction in the case of non-discolored pre-acid.
Example 3. Preparing phosphoric acid by treating non-calcined phosphate at a concentration of 40%. This acid has a color indicator of E1 TB 1.7 and contains 400 ppm of organic carbon / P O 5. The above acid is pre-discolored on a column with a nozzle of granular activated carbon under the same conditions as in the example for granular activated carbon) without pretreatment using powdered activated carbon. The capacity of the column in this case is 2500 kg of P.OJ with a color index of at least 0.10, the average acid obtained contains 130 ppm of organic carbon / P Oy
five
0
five
0
By extracting and de-extracting said pre-decolorized acid in the manner described in Example 1, a purified acid is obtained, which is concentrated from 23 to 62% at 150 ° C. When heated at 150 ° C, the acid obtained is re-colored (color 2AO LrLa) and contains 82 ppm of organic carbon / PjO 5.
Painted acid with a P2.05 content of 62% is treated for 15 minutes at 60 ° C with 5 g. in the calculation of 100% per kg of acid. Acid is obtained with a color of 85 Apha. This acid is treated with O, 5% activated carbon Lkibon C (Norit IV) for 2 hours at 120 C. After filtration, an acid with a P2.0 content of 62% with a color of 7 LrBa containing 28 ppm is obtained organic carbon / P2.05.
In tab. 2 gives the options for purification of the acid outside the specified intervals, and also reproduces examples (1 and 2) of the prototype. In all the examples there are pre-treatment operations on activated carbon and extraction with tributyl phosphate.
Table 2

权利要求:
Claims (1)
[1]
From the data table. 2, it follows that the formula of the invention
processing with hydrogen peroxide or activated carbon alone is not sufficient to reduce the color index of the product.
When the treatment temperature is lower (No. 3) and the concentration of the acid to be treated is nugay 50% (No. 4), the color index of the product remains higher.
55
A method of producing phosphoric acid, which includes the treatment of untreated phosphate ores with sulfuric acid, the separation of calcium sulfate by filtration, the liquid extraction of phosphoric acid from an aqueous solution with tributyl phosphate, the separation of phosphoric acid saturated tributyl
A method of producing phosphoric acid, which includes the treatment of untreated phosphate ores with sulfuric acid, the separation of calcium sulfate by filtration, the liquid extraction of phosphoric acid from an aqueous solution with tributyl phosphate, the separation of phosphoric acid saturated with tributyl 9152657910
phosphate from the depleted aqueous plant liquid liquid stripping process the thief, phosphoric acid reextraction with activated carbon in the amount of tributyl phosphate with water, concentration - 0.4% of the mass for 2 hours with the aqueous reextract from -50 ° C, concentration is carried out to by a further oxidation treatment, its concentration is 55-62 wt.%, with heating and activated carbon, used as an oxidant, characterized in that (hydrogen peroxide is used, it is treated, in order to reduce the content in The product of the impurities that give the stained reextract to the activated product and the simplification of the method, with hydrogen and hydrogen peroxide, will bring the inoculated solution of phosphoric acid in front of 110-130 ° C.

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引用文献:

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JPS5297394A|1976-02-13|1977-08-16|Toyo Soda Mfg Co Ltd|Removal of organic matter in phosphoric acid|

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JPS54119397A|1978-03-10|1979-09-17|Central Glass Co Ltd|Removing method for organic matter in phosphoric acid|

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US4256570A|1979-03-19|1981-03-17|International Minerals & Chemical Corporation|Purification of phosphoric acid|CA1198575A|1981-11-23|1985-12-31|Richard G. Grotyohann|Process for removal of residual organic matter andcolor from purified phosphoric acid|

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US4590051A|1984-10-31|1986-05-20|Fmc Corporation|Sodium tripolyphosphate manufacture|

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JP2535882B2|1987-03-09|1996-09-18|東ソー株式会社|Method for removing dissolved organic matter in purified phosphoric acid|

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DE3806822A1|1988-03-03|1989-09-14|Hoechst Ag|CONTINUOUS PROCESS FOR COMPLETELY REMOVING ORGANIC IMPURITIES AND COMPLETELY DISCHARGING PRE-CLEANED WET PHOSPHORIC ACIDS|

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EP0366189A3|1988-10-24|1992-01-02|Norwich Eaton Pharmaceuticals, Inc.|Novel antimicrobial lactam-quinolones|

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DE102005057913A1|2005-12-02|2007-06-06|Vopelius Chemie Ag|Procedure for removal of impurities and/or decolorization of phosphoric acid, comprises mixing the phosphoric acid with a strong oxidizing agent, and reacting the obtained mixture at above atmospheric pressure|

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CN109941979A|2019-04-30|2019-06-28|舒爱桦|A kind of technique of concentrated fertilizer phosphoric acid food grade phosphoric acid|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR7928530A|FR2470090B1|1979-11-20|1979-11-20|PROCESS FOR THE PURIFICATION OF A WET PHOSPHORIC ACID|

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