Preparation method of catalyst for preparing isononyl alcohol through isononanal liquid phase hydrogenation

Abstract

The invention discloses a preparation method of a catalyst for preparing isononyl alcohol through liquid-phase hydrogenation of isononanal. The preparation method comprises the following steps: 1, weighing a carrier; 2, weighing the soluble salt of the active metal, putting the weighed soluble salt of the active metal into deionized water, mixing to form a solution, adding a precipitant, and carrying out a precipitation reaction to obtain a precipitation reactant; 3, stirring and aging the precipitation reactant at a constant temperature, and washing to obtain active component slurry; and 4, mixing the carrier weighed in the step 1 with the active component slurry obtained in the step 3, adding deionized water and an adhesive, kneading, carrying out extrusion molding, and roasting to obtain the catalyst. The carrier is a mixture of one or two of natural minerals containing SiO2 and natural minerals containing SiO2 subjected to acidification modification according to any ratio. The preparation method is simple to operate, mild in process condition and low in production cost, the aldehyde conversion rate and the alcohol selectivity can reach 99% or above during application, the stability of the catalyst is larger than or equal to 1500, and the preparation method is suitable for industrial production.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and particularly relates to a method for preparing a catalyst for preparing isononanol by liquid-phase hydrogenation of isononanal. Background Art

[0002] Isononyl alcohol (INA), whose full name is 3,5,5-trimethyl-1-hexanol in Chinese, is mainly used to react with phthalic anhydride to produce diisononyl phthalate (DINP), a plasticizer for PVC. DINP is an excellent general non-toxic plasticizer. Compared with dioctyl phthalate (DOP), DINP has a larger relative molecular mass and a longer carbon chain, so it has better aging performance, migration resistance, extraction resistance, higher high temperature resistance, excellent heat resistance, light resistance and electrical insulation. It is mainly used in polyvinyl chloride, vinyl chloride copolymers, cellulose acetate, ethyl cellulose and synthetic rubber, and is widely used in toy films, wires and cables. With the market's gradual recognition of the safety of DINP, the demand for DINP as an environmentally friendly substitute for DOP will grow rapidly, thereby driving the consumption of isononyl alcohol to rise rapidly. The preparation of isononanol includes two main steps. The first step is the hydroformylation reaction of octenes to produce isononanal, and the second step is the hydrogenation reduction reaction of isononanal to produce isononanol. Compared with gas phase hydrogenation, liquid phase hydrogenation has a more favorable energy balance and a higher space-time yield and is widely used. In the prior art, octanol catalyst is generally used for industrial isononanal hydrogenation. For example, a catalyst for isononanal hydrogenation to isononanol and its preparation method and application are disclosed in the Chinese patent with publication number CN115957765A. The catalyst includes an active component, a carrier and an auxiliary agent. The active component: carrier: auxiliary agent is 20%-40%: 50%-80%: 1%-10% by mass percentage. Silica sol, aluminum nitrate or aluminum sulfate or aluminum hydroxide, and alkaline precipitant solution are added to a stirred reactor, and then the nitrate solution of the active component is mixed and added thereto, and then the reaction product is subjected to hydrothermal treatment, and finally washed, filtered, dried, added with auxiliary agents, granulated, roasted, and finally formed into sheets to obtain a catalyst. However, due to the large difference in properties between isononyl alcohol and octanol, the catalytic effect of the octanol catalyst conventionally used in the prior art is not ideal. At the same time, due to the existence of capillary condensation, the auxiliary agent in the catalyst is unevenly distributed on the carrier, so that the stability of the prepared catalyst is insufficient, resulting in the fact that the actual effect of the catalyst is not very obvious, and it still cannot meet people's needs in the actual application process. Summary of the invention

[0003] The present invention aims to solve the technical problems in the prior art that the catalyst used for the catalytic reaction of isononanal liquid phase hydrogenation has poor catalytic effect and insufficient stability; a preparation method of a catalyst for the preparation of isononanol by liquid phase hydrogenation of isononanal is proposed, so as to effectively improve the isononanal conversion rate and isononanol selectivity as well as the stability of the catalyst.

[0004] In order to achieve the above object, the present invention adopts the following technical scheme:

[0005] A method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal comprises the following steps:

[0006] Step 1, weighing the carrier according to weight;

[0007] Step 2, weighing a soluble salt of an active metal by weight, putting the weighed soluble salt of the active metal into deionized water to mix into a solution, and then adding a precipitant to perform a precipitation reaction to obtain a precipitation reaction product;

[0008] Step 3, subjecting the precipitated reactant to constant temperature stirring, aging, and washing to obtain an active component slurry;

[0009] Step 4, mixing the carrier weighed in step 1 with the active component slurry obtained in step 3, adding deionized water and a binder to knead, extruding and calcining to obtain a catalyst;

[0010] The active component content of the catalyst is 10-50% by mass percentage, and the rest is carrier; the carrier contains SiO 2 Natural minerals, acid-modified SiO 2 A mixture of one or two natural minerals in any proportion.

[0011] Furthermore, the soluble salt of the active metal is Ni(NO 3 ) 2 6H 2 O, Cu(NO 3 ) 2 6H 2 Any one of O or a mixture of two of them in any ratio.

[0012] Further, the precipitant is Na 2 CO 3 Solution, K 2 CO 3 solution, NaOH solution, NH 4 HCO 3 Solution, (NH 4 ) 2 CO 3 One of the solutions or ammonia.

[0013] Furthermore, the reaction temperature during the precipitation reaction is 50-70° C., and the endpoint pH value of the precipitation reaction is 7.0-7.5.

[0014] Furthermore, the aging temperature of the constant temperature stirring aging is 60-75° C., and the aging time is 30-50 min.

[0015] Furthermore, the adhesive is any one of methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose or sodium carboxymethyl cellulose.

[0016] Furthermore, the calcination temperature is 350-750°C.

[0017] Furthermore, the SiO 2 The natural mineral is any one of kaolinite, diatomaceous earth, attapulgite, wollastonite, illite or sefoam mud.

[0018] Furthermore, the SiO 2 The acidification modification process of natural minerals is as follows: 2 Add the natural minerals to the acidic modifier, mix, stir and filter.

[0019] Furthermore, the acidic modifier is any one of hydrochloric acid, nitric acid or sulfuric acid.

[0020] The beneficial effects of the present invention are:

[0021] 1. The preparation method of the present invention is simple to operate, has mild process conditions, low production cost, and when used, both the aldehyde conversion rate and the alcohol selectivity can reach more than 99%, and the catalyst stability is ≥1500, which is suitable for industrial mass production application.

[0022] 2. The catalyst of the present invention uses SiO 2 Natural minerals or acid-modified SiO 2 Natural minerals are used as carriers because they contain SiO 2 Natural minerals carry alkali metals or alkaline earth metals, so no additional additives are needed when preparing the catalyst, which reduces the preparation cost of the catalyst. 2 It is contained in natural minerals, so its distribution in the carrier is more uniform, and its combination with the carrier itself is more stable and not easy to lose, which not only reduces the production cost of the catalyst, but also ensures that the catalyst has excellent olefin aldehyde conversion rate, alcohol selectivity and stability in use. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solution and advantages of the embodiment of the present invention clearer, the technical solution of the embodiment of the present invention will be described more clearly and completely below. Obviously, the described embodiment is a part of the embodiment of the present invention, not all of the embodiments. Based on the described embodiment of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein should be the common meaning understood by people with general skills in the field to which the present invention belongs.

[0024] The words "first", "second" and similar words used in the patent application specification and claims of the present invention do not indicate any order, quantity or importance, but are only used to distinguish different components. Similarly, unless the context clearly indicates otherwise, the singular forms of "one", "an" or "the" and similar words do not indicate a quantitative limitation, but indicate the existence of at least one. Words such as "include" or "comprise" mean that the elements or objects appearing before "include" or "comprise" cover the features, wholes, steps, operations, elements and / or components listed after "include" or "comprise", and do not exclude the existence or addition of one or more other features, wholes, steps, operations, elements, components and / or their collections. "Up", "down", "left", "right" and the like are only used to indicate relative positional relationships. When the absolute position of the described object changes, the relative positional relationship may also change accordingly.

[0025] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0026] Example 1

[0027] A method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal comprises the following steps:

[0028] Weigh 200g nickel nitrate hexahydrate and 10g copper nitrate hexahydrate and add 0.5L deionized water to prepare a solution. In a precipitation tank with stirring, the above-prepared solution and a sodium carbonate solution with a mass concentration of 8% are subjected to precipitation reaction. The precipitation temperature is controlled to be 55°C, the reaction neutralization time is 25min, and the precipitation end point pH value is 7.2; then stir and age at 65°C for 30min, and after washing, add 166g diatomaceous earth and mix evenly to obtain a semi-finished catalyst. Add 8% of the weight of the semi-finished catalyst and 3g of methyl cellulose to the semi-finished catalyst, knead, extrude, dry, and then roast at 550°C for 2h to obtain catalyst sample H1. The catalyst contains 10.0wt% nickel, 1.0wt% copper, 2.5wt% aluminum oxide, and the rest is a carrier.

[0029] Example 2

[0030] A method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal comprises the following steps:

[0031] Weigh 95 g of diatomaceous earth, add it into 100 mL of 5% dilute sulfuric acid, stir for 5 min, then filter and wash to obtain modified diatomaceous earth for later use.

[0032] Weigh 400g Ni(NO 3 ) 2 6H 2 O, 10gCu(NO 3 ) 2 6H 2 O is added with 1L of deionized water to prepare a solution, and the above-prepared solution and a potassium carbonate solution with a mass concentration of 8% are subjected to precipitation reaction in a precipitation tank with stirring, the precipitation temperature is controlled at 50°C, the reaction neutralization time is 20min, and the precipitation end point pH value is 7.1, and then stirred and aged at 55°C for 40min, after washing, the above-mentioned modified diatomaceous earth is added and mixed to obtain a semi-finished catalyst. 8% deionized water and 7g methyl cellulose are added to the semi-finished catalyst by weight, kneaded, extruded into strips, dried, and then roasted at 350°C for 2h to obtain catalyst sample H2. The catalyst contains 40.0wt% nickel, 1.0wt% copper, 0.5wt% aluminum oxide, and the rest is carrier.

[0033] Example 3

[0034] A method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal comprises the following steps:

[0035] Weigh 150g nickel nitrate hexahydrate and 75g copper nitrate hexahydrate and add 0.5L deionized water to prepare a solution. In a precipitation tank with stirring, the above-prepared solution and a potassium carbonate solution with a mass concentration of 8% are subjected to precipitation reaction. The precipitation temperature is controlled to be 55°C, the reaction neutralization time is 15min, and the precipitation end point pH value is 7.3; then stir and age at 55°C for 30min, and after washing, add 140g attapulgite powder and mix to obtain a semi-finished catalyst. Add 8% of the weight of the semi-finished catalyst and 3g of methyl cellulose to the semi-finished catalyst, knead, extrude, dry, and then roast at 650°C for 2h to obtain catalyst sample H3. The catalyst contains 15.0wt% nickel, 8.0wt% copper, 0.1wt% sodium, 1.2wt% magnesium, and the rest is a carrier.

[0036] Example 4

[0037] A method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal comprises the following steps:

[0038] Weigh 200 g of grey silica and add it into 2200 mL of 10% nitric acid, stir for 5 minutes, and then filter and wash to obtain modified grey silica for later use.

[0039] Weigh 280g nickel nitrate hexahydrate and 95g copper nitrate hexahydrate and add 1L deionized water to prepare a solution. In a precipitation tank with stirring, the above-prepared solution and a potassium carbonate solution with a mass concentration of 8% are subjected to precipitation reaction. The precipitation temperature is controlled at 60°C, the reaction neutralization time is 20min, and the precipitation end point pH value is 6.9. Then, the mixture is stirred and aged at 65°C for 40min. After washing, the above-mentioned modified gray silica is added and mixed to obtain a semi-finished catalyst. Add 8% deionized water and 5g hydroxypropyl methylcellulose by weight to the semi-finished catalyst, knead, extrude into strips, dry, and then roast at 350°C for 2h to obtain catalyst sample H4. The catalyst contains 26.0wt% nickel, 10.0wt% copper, 1.5wt% calcium, and the rest is a carrier.

[0040] Example 5

[0041] A method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal comprises the following steps:

[0042] Weigh 220 g of kaolin and add it into 1200 mL of 30% nitric acid solution, stir for 5 minutes, then filter and wash to obtain modified kaolin for later use.

[0043] Weigh 360g nickel nitrate hexahydrate and 10g copper nitrate hexahydrate and add 1L deionized water to prepare a solution. In a precipitation tank with stirring, the above-prepared solution and a sodium carbonate solution with a mass concentration of 8% are subjected to precipitation reaction. The precipitation temperature is controlled to be 55°C, the reaction neutralization time is 15min, and the precipitation end point pH value is 7.1. Then, the catalyst is stirred and aged at 65°C for 30min. After washing, the above-mentioned modified kaolin is added and mixed to obtain a semi-finished catalyst. 10% deionized water and 6g hydroxymethyl cellulose are added to the semi-finished catalyst by weight, kneaded, extruded into strips, dried, and roasted at 350°C for 2h to obtain catalyst sample H5. The catalyst contains 36.0wt% nickel, 1.0wt% copper, and the rest is a carrier.

[0044] Example 6

[0045] A method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal comprises the following steps:

[0046] Weigh 340g nickel nitrate hexahydrate and 40g copper nitrate hexahydrate and add 0.5L deionized water to prepare a solution. In a precipitation tank with stirring, the above-prepared solution and a potassium carbonate solution with a mass concentration of 8% are subjected to precipitation reaction. The precipitation temperature is controlled to be 50°C, the reaction neutralization time is 20min, and the precipitation end point pH value is 7.0; then stir and age at 65°C for 30min, and after washing, add 100g illite powder and mix to obtain a semi-finished catalyst. Add 8% of the weight of the semi-finished catalyst and 4g of carboxymethyl cellulose to the semi-finished catalyst, knead, extrude, dry, and then roast at 550°C for 2h to obtain catalyst sample H6. The catalyst contains 34.0wt% nickel, 4.0wt% copper, 0.1wt% calcium, and the rest is carrier.

[0047] Example 7

[0048] A method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal comprises the following steps:

[0049] Weigh 210g nickel nitrate hexahydrate and 58g copper nitrate hexahydrate and add 0.5L deionized water to prepare a solution. In a precipitation tank with stirring, the above-prepared solution and a sodium carbonate solution with a mass concentration of 8% are subjected to precipitation reaction. The precipitation temperature is controlled to be 50°C, the reaction neutralization time is 20min, and the precipitation end point pH value is 7.0; then stir and age at 55°C for 30min, and after washing, add 128g sea bubble mud and mix to obtain a semi-finished catalyst. Add 8% of the weight of the semi-finished catalyst and 3g of methyl cellulose to the semi-finished catalyst, knead, extrude, dry, and then roast at 500°C for 2h to obtain catalyst sample H7. The catalyst contains 21.0wt% nickel, 7.5wt% copper, 2.0wt% (magnesium + sodium), and the rest is carrier.

[0050] Example 8

[0051] A method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal comprises the following steps:

[0052] Weigh 60 g of diatomaceous earth, add it into 60 mL of 5% dilute sulfuric acid, stir for 5 min, then filter and wash to obtain modified diatomaceous earth for later use.

[0053] Weigh 400g nickel nitrate hexahydrate and 10g copper nitrate hexahydrate and add 1L deionized water to prepare a solution. In a precipitation tank with stirring, the above-prepared solution and a potassium carbonate solution with a mass concentration of 8% are subjected to precipitation reaction. The precipitation temperature is controlled to be 50°C, the reaction neutralization time is 20min, and the precipitation end point pH value is 7.1. Then, the mixture is stirred and aged at 65°C for 40min. After washing, the above-mentioned modified diatomaceous earth and 35g illite powder are added and mixed to obtain a semi-finished catalyst. 8% deionized water and 7g hydroxymethyl cellulose are added to the semi-finished catalyst by weight, kneaded, extruded into strips, dried, and roasted at 550°C for 2h to obtain a catalyst sample H8. The catalyst contains 39.0wt% nickel, 1.1wt% copper, 0.1wt% potassium, 0.2wt% aluminum oxide, and the rest is a carrier.

[0054] Example 9

[0055] A method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal comprises the following steps:

[0056] Weigh 220 g of kaolin and add it into 1200 mL of 30% sodium hydroxide solution, stir for 30 min, then filter and wash to obtain modified kaolin for later use.

[0057] Weigh 370g nickel nitrate hexahydrate and 20g copper nitrate hexahydrate and add 1L deionized water to prepare a solution. In a precipitation tank with stirring, the above-prepared solution and a potassium carbonate solution with a mass concentration of 8% are subjected to precipitation reaction. The precipitation temperature is controlled to be 50°C, the reaction neutralization time is 20min, and the precipitation end point pH value is 7.1. Then, the mixture is stirred and aged at 55°C for 40min. After washing, 50g of the above-mentioned modified kaolin and 50g of sepiolite powder are added and mixed evenly to obtain a semi-finished catalyst. 12% deionized water and 20g carboxymethyl cellulose are added to the semi-finished catalyst by weight, kneaded, extruded into strips, dried, and roasted at 600°C for 2h to obtain a catalyst sample H9. The catalyst contains 36.0wt% nickel, 2.1wt% copper, 0.8wt% aluminum oxide, 0.1wt% magnesium, and the rest is a carrier.

[0058] Comparative Example

[0059] The commercially available liquid phase aldehyde hydrogenation catalyst is SNCAT-2800TE.

[0060] Comparative test

[0061] In order to verify the catalytic performance of the catalysts obtained in Examples 1-9 and the comparative examples, the catalysts obtained in the above-mentioned Examples and the comparative examples are now used for the catalytic reaction of liquid-phase hydrogenation of isononanal. The catalytic reaction process is as follows: 50 mL of the catalyst samples prepared in the above-mentioned Examples 1-9 and the commercially available liquid-phase aldehyde hydrogenation catalyst are respectively taken and loaded into a fixed bed reactor, and reduced with hydrogen at a reduction temperature of 450°C, and then isononanal and hydrogen are introduced at a pressure of 3-4 MPa and a temperature of 120-140°C, and the raw material liquid space velocity is 1.0 h -1 , the molar ratio of hydrogen to isononanal is 300:1, and the gas after the reaction is condensed to obtain a liquid product. The liquid product is analyzed by gas chromatography, and the results are shown in Table 1:

[0062] Table 1 Catalyst activity test results for isononanal liquid phase hydrogenation

[0063]

[0064]

[0065] From the test data of the above examples, it can be seen that the catalyst prepared by the method of the present invention has a high aldehyde conversion rate and alcohol selectivity, and the catalyst has high stability. Among them, the aldehyde conversion rate and alcohol selectivity can reach more than 99%, and the catalyst stability is greater than or equal to 1500 hours.

[0066] Finally, it should be noted that these embodiments are only used to illustrate the present invention and do not limit the scope of the present invention. In addition, for those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. The obvious changes or modifications derived from them are still within the scope of protection of the present invention.

Claims

1. A method for preparing a catalyst for liquid phase hydrogenation of isononanal to isononanol, characterized in that: The steps include: Step 1, weighing the carrier according to weight; Step 2, weighing a soluble salt of an active metal by weight, putting the weighed soluble salt of the active metal into deionized water to mix into a solution, and then adding a precipitant to perform a precipitation reaction to obtain a precipitation reaction product; Step 3, subjecting the precipitated reactant to constant temperature stirring, aging, and washing to obtain an active component slurry; Step 4, mixing the carrier weighed in step 1 with the active component slurry obtained in step 3, adding deionized water and a binder to knead, extruding and calcining to obtain a catalyst; Calculated by catalyst mass percentage, the active component content in the catalyst is 10-50%, and the rest is carrier; the carrier is a mixture of one or two of natural minerals containing SiO2 and acid-modified natural minerals containing SiO2 in any proportion.

2. The method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal according to claim 1, characterized in that: The soluble salt of the active metal is any one of Ni(NO3)2·6H2O and Cu(NO3)2·6H2O or a mixture of the two in any ratio.

3. The method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal according to claim 1, characterized in that: The precipitant is one of Na2CO3 solution, K2CO3 solution, NaOH solution, NH4HCO3 solution, (NH4)2CO3 solution or ammonia water.

4. The method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal according to claim 1, characterized in that: The reaction temperature during the precipitation reaction is 50-70° C., and the endpoint pH value of the precipitation reaction is 7.0-7.

5.

5. The method for preparing a catalyst for liquid phase hydrogenation of isononanal to isononanol according to claim 1, characterized in that: The aging temperature of the constant temperature stirring aging is 60-75° C., and the aging time is 30-50 min.

6. The method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal according to claim 1, characterized in that: The adhesive is any one of methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose or sodium carboxymethyl cellulose.

7. The method for preparing a catalyst for liquid phase hydrogenation of isononanal to isononanol according to claim 1, characterized in that: The calcination temperature is 350-750°C.

8. The method for preparing a catalyst for liquid phase hydrogenation of isononanal to isononanol according to claim 1, characterized in that: The natural mineral containing SiO2 is any one of kaolinite, diatomaceous earth, attapulgite, wollastonite, illite or sepiolite.

9. The method for preparing a catalyst for preparing isononanol by liquid phase hydrogenation of isononanal according to claim 1, characterized in that: The acidification modification process of the natural mineral containing SiO2 is as follows: adding the natural mineral containing SiO2 into an acidic modifier, mixing, stirring, and filtering.

10. The method for preparing a catalyst for liquid phase hydrogenation of isononanal to isononanol according to claim 1, characterized in that: The acidic modifier is any one of hydrochloric acid, nitric acid or sulfuric acid.

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