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    • 专利摘要:
    The invention relates to a process for the efficient semicontinuous preparation of manganese thiosulfate (MnS2O3., MnTS) from manganese hydrosulfite and high temperature sulfur. The process comprises the preparation of manganese hydrosulfite from manganese carbonate and sulfur dioxide under certain conditions, i.e., molar ratios, pH, time and temperature.
    公开号:BE1019952A3
    申请号:E2011/0091
    申请日:2011-02-14
    公开日:2013-03-05
    发明作者:Michael Massoud Hojjatie；Constance Lynn Frank Lockhart；Thomas D Fairweather
    申请人:Tessenderlo Kerley Inc；
    IPC主号:
    专利说明:

    "Method and apparatus for preparing a solution of manganese thiosulfate (MnTS)"
    FIELD OF THE INVENTION
    The present invention relates to nutritive solutions for plants, and more particularly to nutrient solutions for plants containing manganese thiosulfate.
    DESCRIPTION OF RELATED ART The thiosulfate ion, S2O32 ', is a structural analogue of the SO42 · ion in which an oxygen atom is replaced by an S atom. However, the two sulfur atoms in S2CV2 are not not equivalent. One of the S atoms is a sulfur-type sulfur which gives the thiosulfate its reducing properties and complexing properties.
    Thiosulphates are used in leather tanning, paper and textile manufacturing, flue gas desulphurisation, cement additives, dechlorination, deactivation of ozone and hydrogen peroxide, coating stabilizers etc.
    Because of their ability to form complexes with metals, thiosulfate compounds have been used in commercial applications such as photography, waste treatment and water treatment.
    The thiosulphates oxidize easily to dithionate, then to tetrathionate and finally to sulphates:
    Because of this transformation, thiosulfates are used as fertilizer in combination with cations such as ammonium, potassium, magnesium and calcium cations. Ammonium, alkali metal and alkaline earth metal thiosulfates are soluble in water. The solubilities of thiosulfates in water decrease from ammonium thiosulfates to alkali metal thiosulfates to alkaline earth metal thiosulfates.
    Manganese is an important element found in free form in nature (often in combination with iron) and in many minerals. Manganese is referred to herein as both "manganese" and "Mn". The free element is a metal having important uses in industrial metal alloys. Manganese (II) ions function as cofactors for a number of enzymes; the element is therefore a mineral trace required for all known living organisms. It is used as a nutrient for animals and plants, for example as food supplements for animals and in plant fertilizers.
    Manganese is important in the photosynthetic evolution of oxygen in chloroplasts of plants, which are also, in terms of evolution, bacterial origin. The oxygen-releasing complex, a water-oxidizing enzyme in the chloroplast membrane, which participates in the terminal photooxidation of water during photosynthesis reactions, has a metal coenzyme nucleus containing four manganese atoms ( G. Charles
    Dismukes, and Rogier T. van Willigen, Encyclopedia of Inorganic Chemistry, Wiley InterScience, 2008). For this reason, most broad-spectrum fertilizers for plants contain manganese.
    The symptoms of manganese deficiency vary among cultivated plant species. Manganese deficiency is widespread in soybeans. The green of the leaves first becomes clearer, then the leaves gradually turn yellow. Manganese deficiency is also prevalent in tomatoes, whether grown in greenhouses or fields. It is manifested firstly by the fact that the green of the leaves in the internervure zone becomes clearer and then gradually turns yellow. For aubergine, Mn deficiency is common in high pH soils and in highly oxidized soils such as dry soils with low organic matter. Deficiencies of manganese have been observed in watermelon, grapes, passion fruit, citrus fruits, tea, blackberries and most other crops.
    Deficiencies of manganese also occur in trees. This usually happens in soil with a high alkaline pH. Manganese deficiency occurs in apple orchards planted in hardwood. Growers often make foliar applications of Mn when tissue analysis indicates low levels or when tree growth is poor due to low levels in the soil. Nurserymen reported manganese deficiency in silver firs. Mn deficiencies have been observed in avocados, peaches, red maples and palms. Soil samples from grass fields in recent years have indicated that manganese levels have dropped. During planting, growers typically spray a solution of manganese sulfate (MnSO4) once a week. Older fields, however, are missing and additional applications are needed.
    Plants can only absorb manganese when in solution as a divalent cation (Mn2 +). Mn2 + is referred to as the reduced form. Mn can also be present in oxidized forms (Mn3 + and Mn4 +), neither of which can be absorbed by plants. Microorganisms in the soil oxidize Mn2 + to Mn3 +, making it unavailable to plants. This biological reaction occurs slowly when the pH of the earth is between 5 and 6.5. However, it occurs more rapidly when pH increases to 7.5 (Russell E. W., Soil Conditions and Plant Growth, 11th Edition, Longman Scientific & Technical, Essex, England, 1988).
    The form of manganese in a soil system largely depends on the functioning of soil micro-organisms, and their activity depends on the pH of the soil. Manganese can be reduced (from Mn3 + to Mn2 +), making it available to plants, either chemically or by other soil microorganisms that function more efficiently at low pH (Russell, 1988). The increased reduction of Mn to Mn2 + can also result from the action of secreted material by the roots of plants. These secretions are solutes that help in the acquisition of nutrients, increase root tolerance at high concentrations of aluminum and / or act as a lubricant when roots grow through the earth. Organic acids contained in root exudates, particularly malic acid, increase the solubility of Mn in the soil, making it available to plants. Attachment of Mn2 + to organic compounds in root exudates (chelation) prevents Mn2 + from re-oxidizing to the unavailable form (J. Atland, North Willamette Research and Extension Center, Oregon State University, 2006).
    Manganese (Mn) is relatively immobile in the earth. Therefore, Mn applied to the soil surface will remain on the surface. To change Mn levels in the soil and prevent Mn deficiencies, the Mn must be distributed through the root zone so that all roots can intercept and absorb it. Plants have a vascular system to move water, metabolites and solutes from one place to another. The vascular system of plants consists of two components, xylem and phloem. The xylem transports dissolved water and nutrients upwards, from the roots to the foliage system, virtually without downward movement. The phloem carries water, metabolites and solutes in all directions across the plant. Mn is absorbed by the roots and rises to the leaves via the xylem; however, Mn can not be transported via phloem. Therefore, Mn accumulated in leaves can not be remobilized in significant amounts (Graham, R.D., Hannan, R.J., and Uren, N.C., Manganese in Plants and S, Kluwe Academie Publishers, Boston, MA, 1988).
    Similarly, the Mn absorbed by the foliage directly via foliar sprays will not leave the foliar system to return to the stem or root tissue. Although foliage may be made more green and healthy by complementary foliar application of Mn, the root systems on these plants will still be deficient. Similarly, the Mn absorbed by one root can not be redistributed to another part of the root system (Nable, RO, and Loneragan, JF, "Translocation of Manganese in Subterranean Clover", Aust J. Plant Physiol., 11, 113-118, 1984).
    Manganese plays four major roles in plant growth and development. He is involved in the ability of the plant to capture the energy of light for use in photosynthesis. In the metabolism of nitrogen (N), it plays a role in the conversion of nitrate to ammonium, probably by interaction with an enzyme known as nitrate reductase (Marschner, H., Mineral Nutrition of Higher Plants, 2nd Edition, Academie Press , Inc., San Diego, CA, 1997). The role of Mn as a precursor of the auxin plant hormone is critical for the production of nursery crops. Mn activates the auxin oxidase system (Russell, Soil Conditions and Plant Growth, 11th edition, Longman Scientific & Technical, Essex, England, 1988). Mn deficiency reduces auxin levels and causes hormonal imbalance. A decrease in the ratio of auxin to other plant hormones reduces lateral root development and root extension 8-12, 1998). (Landis, T.D., and van Steenis, E., "Micronutrients-Manganese", Forest Nursery Notes, Winter: 8-12, 1998). Finally, Mn plays a vital role in the production of carbohydrates. Carbohydrates are molecules containing carbon, hydrogen and oxygen that are used by plants for energy storage. A large amount of carbohydrates are produced in the leaves by photosynthesis. These carbohydrates can be used locally to feed cellular processes within the leaf or they can be transported to other parts of the plant for use as energy sources. During the winter when plants are dormant, carbohydrates are stored in the stem tissue and roots. Carbohydrates stored in the root system are important for root regeneration the following year. Mn deficiency reduces the ability of the plant to produce carbohydrates and thus reduces the ability of the harvested plant to regenerate roots and to grow vigorously when it is replanted the following year. Farmers need to manage soil pH to increase the availability of Mn for plants. For example, for red maple, growers increase or decrease soil pH at the target level from 5.0 to 5.6.
    The most common Mn (II) carriers are manganese sulfate, MnSO 2, manganese carbonate, MnCO 3, and manganese chloride, MnCl 3. These Mn (II) nutrient sources for plants are all in solid form. They must be predisposed to prepare an adequate solution. Dusting is a problem when using these materials. The values of solubility in water and the respective pH values of these plant Mn nutrient sources are reproduced in Table 1 which follows:
    Table 1. Solubility (in 100 g of water @ 25 ° C) and pH of certain manganese compounds
    A key point regarding the availability of manganese (Mn) in soil depends mainly on soil pH. Mn is not mobile in the soil; it must be incorporated in the soil before planting, the Mn passes from the roots of the plant to the foliage but is otherwise immobile in the plants. It must be available for plant roots where it can be absorbed and distributed throughout the plant. Mn deficiency must be prevented by management practices before planting.
    It is very important to have a soil with a low pH and / or adjust the soil pH before planting to avoid manganese deficiency. A minimum pH of 5.0 and a maximum pH of 5.7 have been recommended for effective uptake of Mn by many crops and trees (Atland, J., Oregon State Extension Service Report, March 2006). The three aforementioned common sources (MnSC> 4, MnCCh, and MnCI2) of Mn nutrient for plants are solid. The solubility of the manganese carbonate is very low. Although the solubility of manganese chloride and manganese sulfate is high, the pH values of their solution are higher than the recommended pH for effective Mn uptake by plants.
    Manganese thiosulfate, also referred to herein as "MnTS", is a liquid source of Mn with a concentration of up to 20%. The advantage of this material lies in the fact that it is a high concentration source of Mn (II) in liquid form that could be used easily without premixing, while avoiding the generation of dangerous dust. A solution of manganese thiosulfate has a pH of 5-6 at 25 ° C. Its liquid form and its own pH characteristics make this Mn source a very unique product.
    Surprisingly, a viable commercial approach to the production of manganese thiosulfate is not described in the literature.
    Kvasha, V., Vasillishin, N., Krivonos, V., and Kmita, I. in the Ukrainian Dairy Science Journal, 1991 reported the use of "manganese thiosulphate" as a milk substitute component for calf rearing. . No source of "manganese thiosulfate" is mentioned. Patent Application No. 957638/02, GB-A, 1938, discloses a process for obtaining approximately pure manganese compounds by treating manganese-containing starting materials which have been roasted in their MnO 2 oxide form with dioxide of sulfur to produce manganese dithionate and manganese sulfate at elevated temperature.
    The present invention relates to an efficient and cost-effective method for preparing solutions of manganese thiosulfate. The present invention also relates to the production of high concentration manganese thiosulfate product solutions which utilize relatively inexpensive starting materials and form few by-products.
    SUMMARY OF THE INVENTION
    One aspect of the present invention relates to a process for preparing manganese thiosulfate using manganese carbonate, MgCO 3, sulfur dioxide and sulfur as starting materials. The method comprises providing a suspension of manganese hydrogen sulfite. Sulfur dioxide is purged in a solution of manganese carbonate to produce a suspension of a mixture of manganese hydrogen sulfite and manganese carbonate. Carbon dioxide is formed as a gaseous product. The reaction mixture is heated. Sulfur is then added to the mixture which is reacted under suitable conditions to form manganese thiosulfate and the manganese thiosulfate is recovered.
    It is possible to prepare liquid solutions containing high concentrations of manganese thiosulfate which have only minimal amounts of solid by-products. Solid by-products may optionally be recycled in the batch for later use. Waste by-products consist of manganese carbonate, unreacted excess sulfur and insoluble impurities in the commercial raw material MnC03. The reaction conditions of the manganese carbonate with the sulfur dioxide and the sulfur, for example molar ratios, pH, time and temperature, are preferably selected to minimize the amount of by-products and increase the product yield. , manganese thiosulfate.
    According to another aspect of the invention, a solution of manganese thiosulfate consists of an aqueous medium containing at least about 20% by weight of MnS 2 O 3, up to about 7% by weight of sulfur, and up to about 6% by weight. weight of Mn. The pH of said solution is about 5-6 at 25 ° C. The solid byproducts present in the process preferably represent less than 2% by weight.
    BRIEF DESCRIPTION OF THE DRAWINGS
    The present invention will now be described in more detail with reference to preferred embodiments of the invention, provided by way of example only, and to the drawings in the accompanying drawings in which:
    Figure 1 is a graphical illustration of the reaction kinetics of MnS203 for molar ratios of MnCO3 = 1.00, 1.05, 1.10: 1.00 SO2: 1.20S;
    Figure 2 is a graphical illustration of the reaction time versus concentration of the manganese thiosulfate product;
    Figure 3 is a graphic illustration of the objective concentration of manganese thiosulfate (by raw material) versus the weight of solid and the percentage of solid forms (by raw materials);
    Figure 4 is a graphical illustration of the reaction kinetics of manganese thiosulfate using different amounts of raw materials and comparison of kinetics using tire sulfur (TS) versus purified sulfur (PS);
    Figure 5 is a graphical illustration of residual solid for the manganese thiosulfate reaction, using raw materials for predicted concentrations of 15-20%, the sulfur source being tire sulfur (TS) or industrial sulfur;
    Figure 6 is a graphical illustration of the progression of the manganese thiosulfate reaction for predicted product concentrations of 15-20%;
    Figure 7 is a graphical illustration of the target concentration of the manganese thiosulfate reaction product versus residual solids;
    Figure 8 is a graphical illustration of the reaction kinetics of manganese thiosulfate at 97 ° C versus 90 ° C;
    Fig. 9 is a flowchart of the method, including a schematic illustration of a method according to a first embodiment of the invention; and
    Fig. 10 is a schematic illustration of equipment and flow, according to one embodiment of the present invention.
    DETAILED DESCRIPTION OF THE INVENTION
    The process of the present invention is described herein as proceeding along the following reaction path: 2MgCO3 + 2SO2 + H2O → Mn (HSO3) 2 + MnCO3 + CO2 (g) (1)
    Mn (HSO 3) 2 + MnCO 3 + 2S - 2MnS 2 O 3 + H 2 O + CO 2 (g) (2)
    Reaction (1) involves the synthesis of the intermediate product Mn (HSO3) 2. The intermediate product is a suspension, which typically comprises a mixture of Mn (HSO 3) 2 / MnCO 3 in solution and in the solid state. For convenience, the intermediate product is referred to herein as hydrogen sulfite manganese, Mn (HSO3) 2 or MnHS, because it is the predominant species that has been measured in the solution. Reaction (2) involves the use of this intermediate product for the preparation of the manganese thiosulfate product. As shown above, the total stoichiometric reaction generates one mole of water and two moles of carbon dioxide per two moles of manganese thiosulfate generated.
    Unless otherwise indicated by context, all percentages in this document refer to percentages by weight.
    Referring to Figure 10, the first step of the synthesis, the reaction comprises the synthesis of manganese hydrgenosulfite. Manganese carbonate, MnCO3, is charged to the reactor. Water is charged to the reactor in a volume consistent with the target concentration of the product.
    Effective agitation is applied to the MnCO 3 suspension and throughout the process. SO2 is preferably purged in the MnCO3 slurry to adjust the pH to about 2 to 3. Since the purge process generates heat, external energy application is generally not required at this stage of the process. .
    For the purposes of calculating the quantities of raw materials, the molar ratio of sulfur dioxide is taken as 1. In addition, the quantities of raw materials are adjusted relative to their purity. The new raw materials (eg, MnC03 and S) are also reduced, accordingly, relative to the amount of residual recycled solids produced during the process.
    The product Mn (HS03) 2 is a light suspension. The solubility of this intermediate product depends on such factors as the initial concentration of manganese carbonate, the pH and the temperature of the product. The amount of solid in the slurry increases as the pH increases.
    Reaction (2) comprises the conversion of Mn (HSO 3) 2 to MnS 2 O 3. The prescribed amount of S is charged to the reactor. Sufficient external heating is applied to bring the reaction solution to a temperature of about 96 to about 99 ° C (205-210 ° F). The application of heat is preferably limited to the minimum required to reach the prescribed temperature range. When the heat (temperature) applied is too intense, the temperature of the reaction will not change significantly. However, an increase in applied heat will increase the evaporation of the solution. Evaporation may be deleterious to the reaction, particularly until the poorly soluble Mn (HSO3) 2 has been converted to manganese thiosulfate.
    Once in the temperature range of about 205-210 ° F (96-99 ° C), the reaction continues, with stirring, until conversion to MnS2O3 is complete. It has been shown that reaction kinetics depend on raw materials.
    The reaction can be carried out at lower temperatures; however, for a temperature decrease of 5-10 ° C (40-50 ° F), the reaction time increases from 4-8 hours to 10-12 hours.
    The reaction is carried out for 4-8 hours at 96-99 ° C (205-210 ° F) or until all of the intermediate Mn (HSO3) 2 has been removed by reaction. The bulk of the reaction occurs during the first two hours of the process.
    The reaction can be carried out for product concentrations, effectively up to about 19% MnTS by weight. The optimal reaction is for 15% MnTS, insofar as raw materials are used. The kinetics of the reaction are improved when the raw materials are increased to levels consistent with a 19% product, at the cost of more residual solids. (15-19% of MnTS correspond to 4.9-6.2% of Mn and 5.8-7.3% of S.)
    The conversion of Mn (HS03) 2 to MnS2O3 occurs in the suspension state. The consistency of the suspension diminishes as the reaction progresses. The pH is preferably maintained at about 4-6 during reaction (2), adding incremental amounts of MnCO 3.
    The purity of the raw materials, eg manganese carbonate and sulfur, influences the concentration of the manganese thiosulfate product and the amount of residual solid byproducts. When using reactive and pneumatic type MnCO 3 raw materials, the residual solids range from 0.5% of the raw material weight for a 15% product to 2% by weight of raw material for an 18% product. .
    In order to determine the solubility of manganese thiosulfate (MnTS), MnTS was prepared by salt exchange of MnSO4 with calcium thiosulfate, and was evaporated to the point of crystal formation. A saturated solution of MnTS showed 5.85% Mn (-17% MnTS).
    In order to evaluate the appropriate raw material for the production of MnTS from Mn (HSOs), a series of reactions were performed. The intermediate product was prepared by purging SO 2 either in Mn (OH) 2 or in MnCl 3. All MnO / MnCC> 3 raw materials were added to water at the start of the reaction. The temperature increased to 40-45 ° C while purging the SO 2. An indication that the process was complete was provided by the decrease in the temperature of the suspension. MnTS reactions were performed at 96 ° C. The results showed that MnCO3 was more suitable for the preparation of the target concentration of MnTS. The data are shown in Table 2.
    Table 2. Synthesis of MnTS
    The solubility of MnTS was determined by measuring the amount of solid, generated by evaporation of the MnTS solution that could be redissolved in the aqueous solution at room temperature. Maximum solubility was determined to be about 17-18%, as calculated from the concentration of Mn. We sought to optimize the MnTS solution through the reaction process: 2MnC03 + 2SO2 + H2O → Mn (HS03) 2 + MnCO3 + CO2 (1)
    Mn (HSO 3) 2 + MnCO 3 + 2S 2 MnS 2 O 3 + H 2 O + CO 2 (2)
    It has been determined that excess S and MnCO3 should be used in raw materials to optimize product concentration and process kinetics. In one reaction, the molar ratio of raw materials was 1.05: 1.00: 1.20 MnCO 3: SO 2: S, the relative moles of SO 2 being taken as 1 for the calculation of raw materials S and MnCO 3. S02 was added until the pH stopped decreasing, the temperature began to drop and the Mn (HS03) 2 product was almost completely in solution (i.e., dissolved). The raw materials used were: 65.10 g MnCO 3 499.8 g H 2 O
    S02 at a pH of ~ 1.8 (starting from an initial pH of 6.36), temp. = 42 ° C
    21.37 g of S
    The progression of the associated thiosulfate process follows in Table 3.
    Table 3. Progression of MnTS preparation
    The products of this reaction consisted of 570.1 g of filtrate and 3.7 g of solid. The filtrate showed 14.89% MnTS, 0.06% alkalinity as Mn (OH) 2, MnHS, 4.88% Mn, specific gravity = 1.156 @ 24 ° C. and the pH = 4.93.
    MnTS can not be produced at high concentrations simply by adjusting the molar ratios of raw materials (reagents), as shown below. Reaction kinetics with varying target product concentrations were performed. MnTS reactions were performed to compare reaction kinetics when raw materials were added to obtain 15% to 20% (ie 15-20% by weight of MnTS in water) from MnTS. The theoretical molar ratios = 1.05 MnCO 3: 1.00 SO 2: 1.20 S. The progression of the reaction is demonstrated in FIG. 1. When the raw materials are increased to a level where the projected product (MnTS) must have at a concentration of 20%, the concentration of MnTS is only 3% after 2 hours of reaction compared to the use of raw materials at a level where the projected product (MnTS) must have a concentration of 15% and the MnTS concentration is 10.5% after 2 hours of reaction. Moreover, when the raw materials are increased to a level where the projected product (MnTS) must have a concentration of 20%, the concentration of MnTS only reaches after 9 hours 9%. The product of a projected 15% reaction is 15%. These data illustrate the problem encountered when the raw materials of MnTS are at a level where the corresponding concentration of the product is too high. There must be an appropriate amount of aqueous solvent present in the reaction mixture to allow the relatively insoluble intermediates to enter the solution. An MnTS concentration of up to 17% is preferably produced by the process of the invention, and the concentrate may be increased by evaporation of the water solvent. Thus, the invention provides a method for producing MnTS with a preferred concentration of 17-20% by weight.
    A series of reactions were performed to measure the progress of the reactions over time as well as the amounts of residual solids when raw materials were added in agreement with the target concentrations of 15 to 20% by weight (15, 16, 17 , 18 and 20% by weight) of MnTS. The solubility of MnTS was previously determined to be ~ 17%. In all cases, reactive MnCC 3 was prepared as an aqueous suspension. The suspension was purged with SO2 until the pH was -2. The resulting product was a dilute suspension of manganese hydrogen sulfite. Sulfur was then added to this intermediate and heat was applied to reach temperatures of 97-98 ° C. The molar ratio = 1.05: 1.00: 1.20 MnCO 3: SO 2: S, when the molar amount of SO 2 is theoretically 1.00 for calculation purposes. Each reaction was carried out for 10 hours. Each progress product was analyzed every 2 hours. The progress of the reaction, by MnTS analysis, is plotted in FIG.
    The measurements indicate that the process is most effective the first two hours of the reaction. The reaction is complete after 6 hours at 96-99 ° C. Consistent with solubility studies, MnTS analysis does not exceed 17%. The target product of the analysis, by added raw materials, is only 15%. The actual weight and percent by weight of all raw materials remaining as residual solids are shown in the diagram of Figure 3. The residual solids range from 4 to 14 g, for target product reactions of 15-18%, respectively, for -650 g of raw materials. The percentages by weight of residual solids relative to the raw materials range from 0.5 to 2%. MnTS at 17% can be produced with minimal loss of raw materials.
    Kinetic reaction studies of MnTS were continued at projected MnTS concentrations by comparing sulfur feedstocks, i.e., at target concentrations of tire sulfur and pure sulfur at 15, 16, 17 , 18 and 20% by weight. Three types of sulfur were used as raw material, purified sulfur, industrial sulfur and "tire sulfur". S02 was purged in a suspension of MnCO3 until the pH was ~2. Sulfur was added to the manganese hydrocyanenosulfite intermediate, MnHS, and heated. The MnTS reaction was carried out for 10 hours at 96-99 ° C, the product being evaluated every 2 hours. The molar ratio MnCO3: SO2: S = 1.05: 1.00: 1.20, when the theoretical amount of SO2 was based on stoichiometry. The comparative reaction kinetics, expressed in% MnTS in the product solution, appears in FIG. 4 for reactions using pneumatic sulfur and purified sulfur as raw material, and in FIG. pneumatic and industrial sulfur. The term "tire sulfur" refers to sulfur recovered from spent tires, typically by burning spent tires and recovering sulfur. The term "purified sulfur" refers to reactive sulfur, and the term "industrial sulfur" refers to the type of sulfur commonly used as a refining source and used in industry as a raw material. It has been found that tire sulfur tends to react more rapidly and to give a lower level of residues (by-products) than industrial sulfur.
    On the basis of the final concentration of the product, the optimal reaction kinetics was reached when the raw materials matched a 19% MnTS product. The best concentration obtained in the 19% reaction was MnTS at 17.9%. The reaction was essentially complete after 6 hours of reaction. Figures 4 and 5 show the effects of sulfur as raw material, purified sulfur, industrial sulfur and tire sulfur, on the kinetics of reaction and the formation of residues (by-product).
    With the exception of the reaction carried out using raw materials matching with a 20% product, the reaction progress more than doubled in efficiency when tire sulfur was used as the sulfur raw material.
    Figure 5 illustrates the amounts of residual solid (by-product) that were recovered in each reaction.
    Consistently with the analysis, the residual solid was negligible using raw materials for a projected concentration of up to 19% MnTS, when tire sulfur was used as a sulfur feedstock. The residue ranged from 0.6 to 2.1% raw materials.) When purified sulfur was used for the same projected product concentrations, the residual solids ranged from 6.9 to 15.3% raw material.
    A series of reactions was designed to compare the relative kinetics of varying target product concentrations (15 to 20%, i.e., 15, 16, 17, 18, 19, and 20% by weight). The raw materials consisted of reactive MnCO3 and SO2 and tire sulfur. MnCO3: SO2: S = 1.05: 1.00: 1.20, when the SO2 concentration was based on stoichiometry for determination of other raw materials. The SO 2 was purged in a suspension of MnCO 3 until the pH was ~ 2. The MnTS reaction itself was carried out for 10 hours at reaction temperatures of 97-98 ° C. The analysis for MnTS versus reaction time is shown in Figure 6.
    From Figure 6, the target reactions of 19% and 20% result in MnTS at 17-18%. However, the target reaction of the product at 20% was terminated after 4 hours, while the intended reaction of the product at 19% was completed after 6 hours.
    In Figure 7, the target concentration of MnTS is plotted against the residual solid.
    The solid increases as the levels of raw materials increase. Residual solids are the most abundant in the 20% target reaction. However, even in the 20% reaction, the residual solids represent only 2.4% of the raw materials used.
    The effect of temperature on the kinetics of the manganese thiosulfate process was also studied. The target concentration of the product was 20%. However, in this reaction, the temperature was 90 ± 2 ° C. The comparison of reactions for the target product at 20% produced at 98 ° C versus 90 ° C is shown in Figure 8.
    The MnTS reaction occurred at 90 ° C, but after 10 hours the reaction was still not complete. The pH was also lower (3.7-4.3 vs 5.6-6.1), consistent with higher levels of manganese hydrogen sulfite (0.66 to 2.81% vs. 0-0.44). %), and no alkalinity (0-0.05% vs. 0.09-0.15%) in the reaction performed at 90 ° C. The residual solids weighed 14.2 g, 2.2% of raw materials used. When the reactions were carried out at 97 ° C, the appearance of the residual solid resembled that of the manganese raw materials. The residual solid resulting in the reaction carried out at 90 ° C, of appearance, was only sulfur.
    Characterization of solid byproducts of MnTS reactions was determined. Three different solids from MnTS processes were extracted and analyzed. The solids consisted of residual solid typical of syntheses carried out at 97 ° C., the residual solid similar to the sulfur recovered from the reaction at 90 ° C. and the sediment which appears in the filtrates of MnTS product when the concentration is greater than 17%. The solids were extracted with either 10% HCl to perform analysis for Mn ++ by atomic absorption spectroscopy, deionized water for titration for alkalinity, MnHS and MnTS or CS2 for analysis for the free sulfur. The results are shown in Table 4.
    Table 4. Solids analysis from MnTS synthesis and filtrate sediment
    In the typical solid, Mn ++, which does not come from MnTS or MnHS, was detected by calculation, and unreacted sulfur. Mn ++ is probably raw material MnC03 that has not reacted. The reaction residue at 90 ° C was almost entirely sulfur. (In order to optimally utilize the expensive MnCO3 feedstock, the lower temperature reaction may be more appropriate - at the expense of kinetics.) Finally, the sediment that was removed from 578 g of MnTS filtrate weighed only 0.26 g. Based on the analysis for MnTS, the small amount of sediment appears to be predominantly MnTS from overconcentrated solutions. (The solubility of MnTS is 17-18%.)
    EXAMPLES
    The following examples are provided for illustrative purposes and should not be construed as limiting the scope of the invention. The example illustrates the preparation of MnS203 solution and solid products. The molar ratio of 1.05: 1.00: 1.20 of MnCO3: SO2: S was the basis of the reaction paths described below: 2.10MnCO3 + 2.00SO2 + 1.00H2O 1.00Mn (HSO3) 2 + 1.10MnCO3 + 1.00CO2 (g) (1) 1.00Mn (HSO3) 2 + 1.10MnCO3 + 2.40S 2.00MnS2O3 + 1.00H2O + 1.00CO2 (g) + 0.10MnCO3 + 0.40 S (2)
    Example 1
    This example illustrates a one-pot reaction synthesizing the intermediate hydrogen sulfite (Mn (HSC> 3) 2, MnHS) and the subsequent production of manganese thiosulfate (MnS2C> 3, MnTS) and solid products. The raw materials used were 65.10 g of MnCO3 (purity 99%), 499.8 g of H 2 O (DI), enough SO 2 to lower the pH from an initial pH of 6.36 to a pH of ~ 1, 8. MnCO3 was transferred to a 1000 ml round bottom flask. The prescribed amount of water has been added. The suspension was stirred sufficiently using a rod stirrer (bar and vertical blade). The suspension product was of moderate thickness and was brown in color.
    The SO 2 was then purged at a moderate rate of continuous gas bubbles in the MnCO 3 slurry with gentle stirring. The original pH of MnCO3 was 6.36. Sufficient SO 2 was added to lower the pH to about 1.8 pH units. The addition of SO 2 was slightly exothermic and the temperature rose from room temperature to about 45 ° C. Outer heat was applied until the pH reached the prescribed pH unit and 21.37 g of S was added. The reaction mixture was stirred at 90-99 ° C (194-210 ° F). ) for 6-10 hours, after which it was cooled and filtered.
    The products of this reaction consisted of 570.1 g of filtrate and 3.7 g of solid. The filtrate showed 14.89% MnTS, 0.06% alkalinity as Mn (OH) 2, 0 MnHS, 4.88% Mn, specific gravity = 1.156 @ 24 ° C, and the pH = 4.93. Liquid manganese thiosulfate had a pleasant pink color to the eye.
    Example 2 73.77 g of 99% pure MnCO 3 was introduced into a 1 liter round bottom flask. (Stirring was performed with a single-blade rod shaker and heating was performed using a heating chamber at the base of the flask.) 498.4 g of water was then added. 63.4 g of SO 2 was added to the suspension. The pH after purging SO2 was 2.24. 23.61 g of tire S were added. The reaction was carried out for 10.5 hours in a temperature range of 97-98 ° C. The filtrate had 15.46% MnTS. 579.5 g of filtrate were recovered together with 12.6 g (1.9% of raw materials) of residual solids.
    Example 3 480.8 g of pure MnCO 3 was added to a 4 liter Ace reactor. (The cylindrical reactor was surrounded by a heating chamber.) A multiblade rod stirrer was used for stirring.) 2576.1 grams of water was added to form the slurry. The initial pH of the MnCO 3 suspension was 6.9. S02 was purged in the suspension for 6 hours to reach a final pH of 1.98. 154.54 g of tire S were added. The reaction temperature was brought to 96 ° C. The reaction temperature was maintained at 96-99 ° C for 4 hours. The filtrate had 19.6% MnS2C> 3.
    Example 4 3.45 kg of 96% pure MnCO3 were placed in a 30 liter Ace reactor. (The cylindrical reactor was heated by a heating enclosure at its base as well as by a wrap-around heating jacket.The stirring was accomplished by a multiblade rod stirrer.) 24.2 kg of water was added to form the suspension. SO 2 was slowly added until pH = 2.8. The total purge time was 5.5 hours. 1.1 kg of S was added to the intermediate suspension of Mn (HSO 3) 2. The heating was carried out for 4 hours in the temperature range of 96-98 ° C. Analysis of the final filtrate gave 15.2% MnTS.
    权利要求:
    Claims (16)
    [1]
    A process for preparing a solution of manganese thiosulfate comprising: (a) producing a suspension of manganese carbonate; (b) adding sulfur dioxide to the manganese carbonate slurry to form a mixture; (c) reacting the mixture to form the manganese hydrogen sulfite suspension; (d) adding sulfur to the manganese hydrogen sulfite suspension, and reacting to form a manganese thiosulfate solution; and (e) recovering the manganese thiosulfate solution.
    [2]
    The method of claim 1, wherein steps (bd) and (c) further comprise maintaining a pH of about 2 to 3, and step (d) further comprises maintaining a pH about 4 to 6.
    [3]
    The process of claim 1 wherein step (b) further comprises adding sulfur dioxide to the manganese carbonate slurry until a pH of about 2 to 3 is reached.
    [4]
    The process of claim 1 further comprising an initial step of preparing the manganese carbonate suspension by combining manganese carbonate and water.
    [5]
    The method of claim 3 wherein step (b) takes place without external heating.
    [6]
    The process of claim 3 wherein step (d) further comprises heating the suspension of manganese hydrogen sulfite.
    [7]
    The process of claim 6 wherein step (d) further comprises heating the suspension of manganese hydrogen sulfite to maintain a temperature of at least about 90 ° C.
    [8]
    The process of claim 7 wherein step (d) further comprises heating the suspension of manganese hydrosulfite to maintain a temperature of about 96 ° C to about 99 ° C.
    [9]
    The process of claim 1 wherein step (b) further comprises the combination of manganese carbonate and sulfur dioxide at a molar ratio of manganese carbonate to sulfur dioxide of about 1.00: 1, 00 to 1.10: 1.00.
    [10]
    The process of claim 9 wherein step (d) further comprises adding sulfur to the manganese hydrogen sulfite suspension at a ratio of sulfur to manganese hydrogen sulfite of 1.0: 1.0. at 1.2: 1.0.
    [11]
    The process of claim 1 wherein step (d) further comprises adding sulfur selected from the group consisting of pure sulfur and tire sulfur.
    [12]
    The process of claim 1 wherein the molar ratio of manganese carbonate to sulfur dioxide used is 1.05: 1.00: 1.20.
    [13]
    The process of claim 1, wherein step (d) further comprises producing residual byproducts of manganese carbonate and sulfur, and step (e) further comprises recovering each of the sub-products. Residual products of manganese carbonate and sulfur.
    [14]
    A process for preparing manganese thiosulfate comprising: (a) producing a suspension of manganese carbonate; (b) purging sulfur dioxide in the manganese carbonate slurry to a pH of from about 2 to about 3 to produce a slurry mixture of manganese hydrogen sulfite and manganese carbonate; (c) heating the slurry produced in step (b) at a temperature of about 96 to about 99 ° C to a pH of about 4 to about 6 to form manganese thiosulfate; and (d) recovering the manganese thiosulfate produced in step (c).
    [15]
    The process of claim 14 wherein the molar ratio of manganese carbonate to sulfur dioxide used is 1.05: 1.00: 1.20.
    [16]
    The process of claim 15, wherein step (c) further comprises producing waste byproducts comprising manganese carbonate and sulfur, and wherein step (d) further comprises recovering each of the residual byproducts of manganese carbonate and sulfur.
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    同族专利:
    公开号 | 公开日
    ES2387434B1|2013-08-08|
    DE102011000415A1|2011-08-18|
    TR201101343A2|2011-09-21|
    FR2971502B1|2016-05-06|
    FR2971502A1|2012-08-17|
    US7914763B1|2011-03-29|
    ES2387434A1|2012-09-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB511877A|1938-03-29|1939-08-25|Alfred Augustus Thornton|A process for producing approximately pure manganese compounds from initial substances of a manganese nature|
    EP1526113A1|2003-10-14|2005-04-27|Tessenderlo Kerley, Inc.|Magnesium thiosulfate solution and process for preparing same|
    US528162A|1894-10-30|Christian heinzerling |
    US1855856A|1929-07-01|1932-04-26|Koppers Co Inc|Production of fertilizers|
    US3752875A|1970-12-28|1973-08-14|Owens Illinois Inc|Process for increasing reaction rate in conversion of sulfides and hydrosulfides|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US70595310|2010-02-15|
    US12/705,953|US7914763B1|2010-02-15|2010-02-15|Process and apparatus for preparing manganese thiosulfatesolution|
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