CN114230461B - Preparation method of methyl oleate - Google Patents
Preparation method of methyl oleate Download PDFInfo
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- CN114230461B CN114230461B CN202111632057.XA CN202111632057A CN114230461B CN 114230461 B CN114230461 B CN 114230461B CN 202111632057 A CN202111632057 A CN 202111632057A CN 114230461 B CN114230461 B CN 114230461B
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- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 title claims abstract description 100
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 title claims abstract description 100
- 229940073769 methyl oleate Drugs 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 91
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 69
- 238000003756 stirring Methods 0.000 claims abstract description 58
- HEPLMSKRHVKCAQ-UHFFFAOYSA-N lead nickel Chemical compound [Ni].[Pb] HEPLMSKRHVKCAQ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 13
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 claims description 42
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 claims description 21
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 claims description 17
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 claims description 17
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 claims description 17
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 230000003068 static effect Effects 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 31
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000003225 biodiesel Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of fine chemical engineering, in particular to a preparation method of methyl oleate, which comprises the following steps: step one: adding nickel-lead catalyst into C18 mixed fatty acid methyl ester, and stirring uniformly; step two: introducing hydrogen into the C18 mixed fatty acid methyl ester, and reacting for 4-12 hours at 20-40 ℃ to obtain crude methyl oleate; step three: and filtering the crude methyl oleate, firstly cooling to 2-6 ℃ for the first time, then cooling to-5-0 ℃ for the second time, and filtering after 2-5 hours to obtain the methyl oleate. The preparation method provided by the invention has the advantages of low cost, low energy consumption, good safety, simple process and sufficient hydrogenation reaction, and can improve the yield of methyl oleate in the C18 mixed fatty acid methyl ester and the purity of the methyl oleate.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a preparation method of methyl oleate.
Background
The fatty acid methyl ester is obtained from natural animal and vegetable oil through ester exchange means, and is a good substitute for petroleum diesel oil. Methyl oleate in fatty acid methyl ester has relatively stable property and excellent physical property, and is widely used for synthesizing plant-based lubricating oil raw materials, surface active basic raw materials, leather and rubber softeners, fluorescent-free slurry lubricants for petroleum exploration, plastic plasticizers, water-proofing agents and toughening agents for resins.
The C18 mixed fatty acid methyl ester separated from the biodiesel mainly comprises methyl oleate, methyl linoleate and methyl stearate, wherein two C=C bonds in the methyl linoleate not only affect the storage and use performances of the methyl linoleate as fuel, but also cause problems of reaction disturbance, reduced reaction rate, poor product performance and the like, and the single C=C bond of the methyl oleate can effectively avoid troubles caused by excessive double bonds. However, the content of methyl oleate in the C18 mixed fatty acid methyl ester is only 40-48%, the method for obtaining the methyl oleate by purifying the C18 mixed fatty acid methyl ester has the defects of high cost, complex process, difficult industrial production and the like, and the yield of the finally obtained methyl oleate is lower; the method for preparing methyl oleate from the C18 mixed fatty acid methyl ester by high-temperature high-pressure hydrogenation has the defects of insufficient reaction, high energy consumption, poor safety and the like.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a preparation method of methyl oleate, which utilizes C18 mixed fatty acid methyl ester separated from biodiesel, obtains high-yield and high-purity methyl oleate through normal temperature and normal pressure hydrogenation and staged cooling.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the embodiment of the invention provides a preparation method of methyl oleate, which comprises the following steps:
step one: adding nickel-lead catalyst into C18 mixed fatty acid methyl ester, and stirring uniformly;
step two: introducing hydrogen into the C18 mixed fatty acid methyl ester, and reacting for 4-12 hours at 20-40 ℃ to obtain crude methyl oleate;
step three: filtering the crude methyl oleate, firstly cooling to 2-6 ℃ for the first time, then cooling to-5-0 ℃ for the second time, and filtering after 2-5 hours to obtain methyl oleate; wherein the cooling speed of the first cooling is 2-10 ℃/h, and the cooling speed of the second cooling is 0.5-2 ℃/h.
According to the preparation method of the methyl oleate, the nickel-lead catalyst is used for carrying out normal-temperature normal-pressure selective catalytic hydrogenation on the C18 mixed fatty acid methyl ester separated from the biodiesel, and compared with high-temperature normal-pressure hydrogenation, the normal-temperature normal-pressure hydrogenation does not cause hydrogen overflow, so that the reaction is more sufficient, and the preparation method is low in energy consumption and good in safety; the content of methyl linoleate in the C18 mixed fatty acid methyl ester can be reduced by a normal-temperature normal-pressure selective hydrogenation mode, so that the methyl linoleate is converted into methyl oleate without increasing the content of methyl stearate, and the normal-temperature normal-pressure selective catalytic hydrogenation reaction can be fully performed by limiting the temperature and time of the hydrogenation reaction, so that the yield of the methyl oleate in the C18 mixed fatty acid methyl ester is improved; according to the invention, the methyl oleate is extracted by cooling in stages, and the temperature reduction speed and the temperature range reached by cooling in each stage are controlled, so that the phenomenon that the yield of the methyl oleate is reduced or the purity of the methyl oleate is reduced due to too fast temperature reduction in the cooling process can be avoided, the high-yield and high-purity methyl oleate is ensured, and the defects of the prior art are overcome.
Preferably, in the first step, the content of methyl oleate in the C18 mixed fatty acid methyl ester is 40-48%, the content of methyl linoleate is 45-55%, and the content of methyl stearate is 2-10%. The preparation method of the invention is more suitable for the C18 mixed fatty acid methyl ester with the components and the content proportion. The content of methyl oleate, methyl linoleate and methyl stearate in the biodiesel is mostly in the content range, so the preparation method of the invention can be used for preparing methyl oleate from C18 mixed fatty acid methyl ester separated from the biodiesel.
Preferably, in the first step, the nickel-lead catalyst is nickel-lead powder with granularity of 38-48 mu m, wherein the mass ratio of nickel to lead is 1:0.3 to 1.
The mass ratio of nickel to lead in the nickel-lead catalyst is limited, so that the smooth performance of the selective hydrogenation reaction of the C18 mixed fatty acid methyl ester at normal temperature and normal pressure can be ensured, and the yield of the methyl oleate is improved.
Preferably, the mass of the nickel-lead catalyst is 1-3 per mill of the mass of the C18 mixed fatty acid methyl ester.
The quality of the nickel-lead catalyst is controlled, so that the smooth performance of the selective hydrogenation reaction of the C18 mixed fatty acid methyl ester at normal temperature and normal pressure can be ensured, and the resource waste can not be caused.
Preferably, in the first step, the stirring speed is 60-80 rpm.
By controlling the stirring speed, the nickel-lead catalyst can be ensured to be uniformly dispersed in the C18 mixed fatty acid methyl ester.
Preferably, in the second step, the addition amount of the hydrogen is 3-10 per mill of the mass of the C18 mixed fatty acid methyl ester.
Preferably, hydrogen is introduced into the C18 mixed fatty acid methyl esters by means of a venturi jet and a static mixer.
The high-temperature high-pressure hydrogenation reaction is rapid, the high-pressure hydrogen is easy to overflow, so that the problem of insufficient reaction exists, the energy consumption is high, and the safety is poor.
Preferably, in the third step, stirring is performed at a speed of 60-80 rpm during the first cooling.
Preferably, in the third step, stirring is performed at a speed of 40-60 rpm in the process of second cooling.
In the two-time cooling process, by controlling different cooling speeds and stirring speeds and slowly adjusting the stirring speed and the cooling speed along with the time, the crude methyl oleate can be cooled more uniformly, the reduction of the yield of the methyl oleate or the reduction of the purity of the methyl oleate caused by the too high or too low local cooling speed is avoided, and the high yield and the high purity of the methyl oleate are ensured.
According to the invention, methyl linoleate in the C18 mixed fatty acid methyl ester is converted into methyl oleate at normal temperature and normal pressure, so that the yield of the methyl oleate is increased, and the methyl oleate with the yield of more than 90% and the purity of more than 80% can be obtained through staged cooling. The preparation method provided by the invention has the advantages of low cost, low energy consumption, good safety, simple process and sufficient hydrogenation reaction, and can improve the yield of the methyl oleate in the C18 mixed fatty acid methyl ester and the purity of the methyl oleate, increase the economic benefit of biodiesel and be beneficial to improving the market competitiveness of methyl oleate products.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a preparation method of methyl oleate, which comprises the following steps:
pumping C18 mixed fatty acid methyl ester (40% of methyl oleate, 55% of methyl linoleate and 5% of methyl stearate in the C18 mixed fatty acid methyl ester) into a hydrogenation reaction kettle, adding nickel-lead powder (nickel-lead ratio is 1:1) with granularity of 38 mu m, wherein the adding amount of the nickel-lead powder is 1 per mill of the C18 mixed fatty acid methyl ester, uniformly stirring, and stirring at the speed of 80 revolutions per minute;
starting a self-circulation pump of the hydrogenation reaction kettle, sucking excessive hydrogen through a Venturi jet port, adding the hydrogen into the C18 mixed fatty acid methyl ester in a circulating way through a static mixer, reacting for 4 hours at the normal pressure of 40 ℃ with the hydrogen addition amount of 3 per mill of the C18 mixed fatty acid methyl ester to obtain crude methyl oleate, and starting cooling water to cool if the temperature exceeds 40 ℃ in the reaction process, wherein the excessive hydrogen returns to the Venturi jet device through the top of the hydrogenation reaction kettle again for recycling;
filtering nickel-lead catalyst from crude methyl oleate by a vertical closed filter, pumping the crude methyl oleate into a separation kettle, firstly cooling to 2 ℃ at a cooling speed of 10 ℃/h, stirring at a speed of 80 rpm in the cooling process, slowly slowing down the stirring speed to 60 rpm along with the time, and slowing down the cooling speed to 2 ℃/h;
and then cooling to 0 ℃ at a cooling speed of 1 ℃/h, stirring at a speed of 60 revolutions per minute in the cooling process, slowly slowing down the stirring speed to 40 revolutions per minute along with the time, slowing down the cooling speed to 0.5 ℃/h, and carrying out filter pressing by a plate-and-frame filter press after 5 hours, wherein the filtrate is methyl oleate, and the filter cake is methyl stearate.
Example 2
The embodiment provides a preparation method of methyl oleate, which comprises the following steps:
pumping C18 mixed fatty acid methyl ester (the content of methyl oleate in the C18 mixed fatty acid methyl ester is 48%, the content of methyl linoleate is 50%, and the content of methyl stearate is 2%) into a hydrogenation reaction kettle, adding nickel-lead powder (nickel-lead ratio is 1:0.3) with granularity of 48 mu m, wherein the adding amount of the nickel-lead powder is 3 per mill of the C18 mixed fatty acid methyl ester, uniformly stirring, and the stirring speed is 60 revolutions per minute;
starting a self-circulation pump of the hydrogenation reaction kettle, sucking excessive hydrogen through a Venturi jet port, adding hydrogen into the C18 mixed fatty acid methyl ester in a circulating way through a static mixer (the adding amount of the hydrogen is 10 per mill of that of the C18 mixed fatty acid methyl ester), reacting for 12 hours at the normal pressure of 20 ℃ to obtain crude methyl oleate, and starting cooling water to cool if the temperature exceeds 40 ℃ in the reaction process, wherein the excessive hydrogen returns to the Venturi jet device again through the top of the hydrogenation reaction kettle for recycling;
filtering nickel-lead catalyst from crude methyl oleate by a vertical closed filter, pumping the crude methyl oleate into a separation kettle, cooling to 6 ℃ at a cooling speed of 9 ℃/h, stirring at a speed of 70 rpm in the cooling process, slowly slowing down the stirring speed to 60 rpm along with the time, and slowing down the cooling speed to 2 ℃/h;
and then cooling to-5 ℃ at a cooling speed of 2 ℃/h, stirring at a speed of 55 rpm in the cooling process, slowly regulating the stirring speed to 40 rpm along with the time, and slowing down the cooling speed to 0.5 ℃/h, and after 2 hours, performing filter pressing by a plate-and-frame filter press, wherein the filtrate is methyl oleate, and the filter cake is methyl stearate.
Example 3
The embodiment provides a preparation method of methyl oleate, which comprises the following steps:
pumping C18 mixed fatty acid methyl ester (the content of methyl oleate in the C18 mixed fatty acid methyl ester is 45%, the content of methyl linoleate is 45%, and the content of methyl stearate is 10%) into a hydrogenation reaction kettle, adding nickel-lead powder (nickel-lead ratio is 1:0.6) with granularity of 42 mu m, wherein the adding amount of the nickel-lead powder is 2 per mill of the C18 mixed fatty acid methyl ester, uniformly stirring, and stirring at a speed of 70 revolutions per minute;
starting a self-circulation pump of the hydrogenation reaction kettle, sucking excessive hydrogen through a Venturi jet port, adding the hydrogen into the C18 mixed fatty acid methyl ester in a circulating way through a static mixer, reacting for 8 hours at the normal pressure of 30 ℃ with the hydrogen addition amount of 6 per mill of the C18 mixed fatty acid methyl ester to obtain crude methyl oleate, and starting cooling water to cool if the temperature exceeds 40 ℃ in the reaction process, wherein the excessive hydrogen returns to the Venturi jet device through the top of the hydrogenation reaction kettle again for recycling;
filtering nickel-lead catalyst from crude methyl oleate by a vertical closed filter, pumping the crude methyl oleate into a separation kettle, cooling to 5 ℃ at a cooling speed of 8 ℃/h, stirring at a speed of 70 rpm in the cooling process, slowly slowing down the stirring speed to 60 rpm along with the time, and slowing down the cooling speed to 2 ℃/h;
and then cooling to-3 ℃ at a cooling speed of 0.9 ℃/h, stirring at a speed of 50 rpm in the cooling process, slowly slowing down the stirring speed to 40 rpm along with the time, slowing down the cooling speed to 0.5 ℃/h, and carrying out filter pressing by a plate-and-frame filter press after 4 hours, wherein the filtrate is methyl oleate, and the filter cake is methyl stearate.
Example 4
The embodiment provides a preparation method of methyl oleate, which comprises the following steps:
pumping C18 mixed fatty acid methyl ester (the content of methyl oleate in the C18 mixed fatty acid methyl ester is 42%, the content of methyl linoleate is 50%, and the content of methyl stearate is 8%) into a hydrogenation reaction kettle, adding nickel lead powder (nickel lead ratio is 1:0.8) with granularity of 40 mu m, wherein the adding amount of the nickel lead powder is 1.5 per mill of the C18 mixed fatty acid methyl ester, and stirring uniformly at a stirring speed of 75 rpm;
starting a self-circulation pump of the hydrogenation reaction kettle, sucking excessive hydrogen through a Venturi jet port, adding hydrogen into the C18 mixed fatty acid methyl ester in a circulating way through a static mixer, reacting for 6 hours at 35 ℃ and normal pressure (the adding amount of the hydrogen is 4 per mill of the C18 mixed fatty acid methyl ester) to obtain crude methyl oleate, and starting cooling water to cool if the temperature exceeds 40 ℃ in the reaction process, wherein the excessive hydrogen returns to the Venturi jet device through the top of the hydrogenation reaction kettle again for recycling;
filtering nickel-lead catalyst from crude methyl oleate by a vertical closed filter, pumping the crude methyl oleate into a separation kettle, cooling to 6 ℃ at a cooling speed of 7 ℃/h, stirring at a speed of 75 rpm in the cooling process, slowly slowing down the stirring speed to 60 rpm along with the time, and slowing down the cooling speed to 2 ℃/h;
and then cooling to-1 ℃ at a cooling speed of 1.2 ℃/h, stirring at a speed of 58 rpm in the cooling process, slowly slowing down the stirring speed to 40 rpm along with the time, slowing down the cooling speed to 0.5 ℃/h, and carrying out filter pressing by a plate-and-frame filter press after 4 hours, wherein the filtrate is methyl oleate, and the filter cake is methyl stearate.
Example 5
The embodiment provides a preparation method of methyl oleate, which comprises the following steps:
pumping C18 mixed fatty acid methyl ester (the content of methyl oleate in the C18 mixed fatty acid methyl ester is 46%, the content of methyl linoleate is 52%, and the content of methyl stearate is 2%) into a hydrogenation reaction kettle, adding nickel-lead powder (nickel-lead ratio is 1:0.4) with granularity of 46 mu m, wherein the adding amount of the nickel-lead powder is 2.5%mill of the C18 mixed fatty acid methyl ester, uniformly stirring, and the stirring speed is 65 revolutions per minute;
starting a self-circulation pump of the hydrogenation reaction kettle, sucking excessive hydrogen through a Venturi jet port, adding the hydrogen into the C18 mixed fatty acid methyl ester in a circulating way through a static mixer, reacting for 10 hours at 25 ℃ and normal pressure (the adding amount of the hydrogen is 8 per mill of the C18 mixed fatty acid methyl ester) to obtain crude methyl oleate, and starting cooling water to cool if the temperature exceeds 40 ℃ in the reaction process, wherein the excessive hydrogen returns to the Venturi jet device again through the top of the hydrogenation reaction kettle for recycling;
filtering nickel-lead catalyst from crude methyl oleate by a vertical closed filter, pumping the crude methyl oleate into a separation kettle, cooling to 3 ℃ at a cooling speed of 8 ℃/h, stirring at a speed of 75 rpm in the cooling process, slowly slowing down the stirring speed to 60 rpm along with the time, and slowing down the cooling speed to 2 ℃/h;
and then cooling to-4 ℃ at a cooling speed of 0.6 ℃/h, stirring at a speed of 55 rpm in the cooling process, slowly slowing down the stirring speed to 40 rpm along with the time, slowing down the cooling speed to 0.5 ℃/h, and carrying out filter pressing by a plate-and-frame filter press after 3 hours, wherein the filtrate is methyl oleate, and the filter cake is methyl stearate.
Comparative example 1
The comparative example provides a method for preparing methyl oleate which is tested in the research process, comprising the following steps:
pumping C18 mixed fatty acid methyl ester (the content of methyl oleate in the C18 mixed fatty acid methyl ester is 42%, the content of methyl linoleate is 50%, and the content of methyl stearate is 8%) into a separating and extracting kettle, firstly, cooling to 6 ℃ at a cooling speed of 7 ℃/h, stirring at a speed of 75 rpm in the cooling process, slowly slowing down the stirring speed to 60 rpm along with the time, and slowing down the cooling speed to 2 ℃/h;
and then cooling to-1 ℃ at a cooling speed of 1.2 ℃/h, stirring at a speed of 58 rpm in the cooling process, slowly slowing down the stirring speed to 40 rpm along with the time, slowing down the cooling speed to 0.5 ℃/h, and carrying out filter pressing by a plate-and-frame filter press after 4 hours, wherein the filtrate is methyl oleate, and the filter cake is methyl stearate.
Comparative example 2
The comparative example provides a method for preparing methyl oleate which is tested in the research process, comprising the following steps:
pumping C18 mixed fatty acid methyl ester (the content of methyl oleate in the C18 mixed fatty acid methyl ester is 46%, the content of methyl linoleate is 52%, and the content of methyl stearate is 2%) into a hydrogenation reaction kettle, adding nickel-lead powder (nickel-lead ratio is 1:0.4) with granularity of 46 mu m, wherein the adding amount of the nickel-lead powder is 2.5%mill of the C18 mixed fatty acid methyl ester, uniformly stirring, and the stirring speed is 65 revolutions per minute;
adding hydrogen into the C18 mixed fatty acid methyl ester through a circulating pump (the addition amount of the hydrogen is 8 per mill of the C18 mixed fatty acid methyl ester), reacting for 10 hours at 25 ℃ and normal pressure to obtain crude methyl oleate, opening cooling water to cool if the temperature exceeds 40 ℃ in the reaction process, and returning excessive hydrogen to a venturi jet device again through the top of a hydrogenation reaction kettle for recycling;
filtering nickel-lead catalyst from crude methyl oleate by a vertical closed filter, pumping the crude methyl oleate into a separation kettle, cooling to 3 ℃ at a cooling speed of 8 ℃/h, stirring at a speed of 75 rpm in the cooling process, slowly slowing down the stirring speed to 60 rpm along with the time, and slowing down the cooling speed to 2 ℃/h;
and then cooling to-4 ℃ at a cooling speed of 0.6 ℃/h, stirring at a speed of 55 rpm in the cooling process, slowly slowing down the stirring speed to 40 rpm along with the time, slowing down the cooling speed to 0.5 ℃/h, and carrying out filter pressing by a plate-and-frame filter press after 3 hours, wherein the filtrate is methyl oleate, and the filter cake is methyl stearate.
Comparative example 3
The comparative example provides a method for preparing methyl oleate which is tested in the research process, comprising the following steps:
pumping C18 mixed fatty acid methyl ester (the content of methyl oleate in the C18 mixed fatty acid methyl ester is 46%, the content of methyl linoleate is 52%, and the content of methyl stearate is 2%) into a hydrogenation reaction kettle, adding nickel-lead powder (nickel-lead ratio is 1:0.4) with granularity of 46 mu m, wherein the adding amount of the nickel-lead powder is 2.5%mill of the C18 mixed fatty acid methyl ester, uniformly stirring, and the stirring speed is 65 revolutions per minute;
starting a self-circulation pump of the hydrogenation reaction kettle, sucking excessive hydrogen through a Venturi jet port, adding the hydrogen into the C18 mixed fatty acid methyl ester in a circulating way through a static mixer, reacting for 10 hours at 25 ℃ and normal pressure (the adding amount of the hydrogen is 8 per mill of the C18 mixed fatty acid methyl ester) to obtain crude methyl oleate, and starting cooling water to cool if the temperature exceeds 40 ℃ in the reaction process, wherein the excessive hydrogen returns to the Venturi jet device again through the top of the hydrogenation reaction kettle for recycling; the method comprises the steps of carrying out a first treatment on the surface of the
Filtering nickel-lead catalyst from crude methyl oleate by a vertical closed filter, pumping the crude methyl oleate into a separation kettle, firstly cooling to 4 ℃ at a cooling speed of 15 ℃/h, stirring at a speed of 80 rpm in the cooling process, and slowly slowing down the stirring speed and the cooling speed along with the time;
and then cooling to-3 ℃ at a cooling speed of 10 ℃/h, stirring at a speed of 70 rpm in the cooling process, keeping the stirring speed and the cooling speed unchanged along with the time, and performing filter pressing by a plate-and-frame filter press after 3 hours, wherein the filtrate is methyl oleate, and the filter cake is methyl stearate.
Effect example 1
The methyl oleate prepared in examples 1 to 5 and comparative examples 1 to 3 was tested, and the results of the various indexes of the methyl oleate prepared in examples 1 to 5 and comparative examples 1 to 3 are shown in Table 1:
TABLE 1
From the results of Table 1, it is seen that the methyl oleate of examples 1-5 is higher in both yield and purity than comparative examples 1-3.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (5)
1. The preparation method of the methyl oleate is characterized by comprising the following steps of:
step one: adding nickel-lead catalyst into C18 mixed fatty acid methyl ester, and stirring uniformly;
step two: introducing hydrogen into the C18 mixed fatty acid methyl ester, and reacting for 4-12 hours at 20-40 ℃ to obtain crude methyl oleate;
step three: filtering the crude methyl oleate, firstly cooling to 2-6 ℃ for the first time, then cooling to-5-0 ℃ for the second time, and filtering after 2-5 hours to obtain methyl oleate; wherein the cooling speed of the first cooling is 2-10 ℃/h, and the cooling speed of the second cooling is 0.5-2 ℃/h;
in the first step, the content of methyl oleate in the C18 mixed fatty acid methyl ester is 40-48%, the content of methyl linoleate is 45-55%, and the content of methyl stearate is 2-10%;
in the first step, the nickel-lead catalyst is nickel-lead powder with granularity of 38-48 mu m, wherein the mass ratio of nickel to lead is 1:0.3 to 1;
in the second step, the addition amount of the hydrogen is 3-10 per mill of the mass of the C18 mixed fatty acid methyl ester; wherein the hydrogen is passed into the C18 mixed fatty acid methyl ester by a venturi jet and a static mixer.
2. The method for preparing methyl oleate according to claim 1, wherein: the mass of the nickel-lead catalyst is 1-3 per mill of the mass of the C18 mixed fatty acid methyl ester.
3. The method for preparing methyl oleate according to claim 1, wherein: in the first step, the stirring speed is 60-80 rpm.
4. The method for preparing methyl oleate according to claim 1, wherein: and step three, stirring at a speed of 60-80 rpm in the process of first cooling.
5. The method for preparing methyl oleate according to claim 1, wherein: and step three, stirring at a speed of 40-60 rpm in the second cooling process.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5861521A (en) * | 1994-10-28 | 1999-01-19 | Bayer Aktiengesellschaft | Process for the hydrogenation of esters of unsaturated fatty acids |
| CN111777513A (en) * | 2020-07-02 | 2020-10-16 | 杭州国盛新材料科技有限公司 | Preparation method of high-purity methyl oleate |
| CN112961053A (en) * | 2021-02-26 | 2021-06-15 | 华南理工大学 | Method for preparing branched fatty acid methyl ester by using modified ZSM-5 molecular sieve catalyst |
| CN112973697A (en) * | 2021-03-01 | 2021-06-18 | 广东工业大学 | Catalyst for hydrogenation reaction and synthesis method for catalyzing fatty acid methyl ester by using catalyst |
| CN113061489A (en) * | 2021-03-26 | 2021-07-02 | 河北金谷再生资源开发有限公司 | Device and method for separating methyl oleate and methyl linoleate from biodiesel |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2833006A1 (en) * | 2001-11-30 | 2003-06-06 | Cognis France Sa | PROCESS FOR THE PREPARATION OF METHYL ESTER OF INDUSTRIAL OLEIC ACID |
-
2021
- 2021-12-28 CN CN202111632057.XA patent/CN114230461B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5861521A (en) * | 1994-10-28 | 1999-01-19 | Bayer Aktiengesellschaft | Process for the hydrogenation of esters of unsaturated fatty acids |
| CN111777513A (en) * | 2020-07-02 | 2020-10-16 | 杭州国盛新材料科技有限公司 | Preparation method of high-purity methyl oleate |
| CN112961053A (en) * | 2021-02-26 | 2021-06-15 | 华南理工大学 | Method for preparing branched fatty acid methyl ester by using modified ZSM-5 molecular sieve catalyst |
| CN112973697A (en) * | 2021-03-01 | 2021-06-18 | 广东工业大学 | Catalyst for hydrogenation reaction and synthesis method for catalyzing fatty acid methyl ester by using catalyst |
| CN113061489A (en) * | 2021-03-26 | 2021-07-02 | 河北金谷再生资源开发有限公司 | Device and method for separating methyl oleate and methyl linoleate from biodiesel |
Non-Patent Citations (2)
| Title |
|---|
| Raney-Ni催化下菜籽油生物柴油催化转移加氢的研究;夏燕 等;浙江工业大学学报;第40卷(第03期);第261-264页 * |
| 多不饱和脂肪酸及其酯的选择性加氢研究进展;辛宗武 等;精细化工;第37卷(第06期);第1136-1144/1198页 * |
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