Recovery method of ethanol in precipitation type carrier mother liquor and application of recovery method

Abstract

The invention discloses a method for recovering ethanol in precipitation type carrier mother liquor, and relates to the technical field of catalyst preparation, in particular to a method for recovering ethanol in precipitation type carrier mother liquor, which comprises the following steps: adding hydrogen chloride into the precipitation type carrier mother liquor, reacting I, and distilling to obtain recovered ethanol; the precipitation type carrier mother liquor is obtained in precipitation type carrier preparation; the preparation method of the precipitation type carrier comprises the following steps: emulsifying a mixture of magnesium halide, an alcohol compound and an optional inert liquid medium to obtain an emulsified product, reacting the emulsified product with an ethylene oxide compound II, and separating to obtain the precipitation type carrier and a precipitation type carrier mother solution; according to the present invention, the residual carrier in the precipitation type carrier mother liquor can promote the reaction of hydrogen chloride and the ethylene oxide compound to generate the halogenated alcohol, the ethanol recovery can be achieved through distillation, the cost is saved, the additional addition of the catalyst for the reaction of the hydrogen chloride and the ethylene oxide compound is not required, the cost is saved, and the re-separation of the catalyst is not required.

Description

Technical Field

[0001] This invention relates to the field of catalyst preparation technology, specifically to a method for recovering ethanol from a precipitated support mother liquor and its application. Background Technology

[0002] As is well known, catalysts supported on magnesium chloride hydrides exhibit significantly superior performance compared to catalysts supported on other supports in propylene polymerization. Furthermore, this support is easily prepared into spherical shapes to obtain spherical catalysts. Therefore, most catalysts currently used for olefin polymerization are prepared by supporting titanium halide on magnesium chloride hydrides. These spherical supports can be prepared using methods disclosed in US4399054A, such as emulsifying a magnesium chloride hydride system at high temperature and high speed followed by rapid cooling to form spherical hydrides. They can also be prepared using methods such as spray drying, spray cooling, high-pressure extrusion, high-speed stirring, emulsification, and rotating bed methods. However, these methods consume significant energy, involve complex processes, require multiple reactors, and result in magnesium chloride hydrides with a wide particle size distribution.

[0003] To address this issue, Chinese patent CN102040683A discloses a method for preparing a catalyst support by reacting magnesium halide alcohols with ethylene oxide compounds. Specifically, it discloses either adding the ethylene oxide compound after melting and dispersing the magnesium halide alcohol, or directly adding the melted and dispersed magnesium halide alcohol to a reactor containing ethylene oxide compounds. However, this method requires a large amount of ethanol to prepare the catalyst support, which increases the cost of using the support.

[0004] Therefore, how to recover the ethanol used in the preparation of the above-mentioned catalyst support is of great significance for further reducing the cost of the above-mentioned new olefin polymerization catalyst support and overcoming the above-mentioned defects of the prior art. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a method for recovering ethanol from a precipitated carrier mother liquor and its application. In this recovery method, the residual carrier in the precipitated carrier mother liquor can promote the reaction of hydrogen chloride with ethylene oxide compounds to generate haloalcohols. Ethanol can then be recovered by distillation, saving costs. Furthermore, it eliminates the need for additional catalysts for the reaction of hydrogen chloride with ethylene oxide compounds, further reducing costs and eliminating the need for catalyst separation.

[0006] To solve the above-mentioned technical problems, the first aspect of the present invention provides a method for recovering ethanol from a precipitated carrier mother liquor, comprising adding hydrogen chloride to the precipitated carrier mother liquor, reacting I and then distilling to obtain recovered ethanol;

[0007] The precipitating carrier mother liquor is obtained in the preparation of the precipitating carrier;

[0008] The method for preparing the precipitated carrier includes: emulsifying a mixture of magnesium halide, an alcohol compound, and an optional inert liquid medium to obtain an emulsion product; reacting the emulsion product with an ethylene oxide compound to obtain a precipitated carrier and the mother liquor of the precipitated carrier.

[0009] The precipitated support described in this invention is an olefin polymerization catalyst support, used to prepare olefin polymerization catalysts.

[0010] The inventors of this invention unexpectedly discovered that adding hydrogen chloride to the mother liquor of the olefin polymerization catalyst support can remove unreacted ethylene oxide compounds from the mother liquor, and can also recover ethanol by distillation by utilizing the boiling point difference between the product haloalcohol and ethanol; wherein, the residual support in the mother liquor can promote the reaction between hydrogen chloride and ethylene oxide compounds, so that the reaction is complete, making distillation recovery possible.

[0011] According to some embodiments of the present invention, the formula for calculating the amount of hydrogen chloride is = (amount of ethylene oxide compound - amount of magnesium halide × 2) × K; wherein, the value of K is in the range of 1 to 2, preferably 1.02 to 1.1, for example 1.02, 1.03, 1.04, 1.05, 1.06.

[0012] In this invention, there is no particular limitation on the method of adding hydrogen chloride. Hydrogen chloride can be added directly or in an alcoholic solution of hydrogen chloride. The alcohol is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isoamyl alcohol, n-hexanol, n-octanol, and 2-ethylhexanol.

[0013] According to some embodiments of the present invention, the conditions for reaction I include: a temperature of 0°C to 80°C, preferably 60°C to 80°C, for example 60°C or 80°C; a time of 10 min to 3 h, preferably 30 min to 1 h, for example 30 min or 40 min; and a stirring rate of 30 rpm to 1000 rpm, preferably 100 rpm to 600 rpm, for example 100 rpm or 600 rpm.

[0014] According to some embodiments of the present invention, the distillation conditions include: a temperature of 50°C to 100°C, preferably 60°C to 80°C, such as 60°C, 65°C, or 80°C; and a time of 1 hour to 20 hours, preferably 1 hour to 2 hours, such as 1 hour, 1.5 hours, or 2 hours.

[0015] And / or, the distillation further includes rectification; preferably, the rectification conditions include a pressure of -0.09 MPa to -0.01 MPa, for example -0.06 MPa, -0.08 MPa, or -0.09 MPa.

[0016] According to some embodiments of the present invention, the magnesium halide has the general formula MgXY, where X is a halogen, Y is a halogen, and C1-C2 is a halogen. 14 Alkyl, C1-C 14 alkoxy groups, C6-C 14 aryl or C6-C 14 One of the aryloxy groups; preferably, X is chlorine or bromine, and Y is chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, C6-C 10 aryl or C6-C 10 One of the aryloxy groups; the C1-C5 alkyl group may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, or neopentyl; the C1-C5 alkoxy group may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, or isobutoxy; the C6-C... 10 The aryl group can be, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, or naphthyl, wherein the C6-C 10 The aryloxy group can be, for example, phenoxy or naphthoxy; the magnesium halide can be a single magnesium halide or a mixture of multiple magnesium halides; more preferably, the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, magnesium phenoxy chloride, magnesium isopropoxy chloride, and magnesium n-butoxy chloride; from the perspective of raw material availability, magnesium chloride is preferred;

[0017] And / or, the general formula of the alcohol compound is ROH, in which R is a C1-C8 alkyl or a C3-C8 cycloalkyl; the C1-C8 alkyl can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, isohexyl, octyl, or isooctyl; preferably, the alcohol compound is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentyl alcohol, n-hexanol, n-octanol, and 2-ethylhexanol;

[0018] And / or, the structural formula of the ethylene oxide compound is shown in Formula I:

[0019]

[0020] In Formula I, R5 and R6 may be the same or different, and each is independently selected from hydrogen, C1-C5 alkyl, or C1-C5 haloalkyl; preferably, R5 and R6 may be the same or different, and each is independently selected from hydrogen, C1-C3 alkyl, or C1-C3 haloalkyl; more preferably, the ethylene oxide compound is selected from at least one of ethylene oxide, propylene oxide, butane oxide, epichlorohydrin, chlorobutane, bromopropane, and bromobutane.

[0021] According to the invention, trace amounts of water in each reactant used in the preparation of the olefin polymerization catalyst support can also participate in the reaction that forms the olefin polymerization catalyst support.

[0022] According to the present invention, the content of each component used in the preparation process of the olefin polymerization catalyst support can be selected and varied within a wide range.

[0023] According to some embodiments of the present invention, based on 1 mol of magnesium halide, the amount of alcohol compound used is 4 mol to 30 mol, preferably 6 mol to 20 mol, for example 15 mol; the amount of ethylene oxide compound with the structural formula shown in Formula I is 1 mol to 10 mol, preferably 2 mol to 6 mol, for example 3.75 mol.

[0024] According to some embodiments of the present invention, the average diameter of the precipitation carrier is 10 micrometers to 100 micrometers, preferably 40 micrometers to 90 micrometers; the particle size distribution is less than 1.2, preferably 0.2-0.8.

[0025] According to the present invention, the olefin polymerization catalyst support may contain water, and the water contained therein comes from trace amounts of water carried by the synthesis raw materials and reaction medium.

[0026] According to some embodiments of the present invention, the mixture includes a heating step before emulsification; preferably, the heating conditions include: a temperature of 80°C to 120°C, more preferably 80°C to 100°C, for example 80°C; and a time of 0.5 hours to 5 hours, more preferably 0.5 hours to 3 hours, for example 2 hours.

[0027] According to some embodiments of the present invention, there are no particular limitations on the heating conditions for the mixture of magnesium halide, alcohol compound, and optionally inert liquid medium, as long as the heating conditions are sufficient to allow the magnesium halide to melt and react fully.

[0028] According to some embodiments of the present invention, the amount of the inert liquid medium can be selected based on the amount of magnesium halide. Generally, based on 1 mol of magnesium halide, the amount of the inert liquid medium can be 0.8 L to 10 L, preferably 2 L to 8 L. The inert liquid medium can be any liquid medium commonly used in the art that does not chemically interact with the reactants and reaction products. For example, the inert liquid medium can be silicone oil and / or inert liquid hydrocarbon solvents. Specifically, the inert liquid medium can be at least one selected from kerosene, paraffin oil, petrolatum oil, white oil, methyl silicone oil, ethyl silicone oil, methylethyl silicone oil, phenyl silicone oil, and methylphenyl silicone oil. The inert liquid medium of the present invention is particularly preferably white oil.

[0029] According to some embodiments of the present invention, a mixture of magnesium halide, alcohol compounds, and optionally an inert liquid medium can be emulsified using various methods known to those skilled in the art. For example, the mixture can be emulsified by subjecting it to low-speed or high-speed shearing. The stirring rate for low-speed shearing is typically 400 rpm to 800 rpm. The high-speed shearing method is known to those skilled in the art, such as the high-speed stirring method disclosed in Chinese Patent CN1151183C (i.e., stirring a solution containing liquid magnesium halide adduct at a speed of 2000 rpm to 5000 rpm). In addition, the mixture can be emulsified by referring to the methods disclosed in the following patents: Chinese Patent CN1267508C discloses the rotational dispersion of a solution containing liquid magnesium halide adduct in a hypergravity bed (the rotational speed can be 100 rpm to 3000 rpm); Chinese Patent CN1463990A discloses the output of a solution containing liquid magnesium halide adduct in an emulsifier at a speed of 1500 rpm to 8000 rpm; US Patent US6020279A discloses the emulsification of a solution containing liquid magnesium halide adduct by spraying.

[0030] In this invention, a method of adding a surfactant is preferred, that is, the method of emulsifying a mixture of magnesium halide, alcohol compounds, and optionally an inert liquid medium is to contact the mixture with a surfactant.

[0031] In this invention, the surfactant is preferably selected from at least one of ethyl acetate, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyacrylate, polyacrylamide, polystyrene sulfonate, naphthalenesulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkyl acrylate copolymer modified polyethyleneimine, polymer of 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyltrimethylamine salt, polyethylene oxide-propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether, and polyalkyl methacrylate.

[0032] In this invention, the amount of surfactant used is aimed at achieving sufficient emulsification. Preferably, based on 1 mol of magnesium halide, the amount of surfactant used is preferably 1 g to 20 g, for example, 1.25 g.

[0033] According to the present invention, the conditions for reacting the emulsion product with ethylene oxide compounds can be any of the existing conditions capable of forming olefin polymerization catalyst supports.

[0034] According to some embodiments of the present invention, the conditions for reaction II include: a temperature of 50°C to 120°C, preferably 60°C to 100°C, for example 80°C; and a time of 20 minutes to 60 minutes, preferably 20 minutes to 50 minutes, for example 30 minutes.

[0035] According to the present invention, the preparation method of the olefin polymerization catalyst support may further include solid-liquid separation of the product obtained from the contact reaction, washing and drying the solid product. The solid-liquid separation can be any existing method capable of separating the solid and liquid phases, such as vacuum filtration, pressure filtration, or centrifugation. Preferably, the solid-liquid separation method is pressure filtration. The present invention does not particularly limit the conditions of pressure filtration, aiming to achieve the most complete separation of the solid and liquid phases possible.

[0036] A second aspect of the present invention provides the application of the above-described recovery method or the ethanol recovered by the above-described recovery method in the preparation of an olefin polymerization catalyst support.

[0037] Beneficial effects:

[0038] This invention provides a method for recovering ethanol from a precipitated carrier mother liquor. The inventors unexpectedly discovered that the residual carrier in the precipitated carrier mother liquor can promote the reaction of hydrogen chloride with ethylene oxide compounds to generate haloalcohols. Ethanol can be recovered by distillation, saving costs. Furthermore, there is no need to add an additional catalyst for the reaction of hydrogen chloride with ethylene oxide compounds, saving costs and eliminating the need for further catalyst separation. Attached Figure Description

[0039] Figure 1 This is an optical microscope image of the catalyst support for olefin polymerization prepared in Application Example 1 of the present invention. Detailed Implementation

[0040] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to these embodiments.

[0041] Unless otherwise specified in the embodiments of this invention, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0042] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0043] In this embodiment of the invention, the heating process is not specifically limited, and any known method can be used for heating, such as slow, stepwise, rapid, or programmed heating. The specific heating method can be adjusted according to the specific formula, contact temperature, etc.

[0044] According to the preparation method of the present invention, under the same conditions, different heating processes will affect the particle morphology, particle size distribution, catalyst activity and copolymer properties of the final catalyst; specifically, a slower heating process can obtain better particle morphology, while a faster heating rate will lead to poorer particle shape and decreased sphericity.

[0045] In this invention and its embodiments, the average particle diameter and particle size distribution of the olefin polymerization catalyst support can be measured using a Master Sizer 2000 laser particle size analyzer (manufactured by Malvern Instruments Ltd).

[0046] In this invention and its embodiments, the morphology of the olefin polymerization catalyst support was observed using an optical microscope, model Eclipse E200, purchased from Nikon.

[0047] Example 1

[0048] This embodiment provides a method for recovering ethanol from the mother liquor of a precipitated carrier.

[0049] In a 2L reactor, 0.8 mol magnesium chloride, 12 mol ethanol, 1 g polyvinylpyrrolidone (PVP), and 0.1 g ethyl acetate were added. The mixture was heated to 80°C with stirring and reacted at a constant temperature for 2 hours. Then, 3 mol epichlorohydrin was added, and the reaction was continued at 80°C for 30 minutes. After pressure filtration, a precipitated support mother liquor and a pressure filtration product (olefin polymerization catalyst support) were obtained.

[0050] Take the above-mentioned precipitated carrier mother liquor, add 1.484 mol of hydrogen chloride, and stir the reaction at 600 rpm for 30 min at 80℃. The resulting reaction solution is distilled at 80℃ for 1 h under total reflux and the pressure is set to -0.09 MPa. The collected ethanol fraction is subjected to gas chromatography-mass spectrometry (GC-MS) analysis.

[0051] The purity of the recovered ethanol (ethanol fraction) was tested to be 98.3%.

[0052] Example 2

[0053] This embodiment provides a method for recovering ethanol from the mother liquor of a precipitated carrier.

[0054] In a 2L reactor, 80g (0.8mol) magnesium chloride, 12mol ethanol, 1g polyvinylpyrrolidone (PVP), and 0.1g ethyl acetate were added. The mixture was heated to 80℃ with stirring and reacted at a constant temperature for 2 hours. Then, 3mol epichlorohydrin was added, and the reaction was continued at 80℃ for 30 minutes. After pressure filtration, the precipitated support mother liquor and the pressure filtration product (olefin polymerization catalyst support) were obtained.

[0055] Take the above-mentioned precipitated carrier mother liquor, add 1.428 mol of hydrogen chloride, and stir the reaction at 100 rpm for 30 min at 60℃. The resulting reaction solution is distilled at 60℃ for 1.5 h under total reflux and the pressure is set to -0.08 MPa. The collected ethanol fraction is subjected to gas chromatography-mass spectrometry (GC-MS) analysis.

[0056] The purity of the obtained ethanol fraction was tested to be 98.2%.

[0057] Example 3

[0058] This embodiment provides a method for recovering ethanol from the mother liquor of a precipitated carrier.

[0059] In a 2L reactor, 80g (0.8mol) magnesium chloride, 12mol ethanol, 1g polyvinylpyrrolidone (PVP), and 0.1g ethyl acetate were added. The mixture was heated to 80℃ with stirring and reacted at a constant temperature for 2 hours. Then, 3mol epichlorohydrin was added, and the reaction was continued at 80℃ for 30 minutes. After pressure filtration, the precipitated support mother liquor and the pressure filtration product (olefin polymerization catalyst support) were obtained.

[0060] Take the above-mentioned precipitated carrier mother liquor, add 1.442 mol of hydrogen chloride, and stir the reaction at 100 rpm for 30 min at 60℃. The resulting reaction solution is distilled at 65℃ for 2 h under total reflux and the pressure is set to -0.08 MPa. The collected ethanol fraction is subjected to gas chromatography-mass spectrometry (GC-MS) analysis.

[0061] The purity of the obtained ethanol fraction was tested to be 98.3%.

[0062] Example 4

[0063] This embodiment provides a method for recovering ethanol from the mother liquor of a precipitated carrier.

[0064] In a 2L reactor, 80g (0.8mol) magnesium chloride, 12mol ethanol, 1g polyvinylpyrrolidone (PVP), and 0.1g ethyl acetate were added. The mixture was heated to 80℃ with stirring and reacted at a constant temperature for 2 hours. Then, 3mol epichlorohydrin was added, and the reaction was continued at 80℃ for 30 minutes. After pressure filtration, the precipitated support mother liquor and the pressure filtration product (olefin polymerization catalyst support) were obtained.

[0065] Take the above-mentioned precipitated carrier mother liquor, add 1.456 mol of hydrogen chloride, and stir the reaction at 100 rpm for 40 min at 60℃. The resulting reaction solution is distilled at 60℃ for 2 h under total reflux, with the pressure set at -0.06 MPa. The collected ethanol fraction is then subjected to gas chromatography-mass spectrometry (GC-MS) analysis.

[0066] The purity of the obtained ethanol fraction was tested to be 98.2%.

[0067] Comparative Example 1

[0068] This comparative example provides a method for recovering ethanol from the mother liquor of a precipitation-type carrier.

[0069] In a 2L reactor, 80g (0.8mol) magnesium chloride, 12mol ethanol, 1g polyvinylpyrrolidone (PVP), and 0.1g ethyl acetate were added. The mixture was heated to 80℃ with stirring and reacted at a constant temperature for 2 hours. Then, 3mol epichlorohydrin was added, and the reaction was continued at 80℃ for 30 minutes. All the liquid was then distilled off under reduced pressure at 180℃ and -0.005MPa to remove the solid components. The distilled liquid was collected as the mother liquor.

[0070] Take the above mother liquor, add 1.414 mol of hydrogen chloride, and stir the reaction at 600 rpm for 30 min at 80 °C. The resulting reaction solution is distilled at 80 °C for 1 h under total reflux and pressure set at -0.09 MPa. The collected ethanol fraction is subjected to gas chromatography-mass spectrometry (GC-MS) analysis.

[0071] The purity of the obtained ethanol fraction was tested to be 81.6%.

[0072] Comparative Example 2

[0073] This comparative example provides a method for recovering ethanol from the mother liquor of a precipitation-type carrier.

[0074] In a 2L reactor, 80g (0.8mol) magnesium chloride, 12mol ethanol, 1g polyvinylpyrrolidone (PVP), and 0.1g ethyl acetate were added. The mixture was heated to 80℃ with stirring and reacted at a constant temperature for 2 hours. Then, 3mol epichlorohydrin was added, and the reaction was continued at 80℃ for 30 minutes. After pressure filtration, the precipitated support mother liquor and the pressure filtration product (olefin polymerization catalyst support) were obtained.

[0075] Take the above-mentioned precipitated carrier mother liquor, add 2.8 mol of hydrogen chloride, and stir the reaction at 100 rpm for 30 min at 60℃. The resulting reaction solution is distilled at 60℃ for 1.5 h under total reflux and the pressure is set to -0.08 MPa. The collected ethanol fraction is subjected to gas chromatography-mass spectrometry (GC-MS) analysis.

[0076] The purity of the obtained ethanol fraction was tested to be 95.1%.

[0077] Application Example 1

[0078] This application example provides an application for recovering ethanol, which is the ethanol obtained in Example 1.

[0079] In a 2L reactor, 80g (0.8mol) magnesium chloride, 12mol recovered ethanol (obtained in Example 1), 1g polyvinylpyrrolidone (PVP), and 0.1g ethyl acetate were added. The mixture was heated to 80°C with stirring and reacted at a constant temperature for 2 hours. Then, 3mol epichlorohydrin was added, and the reaction was continued at 80°C for 30 minutes. After pressure filtration, the precipitated support mother liquor and the pressure filtration product (olefin polymerization catalyst support) were obtained.

[0080] The filter press product was washed five times with hexane, and finally vacuum dried to obtain olefin polymerization catalyst support Y1.

[0081] The particle morphology of the olefin polymerization catalyst support Y1 observed by an optical microscope shows that the particles of the olefin polymerization catalyst support Y1 have a relatively regular shape, a smooth surface, are basically spherical, have a relatively concentrated particle size distribution, and there are basically no irregular particles.

[0082] The olefin polymerization catalyst support Y1 has a particle size of 66 micrometers and a particle size distribution of 0.7.

[0083] Comparative Application Example 1

[0084] This comparative application example provides an application for ethanol recovery.

[0085] The preparation of the precipitation carrier is the same as in Application Example 1, except that the recovered ethanol obtained in Comparative Example 1 is used instead of the recovered ethanol obtained in Example 1.

[0086] The filter press product was washed five times with hexane, and finally vacuum dried to obtain olefin polymerization catalyst support DY1.

[0087] The olefin polymerization catalyst support DY1 was observed using an optical microscope. It was found that the olefin polymerization catalyst support DY1 contained a large number of irregularly shaped particles and had a relatively rough surface.

[0088] The olefin polymerization catalyst support DY1 has a particle size of 102 micrometers and a particle size distribution of 1.8.

[0089] Comparative Application Example 2

[0090] This comparative application example provides an application for ethanol recovery.

[0091] The preparation of the precipitation carrier is the same as in Application Example 1, except that the recovered ethanol obtained in Comparative Example 2 is used instead of the recovered ethanol obtained in Example 1.

[0092] The filter press product was washed five times with hexane, and finally vacuum dried to obtain olefin polymerization catalyst support DY2.

[0093] The olefin polymerization catalyst support DY2 was observed using an optical microscope, revealing a large number of irregularly shaped particles and a relatively rough surface.

[0094] The olefin polymerization catalyst support DY2 has a particle size of 92 micrometers and a particle size distribution of 1.3.

[0095] Comparative Application Example 3

[0096] This comparative application example provides an application for ethanol recovery.

[0097] The preparation of the precipitating carrier is the same as in Application Example 1, except that the same volume of the precipitating carrier mother liquor prepared in Example 1 is used instead of the recovered ethanol obtained in Example 1.

[0098] The filter press product was washed five times with hexane, and finally vacuum dried to obtain olefin polymerization catalyst support DY3.

[0099] The olefin polymerization catalyst support DY3 was observed using an optical microscope. It was found that the olefin polymerization catalyst support DY3 contained a large number of irregularly shaped particles and had a relatively rough surface.

[0100] The olefin polymerization catalyst support DY3 has a particle size of 95 micrometers and a particle size distribution of 1.3.

[0101] The application results of the above embodiments and comparative examples show that the method for recovering ethanol from the mother liquor of a precipitated carrier provided by the present invention can effectively recover ethanol from the mother liquor of the precipitated carrier, and the purity of the recovered ethanol is high. At the same time, the olefin polymerization catalyst support prepared by using the recovered ethanol has good particle morphology, smooth surface, and basically no irregular particles.

[0102] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for recovering ethanol from a mother liquor containing a precipitating carrier, characterized in that, This involves adding hydrogen chloride to the mother liquor of a precipitating carrier, reacting with reaction I, and then distilling to obtain recovered ethanol. The precipitating carrier mother liquor is obtained in the preparation of the precipitating carrier; The method for preparing the precipitated carrier includes: emulsifying a mixture of magnesium halide, an alcohol compound, and an optional inert liquid medium to obtain an emulsion product; reacting the emulsion product with an ethylene oxide compound to obtain a precipitated carrier and the mother liquor of the precipitated carrier.

2. The recycling method according to claim 1, characterized in that, The formula for calculating the amount of hydrogen chloride is = (amount of ethylene oxide compound - amount of magnesium halide × 2) × K; where K ranges from 1 to 2, preferably from 1.02 to 1.

1.

3. The recycling method according to claim 1 or 2, characterized in that, The conditions for reaction I include: a temperature of 0℃ to 80℃, preferably 60℃ to 80℃; a time of 10min to 3h, preferably 30min to 1h; and a stirring rate of 30rpm to 1000rpm, preferably 100rpm to 600rpm.

4. The recycling method according to any one of claims 1-3, characterized in that, The distillation conditions include: a temperature of 50℃ to 100℃, preferably 60℃ to 80℃, and a time of 1h to 20h, preferably 1h to 2h. And / or, the distillation process further includes rectification; preferably, the rectification conditions include a pressure of -0.09 MPa to 0.01 MPa.

5. The recycling method according to any one of claims 1-4, characterized in that, The general formula for the magnesium halide is MgXY, where X is a halogen, Y is a halogen, and C1-C2 is a halogen. 14 Alkyl, C1-C 14 alkoxy groups, C6-C 14 aryl or C6-C 14 One of the aryloxy groups; preferably, X is chlorine or bromine, and Y is chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, C6-C 10 aryl or C6-C 10 The magnesium halide is selected from at least one of the aryloxy groups; more preferably, the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, magnesium phenoxy chloride, magnesium isopropoxy chloride, and magnesium n-butoxy chloride. And / or, the general formula of the alcohol compound is ROH, in which R is a C1-C8 alkyl or a C3-C8 cycloalkyl; preferably, the alcohol compound is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isoamyl alcohol, n-hexanol, n-octanol and 2-ethylhexanol. And / or, the structural formula of the ethylene oxide compound is shown in Formula I: In Formula I, R5 and R6 may be the same or different, and each is independently selected from hydrogen, C1-C5 alkyl, or C1-C5 haloalkyl; preferably, R5 and R6 may be the same or different, and each is independently selected from hydrogen, C1-C3 alkyl, or C1-C3 haloalkyl; more preferably, the ethylene oxide compound is selected from at least one of ethylene oxide, propylene oxide, butane oxide, epichlorohydrin, chlorobutane, bromopropane, and bromobutane.

6. The recycling method according to any one of claims 1-5, characterized in that, Based on 1 mol of magnesium halide, the amount of alcohol compound used is 4 mol to 30 mol, preferably 6 mol to 20 mol; the amount of ethylene oxide compound with the structural formula shown in Formula I is 1 mol to 10 mol, preferably 2 mol to 6 mol.

7. The recycling method according to any one of claims 1-6, characterized in that, The average diameter of the precipitation carrier is 10 micrometers to 100 micrometers, preferably 40 micrometers to 90 micrometers; the particle size distribution is less than 1.2, preferably 0.2 to 0.

8.

8. The recycling method according to any one of claims 1-7, characterized in that, Before emulsification, the mixture includes a heating step; preferably, the heating conditions include: a temperature of 80℃~120℃, more preferably 80℃~100℃; and a time of 0.5 hours~5 hours, more preferably 0.5 hours~3 hours.

9. The recycling method according to any one of claims 1-8, characterized in that, The conditions for reaction II include: a temperature of 50°C to 120°C, preferably 60°C to 100°C; and a time of 20 minutes to 60 minutes, preferably 20 minutes to 50 minutes.

10. The use of a recovery method according to any one of claims 1-9, or the ethanol recovered by the recovery method according to any one of claims 1-9, in the preparation of an olefin polymerization catalyst support.

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