• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Method for the preparation of phosphoric acid and calcium sulphate wherein calcium phosphate is attacked by a mixture of sulphuric acid and phosphoric acid comprising at least three successive crystallization steps: a first step (1) for the reaction between the phosphate (2) and the phosphoric and sulphuric acids (3 and 4) forming hemihydrate alpha of calcium sulphate, a second step (12) recrystallizing the hemihydrate alpha into dehydrate and a third step (18) transforming the latter into hemihydrate alpha , anhydrite II or a mixture of the two, the latter being then subjected to a separation process (22), the product phosphoric acid (10) being drawn off in the first step.
    公开号:SU1653540A3
    申请号:SU853891173
    申请日:1985-04-24
    公开日:1991-05-30
    发明作者:Лоран Давистер Арман；Робер Дюбрек Андре；Артур Тирьон Франсис
    申请人:Прейон Девлоппман С.А. (Фирма)；
    IPC主号:
    专利说明:


    1/1
    The invention relates to a process for the production of phosphoric acid and calcium sulfate by sulfuric acid by phosphate feedstock followed by
    recrystallized calcium sulphate
    The purpose of the invention is to provide the possibility of obtaining various guides.
    316
    calcium sulphate, reduced impurities while maintaining high yield and product concentration
    Example. A mixture of phosphates i from Cola-Togo deposits in proportion of 1: 1 is fed to the first reactor with sulfuric acid at a concentration of 99%, the solids content in the reactor is controlled by recycling the production phosphoric acid, the PjOy content in the liquid phase is maintained by recycling the filtrate obtained in the third stage (recrystallization of the dihydrate). The reaction conditions in the reactor are as follows: temperature 85 ° С, percentage solids in the pulp 25%, content in the liquid phase 43%, content of sulfuric acid in the liquid phase 1.2%. Calcium sulfate is precipitated in the form of the Oi-semi CaSO 1/2 hydrate in the form of double crystals of good filterability. The degree of decomposition of the raw material is 96.5%, and the hemihydrate contains 1% RlOg in the solid phase, which is calculated dry at 250 ° C.
    The hemihydrate precipitate on the filter contains 25% of the associated liquid and is sent to the conversion tank (second stage) to the dihydrate, where the temperature is reduced to 60 ° C as a result of cooling. The solids content is 35% by recirculating the filtrates from the second i - the third stage, and the content of P% 05 in the liquid phase is up to 21.5% as a result of recirculating the filtrate after the third stage, the concentration of sulfuric acid is maintained in the range of 8.5-12.0%, time 8-12 hours. hydration the pulp is filtered, the filtrate is directed for the hemihydrate conversion (second step), and the wet calcium sulphate dihydrate precipitate is sent to a dehydration tank (third step).
    In the tank, the conditions of temperature, concentration and regulate so as to obtain in the first variant ob-hemihydrate, in the second variant predominantly the anhydride (II), and in the third variant the mixture in a certain proportion of the fci-semi-subdigital and anhydride (II). The temperature in the tank is controlled by the steam supply, the concentration of sulfuric acid in the liquid phase of the pulp is maintained by the supply of concentrated sulfuric acid, and



    0
    five
    0
    five
    0
    five
    0
    total recovery ratio of P20g. phosphate
    The P20 radio set and the solids content in the pulp are maintained by supplying a portion of the production phosphoric acid and filtrates from the third stage filter.
    In the first embodiment, the dihydrate is converted to hemihydrate by raising the temperature to 85 ° C and increasing the concentration of sulfuric acid to 9.5% with the solid content of h; 30% caps and 30.7% content in the liquid phase 0 Dehydration time 0.5-1 h.
    Calcium sulphate hemihydrate obtained at the outlet contains 0.15%, that is. of phosphate was 99.5%
    Due to the favorable size and shape of the crystals, the moisture content of the precipitate was increased to 19%, and the filtration performance of PrOy was 99.8%,
    In the second variant, the dihydrate converts p-anhydrite (II) by raising the temperature to 73 ° C and increasing the concentration of sulfuric acid to 16% with a solids content of 28% and a content of 18% in the liquid phase. Dehydration time 1.5-3 hours
    Anhydrite contains no more than 0.25% P.Oj-, which corresponds to the degree of extraction of Р205 from phosphate, equal to 99%.
    The moisture content of the precipitate was 25%, and the filtration rate was 99.2%.
    In the third variant, the dihydrate is converted to calcium sulphate, consisting of 80% of β-hemihydrate and 20% of anhydrite (II) o With this purpose, the temperature is raised to 80 ° C, the concentration of sulfuric acid is adjusted to 13%, and the content is maintained at the level of 27%, the solids content in the pulp is 20-26%.
    Alternatively, the dehydration is carried out under the condition: the content is 23%, the concentration of sulfuric acid is 15%, the temperature is 78 ° C0. These conditions make it possible to obtain calcium sulfate consisting of 40% of the & J-hemihydrate and 60% of the anhydrite ( Ii)
    According to a known method, phosphoric acid is obtained by treating phosphorite with circulating phosphoric (36-44%) and sulfuric acids for 1-2.5 hours at 90-100 ° С with precipitation of calcium sulfate hemihydrate precipitate, while the concentration of phosphoric acid in the liquid phase of the pulp sulfuric acid is maintained in the range of 40-55% and
    516
    2-3% respectively. As a result of filtration of the pulp, phosphoric acid with a content of 40-55% PjOj- is obtained as a product. Calcium sulphate helihydrate is washed on the filter with a washing solution followed by a step and a circulating phosphoric acid is obtained, which is sent to the phosphate treatment. sulfuric acid. During the recrystallization process, the solids content in the pulp is 20-45%. The pulp is filtered, the calcium sulfate diggrate precipitate is washed with water. The resulting main filtrate is directed to washing the hemihydrate, the washing filtrate to recrystallization. Washed calcium sulfate dehydrate contains 0.15-0.182
    and 0.03-0.04% P Ovodooretv it can also be used in the production of gypsum cement and portland cement after additional processing. Extraction from phosphate reaches 99.3%.
    Other examples according to the invention are summarized in table. one.
    In tab. 2 presents comparative data on the purity of calcium sulfate according to the known (obtained by the applicant) and the present invention. In both cases, the calcium sulphate is dried at 250 ° C.
    From the data in Table 2, it follows that calcium sulfate obtained by the proposed method is cleaner in terms of the content of phosphorus, fluorine, sodium, calcium, uranium. These impurities are the most aggressive and, due to their low content, the calcium sulphate obtained in accordance with the present invention in the form of amp-hemihydrate, anhydride (II) or a mixture thereof can be directly used in various engineering fields without additional processing.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A method for producing phosphoric acid and calcium sulfate, comprising:
    five
    406
    the processing of phosphate raw materials of circulating phosphoric and sulfuric acids at 70-100 ° C with the formation of a precipitate (calcium sulfate Y-hemihydrate while maintaining phosphorus pentoxide and sulfuric acid in the liquid phase of the pulp, 38-50 and 0.25-2.5%, respectively with subsequent separation of phosphoric acid from the precipitate by filtration, washing it with solutions from the subsequent stages and directing the wash water to the raw material, recrystallizing the Ob-hemihydrate into calcium sulfate dihydrate at 40-80 ° C in a solution of phosphoric and sulfuric acid while maintaining the concentration phosphorus and sulfuric acid pentoxide in the liquid phase of pulp 15-35 0.5-17.5%, respectively, and a concentration of solids in the pulp 22-60%, followed by filtration, pulp with the separation of calcium sulfate dihydrate and filtrate, directed to recrystallization (Vi-semi-hydrate, characterized in that, in order to ensure the formation of various hydrated forms of calcium sulfate, to reduce the content of impurities in it while maintaining a high yield to the concentration of the product, calcium sulfate dihydrate is subjected to recrystallization in phosphorus solutions oh and sulfuric acid either in bt-hemihydrate while maintaining the following regime: temperature 78 ° C ° C, concentration in the liquid phase of the pulp is 22-34% phosphorus pentoxide and 7-15% sulfuric acid and the concentration of solids in the pulp 24-34%, or to anhydride (II) while maintaining the following regime: temperature 60–75 ° C, concentration in the liquid phase of pulp 15-18% phosphorus pentoxide and 16-25% sulfuric acid and concentration of solids in the pulp 20-35%, or in a mixture
    5 sat-hemihydrate and anhydride (II) with
    five
    0
    five
    0
    maintaining the following mode: temperature 70-85 ° C, the concentration in the liquid phase of the pulp is 18-27% phosphorus pentoxide and 13-17% sulfuric acid and the concentration of solids in the pulp 20-30%, the process takes 0.5-3.0 hours, Calcium sulfate is separated by filtration, washed with water, the filtrate and the washings are sent for processing the raw material, washing the oh-hemihydrate and recrystallization.
    Table 1
    Options
    Note. DGSK - calcium sulfate dihydrate, PGGC - calcium sulfate hemihydrate, ATSK P - calcium (II) sulfate anhydride.
    Continuation of table 1
    Examples
    Kurbig Phosphate
    (Morocco) 31.3 49.1 1.7 3.8 3.60.65 0.30 0.67 0.055 0.50 0.0146
    Dng Drat sulphate kalsm (nzrest-
    YUL) 18-19 0.25-30 38.5 55.3 0.7 2.5 2.5 0.055 0.010 0.39 0.10-0.003
    "T-Iopuhydrate + (5-10Z) anhydride (II) (proposed) 5.8-6.1 0.15-0.2040.7 58.4 0.07 1.2 0.073 0.013 0.088 0.019 0.005 0.001 Florida phosphate
     BPL32,8 47,11,0 3,9 6,31,5 1,0 0,45 0,081 0,32 0,0154
    Dng Calcium Sulfate Drat
    (from native) 18-19 0,30-0,3839,3 57,00,15-0,451,4 0,045 0,031 0,25 0,05 0,004 0,00060, 0010
    e-Ps ugidrat + (5-101) anhydride (II) (pre-agaos) 5.8-, 2 0.18-0.25 39.9 58.6 0.10 1.50.06 0.064 0.06 0.015 0.005 0.0005
    table 2
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1653540A3|1991-05-30|Process for producing phosphoric acid and calcium sulfate
    US3410655A|1968-11-12|Production of alpha-calcium sulfate hemihydrate
    SU867292A3|1981-09-23|Method of producing extractional phosphoric acid
    US3632307A|1972-01-04|Process for the preparation of phosphoric acid and gypsum from phosphate rock
    MX2012006380A|2012-06-19|Method for producing phosphoric acid.
    GB1205122A|1970-09-16|Process for the production of phosphoric acid
    CN103435024A|2013-12-11|Method for producing feed grade calcium hydrophosphate
    US3745208A|1973-07-10|Wet process manufacture of phosphoric acid and calcium sulphate
    CN108502861A|2018-09-07|Method and the crystallization in motion agent of concentrated phosphoric acid coproduction semi-hydrated gypsum whisker are produced using low-grade phosphate ore
    EP0672634A2|1995-09-20|Process for continuous production of alpha-calcium sulphate hemihydrate from calcium sulphate dihydrate
    CA1045340A|1979-01-02|Process for the manufacture of stabilised, hardenable calcium sulphate by reacting crude phosphate with sulphuric acid
    US4026990A|1977-05-31|Production of low-fluorine gypsum as a by-product in a phosphoric acid process
    US4113835A|1978-09-12|Process for preparing pure synthetic calcium sulfate semihydrate
    US4853201A|1989-08-01|Recovery of P2 O5 values from phosphoric acid hemihydrate crystals
    CN214495742U|2021-10-26|Two-step method wet-process phosphoric acid coproduction alpha-hemihydrate gypsum production device
    GB1184585A|1970-03-18|A Method for Manufacturing Pure Gypsum.
    SU945076A1|1982-07-23|Process for purifying phosphogypsum
    SU1399266A1|1988-05-30|Method of producing phosphoric acid
    SU1002235A1|1983-03-07|Method of producing phosphoric acid
    CN111320403B|2022-01-25|Method for preparing multi-morphology alpha semi-hydrated gypsum through titanium dioxide waste acid and obtained gypsum
    US4994248A|1991-02-19|P2 O5 recovery and phosphoric acid purification
    SU1474082A1|1989-04-23|Method of producing phosphoric acid
    SU882922A1|1981-11-23|Method of producing phosphoric acid and calcium sulfate dihydrate
    SU1147694A1|1985-03-30|Method of obtaining phosporic acid
    SU1370074A1|1988-01-30|Method of obtaining phosphoric acid
    同族专利:
    公开号 | 公开日
    FI78054B|1989-02-28|
    BR8407074A|1985-08-27|
    IT1173450B|1987-06-24|
    ZA842107B|1984-10-31|
    DK558184D0|1984-11-23|
    DE3473867D1|1988-10-13|
    LU84713A1|1984-11-14|
    AU2651484A|1984-10-09|
    IT8420123D0|1984-03-19|
    WO1984003690A1|1984-09-27|
    PH21586A|1987-12-11|
    AU569070B2|1988-01-21|
    IL71295A|1987-10-20|
    MX168186B|1993-05-10|
    EP0169842B1|1988-09-07|
    IN160318B|1987-07-04|
    DK558184A|1984-11-23|
    IL71295D0|1984-06-29|
    OA07998A|1987-01-31|
    JPS60500909A|1985-06-20|
    FI851524A0|1985-04-17|
    MA20070A1|1984-10-01|
    CA1211919A|1986-09-30|
    GR81479B|1984-12-11|
    FI851524L|1985-04-17|
    JPH0454615B2|1992-08-31|
    EP0169842A1|1986-02-05|
    ES530972A0|1985-09-16|
    US4588570A|1986-05-13|
    FI78054C|1989-06-12|
    AT37017T|1988-09-15|
    ES8507078A1|1985-09-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    NL29556C|1930-02-13|
    GB1092055A|1964-03-06|1967-11-22|Roman Chelminski|Process for the production of phosphoric acid|
    US3416887A|1964-08-05|1968-12-17|Central Glass Co Ltd|Method of manufacturing wet process phosphoric acid|
    US3632307A|1969-04-09|1972-01-04|Albatros Super Fosfaatfabrieke|Process for the preparation of phosphoric acid and gypsum from phosphate rock|
    JPS5035519B2|1971-12-27|1975-11-17|
    GB1520273A|1974-07-06|1978-08-02|Fisons Ltd|Phosphoric acid and gypsum from phosphatic material|
    JPS5851884B2|1975-08-13|1983-11-18|Nissan Chemical Ind Ltd|
    FR2409230B1|1977-11-16|1981-05-29|Rhone Poulenc Ind|
    NL7909057A|1979-12-15|1981-07-16|Unie Van Kunstmestfab Bv|Wet-process phosphoric acid prodn. - with calcium sulphate recovery as hemi:hydrate via di:hydrate|DE3583209D1|1984-11-05|1991-07-18|Prayon Dev Sa|CONTINUOUS PROCESS FOR PRODUCING PHOSPHORIC ACID AND CALCIUM SULFATE.|
    US5169444A|1986-02-20|1992-12-08|Gebruder Knauf Westdeutsche Gipswerke Kg|Process for preparing calcium sulfate anhydrite|
    JPH044968B2|1986-12-08|1992-01-30|
    BE1019055A3|2009-12-02|2012-02-07|Prayon Technologies|PROCESS FOR PRODUCING PHOSPHORIC ACID|
    CA2837495C|2011-06-01|2018-01-09|Prayon Technologies|A method for producing phosphoric acid of the dihydrate/hemihydrate type|
    WO2013060689A1|2011-10-24|2013-05-02|Prayon Sa|Method for treating phosphate rock|
    BR112015021526A2|2013-03-08|2017-07-18|Mosaic Co|phosphoric acid production by a two stage crystallization process|
    RU2599525C1|2015-04-23|2016-10-10|Открытое акционерное общество "Научно-исследовательский институт по удобрениям и инсектофунгицидам имени профессора Я.В. Самойлова" |Method of producing wet-process phosphoric acid|
    CN105776303A|2016-01-30|2016-07-20|瓮福（集团）有限责任公司|Production method of alpha-hemihydrate gypsum|
    BE1023754B1|2016-06-23|2017-07-12|Prayon Technologies|PROCESS FOR PRODUCING CALCIUM SULPHATE|
    DE102016212242B4|2016-07-05|2019-02-07|Technische Universität Bergakademie Freiberg|Process for the production of phosphoric acid from phosphorus-containing primary and secondary raw materials|
    DE102020100241A1|2020-01-08|2021-07-08|Thyssenkrupp Ag|Process for the production of phosphoric acid and calcium sulphate quality suitable for clinker process for the commercial and industrial utilization of calcium sulphate|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    LU84713A|LU84713A1|1983-03-25|1983-03-25|PROCESS AND PREPARATION OF PHOSPHORIC ACID AND CALCIUM HEMIHYDRATE ALPHA SULFATE|
    [返回顶部]