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    • 专利摘要:
    The present invention relates to a method of producing hydroxyapatite comprising a step of dissolving mineral ash from calcined animal meal or calcined animal protein, implemented in hydrochloric acid, followed by a filtration step of the solution obtained acid, and then precipitation steps by neutralization and washing, to effectively remove both the heavy metals and the sodium and chlorine phases initially present in the ash, and thus to obtain, after drying at a temperature n not exceeding 60 ° C, a very pure hydroxyapatite with a large specific surface area.
    公开号:FR3077285A1
    申请号:FR1850842
    申请日:2018-02-01
    公开日:2019-08-02
    发明作者:Joelle Carpena
    申请人:Saria Industries SAS；
    IPC主号:
    专利说明:

    Process for the production of very pure hydroxyapatites from waste containing calcium phosphates, in particular animal meal
    The present invention relates to a process for the production of very pure hydroxyapatites with a large specific surface.
    The apatites form a large family of isomorphic minerals of general formula Me 10 (XO 4 ) 6 Y 2 where Me represents a cation, XO 4 and Y represent anionic groups. A representative member of apatites is hydroxyapatite (here called hydroxyapatite) of formula Ca 10 (PO 4 ) 6 (OH) 2 . Among the main properties of apatites, we can cite their strong resistance to chemical corrosion in neutral to alkaline environments, their weak and retrograde solubility, their potential to restore damage due to irradiation and their capacity to trap heavy elements. Due to these properties, apatites are used to clean up soils, effluents and water or to immobilize dangerous heavy metals and radioactive waste.
    Hydroxyapatite can typically be produced from geological phosphates.
    Thus, application WO 2016/193429 describes a process for the preparation of a calcium phosphate reagent comprising apatite, comprising, in a first step, the use of a source of calcium and of phosphoric acid as a source of phosphate ions in water, in a molar ratio such that the Ca / P molar ratio is between 0.5 and 0.6, and the reaction of the calcium source with phosphoric acid at a pH between 2 and 8, so as to obtain a suspension A of calcium phosphate; and, in a second step, adding to suspension A an alkaline compound comprising hydroxide ions, in order to adjust the pH to more than 8, and an additional source of calcium in order to obtain a suspension B of calcium phosphate reagent having a Ca / P molar ratio of 1.6.
    As the resources of geological phosphates are becoming scarce, geological phosphates have chemical compositions that are increasingly rich in heavy metals (Cd, Cr, V, Ni, As, U, ...), producers exploiting the deposits that remain. As a result, the end products of the phosphate industry (phosphoric acid, food phosphates, medical phosphates, fertilizers, ...) also contain heavy metals and their purification has a very high cost.
    There is therefore a significant need for a process for the production of very pure hydroxyapatites from alternative phosphate sources.
    The interest in the recovery of phosphates contained in waste is a response to the context of this scarcity of geological phosphate resources.
    The idea of recovering phosphates of animal origin and in particular the phosphates contained in the mineral part of animal waste (animal meal, processed animal protein (PAT), slaughterhouse waste, dead animals, fish, fish, game, meat) would make it possible to compensate for the decrease in geological resources, the "phosphate peak" having been predicted in 2020, when the USA would have no more resources.
    In order to recover the mineral part of animal waste, in particular animal meal and PAT, calcination is necessary to remove organic matter. This calcination is carried out at a temperature of 650 to 800 ° C for 2 to 3 hours. At the end of this calcination step, the ash recovered, 25% by mass of the initial mass, is greyish to whitish in color, and consists of a majority of hydroxyapatite phase of chemical formula Ca 10 (PO 4 ) 6 (OH) 2 .
    However, this chemical formula may contain heavy metals, in particular in the case of type C1 animal meal, because of the industrial process used for processing or because of the initial contamination of the geological phosphates which are found in the food chain. However, the presence of such heavy metals in hydroxyapatite is not compatible with its subsequent uses, in particular for the production of good quality phosphoric acid from European phosphate resources.
    In addition, accompanying this majority mineral phase, other minority mineral phases are present and contain sodium and chlorine. These are the KCI sylvite, the Rhenanite NaCaPO 4 , a triple phosphate Ca 9 NaMg (PO 4 ) 7 , the vishnevite Na 8 AI 6 (SiO 4 ) 6 (SO 4 ), 12H 2 O. These mineral phases are formed during the calcination of animal waste, in particular animal meal or PAT, because these contain NaCl salt. When the ash obtained is used as a starting product for the preparation of hydroxyapatite or phosphoric acid by conventional methods, it contains a mass fraction of salt and chlorine, which is unacceptable for industrial installations. In fact, chlorides cause the formation of hydrochloric acid, incompatible with industrial installations for the production of hydroxyapatite or phosphoric acid. The sodium salts also prevent the development of gypsum, a byproduct of the production of phosphoric acids, because they migrate to the surface of plasterboards.
    There is therefore a significant need for processes for the preparation of purified hydroxyapatite, and more generally of purified calcium phosphates, without mineral phase containing sodium and chlorine, and without heavy metals, from animal waste containing calcium phosphates, in particular from animal meal or PAT.
    Obtaining such a purified hydroxyapatite would also make it possible to prepare, from this hydroxyapatite, products of phosphoric acid or phosphogypsum type which are themselves very pure without heavy metals, allowing their subsequent development.
    In addition, the chemical reactivity of hydroxyapatite being higher when its specific surface is large, it would be advantageous to have a preparation process which also makes it possible to obtain a hydroxyapatite having a large specific surface.
    The method according to the present invention makes it possible to meet all of these needs.
    The present invention results from the unexpected discovery by the inventors that by combining a step of dissolving mineral ash from animal waste such as animal meal or PAT, specifically implemented in hydrochloric acid, followed by a step filtration of the acid solution obtained, it was possible, after precipitation by neutralization and washing, to efficiently remove both the heavy metals and the sodium and chlorine phases, thus making it possible to obtain a very pure hydroxyapatite having a large specific surface.
    The present invention therefore relates to a process for the preparation of purified calcium phosphate (s) comprising:
    (a) a step of supplying mineral ash from calcined animal waste comprising calcium phosphates, in particular from calcined animal meal or calcined transformed animal protein (PAT);
    (b) a step of dissolving the mineral ash in a hydrochloric acid solution;
    (c) a step of filtering the acid solution obtained in step (b) in order to eliminate the metal phases;
    (d) a precipitation step by neutralization by mixing the filtered solution obtained in step (c) with a NaOH or KOH solution, so as to obtain a precipitate comprising calcium phosphate (s), chlorine and sodium compounds;
    (e) a step of washing, in water, the precipitate obtained in step (d), allowing the elimination of chlorinated and sodic compounds from the precipitate and obtaining a mud of calcium phosphate (s) purified;
    (f) optionally a step of drying the purified calcium phosphate mud (s) obtained in step (e), at a temperature less than or equal to 60 ° C., and (g) optionally a step of recovery of the purified calcium phosphate (s) thus prepared.
    In a particular embodiment, the preparation process according to the invention is a process for the preparation of purified hydroxyapatite and comprises the following steps:
    (a) a step of supplying mineral ash from calcined animal waste comprising calcium phosphates, in particular from calcined animal meal or calcined transformed animal protein (PAT);
    (b) a step of dissolving the mineral ash in a hydrochloric acid solution;
    (c) a step of filtering the acid solution obtained in step (b) in order to eliminate the metal phases;
    (d) a precipitation step by neutralization by adding the filtered solution obtained in step (c) in a NaOH or KOH solution, so as to obtain a precipitate comprising hydroxyapatite, chlorinated compounds and compounds soda;
    (e) a step of washing, in water, the precipitate obtained in step (d), allowing the elimination of chlorinated and sodium compounds from the precipitate and obtaining a purified hydroxyapatite mud;
    (f) optionally a step of drying the purified hydroxyapatite mud obtained in step (e), at a temperature less than or equal to 60 ° C., and (g) optionally a step of recovering the purified hydroxyapatite thus prepared.
    In an alternative embodiment, the preparation process according to the invention is a process for the preparation of non-apatitic calcium phosphate (s) such as monocalcium phosphate and / or dicalcium phosphate, and comprises the following: following steps :
    (a) a step of supplying mineral ash from calcined animal waste comprising calcium phosphates, in particular from calcined animal meal or calcined transformed animal protein (PAT);
    (b) a step of dissolving the mineral ash in a hydrochloric acid solution;
    (c) a step of filtering the acid solution obtained in step (b) in order to eliminate the metal phases;
    (d) a precipitation step by neutralization by adding a NaOH or KOH solution to the filtered solution obtained in step (c), so as to obtain a precipitate comprising calcium phosphate (s) non-apatitic (s), chlorinated compounds and sodium compounds;
    (e) a step of washing, in water, the precipitate obtained in step (d), allowing the elimination of chlorinated and sodic compounds from the precipitate and obtaining a mud of calcium phosphate (s) non-apatitic (s) purified;
    (f) optionally a step of drying the purified non-apatitic calcium phosphate mud (s) obtained in step (e), at a temperature less than or equal to 60 ° C., and (g ) optionally a step of recovering the purified non-apatitic calcium phosphate (s) thus prepared.
    Insofar as the process for the preparation of purified hydroxyapatite developed by the inventors makes it possible to remove the heavy metals present in the source of hydroxyapatite supplied, this process also makes it possible to regenerate hydroxyapatites loaded with heavy metals which were used for the depollution of heavy metals from soils or effluents, or to purify geological hydroxyapatites loaded with heavy metals, in order to obtain, in both cases, purified hydroxyapatites without heavy metals and with a large specific surface.
    Thus, the present invention also relates to a process for the purification of hydroxyapatite from hydroxyapatite loaded with heavy metals, comprising:
    (a) a step of supplying hydroxyapatite loaded with heavy metals;
    (b) a step of dissolving the hydroxyapatite loaded with heavy metals in a hydrochloric acid solution;
    (c) a step of filtering the acid solution obtained in step (b) in order to remove the heavy metals;
    (d) a precipitation step by neutralization by adding the filtered solution obtained in step (c) in a NaOH or KOH solution, so as to obtain a precipitate comprising hydroxyapatite, chlorinated compounds and compounds soda;
    (e) a step of washing, in water, the precipitate obtained in step (d), allowing the elimination of chlorinated and sodium compounds from the precipitate and obtaining a purified hydroxyapatite mud;
    (f) optionally, a step of drying the purified hydroxyapatite mud obtained in step (e), at a temperature less than or equal to 60 ° C; and (g) optionally, a step for recovering the purified hydroxyapatite thus prepared.
    Detailed description of the invention
    By "calcium phosphate" is meant here a family of materials and minerals containing calcium ions and inorganic phosphate anions. Calcium phosphates include in particular apatites or hydroxyapatites and non-apatitic calcium phosphates.
    By "hydroxyapatite" is meant here a calcium phosphate of formula Cai 0 (PO 4 ) 6 (OH) 2 , with a Ca / P ratio of 1.6.
    The term “non-apatitic calcium phosphates” is understood here to mean calcium phosphates having a Ca / P ratio <1.6, such as monocalcium phosphate (Ca (H 2 PO 4 ) 2 with Ca / P = 0.5 ), monocalcium phosphate hydrate (Ca (H 2 PO 4 ) 2 , H 2 O with Ca / P = 0.5), dicalcium phosphate (CaHPO 4 with Ca / P = 1), dicalcium phosphate dihydrate (CaHPO 4 , 2H 2 O with Ca / P = 1) or tricalcium phosphate (Ca 3 (PO 4 ) 2 with Ca / P = 1.5).
    In the context of the invention, the term “animal waste comprising calcium phosphates” includes animal carcasses of large animals or domestic or wild animals, dead or stillborn, or parts thereof, such as only slaughterhouse waste, spoiled food of animal origin and animal by-products including calcium phosphates. Animal waste within the meaning of the invention thus includes meat and animal by-products from domestic animals, wild animals or livestock which have been killed or died as a result of an illness, in particular contaminated carcasses by transmissible spongiform encephalopathies, animals contaminated with chemical or prohibited substances or test animals. Also covered are meat and by-products that pose a risk of other non-communicable diseases.
    The term "animal waste including calcium phosphates" also includes dead animals not slaughtered, animal by-products and any animal product containing drug residues, all waste and by-products from slaughterhouses, waste cooking and food waste including calcium phosphates, foods of animal origin which are no longer suitable for human consumption, fresh fish or fresh fish by-products. Particularly envisaged are kitchen waste and food waste of all kinds including calcium phosphates, fish or other aquatic animals as well as fish waste of all types, old food products based on animals which are no longer suitable for human consumption for reasons other than health risks, parts of slaughtered animals including calcium phosphates, shells and hatchery by-products and cracked egg by-products, animal waste from food industry including calcium phosphates, hooves or horn, meat kept too long, low quality meat, meat from animals under considerable stress, parts of slaughtered animals and animal by-products that have been attributed to the production of products for human consumption, defatted bones and animal meal.
    In a particular embodiment, the animal waste comprising calcium phosphates used in the context of the invention are animal meal or processed animal proteins.
    By "animal meal" is meant here a flour produced from animal products which are not consumable by humans and harvested by the animal breeding and fishing industry.
    The animal meal which can be used in the context of the invention can be chosen from most animal meal. Animal meal well adapted to the implementation of the invention are in particular animal meal called type C1 or C2 according to European regulations.
    In a particular embodiment, the mineral ash used in the context of the invention comes from C1 type animal meal.
    By “transformed animal proteins” or “PAT”, we mean here healthy animal by-products (animal flour of type C3 according to European regulations), typically from the conventional food chain, for example slaughtered for food purposes. human but some parts of which are not consumed for commercial reasons.
    By “mineral ash from calcined animal waste”, is meant here the animal waste residues comprising calcium phosphates, as defined above having undergone a calcination process.
    By "calcination" of animal waste is meant here a heat treatment sufficient to dehydrate animal waste and substantially eliminate the organic compounds originally present in animal waste, this calcination can in particular be carried out under conditions suitable for destroying all traces of prion possibly suspected. Thus, typically, the calcination of animal waste, in particular an animal meal or PAT, which can be used according to the invention can be implemented by a heat treatment of animal waste, in particular an animal meal or PAT, at a temperature above 400 ° C, preferably at least 500 ° C, more preferably at least 600 ° C, for example between 650 ° C and 800 ° C, for a period typically at least 30 min, in particular from 1 to 5 h, preferably from 1 h 30 to 4 h, more preferably for 2 to 3 h.
    In a particular embodiment, the mineral ash from calcined animal waste comprising calcium phosphates, in particular from calcined animal meal or PAT, supplied in step (a) are obtained by calcination of animal waste comprising phosphates from calcium, in particular from animal meal or PAT, at a temperature between 650 and 800 ° C for 2 to 3 h.
    The mineral ash used in the context of the invention typically comprises hydroxyapatite (Ca 10 (PO 4 ) 6 (OH) 2 ), triple phosphate Ca, Na, Mg (Ca 9 NaMg (PO 4 ) 7 ), rhenanite (CaNaPO 4 ), vishnevite (Na 8 AI 6 (SiO 4 ) 6 (SO 4 ), 12 H 2 O), sylvite (KCI), quartz (SiO 2 ) and possibly redistributed metals in phosphates.
    Step (b) of the process according to the invention consists in dissolving mineral ash as defined above in a hydrochloric acid solution.
    The inventors have in fact surprisingly shown that while one of the aims of the preparation process is to eliminate the chlorides present in the mineral ash from calcined animal waste comprising calcium phoshates, it is possible to eliminate these chlorides (following the precipitation step) using specifically hydrochloric acid, and not another acid, to dissolve these mineral ashes.
    Indeed, without being bound by theory, the dissolution of mineral ash as defined above in a hydrochloric acid solution involves in particular the following reaction:
    Ca 10 (PO 4 ) 6 (OH) 2 + 20 HCl θ 6 H 3 PO 4 + 10 CaCl 2 + 2 H 2 O and the acid solution obtained at the end of step (b) typically comprises in solution the H 3 O + , PO , Ca 2+ , CL, CO 3 2 ', Mg 2+ and Na + ions.
    This dissolution step (b) is typically carried out at room temperature.
    The hydrochloric acid solution used during step (b) of dissolution can be of any suitable concentration. As will be well understood by those skilled in the art, the amount of ash dissolved during step (b) of dissolution will depend on the concentration of the hydrochloric acid solution used.
    Typically, the hydrochloric acid solution used in the context of the invention can be a hydrochloric acid solution at a concentration of between 1 mole / L and 15 moles / L, preferably between 6 moles / L and 11 moles / L, or between 6.3 moles / L and 9.46 moles / L, for example between 6.5 moles / L and 7 moles / L, in particular 7 moles / L.
    Typically, the hydrochloric acid solution used in the context of the invention can be a hydrochloric acid solution at a concentration of between 3.5% and 37%, preferably between 23% and 30%, in particular 23 %.
    The inventors have also shown that by adding specific metallic elements at the end of step (b) of dissolution, it was possible at the end of the process for preparing or purifying hydroxyapatite, to obtain a hydroxyapatite functional, in other words a hydroxyapatite inserting specific metallic elements capable of specifically depolluting the soil or water with certain contaminants.
    The inventors have shown, for example, that by adding iron chloride at the end of step (b) of dissolution, it was possible to obtain a functional hydroxyapatite capable of specifically depolluting the soils or the arsenic waters; by adding copper chloride, it was possible to obtain a functional hydroxyapatite capable of specifically depolluting soils, waters or gases in selenium and / or iodine.
    Thus, in a particular embodiment, the process for preparing hydroxyapatite according to the invention, further comprises, at the end of the dissolution step (b), a step of adding metallic elements such as iron chloride, copper chloride or titanium oxide.
    Step (c) of the process according to the invention consists in filtering the acid solution obtained at the end of step (b) in order to remove the metal phases.
    By “metallic phase” is meant here the phase of the acid solution, obtained by dissolving mineral ash from animal waste calcined in hydrochloric acid, comprising metallic elements such as magnesium, aluminum, titanium , vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, niobium, cadmium, indium, antimony, tungsten, mercury, lead, thorium, arsenic or uranium in particular heavy metals such as vanadium, chromium, nickel, cadmium, mercury, lead, arsenic or uranium.
    The filtration step can be implemented by any suitable technique well known to those skilled in the art, making it possible to eliminate the metal phases. Typically, the filtration step can be carried out by gravity, with or without suction, with a filter press or by centrifugation.
    In a particular embodiment, the filtration step (c) also makes it possible to remove the remains of organic matter and the silica grains originating from the mineral ash.
    In a particular embodiment, the filtration step (c) is carried out by gravity, in particular in a decanter.
    Depending on the animal waste used to obtain the mineral ash, the concentration of heavy metals in the acid solution obtained in step (b) may be high enough for it to be advantageous to recover these eliminated heavy metals in order to recover them.
    Thus, in a particular embodiment, the metal phases eliminated from the acid solution are recovered in order to be optionally recovered. These metal phases are typically mainly oxides and chlorides of metals.
    Step (d) of the process according to the invention is a precipitation step by neutralization by mixing the filtered solution obtained at the end of step (c) with an NaOH or KOH solution, so as to obtain a precipitate comprising calcium phosphate (s), chlorinated compounds and sodium compounds.
    In particular, in the context of the invention, the precipitate obtained at the end of step (d) comprises, in addition to the calcium phosphate (s) of interest, as chlorinated compounds, NaCl, KCI, CaCI 2 and MgCI 2 and / or as sodium compounds of NaCI and Na 2 CO 3 .
    Depending on the calcium phosphate (s) to be prepared by the process of the invention, either the filtered solution will be added to the NaOH or KOH solution, or the NaOH or KOH solution will be added to the filtered solution .
    Thus, in the context of a process for the preparation of purified hydroxyapatite, step (d) of the process according to the invention is a precipitation step by neutralization by adding the filtered solution obtained at the end of the step. (c) in a solution of NaOH or KOH, so as to obtain a precipitate comprising hydroxyapatite, chlorinated compounds and sodium compounds.
    Alternatively, in the context of a process for the preparation of non-apatitic calcium phosphate (s), step (d) of the process according to the invention is a precipitation step by neutralization by adding a solution of NaOH or KOH in the filtered solution obtained at the end of step (c), so as to obtain a precipitate comprising non-apatitic calcium phosphate (s), chlorinated compounds and compounds sodes.
    Preferably, the addition of the filtered solution in a solution of NaOH or KOH, or respectively the addition of the solution of NaOH or KOH in the filtered solution, is carried out with stirring, for example under magnetic stirring.
    Preferably, when the filtered solution is added to the NaOH or KOH solution, the filtered solution is added dropwise to the NaOH or KOH solution. Alternatively, preferably, when the NaOH or KOH solution is added to the filtered solution, the NaOH or KOH solution is added dropwise to the filtered solution.
    At the end of the neutralization precipitation step, in the case of obtaining hydroxyapatite, the reaction medium has a pH greater than or equal to 7, preferably between 7 and 8. The final pH should not however not be less than 7.
    At the end of the precipitation by neutralization step, in the case of obtaining non-apatitic calcium phosphate (s), the reaction medium has a pH less than or equal to 7, preferably between 6 and 7. The final pH, however, must not be greater than 7.
    The NaOH or KOH solution used during precipitation step (d) can be of any suitable concentration.
    Typically, the NaOH solution used in the context of the invention can be a NaOH solution at a concentration of between 1 mol / L and 10 mol / L.
    Typically, the NaOH solution used in the context of the invention can be a NaOH solution at a concentration of between 4 and 30%, in particular 30%.
    Typically, the KOH solution used in the context of the invention can be a KOH solution at a concentration of between 1 mol / L and 10 mol / L.
    Typically, the KOH solution used in the context of the invention can be a KOH solution at a concentration of between 5.6% and 56%.
    As will be obvious to a person skilled in the art, the rate of neutralization of the NaOH or KOH solution with the filtered acid solution obtained at the end of step (c) (or respectively of the filtered acid solution obtained at step (c) with the NaOH or KOH solution) will depend on the concentration of the NaOH or KOH solution used and on the concentration of the hydrochloric acid solution used in step (b). Typically, if the hydrochloric acid solution used in step (b) is a 23% hydrochloric acid solution, it will be necessary to use in step (d) a volume of NaOH solution at 30% equal to the volume hydrochloric acid solution used in step (b) to obtain a final pH between 7 and 8.
    In a preferred embodiment, the precipitation step (d) is carried out by mixing, in particular by adding, the filtered solution obtained in step (c) in a NaOH solution.
    Stage (e) of the process according to the invention consists in washing, in water, the precipitate obtained at the end of stage (d), allowing the elimination of chlorinated compounds and sodium compounds from the precipitate and obtaining a slurry of purified calcium phosphate (s), in particular purified hydroxyapatite, the calcium phosphate (s), in particular hydroxyapatite, remaining insoluble in water at neutral pH unlike the chlorinated and sodium compounds mentioned above.
    This washing step is particularly important since it makes it possible to remove the large quantities of chlorinated and sodium compounds contained in the precipitate, which are soluble in water at neutral pH.
    Preferably, the washing step (e) is an abundant washing step, in particular a washing with water, typically at room temperature or at a temperature of 10 to 40 ° C.
    The optional step (f) of the process according to the invention consists in drying the slurry of purified calcium phosphate (s), in particular purified hydroxyapatite, obtained in step (e), at a lower temperature. or equal to 60 ° C.
    This optional step (f) is in particular not necessary when the purified calcium phosphate (s), in particular the purified hydroxyapatite, is (are) intended for certain applications, such as the depollution of soils or effluents, which do not require this drying phase.
    The use of a drying temperature less than or equal to 60 ° C. advantageously makes it possible to retain the low crystallinity of the hydroxyapatite which gives it properties of chemical reactivity of interest.
    Preferably, the hydroxyapatite mud is dried at a temperature between room temperature and 60 ° C., more preferably at a temperature of 60 ° C.
    The drying step can be carried out by any conventional drying technique at a temperature less than or equal to 60 ° C., such as by drying in an oven or in a drying tunnel.
    In a preferred embodiment, the drying step (f) is carried out by drying in an oven.
    The hydroxyapatite powder thus obtained has the advantage of having a very large specific surface, typically between 90 and 145 m 2 / g, giving it a very high chemical reactivity.
    The hydroxyapatite obtained by the process according to the invention has the advantage of being particularly pure, in particular free of heavy metals. It is therefore a prime raw material for the subsequent production of phosphoric acid and phosphogypsum, the use of which requires the absence of heavy metals.
    Thus, the present invention also relates to a process for the preparation of purified phosphoric acid not comprising heavy metals, comprising the steps consisting in:
    (i) providing purified hydroxyapatite obtained by the preparation process according to the invention; or implement the process for the preparation of purified hydroxyapatite according to the invention;
    (ii) dissolving the purified hydroxyapatite obtained in step (i) with sulfuric acid so as to produce purified phosphoric acid and purified phosphogypsum not comprising heavy metals, (iii) recovering the acid purified phosphoric thus produced; and (iv) optionally recovering the phosphogypsum not comprising heavy metals obtained in step (ii).
    Another object of the invention relates to a process for the preparation of purified phosphogypsum not comprising heavy metals, comprising the steps consisting in:
    (i) supplying purified hydroxyapatite obtained by the preparation process according to the invention, or implementing the process for preparing purified hydroxyapatite according to the invention, (ii) dissolving the purified hydroxyapatite obtained in step (i) with sulfuric acid so as to produce purified phosphoric acid and purified phosphogypsum not comprising heavy metals, (iii) recover the purified phosphogypsum thus produced, and (iv) optionally recover the phosphoric acid obtained in step (ii).
    Step (ii) of dissolving hydroxyapatite to produce phosphoric acid and phosphogypsum can be carried out by any technique well known to those skilled in the art.
    The present invention will be presented in more detail in the example below.
    Example
    This example shows that it is possible, from mineral ash obtained from calcined C1 type animal meal, to obtain purified hydroxyapatite by eliminating the heavy metals and the chlorinated and sodium compounds initially present without the mineral ash.
    The process for preparing hydroxyapatite used is as follows:
    (1) Dissolution: the mineral ash is dissolved at room temperature in a 23% hydrochloric acid solution. This concentration of hydrochloric acid dissolves 50 to 300 g of ash per liter.
    (2) Filtration: the acid obtained contains insoluble phases such as a residue of organic matter, grains of silica and metallic phases. Filtration of this acid eliminates these impurities.
    (3) Precipitation: the acid solution is neutralized with soda, by pouring the acid solution into the soda, drop by drop, with stirring. The reaction is exothermic and an abundant white precipitate is formed. The volume of 30% sodium hydroxide used is equal to the volume of hydrochloric acid used for dissolution and allows a final pH of between 7 and 8 to be obtained.
    (4) Washing: This step is very important because it eliminates the large quantities of sodium and chlorine phases contained in the precipitate. These highly soluble phases are easily removed by abundant washing with water. At the end, hydroxyapatite remains, which remains insoluble at neutral pH.
    (5) Drying: The very fine hydroxyapatite mud obtained is allowed to dry at a temperature not exceeding 60 ° C., so as to maintain the low crystallinity of the hydroxyapatite, the latter giving it properties of chemical reactivity .
    The chemical composition of the various products obtained was analyzed.
    a - Ash of animal meal type C1, before and after treatment
    elements Before treatment (pg / g) After treatment (pg / g) N / A 26,184.71 <175.57 Cl 18,642.50 <2.84 It 258,384.67 327,952.03 P 52,040.69 117,654.81 mq 1,721.35 8,274.03 al 43,369.73 9,041.60 Yes 56,905.74 29,472.44 S 24,030.75 712.80 K 37,872.22 1,290.62 Fe 6,095.19 6,104.50
    It is observed that all the contents decreased, except those in Ca and P.
    In particular, it is observed that the Na and Cl contents have almost disappeared.
    The final hydroxyapatite is thus purer with oxides: CaO = 46.18% and P 2 O 5 = 26.82%.
    b - Insoluble fraction eliminated during the filtration step
    For 1 kg of ash of type C1 processed animal meal, it is possible to extract 135 g of insoluble fraction during the filtration step.
    This insoluble fraction contains metallic elements with the following concentrations:
    elements pg / g insoluble pg / kg ash mg 2,407.05 324,951.75 al 25,077.43 3,385,453.05 Ti 1,116.85 150,774.75 V 43.85 5,919.75 Cr 157,22 21,224.70 mn 134.39 18,142.65 Fe 5,754.57 776,866.95 Co 10.57 1,426.95 Or 30.21 4,078.35 Cu 28.38 3,831.3 Zn 762.84 102,983.40 ga 12.53 1,691.55 Y 2.79 376.65 Nb 2.78 375.3 CD 4.60 621.0 in 4.55 614.25 Sb 25,14 3,393.9 W 13.06 1,763.1 Hg 4.76 642.6 Pb 46,90 6,331.5 Th 1.48 199.8 Total 35,533.68 4,692,670.2
    Thus in total, 4.7 kg of metals per tonne of mineral ash can be eliminated using the process according to the present invention.
    The process according to the present invention thus makes it possible both to very effectively remove the metals present in the mineral ash obtained from calcined animal meal, including animal meal of type C1, and to obtain a substantially purer hydroxyapatite which is almost devoid of Na and Cl.
    权利要求:
    Claims (10)
    [1" id="c-fr-0001]
    1. Process for the preparation of purified calcium phosphate (s) comprising:
    (a) a step of supplying mineral ash from calcined animal waste comprising calcium phosphates, in particular calcined animal meal or calcined transformed animal protein (PAT);
    (b) a step of dissolving the mineral ash in a hydrochloric acid solution;
    (c) a step of filtering the acid solution obtained in step (b) in order to eliminate the metal phases;
    (d) a precipitation step by neutralization by mixing the filtered solution obtained in step (c) with a NaOH or KOH solution, so as to obtain a precipitate comprising calcium phosphate (s), chlorine and sodium compounds;
    (e) a step of washing, in water, the precipitate obtained in step (d), allowing the elimination of chlorinated and sodic compounds from the precipitate and obtaining a mud of calcium phosphate (s) purified;
    (f) optionally, a step of drying the purified calcium phosphate mud (s) obtained in step (e), at a temperature less than or equal to 60 ° C; and (g) optionally, a step of recovering the purified calcium phosphate (s) thus prepared.
    [2" id="c-fr-0002]
    2. Preparation process according to claim 1, in which the purified calcium phosphate prepared is purified hydroxyapatite, and stage (d) of the process is a stage of precipitation by neutralization by addition of the filtered solution obtained in l 'resulting from step (c) in a NaOH or KOH solution, so as to obtain a precipitate comprising hydroxyapatite, chlorinated compounds and sodium compounds.
    [3" id="c-fr-0003]
    3. Preparation process according to claim 1, in which the purified calcium phosphate (s) prepared is (are) purified non-apatitic calcium phosphate (s) (s), and step (d) of the process is a precipitation step by neutralization by adding a solution of NaOH or KOH in the filtered solution obtained at the end of step (c), so obtaining a precipitate comprising non-apatitic calcium phosphate (s), chlorinated compounds and sodium compounds.
    [4" id="c-fr-0004]
    4. Preparation process according to any one of claims 1 to 3, wherein the hydrochloric acid solution used in step (b) is a hydrochloric acid solution at 7 moles / L.
    [5" id="c-fr-0005]
    5. Preparation process according to any one of claims 1 to 4, in which the filtration step (c) is carried out by gravity in a decanter and also makes it possible to remove the remains of organic matter and the grains silica.
    [6" id="c-fr-0006]
    6. Preparation process according to any one of claims 1 to 5, in which the metal phases removed from the acid solution are recovered in order to be optionally recovered.
    [7" id="c-fr-0007]
    7. Preparation process according to any one of claims 1 to 6, in which the drying step (f) is carried out by heating at 60 ° C in an oven.
    [8" id="c-fr-0008]
    8. Process for the preparation of purified phosphoric acid not comprising heavy metals, comprising the steps consisting in:
    (i) providing purified hydroxyapatite obtained by the preparation process according to any one of claims 2 and 4 to 7, or implementing the process for preparing purified hydroxyapatite according to any one of claims 2 and 4 at 7;
    (ii) dissolving the purified hydroxyapatite obtained in step (i) with sulfuric acid so as to produce purified phosphoric acid and purified phosphogypsum not comprising heavy metals, (iii) recovering the acid purified phosphoric thus produced; and (iv) optionally recovering the phosphogypsum not comprising heavy metals obtained in step (ii).
    [9" id="c-fr-0009]
    9. Process for the preparation of purified phosphogypsum not comprising heavy metals, comprising the steps consisting in:
    (i) providing purified hydroxyapatite obtained by the preparation process according to any one of claims 2 and 4 to 7, or implementing the process for preparing purified hydroxyapatite according to any one of claims 2 and 4 at 7;
    (ii) dissolving the purified hydroxyapatite obtained in step (i) with sulfuric acid so as to produce purified phosphoric acid and purified phosphogypsum not comprising heavy metals, (iii) recovering the purified phosphogypsum thus produced, and (iv) optionally recovering the phosphoric acid obtained in step (ii).
    [10" id="c-fr-0010]
    10. Process for the purification of hydroxyapatite from hydroxyapatite loaded with heavy metals, comprising:
    (a) a step of supplying hydroxyapatite loaded with heavy metals;
    (b) a step of dissolving the hydroxyapatite loaded with heavy metals in a hydrochloric acid solution;
    (c) a step of filtering the acid solution obtained in step (b) in order to remove the heavy metals;
    (d) a precipitation step by neutralization by adding the filtered solution obtained in step (c) in a NaOH or KOH solution, so as to obtain a precipitate comprising hydroxyapatite, chlorinated compounds and compounds soda;
    (e) a step of washing, in water, the precipitate obtained in step (d), allowing the elimination of chlorinated and sodium compounds from the precipitate and obtaining a purified hydroxyapatite mud;
    (f) optionally, a step of drying the purified hydroxyapatite mud obtained in step (e), at a temperature less than or equal to 60 ° C; and (g) optionally, a step for recovering the purified hydroxyapatite thus prepared.
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    同族专利:
    公开号 | 公开日
    RU2020125552A|2022-01-31|
    EP3746400A1|2020-12-09|
    WO2019149898A1|2019-08-08|
    FR3077285B1|2022-01-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    BE402023A|
    JPH02188415A|1989-01-17|1990-07-24|Toyo Denka Kogyo Kk|Natural hydroxyapatite, or the like and production thereof|
    FR2678258A1|1991-06-28|1992-12-31|Metallisation Ind Ste Nle|Process for the preparation of natural or semi-synthetic hydroxylapatite or of tricalcium phosphate from natural apatites|
    WO1996037433A1|1995-05-22|1996-11-28|Advance Co., Ltd.|Method of treating bone charcoal, product of said method, method of extracting apatite from untreated bone or bone ash, and apatitic material|CN111892314A|2020-08-17|2020-11-06|云南磷化集团有限公司|Deep purification method of phosphogypsum|EP3302763A1|2015-06-03|2018-04-11|Solvay SA|Process for treating a gas contaminated by metals or organics compounds using a calcium-phosphate reactant comprising apatite|CN111017894A|2019-12-31|2020-04-17|云南力达一矿物技术有限公司|Method for preparing clean phosphoric acid and high-purity gypsum by decomposing ground phosphate rock with hydrochloric acid|
    法律状态:
    2018-12-20| PLFP| Fee payment|Year of fee payment: 2 |
    2019-08-02| PLSC| Publication of the preliminary search report|Effective date: 20190802 |
    2020-01-13| PLFP| Fee payment|Year of fee payment: 3 |
    2021-01-22| PLFP| Fee payment|Year of fee payment: 4 |
    2022-01-12| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1850842A|FR3077285B1|2018-02-01|2018-02-01|METHOD FOR THE PRODUCTION OF VERY PURE HYDROXYAPATITES FROM WASTE CONTAINING CALCIUM PHOSPHATES, IN PARTICULAR ANIMAL MEAL|
    FR1850842|2018-02-01|FR1850842A| FR3077285B1|2018-02-01|2018-02-01|METHOD FOR THE PRODUCTION OF VERY PURE HYDROXYAPATITES FROM WASTE CONTAINING CALCIUM PHOSPHATES, IN PARTICULAR ANIMAL MEAL|
    PCT/EP2019/052519| WO2019149898A1|2018-02-01|2019-02-01|Method for producing very pure hydroxyapatites from waste containing calcium phosphates, particularly meat and bone meal|
    EP19702277.5A| EP3746400A1|2018-02-01|2019-02-01|Method for producing very pure hydroxyapatites from waste containing calcium phosphates, particularly meat and bone meal|
    RU2020125552A| RU2020125552A|2018-02-01|2019-02-01|METHOD FOR PRODUCING VERY PURE HYDROXYAPATITES FROM WASTE CONTAINING CALCIUM PHOSPHATES, IN PARTICULAR FROM ANIMAL MEAL|
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