CN113634242A - Trimethylolpropane hydrogenation catalyst and preparation method thereof - Google Patents

Trimethylolpropane hydrogenation catalyst and preparation method thereof Download PDF

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CN113634242A
CN113634242A CN202010394532.3A CN202010394532A CN113634242A CN 113634242 A CN113634242 A CN 113634242A CN 202010394532 A CN202010394532 A CN 202010394532A CN 113634242 A CN113634242 A CN 113634242A
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spraying
drying
solution
trimethylolpropane
carrier
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CN113634242B (en
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詹吉山
梁广荣
沙宇
李作金
燕宸
于海波
孙康
黎源
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Wanhua Chemical Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases

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Abstract

The invention discloses a trimethylolpropane hydrogenation catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: 1) adding a zirconium oxychloride aqueous solution into an ethyl orthosilicate ethanol solution to obtain a mixed solution, hydrolyzing, adding ammonia water into the mixed solution to control precipitation during the addition of the zirconium oxychloride, and adjusting the pH to 6.5-7.5 after the addition of the zirconium oxychloride is finished; then aging, filtering, drying and roasting the mixed solution to obtain a carrier; 2) dissolving nickel nitrate and copper nitrate to prepare a salt solution, adding ethanol and a stabilizer into the salt solution, uniformly stirring, spraying the salt solution onto a carrier, and drying after spraying to obtain a precursor; 3) preparing ammonium carbonate into an aqueous solution, adding ethanol, spraying the ammonium carbonate solution into the precursor, drying after spraying, and roasting to obtain the catalyst. When the catalyst is applied to a trimethylolpropane hydrogenation process, the amount of organic acid in a product can be reduced, the quality of the product can be improved, and the hydrogenolysis side reaction can be inhibited.

Description

Trimethylolpropane hydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of trimethylolpropane catalysts, and particularly relates to a trimethylolpropane hydrogenation catalyst and a preparation method thereof.
Background
Trimethylolpropane (TMP for short) has a chemical name of 2-ethyl-2-hydroxymethyl-1, 3-propanediol, also known as Trimethylolpropane and 2, 2-dimethylolbutanol, and is white crystal or powder in appearance. Trimethylolpropane, an important triol, can react with organic acid to form monoester or multiester, with ketone, aldehyde and the like to form ketal, acetal, with diisocyanate to form carbamate and the like, and is an important fine chemical product and organic chemical raw material. TMP is widely used in the fields of alkyd resins, polyurethanes, unsaturated resins, polyester resins, paints, synthetic aviation lubricants, plasticizers, surfactants, wetting agents, explosives, printing inks, etc., and may be directly used as textile assistants, heat stabilizers for PVC resins, etc.
Trimethylolpropane is a stable trihydric alcohol, the main raw materials for preparation are formaldehyde and n-butyl aldehyde, and the current synthesis processes mainly comprise two types: one is the cornnizzaro process (Cannizzaro) and one is the catalytic hydrogenation process. The Cannizzaro method adopts inorganic strong base as a catalyst, and because the product sodium formate is easy to dissolve in water, a large amount of salt-containing wastewater is generated, so that the three-waste treatment cost is increased, and the key point of purifying TMP by adopting desalination is. In addition, the amount of formaldehyde consumed in the disproportionation reaction is higher, which causes an increase in economic cost and affects the economy. As a novel industrial production technology, the hydrogenation reduction method can save a large amount of formaldehyde and alkali, has few reaction byproducts, simple product separation and purification, few devices and equipment and low cost, is suitable for large-scale industrial production, and is the mainstream of future technical development.
BASF patents (DE3,340,791, EP142,090, US4,594,461). N-butyl aldehyde and 30% formaldehyde water solution are adopted, triethylamine is used as a catalyst, aldol condensation is firstly carried out at 70 ℃, and hydrogenation reaction is carried out under the condition of 120 ℃/6 MPa. Then distilling off H2O、N(C2H5)3、HCOONH485% TMP and 7.6% bis-trimethylolpropane are obtained.
Mitsubishi gas patent (US5395989) discloses a chromium-free green catalyst exhibiting high conversion and stability, the catalyst being ZrO2Is used as a carrier, Cu is used as a catalytic active component, and Zn is used as a cocatalyst, so that the harm of metal Cr to the environment is avoided.
DE43100538 describes a Ni-based aldehyde hydrogenation catalyst with the addition of the alkaline earth metal Mg as an auxiliary. The catalyst consists of NiO 10-35 wt%, Mg 4-12 wt% and NaO 1-5 wt%, and adopts Al2O3And (or) SiO2Diatomite is used as a carrier.
Chinese patent CN 110372475 a introduces a trimethylolpropane hydrogenation process, which can reduce the dosage of aldehyde and alkali, reduce the acidity in the reaction process and the product, and improve the product quality by controlling the dropping speed of butyraldehyde and liquid alkali in the condensation process, the reaction temperature, and the optimization of the process conditions of hydrogenation mode.
Chinese patent CN 102408304 a provides a method and catalyst for preparing alcohol by aldehyde hydrogenation. The silane group modification on the surface of the catalyst used in the method can obviously inhibit side reactions such as aldehyde self-condensation, aldol condensation, etherification and the like, the selectivity of a target product is high, the downstream separation process is simplified, and the energy consumption is reduced. The silane modified catalyst can cause the hydrophobicity of the catalyst to change, the conversion rate of the catalyst is reduced from 95.6% to 91.0% after the catalyst runs for 1500 hours, and the stability of the catalyst needs to be improved.
However, the prior hydrogenation process and catalyst mostly contain Cr element, so the environmental pollution is serious; the quality of the product is influenced by the excessive acid content in the reaction process and the product; DMB is easy to be hydrogenolyzed in the hydrogenation process to generate byproducts, thus reducing the yield of target products and the like.
Disclosure of Invention
In view of the above, an object of an aspect of the present invention is to provide a method for preparing a trimethylolpropane hydrogenation catalyst, in which the obtained catalyst does not contain Cr elements that pollute the environment, and when the catalyst is applied to a trimethylolpropane hydrogenation process, the catalyst of the present invention can improve the decomposition effect of formate, reduce the amount of organic acids in the product, improve the product quality, and inhibit the side reactions of hydrogenolysis.
In order to realize the purpose, the invention adopts the following technical scheme: a preparation method of a trimethylolpropane hydrogenation catalyst comprises the following steps:
1) adding a zirconium oxychloride aqueous solution into an ethyl orthosilicate ethanol solution to obtain a mixed solution, hydrolyzing, adding ammonia water into the mixed solution to control precipitation in the adding process of the zirconium oxychloride aqueous solution, and adjusting the pH to 6.5-7.5 after the zirconium oxychloride aqueous solution is added; then aging, filtering, drying and roasting the mixed solution to obtain a carrier;
2) dissolving nickel nitrate and copper nitrate to prepare a salt solution, adding ethanol and a stabilizer into the salt solution, uniformly stirring, spraying the salt solution onto the carrier obtained in the step 1), and drying after spraying to obtain a precursor;
3) preparing ammonium carbonate into an aqueous solution, adding ethanol into the aqueous solution, spraying the ammonium carbonate solution into the precursor obtained in the step 2), drying after spraying, and roasting to obtain the catalyst.
In the present invention, in step 1), the controlling precipitation comprises: controlling the pH value to be 4.5-6, for example: 4.5, 5 or 6, the precipitation time is 1-3h, the precipitation temperature is 30-50 ℃, and the pH value is not changed to be the end of precipitation.
The preparation of the carrier in the invention is a double hydrolysis process, wherein the ethyl silicate is hydrolyzed to generate silicon oxide. The hydrolysis of zirconium oxychloride to zirconium oxide is promoted by the water in the aqueous ammonia, which promotes the hydrolysis of ethyl silicate, and the pH adjustment of the aqueous ammonia promotes the hydrolysis of zirconium oxychloride. Preferably, the mixed liquid formed in the step 1) has a molar ratio of the ethyl silicate to the zirconium oxychloride in the range of 1:1 to 1: 2.
In the present invention, in step 1), the aging includes: the aging time is 1-3h, and the aging temperature is 60-80 ℃.
In the present invention, in step 1), the drying includes: the drying temperature is 80-120 ℃, and the drying time is 4-6 h.
In the present invention, in step 1), the firing includes: introducing nitrogen and heating to 1000-1200 ℃, wherein the heating rate is 1-3 ℃/min, roasting for 2-4h, and modifying partial nitrogen of silicon oxide and zirconium oxide to generate Si3N4And a ZrN structure, which can improve the catalyst alkalinity and enhance the formate decomposition capability.
In the present invention, in step 2), the spraying includes: the spraying time is 0.5-1h, hot air is introduced for blowing in the spraying process, preferably, the temperature of the carrier is kept to be more than or equal to 80 ℃ in the blowing process, for example, 80-120 ℃, so that the temperature is above the boiling point of the ethanol water solution, and the drying effect is ensured. The spraying is preferably carried out in a rotary coating machine, and the carrier is in a rolling state during the spraying.
In the present invention, in step 2), the drying includes: drying at 80-120 deg.C for 2-4 h.
In the present invention, in step 3), the spraying includes: the spraying time is 0.5-1h, preferably, the spraying is carried out in a rotary coating machine, hot air is introduced for blowing in the spraying process, and preferably, the temperature of the precursor is kept to be more than or equal to 80 ℃ in the blowing process.
In the present invention, in step 3), the drying includes: drying at 80-120 deg.C for 2-4 h.
In the present invention, in step 3), the firing includes: the roasting temperature is 400-.
In a preferred embodiment, the stabilizer in step 2) is one or more of glycerol, polyvinyl alcohol, polymethacrylic acid and paraffin wax, and is preferably added in an amount of 0.5-2% by mass of the carrier in step 1). The stabilizer has the advantages of preventing the processes of nickel and copper clusters and sintering in the drying and roasting processes after spraying and being beneficial to keeping higher active components. Preferably, in the step 2), the nickel nitrate and the copper nitrate are dissolved to prepare a salt solution with the concentration of 0.5-1M/L.
In a preferred embodiment, the ethanol content in the step 2) salt solution or the step 3) aqueous solution is 3-5% by mass. And 3) adding ethanol into the ammonium carbonate solution to form a solution, so that the drying efficiency of the water and ethanol solution after precipitation is convenient. Preferably, the concentration of ammonium carbonate is 15-25 wt%, more preferably 20%.
In the step 2), the ethanol solution is adopted and hot air is introduced to ensure that the surface of the catalyst is subjected to hydrothermal rapid evaporation to dryness, so that active components of the catalyst are prevented from entering the inside of a catalyst carrier, and the active components are precipitated outside the carrier after drying to form the core-shell structure catalyst. The core-shell structure catalyst is beneficial to controlling the reaction process, avoids the hydrogenolysis of deep reaction to 2-ethylacrolein and improves the yield of target products.
The purpose of spraying ammonium carbonate in the step 3) is similar to two processes of dipping and precipitation, the addition of ammonium carbonate can enable nitrate on the surface to be rapidly precipitated to generate basic copper carbonate and nickel carbonate, and stabilizers such as glycerin and the like are used for avoiding clustering of active particles in two spraying processes, controlling the size of smaller particles and improving the activity of the catalyst.
Another aspect of the present invention is to provide a trimethylolpropane hydrogenation catalyst prepared by the above method, wherein the catalyst comprises the following components by mass: CuO content of 20-40%, NiO content of 2-12%, SiO220-30% of ZrO2The content is 30-40%; in a preferred embodiment, the CuO content is 25 to 35%, the NiO content is 5 to 10%, and SiO2Content of 25-30%, ZrO2The content is 30-35%.
Compared with the prior art, the invention has the following advantages:
(1) the carrier prepared by the double hydrolysis method has weaker acidity under the particle size and can be mixed with an active component (Ni)2+、Cu2+) The catalyst has strong interaction, enhances the adhesive force of the sprayed active component on the surface of the catalyst, has larger pore canals, and can effectively improve the heat transfer effect of the carrier. In the preparation method, the active components of the catalyst prepared by the spray coating method are concentrated on the surface of the catalyst, the reaction is also concentrated on the surface of the catalyst in the hydrogenation process reaction process, the excessive hydrogenation reaction and the generation of hydrogenolysis byproducts can be inhibited by adjusting the retention time, the hydrogenation activity is ensured, and the selectivity and the yield of TMP are improved.
(2) SiO prepared by the double hydrolysis method of the invention2-ZrO2The load carrier is beneficial to the decomposition of formate, reduces the occurrence of yellowing of products, and improves the quality and purity of the products.
(3) The stabilizer added in the step 2) can prevent the cluster of the active component from growing up in the processes of preparation, spraying, drying and roasting, and improve the activity of the catalyst.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the examples listed, and it should also include equivalent modifications and variations to the technical solutions defined in the claims appended to the present application.
The method and parameters related to the embodiment of the invention are as follows:
chromatographic analysis conditions: the analysis was carried out using a DB-5MS (30 m.times.0.25 mm.times.0.25 μm) column, under the following operating conditions: keeping the temperature at 50 ℃ for 2 minutes, heating to 100 ℃ at 5 ℃/min, keeping the temperature for 5 minutes, heating to 260 ℃ at 15 ℃/min, and keeping the temperature for 5 minutes. The injector temperature was 240 ℃ and the detector temperature was 260 ℃.
DMB (dimethylaminoethyl benzoate) was synthesized in the laboratory.
The nickel nitrate is provided by Komm Europe reagent company and is analytically pure.
Copper nitrate was provided by komi european reagent company and was analytically pure.
Ethyl silicate was provided by komi european reagent, inc.
Zirconium oxychloride was provided by komi ohu reagent, inc.
The ammonia water is provided for chemical industry of the west longas and is analytically pure.
Methanol is provided for chemical industry of Xilonga and is analytically pure.
The ethanol is provided for chemical industry of Xilonga and is analytically pure.
The glycerol is provided for chemical industry of jujude and is analytically pure.
Unless otherwise specified, the chemicals used below were analytical grade, and the contents referred to in the examples of the present invention were mass contents.
Example 1
97.22g of tetraethoxysilane is dissolved in 100g of pure ethanol to prepare ethanol solution, and the ethanol solution is stirred uniformly. Adding 330g of water into 104.8 g of zirconium oxychloride to prepare a zirconium oxychloride aqueous solution, adding the zirconium oxychloride aqueous solution into an ethyl silicate ethanol solution for hydrolysis, controlling the precipitation pH to be 4.5 by ammonia water, precipitating for 3 hours at 50 ℃, adjusting the pH to 6.5 after the zirconium oxychloride is added, and judging that the precipitation is finished without changing the pH. Followed by aging for 3 hours at an aging temperature of 80 ℃. Filtering, drying and roasting to obtain the carrier. The drying temperature is 80 ℃ and the drying time is 6 h. Introducing nitrogen for replacement before roasting, heating to 1000 ℃ at the heating rate of 1 ℃/min for nitrogen modification after replacement, and roasting for 4h to obtain the carrier A. The carrier A was extruded into a phi 3 cylinder for use.
46.5g of nickel nitrate hexahydrate and 60.4g of copper nitrate trihydrate were dissolved in 410g of water to prepare a salt solution, and 12.3g of ethanol and 0.34g of glycerol (5% by mass of carrier A) were added to the salt solution and stirred uniformly. Adding the carrier A into a rotary coating machine, spraying or sprinkling a salt solution into the rolling carrier, wherein the spraying time is 0.5h, hot air is introduced in the spraying process to heat the carrier to 80 ℃, and after the spraying is finished, drying the carrier at 80 ℃ for 4 h. Obtaining a precursor B.
43.3g of ammonium carbonate was prepared into a 20 wt% aqueous solution, and 6.5g of ethanol was added thereto and stirred uniformly. And adding the precursor B into a rotary coating machine, heating to 80 ℃, spraying the ammonium carbonate solution into the coating machine for 0.5h, drying at 80 ℃ for 4h after spraying, and roasting at 400 ℃ for 6 h. The catalyst No. 1 was obtained.
The 1# catalyst comprises the following components: the total mass is 100%, and the components comprise: NiO 12%, CuO 20%, 28% SiO2(containing Si)3N4)；40％ZrO2(containing ZrN).
And (3) catalyst reduction: the No. 1 catalyst was charged to a fixed bed hydrogenation reactor at a 50ml loading. The reactor temperature was first raised to 150 ℃ and H containing a volume fraction of 5 v% was passed2The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v% and 50 v%, the hot point temperature of the catalyst bed layer in the process is controlled not to exceed 220 ℃ and reduction is carried out for 3h under the pure hydrogen atmosphere, and then pure hydrogen is introduced to raise the temperature to 400 ℃ and reduction is carried out for 1 h. Volume space velocity of gas 500h-1。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 3MPa, the reaction inlet temperature is about 110 ℃, the hot spot temperature is 125 ℃, the hydrogen-oil ratio is 100:1, and the liquid hourly space velocity is 3.15g/g/h-1. DMB conversion rate 99.4%, TMP selectivity 97.2%, TMP methyl ester 0.05%, TMP methyl ether 0.24%, 2-ethylacrolein 1.41%.
Example 2
According to 69.4g of tetraethoxysilane, the tetraethoxysilane is dissolved in 100g of ethanol to prepare a solution, and the solution is stirred uniformly. Adding 310g of water into 99.5g of zirconium oxychloride to prepare a zirconium oxychloride aqueous solution, adding the zirconium oxychloride aqueous solution into an ethyl silicate ethanol solution for hydrolysis, controlling the precipitation pH to be 4.5 by ammonia water, controlling the precipitation time to be 2.5h, controlling the precipitation temperature to be 45 ℃, adjusting the pH to be 6.5 after the zirconium oxychloride is added, and keeping the pH unchanged until the precipitation is finished. Aging for 2.5h at 75 deg.C. Filtering, drying and roasting to obtain the carrier. The drying temperature is 90 ℃ and the drying time is 5 h. Introducing nitrogen for replacement before roasting, heating to 1050 ℃ at the heating rate of 1.5 ℃/min for nitrogen modification after replacement, and roasting for 3h to obtain the carrier A. The carrier A was extruded into a phi 3 cylinder for use.
A salt solution was prepared by dissolving 7.75g of nickel nitrate and 120.8g of copper nitrate in 530g of water, and 15.8g of ethanol and 0.29g of glycerol (5% by mass of carrier A) were added to the salt solution and stirred uniformly. Adding the carrier A into a rotary coating machine, spraying a salt solution onto the rolling carrier for 0.5h, introducing hot air in the spraying process to heat the carrier to 90 ℃, and drying at 90 ℃ for 3h after the spraying is finished. Obtaining a precursor B.
55.7g of ammonium carbonate is prepared into a 15 wt% aqueous solution, 11.1g of ethanol is added, and the mixture is stirred uniformly. And adding the precursor B into a rotary coating machine, heating to 90 ℃ through hot air, spraying an ammonium carbonate solution into the coating machine for 0.5h, drying at 90 ℃ for 3h after spraying is finished, and roasting at 450 ℃ for 5 h. The catalyst No. 2 was obtained.
Composition of catalyst # 2: the total mass is 100%, and the components comprise: NiO 2%, CuO 40%, 20% SiO2(containing Si)3N4)；38％ZrO2(containing ZrN).
The reduction and activity evaluation conditions were as described in example 1. The DMB conversion rate is 97.8 percent, the TMP selectivity is 98.6 percent, the TMP methyl ester is 0.03 percent, the TMP methyl ether is 0.28 percent, and the 2-ethylacrolein is 0.90 percent.
Example 3
86.8g of tetraethoxysilane is dissolved in 100g of ethanol to prepare a solution, and the solution is stirred uniformly. Adding 280g of water into 91.7g of zirconium oxychloride to prepare an aqueous solution, adding the aqueous solution of the zirconium oxychloride into an ethyl silicate ethanol solution for hydrolysis, controlling the pH of the precipitate to be 5 by ammonia water, controlling the precipitation time to be 2 hours, controlling the precipitation temperature to be 40 ℃, adjusting the pH to 7 after the zirconium oxychloride is added, and keeping the pH unchanged until the precipitation is finished. Aging for 2h at 70 ℃. Filtering, drying and roasting to obtain the carrier. The drying temperature is 100 ℃, and the drying time is 4 h. Introducing nitrogen for replacement before roasting, heating to 1100 ℃ at the heating rate of 2.0 ℃/min for nitrogen modification after replacement, and roasting for 3h to obtain the carrier A. The carrier A was extruded into a phi 3 cylinder for use.
19.4g of nickel nitrate and 105.6g of copper nitrate were dissolved in 680g of water to prepare a salt solution, and 26.9g of ethanol and 0.60g of glycerol (10% by mass of the carrier A) were added to the salt solution and stirred uniformly. Adding the carrier A into a rotary coating machine, spraying a salt solution onto the rolling carrier for 0.75h, introducing hot air in the spraying process to heat the carrier to 100 ℃, and drying for 2h at 100 ℃ after the spraying is finished. Obtaining a precursor B.
53.3g of ammonium carbonate is prepared into a 17 wt% aqueous solution, and 12.5g of ethanol is added to be uniformly stirred. And adding the precursor B into a rotary coating machine, heating the precursor to 100 ℃ by introducing hot air, spraying an ammonium carbonate solution into the coating machine for 0.75h, drying for 2h at 100 ℃ after the spraying is finished, and roasting for 4h at 500 ℃. The catalyst # 3 was obtained.
Composition of catalyst # 3: the total mass is 100%, and the components comprise: NiO 5%, CuO 35%, and SiO 25%2(containing Si)3N4)；35％ZrO2(containing ZrN).
The reduction and activity evaluation conditions were as described in example 1. DMB conversion rate 98.8%, TMP selectivity 98.6%, TMP methyl ester 0.01%, TMP methyl ether 0.30%, 2-ethylacrolein 0.88%.
Example 4
104.2g of tetraethoxysilane is dissolved in 100g of ethanol to prepare a solution, and the solution is stirred uniformly. Adding 280g of water into 91.7g of zirconium oxychloride to prepare an aqueous solution, adding the aqueous solution of the zirconium oxychloride into an ethyl silicate ethanol solution for hydrolysis, controlling the pH of the precipitate to be 6 by ammonia water, controlling the precipitation time to be 1h, controlling the precipitation temperature to be 30 ℃, adjusting the pH to be 7.5 after the zirconium oxychloride is added, and judging that the precipitation is finished without changing the pH. Aging for 1h at 60 ℃. Filtering, drying and roasting to obtain the carrier. The drying temperature is 120 ℃, and the drying time is 4 h. Introducing nitrogen for replacement before roasting, heating to 1200 ℃ at the heating rate of 3.0 ℃/min after replacement is finished, and carrying out nitrogen modification for 2h to obtain the carrier A. The carrier A was extruded into a phi 3 cylinder for use.
38.8g of nickel nitrate and 75.5g of copper nitrate were dissolved in 900g of water to prepare a salt solution, and 44.6g of ethanol and 1.2g of glycerol (20% by mass of the carrier A) were added to the salt solution and stirred uniformly. Adding the carrier A into a rotary coating machine, spraying a salt solution onto the rolling carrier for 1h, introducing hot air in the spraying process to heat the carrier to 120 ℃, and drying at 120 ℃ for 2h after the spraying is finished. Obtaining a precursor B.
47.1g of ammonium carbonate was prepared into a 22 wt% aqueous solution, and 10.7g of ethanol was added thereto and stirred uniformly. And adding the precursor B into a rotary coating machine, heating the precursor to 100 ℃ by introducing hot air, spraying an ammonium carbonate solution into the coating machine for 1h, drying at 120 ℃ for 2h after the spraying is finished, and roasting at 600 ℃ for 4 h. The catalyst No. 4 was obtained.
Composition of catalyst # 4: the total mass is 100%, and the components comprise: NiO 10%, CuO 25%, and SiO 30%2(containing Si)3N4)；35％ZrO2(containing ZrN).
The reduction and activity evaluation conditions were as described in example 1. The DMB conversion rate is 99.2 percent, the TMP selectivity is 98.2 percent, the TMP methyl ester is less than 0.01 percent, the TMP methyl ether is 0.21 percent, and the 2-ethylacrolein is 1.12 percent.
Example 5
104.2g of tetraethoxysilane is dissolved in 100g of ethanol to prepare a solution, and the solution is stirred uniformly. Adding 270g of water into 86.5g of zirconium oxychloride to prepare an aqueous solution, adding the aqueous solution of zirconium oxychloride into an ethyl silicate ethanol solution for hydrolysis, controlling the pH of the precipitate to be 6 by ammonia water, controlling the precipitation time to be 1h, controlling the precipitation temperature to be 30 ℃, adjusting the pH to be 7.5 after the zirconium oxychloride is added, and judging that the precipitation is finished without changing the pH. Aging for 1h at 60 ℃. Filtering, drying and roasting to obtain the carrier. The drying temperature is 120 ℃, and the drying time is 4 h. Introducing nitrogen for replacement before roasting, heating to 1200 ℃ at the heating rate of 3.0 ℃/min after replacement is finished, and carrying out nitrogen modification for 2h to obtain the carrier A. The carrier A was extruded into a phi 3 cylinder for use.
27.1g of nickel nitrate and 90.6g of copper nitrate were dissolved in 940g of water to prepare a salt solution, and 46.8g of ethanol and 1.2g of glycerol (20% by mass of the carrier A) were added to the salt solution and stirred uniformly. Adding the carrier A into a rotary coating machine, spraying a salt solution onto the rolling carrier for 1h, introducing hot air during the spraying process, heating the carrier to 120 ℃, and drying at 120 ℃ for 2h after the spraying is finished. Obtaining a precursor B.
49.5g of ammonium carbonate is prepared into a 25 wt% aqueous solution, and 9.9g of ethanol is added to be uniformly stirred. And adding the precursor B into a rotary coating machine, heating the precursor to 100 ℃ by introducing hot air, spraying an ammonium carbonate solution into the coating machine for 1h, drying at 120 ℃ for 2h after the spraying is finished, and roasting at 600 ℃ for 4 h. The 5# catalyst was obtained.
Composition of catalyst # 5: the total mass is 100%, and the components comprise: NiO 7%, CuO 30%, and SiO 30%2(containing Si)3N4)；33％ZrO2(containing ZrN).
The reduction and activity evaluation conditions were as described in example 1. The DMB conversion rate is 99.0 percent, the TMP selectivity is 98.4 percent, the TMP methyl ester is less than 0.01 percent, the TMP methyl ether is 0.23 percent, and the 2-ethylacrolein is 0.92 percent.
Comparative example 1
Commercially available 30% CuO-60% ZnO-10% Al2O3A catalyst.
And (3) catalyst reduction: the catalyst is filled into a fixed bed hydrogenation reactor, and the filling amount is 50 ml. The reactor temperature was first raised to 150 ℃ and H containing a volume fraction of 5 v% was passed2The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, and the hot spot temperature of the catalyst bed in the process is controlled not to exceed 230 ℃ and is reduced for 3h under the pure hydrogen atmosphere. Volume space velocity of gas 500h-1。
The performance of the activated catalyst is evaluated, and the catalyst evaluation conditions are as follows: the reaction pressure is 3MPa, the reaction inlet temperature is about 110 ℃, the hot spot temperature is 125 ℃, the hydrogen-oil ratio is 100:1, and the liquid hourly space velocity is 3.15g/g/h-1. The DMB conversion rate is 95.2 percent, the TMP selectivity is 97.1 percent, the TMP methyl ester is 0.23 percent, the TMP methyl ether is 0.58 percent, and the 2-ethylacrolein is 1.69 percent.
Comparative example 2
Commercially available 40% CuO-60% Al2O3A catalyst.
And (3) catalyst reduction: the catalyst is filled into a fixed bed hydrogenation reactor, and the filling amount is 50 ml. The reactor temperature was first raised to 150 ℃ and H containing a volume fraction of 5 v% was passed2The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of the hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, and the hot spot temperature of the catalyst bed layer in the process is controlledReducing for 3h under pure hydrogen atmosphere at the temperature of not more than 230 ℃. Volume space velocity of gas 500h-1。
The reaction conditions were the same as in example 1. The DMB conversion rate is 92.5 percent, the TMP selectivity is 97.1 percent, the TMP methyl ester is 0.18 percent, the TMP methyl ether is 0.51 percent, and the 2-ethylacrolein is 1.72 percent.
Comparative example 3
208.33g of tetraethoxysilane is dissolved in 150g of ethanol to prepare a solution, and the solution is stirred uniformly. Controlling the pH value of the precipitate to be 4.5 by ammonia water, controlling the precipitation time to be 3h, controlling the precipitation temperature to be 50 ℃, adjusting the pH value to be 7 after the zirconium oxychloride is added, and determining that the precipitation is finished when the pH value is not changed. Aging for 3h at 80 ℃. Filtering, drying and roasting to obtain the carrier. The drying temperature is 80 ℃ and the drying time is 6 h. The roasting temperature is 500 ℃, and the roasting time is 4 hours, thus obtaining the carrier A. The carrier A was extruded into a phi 3 cylinder for use.
120.8g of copper nitrate is dissolved in 500g of prepared salt solution, 15.0g of ethanol and 0.3g of glycerol (5% of the carrier A by mass) are added into the salt solution, and the mixture is stirred uniformly. Adding the carrier A into a rotary coating machine, spraying a salt solution into the rolling carrier for 0.5h, introducing a hot air precursor in the spraying process, heating to 80 ℃, and drying at 80 ℃ for 4h after the spraying is finished. Obtaining a precursor B.
52.8g of ammonium carbonate is prepared into a 20 wt% aqueous solution, and 13.2g of ethanol is added to be uniformly stirred. And adding the precursor B into a rotary coating machine, heating to 80 ℃, spraying the ammonium carbonate solution into the coating machine for 1h, drying at 80 ℃ for 4h after spraying, and roasting at 400 ℃ for 6 h. To obtain catalyst No. 6.
Composition of catalyst # 6: the total mass is 100%, and the components comprise: CuO 40%, 60% SiO2。
The reduction and activity evaluation conditions were as shown in comparative example 1. The DMB conversion rate is 95.8 percent, the TMP selectivity is 95.8 percent, the TMP methyl ester is 0.08 percent, the TMP methyl ether is 0.32 percent, and the 2-ethylacrolein is 3.22 percent.
Comparative example 4
490g of water is added into 157.2g of zirconium oxychloride to prepare an aqueous solution, the pH value of the precipitate is controlled to be 6 by ammonia water, the pH value of a reaction system is adjusted to hydrolyze the zirconium oxychloride, the hydrolysis time is 1h, the precipitation temperature is 30 ℃, the pH value is adjusted to 7 after the zirconium oxychloride is added, and the pH value is not changed and the precipitation is finished. Aging for 1h at 60 ℃. Filtering, drying and roasting to obtain the carrier. The drying temperature is 120 ℃, and the drying time is 4 h. The roasting temperature is 700 ℃, and the roasting time is 2 hours, thus obtaining the carrier A. The carrier A was extruded into a phi 3 cylinder for use.
120.8g of copper nitrate is dissolved in 500g of prepared salt solution, 15.0g of ethanol and 0.3g of glycerol (5% of the carrier A by mass) are added into the salt solution, and the mixture is stirred uniformly. Adding the carrier A into a rotary coating machine, spraying a salt solution into the rolling carrier for 0.5h, introducing a hot air precursor in the spraying process, heating to 80 ℃, and drying at 80 ℃ for 4h after the spraying is finished. Obtaining a precursor B.
52.8g of ammonium carbonate is prepared into a 20 wt% aqueous solution, and 13.2g of ethanol is added to be uniformly stirred. And adding the precursor B into a rotary coating machine, heating to 80 ℃, spraying the ammonium carbonate solution into the coating machine for 1h, drying at 80 ℃ for 4h after spraying, and roasting at 400 ℃ for 6 h. To obtain catalyst # 7.
Composition of catalyst # 7: the total mass is 100%, and the components comprise: 40% of CuO and 60% of ZrO2。
The reduction and activity evaluation conditions were as shown in comparative example 1. The DMB conversion rate is 96.3 percent, the TMP selectivity is 96.2 percent, the TMP methyl ester is 0.10 percent, the TMP methyl ether is 0.29 percent, and the 2-ethylacrolein is 2.57 percent.
Inventive examples it can be seen that the inventive examples have higher DMB conversion rates than the commercially available catalysts by comparison with comparative examples 1 and 2.
Comparing the examples of the present invention with comparative examples 3 and 4, it can be seen that the examples of the present invention can effectively reduce the generation of 2-ethylacrolein, which is a hydrogenolysis product, by using the composite carrier and reducing the acidity of the catalyst through nitrogen modification, thereby increasing the yield of TMP.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes or modifications of the technical solution of the present invention are within the spirit of the present invention.

Claims (10)

1. A preparation method of a trimethylolpropane hydrogenation catalyst is characterized by comprising the following steps: the method comprises the following steps:
1) adding a zirconium oxychloride aqueous solution into an ethyl orthosilicate ethanol solution to obtain a mixed solution, hydrolyzing, adding ammonia water into the mixed solution in the adding process of the zirconium oxychloride aqueous solution to control precipitation, and adjusting the pH of the mixed solution to 6.5-7.5 after the zirconium oxychloride aqueous solution is added; then aging, filtering, drying and roasting the mixed solution to obtain a carrier;
2) dissolving nickel nitrate and copper nitrate to prepare a salt solution, adding ethanol and a stabilizer into the salt solution, uniformly stirring, spraying the salt solution onto the carrier obtained in the step 1), and drying after spraying to obtain a precursor;
3) preparing ammonium carbonate into an aqueous solution, adding ethanol into the aqueous solution, spraying the ammonium carbonate solution into the precursor obtained in the step 2), drying after spraying, and roasting to obtain the catalyst.
2. The method of producing a trimethylolpropane hydrogenation catalyst according to claim 1, characterized in that: in step 1), the controlling precipitation comprises: controlling the pH value to be 4.5-6, the precipitation time to be 1-3h, the precipitation temperature to be 30-50 ℃, and regarding the pH value of the mixed solution as the completion of precipitation when the pH value of the mixed solution is not changed.
3. The method of producing a trimethylolpropane hydrogenation catalyst according to claim 1 or 2, characterized in that: in step 1), the aging comprises: aging for 1-3h at 60-80 deg.C; preferably, the drying comprises: the drying temperature is 80-120 ℃, and the drying time is 4-6 h.
4. The method of producing a trimethylolpropane hydrogenation catalyst according to claim 1 or 2, characterized in that: introducing nitrogen gas during the roasting in the step 1), heating to 1000-1200 ℃, wherein the heating rate is 1-3 ℃/min, and the roasting time is 2-4 h.
5. The method of producing a trimethylolpropane hydrogenation catalyst according to claim 1, characterized in that: in step 2), the spraying comprises: spraying for 0.5-1h, introducing hot air for blowing in the spraying process, preferably, keeping the temperature of the carrier to be more than or equal to 80 ℃ in the blowing process; the spraying is preferably carried out in a rotary coating machine; preferably, the drying comprises: drying at 80-120 deg.C for 2-4 h.
6. The method of producing a trimethylolpropane hydrogenation catalyst according to claim 1 or 5, characterized in that: in step 3), the spraying comprises: spraying for 0.5-1h, preferably, the spraying is carried out in a rotary coating machine, hot air is introduced for blowing in the spraying process, and preferably, the temperature of the precursor is kept to be more than 80 ℃ in the blowing process; preferably, the drying comprises: drying at 80-120 deg.C for 2-4 h; the roasting comprises the following steps: the roasting temperature is 400-.
7. The method of producing a trimethylolpropane hydrogenation catalyst according to any one of claims 1 to 6, characterized in that: the stabilizer in the step 2) is one or more of glycerol, polyvinyl alcohol, polymethacrylic acid and paraffin, and preferably, the adding amount is 0.5-2% of the mass of the carrier in the step 1).
8. The method of producing a trimethylolpropane hydrogenation catalyst according to any one of claims 1 to 7, characterized in that: the ethanol content in the salt solution in the step 2) or the water solution in the step 3) is 3-5% by mass.
9. A trimethylolpropane hydrogenation catalyst prepared according to any one of claims 1 to 8.
10. The trimethylolpropane hydrogenation catalyst according to claim 9, characterized in that: the catalystThe chemical agent comprises the following components in parts by mass: CuO content of 20-40%, NiO content of 2-12%, SiO220-30% of ZrO2The content is 30-40%; preferably, the CuO content is 25-35%, the NiO content is 5-10%, and SiO2Content of 25-30%, ZrO2The content is 30-35%.
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