Immobilized catalyst as well as preparation method and application thereof

Abstract

The invention provides an immobilized catalyst as well as a preparation method and application thereof. The immobilized catalyst is prepared from zinc oxide, a mesoporous silicate carrier and a surface modifier, the specific surface area of the mesoporous silicate carrier is larger than or equal to 200 m / g, the pore diameter of the mesoporous silicate carrier is 2-50 nm, and the mass ratio of the zinc oxide to the mesoporous silicate carrier is 1: 2-1: 11. The fatty acyl amino acid salt is prepared by catalyzing an amino acid salt and a carboxylic acid compound to react by an immobilized catalyst. When the prepared catalyst is used for preparing fatty acyl amino acid salt, the conversion rate of the amino acid salt is increased to 98.2% or above, and the content of the fatty acyl amino acid salt is 96.9% or above; and compared with a conventional catalyst which is repeatedly used, the catalyst prepared by the method still has higher amino acid salt conversion rate and higher fatty acyl amino acid salt content after being repeatedly used for multiple times.

Description

Technical Field

[0001] This invention belongs to the field of daily chemical materials technology, specifically relating to supported catalysts, their preparation methods, and applications. Background Technology

[0002] Fatty acyl amino acid salts are a class of amino acid-type anionic surfactants prepared by reacting amino acid salts with carboxylic acid compounds. They are widely used in shampoos, facial cleansers, and bath products due to their resistance to hard water, acids and alkalis, good foaming properties, and pleasant hand feel after use. However, with ongoing research into amino acid-type anionic surfactants, it has been discovered that they are not only widely used in shampoos, facial cleansers, and bath products, but are also increasingly being applied in agriculture, biological products, and the silk printing and dyeing industry. This has led to a continuous increase in the demand for fatty acyl amino acid salts.

[0003] Existing technologies for preparing fatty acyl amino acid salts generally suffer from the core problems of harsh reaction conditions and insufficient conversion efficiency: First, the reaction temperature is too high, usually requiring control within the high-temperature range of 180–250°C, which not only significantly increases energy consumption but also necessitates the use of reaction vessels and pipelines made of special high-temperature resistant materials, directly driving up equipment costs; Second, the reaction time is too long, and the limited mass transfer efficiency severely restricts production efficiency; Third, the raw material conversion rate is low. Due to insufficient matching between reaction conditions and catalysts, the product content of fatty acyl amino acid salts is low, and the fatty acyl amino acid salts contain unreacted raw materials with high residual levels, which reduces product yield and increases the burden of subsequent separation and purification, while the catalyst recovery rate is low.

[0004] To improve the content (i.e., purity) and conversion rate of fatty acyl amino acid salts, existing catalysts used in their preparation are mostly single metal oxides such as zinc oxide or titanium oxide, or amorphous particles such as activated carbon. However, there are still challenges in simultaneously achieving high-efficiency catalysis, stable reuse, and convenient recovery. This results in fatty acyl amino acid salts still suffering from high-temperature energy consumption, prolonged inefficiency, low conversion rates, and difficulties in recovery. Furthermore, there is currently no integrated process in the industry that combines column-supported catalysts, filter recovery, and granulation for discharge.

[0005] In view of the problems existing in the prior art, how to provide a catalyst that can solve the problems of high temperature energy consumption, long-term inefficiency, low conversion rate and recovery when preparing fatty acyl amino acid salts, and how to provide a fatty acyl amino acid salt with high content are the problems that this invention urgently needs to solve. Summary of the Invention

[0006] The purpose of this invention is to provide supported catalysts, their preparation methods, and applications to solve the problems mentioned in the background art.

[0007] To achieve the above objectives, the present invention provides the following technical solution: On one hand, the present invention provides a supported catalyst, the raw materials for preparing the supported catalyst include zinc oxide, mesoporous silicate support and surface modifier, wherein the specific surface area of ​​the mesoporous silicate support is ≥200m² / g and the pore size is 2-50nm, and the mass ratio of zinc oxide to mesoporous silicate support is 1:2-1:11.

[0008] In some embodiments, the surface modifier is 5-15% of the total mass of zinc oxide and mesoporous silicate carrier.

[0009] In some embodiments, the surface modifier is a nonionic surfactant.

[0010] In some embodiments, the surface modifier is preferably polyethylene glycol or polyvinyl alcohol; more preferably, the surface modifier is preferably polyethylene glycol-4000, polyethylene glycol-6000, or polyvinyl alcohol-1788.

[0011] In some embodiments, the supported catalyst is columnar.

[0012] In some embodiments, in order to avoid the sedimentation and agglomeration of traditional fine particles (particle size of 0.5-1 mm) and improve the contact efficiency between active sites and raw materials by more than 40%, thereby reducing the reaction temperature and shortening the time, the supported catalyst is preferably columnar particles, and the columnar particles are uniformly suspended at a stirring speed of 200-500 r / min. During stirring, a kettle stirring is preferred.

[0013] In some embodiments, to ensure that the supported catalyst has excellent shear resistance and its integrity is ≥90% after being reused 5 times, and to avoid the problem of easy breakage under traditional particle stirring, the supported catalyst is preferably columnar particles.

[0014] In some embodiments, when the supported catalyst is in the form of columnar particles, its diameter is 2 mm and its length is 5 mm.

[0015] In some embodiments, the surface modifier is polyethylene glycol or polyvinyl alcohol.

[0016] In some embodiments, the average molecular weight of the polyethylene glycol is ≥4000.

[0017] In some embodiments, the polyethylene glycol-4000 used in the present invention was purchased from Taizhou Jiayin Chemical Co., Ltd.

[0018] On the other hand, the present invention also provides a method for preparing a supported catalyst, comprising the following steps: (1) The mesoporous silicate support is calcined, and the calcined mesoporous silicate support is fully impregnated in zinc oxide solution, and then a surface modifier is added and stirred thoroughly to obtain an intermediate. (2) After drying, crushing and calcining the intermediate, it is cooled, deionized water is added for kneading, and then extruded and granulated by an extrusion granulator and dried to obtain a supported catalyst.

[0019] In some embodiments, to ensure the stability of the columnar structure of the supported catalyst and prevent clogging of the support, 5-8% of deionized water by weight of the mesoporous silicate support and zinc oxide is added as a binder; at the same time, to facilitate the solidification of the supported catalyst, after being granulated into columnar particles by a granulator, it is dried at a temperature of 60-250℃ for 1-5 hours, and the preferred rotation speed of the granulator is 30-50 r / min; wherein, in the specific embodiments of the present invention, the rotation speed of the granulator is 50 r / min.

[0020] In some embodiments, the mesoporous aluminum silicate and magnesium silicate of the present invention can be purchased from suppliers or prepared by the manufacturer according to actual needs. In a specific embodiment of the present invention, the mesoporous aluminum silicate of the present invention can be prepared by the following method: At room temperature, 1.2 g of surfactant, 1 mL of concentrated hydrochloric acid and 2.3 mL of glacial acetic acid are added to 35 mL of anhydrous ethanol and stirred until the surfactant is completely dissolved. Then, 1.2 mL of tetraethyl orthosilicate and 1.3 g of aluminum sec-butoxide are added to the above solution and stirred for another 2.5 h. The resulting sol is then poured into a petri dish and evaporated at 40 °C for 6 h to obtain a gel. The gel is then aged in a 65 °C oven for 30 h and then calcined in a muffle furnace at 550 °C for 5.5 h to remove the surfactant, finally obtaining the desired mesoporous aluminum silicate. The surfactant is Pluronic® F-127, purchased from Merck.

[0021] On the other hand, the present invention also provides the application of supported catalysts in the preparation of fatty acyl amino acid salts, wherein the fatty acyl amino acid salts are prepared by reacting amino acid salts and carboxylic acid compounds catalyzed by the supported catalyst.

[0022] In some embodiments, the fatty acyl amino acid salt includes, but is not limited to, at least one of the following: sodium fatty acyl methyl taurate, sodium fatty acyl glycinate, sodium fatty acyl alanine, sodium fatty acyl sarcosine, potassium fatty acyl methyl taurate, potassium fatty acyl glycinate, potassium fatty acyl alanine, and potassium fatty acyl sarcosine.

[0023] In some embodiments, the fatty acyl amino acid salt includes, but is not limited to, at least one of sodium lauroyl methyl taurate, sodium cocoyl methyl taurate, sodium myristoyl glycinate, potassium stearoyl alanine, sodium lauroyl sarcosinate, sodium n-decanoyl methyl taurate, sodium oleoyl methyl taurate, potassium lauroyl glycinate, sodium palmitoyl alanine, sodium palmitoyl / stearoyl alanine, and sodium n-octanoyl glycinate.

[0024] In some embodiments, the amino acid salt includes, but is not limited to, at least one of sodium methyl taurate, sodium glycine, sodium alanine, sodium sarcosinate, potassium alanine, potassium sarcosinate, sodium alanine, and potassium glycine. Specifically, in a particular embodiment of the present invention, the CAS number of potassium alanine is 93893-38-0; the CAS number of potassium sarcosinate is 56935-86-5; and the CAS number of sodium alanine is 16480-55-0.

[0025] In some embodiments, the molar ratio of the carboxylic acid compound to the amino acid salt is 1.25-5:1.

[0026] In some embodiments, to combine the high catalytic efficiency of the supported catalyst with a reduction in fatty acid usage and subsequent distillation load, the molar ratio of carboxylic acid compound to amino acid salt is controlled at 1.25-2:1.

[0027] In some embodiments, in order to achieve a conversion rate of over 99.4% for the amino acid salt and a yield (content) of over 99.4% for the fatty acyl amino acid salt, preferably, the molar ratio of the carboxylic acid compound to the amino acid salt is controlled at 1.34-1.48:1.

[0028] In some embodiments, in order to achieve a conversion rate of over 99.5% for the amino acid salt and a yield (content) of over 99.5% for the fatty acyl amino acid salt, preferably, the carboxylic acid compound is coconut oil acid and the amino acid salt is sodium methyl taurate.

[0029] In some embodiments, the carboxylic acid compound is a saturated or unsaturated fatty acid containing 6-22 carbon atoms.

[0030] In some embodiments, the carboxylic acid compound includes, but is not limited to, at least one of lauric acid, coconut acid, myristic acid, palmitic acid, oleic acid, stearic acid, n-decanoic acid, and n-octanoic acid.

[0031] In some embodiments, the method for preparing the fatty acyl amino acid salt includes the following steps: (1) Mix the amino acid salt and the molten carboxylic acid compound, then heat it to 60-120℃ and keep it at that temperature for reaction. Then add the supported catalyst and stir it thoroughly to suspend the catalyst. (2) Then the substance from step (1) is heated and the reaction temperature is controlled at 120-180℃. The filtrate is granulated, purified and dried to obtain fatty acyl amino acid salt.

[0032] In some embodiments, when the amino acid salt in the present invention is dehydrated sodium methyl taurate, the dehydration process of sodium methyl taurate is as follows: a 40% sodium methyl taurate aqueous solution is added to a rotary evaporator and dehydrated under reduced pressure for 2 hours at a temperature of 80°C and a pressure of -0.08 MPa until constant weight is achieved. The solution is then transferred to a drying bottle to obtain dehydrated sodium methyl taurate.

[0033] In some embodiments, in order to achieve a 40% reduction in energy consumption relative to powder drying and to meet the direct feeding requirements of the daily chemical industry, step (2) in the preparation of fatty acyl amino acid salts uses a granulator (60-80℃, 1-3mm screen) to directly granulate the reaction product. The product moisture content is ≤1.5%, the angle of repose is ≤35°, and the granulated product has a uniform particle size of 1-3mm, thereby making the material flowability after granulation better. In the embodiments of the present invention, the granulation temperature is 80℃ and the screen size is 1-3mm.

[0034] In some embodiments, the supported catalyst in step (1) of the preparation of fatty acyl amino acid salts is 0.5-1.5% of the total mass of the amino acid salt and carboxylic acid compound.

[0035] In some embodiments, the purification step (2) in the preparation of fatty acyl amino acid salts is to mix the granulated material with 70% ethanol aqueous solution at a solid-liquid ratio of 1g:3-7mL, stir at 50-60℃ for 0.5-2h, cool to 25-50℃ and filter, repeat the above operation, and wash with 70% ethanol aqueous solution 2-4 times.

[0036] In the specific embodiment of the present invention, the purification in step (2) of the preparation of fatty acyl amino acid salt is to mix the granulated material with 70% ethanol aqueous solution at a solid-liquid ratio of 1g:5mL, stir at 50℃ for 1h, cool to 40℃ and filter, repeat the above operation, and wash twice with 70% ethanol aqueous solution.

[0037] In some embodiments, the drying temperature of step (2) in the preparation of fatty acyl amino acid salts is 50-70°C and the drying time is 1-6 hours.

[0038] In the specific embodiments of the present invention, the drying temperature of step (2) in the preparation of fatty acyl amino acid salts is 60°C and the drying time is 2h.

[0039] In some embodiments, when the amino acid salt in step (1) of the preparation of fatty acyl amino acid salt is sodium glycinate, sodium alanine, or sodium sarcosinate, the reaction temperature in step (2) is 100-160℃ (20-50℃ lower than the conventional method).

[0040] In some embodiments, when the amino acid salt in step (1) of the preparation of fatty acyl amino acid salt is sodium methyl taurate, the reaction temperature in step (2) is 120-180℃ (30-70℃ lower than the conventional temperature).

[0041] In some embodiments, the reaction time of step (2) in the preparation of fatty acyl amino acid salts is shortened to 15-50 min (30-50% less than the conventional method).

[0042] In some embodiments, amino acid salts can be dehydrated at a temperature of 60-120°C and a pressure of -0.1 to -0.05 MPa.

[0043] In some embodiments, to ensure that the recovery rate of the supported catalyst is ≥95% and to avoid fine particles passing through the filter or clogging the filter screen, the supported catalyst is preferably columnar particles with a diameter of 2 mm.

[0044] In some implementations, during catalyst recovery, a 316L stainless steel 50-mesh filter (pore size 300μm) is used for filtration at 80-100℃ and 0.1-0.2MPa pressure. The columnar catalyst is completely retained, and the filtrate clarity is ≥98%. This solves the problems of easy clogging of traditional 400-mesh filters and loss of 200-mesh filters when using fine particles, and improves the catalyst recovery efficiency by 5-10%.

[0045] Compared with the prior art, the beneficial effects of the present invention are: compared with the use of conventional catalysts or no catalyst, when the catalyst prepared by the present invention is used to prepare fatty acyl amino acid salts, the conversion rate of amino acid salts is increased to more than 98.2% and the content of fatty acyl amino acid salts is more than 96.9%. Even when the reaction temperature for preparing fatty acyl amino acid salts is reduced by 30-80°C and the time is shortened to 60 min, it still has a high conversion rate of amino acid salts and a high content of fatty acyl amino acid salts. Moreover, compared to the repeated use of conventional catalysts, the catalyst prepared in this invention, although the amino acid salt conversion rate and fatty acyl amino acid salt content decrease after repeated use, the decrease is not significant, and it still has a higher amino acid salt conversion rate and a higher fatty acyl amino acid salt content. Detailed Implementation

[0046] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0047] The preparation of supported catalyst-1 includes the following steps: (1) Weigh 60g of mesoporous aluminum silicate (specific surface area of ​​220m² / g, pore size of 5-7nm, average pore size of 6nm) as mesoporous aluminum silicate carrier, place it in a muffle furnace and calcine at 500℃ for 2h, and cool it naturally to room temperature; take another 20g of zinc oxide, add 100mL of 0.5mol / L nitric acid solution, and stir magnetically for 30min until completely dissolved to obtain zinc oxide solution; immerse the calcined mesoporous aluminum silicate carrier in zinc oxide solution, stir mechanically at 30℃ for 4h (speed 200r / min), then add 8g of polyethylene glycol-4000 (added in three parts, 2g, 3g, and 3g respectively, with an interval of 20min), and continue stirring for 2h; (2) Transfer the mixture from step (1) to a tray, dry it at 100°C for 4 hours, then pulverize it through an 80-mesh sieve, and then continue to calcine it at 450°C for 2 hours. After calcination, cool the material to 40°C, add 6g of deionized water, knead it for 10 minutes to form a plastic dough, and then collect the extruded strips through an extruder, cut them into columnar particles with a length of 5mm and a diameter of 2mm, and then continue to dry them at 200°C for 2 hours to obtain the supported catalyst-1.

[0048] The compressive strength of the supported catalyst-1, as measured by international standard ASTM D6175-03 (2018), is ≥5 N / mm². 2 .

[0049] The preparation of supported catalyst-2 includes the following steps: (1) Weigh 210g of mesoporous magnesium silicate (specific surface area of ​​210m² / g, pore size of 6-8nm, average pore size of 7nm) as mesoporous magnesium silicate support, place it in a muffle furnace and calcine at 500℃ for 2h, and cool it naturally to room temperature; take another 20g of zinc oxide, add 100mL of 0.5mol / L nitric acid solution, and stir magnetically for 30min until completely dissolved to obtain zinc oxide solution; immerse the calcined mesoporous magnesium silicate support in zinc oxide solution, stir mechanically at 30℃ for 4h (speed 200rpm), then add 23g of polyethylene glycol-4000 (added in three parts, 7g, 8g, and 8g respectively, with an interval of 20min), and continue stirring for 2h; (2) Transfer the mixture from step (1) to a tray, dry it at 100°C for 4 hours, then pulverize it through an 80-mesh sieve, and then continue to calcine it at 450°C for 2 hours. After calcination, cool the material to 40°C, add 17.25g of deionized water, knead it for 10 minutes to form a plastic dough, and then collect the extruded strips through an extruder, cut them into columnar particles with a length of 5mm and a diameter of 2mm, and then continue to dry them at 200°C for 2 hours to obtain the supported catalyst-2.

[0050] The compressive strength of the supported catalyst-2, as measured by international standard ASTM D6175-03 (2018), is ≥5 N / mm². 2 .

[0051] Example 1 (Sodium lauroyl methyl taurate): (1) Place 120g of lauric acid in a 250mL beaker and heat it to 60℃ until it melts. Then add 120g of molten lauric acid and 60g of dehydrated sodium methyl taurate to a 500mL stainless steel reactor. Melt it to a slurry at 80℃. Turn on the stirring (300r / min). Then add 2g of supported catalyst-1, turn on the nitrogen gas, and gradually raise the temperature to 150℃. React for 50min. (2) After the reaction in step (1) is completed, the temperature is reduced to 90°C, the stirring is maintained at 150 r / min, the bottom valve of the vessel is connected to the filter screen, the nitrogen pressure is set to 0.15 MPa, the valve is opened to filter the material (the filter screen is 50 mesh), the trapped catalyst is collected, and the filtered liquid is sent to the hopper of the granulator. The granulation temperature is set to 25°C and the machine is started to granulate. The particles are collected to obtain the high acid product. (3) After purification and drying, the high-acid product is obtained as a white powder, which is sodium lauroyl methyl taurate.

[0052] According to the test results, the raw material conversion rate of sodium methyl taurate in Example 1 was 99.2%, the catalyst recovery rate was 97%, and the content of sodium lauroyl methyl taurate was 99.5%.

[0053] Example 2 (Sodium cocoyl methyl taurate): (1) Add 330g of coconut oil acid (65wt% lauric acid, 25wt% myristic acid, 6wt% octanoic acid, and 4wt% decanoic acid) to the reactor and heat it to 80℃ until it melts. Then add 330g of molten coconut oil acid and 195g of dehydrated sodium methyl taurate to a 500mL stainless steel reactor and melt it into a slurry at 120℃. Start stirring (300r / min), then add 3.2g of supported catalyst-1, turn on nitrogen gas, and gradually raise the temperature to 135℃ and react for 45min. (2) After the reaction in step (1) is completed, the temperature is reduced to 90°C, the stirring is maintained at 150 r / min, the bottom valve of the vessel is connected to the filter screen, the nitrogen pressure is set to 0.15 MPa, the valve is opened to filter the material (the filter screen is 50 mesh), the trapped catalyst is collected, and the filtered liquid is sent to the hopper of the granulator. The granulation temperature is set to 25°C, the machine is started to granulate, the particles are collected, and a high acid product is obtained. (3) After purification and drying, the high-acid product is obtained as a white powder, which is sodium cocoyl methyl taurate.

[0054] According to the test results, in Example 2, the conversion rate of sodium methyl taurate was 99.5%, the catalyst recovery rate was 99.1%, and the content of sodium cocoyl methyl taurate was 99.6%.

[0055] Example 3 (Sodium myristoyl glycinate): (1) Place 120g of myristic acid in a 250mL beaker and heat it to 80℃ until it melts. Then add 120g of molten myristic acid and 35g of sodium glycine to a 500mL stainless steel reactor and melt it into a slurry at 120℃. Turn on the stirring (300r / min), then add 2.1g of supported catalyst-1, turn on the nitrogen gas, and gradually raise the temperature to 138℃. React for 45min. (2) After the reaction in step (1) is completed, the temperature is reduced to 90°C, the stirring is maintained at 150 r / min, the bottom valve of the vessel is connected to the filter screen, the nitrogen pressure is set to 0.15 MPa, the valve is opened to filter the material (the filter screen is 50 mesh), the trapped catalyst is collected, and the filtered liquid is sent to the hopper of the granulator. The granulation temperature is set to 25°C, the machine is started to granulate, the particles are collected, and a high acid product is obtained. (3) After purification and drying, the high-acid product is obtained as a white powder, which is sodium myristoyl glycinate.

[0056] The conversion rate of sodium glycinate in Example 3 was 99.1%, the catalyst recovery rate was 98.6%, and the content of sodium myristoyl glycinate was 99.3%.

[0057] Example 4 (Potassium stearoylalanine): (1) Place 200g of stearic acid in a 250mL beaker and heat it to 80℃ until it melts. Then add 200g of molten stearic acid and 60g of potassium alanine to a 500mL stainless steel reactor. Melt it to a slurry at 120℃. Turn on the stirrer (300r / min). Then add 2.3g of supported catalyst-1, turn on the nitrogen gas, and gradually raise the temperature to 155℃. React for 40min. (2) After the reaction in step (1) is completed, the temperature is reduced to 90°C, the stirring is maintained at 150 r / min, the bottom valve of the vessel is connected to the filter screen, the nitrogen pressure is set to 0.15 MPa, the valve is opened to filter the material (the filter screen is 50 mesh), the trapped catalyst is collected, and the filtered liquid is sent to the hopper of the granulator. The granulation temperature is set to 25°C, the machine is started to granulate, the particles are collected, and a high acid product is obtained. (3) After purification and drying, the high-acid product is obtained as a white powder, which is potassium stearoyl alanine.

[0058] The tests showed that the potassium alanine conversion rate in Example 4 was 99.0%, the catalyst recovery rate was 95.2%, and the content of potassium stearoyl alanine was 98.4%.

[0059] Example 5 (Sodium lauroyl sarcosinate): (1) Place 250g of lauric acid in a 250mL beaker and heat it to 80℃ until it melts. Then add 250g of molten lauric acid and 94g of dehydrated sodium sarcosinate to a 500mL stainless steel reactor. Melt it to a slurry at 120℃. Turn on the stirrer (300r / min). Then add 1.9g of supported catalyst-1, turn on the nitrogen gas, and gradually raise the temperature to 140℃. React for 50min. (2) After the reaction in step (1) is completed, the temperature is reduced to 90°C, the stirring is maintained at 150 r / min, the bottom valve of the vessel is connected to the filter screen, the nitrogen pressure is set to 0.15 MPa, the valve is opened to filter the material (the filter screen is 50 mesh), the trapped catalyst is collected, and the filtered liquid is sent to the hopper of the granulator. The granulation temperature is set to 25°C, the machine is started to granulate, the particles are collected, and a high acid product is obtained. (3) After purification and drying, the high-acid product is obtained as a white powder, which is sodium lauroyl sarcosinate.

[0060] According to the test results, the conversion rate of sodium sarcosinate in Example 5 was 99.4%, the catalyst recovery rate was 97.8%, and the content of sodium lauroyl sarcosinate was 99.4%.

[0061] Example 6 (Sodium n-decanoylmethyltaurate): (1) Place 112g of n-decanoic acid in a 250mL beaker and heat it to 80℃ until it melts. Then add 112g of molten n-decanoic acid and 81.5g of dehydrated sodium methyl taurate to a 500mL stainless steel reactor. Melt it to a slurry at 120℃. Turn on the stirring (300r / min). Then add 1.94g of supported catalyst-1, turn on the nitrogen gas, and gradually raise the temperature to 125℃. React for 50min. (2) After the reaction in step (1) is completed, the temperature is reduced to 90°C, the stirring is maintained at 150 r / min, the bottom valve of the vessel is connected to the filter screen, the nitrogen pressure is set to 0.15 MPa, the valve is opened to filter the material (the filter screen is 50 mesh), the trapped catalyst is collected, and the filtered liquid is sent to the hopper of the granulator. The granulation temperature is set to 25°C, the machine is started to granulate, the particles are collected, and a high acid product is obtained. (3) After purification and drying, the high-acid product is obtained as a white powder, which is sodium decanoyl methyl taurate.

[0062] According to the test results, the conversion rate of sodium methyl taurate in Example 6 was 99.6%, the catalyst recovery rate was 97.1%, and the content of sodium n-decanoyl methyl taurate was 98.2%.

[0063] Example 7 (Potassium Oleylsarcosinate): (1) Place 198g of oleic acid in a 250mL beaker and heat it to 80℃ until it melts. Then add 198g of molten oleic acid and 120g of potassium sarcosinate to a 500mL stainless steel reactor. Melt it to a slurry at 120℃. Turn on the stirrer (300r / min). Then add 3.06g of supported catalyst-1, turn on the nitrogen gas, and gradually raise the temperature to 150℃. React for 35min. (2) After the reaction in step (1) is completed, the temperature is reduced to 90°C, the stirring is maintained at 150 r / min, the bottom valve of the vessel is connected to the filter screen, the nitrogen pressure is set to 0.15 MPa, the valve is opened to filter the material (the filter screen is 50 mesh), the trapped catalyst is collected, and the filtered liquid is sent to the hopper of the granulator. The granulation temperature is set to 25°C, the machine is started to granulate, the particles are collected, and a high acid product is obtained. (3) After purification and drying, the high-acid product is obtained as a white powder, which is sodium oleoylmethyl taurate.

[0064] Tests showed that in Example 7, the conversion rate of potassium sarcosinate was 98.5%, the catalyst recovery rate was 98.2%, and the content of sodium oleoyl methyl taurate was 97.8%.

[0065] Example 8 (Potassium lauroylglycinate): (1) Place 125g of lauric acid in a 250mL beaker and heat it to 80℃ until it melts. Then add 125g of molten lauric acid and 56.5g of potassium glycine to a 500mL stainless steel reactor and melt it into a slurry at 120℃. Turn on the stirring (300r / min), then add 1.81g of supported catalyst-1, turn on the nitrogen gas, and gradually raise the temperature to 140℃. React for 30min. (2) After the reaction in step (1) is completed, the temperature is reduced to 90°C, the stirring is maintained at 150 r / min, the bottom valve of the vessel is connected to the filter screen, the nitrogen pressure is set to 0.15 MPa, the valve is opened to filter the material (the filter screen is 50 mesh), the trapped catalyst is collected, and the filtered liquid is sent to the hopper of the granulator. The granulation temperature is set to 25°C, the machine is started to granulate, the particles are collected, and a high acid product is obtained. (3) After purification and drying, the high-acid product is obtained as a white powder, which is potassium lauroylglycinate.

[0066] The conversion rate of potassium glycinate in Example 8 was 98.2%, the catalyst recovery rate was 98.1%, and the content of potassium lauroyl glycinate was 96.9%.

[0067] Example 9 (Sodium palmitoyl alanine): (1) Place 192g of palmitic acid in a 250mL beaker and heat it to 80℃ until it melts. Then add 192g of molten palmitic acid and 56g of sodium alanine to a 500mL stainless steel reactor. Melt it to a slurry at 120℃. Turn on the stirrer (300r / min). Then add 2g of supported catalyst-1, turn on the nitrogen gas, and gradually raise the temperature to 155℃. React for 40min. (2) After the reaction in step (1) is completed, the temperature is reduced to 90°C, the stirring is maintained at 150 r / min, the bottom valve of the vessel is connected to the filter screen, the nitrogen pressure is set to 0.15 MPa, the valve is opened to filter the material (the filter screen is 50 mesh), the trapped catalyst is collected, and the filtered liquid is sent to the hopper of the granulator. The granulation temperature is set to 25°C, the machine is started to granulate, the particles are collected, and a high acid product is obtained. (3) After purification and drying, the high-acid product is obtained as a white powder, which is sodium palmitoyl alanine.

[0068] According to the test results, the conversion rate of sodium alanine in Example 9 was 98.8%, the catalyst recovery rate was 97.6%, and the content of sodium palmitoyl alanine was 98.7%.

[0069] The preparation of Example 10 (sodium lauroyl methyl taurate) is basically the same as that of Example 1, except that the supported catalyst-1 in Example 10 is the catalyst after the same batch of supported catalyst-1 was reused 6 times when Example 1 was prepared repeatedly.

[0070] According to the test results, the raw material conversion rate of sodium methyl taurate in Example 10 was 95.9%, the catalyst recovery rate was 96%, and the content of sodium lauroyl methyl taurate was 95.8%.

[0071] Example 11 (Palmyl / Stearylalanine Sodium): (1) Place 60g palmitic acid and 40g stearic acid in a 250mL beaker and heat to 80℃ until melted. Then add 60g molten palmitic acid, 40g molten stearic acid and 24g sodium alanine to a 500mL stainless steel reactor and melt to a slurry at 120℃. Turn on the stirrer (300r / min), then add 1.4g supported catalyst-1, turn on the nitrogen gas, and gradually raise the temperature to 135℃ and react for 45min. (2) After the reaction in step (1) is completed, the temperature is reduced to 90°C, the stirring is maintained at 150 r / min, the bottom valve of the vessel is connected to the filter screen, the nitrogen pressure is set to 0.15 MPa, the valve is opened to filter the material (the filter screen is 50 mesh), the trapped catalyst is collected, and the filtered liquid is sent to the hopper of the granulator. The granulation temperature is set to 25°C, the machine is started to granulate, the particles are collected, and a high acid product is obtained. (3) After purification and drying, the high-acid product is obtained as a white powder, which is palmitoyl / stearoyl alanine sodium.

[0072] The conversion rate of sodium alanine in Example 11 was 99.1%, the catalyst recovery rate was 97.5%, and the content of palmitoyl / stearoyl alanine sodium was 99.3%.

[0073] The preparation of Example 12 (sodium lauroyl methyl taurate) is basically the same as that of Example 1, except that: in step (1) of Example 12, 2g of supported catalyst-1 is not added, and the phrase "and gradually increase the temperature to 150°C and react for 50 min" in step (1) is replaced with "and gradually increase the temperature to 220°C and react for 60 min".

[0074] According to the test results, the raw material conversion rate of sodium methyl taurate in Example 12 was 90.5%, the catalyst recovery rate was 96.2%, and the content of sodium lauroyl methyl taurate was 94.6%.

[0075] Example 13 (Sodium n-octanoylglycine): (1) Place 108g of octanoic acid in a 250mL beaker and heat it to 80℃ until it melts. Then add 108g of molten octanoic acid and 49g of sodium glycine to a 500mL stainless steel reactor. Melt it to a slurry at 120℃. Turn on the stirrer (300r / min). Then add 1.57g of supported catalyst-1, turn on the nitrogen gas, and gradually raise the temperature to 150℃. React for 35min. (2) After the reaction in step (1) is completed, the temperature is reduced to 90°C, the stirring is maintained at 150 r / min, the bottom valve of the vessel is connected to the filter screen, the nitrogen pressure is set to 0.15 MPa, the valve is opened to filter the material (the filter screen is 50 mesh), the trapped catalyst is collected, and the filtered liquid is sent to the hopper of the granulator. The granulation temperature is set to 25°C, the machine is started to granulate, the particles are collected, and a high acid product is obtained. (3) After purification and drying, the high-acid product is obtained as a white powder, which is sodium n-octanoylglycine.

[0076] According to the test results, the conversion rate of sodium glycinate in Example 13 was 99.77%, the catalyst recovery rate was 98.3%, and the content of sodium n-octanoyl glycinate was 99.5%.

[0077] The preparation of Example 14 (sodium lauroyl methyl taurate) is basically the same as that of Example 1, except that: "add 2g of supported catalyst-1" in step (1) of Example 1 is replaced with "add 2g of conventional catalyst, the conventional catalyst is potassium tert-butoxide", and "gradually heat up to 150°C and react for 50 min" in step (1) is replaced with "gradually heat up to 180°C and react for 6 h".

[0078] According to the test results, the raw material conversion rate of sodium methyl taurate in Example 14 was 99.4%, the catalyst recovery rate was 96.9%, and the content of sodium lauroyl methyl taurate was 99%.

[0079] The preparation of Example 15 (sodium myristoyl glycinate) is basically the same as that of Example 3, except that the supported catalyst-1 in Example 15 is the catalyst after the same batch of supported catalyst-1 was reused 6 times when Example 3 was repeatedly prepared.

[0080] The conversion rate of sodium glycinate in Example 15 was 97.6%, the catalyst recovery rate was 95.6%, and the content of sodium myristoyl glycinate was 95.7%.

[0081] The preparation of Example 16 (sodium lauroyl methyl taurate) is basically the same as that of Example 14, except that the supported catalyst-1 in Example 16 is the catalyst after the same batch of supported catalyst-1 was reused 6 times when Example 14 was repeatedly prepared.

[0082] According to the test results, the raw material conversion rate of sodium methyl taurate in Example 16 was 89.2%, the catalyst recovery rate was 95%, and the content of sodium lauroyl methyl taurate was 94.8%.

[0083] The preparation of Example 17 (sodium lauroyl methyl taurate) is basically the same as that of Example 1, except that "add 2g of supported catalyst-1" in step (1) of Example 1 is replaced with "add 2g of conventional catalyst, which is potassium tert-butoxide".

[0084] According to the test results, the raw material conversion rate of sodium methyl taurate in Example 17 was 99.5%, the catalyst recovery rate was 96.3%, and the content of sodium lauroyl methyl taurate was 96.8%.

[0085] The preparation of Example 18 (sodium lauroyl methyl taurate) is basically the same as that of Example 1, except that “supported catalyst-1” in step (1) of Example 1 is replaced with “supported catalyst-2”.

[0086] According to the test results, the raw material conversion rate of sodium methyl taurate in Example 18 was 99.7%, the catalyst recovery rate was 97.3%, and the content of sodium lauroyl methyl taurate was 99.3%.

[0087] A comparison of Example 1 and Example 12 shows that, under the condition of not using a catalyst in Example 12, even with a high reaction temperature and reaction time, the raw material conversion rate of amino acid salts, the catalyst recovery rate, and the content of fatty acyl amino acid salts are still low. However, when the catalyst provided by the present invention is used for the reaction, although the reaction temperature is lower and the reaction time is shorter, the raw material conversion rate of amino acid salts, the catalyst recovery rate, and the content of fatty acyl amino acid salts are higher. As can be seen from the comparison between Example 1 and Examples 14 and 17, when preparing fatty acyl amino acid salts using conventional catalysts, the reaction conditions of the present invention, namely reaction temperature and reaction time, have a higher conversion rate, but the product content is low and the catalyst recovery rate is low. Even with a higher reaction temperature and a longer reaction time, the product content is still lower than that of fatty acyl amino acid salts prepared using the catalyst provided by the present invention. A comparison of Example 1 with Examples 14 and 16 shows that when using a conventional catalyst to prepare fatty acyl amino acid salts, and with a high reaction temperature and a long reaction time, although the conversion rate is high, the product content is low. Furthermore, after multiple uses of the conventional catalyst, although the reaction temperature and reaction time are still high, the conversion rate decreases significantly and the product content also decreases. As can be seen from the comparison of Examples 1 to 10, 11, 13 and 18, when the supported catalyst provided by the present invention is used to prepare fatty acyl amino acid salts, even with a lower reaction temperature and a shorter reaction time, it still has a high raw material conversion rate of amino acid salts, a high catalyst recovery rate and a high content of fatty acyl amino acid salts. Even if the supported catalyst that has been used multiple times is used to prepare fatty acyl amino acid salts again, although the amino acid salt conversion rate, fatty acyl amino acid salt content and catalyst recovery rate decrease, the decrease is not significant, and it still has a high amino acid salt conversion rate and a high content of fatty acyl amino acid salts, as well as a high catalyst recovery rate. As can be seen from Examples 1-9, 10, 3 and 15, when the supported catalyst provided by the present invention is used to prepare fatty acyl amino acid salts, even with a low reaction temperature and a short reaction time, it still has a high raw material conversion rate of amino acid salts, a high catalyst recovery rate and a high content of fatty acyl amino acid salts.

[0088] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A supported catalyst characterized in that: The raw materials for preparing the supported catalyst include zinc oxide, a mesoporous silicate carrier with a specific surface area of ≥200 m² / g and a pore size of 2-50 nm, and a surface modifier, and the mass ratio of zinc oxide to the mesoporous silicate carrier is 1:2-1:

11.

2. The supported catalyst of claim 1, wherein: The surface modifier accounts for 5-15% of the total mass of zinc oxide and the mesoporous silicate carrier.

3. The supported catalyst of claim 1, wherein: The surface modifier is a non-ionic surfactant.

4. The supported catalyst of claim 3, wherein: The surface modifier is at least one of polyethylene glycol and polyvinyl alcohol.

5. The supported catalyst of claim 4, wherein: The average molecular weight of the polyethylene glycol is ≥4000.

6. Process for the preparation of the supported catalyst according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: (1) calcining the mesoporous silicate carrier, fully immersing the calcined mesoporous silicate carrier in a zinc oxide solution, adding a surface modifier, and fully stirring to obtain an intermediate; (2) drying, crushing, and calcining the intermediate, cooling, adding deionized water for kneading, and extruding and granulating through an extrusion granulator and drying to obtain the supported catalyst.

7. Use of the supported catalyst according to any one of claims 1 to 5 for the preparation of a fatty acyl amino acid salt, characterized in that: The fatty acyl amino acid salt is prepared by reacting an amino acid salt and a carboxylic compound under the catalysis of the supported catalyst.

8. Use according to claim 7, characterized in that: The molar ratio of the carboxylic compound to the amino acid salt is 1.25-2.0:

1.

9. Use according to claim 7, characterized in that: The carboxylic compound is a saturated or unsaturated fatty acid containing 6-22 carbon atoms.

10. Use of a supported catalyst according to claim 7, characterized in that: The method for preparing the fatty acyl amino acid salt comprises the following steps: (1) mixing the amino acid salt and the molten carboxylic compound, then heating to 60-120°C, and performing a heat preservation reaction, then adding the supported catalyst, and fully stirring to suspend the catalyst; (2) then heating the substance of step (1) and controlling the reaction temperature to be 120-180°C, granulating, purifying, and drying the filtered filtrate to obtain the fatty acyl amino acid salt.