(19)
(11)EP 2 924 003 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
08.05.2019 Bulletin 2019/19

(21)Application number: 14161685.4

(22)Date of filing:  26.03.2014
(51)Int. Cl.: 
C01B 25/234  (2006.01)

(54)

Method for purifying phosphoric acid

Verfahren zur Reinigung von Phosphorsäure

Procédé de purification de l'acide phosphorique


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(43)Date of publication of application:
30.09.2015 Bulletin 2015/40

(73)Proprietor: LXP Group GmbH
16348 Marienwerder (DE)

(72)Inventor:
  • Streffer, Friedrich
    14052 Berlin (DE)

(74)Representative: Eisenführ Speiser 
Patentanwälte Rechtsanwälte PartGmbB Postfach 31 02 60
80102 München
80102 München (DE)


(56)References cited: : 
WO-A1-2010/043424
US-A- 3 318 661
GB-A- 1 240 285
US-A- 3 903 247
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description


    [0001] The present invention relates to a method for purifying phosphoric acid from a mixture which comprises organic compounds and water. Preferably, the present invention relates to a method for purifying phosphoric acid from a mixture comprising organic solvents as well as (polymeric) organic compounds, for example, a mixture derived from a pulping process.

    [0002] Phosphoric acid is frequently used as a solvent for releasing polysaccharides from lignocellulosic material in pulping processes because it does not interfere with subsequent fermentation. Treatment of lignocellulose with concentrated phosphoric acid allows to separate cellulose and hemicellulose from lignin by dissolving the polysaccharides while the lignin remains undissolved. In most cases this step is followed by subsequent enzymatic or chemical hydrolysis and fermentation. After the process, the phosphoric acid is largely contaminated with organic solvents and monomeric and/or polymeric side products. Efficient recovery of clean phosphoric acid from a pulping slurry is challenging because of the diversity of the impurities. The required purification steps that need to be undertaken in order to be able to reuse the phosphoric acid and the associated high energy costs still pose a problem for industrial biorefineries.

    [0003] Methods for the purification of phosphoric acid obtained from phosphate rock in a so-called wet process by extraction with organic solvents are described in US patents US 3,947,499 and US 3,318,661.

    [0004] In the wet process, phosphate rock is acidulated with a strong mineral acid such as sulphuric acid, hydrochloric or nitric acid. The primary object of the described methods is the removal of inorganic contaminations such as metal cations and silica, fluorine and sulfur compounds which are either released from the rock in the process or added in form of the mineral acid.

    [0005] An excess of solvent, e.g. diisopropyl ether, is mixed with the wet process acid and purified phosphoric acid is extracted into the organic phase from which it is recovered by washing with water. The above mentioned patents disclose the formation of a solid compound or a liquid complex, respectively, between the diisopropyl ether and the phosphoric acid which facilitates the separation of the phosphoric acid from the undesired contaminations.

    [0006] According to US 3,318,661, phase separation occurs between an aqueous fraction containing the impurities and a complex layer when 68% to 85% H3PO4 is mixed with enough diisopropyl ether to form the liquid H3PO4 · H2O · (CH3)2CHOCH(CH3)2 complex in a slightly exothermic reaction. The optimum of H3PO4 recovery is reached when 85% H3PO4 is mixed with enough diisopropyl ether to form a maximum amount of complex without separating in a third phase of excess ether. The complex layer contains about 45% H3PO4, 8% H2O und 47% diisopropyl ether and can be separated by distillation. The separation can be improved by heating the complex layer to about 68 °C where roughly half of the diisopropyl ether separates to the top and can be drawn off. Alternatively, efficient separation of phosphoric acid from the diisopropyl ether is achieved, when just enough water is added to the complex layer to dilute the 85% of acid strength down to 68% or below, at which point the complex cannot exist anymore and the ether separates to the top. This process is endothermic and can therefore be controlled by temperature. WO2010043424 discloses a method for digesting a biomass comprising lignin together with cellulose and/or hemicellulose using phosphoric acid as a solvent and an ether as a precipitant.

    [0007] Extensive studies on the phase equilibria of the system water/phosphoric acid/ diisopropyl ether at different temperatures have followed the discovery of the above described effects. Areas of one, two and three coexisting phases comprising aqueous, ether and complex phases are found depending on the composition and temperature. Ruiz et al. describe three phase regions at 25 °C and 40 °C in Solvent Extraction and Ion Exchange, 4 (4), 789-802 (1986). Harrison und Roquero observed three two-phase and one three phase zones at 0 °C, 10 °C and 30 °C (Journal of Chemical and Engineering Data, 49 (2), 218-220 (2004)). The former study moreover indicates that the structural element of a secondary carbon atom attached to the ether oxygen may play a role in the efficiency of the complex formation and phase separation by comparing diisopropyl ether with a corresponding system comprising di-n-propylether.

    [0008] All of the above mentioned literature, however, exclusively focuses on the purification of wet process phosphoric acid but does not address the problem of removing organic impurities including organic solvents as well as non-solvent organic compounds and polymers from phosphoric acid.

    [0009] A primary objective of the present invention was therefore to efficiently isolate phosphoric acid from mixtures comprising organic compounds.

    [0010] A further objective of the present invention was to provide a simple and energy efficient way to purify phosphoric acid from a complex mixture comprising organic compounds and solvents.

    [0011] In particular, it was an objective of the present invention to recover phosphoric acid of a sufficiently purity to be reused in subsequent processes from mixtures such as are obtained in a pulping process.

    [0012] Due to the complexity of the system water/phosphoric acid/diisopropyl ether in terms of phase equilibria, it could not be expected that such systems would present a viable option to facilitate the purification of phosphoric acid from organic impurities and, in particular, apply the described effects to such complex mixtures as are obtained for example in a pulping process.

    [0013] Surprisingly, however, the formation of a complex layer as described above and the observed temperature dependent phase separation may be implemented in a method for the purification of phosphoric acid from a mixture of organic compounds, polymers and solvents, significantly improving the energy efficiency with respect to conventional recovery processes.

    [0014] The objectives as set out above are met by a method as defined in claim 1.

    [0015] The starting mixture provided in step i) may comprise a plurality of organic compounds including monomeric, oligomeric and polymeric biomolecules as well as diverse organic solvents and precipitants.

    [0016] The phosphoric acid to be purified may comprise or consist of a poly-phosphoric acid or a mixture of phosphoric acids. In this case the adjustment of the molar ratio is based on mono-phosphate unit equivalents.

    [0017] Substance S represents an ether compound featuring the structural element of a secondary carbon atom attached to the bridging ether oxygen which has proved to be important for the efficient formation of the above described complex. One or more substance(s) S may already be among the organic compounds present in the starting mixture and thus be taken into account when adjusting the molar ratio of phosphoric acid to the total of substance(s) S. A mixture of different substances S does not hinder complex formation as long as the molar ratio requirements as set out above are met. Therefore, the adjustment can be performed by adding any kind of substance S or phosphoric acid to the mixture.

    [0018] Unexpectedly, when the molar ratio of phosphoric acid to the total of substance(s) S is adjusted accordingly, spontaneous phase separation occurs. A light organic phase comprising solvents and precipitants other than substance(s) S and only residual amounts of phosphoric acid is formed while the heavy phase constitutes the complex layer comprising the bulk phosphoric acid.

    [0019] The presence of further organic compounds and polymers does not impede complex formation and phase separation. Consequently, the method can easily be integrated with hydrolysation, precipitation, extraction and fermentation steps, where other components of the mixture need to be processed or removed.

    [0020] After the light organic phase is removed, the purified phosphoric acid can be recovered from the complex layer.

    [0021] The separation of step iv) may be conducted by any suitable method such as distillation or extraction, e.g. with water.

    [0022] In a preferred embodiment the separation of step iv) may be facilitated by heating the heavy phase to a temperature of 60 °C or more, preferably 65 °C or more, particularly preferably 68 °C or more and/or adding water to dilute the phosphoric acid strength to below 80 %, preferably below 70 %, particularly preferably below 68 %.

    [0023] As already described in the introduction, when heating the heavy phase which constitutes the complex layer, to a temperature of 68 °C and more, a large portion of substance(s) S separates off to the top. Moreover, at a dilution of below 68 % phosphoric acid strength, the complex can not exist anymore and the substance(s) S separate(s) of to the top, where it can be drawn off. Both effects may thus be employed to simplify the recovery of the phosphoric acid from the heavy phase.

    [0024] The method may further comprise the step v) of separating substance(s) S from the heavy phase.

    [0025] As indicated above, substance(s) S may be separated by distillation from the heavy phase as well as by employing the temperature and/or dilution dependent phase separation effect, where the substance(s) S separate to the top and can be drawn off.

    [0026] In a preferred embodiment of the method according to the invention, the substance(s) S obtained in step v) is reused in a further step i) as defined above.

    [0027] The recycling of substance(s) S in a continuous process allows cost efficient use of the material and keeps the production of waste at a minimum.

    [0028] The starting mixture provided in step i) of a method according to the invention may also comprise CO2. CO2 may be present in the starting mixture depending of the origin and previous processing steps of the starting mixture. For example, if the starting mixture originates from a pulping slurry, CO2 may have been used as a lignin precipitant.

    [0029] One or more of the further organic compounds present in the mixture provided in step i) of the method according to the invention may be selected from the group consisting of hydrocarbons, alcohols, aldehydes, ketones, acids, esters, ethers, carbohydrates, amino acids and derivates thereof as well as di-, tri-, oligo- or polymers thereof.

    [0030] Depending on where the starting mixture provided in step i) of the method according to the invention originates from, a large diversity of organic compounds and solvents may be present. Previous processing including steps of dissolving, dilution, extraction or precipitation may have lead to the presence of large quantities of organic solvents and solvent mixtures of varying composition.

    [0031] One or more of the further organic compounds are selected from the group consisting of organic solvents.

    [0032] As mentioned above, the organic solvents may also include substance(s) S, but are not limited to any class of organic molecules and may exhibit different polarity and solubility. Unexpectedly, they do not infer with the formation of the complex and the phase separation.

    [0033] Preferably, the further organic solvent(s) has/have a miscibility gap with water.

    [0034] If the further organic solvent(s) exhibit a miscibility gap with water, the phase separation is facilitated and allows a more efficient recovery of phosphoric acid from the mixture.

    [0035] Starting materials of previous processing of the mixture provided in step i) of the method according to the present invention may include any kind of biomass comprising macromolecules of biological origin such as lignin, cellulose, other oligo and polysaccharides, proteins and nucleic acids as well as their degradation products. Furthermore, enzymes or microorganisms may have been added, for example, in a digestion or fermentation step.

    [0036] One or more of the further organic compounds are selected from the group consisting of polysaccharides, oligosaccharides and hydrolysation products thereof.

    [0037] In particular, one or more of the further organic compound(s) may be selected from the group consisting of cellulose, hemicellulose and lignin.

    [0038] A primary advantage of the method according to the present invention is the fact that it may be applied to a mixture as derived from a pulping process, in which phosphoric acid has been used as a solvent. Pulping slurries generally comprise a large number of different organic compounds, solvents and (residual) polymers such as cellulose, hemicellulose and lignin, which complicate the efficient recovery of the phosphoric acid. The method according to the invention, however, provides a simple and energy efficient way to recover phosphoric acid from mixtures originating from a pulping slurry by employing effects, which have never been observed and could not have been expected to be of use in the context of pulping processes. In particular, it was not expected that the formation of the above described complex as well as the phase separation would not be impeded by the presence of a complex mixture of organic compounds, polymers and solvents.

    [0039] In the method according to the invention, the substance(s) S is/are selected from the group consisting of methyl-isopropyl ether, ethyl-isopropyl ether, propyl-isopropyl ether, di-isopropyl ether, sec-butyl-methyl ether, sec-butyl-ethyl ether, sec-butyl-propyl ether, sec-butyl-isopropyl ether, sec-butyl-butyl ether, bis(sec-butyl) ether, sec-butyl-tert.-butyl ether, 3-methoxy-pentane, 3-ethoxy pentane, 3-propoxy pentane, 3-(1-methyl-ethoxy)-pentane, 3-butoxy-pentane, 3-(2-methyl-propoxy)-pentane, 3-(1-methyl-propoxy)-pentane, 3-(1,1-methyl-ethoxy)-pentane, 3-pentoxy-pentane, 3-(1-methyl-butoxy)-pentane, 3-(2-methyl-butoxy)-pentane, 3-(3-methyl-butoxy)-pentane, 3-(1-ethyl-propxy)-pentane, 3-(2-ethyl-propxy)-pentane, 2-methoxy-pentane, 2-ethoxy pentane, 2-propoxy pentane, 2-(1-methyl-ethoxy)-pentane, 2-butoxy-pentane, 2-(2-methyl-propoxy)-pentane, 2-(1-methyl-propoxy)-pentane, 2-(1,1-methyl-ethoxy)-pentane, 2-pentoxy-pentane, 2-(1-methyl-butoxy)-pentane, 2-(2-methyl-butoxy)-pentane, 2-(3-methyl-butoxy)-pentane, 2-(1-ethyl-propxy)-pentane, 2-(2-ethyl-propxy)-pentane, 2-methoxy-3-methyl-butane, 2-ethoxy-3-methyl-butane, 2-propoxy-3-methyl-butane, 2-(1-methyl-ethoxy)-3-methyl-butane, 2-butoxy-3-methyl-butane, 2-(2-methyl-propoxy)-3-methyl-butane, 2-(1-methyl-propoxy)-3-methyl-butane, 2-(1,1-methyl-ethoxy)-3-methyl-butane, 1-(3-methyl-butoxy)-pentane, 2-(1-methyl-butoxy)-3-methyl-butane, 2-(2-methyl-butoxy)-3-methyl-butane, 2-(3-methyl-butoxy)-3-methyl-butane, 2-(1-ethyl-propxy)-3-methyl-butane, 2-(2-ethyl-propxy)-3-methylbutane.

    [0040] The structural element of a secondary carbon atom attached to an alkoxy group is a feature present in many different ethers. Therefore, a large variety of compounds and compound mixtures may be used as substance(s) S in a method according to the invention to fulfill the requirements for complex formation with phosphoric acid and facilitate phase separation. As the ethers generally have a boiling point which is significantly different from phosphoric acid, they can easily be separated from the phosphoric acid and water by distillation once the complex has been isolated. Moreover, a phase separation between an aqueous phase comprising the phosphoric acid and an ether phase may be facilitated by heating the complex layer or dilution with water as described above. Once the ether separates to the top it may easily been drawn off and the purified phosphoric acid can be recovered from the complex.

    [0041] In a preferred embodiment of the method according to the invention, the substance S or one of the substances S is diisopropyl ether.

    [0042] As the liquid-liquid phase equilibrium of the ternary system water/phosphoric acid/ diisopropyl ether has been extensively studied at various temperatures, it is especially easy to control the formation of the different two and three phase systems according to the determined experimental data if diisopropyl ether is used as substance S or as one of the substances S. Diisopropyl ether has furthermore been proven to be able to completely complex the phosphoric acid when adequate amounts are available in the mixture and thus to facilitate a maximum recovery of phosphoric acid after phase separation.

    [0043] In a further preferred embodiment of the method according to the invention, the light phase formed in step ii) contains 10 wt.-% or less phosphoric acid.

    [0044] When the phase separation occurs at the optimal conditions in terms of molar ratio between phosphoric acid and substance(s) S and temperature as set out above, it is possible to recover a maximum amount of phosphoric acid from the mixture. Thus, the light phase comprises little or no phosphoric acid at all.

    [0045] In the method according to the invention, the mixture may be heated to 30 °C or more, preferably 40 °C or more, particularly preferably 50 °C or more in step ii).

    [0046] Due to the temperature dependence of the phase composition, the portion of phosphoric acid in the heavy phase shifts towards a higher phosphoric acid content with increasing temperature. By heating the mixture to temperatures above room temperature the yield of phosphoric acid recovery may therefore be improved. In particular, the percentage of recovered phosphoric acid (PA) in the heavy phase may be described by

    with ma denoting the masses of phases with a = t(total), h(heavy) and l(light) and xa(pa) the mass percentages of phosphoric acid in the corresponding phases.

    [0047] The mass of the heavy phase is assessable from the mass balance and the phase compositions



    [0048] Therefore the %PA may be expressed by the xt(pa) and the composition of the light and heavy phase:



    [0049] Investigating the temperature dependence of the function (3) with the knowledge that the heavy phase shifts to high xh(pa) at higher temperatures (for DIPE/PA/H2O form 30% to 46% when the temperature rises from 0°C to 40°C) and that the light phase shifts to lower xl(pa) at higher temperatures (for DIPE/PA/H2O form 10% to 4% when the temperature rises from 0°C to 40°C), one finds that for a given xt(pa) the function has a minimum for intermediate temperatures and approximates 100% for low and high temperatures. At low temperatures approximately the whole mass is found in the heavy phase which is not favorable, whereas at high temperatures the mass is more evenly distributed between the light and heavy phase.

    [0050] This qualitative behavior is not disrupted by (also larger) amounts of other solvent, but the minimum of the function at intermediate temperatures is shifted to higher temperatures by some degrees.

    [0051] Step ii) of a method according to the invention may also be conducted under pressurized conditions.

    [0052] Pressurized conditions may be applied to the system when conducting step ii) of the method according to the invention in order to prevent the solvents (including the substance(s) S) from evaporating when the mixture is heated. Thus, the composition of the mixture is kept constant and the phase equilibrium may be controlled.

    [0053] In a further preferred embodiment of the method according to the invention, additional water may be added in step ii).

    [0054] The addition of water during step ii) may also facilitate phase separation and improve recovery yield by shifting the composition of the mixture towards the region where maximum complex formation is possible.

    [0055] The following examples are added to illustrate the method according to the invention without limiting the scope of protection.

    Example 1



    [0056] A solution of 42 g phosphoric acid (85 wt%), 30 g ethanol and 5 g saccharose was admixed with 34 g diisopropyl ether at room temperature. Instantaneously 4.7 g of a white substance crystallized and was filtered off.

    [0057] Afterwards the filtrate was heated to 45°C and a spontaneous phase separation occurred. The light, clear phase had a volume of 20 ml and a phosphoric acid content of 5 wt%. Further heating to 65°C enlarged the light phase to 45 ml while the content of phosphoric acid was reduced to 2 wt%.

    Example 2



    [0058] A solution of 42 g phosphoric acid (85 wt%), 38 g ethyl acetate und 7g cellobiose was admixed with 46 g diisopropyl ether at room temperature. Instantaneously 6.8 g of a white substance crystallized and was filtered off.

    [0059] Afterwards the filtrate was heated to 40°C and a spontaneous phase separation occurred. The light, clear phase had a volume of 15 ml and a phosphoric acid content of 6 wt%. Further heating to 65°C enlarged the light phase to 65 ml.

    Example 3 (not according to the invention)



    [0060] A solution of 42 g phosphoric acid (85 wt%), 34 g acetone und 10 g lignin was admixed with 46 g sec-butyl-isopropyl ether at room temperature. Instantaneously 6.8 g of a white substance crystallized and was filtered off.

    [0061] Afterwards the filtrate was heated to 45°C and a spontaneous phase separation occurred. The light, clear phase had a volume of 45 ml and a phosphoric acid content of 5.4 wt%.


    Claims

    1. Method for purifying phosphoric acid from a mixture, in particular a pulping slurry, containing or consisting of phosphoric acid, organic compounds and water, comprising or consisting of the following steps:

    i) providing a mixture containing or consisting of phosphoric acid, one or more substance(s) S having at least one secondary carbon atom attached to an alkoxy group, wherein the substance(s) S is/are selected from the group consisting of methyl-isopropyl ether, ethyl-isopropyl ether, propyl-isopropyl ether, di-isopropyl ether, sec-butyl-methyl ether, sec-butyl-ethyl ether, sec-butyl-propyl ether, sec-butyl-isopropyl ether, sec-butyl-butyl ether, bis(sec-butyl) ether, sec-butyl-tert.-butyl ether, 3-methoxy-pentane, 3-ethoxy pentane, 3-propoxy pentane, 3-(1-methyl-ethoxy)-pentane, 3-butoxy-pentane, 3-(2-methyl-propoxy)-pentane, 3-(1-methyl-propoxy)-pentane, 3-(1,1-methyl-ethoxy)-pentane, 3-pentoxy-pentane, 3-(1-methyl-butoxy)-pentane, 3-(2-methyl-butoxy)-pentane, 3-(3-methyl-butoxy)-pentane, 3-(1-ethyl-propxy)-pentane, 3-(2-ethyl-propxy)-pentane, 2-methoxy-pentane, 2-ethoxy pentane, 2-propoxy pentane, 2-(1-methyl-ethoxy)-pentane, 2-butoxy-pentane, 2-(2-methyl-propoxy)-pentane, 2-(1-methyl-propoxy)-pentane, 2-(1,1-methyl-ethoxy)-pentane, 2-pentoxy-pentane, 2-(1-methyl-butoxy)-pentane, 2-(2-methyl-butoxy)-pentane, 2-(3-methyl-butoxy)-pentane, 2-(1-ethyl-propxy)-pentane, 2-(2-ethyl-propxy)-pentane, 2-methoxy-3-methyl-butane, 2-ethoxy-3-methyl-butane, 2-propoxy-3-methyl-butane, 2-(1-methyl-ethoxy)-3-methylbutane, 2-butoxy-3-methyl-butane, 2-(2-methyl-propoxy)-3-methyl-butane, 2-(1-methyl-propoxy)-3-methyl-butane, 2-(1,1-methyl-ethoxy)-3-methyl-butane, 1-(3-methyl-butoxy)-pentane, 2-(1-methyl-butoxy)-3-methyl-butane, 2-(2-methyl-butoxy)-3-methyl-butane, 2-(3-methyl-butoxy)-3-methyl-butane, 2-(1-ethyl-propxy)-3-methyl-butane, 2-(2-ethyl-propxy)-3-methyl-butane, further organic compounds, wherein one or more of the further organic compounds is/are selected from the group consisting of polysaccharides, oligosaccharides and hydrolysation products thereof, and wherein one or more of the further organic compounds is/are selected from the group consisting of organic solvents and water, and
    adjusting the molar ratio of phosphoric acid to the total of one or more substance(s) S as defined above in the mixture to be in the range of from 1 : 0.4 to 1 : 10, preferably to be in the range of approximately 1 : 0.6 to 1: 4, especially preferably to be approximately 1 : 0.85 to 1:2,

    ii) heating the mixture to 25 °C or more until phase separation occurs,

    iii) removing the light phase, and

    iv) separating the phosphoric acid from the heavy phase.


     
    2. Method according to claim 1, wherein the separation of step iv) is conducted by distillation or extraction.
     
    3. Method according to any of the preceding claims, further comprising the step v) of separating substance(s) S from the heavy phase obtained in step iv).
     
    4. Method according to claim 3, wherein substance(s) S obtained in step v) is reused in a further step i) as defined in claim 1.
     
    5. Method according to any of the preceding claims, wherein the mixture provided in step i) contains CO2.
     
    6. Method according to any of the preceding claims, wherein one or more of the further organic compounds is/are selected from the group consisting of hydrocarbons, alcohols, aldehydes, ketones, acids, esters, ethers, carbohydrates, amino acids and derivates thereof as well as di-, tri-, oligo- or polymers thereof.
     
    7. Method according to any of the preceding claims, wherein the organic solvent(s) has/have a miscibility gap with water.
     
    8. Method according to any of the preceding claims, wherein one or more of the further organic compounds is/are selected from the group consisting of cellulose, hemicellulose and lignin.
     
    9. Method according to any of the preceding claims, wherein the substance S or one of the substances S is di-isopropyl ether.
     
    10. Method according to any of the preceding claims, wherein the mixture is heated to 30 °C or more, preferably 40 °C or more, particularly preferably 50 °C or more in step ii).
     
    11. Method according to any of the preceding claims, wherein step ii) is conducted under pressurized conditions and/or wherein additional water is added in step ii).
     


    Ansprüche

    1. Verfahren zur Aufreinigung von Phosphorsäure aus einer Mischung, insbesondere einer Aufschlämmung in der Zellstoffherstellung, umfassend oder bestehend aus Phosphorsäure, organischen Bestandteilen und Wasser, umfassend oder bestehend aus den folgenden Schritten:

    i) Bereitstellen einer Mischung enthaltend oder bestehend aus Phosphorsäure, einer oder mehreren Substanz(en) S mit mindestens einem sekundären Kohlenstoffatom, das an einen Alkoxyrest gebunden ist, wobei die Substanz(en) S ausgewählt ist/sind aus der Gruppe bestehend aus Methylisopropylether, Ethylisopropylether, Propylisopropylether, Di-isopropylether, Sec-butylmethylether, Sec-butylethylether, Secbutylpropylether, Sec-butylisopropylether, Sec-butylbutylether, Bis(sec-butyl)ether, Sec-butyl-tert.-butylether, 3-Methoxypentan, 3-Ethoxypentan, 3-Propoxypentan, 3-(1-Methyl-ethoxy)-pentan, 3-Butoxypentan, 3-(2-Methyl-propoxy)-pentan, 3-(1-Methyl-propoxy)-pentan, 3-(1,1-Methyl-ethoxy)-pentan, 3-Pentoxypentan, 3-(1-Methyl-butoxy)-pentan, 3-(2-Methyl-butoxy)-pentan, 3-(3-Methyl-butoxy)-pentan, 3-(1-Ethyl-propxy)-pentan, 3-(2-Ethyl-propxy)-pentan, 2-Methoxypentan, 2-Ethoxypentan, 2-Propoxypentan, 2-(1-Methyl-ethoxy)-pentan, 2-Butoxypentan, 2-(2-Methyl-propoxy)-pentan, 2-(1-Methyl-propoxy)-pentan, 2-(1,1-Methyl-ethoxy)-pentan, 2-Pentoxypentan, 2-(1-Methyl-butoxy)-pentan, 2-(2-Methyl-butoxy)-pentan, 2-(3-Methyl-butoxy)-pentan, 2-(1-Ethyl-propxy)-pentan, 2-(2-Ethyl-propxy)-pentan, 2-Methoxy-3-methylbutan, 2-Ethoxy-3-methylbutan, 2-Propoxy-3-methylbutan, 2-(1-Methyl-ethoxy)-3-methylbutan, 2-Butoxy-3-methylbutan, 2-(2-Methyl-propoxy)-3-methyl-butan, 2-(1-Methyl-propoxy)-3-methylbutan, 2-(1,1-Methyl-ethoxy)-3-methylbutan, 1-(3-Methyl-butoxy)-pentan, 2-(1-Methyl-butoxy)-3-methyl-butan, 2-(2-Methyl-butoxy)-3-methylbutan, 2-(3-Methyl-butoxy)-3-methylbutan, 2-(1-Ethyl-propxy)-3-methylbutan, 2-(2-Ethyl-propxy)-3-methylbutan, weiteren organischen Bestandteilen, wobei ein oder mehrere der weiteren organischen Bestandteile ausgewählt ist/sind aus der Gruppe bestehend aus Polysacchariden, Oligosacchariden und Hydrolysierungsprodukten davon, und wobei einer oder mehrere der weiteren organischen Bestandteile ausgewählt ist/sind aus der Gruppe bestehend aus organischen Lösungsmitteln und Wasser, und
    Einstellen des molaren Verhältnisses von Phosphorsäure und der Gesamtmenge der einen oder mehreren Substanz(en) S wie oben definiert in der Mischung auf einen Bereich von 1 : 0,4 bis 1 : 10, vorzugsweise einen Bereich von etwa 1 : 0,6 bis 1 : 4, besonders bevorzugt von etwa 1 : 0,85 bis 1 : 2,

    ii) Erhitzen der Mischung auf 25 °C oder mehr bis eine Phasentrennung erfolgt,

    iii) Entfernen der leichten Phase, und

    iv) Trennen der Phosphorsäure von der schweren Phase.


     
    2. Verfahren gemäß Anspruch 1, wobei das Trennen in Schritt iv) mittels Destillation oder Extraktion durchgeführt wird.
     
    3. Verfahren gemäß einem der vorangehenden Ansprüche, zudem umfassend den Schritt v) Trennen von Substanz(en) S von der schweren Phase, die in Schritt iv) erhalten wurde.
     
    4. Verfahren gemäß Anspruch 3, wobei die in Schritt v) erhaltene(n) Substanz(en) S in einem weiteren Schritt i) wie in Anspruch 1 definiert wiederverwendet wird.
     
    5. Verfahren gemäß einem der vorangehenden Ansprüche, wobei die Mischung, die in Schritt i) bereitgestellt wird, CO2 enthält.
     
    6. Verfahren gemäß einem der vorangehenden Ansprüche, wobei einer oder mehrere der weiteren organischen Bestandteile ausgewählt ist/sind aus der Gruppe bestehend aus Kohlenwasserstoffen, Alkoholen, Aldehyden, Ketonen, Säuren, Estern, Ethern, Kohlenhydraten, Aminosäuren und Derivaten davon, sowie Di-, Tri-, Oligo- oder Polymeren davon.
     
    7. Verfahren gemäß einem der vorangehenden Ansprüche, wobei das/die organische(n) Lösungsmittel eine Mischungslücke mit Wasser hat/haben.
     
    8. Verfahren gemäß einem der vorangehenden Ansprüche, wobei einer oder mehrere der weiteren organischen Bestandteile ausgewählt ist/sind aus der Gruppe bestehend aus Zellulose, Hemizellulose und Lignin.
     
    9. Verfahren gemäß einem der vorangehenden Ansprüche, wobei die Substanz S oder eine der Substanzen S Di-Isopropylether ist.
     
    10. Verfahren gemäß einem der vorangehenden Ansprüche, wobei die Mischung in Schritt ii) auf 30 °C oder mehr erhitzt wird, vorzugsweise 40 °C oder mehr, besonders bevorzugt 50 °C oder mehr.
     
    11. Verfahren gemäß einem der vorangehenden Ansprüche, wobei Schritt ii) unter Druck durchgeführt wird und/oder wobei in Schritt ii) zusätzliches Wasser hinzugegeben wird.
     


    Revendications

    1. Procédé pour épurer l'acide phosphorique à partir d'un mélange, en particulier d'une boue liquide dans la production de pâte à papier, comprenant ou consistant en l'acide phosphorique, des composés organiques et de l'eau, comprenant ou consistant en les étapes suivantes :

    i) fournir un mélange contenant ou composé d'acide phosphorique, une ou plusieurs substance(s) S avec au moins un atome de carbone secondaire qui est lié à un radical alcoxy, sachant que la/les substance(s) S est/sont sélectionnée(s) à partir du groupe composé d'éther de méthyle-isopropyle, éther d'éthyle-isopropyle, éther propyle-isopropylique, éther di-isopropylique, l'éther de sec-butyle et de méthyle, éther de sec-butyle et d'éthyle, éther de sec-butyle et de propyle, éther de sec-butyle et d'isopropyle, éther de butyle sec-butyle, éther de bis(sec-butyle), éther sec-butyle tert.-butyle, 3-méthoxypentane, 3-éthoxypentane, 3-propoxypentane, 3-(1-méthyléthoxy)-pentane, 3-butoxypentane, 3-(2-méthyle-propoxy)-pentane, 3-(1-méthyle-propoxy)-pentane, 3-(1,1-méthyle-éthoxy)-pentane, 3-pentoxy-pentane, 3-(1-méthyle-butoxy)-pentane, 3-(2-méthyle-butoxy)-pentane, 3-(3-méthyle-butoxy)-pentane, 3-(1-éthyle-propxy)-pentane, 3-(2-éthyle-propxy)-pentane, 2-méthoxypentane, 2-éthoxypentane, 2-propoxypentane, 2-(1-méthyle-éthoxy)-pentane, 2-butoxypentane, 2-(2-méthyle-propoxy)-pentane, 2-(1-méthyle-propoxy)-pentane, 2-(1,1-méthyle-éthoxy)-pentane, 2-pentoxypentane, 2-(1-méthyle-butoxy)-pentane, 2-(2-méthyl-butoxy)-pentane, 2-(3-méthyle-butoxy)-pentane, 2-(1-éthyle-propxy)-pentane, 2-(2-éthyle-propxy)-pentane, 2-méthoxy-3-méthylbutane, 2-éthoxy-3-méthyl-butane, 2-propoxy-3-méthylbutane, 2-(1-méthyle-éthoxy)-3-méthylbutane, 2-butoxy-3-méthylbutane, 2-(2-méthyle-propoxy)-3-méthyl-butane, 2-(1-méthyle-propoxy)-3-méthylbutane, 2-(1,1-méthyle-éthoxy)-3-méthylbutane, 1-(3-méthyle-butoxy)-pentane, 2-(1-méthyle-butoxy)-3-méthyle-butane, 2-(2-méthyle-butoxy)-3-méthylbutane, 2-(3-méthyle-butoxy)-3-méthylbutane, 2-(1-éthyle-propxy)-3-méthylbutane, 2-(2-éthyle-propxy)-3-méthylbutane, d'autres composés organiques, sachant qu'un ou plusieurs desdits autres composés organiques est/sont sélectionné(s) à partir du groupe composé de polysaccharides, d'oligosaccharides et de leurs produits d'hydrolyse, et sachant qu'un ou plusieurs desdits autres composés organiques est/sont sélectionné(s) à partir du groupe constitué de solvants organiques et d'eau, et régler le rapport molaire de l'acide phosphorique et de la quantité totale de la une ou des plusieurs substance(s) S telles que défini ci-dessus dans le mélange sur une plage de 1 : 0,4 à 1 : 10, de préférence, de 1 : 0,6 à 1 : 4 environ, de manière particulièrement préférée, de 1 : 0,85 à 1 : 2 environ,

    ii) chauffer le mélange à 25 °C ou plus jusqu'à ce qu'intervienne une séparation de phases,

    iii) supprimer la phase légère et

    iv) séparer l'acide phosphorique de la phase lourde.


     
    2. Procédé selon la revendication 1, dans lequel la séparation de l'étape iv) est effectuée par distillation ou extraction.
     
    3. Procédé selon l'une des revendications précédentes, comprenant en outre l'étape consistant à v) séparer la/les substance(s) S de la phase lourde obtenue de l'étape iv).
     
    4. Procédé selon la revendication 3, dans lequel la/les substance(s) S obtenue à l'étape v) est/sont réutilisée(s) dans une étape supplémentaire i) telle que définie dans la revendication 1.
     
    5. Procédé selon l'une des revendications précédentes, dans lequel le mélange fourni à l'étape i) contient du CO2.
     
    6. Procédé selon l'une des revendications précédentes, dans lequel un ou plusieurs des autres composés organiques est/sont sélectionné(s) depuis le groupe constitué d'hydrocarbures, d'alcools, d'aldéhydes, de cétones, d'acides, d'esters, d'éthers, de carbohydrates, d'aminoacides et de leurs dérivés, ainsi que leurs di-, tri-, oligo- ou polymères.
     
    7. Procédé selon l'une des revendications précédentes, dans lequel la/les solvant(s) organique(s) présente(nt) une lacune de miscibilité avec l'eau.
     
    8. Procédé selon l'une des revendications précédentes, dans lequel un ou plusieurs des autres composés organiques est/sont sélectionné(s) depuis le groupe constitué de cellulose, d'hémicellulose et de lignine.
     
    9. Procédé selon l'une des revendications précédentes, dans lequel la substance S ou l'une des substances S est de l'éther di-isopropylique.
     
    10. Procédé selon l'une des revendications précédentes, dans lequel le mélange de l'étape ii) est chauffé à 30 °C ou plus, de préférence, à 40 °C ou plus, de manière particulièrement préférée, à 50 °C ou plus.
     
    11. Procédé selon l'une des revendications précédentes, dans lequel l'étape ii) est effectuée sous pression et/ou dans lequel de l'eau supplémentaire est ajoutée à l'étape ii).
     




    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description




    Non-patent literature cited in the description