Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
  • C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
  • C10G73/04—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of filter aids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/26—Synthetic macromolecular compounds
  • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
  • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/10—Lubricating oil

Definitions

• the present invention relates to a dewaxing aid in solvent dewaxing. More specifically, the present invention relates to an auxiliary agent for improving the filterability when filtering and removing wax from mineral oil or the like.
• the lubricating oil base oil generally used in a lubricating oil composition is produced so as to have desired physical properties by subjecting crude oil to a distillation treatment and then various refining treatments.
• the unrefined distillate oil that has been distilled has a high pour point because it contains a large amount of paraffin wax (hereinafter, also simply referred to as “wax content”).
• wax content paraffin wax
• a dewaxing treatment is performed to remove wax from the distillate oil.
• a solvent dewaxing device is used to add a solvent such as methyl ethyl ketone to a dewaxing raw material which is a distillate oil containing a wax content and mix the mixture to obtain a mixed oil, and then the mixed oil is desired.
• the wax is precipitated by cooling to a temperature below the pour point of.
• the mixed oil in which the wax component is precipitated is passed through a filter and filtered and separated into the wax component and the dewaxed oil.
• Patent Document 1 a mixed system of an olefin-vinyl acetate copolymer and a polyalkyl (meth) acrylate is used, in Patent Document 2, a condensate of chlorinated paraffin and biphenyl is used, and in Patent Document 3, polyalkyl (a polyalkyl (meth) acrylate) is used. Dewaxing aids consisting of meta) acrylates are disclosed respectively.
• JP-A-54-0111104 Japanese Unexamined Patent Publication No. 04-07759 Japanese Unexamined Patent Publication No. 2004-231928
• An object of the present invention is to provide a dewaxing aid having excellent filterability.
• the present inventors have made a dewaxing aid containing a specific ethylene- ⁇ -olefin copolymer obtained from ethylene and a specific ⁇ -olefin filterable. It was found to be excellent in improving. That is, the present invention provides the following [1] to [2]. [1] The molar ratio [(a) / (b)] of (a) ethylene and (b) ⁇ -olefin having 3 to 12 carbon atoms is 93/7 to 75/25, and the weight average molecular weight is 10.
• a dewaxing aid comprising an ethylene- ⁇ -olefin copolymer (A) of 000 to 500,000.
• the dewaxing aid of the present invention is excellent in the effect of improving the filterability when filtering and removing wax from mineral oil or the like using a solvent.
• ethylene and (b) ⁇ -olefin having 3 to 12 carbon atoms have a molar ratio [(a) / (b)] of 93/7 to 75/25 and a weight average molecular weight of 10.
• a dewaxing aid characterized by containing an ethylene- ⁇ -olefin copolymer (A) of 000 to 500,000.
• the ethylene- ⁇ -olefin copolymer (A) in the present invention is a copolymer obtained by polymerizing ethylene and an ⁇ -olefin having 3 to 12 carbon atoms.
• An ⁇ -olefin having 3 to 12 carbon atoms is used as a raw material for the copolymer in the present invention. From the viewpoint of filterability, it is preferably an ⁇ -olefin having 4 to 8 carbon atoms, and more preferably an ⁇ -olefin having 4 carbon atoms.
• the ⁇ -olefin having 3 to 12 carbon atoms includes, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like. Can be mentioned.
• the weight average molecular weight of the ethylene- ⁇ -olefin copolymer (A) in the present invention is 10,000 to 500,000.
• the weight average molecular weight is preferably 30,000 to 300,000, more preferably 40,000 to 200,000, and even more preferably 50,000 to 150,000. If the weight average molecular weight is less than 10,000, the filterability may not be improved. On the other hand, if it exceeds 500,000, the viscosity may be high and the handleability may be deteriorated.
• the weight average molecular weight in the present invention is a value obtained in terms of polystyrene by measuring using gel permeation chromatography (GPC) under the following conditions.
• the molar ratios of (a) ethylene and (b) ⁇ -olefin having 3 to 12 carbon atoms are the ethylene-derived structural unit existing in the ethylene- ⁇ -olefin copolymer and 3 to 12 carbon atoms. It means the molar ratio with the constituent unit derived from ⁇ -olefin.
• the molar ratio of (a) ethylene and (b) ⁇ -olefin having 3 to 12 carbon atoms [(a) / (b)] is preferably 92/8 to 80/20, more preferably 90/10 to 90/10. It is 83/17, more preferably 90/10 to 85/15. If the molar ratios of (a) ethylene and (b) ⁇ -olefin having 3 to 12 carbon atoms deviate from 93/7 to 75/25, the filterability may not be improved.
• the "molar ratio" in the present invention can be calculated by dissolving an ethylene- ⁇ -olefin copolymer in heavy toluene and measuring 1 HNMR. Specifically, a peak derived from the terminal methyl of the ⁇ -olefin (0.40 to 0.60 ppm), a peak derived from ethylene, and a peak derived from an alkyl other than the terminal methyl of the ⁇ -olefin (0.85 to 1.05 ppm).
• the molar ratio of ethylene and ⁇ -olefin can be calculated from the ratio of the integrated values of.
• the ethylene- ⁇ -olefin copolymer (A) contained in the dewaxing aid in the present invention is a combination of two or more kinds of ethylene- ⁇ -olefin copolymers having different molar ratios [(a) / (b)]. It is preferable to do so. More particularly, the molar ratio [(a) / (b) ] are different from each other, the two ethylene - ⁇ - olefin copolymer (A H), and ethylene - ⁇ - olefin copolymer (A L) It is more preferable to use them together.
• the mixing ratio of (A H ) and ( AL ) is not particularly limited, but the mass ratio of (A H ) / ( AL ) is preferably 90/10 to 10/90.
• the mass ratio of (A H ) / ( AL ) is more preferably 75/25 to 25/75, still more preferably 60/40 to 40/60, and particularly preferably 50/50. When it is in the range of 90/10 to 10/90, it is easy to further enhance the effect of improving the filterability.
• (A H ) and ( AL ) are used in combination, it is preferable to use the following (A H ) and ( AL).
• (A L) ( a) is a ethylene and (b) alpha-olefin molar ratio of carbon atoms 3 ⁇ 12 [(a) / (b)] is 87/13 less 75/25 or more, weight average molecular weight Ethylene- ⁇ -olefin copolymer of 10,000 to 500,000
• the ⁇ -olefin contents of (A H ) and ( AL ) are preferably different by 1 mol% or more, and more preferably 2 mol% or more.
• the ethylene- ⁇ -olefin copolymer (A) in the present invention can be used in combination with a specific ethylene-ethyl acrylate to further enhance the effect of improving the filterability. More specifically, the molar ratios of (c) ethylene and (d) ethyl acrylate [(c) / (d)] are 98/2 to 80/20, and the weight average molecular weight is 50,000 to 1,000.
• the mass ratio of (A) / (B) is more preferably 90/10 to 75/25, and even more preferably 85/15 to 75/25. The effect of improving the filterability can be further enhanced by using the mixture in a ratio within this range.
• the weight average molecular weight of the ethylene-ethyl acrylate copolymer (B) is 50,000 to 1,000,000.
• the weight average molecular weight is preferably 60,000 to 800,000, more preferably 70,000 to 600,000, and even more preferably 75,000 to 500,000.
• the ethylene-ethyl acrylate copolymer (B) has a molar ratio of (c) ethylene and (d) ethyl acrylate [(c) / (d)] of 98/2 to 80/20.
• the molar ratio of (c) ethylene and (d) ethyl acrylate means the molar ratio of the ethylene-derived structural unit present in the ethylene-ethyl acrylate copolymer and the ethyl acrylate-derived structural unit.
• the molar ratio of (c) ethylene and (d) ethyl acrylate [(c) / (d)] is preferably 98/2 to 82/18, more preferably 96/4 to 84/16, and further.
• ethylene-ethyl acrylate copolymer having a molar ratio [(c) / (d)] in this range in combination the effect of improving the filterability can be further enhanced.
• the "molar ratio" of (c) ethylene and (d) ethyl acrylate can be calculated by dissolving an ethylene-ethyl acrylate copolymer in deuterated chloroform and measuring 1 1 HNMR.
• the molar ratio of ethylene and ethyl acrylate can be calculated from the ratio of the integrated values of .70 to 1.70 ppm).
• the dewaxing aid may be diluted with a diluent before use.
• a diluent include mineral oils and aromatic solvents using crude oil as a starting material, and examples thereof include kerosene base material components, light oil base material components, toluene, and xylene.
• the amount of the diluent is, for example, 0.05 to 20 parts by mass, preferably 1 to 15 parts by mass, based on 1 part by mass of the dewaxing aid. Yes, more preferably 2 to 10 parts by mass.
• the dewaxing aid of the present invention may contain other optional components, if necessary.
• the optional component include polyalkyl (meth) acrylates and alkylated aromatic compounds.
• the dewaxing aid may be adjusted by appropriately mixing these optional components with the ethylene- ⁇ -olefin copolymer in an amount within a range that does not hinder the object of the present invention.
• the dewaxing aid of the present invention may be diluted with a diluent before use. The diluent is blended with the dewaxing aid, and is a component other than the components that can be contained in the dewaxing aid.
• the dewaxing aid of the present invention can be suitably used for filtering and removing wax from mineral oil and the like. Specifically, the dewaxing aid of the present invention is suitably used for filtering and removing wax by adding it to a hydrocarbon oil containing wax such as petroleum distillate.
• the amount added is not particularly limited, but the amount of the ethylene- ⁇ -olefin copolymer contained in the dewaxing aid is not particularly limited.
• the wax-containing hydrocarbon oil for example, it is added so as to be 10 to 3,000 ppm, preferably 50 to 500 ppm, and more preferably 200 to 500 ppm. If the amount added is too small, a sufficient effect cannot be obtained, and on the other hand, even if added more than necessary, the effect may not be improved, but may be lowered.
• the dewaxing aid is preferably added to a mixed oil in which a wax-containing hydrocarbon oil and a solvent are mixed.
• the solvent include methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, butane, pentane and the like, and two or more kinds of solvents may be mixed and used.
• the mass ratio of the wax-containing hydrocarbon oil to the solvent is not particularly limited, but is preferably 50/50 to 5/95, more preferably 30/70 to 10/90. ..
• the mixed oil After adding the dewaxing aid to the mixed oil, the mixed oil is heated to uniformly dissolve it, and then cooled to precipitate wax, and the precipitated wax is filtered and removed.
• the heating temperature for heating is preferably 40 to 90 ° C
• the cooling temperature for cooling is preferably ⁇ 40 to ⁇ 20 ° C. Since the dewaxing aid of the present invention has excellent filterability of wax, it is possible to efficiently remove wax.
• wax-containing hydrocarbon oil examples include petroleum distillate, and the petroleum distillate used in the present invention is, for example, atmospheric distillation of crude oil such as paraffin-based crude oil, intermediate-based crude oil, and naphthen-based crude oil.
• crude oil such as paraffin-based crude oil, intermediate-based crude oil, and naphthen-based crude oil.
• residual oil or the like accumulated at the bottom of a distillation column obtained by distillation under reduced pressure can be mentioned.
• the residual oil has a high weight average molecular weight and is a raw material for bright stock obtained by subjecting it to a dewaxing treatment or various refining treatments.
• the weight average molecular weight of the petroleum distillate used in one embodiment of the present invention is 900 or more, preferably 1000 or more, more preferably 1100 or more, still more preferably 1200 or more, still more preferably 1300 or more. Moreover, it is usually 3000 or less.
• the kinematic viscosity at 100 ° C. petroleum distillate used in one embodiment of the present invention preferably 20.0 ⁇ 60.0mm 2 / s, more preferably 23.0 ⁇ 55.0mm 2 / s, more preferably It is 25.0 to 50.0 mm 2 / s.
• the kinematic viscosity in the present specification means a value measured and calculated in accordance with JIS K2283: 2000.
• the flash point of the petroleum distillate used in one aspect of the present invention is preferably 300 ° C. or higher, more preferably 310 ° C. or higher, further preferably 320 ° C. or higher, and usually 350 ° C. or lower.
• the flash point in the present specification means a value measured by the Cleveland opening method (COC) method in accordance with JIS K2265-4.
• the pour point of the petroleum distillate used in one aspect of the present invention is usually 40 to 50 ° C.
• the pour point in the present specification means a value measured in accordance with JIS K2269: 1987.
• the polymers A H- 2 and Table 1 in Table 1 and A H- 3 polymers A L -1 and A L -2 in Table 2, and polymers A'-1 and A'-2 in Table 3 were obtained.
• azo-based initiator 2, 2-Azobis-2,4-dimethylvaleronitrile was used.
• C12 and the like indicate that the alkyl group has 12 carbon atoms.
• Preparation Example 1 Polymer A H- 1, polymer A L- 1, and polymer B 1 were charged at a ratio of 40:40:20 (mass ratio) and mixed at a temperature of 100 ° C. to prepare a dewaxing aid D1.
• the dewaxing aids D2 and D3 shown in Table 5 were prepared by changing the polymer in Preparation Example 1 and performing an operation according to Preparation Example 1. Further, the polymers shown in Table 5 were designated as dewaxing aids D4 to D12.
• the mixed oil was placed in a test vessel and cooled to a temperature of ⁇ 30 ° C. at a rate of 2 ° C./min with stirring. After cooling, the slurry in which wax was precipitated was placed in a suction filter and filtered under reduced pressure at a temperature of ⁇ 30 ° C. and 200 mmHg.
• the time when the slurry was put into the filter was set to 0 seconds, and the time when 100 mL of the filtrate flowed was measured. The time when 100 mL has flowed is defined as the filtration time, and the shorter the filtration time, the better the filterability.
• Table 6 The results are shown in Table 6.
• the filter medium used in this test has an aeration rate of about 100 cm 3 / cm 2 ⁇ sec, and the "hydrocarbon oil” is the residual oil remaining on the bottom of the column when the crude oil is distilled under reduced pressure. It is a residual oil containing a wax component obtained by chemical purification.
• Examples 2 to 8 Comparative Examples 1 to 4> The filtration time was measured in the same manner as in Example 1 except that the dewaxing aid used in Example 1 was changed as shown in Table 6. The results are shown in Table 6.
• Example 9 The same operation as in Example 1 was carried out except that the amount of the diluted solution E1 of the dewaxing aid was changed to 0.11 g (150 ppm as a polymer). The results are shown in Table 7.
• Examples 10 to 12 Comparative Examples 5 to 6>
• the filtration time was measured in the same manner as in Example 9 except that the dewaxing aid used in Example 9 was changed as shown in Table 7. The results are shown in Table 7.

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• 2021
  • 2021-01-12 CN CN202180007838.1A patent/CN114945651B/zh active Active
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