阅读说明：本技术 用于油脂加氢制备含氧化合物的工艺方法 (Process method for preparing oxygen-containing compound by grease hydrogenation ) 是由 周桂林 王凤娇 谢红梅 苗彩霞 程志发 焦昭杰 张贤明 于 2019-11-08 设计创作，主要内容包括：本发明公开了一种用于油脂加氢制备含氧化合物的工艺方法,包括以下步骤：S01,负载型介孔Cu/γ-Al<Sub>2</Sub>O<Sub>3</Sub>催化剂的制备方法：选择Cu源,溶于蒸馏水中,充分搅拌后,加入载体γ-Al<Sub>2</Sub>O<Sub>3</Sub>,均匀搅拌后加热,直至水分完全蒸发,制得干料,所得干料于100℃恒温烘箱中干燥至少12.0h后,高温焙烧4.0～5.0h,经高温焙烧制得CuO/γ-Al<Sub>2</Sub>O<Sub>3</Sub>前驱体；CuO/γ-Al<Sub>2</Sub>O<Sub>3</Sub>前驱体经H<Sub>2</Sub>于350～370℃下恒温还原2.0～2.5h,制得负载型介孔Cu/γ-Al<Sub>2</Sub>O<Sub>3</Sub>催化剂。本发明简单易行,成本低,且能够大幅度提升月桂酸甲酯加氢反应转化率,大幅度提升产能。(The invention discloses a process method for preparing an oxygen-containing compound by grease hydrogenation, which comprises the following steps: s01, load type mesoporous Cu/gamma-Al 2 O 3 The preparation method of the catalyst comprises the following steps: selecting Cu source, dissolving in distilled water, stirring, adding carrier gamma-Al 2 O 3 Uniformly stirring and heating until water is completely evaporated to prepare a dry material, drying the obtained dry material in a constant-temperature oven at 100 ℃ for at least 12.0h, roasting at high temperature for 4.0-5.0 h, and roasting at high temperature to prepare CuO/gamma-Al 2 O 3 A precursor; CuO/gamma-Al 2 O 3 Precursor solution H 2 Reducing at the constant temperature of 350-370 ℃ for 2.0-2.5 h to prepare the loaded mesoporous Cu/gamma-Al 2 O 3 A catalyst. The method is simple and easy to implement, has low cost, and can greatly improve the conversion rate of the methyl laurate hydrogenation reaction and the productivity.)

1. The process method for preparing the oxygen-containing compound by hydrogenating the grease is characterized by comprising the following steps of:

s01, load type mesoporous Cu/gamma-Al₂O₃The preparation method of the catalyst comprises the following steps: selecting Cu source, dissolving in distilled water, stirring, adding carrier gamma-Al₂O₃Uniformly stirring and heating until water is completely evaporated to prepare a dry material, drying the obtained dry material in a constant-temperature oven at 100 ℃ for at least 12.0h, roasting at high temperature for 4.0-5.0 h, and roasting at high temperature to prepare CuO/gamma-Al₂O₃A precursor; CuO/gamma-Al₂O₃Precursor solution H₂Reducing at the constant temperature of 350-370 ℃ for 2.0-2.5 h to prepare the loaded mesoporous Cu/gamma-Al₂O₃A catalyst;

s02, taking a proper amount of load type mesoporous Cu/gamma-Al₂O₃The catalyst is placed in a tubular fixed bed reactor (1) at 300 ℃, and H in the tubular fixed bed reactor (1)₂Flow LHSV of 1.5h^-1，H₂Pressure P_H2Pumping a certain amount of raw material methyl laurate by a double-plunger micro pump (13) under the pressure of 2MPa, and then starting the reaction at the reaction temperature of 300-₂and/Oil is 500N, and after the reaction is finished, the lauric acid oxygenated compound is prepared.

2. The process for preparing oxygen-containing compounds by hydrogenating oil and fat according to claim 1, wherein the Cu source is Cu (NO)₃)₂·3H₂O, weight of distilled water is Cu (NO)₃)₂·3H₂4-24 times of O and a carrier gamma-Al₂O₃Is Cu (NO)₃)₂·3H₂1.5 to 8.6 times the amount of O.

3. The process for preparing oxygen-containing compounds by hydrogenating oil and fat according to claim 2The method is characterized in that the supported mesoporous Cu/gamma-Al₂O₃The Cu content in the catalyst is 10 percent, namely the carrier gamma-Al₂O₃Is Cu (NO)₃)₂·3H₂2.3 to 2.4 times of O.

4. The process for preparing the oxygen-containing compound by hydrogenating the grease according to claim 1, wherein the temperature of the high-temperature calcination is 400 ℃.

5. The process for preparing the oxygenated compounds by the hydrogenation of the Oil and fat according to claim 1, wherein the Oil is methyl laurate.

6. The process for preparing oxygen-containing compounds by hydrogenating oil and fat according to claim 1, wherein the CuO/gamma-Al is₂O₃The dosage of the precursor is 15mL, 15 mLCuO/gamma-Al₂O₃The weight of the precursor is 26-28 g, and the volume flow of the methyl laurate is 0.38 mL/min.

7. The process for preparing the oxygen-containing compound by hydrogenating the oil and fat according to claim 1, wherein the lauric acid oxygen-containing compound comprises lauraldehyde, lauryl alcohol, lauric acid and dodecyl laurate.

8. The process method for preparing the oxygenated compounds by hydrogenating the oil and fat according to claim 1, wherein the detecting method of the lauric acid oxygenated compounds is as follows: the method comprises the following steps of (1) carrying out off-line detection on the content of a mixture in a lauric acid oxygenated compound sample by SC-3000B type gas chromatography with an FID detector under the following detection conditions: the temperature of the detector is 280 ℃, the temperature of the vaporization chamber is 280 ℃, and the temperature of the column box is programmed to be 270 ℃ from 60 ℃ at the speed of 10 ℃/min.

Technical Field

The invention relates to a process method for preparing an oxygen-containing compound by grease hydrogenation, belonging to the technical field of grease hydroconversion.

Background

Lauraldehyde, lauryl alcohol, lauric acid and dodecyl laurate can be used to make high-performance detergents, surfactants, foam-wrapping agents, hair-growth regulators, emulsifiers, textile oils, bactericides, cosmetics, plasticizers, plant growth regulators, lubricant additives and other specialty chemicals. The oxygen-containing compounds are used as organic chemical raw materials, widely applied to industries such as light industry, chemical industry, metallurgy, medicine and the like, and have wide application prospects. Chemical industry has a close relationship with national defense, people's life and advanced science, and is an important industrial department closely related to economic construction and people's life, so that the development of chemical industry and the production of chemical products become urgent matters. Methyl laurate, a chemical product with great production capacity in China, has mature production technology and high product purity, and has a more-than-required pattern on the market, so the problem of excess capacity is concerned. At present, the hydrogen production technology is developed rapidly, and industrialization is basically realized through technologies such as water electrolysis hydrogen production, water photolysis hydrogen production, biomass hydrogen production and the like, so that under the condition of abundant hydrogen sources, the catalytic hydrogenation of methyl laurate is concerned widely to prepare other functional chemicals, and the process method for preparing oxygen-containing compounds such as lauraldehyde and lauryl laurate through the hydrogenation of methyl laurate is reported only rarely.

In the conventional hydrogenation reaction, noble metals such as Pt, Pd, Rh, Ru, and the like are mostly used as the catalyst active component because the d electron orbitals thereof are not filled, easily adsorb reactants, have strong hydrogen storage capacity, and have high catalytic hydrogenation activity, but their price is high, high temperature resistance is poor, and the selectivity of target products is poor, etc., which limits the application thereof in the hydrogenation reaction.

Therefore, the existing hydrogenation reaction has the problems that the catalyst cost is high, the high-efficiency conversion of the methyl laurate cannot be realized, and the selectivity of the target product, namely the oxygen-containing compound is low, and the like, which undoubtedly limits the further development and utilization of the methyl laurate.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a process method for preparing an oxygen-containing compound by grease hydrogenation, the process method is simple and easy to implement and low in cost, and can greatly improve the conversion rate of the hydrogenation reaction of methyl laurate and greatly improve the productivity.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the device for preparing the oxygen-containing compound by grease hydrogenation comprises a tubular fixed bed reactor, wherein a heating furnace is arranged on the periphery of the tubular fixed bed reactor, the heating furnace is connected with an integrated temperature controller, the integrated temperature controller is also connected with a thermocouple, the temperature detection end of the thermocouple is positioned at the catalyst bed layer of the tubular fixed bed reactor, the feed inlet of the tubular fixed bed reactor is connected with a first port of a first three-way valve, a second port of the first three-way valve is connected with a first pressure gauge, the first pressure gauge is connected with one end of a second three-way valve, the other two ends of the second three-way valve and a third port of the first three-way valve are respectively connected with a mass flow meter, the mass flow meter is connected with first valves, the three first valves are respectively connected with a hydrogen steel cylinder, a nitrogen steel cylinder and a double-plunger micro pump, and pressure reducing valves are arranged on the hydrogen steel cylinder and the nitrogen steel cylinder; the double-plunger micro pump is connected with the raw material bottle; the discharge gate of tubular fixed bed reactor links to each other with the condenser, the condenser links to each other with vapour and liquid separator, vapour and liquid separator's gas outlet links to each other with the second manometer, the second manometer links to each other with the back pressure valve, the back pressure valve links to each other with the gas washing bottle, vapour and liquid separator's liquid outlet links to each other with the second valve.

The heating furnace is an open-close type three-section heating furnace.

The process method for preparing the oxygen-containing compound by hydrogenating the grease comprises the following steps:

s01, load type mesoporous Cu/gamma-Al₂O₃The preparation method of the catalyst comprises the following steps: selecting Cu source, dissolving in distilled water, stirring, adding carrier gamma-Al₂O₃Uniformly stirring and heating until water is completely evaporated to prepare a dry material, drying the obtained dry material in a constant-temperature oven at 100 ℃ for at least 12.0h, roasting at high temperature for 4.0-5.0 h, and roasting at high temperature to prepare CuO/gamma-Al₂O₃A precursor; CuO/gamma-Al₂O₃Precursor solution H₂Reducing at the constant temperature of 350-370 ℃ for 2.0-2.5 h to prepare the loaded mesoporous Cu/gamma-Al₂O₃A catalyst;

s02, taking a proper amount of load type mesoporous Cu/gamma-Al₂O₃The catalyst is placed in a tubular fixed bed reactor at 300 ℃, and H in the tubular fixed bed reactor₂Flow LHSV of 1.5h^-1，H₂Pressure P_H2Pumping a certain amount of raw material methyl laurate by a double-plunger micro pump under the pressure of 2MPa, and then starting the reaction at the reaction temperature of 300 ℃ and 360 ℃ under the pressure of H₂and/Oil is 500N, and after the reaction is finished, the lauric acid oxygenated compound is prepared.

The Cu source is Cu (NO)₃)₂·3H₂O, weight of distilled water is Cu (NO)₃)₂·3H₂4-24 times of O and a carrier gamma-Al₂O₃Is Cu (NO)₃)₂·3H₂1.5 to 8.6 times the amount of O.

The supported mesoporous Cu/gamma-Al₂O₃The Cu content in the catalyst is 10 percent, namely the carrier gamma-Al₂O₃Is Cu (NO)₃)₂·3H₂2.3 to 2.4 times of O.

The temperature of the high-temperature calcination is 400 ℃.

The Oil is methyl laurate.

The CuO/gamma-Al₂O₃The dosage of the precursor is 15mL, 15 mLCuO/gamma-Al₂O₃The weight of the precursor is 26-28 g per monthThe volume flow rate of methyl laurate was 0.38 mL/min.

The lauric acid oxygen-containing compound comprises lauraldehyde, lauryl alcohol, lauric acid and dodecyl laurate.

The detection method of the lauric acid oxygenated compounds comprises the following steps: the method comprises the following steps of (1) carrying out off-line detection on the content of a mixture in a lauric acid oxygenated compound sample by SC-3000B type gas chromatography with an FID detector under the following detection conditions: the temperature of the detector is 280 ℃, the temperature of the vaporization chamber is 280 ℃, and the temperature of the column box is programmed to be 270 ℃ from 60 ℃ at the speed of 10 ℃/min.

The invention has the beneficial effects that:

the invention provides a process method for preparing oxygen-containing compounds by grease hydrogenation, which adopts self-made supported mesoporous Cu/gamma-Al₂O₃As a catalyst for methyl laurate hydrogenation reaction, the catalyst can selectively hydrogenate C-O and C ═ O bonds, and is relatively inactive in the hydrogenolysis reaction of the C-C bonds, especially the supported mesoporous Cu/gamma-Al with the Cu content of 10 percent₂O₃The catalyst, abbreviated as CA10, has more excellent high-efficiency conversion rate of methyl laurate and higher selectivity of the target product, namely the oxygenated chemicals. In the invention, the catalytic hydrogenation reaction is not only related to the catalyst, but also related to the reaction conditions in the reaction process, and the invention changes the reaction pressure, the reaction temperature and the H in the hydrogenation reaction process₂The Oil reaction condition enables the methyl laurate to be efficiently converted, and meanwhile, the high selectivity of the target product oxygen-containing compound is obtained, so that the method has important practical application value and scientific significance for improving the additional values of the methyl laurate and the grease compound.

Drawings

FIG. 1 is a schematic diagram of the apparatus of the present invention;

FIG. 2 shows the present invention of a supported mesoporous Cu/gamma-Al₂O₃XRD characterization pattern of the catalyst;

FIG. 3 shows the present invention of a supported mesoporous Cu/gamma-Al₂O₃BET characterization of the catalyst;

FIG. 4 shows the present invention of a supported mesoporous Cu/gamma-Al₂O₃The pore size distribution diagram of the catalyst;

FIG. 5 shows the present invention of a supported mesoporous Cu/gamma-Al₂O₃H of catalyst₂Temperature programmed reduction curve;

fig. 6 is an enlarged view of fig. 5.

Detailed Description

The present invention will be further described with reference to the accompanying drawings.