A process for the preparation of 1,3-propanediol from acrolein

Abstract

The present application relates to a kind of 1,3-propanediol prepared from acrolein method, comprising: S1: under the catalysis of Y / P-Al2O3, acrolein solution is born hydration reaction, and 3-hydroxypropionaldehyde is prepared;The Y / P-Al2O3 includes phosphorus-doped Al2O3 carrier and hydration reaction active component supported on the carrier;S2: 3-hydroxypropionaldehyde is carried out hydrogenation reaction under the catalysis of Ni-Mo-X / Z, and 1,3-propanediol is prepared.Compared with prior art, the present application uses phosphorus-doped solid acid catalyst as hydration section catalyst, and 3-hydroxypropionaldehyde is prepared by catalyzing acrolein hydration reaction, then Mo-X double promoter component modified nickel-based catalyst is used as hydrogenation section catalyst, and 1,3-propanediol is prepared by catalyzing 3-hydroxypropionaldehyde hydrogenation reaction, above-mentioned catalyst all has the characteristics such as high activity, high selectivity, good stability, cheap and easy to obtain, and 1,3-propanediol selectivity reaches more than 99.5%.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology and relates to a method for preparing 1,3-propanediol from acrolein. Background Technology

[0002] 1,3-Propanediol (1,3-PDO), an important chemical raw material, is the main monomer for synthesizing polyester fiber—polypropylene terephthalate (PTT). PTT materials have excellent properties and are widely used in clothing, textiles, engineering plastics, automobiles, and other fields, showing a very broad market prospect. There are three main methods for synthesizing 1,3-PDO: microbial fermentation, ethylene oxide hydroformylation, and acrolein hydration hydrogenation. Among them, the acrolein hydration hydrogenation method has the greatest potential for industrial application, including two processes: the hydration of acrolein to 3-hydroxypropanal and the hydrogenation of 3-hydroxypropanal to 1,3-propanediol.

[0003] The main problems in the process of hydrating acrolein to produce 3-hydroxypropional are: first, the low solubility of acrolein and water hinders mass transfer, affecting the conversion rate; second, the hydration process is often accompanied by side reactions such as condensation polymerization and self-polymerization, and the resulting byproducts are difficult to separate and easily deposit on the catalyst, affecting the reaction activity and catalyst lifespan. Therefore, selecting a hydration catalyst with high conversion rate, high selectivity, long service life, and easy regeneration is key to improving the acrolein hydration reaction process.

[0004] Currently, catalysts for the hydration of acrolein to 3-hydroxypropional can be divided into homogeneous and heterogeneous catalysts. Homogeneous catalysts mainly include protic acids and acid salts, as well as some buffer solutions. These catalytic systems suffer from product separation problems, limiting their industrial application prospects. Heterogeneous catalysts mainly consist of ion exchange resins and some solid acid catalysts. Resin catalysts exhibit superior catalytic activity; however, their active groups are prone to detachment during long-term operation, and the regeneration of the polymer is difficult, resulting in high operating and processing costs. Therefore, the development of solid acid catalysts has become a major research direction.

[0005] Patent US5276201 synthesizes an H3PO4 / TiO2 catalyst, achieving a 50% conversion rate of acrolein and a selectivity of approximately 81% for 3-hydroxypropionaldehyde at a reaction temperature of 50–70 °C and a space velocity of 0.25 h⁻¹. Patent CN 115626869A uses an acid-modified molecular sieve as a catalyst, adding an organic solvent to an aqueous solution of acrolein to improve its solubility; however, the resulting acrolein conversion rate is only 57.4%. Patent CN116637647A synthesizes a transition metal-supported molecular sieve for acrolein hydration through alkali treatment, metal loading, and ion exchange steps; however, this catalyst preparation process is complex, requiring multiple steps before it can be used in the reaction. Patent CN112892584A discloses a metal-modified silica-alumina molecular sieve catalyst. Although this catalyst achieves an 88% conversion rate and a 93% selectivity for 3-hydroxypropionaldehyde in the acrolein hydration reaction, the excessive amount of polymerization inhibitor added during the reaction increases the difficulty of subsequent separation of the target product and results in high process costs. Patent CN114409518A uses boron-phosphorus-gallium modified alumina as a catalyst for the acrolein hydration reaction. In the examples, the highest acrolein conversion rate was 83.6%, and the selectivity was 93.4%, which is not high enough.

[0006] Therefore, the use of solid acid catalysts for the hydration of acrolein to prepare 3-hydroxypropional has problems such as low reaction conversion rate, low selectivity, and complex catalyst preparation process.

[0007] For the hydrogenation of 3-hydroxypropanal to 1,3-propanediol, the research focus is on catalyst development. Existing studies have shown that the composition and structure of the catalyst affect its activity and stability. Hydrogenation catalysts are mainly classified into Raney nickel catalysts and supported catalysts.

[0008] Patent CN 1122568 C discloses a Raney nickel catalyst with an Al-Ni-A composition. This catalyst exhibits good activity and selectivity in the hydrogenation reaction of 3-hydroxypropanal, achieving 100% activity and selectivity under conditions of reaction temperature 50-130℃, pressure 6MPa, and 3-hydroxypropanal concentration of 12wt%. However, the reaction is carried out in a high-pressure reactor, making catalyst-product separation difficult. The catalyst's stability and activity decrease significantly as the reaction proceeds, hindering large-scale industrial application.

[0009] Patent CN105709778A discloses a catalyst for the hydrogenation of 3-hydroxypropanal to 1,3-propanediol, which is a Ni-Rh-X / A catalyst; wherein the active component X is any one or a combination of rhenium, tungsten, chromium, lanthanum, iron, molybdenum, or cobalt. The addition of the noble metal Rh effectively reduces the reaction pressure; the addition of an acidic catalyst in the second stage improves the selectivity of 1,3-propanediol. However, the introduction of the noble metal increases the catalyst cost, and the two-stage hydrogenation reaction makes the process more complex.

[0010] Patent CN115141083A discloses a method for the hydrogenation of 3-hydroxypropanal to 1,3-propanediol. This method uses a PtNiGaMo multimetallic catalyst to catalyze the hydrogenation reaction, wherein the platinum content is 0.1wt%–1wt%, the nickel content is 2wt%–7wt%, the gallium content is 0.2wt%–2wt%, the molybdenum content is 0.1wt%–1wt%, and the remainder is α-alumina support. This catalyst allows the hydrogenation reaction to proceed at low temperatures, suppresses the decomposition of 3-hydroxypropanal and the occurrence of side reactions, and improves the selectivity of 3-hydroxypropanal and the stability of the catalyst. However, the introduction of precious metals still leads to increased reaction costs.

[0011] Chinese patent CN 114011432 A describes the synthesis of a catalyst using nickel oxide, ruthenium oxide, cerium oxide, and a support for the hydrogenation of 3-hydroxypropanal to 1,3-propanediol. The conversion rate of 3-hydroxypropanal in this reaction is higher than 99.9%, but the overall yield from acrolein to 1,3-propanediol is low, with a minimum of only 78%.

[0012] Therefore, most existing nickel-based supported hydrogenation catalysts incorporate noble metal elements to reduce the reaction conditions and improve catalyst stability. However, this leads to problems such as high catalyst production costs and complex reaction conditions.

[0013] In summary, both the hydration and hydrogenation stages of the existing acrolein hydration hydrogenation process for 1,3-propanediol suffer from problems such as high catalyst costs and complex preparation. Furthermore, catalyst defects lead to low conversion rates, low selectivity, or complex processes for the target product. Summary of the Invention

[0014] The purpose of this invention is to provide a method for preparing 1,3-propanediol from acrolein. A phosphorus-doped solid acid catalyst is used as the catalyst in the hydration stage to catalyze the hydration reaction of acrolein to obtain 3-hydroxypropane. Then, a nickel-based catalyst modified with molybdenum-X dual-auxiliary component is used as the catalyst in the hydrogenation stage. The multi-component synergistic catalysis of the hydrogenation reaction of 3-hydroxypropane to obtain 1,3-propanediol results in the production of 1,3-propanediol. Both the phosphorus-doped solid acid catalyst and the molybdenum-X dual-auxiliary component modified nickel-based catalyst have the characteristics of high activity, high selectivity for the target product, good stability, and low cost and availability. Therefore, the 1,3-propanediol preparation process of this invention has the advantages of high production efficiency, good operational stability, and low cost.

[0015] The objective of this invention can be achieved through the following technical solutions:

[0016] A method for preparing 1,3-propanediol from acrolein, comprising:

[0017] S1: Under the condition of a catalyst, acrolein solution is hydrated to obtain 3-hydroxypropionaldehyde.

[0018] S2: 3-Hydroxypropanal was hydrogenated in the presence of Ni-Mo-X / Z catalyst to produce 1,3-propanediol;

[0019] In step S1, the catalyst in the hydration reaction is Y / P-Al2O3, comprising a phosphorus-doped Al2O3 support and a hydration reaction active component supported on the support; the hydration reaction active component is selected from at least one of cerium, indium, cobalt, tungsten, lanthanum, molybdenum, and zirconium.

[0020] In step S2, the hydrogenation reaction includes a support Z and a hydrogenation active component Ni, a first auxiliary component Mo, and a second auxiliary component X supported on the support; the second auxiliary component X is selected from at least one of iron, manganese, cobalt, chromium, zirconium, phosphorus, boron, lanthanum, cerium, yttrium, copper, gallium, indium, niobium, germanium, or tungsten.

[0021] This invention utilizes a Y / P-Al₂O₃ catalyst with an ordered mesoporous structure and in-situ phosphorus-doped supported metal X as a hydration reaction catalyst. The hydration reaction active component can generate different electronic effects with the in-situ doped P in the P-Al₂O₃ support, effectively regulating the catalyst's acidity and distribution, and improving its reaction activity. Simultaneously, the interaction between the supported metal and the framework phosphorus can stabilize the active sites, improving catalyst stability.

[0022] Experiments show that by doping phosphorus into the support, the activity, selectivity, and stability of the resulting hydration reaction catalyst are significantly improved. The conversion rate of acrolein reaches over 78%, with a maximum of 90%; the selectivity of 3-hydroxypropionaldehyde reaches over 80%, with a maximum of 90%; and after 500 hours of operation, both the conversion rate and selectivity decrease by only 1%.

[0023] The main active component of the hydrogenation reaction catalyst in this invention is nickel, the first auxiliary component is molybdenum, and by introducing a second auxiliary component, the interaction between the active metal nickel and the first auxiliary component molybdenum is improved. The active metal nickel, the first auxiliary component molybdenum and the second auxiliary component form a good synergistic effect, which makes the active sites of the catalyst more stable. Under the condition of avoiding the use of precious metals, the catalyst of this technology has the characteristics of high activity, high selectivity, high stability and low cost.

[0024] Experiments show that the introduction of molybdenum as an auxiliary component effectively improves the conversion rate, selectivity and stability of the catalyst in the hydrogenation of 3-hydroxypropanal to 1,3-propanediol. After 50 h of reaction, the conversion rate reaches 99.1-100% and the selectivity reaches 99.5-99.9%. Moreover, during a long-term operation of 2200 h, the conversion rate only decreases by 2% and the selectivity fluctuates only within the range of 2%.

[0025] Furthermore, the catalyst is a phosphorus-doped Al2O3 support in Y / P-Al2O3, and the doping method is in-situ doping.

[0026] The phosphorus content is 0.1-15% by mass; the hydration reaction active component has a mass content of 1-20%.

[0027] As a preferred technical solution, the phosphorus content in the Y / P-Al2O3 is 0.5-8% by mass.

[0028] As a preferred technical solution, the mass content of the hydration reaction active component in the Y / P-Al2O3 is 2-10%.

[0029] Furthermore, the preparation method of the phosphorus-doped Al2O3 support includes: dissolving the template agent in a mixed solution of ethanol, isopropanol, and glacial acetic acid; adding a phosphorus source and an aluminum source to mix and obtain a suspension; aging, drying, and calcining to obtain the phosphorus-doped Al2O3 support.

[0030] Furthermore, the template agent is selected from one of cetyltrimethylammonium bromide, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), and polyethylene glycol (PEG).

[0031] Furthermore, the volume ratio of ethanol, isopropanol, and glacial acetic acid is (100-200):(40-80):1.

[0032] Furthermore, the phosphorus source is selected from phosphoric acid, phosphorous acid, and ammonium dihydrogen phosphate.

[0033] Furthermore, the aluminum source is selected from aluminum isopropoxide, aluminum nitrate, and aluminic acid.

[0034] Furthermore, after the phosphorus source and aluminum source are added, they are stirred and mixed for 2 to 6 hours.

[0035] Furthermore, in the aging process, the aging temperature is room temperature, and the aging time is 4 to 8 hours.

[0036] Furthermore, the drying temperature is 50–80°C during the drying process.

[0037] Further, the calcination includes: maintaining a constant temperature at 300-600°C for 3-6 hours to remove the template agent, and then calcining at 600-1000°C for 1-2 hours to obtain γ-Al2O3.

[0038] As a preferred technical solution, in the roasting process: first, at 2℃ for 2 minutes -1 The temperature is increased to 300-600℃ and held for 3-6 hours, then increased to 800-1000℃ at a rate of 10℃ / min for 1-2 hours.

[0039] This invention synthesizes in situ phosphorus-doped ordered mesoporous alumina supports. First, in-situ phosphorus doping is introduced into the alumina lattice, replacing some aluminum atomic sites. Phosphorus doping increases the thermal stability and specific surface area of ​​alumina. Simultaneously, phosphorus doping into the alumina framework reduces the electron cloud density of aluminum, enhancing the Lewis acidity of alumina. Phosphorus doping also generates P-OH groups on the Al₂O₃ surface, altering its acidic site properties. Second, the synthesized support possesses an ordered mesoporous structure, providing effective diffusion channels for reactants.

[0040] Furthermore, the preparation method of Y / P-Al2O3 includes: immersing a phosphorus-doped Al2O3 support in a solution containing a hydrated reactive component precursor, drying, and calcining to obtain Y / P-Al2O3;

[0041] The precursor of the hydration reactive component is a water-soluble salt containing the hydration reactive component;

[0042] As a preferred technical solution, the water-soluble salt is selected from at least one of nitrates, carbonates, acetates, oxalates, and ammonium salts.

[0043] During the roasting process, the roasting temperature is 450–650℃ and the roasting time is 4–12 hours.

[0044] Further, in step S1, the hydration temperature in the hydration reaction is 35–90°C, the acrolein solution is prepared by mixing an acrolein aqueous solution with a polymerization inhibitor, the concentration of acrolein in the acrolein aqueous solution is 5–20 wt%, and the polymerization inhibitor is selected from one or more of hydroquinone, 4-methylphenol, phenothiazine, ZJ-705, p-benzoquinone, 2,6-dinitro-p-cresol, and 4-tert-butylcatechol, with a polymerization inhibitor content of 200–2000 ppm.

[0045] The reaction space velocity, calculated based on acrolein, is 0.1–3 h⁻¹. -1 ;

[0046] Further, in step S2, in the Ni-Mo-X / Z, the mass content of the hydrogenation active component Ni is 5-40%; the mass content of the first auxiliary component Mo is 0.1-5.9%; the mass content of the second auxiliary component X is 0.1-15%; and the carrier Z is selected from one or more combinations of silica, alumina, ZSM-5, MCM-41, MCM-49, SBA-15, MCM-22, mordenite, SAPO-11, SAPO-34, L zeolite, β zeolite, Y zeolite, or ultrastable Y zeolite.

[0047] As a preferred technical solution, in the Ni-Mo-X / Z, the mass content of the hydrogenated active component Ni is 6-35%.

[0048] As a preferred technical solution, in the Ni-Mo-X / Z, the mass content of the first auxiliary component Mo is 0.5% to 5.5%.

[0049] As a preferred technical solution, in the Ni-Mo-X / Z, the mass content of the second auxiliary component X is 0.5-13%.

[0050] Further, in step S2, the Ni-Mo-X / Z is prepared by an impregnation method, wherein the impregnation method is selected from one of the following: equal volume impregnation method, excess impregnation method, and multiple impregnation method. Preferably, it is the equal volume impregnation method or the multiple impregnation method.

[0051] Furthermore, the preparation method of Ni-Mo-X / Z includes: immersing the support in a solution containing a hydrogenation active component precursor, a first auxiliary component precursor, and a second auxiliary component precursor, drying, and calcining to obtain Ni-Mo-X / Z.

[0052] Furthermore, the hydrogenation active component precursor is a water-soluble salt containing a hydrogenation active component, the first auxiliary component precursor is a water-soluble salt containing a first auxiliary component Mo, and the second auxiliary component precursor is a water-soluble salt containing a second auxiliary component X.

[0053] As a preferred technical solution, the water-soluble salt is selected from at least one of nitrates, carbonates, acetates, oxalates, and ammonium salts.

[0054] As a preferred technical solution, the drying temperature is 50-150℃ and the drying time is 1-24h.

[0055] Furthermore, in the calcination process, the calcination temperature is 300–650°C, and the calcination time is 1–12 hours.

[0056] Further, in step S2, before the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol, the Ni-Mo-X / Z is subjected to a reduction treatment; in the reduction treatment, the reduction temperature is 200-600℃, the reducing gas is a mixture of hydrogen and nitrogen, the hydrogen gas fraction is 5-30 vol%, the reducing gas pressure is 0.1-1 MPa, and the reducing gas space velocity is 500-5000 h⁻¹. -1 The restoration time is 4 to 50 hours.

[0057] Further, in step S2, the reaction temperature for the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol is 50–130°C, the reaction pressure is 2–15 MPa, and the molar ratio of hydrogen to 3-hydroxypropanal is 4–40:1.

[0058] Based on a 3–21 wt% aqueous solution of 3-hydroxypropanal, the liquid hourly space velocity (LHSV) of the 3-hydroxypropanal is 0.1–2 h⁻¹. -1 .

[0059] Compared with the prior art, the present invention has the following characteristics:

[0060] 1) This invention synthesizes phosphorus-doped ordered mesoporous alumina in situ and uses it as a support to synthesize a solid acid catalyst for hydration reactions. Phosphorus has five electrons in its outermost electron orbital. Utilizing its multi-electron characteristic, the electronic properties of active metal species can be altered through electronic interactions. The supported metal X can produce different electronic effects with the in-situ doped P in the P-Al2O3 support, effectively regulating the acidity and distribution of the catalyst and improving its reactivity. Simultaneously, the interaction between the supported metal X and the framework phosphorus can stabilize the active sites, improve catalyst stability, and has the advantages of long lifespan and easy regeneration. Experiments show that the hydration reaction catalyst prepared in this invention can achieve acrolein conversion of up to 90%, 3-hydroxypropionaldehyde selectivity of up to 90%, and a lifespan of over 100 hours.

[0061] 2) The main active component of the hydrogenation reaction catalyst of the present invention is nickel, the first auxiliary component is molybdenum, and by introducing a second auxiliary component, the interaction between the active metal nickel and the first auxiliary component molybdenum is improved. The active metal nickel, the first auxiliary component molybdenum and the second auxiliary component form a good synergistic effect, which makes the active sites of the catalyst more stable. Under the condition of avoiding the use of precious metals, the catalyst of this technology has the characteristics of high activity, high selectivity, high stability and low cost. Experiments show that the hydrogenation reaction catalyst prepared by the present invention can achieve a conversion rate of 3-hydroxypropionaldehyde of more than 99.0% and a lifetime of more than 2000h.

[0062] 3) In the hydrogenation reaction section, because 3-hydroxypropanal is thermosensitive, it is prone to polymerization at high temperatures. Under this catalytic system, the reaction temperature is relatively low, which inhibits the side reactions of 3-hydroxypropanal and improves the selectivity of the catalyst. Experiments show that the catalyst prepared by this invention can achieve a selectivity of 1,3-propanediol of more than 99.5%.

[0063] 4) The hydrogenation reaction catalyst prepared by the present invention can realize the one-step hydrogenation of 3-hydroxypropionaldehyde, with high equipment utilization and low energy consumption. Detailed Implementation

[0064] The present invention will now be described in detail with reference to specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0065] In the following embodiments, unless otherwise specified, the raw materials, reagents or processing techniques are all conventional commercial products or conventional processing techniques in the art.

[0066] In the following embodiments, the auxiliary components cerium, indium, cobalt, tungsten, lanthanum, molybdenum, zirconium, nickel, iron, manganese, chromium, phosphorus, boron, yttrium, copper, gallium, niobium, and germanium are added in the form of corresponding soluble salts, such as nitrates, carbonates, acetates, oxalates, and ammonium salts; more specifically, they include cerium nitrate, indium nitrate, cobalt nitrate, ammonium metatungstate, lanthanum nitrate, ammonium molybdate, zirconium nitrate, nickel nitrate, iron nitrate, manganese nitrate, chromium nitrate, ammonium phosphate, ammonium borate, yttrium nitrate, copper nitrate, gallium nitrate, ammonium niobate oxalate, and ammonium hexafluorogermanate used in the following embodiments.

[0067] Example 1:

[0068] A Ce / P-Al2O3 catalyst for the hydration of acrolein to 3-hydroxypropionaldehyde, the preparation method of which includes:

[0069] S1: Weigh 7.5g of P123 and dissolve it in a mixed solution of 150mL anhydrous ethanol, 50mL isopropanol and 0.9mL glacial acetic acid. After P123 is completely dissolved, slowly add 3.5g of diammonium hydrogen phosphate and 15.3g of aluminum isopropoxide in sequence, and stir vigorously for 4h to obtain a suspension.

[0070] S2: The above suspension was aged at room temperature for 8 hours, and then transferred to an oven at 60°C for solvent evaporation to obtain a dry sol.

[0071] S3: Place the dry sol in a muffle furnace and heat it in air at 2°C·min. -1 The temperature was increased to 500℃ and held for 4 hours, then calcined at 800℃ for 1 hour at a rate of 10℃ / min to obtain P-Al2O3.

[0072] S4: Dissolve 0.23g of cerium nitrate in water, add it dropwise to 10g of P-Al2O3, stir, dry in an oven at 60℃, and then calcine at 450℃ for 4h to obtain Ce / P-Al2O3.

[0073] Examples 2-10:

[0074] A catalyst Y / P-Al2O3 for the hydration of acrolein to 3-hydroxypropionaldehyde, the preparation method of which differs from that in Example 1 only in that:

[0075] Active components and content: Indium nitrate, cobalt nitrate, ammonium tungstate, lanthanum nitrate, ammonium molybdate, and zirconium nitrate were used in appropriate amounts to replace 1.17g of cerium nitrate in step S4 of Example 1;

[0076] Phosphorus content in the carrier: Adjust the amount of diammonium hydrogen phosphate used in step S4;

[0077] The rest is the same as in Example 1.

[0078] For example: Example 10

[0079] A catalyst W / P-Al2O3 for the hydration of acrolein to 3-hydroxypropionaldehyde, the preparation method of which includes:

[0080] S1: Weigh 7.5g of P123 and dissolve it in a mixed solution of 150mL anhydrous ethanol, 50mL isopropanol and 0.9mL glacial acetic acid. After P123 is completely dissolved, slowly add 1.8g of diammonium hydrogen phosphate and 15.3g of aluminum isopropoxide in sequence, and stir vigorously for 4h to obtain a suspension.

[0081] S2: The above suspension was aged at room temperature for 8 hours, and then transferred to an oven at 60°C for solvent evaporation to obtain a dry sol.

[0082] S3: Place the dry sol in a muffle furnace and heat it in air at 2°C·min.-1 The temperature was increased to 500℃ and held for 4 hours, then calcined at 800℃ for 1 hour at a rate of 10℃ / min to obtain P-Al2O3.

[0083] S4: Dissolve 0.6g of ammonium tungstate in water, add it dropwise to 10g of P-Al2O3, stir, dry in a 60℃ oven, and then calcine at 450℃ for 4h to obtain W / P-Al2O3.

[0084] Comparative Example 1:

[0085] A catalyst, Ce-P / γ-Al₂O₃, for the hydration of acrolein to 3-hydroxypropionaldehyde, is prepared by means of:

[0086] S1: Weigh 7.5g of P123 and dissolve it in a mixed solution of 150mL anhydrous ethanol, 50mL isopropanol and 0.9mL glacial acetic acid. After P123 is completely dissolved, slowly add 15.3g of aluminum isopropoxide and stir vigorously for 4 hours to obtain a suspension.

[0087] S2: The above suspension was aged at room temperature for 8 hours, and then transferred to an oven at 60°C for solvent evaporation to obtain a dry sol.

[0088] S3: Place the dry sol in a muffle furnace and heat it in air at 2°C·min. -1 The temperature was increased to 500℃ and held for 4 hours, then calcined at 600℃ for 1 hour at a rate of 10℃ / min to obtain γ-Al2O3.

[0089] S4: Dissolve 0.23g cerium nitrate and 6.39g diammonium hydrogen phosphate in water, add dropwise to 10g γ-Al2O3, stir, and then dry in a 60℃ oven. Then calcine at 450℃ for 4h to obtain Ce-P / γ-Al2O3.

[0090] The catalyst samples prepared in Examples 1-10 and Comparative Example 1 were subjected to atomic emission spectroscopic elemental analysis using inductively coupled plasma optical emission spectrometry (ICP-OES), and the results are shown in Table 1.

[0091] Table 1 Catalyst composition of examples and comparative examples

[0092] Metal Y Metallic Y content (wt%) Phosphorus content in the carrier (wt%) Example 1 Ce 1 15 Example 2 In 2 10 Example 3 Co 5 8 Example 4 W 8 8 Example 5 La 8 5 Example 6 Mo 10 0.5 Example 7 Zr 20 0.1 Example 8 Ce 5 8 Example 9 Mo 5 8 Example 10 W 5 8 Comparative Example 1 Ce 1 15

[0093] Application Example 1:

[0094] This example is used to evaluate the catalytic performance of the catalyst prepared in Example 1 in the reaction of acrolein hydration to 3-hydroxypropionaldehyde, specifically including:

[0095] 3g of catalyst was loaded into a fixed-bed tubular reactor, and the reactor temperature was raised to 50°C. A 5wt% aqueous solution of acrolein containing 2000ppm hydroquinone polymerization inhibitor was then introduced into the reactor at a space velocity of 1.0 h⁻¹. -1 After reacting for 10 hours, the effluent was cooled and collected, and the product composition was analyzed by gas chromatography. The reactant conversion rate and product selectivity were calculated using the following formulas:

[0096] Acrolein conversion rate = (Amount of acrolein converted in the reaction / Amount of acrolein entering the reactor) * 100%

[0097] 3-Hydroxypropanal selectivity = Amount of 3-hydroxypropanal generated / Amount of acrolein converted in the reaction * 100%.

[0098] The specific steps in the reaction of Examples 12-28 and Comparative Examples 2-4 are the same as those in Application Example 1, but the reaction conditions are different.

[0099] The reaction conditions and results of the catalysts prepared in Examples 1-10 and Comparative Example 1 in the reaction of acrolein hydration to 3-hydroxypropionaldehyde are shown in Table 2.

[0100] Table 2

[0101]

[0102] As can be seen from Table 2, when the phosphorus doping amount in the catalyst is similar, the catalyst doped with phosphorus by co-impregnation with the active component (Comparative Example 1) exhibits poor activity and selectivity in the reaction of acrolein hydration to 3-hydroxypropional. After 10 hours of reaction, the acrolein conversion rate is only 70%, and the 3-hydroxypropional selectivity is only 76%. However, by doping phosphorus during the preparation of the alumina support, both its activity and selectivity are significantly improved, with the acrolein conversion rate reaching over 78%, and up to 90%, and the 3-hydroxypropional selectivity reaching over 80%, and up to 90%.

[0103] Stability evaluation example 1:

[0104] This example is used to evaluate the stability of the catalysts prepared in Example 10 and Comparative Example 1. The only difference between this example and Application Example 1 is that the reaction times are 10h, 100h, and 500h, respectively; the rest is the same as Application Example 1.

[0105] The results are shown in Table 3.

[0106] Table 3. Stability test of the catalyst prepared in Example 10

[0107] Reaction run time / h Conversion rate / % Selectivity / % 10 88 90 100 88 90 500 87 89

[0108] Table 4 shows the stability test results of the catalysts prepared in Comparative Example 1.

[0109] Reaction run time / h Conversion rate / % Selectivity / % 10 70 76 100 64 75 500 40 71

[0110] As can be seen from Table 3, the catalyst prepared in Example 10 using phosphorus-doped alumina as a support exhibits high stability. Within 100 h of reaction, neither the acrolein conversion rate nor the 3-hydroxypropionaldehyde selectivity decreased significantly, and after 500 h of reaction, the acrolein conversion rate and the 3-hydroxypropionaldehyde selectivity decreased by only 1%.

[0111] Example 11:

[0112] A Ni-Mo-X / Z type catalyst was synthesized using an equal-volume impregnation method. The synthesis method is illustrated in Example 28, and the specific steps are as follows:

[0113] 9.9g of nickel nitrate hexahydrate, 1.02g of ammonium molybdate, and 0.82g of cerium nitrate were weighed and dissolved in 20g of water. 10g of alumina was immersed in the above solution for 12 hours. After immersion, the alumina was dried at 110℃ for 4 hours and then calcined in a muffle furnace at 400℃ for 5 hours in air atmosphere to obtain a catalyst of 20wt% Ni-5wt% Mo-3.5wt% Ce / alumina.

[0114] Comparative Example 2:

[0115] A Ni-Mo / alumina catalyst was synthesized using an equal-volume impregnation method. The specific steps are as follows:

[0116] 9.9g of nickel nitrate hexahydrate and 1.02g of ammonium molybdate were weighed and dissolved in 20g of water. 10g of alumina was immersed in the above solution for 12 hours. After immersion, the alumina was dried at 110℃ for 4 hours and then calcined in a muffle furnace at 400℃ for 5 hours in an air atmosphere to obtain a catalyst of 20wt% Ni-5wt% Mo / alumina.

[0117] Comparative Example 3:

[0118] A Ni-Y / alumina catalyst was synthesized using an equal-volume impregnation method. The specific steps are as follows:

[0119] 9.9g of nickel nitrate hexahydrate and 0.82g of cerium nitrate were weighed and dissolved in 20g of water. 10g of alumina was immersed in the above solution for 12 hours. After immersion, the solution was dried at 110℃ for 4 hours and then calcined in a muffle furnace at 400℃ for 5 hours in air atmosphere to obtain a catalyst of 20wt% Ni-3.5wt% Ce / alumina.

[0120] Comparative Example 4:

[0121] A Ni / alumina catalyst was synthesized using an equal-volume impregnation method. The specific steps are as follows:

[0122] 9.9g of nickel nitrate hexahydrate was dissolved in 20g of water. 10g of alumina was immersed in the above solution for 12 hours. After immersion, the alumina was dried at 110℃ for 4 hours and then calcined in a muffle furnace at 400℃ for 5 hours in air atmosphere to obtain a catalyst of 20wt% Ni- / alumina.

[0123] Atomic emission spectroscopic elemental analysis was performed on each catalyst sample using inductively coupled plasma optical emission spectrometry (ICP-OES), and the results are shown in Table 5.

[0124] Table 5 Catalyst composition of Examples 11-28 and Comparative Examples 2-4

[0125]

[0126]

[0127] Application Example 2:

[0128] This example is used to evaluate the activity of the catalysts prepared in Examples 11-28 and Comparative Examples 2-4. The specific steps in Example 11 include:

[0129] 5g of catalyst was loaded into a fixed-bed reactor and subjected to an incubation period of 450℃, 0.3MPa, and 2000h⁻¹. -1 Hydrogen was reduced for 25 hours under the specified conditions, and then the temperature was lowered to the reaction temperature after the reduction was completed.

[0130] A 7 wt% aqueous solution of 3-hydroxypropanal was mixed with hydrogen gas, preheated at 50°C, and then fed into a fixed-bed reactor for reaction. The resulting product solution was cooled and analyzed by gas chromatography to determine its composition. The reactant conversion rate and product selectivity were calculated using the following formulas:

[0131] 3-Hydroxypropanal conversion rate = (Amount of 3-hydroxypropanal converted in the reaction / Amount of 3-hydroxypropanal entering the reactor) * 100%

[0132] 1,3-Propanediol selectivity = Amount of 1,3-propanediol produced / Amount of 3-hydroxypropanal converted in the reaction * 100%.

[0133] The specific steps in the reaction of Examples 12-28 and Comparative Examples 2-4 are the same as those in Application Example 2, but the reaction conditions are different.

[0134] The reaction conditions and results of the above embodiments and comparative examples are shown in Table 2, where the hydrogen-aldehyde ratio is the molar ratio of hydrogen to 3-hydroxypropanal, and the liquid hourly space velocity is the liquid hourly space velocity of 3-hydroxypropanal relative to the catalyst bed.

[0135] Table 6. Reaction conditions and results for each example.

[0136]

[0137]

[0138] As can be seen from Table 6, the catalysts in Comparative Example 2 (which only introduced molybdenum as an auxiliary component but not cerium), Comparative Example 3 (which only introduced cerium as an auxiliary component but not molybdenum), and Comparative Example 4 (which only supported nickel as the active component) all exhibited poor conversion and selectivity in the hydrogenation of 3-hydroxypropanal to 1,3-propanediol. After 50 hours of reaction, the conversion rates were only 96.7%, 92.1%, and 85.7%, respectively, and the selectivities were only 95.4%, 94.5%, and 90.1%, respectively. However, for the catalysts that introduced molybdenum as an auxiliary component, namely the Ni-Mo-X / Z catalysts prepared in Examples 11-28, the conversion and selectivity were significantly improved. After 50 hours of reaction, the conversion rate reached 99.1-100%, and the selectivity reached 99.5-99.9%.

[0139] Stability evaluation example 2:

[0140] This example is used to evaluate the stability of the catalysts prepared in Example 28, Comparative Example 2, Comparative Example 3, and Comparative Example 4. The specific process differs from that in Example 2 only in that:

[0141] For the catalyst prepared in Example 28, the reaction times were 50 h, 100 h, 500 h, 1000 h, 1500 h, and 2200 h, respectively.

[0142] For the catalysts prepared in Comparative Examples 2, 3, and 4, the reaction times were 50 h, 100 h, 200 h, and 500 h, respectively.

[0143] The rest is the same as in Application Example 2.

[0144] Table 7. Stability test of the catalyst prepared in Example 28

[0145]

[0146]

[0147] Table 8 shows the stability test results of the catalysts prepared in Comparative Example 2.

[0148] Reaction run time / h Conversion rate / % Selectivity / % 50 96.7 95.4 100 92.3 95.1 200 90.2 90.3 500 85.4 84.9

[0149] Table 9 shows the stability test results of the catalysts prepared in Comparative Example 3.

[0150] Reaction run time / h Conversion rate / % Selectivity / % 50 92.1 94.5 100 91.3 94.2 200 88.6 91.5 500 84.6 87.3

[0151] Table 10 shows the stability experiments of the catalysts prepared in Comparative Example 4.

[0152] Reaction run time / h Conversion rate / % Selectivity / % 50 85.7 90.1 100 84.2 88.7 200 79.2 82.1 500 60.1 73.4

[0153] Comparing Tables 7-10, it can be seen that for the catalyst without the first auxiliary agent molybdenum and the second auxiliary agent cerium (Comparative Example 4), the conversion rate of 3-hydroxypropionaldehyde decreased by 25.6% and the selectivity of 1,3-propanediol decreased by 16.7% after 500 hours of reaction compared to 50 hours of operation. Based on this, the catalyst with only the first auxiliary agent molybdenum (Comparative Example 2) showed a decrease in conversion rate of 11.3% and a decrease in selectivity of 10.5% after 500 hours of reaction compared to 50 hours of operation, indicating that the introduction of the first auxiliary agent molybdenum can improve the stability of conversion rate and selectivity to some extent. For the catalyst with only the second auxiliary agent cerium (Comparative Example 3), the conversion rate decreased by 7.5% and the selectivity decreased by 7.2% after 500 hours of reaction compared to 50 hours of operation, indicating that the introduction of the first auxiliary agent niobium can better improve the stability of conversion rate and selectivity. However, for the catalyst modified with molybdenum and cerium dual additives (Example 28), the conversion rate and selectivity did not change significantly during the reaction time of up to 2200 h, with the maximum fluctuation range being only 0.2%; while for the unmodified catalyst in Comparative Example 2, the conversion rate and selectivity decreased significantly after 100 h of reaction, and after 500 h of reaction, the conversion rate decreased by 11.4% and the selectivity decreased by 10.6%.

[0154] Therefore, it can be seen that the present invention, by using molybdenum as the first auxiliary component and supplementing it with chromium, zirconium, cerium, yttrium, copper, indium, gallium and other modified nickel-based catalysts, not only effectively improves the activity and selectivity of the catalyst, but also significantly improves its stability, which is conducive to its industrial application.

[0155] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for preparing 1,3-propanediol from acrolein, characterized in that, include: S1: Under the condition of a catalyst, acrolein solution is hydrated to obtain 3-hydroxypropionaldehyde. S2: 3-Hydroxypropanal was hydrogenated in the presence of Ni-Mo-X / Z catalyst to produce 1,3-propanediol; In step S1, the catalyst in the hydration reaction is Y / P-Al2O3, comprising a phosphorus-doped Al2O3 support and a hydration reaction active component supported on the support; the hydration reaction active component is selected from at least one of cerium, indium, cobalt, tungsten, lanthanum, molybdenum, and zirconium. In step S2, the hydrogenation reaction includes a support Z and a hydrogenation active component Ni, a first auxiliary component Mo, and a second auxiliary component X supported on the support; the second auxiliary component X is selected from at least one of iron, manganese, cobalt, chromium, zirconium, phosphorus, boron, lanthanum, cerium, yttrium, copper, gallium, indium, niobium, germanium, or tungsten.

2. The method for preparing 1,3-propanediol from acrolein according to claim 1, characterized in that, The phosphorus-doped Al2O3 support in the Y / P-Al2O3 is doped in situ. The phosphorus content is 0.1% to 15% by mass; The mass content of the hydration reaction active component is 1-20%.

3. The method for preparing 1,3-propanediol from acrolein according to claim 1 or 2, characterized in that, The preparation method of the phosphorus-doped Al2O3 support includes: dissolving the template agent in a mixed solution of anhydrous ethanol, isopropanol and glacial acetic acid, adding phosphorus source and aluminum source to obtain a suspension; aging, drying and calcining to obtain the phosphorus-doped Al2O3 support.

4. The method for preparing 1,3-propanediol from acrolein according to claim 3, characterized in that, The template agent is selected from one of cetyltrimethylammonium bromide, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and polyethylene glycol; The volume ratio of ethanol, isopropanol, and glacial acetic acid is (100-200):(40-80):1; The phosphorus source is selected from one of phosphoric acid, phosphorous acid, and ammonium dihydrogen phosphate; The aluminum source is selected from aluminum isopropoxide, aluminum nitrate, and aluminic acid.

5. The method for preparing 1,3-propanediol from acrolein according to claim 3, characterized in that, During the aging process, the aging temperature is room temperature, and the aging time is 4 to 8 hours. During the drying process, the drying temperature is 50–80°C; The calcination includes: maintaining a constant temperature at 300-600℃ for 3-6 hours, followed by calcination at 600-1000℃ for 1-2 hours; Preferably, in the roasting process: first at 2°C for 2 minutes -1 The temperature is increased to 300-600℃ at a rate of 3-6 hours, and then calcined at 600-1000℃ at a rate of 10℃ / min for 1-2 hours.

6. The method for preparing 1,3-propanediol from acrolein according to claim 1 or 2, characterized in that, The preparation method of Y / P-Al2O3 includes: immersing a phosphorus-doped Al2O3 support in a solution containing a hydrated reactive component precursor, drying, and calcining to obtain Y / P-Al2O3; Preferably, the hydration reactive component precursor is a water-soluble salt containing the hydration reactive component; Preferably, the roasting temperature is 450–650°C and the roasting time is 4–12 hours.

7. The method for preparing 1,3-propanediol from acrolein according to claim 1, characterized in that, In step S1, the hydration temperature in the hydration reaction is 35-90°C, and the acrolein solution is prepared by mixing an acrolein aqueous solution with a polymerization inhibitor, wherein the concentration of acrolein in the acrolein aqueous solution is 5-20 wt%. The space velocity of acrolein is 0.1–3 h⁻¹. -1 ; Preferably, the polymerization inhibitor is selected from one or more of hydroquinone, 4-methylphenol, phenothiazine, ZJ-705, p-benzoquinone, 2,6-dinitro-p-cresol, and 4-tert-butylcatechol, and the content of the polymerization inhibitor is 200 to 2000 ppm.

8. The method for preparing 1,3-propanediol from acrolein according to claim 1, characterized in that, In step S2, the mass content of the hydrogenated active component Ni in the Ni-Mo-X / Z is 5-40%; The mass content of the first auxiliary component Mo is 0.1-5.9%; The mass content of the second auxiliary agent component X is 0.1-15%; Preferably, the carrier Z is selected from one or more combinations of silica, alumina, ZSM-5, MCM-41, MCM-49, SBA-15, MCM-22, mordenite, SAPO-11, SAPO-34, L zeolite, β zeolite, Y zeolite, or ultrastable Y zeolite.

9. The method for preparing 1,3-propanediol from acrolein according to claim 7, characterized in that, The preparation method of Ni-Mo-X / Z includes: immersing the support Z in a solution containing a hydrogenation active component precursor, a first auxiliary component precursor, and a second auxiliary component precursor, drying, and calcining to obtain Ni-Mo-X / Z; Preferably, the hydrogenation active component precursor is a water-soluble salt containing a hydrogenation active component, the first auxiliary component precursor is a water-soluble salt containing a first auxiliary component Mo, and the second auxiliary component precursor is a water-soluble salt containing a second auxiliary component X. Preferably, the roasting temperature is 300–650°C and the roasting time is 1–12 h.

10. The method for preparing 1,3-propanediol from acrolein according to claim 1, characterized in that, In step S2, the reaction for preparing 1,3-propanediol by hydrogenation of 3-hydroxypropanal is carried out at a temperature of 50–130°C, a pressure of 2–15 MPa, a molar ratio of hydrogen to 3-hydroxypropanal of 4–40:1, and a liquid hourly space velocity (LHSV) of 3-hydroxypropanal of 0.1–2 h⁻¹. -1 The concentration of 3-hydroxypropionaldehyde aqueous solution is 3-21 wt%. Preferably, in step S2, before the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol, the Ni-Mo-X / Z is subjected to a reduction treatment; in the reduction treatment, the reduction temperature is 200-600℃, the reducing gas is a mixture of hydrogen and nitrogen, the reducing gas pressure is 0.1-1 MPa, and the reducing gas space velocity is 500-5000 h⁻¹. -1 The restoration time is 4 to 50 hours.

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