公开(公告)号：US4828811A

公开(公告)日：1989-05-09

申请号：US078608

申请日：1987-07-28

Applicant: Gary D. Derdall ,  William R. Erickson ,  Robin L. Phinney ,  James D. Wilson

Inventor： Gary D. Derdall ,  William R. Erickson ,  Robin L. Phinney ,  James D. Wilson

IPC: C01B25/225 ,  C01B25/226

CPC classification number: C01B25/225 ,  C01B25/226

Abstract: A process and apparatus for producing phosphoric acid by the recovery of P.sub.2 O.sub.5 from a phosphate ore is disclosed. A slurry of a phosphate ore in an aqueous phosphoric acid solution is formed in each of a plurality of reaction zones connected in series. Phosphate ore is introduced into the first reaction zone and phosphoric acid into the last reaction zone whereby the reaction of the phosphoric acid with the ore forms a slurry of coarse solids, fine solids and monocalcium phosphate in the phosphoric acid solution. A first process stream comprising coarse solids is removed from the first reaction zone and each of the other reaction zones and is transferred to the adjacent, successive reaction zone. A second process stream comprising fine solids is removed from the last reaction zone and the other reaction zones and is transferred into the adjacent, preceding zone in a direction which is countercurrent to the direction of flow of the first process stream and is concurrent with the direction of flow of the phosphoric acid from the last to the first reaction zones. A differential of phosphoric acid concentration is maintained between the reaction zones with the concentration decreasing in each reaction zone in the direction of flow of the first process stream.

Abstract translation: 公开了一种通过从磷酸盐矿石回收P2O5来生产磷酸的方法和装置。 在串联连接的多个反应区域中的每一个中形成磷酸盐矿物在磷酸水溶液中的浆料。 将磷酸盐矿石引入第一反应区和磷酸进入最后的反应区，由此磷酸与矿石的反应在磷酸溶液中形成粗固体，细固体和磷酸一磷酸钙的浆料。 从第一反应区和每个其它反应区除去包含粗固体的第一工艺流，并转移到相邻的连续反应区。 从最后的反应区和其他反应区除去包含细固体的第二工艺流，并沿与第一工艺流的流动方向相反的方向转移到相邻的先前区，并且与方向 从最后到第一反应区的磷酸流动。 在反应区之间保持磷酸浓度的差异，每个反应区中的浓度在第一工艺流的流动方向上减小。

公开(公告)号：US4777027A

公开(公告)日：1988-10-11

申请号：US792495

申请日：1985-10-29

Applicant: Armand L. Davister ,  Francis A. Thirion

Inventor： Armand L. Davister ,  Francis A. Thirion

IPC: C01B25/22 ,  C01B25/222 ,  C01B25/223 ,  C01B25/225 ,  C01B25/226 ,  C01B25/228 ,  C01B25/229 ,  C01B25/231 ,  C01F11/46 ,  C01B25/16

CPC classification number: C01B25/229 ,  C01B25/222 ,  C01B25/225 ,  C01B25/226 ,  C01B25/2285 ,  C01B25/231 ,  Y02P20/582

Abstract: There is described a process which comprises adjusting on the one hand the flow rates of a circulating mixture relative to a base flow rate according to very specific specifications, and on the other hand so adjusting the reaction conditions in succeeding reaction zones as to obtain a production phosphoric acid with a P.sub.2 O.sub.5 concentration between 33 and 52%, and a H.sub.2 SO.sub.4 concentration between 0.25 and 2.5%, and calcium sulphate in the form of dihydrate, hemihydrate, anhydrite or a mixture of at least two said crystalline forms.

Abstract translation: 描述了一种方法，其一方面根据非常具体的规格一方面调节循环混合物相对于基本流速的流速，另一方面调节后续反应区中的反应条件以获得生产 P2O5浓度在33和52％之间的磷酸，以及0.25至2.5％之间的H 2 SO 4浓度，以及二水合物，半水合物，无水石膏或至少两种所述晶形的混合物形式的硫酸钙。

公开(公告)号：US4557915A

公开(公告)日：1985-12-10

申请号：US627672

申请日：1984-07-05

Applicant: Guy Nineuil

Inventor： Guy Nineuil

IPC: C01B33/18 ,  C01B25/22 ,  C01B25/225 ,  C01B25/16

CPC classification number: C01B25/225 ,  C01B25/22 ,  C01B25/2208

Abstract: Phosphoric acid is produced, with concomitant recovery of solids comprising compounds of fluorine and silica, by (i) acidulating a first amount of phosphate ore with a strong acid to produce a first phosphoric acid slurry, (ii) filtering said first slurry to separate the liquid phosphoric acid content therefrom, (iii) concentrating a fraction of the phosphoric acid thus separated, (iv) recovering same, and (v) condensing the evolved vapors of concentration with a liquid absorbent to produce a solution of fluosilicic acid, (vi) acidulating a second amount of phosphate ore with said solution of fluosilicic acid together with a fraction of said first slurry, or together with a fraction of the phosphoric acid separated in the step (ii), to produce a second phosphoric acid slurry, (vii) filtering said second slurry to separate both the liquid phosphoric acid content and a solids fraction therefrom, said solids fraction comprising fluorine and silica compounds, (viiia) recycling the phosphoric acid thus separated from said second slurry to the step (i), or (viiib) combining same with the fraction of separated phosphoric acid to be downstream concentrated in the step (iii).

Abstract translation: 通过（i）用强酸酸化第一量的磷酸盐矿石以产生第一种磷酸浆料，（ii）过滤所述第一种浆料以分离出磷酸， 液体磷酸含量，（iii）浓缩所分离的一部分磷酸，（iv）回收它们，和（v）浓缩放出的浓度的蒸气与液体吸收剂以产生氟硅酸溶液，（vi） 用所述氟硅酸溶液与所述第一浆料的一部分酸化第二量的磷酸盐矿石，或与步骤（ii）中分离的一部分磷酸一起产生第二种磷酸浆料，（vii） 过滤所述第二浆料以分离液体磷酸含量和固体分数，所述固体馏分包含氟和二氧化硅化合物，（viiia）将磷光体再循环 （i）中分离出的酸，或（viiib）将步骤（iii）中的分离的磷酸的馏分与下游浓缩相结合。

公开(公告)号：US4485078A

公开(公告)日：1984-11-27

申请号：US471421

申请日：1983-03-08

Applicant: Charles W. Weston ,  John W. Wen ,  Frederick S. Mandel

Inventor： Charles W. Weston ,  John W. Wen ,  Frederick S. Mandel

IPC: C01B25/225 ,  C01B25/238 ,  C01B25/16

CPC classification number: C01B25/225 ,  C01B25/238

Abstract: Phosphoric acid is produced by the wet process from phosphate rock containing fluochlorapatite. The rock is ground in a crusher (10) to a size such that from about 50% to about 90% by weight will be passed by a -200 mesh U.S.S. sieve before being passed into a digestor (14) where it is mixed with sulfuric acid and recycled phosphoric acid to form a slurry. A suitable reductant such as sulphur dioxide is added to the slurry to maintain the oxidation-reduction potential in the range from about +150 mv to about +750 mv. The gypsum by-products are then removed from the slurry at filter (16) and a portion of the acid is recycled to digestor (14). The remaining acid is either concentrated and further processed to make fertilizers or is further processed via path (20) to remove aluminum and/or iron impurities. Select amounts of fluoride and sodium containing compounds are added to the acid in a stirred reactor (30) to cause precipitation of aluminum, principally as Na.sub.2 AlF.sub.5. After about 15 to about 60 minutes of stirring at a temperature below about 70.degree. C., the precipitate is removed at filter (32) where the acid is either processed to make fertilizer or subjected to additional processing to remove iron contaminants. Iron contaminants are removed from the filter acid or from aluminum removed acid from filter (32) by adding sufficient ammonia to the acid in a stirring reactor (40) to cause precipitation of iron principally as NH.sub.4 Fe.sub.2 H.sub.8 (PO.sub.4).sub.5.AH.sub.2 O, to reduce the level of iron to desired levels. After aging in the reactor from about 2 to about 24 hours at a temperature below the boiling point of the acid, the precipitate is removed at filter (42) and the resulting iron reduced acid is concentrated and subjected to conventional processing for making fertilizers.

Abstract translation: 磷酸由含氟氯磷灰石的磷酸盐岩由湿法生产。 将岩石在破碎机（10）中研磨成一定尺寸，使得约50％至约90％重量将通过-200目的U.S.S. 筛，然后通入消化器（14），在其中与硫酸和再循环的磷酸混合形成浆料。 将适当的还原剂如二氧化硫加入到浆料中以将氧化还原电位维持在约+ 150mv至约+ 750mv的范围内。 然后在过滤器（16）从浆料中除去石膏副产物，将一部分酸再循环至消化器（14）。 将剩余的酸浓缩并进一步加工以制备肥料，或通过路径（20）进一步加工以除去铝和/或铁杂质。 在搅拌的反应器（30）中，将选择量的氟化物和含钠化合物加入到酸中，导致铝沉淀，主要为Na 2 AlF 5。 在低于约70℃的温度下搅拌约15至约60分钟后，在过滤器（32）处除去沉淀物，其中酸被处理以制备肥料或进行额外处理以除去铁污染物。 通过在搅拌的反应器（40）中向酸中加入足够的氨以使铁主要沉淀为NH 4 Fe 2 H 8（PO 4）5.A·H 2 O，从过滤器（32）中除去铁污染物或从过滤器（32）中除去的铝去除酸，以减少 铁水平达到所需水平。 在低于沸点的温度下在反应器中老化约2至约24小时后，在过滤器（42）处除去沉淀物，并将所得的铁还原酸浓缩并进行常规加工以制备肥料。

公开(公告)号：US4276270A

公开(公告)日：1981-06-30

申请号：US82258

申请日：1979-10-05

Applicant: F. Michael Gragg ,  James Self

Inventor： F. Michael Gragg ,  James Self

IPC: B01D19/02 ,  B01F1/00 ,  B01F13/02 ,  B01J16/00 ,  C01B25/22 ,  C01B25/225 ,  C01B25/226 ,  C01F11/46

CPC classification number: C01B25/226 ,  B01D19/02 ,  B01F1/0005 ,  B01F1/0038 ,  B01F13/0294 ,  B01J16/00 ,  C01B25/2204 ,  C01B25/225

Abstract: In a multi-stage, multi-vessel phosphoric acid production system where a first reaction vessel contains a first slurry comprising calcium sulfate hemihydrate, monocalcium phosphate and phosphoric acid and a second reaction vessel contains a second slurry comprising calcium sulfate hemihydrate, sulfuric acid and phosphoric acid, in which the reaction slurry undergoes intra- and inter-vessel circulation, preferably through a draft tube, an improved start-up procedure involves filling the system with heated phosphoric acid having a P.sub.2 O.sub.5 analysis in the range of about 28 to about 38% (e.g. 31%), then feeding phosphate rock to the system, preferably in a separate reaction vessel, while phosphoric acid is recycled from a fourth, filter feed vessel, until the solids content in said slurry is in the range of 25-35% (e.g. about 30%) while the sulfate content in the first vessel is maintained at a negative level (e.g. excess calcium ion) and at a positive level in the second, crystallizer vessel. When the solids content, calcium, and sulfate content are at the proper level (e.g. about 30% solids, -5 to -2% sulfate in the first vessel and +2 to +3% sulfate in the second vessel) the slurry is then transported to a filter and the phosphoric acid is separated from the calcium sulfate hemihydrate.

Abstract translation: 在多级多容量磷酸生产系统中，其中第一反应容器含有包含硫酸钙半水合物，磷酸一磷酸钙和磷酸的第一浆料，第二反应容器含有包含硫酸钙半水合物，硫酸和磷酸的第二浆料 酸，其中反应浆料经受血管内和血管间循环，优选通过引流管，改进的启动程序包括用具有约28至约38％范围内的P2O5分析的加热磷酸填充系统， （例如31％），然后将磷酸盐岩石送入系统，优选在单独的反应容器中，同时从第四个过滤器进料容器再循环磷酸，直到所述浆料中的固体含量在25-35％ （例如约30％），而第二容器中的硫酸盐含量在第二容器中维持在负的水平（例如过量的钙离子），并且在第二容器 。 当固体含量，钙和硫酸盐含量处于适当水平（例如，约30％固体，第一容器中为-5至-2％硫酸盐，第二容器中为+2至+ 3％硫酸盐时），然后将浆液 运送到过滤器，磷酸与半水合硫酸钙分离。

公开(公告)号：US4260584A

公开(公告)日：1981-04-07

申请号：US910163

申请日：1978-05-26

Applicant: Fernando Ore ,  John D. Ellis ,  James H. Moore

Inventor： Fernando Ore ,  John D. Ellis ,  James H. Moore

IPC: B01D9/00 ,  B01D19/02 ,  B01J16/00 ,  B01J19/18 ,  C01B25/22 ,  C01B25/223 ,  C01B25/225 ,  C01B25/226 ,  C01B25/222

CPC classification number: C01B25/226 ,  B01D19/02 ,  B01D9/0018 ,  B01J16/00 ,  B01J19/1868 ,  C01B25/2204 ,  C01B25/2235 ,  C01B25/225

Abstract: The invention comprises a multi-vessel reaction apparatus useful for reacting phosphate rock and sulfuric acid in which the reaction slurry undergoes intra- and inter- vessel circulation (preferably through a draft tube). The solution portion of the slurry in a first vessel or set of vessels (the "dissolver") is preferably maintained at at lower sulfate ion concentration and the solution portion of the slurry in the second vessel or system of vessels (the "crystallizer") is preferably maintained at a positive sulfate ion concentration. Also preferred are means for maintaining the second vessel or set of vessels at a reduced pressure. Most preferred is that means be included in at least one said vessel for incorporating a crystal modifier (e.g. a sulfonic acid, a sulfonic acid salt, tall oil fatty acids or alkoxylated or esterified tall oil fatty acids) in the crystallizer. The system can be used in the anhydrite, hemihydrate or gypsum types of processes.

Abstract translation: 本发明包括用于使磷酸盐岩和硫酸反应的多容器反应装置，其中反应浆料经受血管内和血管间循环（优选通过引流管）。 第一容器或一组容器（“溶解器”）中的浆液的溶液部分优选保持在较低的硫酸根离子浓度，并且浆液在第二容器或容器系统（“结晶器”）中的溶液部分 优选维持在正硫酸根离子浓度。 还优选的是用于在减压下维持第二容器或容器组的装置。 最优选的是，该方法包括在至少一个所述容器中，用于在结晶器中引入结晶改性剂（例如磺酸，磺酸盐，妥尔油脂肪酸或烷氧基化或酯化的妥尔油脂肪酸）。 该系统可用于无水石膏，半水合物或石膏类型的工艺。

公开(公告)号：US4191734A

公开(公告)日：1980-03-04

申请号：US888038

申请日：1978-03-20

Applicant: Erhart K. Drechsel ,  John B. Sardisco

Inventor： Erhart K. Drechsel ,  John B. Sardisco

IPC: C01B25/225 ,  C01B25/237 ,  C01B25/30 ,  C05B11/08 ,  C01B25/22

CPC classification number: C01B25/303 ,  C01B25/225 ,  C01B25/2375 ,  C05B11/08

Abstract: Substantially fluoride-free phosphoric acid is produced by the acidulation of phosphate rock with sulfuric acid wherein the acidulation reaction is conducted in the presence of added potassium as K.sub.2 O bearing compounds, e.g. KHSO.sub.4, K.sub.2 SO.sub.4, KH.sub.2 PO.sub.4 or KOH, and additional silica, to precipitate fluorides and silica as potassium silicofluoride and then removed on separation of the gypsum formed. Optionally, additional silica may be added to the phosphoric acid solution recovered after precipitation and removal of the gypsum, to precipitate additional fluoride as potassium silicofluoride to further purify the phosphoric acid. In a further embodiment sufficient potassium may be added along with additional silica in the acidulation step to produce potassium dihydrogen phosphate and phosphoric acid as additional products. The phosphoric acid and potassium dihydrogen phosphate are recovered substantially free from fluoride contamination and the reaction is carried out in the substantial absence of fluorine evolution into the atmosphere. Also disclosed is a process for conducting a conventional phosphoric acid facility to produce phosphoric acid and gypsum wherein defluorination of the phosphoric acid recovered is achieved by silicon dioxide and K.sub.2 O addition and the fluorides are removed from the system, the process including steps for production of pure phosphoric acid and potassium dihydrogen phosphate.

Abstract translation: 通过用硫酸酸化磷酸盐岩产生基本上不含氟化物的磷酸，其中酸化反应在加入的K 2存在下作为带有K2O的化合物，例如， KHSO 4，K 2 SO 4，KH 2 PO 4或KOH和另外的二氧化硅，以氟硅酸钠和二氧化硅的形式沉淀，然后在形成的石膏分离后除去。 任选地，可以在沉淀和除去石膏之后回收的磷酸溶液中加入另外的二氧化硅，以沉淀另外的氟化硅作为氟硅酸钾以进一步纯化磷酸。 在进一步的实施方案中，在酸化步骤中可以连同另外的二氧化硅一起加入足量的钾，以产生磷酸二氢钾和磷酸作为附加产物。 基本上没有氟化物污染物回收磷酸和磷酸二氢钾，并且基本上没有氟进入大气中进行反应。 还公开了一种用于进行常规磷酸设备来生产磷酸和石膏的方法，其中通过二氧化硅和K 2 O添加实现回收的磷酸的脱氟，并且从体系中除去氟化物，该方法包括生产纯的 磷酸和磷酸二氢钾。

公开(公告)号：US4105748A

公开(公告)日：1978-08-08

申请号：US785772

申请日：1977-04-07

Applicant: Erhart K. Drechsel ,  John B. Sardisco

Inventor： Erhart K. Drechsel ,  John B. Sardisco

IPC: C01B25/222 ,  C01B25/225 ,  C01B25/237 ,  C01B25/30 ,  C05B11/08 ,  C01B25/16

CPC classification number: C05B11/08 ,  C01B25/225 ,  C01B25/2375 ,  C01B25/303

Abstract: Substantially fluoride-free phosphoric acid is produced by the acidulation of phosphate rock with sulfuric acid wherein the acidulation reaction is conducted in the presence of added potassium as K.sub.2 O bearing compounds, e.g. KHSO.sub.4, K.sub.2 SO.sub.4, KH.sub.2 PO.sub.4 or KOH, and additional silica, to precipitate fluorides and silica as potassium silicofluoride and then removed on separation of the gypsum formed. Optionally, additional silica may be added to the phosphoric acid solution recovered after precipitation and removal of the gypsum, to precipitate additional fluoride as potassium silicofluoride to further purify the phosphoric acid. In a further embodiment sufficient potassium may be added along with additional silica in the acidulation step to produce potassium dihydrogen phosphate and phosphoric acid as additional products. The phosphoric acid and potassium dihydrogen phosphate are recovered substantially free from fluoride contamination and the reaction is carried out in the substantial absence of fluorine evolution into the atmosphere. Also disclosed is a process for conducting aconventional phosphoric acid facility to produce phosphoric acid and gypsum wherein defluorination of the phosphoric acid recovered is achieved by silicon dioxide and K.sub.2 O addition and the fluorides are removed from the system, the process including steps for production of pure phosphoric acid and potassium dihydrogen phosphate.

Abstract translation: 通过用硫酸酸化磷酸盐岩产生基本上不含氟化物的磷酸，其中酸化反应在加入的K 2存在下作为带有K2O的化合物，例如， KHSO 4，K 2 SO 4，KH 2 PO 4或KOH和另外的二氧化硅，以氟硅酸钠和二氧化硅的形式沉淀，然后在形成的石膏分离后除去。 任选地，可以在沉淀和除去石膏之后回收的磷酸溶液中加入另外的二氧化硅，以沉淀另外的氟化硅作为氟硅酸钾以进一步纯化磷酸。 在进一步的实施方案中，在酸化步骤中可以连同另外的二氧化硅一起加入足量的钾，以产生磷酸二氢钾和磷酸作为附加产物。 基本上没有氟化物污染物回收磷酸和磷酸二氢钾，并且基本上没有氟进入大气中进行反应。 还公开了一种用于进行常规磷酸设备以生产磷酸和石膏的方法，其中通过二氧化硅和K 2 O添加实现回收的磷酸的脱氟，并且从体系中除去氟化物，该方法包括生产纯磷酸的步骤 酸和磷酸二氢钾。

公开(公告)号：US3949047A

公开(公告)日：1976-04-06

申请号：US350476

申请日：1973-04-12

Applicant: Egon Cherdron ,  Hans-Joachim Forster ,  Istvan Potencsik

Inventor： Egon Cherdron ,  Hans-Joachim Forster ,  Istvan Potencsik

IPC: C01B25/225 ,  C01B25/22 ,  C01B33/10 ,  C01F11/46 ,  C01F13/00

CPC classification number: C01F11/46 ,  C01B25/22 ,  C01B33/103

Abstract: In the manufacture of phosphoric acid by treatment of phosphate ores with excess phosphoric acid and precipitation of calcium ions as calcium sulfate, the purity and quality of the byproduct calcium sulfate is substantially improved by subjecting the monocalcium phosphate extract of the ore before precipitation of calcium sulfate to one or more preliminary treatments, whereby contaminent ions are substantially and preferentially removed from the extract while the calcium remains substantially in solution. These preliminary treatments may include separation of fluoride by reaction with silicon compounds, separation of radium by reaction with barium compounds in the presence of sulfate ions, and separation of strontium as strontium sulfate.

Abstract translation: 在通过用过量磷酸处理磷酸盐矿物和用钙离子作为硫酸钙沉淀来制造磷酸的过程中，通过在沉淀硫酸钙之前对矿石的一磷酸钙提取物进行处理，使副产物硫酸钙的纯度和质量得到显着改善 到一个或多个初步处理，其中污染物离子基本上和优先从提取物中除去，同时钙基本上保留在溶液中。 这些初步处理可以包括通过与硅化合物的反应分离氟化物，在硫酸根离子的存在下通过与钡化合物的反应分离镭，以及分离作为硫酸锶的锶。

公开(公告)号：US3793436A

公开(公告)日：1974-02-19

申请号：US3793436D

申请日：1971-11-24

Applicant: HARTIG R

Inventor： HARTIG R

IPC: C01B25/225 ,  C01B33/10 ,  C02F1/58 ,  C01B33/08 ,  C01B15/16

CPC classification number: C01B33/103 ,  C01B25/225 ,  C02F1/583

Abstract: CLOSED POND SYSTEM OR PROCESS FOR ELIMINATING THE CONVENTIONAL POND SYSTEMS OF WET PROCESS PHOSPHORIC ACID COMPLEXES, AND TO REMOVE FLUORINE FROM PROCESS GAS STREAMS, WHEREIN LIQUID EFFLUENTS FROM WET PROCESS PHOSPHORIC ACID COMPLEXES, INCLUDING SCRUBBER LIQUOR FROM GAS SCRUBBING OPERATIONS OF THE COMPLEX, ARE COOLED AND CLARIFIED, AND THE LIQUID FROM THE CLARIFIER, NEUTRALIZED WITH AMMONIA, IS RECYCLED TO THE PHOSPHATE COMPLEX, THE SLUDGE OR SLURRY BEING FILTERED TO REMOVE SOLIDS, THE SOLIDS BEING CALCINED TO DRIVE OFF FLUORINE-CONTAINING GASES. THE CALCINED SOLIDS CONSIST PRINCIPALLY OF SODIUM FLUORIDE (NAF) WHICH RECYCLED TO THE CLARIFIER OVERFLOW TO BE MIXED WITH THE LIQUID RETURNED TO THE PHOSPHATE COMPLEX. IN THE PHOSPHATE THE AMMONIATED LIQUID FROM THE CLARIFIER IS USED TO SCRUB PLANT GASES, AND IS MIXED WITH OTHER SCRUBBER LIQUORS FROM THE PLANT, AND RECYCLED AGAIN TO THE COOLING TOWER AND CLARIFIER. THE HF IN THE EFFLUENT PLANT LIQUIDS IS CONVERTED TO SIF4 BY MAINTAINING AN EXCESS OF SIO2, AND THE NAF REACTS WITH THE SIF4 TO FORM NA2SIF6. THE NA2SIF6 IS CALCINED TO PRODUCE NAF AND GASEOUS SIF4, THE LATTER BEING SCRUBBED WITH WATER TO FORM H2SIF6 OF COMMERCIAL QUALITY.