WO2024012352A1 - 粗对苯二甲酸加氢精制催化剂及其制备方法和应用 - Google Patents

粗对苯二甲酸加氢精制催化剂及其制备方法和应用 Download PDF

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WO2024012352A1
WO2024012352A1 PCT/CN2023/106209 CN2023106209W WO2024012352A1 WO 2024012352 A1 WO2024012352 A1 WO 2024012352A1 CN 2023106209 W CN2023106209 W CN 2023106209W WO 2024012352 A1 WO2024012352 A1 WO 2024012352A1
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catalyst
palladium
ruthenium
terephthalic acid
carrier
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PCT/CN2023/106209
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English (en)
French (fr)
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肖忠斌
朱小丽
罗伟
孙广斌
何丽敏
高晓晨
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中国石油化工股份有限公司
中石化（上海）石油化工研究院有限公司
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Publication of WO2024012352A1 publication Critical patent/WO2024012352A1/zh

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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • 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
    • 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
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/14—Monocyclic dicarboxylic acids
    • C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
    • C07C63/26—1,4 - Benzenedicarboxylic acid

Definitions

  • the present invention relates to a crude terephthalic acid hydrorefining catalyst, and in particular to a carrier-type crude terephthalic acid hydrorefining catalyst containing a variety of active components and its preparation method and application.
  • Terephthalic Acid is an important industrial raw material. It is used to produce polyethylene terephthalate (PET), which is in turn used to produce fibers, bottles, films and other products. Terephthalic acid can also be used to produce polybutylene terephthalate (PBT) engineering plastics. Terephthalic acid currently mainly uses paraxylene as raw material, acetic acid as solvent, air as oxidant, and is produced through liquid phase oxidation method under Co/Mn/Br catalyst system. The obtained product after the reaction contains by-products and impurities, and is generally called crude terephthalic acid (CTA).
  • CTA crude terephthalic acid
  • By-products include p-toluyl alcohol (TALC), p-toluylic acid (TALD), p-toluylic acid, p-carboxybenzaldehyde (4-CBA), etc.
  • TALC p-toluyl alcohol
  • TALD p-toluylic acid
  • 4-CBA p-carboxybenzaldehyde
  • Crude terephthalic acid typically contains up to 9,000 ppm of 4-CBA, making crude terephthalic acid unable to meet standards for use in the production of polyester.
  • Various methods have been proposed to remove impurities and by-products in crude terephthalic acid, especially 4-CBA, thereby obtaining purified terephthalic acid (PTA).
  • Purified terephthalic acid can broadly refer to a purified product that has at least a lower content of 4-CBA than crude terephthalic acid.
  • Polymeric grade purified terephthalic acid may contain 25 ppm or less of 4-CBA.
  • 4-CBA in crude terephthalic acid can usually be removed by hydrorefining, that is, it is hydrogenated and converted into other compounds (such as p-toluic acid), and then separated and purified by crystallization. Hydrorefining of crude terephthalic acid usually uses palladium/carbon catalyst.
  • Palladium/carbon catalysts use a single active component. Therefore, the distribution of metallic palladium on the carrier has a great impact on the performance of the catalyst.
  • the hydrorefining reaction is a first-order reaction and the reaction speed is fast. Therefore, it is difficult for the reactant molecules to penetrate into the interior of the catalyst particles to react during the reaction. This means that the active components inside the particles cannot reach the reactant molecules due to steric hindrance and thus cannot function. At this time, only the active components on the outer surface show catalytic activity.
  • the palladium/carbon catalyst is usually made into an eggshell type (core-shell type), in which the active component (palladium) is mainly loaded on the surface of the carrier.
  • the active component (palladium) of the eggshell catalyst is mainly concentrated on the surface of the carrier, the surface area in contact with the reactant molecules is larger, so it is more efficient than a catalyst with the same amount of active components dispersed throughout the carrier. Catalytic ability.
  • hydrorefining is usually carried out under the conditions of reaction pressure of 6.5-8.5MPa and reaction temperature of 250-290°C. Such reaction conditions make the grain growth of the active component (palladium) inevitable.
  • One of the main causes of catalyst deactivation is the growth of palladium grains.
  • the palladium grains will grow to more than 20nm, while the corresponding palladium grains of the fresh catalyst are between 2-5nm. The faster the palladium grains grow, the shorter the service life of the catalyst will be, resulting in significant economic losses.
  • patent US 4,892,972 discloses a double-layer catalyst using Pd/C and Rh/C, and the ratio of Pd to Rh is 10:1. It was used for hydrorefining crude terephthalic acid, and it was found that the life of the catalyst was significantly improved. However, Rh crystal grains are not easy to grow, and the price of Rh is ten times that of Pd. Therefore, this catalyst is not suitable in practice. It has also been suggested to use bimetallic supported catalysts containing Pd and Ru. In the preparation of this catalyst, the Ru source is not easily reduced to elemental Ru. Moreover, this catalyst may require the use of carriers such as titanium dioxide. This type of carrier has poor acid and alkali resistance and is not suitable for the reaction conditions of hydrogenation and purification of crude terephthalic acid.
  • the technical problem to be solved by the present invention is that in the existing technology of hydrorefining reaction of crude terephthalic acid, there are problems such as low conversion rate of 4-CBA and poor thermal stability of the catalyst. Therefore, the present invention provides a new catalyst for hydrorefining crude terephthalic acid, which contains a variety of active components.
  • the catalyst of the present invention has outstanding catalytic activity and anti-sintering properties, and is particularly suitable for the hydrorefining reaction of crude terephthalic acid.
  • the catalyst of the present invention can make the hydrorefining reaction proceed efficiently and stably.
  • the present invention also relates to a preparation method of the catalyst and the application of the catalyst in the hydrorefining reaction of crude terephthalic acid.
  • the present invention provides a crude terephthalic acid hydrorefining catalyst, which includes a carrier and an active component;
  • the active component includes palladium and ruthenium
  • the weight ratio of palladium to ruthenium is (3-10):1, based on the weight of the element;
  • palladium is Pd 0
  • ruthenium includes Ru 0 and Ru 4+ ;
  • the weight ratio of Ru 4+ to Ru 0 is 0.1-1.0.
  • the present invention provides a method for preparing the above-mentioned crude terephthalic acid hydrorefining catalyst, which includes the following steps:
  • step (2) Mix the catalyst carrier of step (1) with an active metal source and an alkyl amine, and subject the mixture to aging and first heat treatment to obtain a catalyst precursor;
  • step (3) Use a reducing agent to reduce the catalyst precursor in step (2) to obtain the catalyst.
  • the present invention provides the use of the above crude terephthalic acid hydrorefining catalyst in the hydrorefining reaction of crude terephthalic acid.
  • the present invention can be embodied in the following items:
  • a crude terephthalic acid hydrorefining catalyst the catalyst includes a carrier and an active component; wherein, the active component is palladium metal and ruthenium metal, and the weight ratio of the palladium metal to ruthenium metal is (3-10):1;
  • the valence state of the palladium metal is Pd 0
  • the valence state of the ruthenium metal includes Ru 0 and Ru 4+ .
  • the catalyst according to item 1 characterized in that the carrier is activated carbon; the activated carbon is preferably at least one of coal-based charcoal, wood charcoal or nutshell charcoal.
  • the preparation method of the catalyst described in any one of items 1 to 3 includes the following steps:
  • step (3) Mix the catalyst carrier of step (1) with the catalyst precursor i of step (2), age, remove solvent, and heat treat to obtain catalyst precursor ii;
  • step (3) Use a reducing agent to reduce the catalyst precursor ii in step (3) and heat treat it to obtain the catalyst.
  • step (2) characterized in that the active metals described in step (2) are palladium and ruthenium; wherein the palladium source and the ruthenium source are palladium salts and ruthenium salts; the palladium salts are selected from palladium nitrate, At least one of palladium acetate, chloropalladic acid and its salts, and dichlorotetraammine palladium, preferably palladium acetate; the ruthenium salt is selected from at least one of ruthenium nitrate, ruthenium acetate, and ruthenium trichloride, preferably Ruthenium acetate.
  • step (2) the mass ratio of the solvent, alkylamine and active metal is (5000-30000): (20-50): (5-20) ; Among them, the mass ratio of palladium and ruthenium in the active metal is (3-6):1.
  • step (4) is selected from at least one of hydrogen, hydrazine hydrate, formaldehyde formic acid, formaldehyde or formate, preferably hydrazine hydrate.
  • the present invention has the following advantages:
  • the crude terephthalic acid hydrorefining catalyst provided by the present invention contains Pd and Ru as active components, especially by controlling the weight ratio of Ru 4+ to Ru 0 within a specific range (0.1-1.0). Good anti-sintering properties.
  • the preparation method of the crude terephthalic acid hydrorefining catalyst provided by the present invention is simple to operate. Through the selection of materials and process conditions, Ru 4+ and Ru 0 were introduced into the catalyst and effective control of their weight ratio was achieved, thereby obtaining the above crude terephthalic acid hydrorefining catalyst.
  • the catalyst of the present invention is used for the hydrorefining reaction of crude terephthalic acid. On the premise of ensuring catalytic performance, it also has the characteristics of high heat resistance and stability, and has achieved outstanding technical effects.
  • Figure 1 is the XPS pattern of Pd 0 in the 3d zone in the catalyst prepared in Example 1;
  • Figure 2 is the XPS pattern of Ru 4+ in the 3p region of the catalyst prepared in Example 1.
  • the present invention relates to a crude terephthalic acid hydrorefining catalyst, which includes a carrier and an active component;
  • the active component includes palladium and ruthenium
  • the weight ratio of palladium to ruthenium is (3-10):1, based on the weight of the element;
  • palladium is Pd 0
  • ruthenium includes Ru 0 and Ru 4+ ;
  • the weight ratio of Ru 4+ to Ru 0 is 0.1-1.0.
  • crude terephthalic acid refers to terephthalic acid products containing higher concentrations of p-carboxybenzaldehyde (4-CBA).
  • the crude terephthalic acid contains, for example, at least 1000 ppm, at least 2500 ppm, at least 5000 ppm or at least 8000 ppm p-carboxybenzaldehyde.
  • crude terephthalic acid hydrotreating refers to the process of converting and eliminating p-carboxybenzaldehyde by reacting crude terephthalic acid with hydrogen.
  • the product with reduced p-carboxybenzaldehyde content relative to crude terephthalic acid is called "purified terephthalic acid".
  • the p-carboxybenzaldehyde content of purified terephthalic acid is at least 100 ppm, at least 500 ppm, at least 1000 ppm, at least 2500 ppm, at least 5000 ppm or at least 8000 ppm lower than crude terephthalic acid.
  • the purified terephthalic acid has a p-carboxybenzaldehyde content of 25 ppm or less and can thus be used directly as a raw material for the synthesis of polyesters such as polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the crude terephthalic acid hydrotreating catalyst contains 0.3-1 wt% active components.
  • the active component includes palladium and ruthenium, wherein the weight ratio of palladium to ruthenium is (3-10):1, preferably (3-6):1, based on the weight of the elements.
  • the palladium is Pd 0
  • the ruthenium includes Ru 0 and Ru 4+ ; and wherein the weight ratio of Ru 4+ to Ru 0 is 0.1-1.0, preferably 0.2-0.8.
  • the present invention has no particular restrictions on the distribution of active components on the carrier.
  • at least 50%, at least 75%, at least 90%, or at least 95% of the active ingredient is dispersed on the surface of the carrier.
  • the crude terephthalic acid hydrorefining catalyst has a core-shell structure, in which the core contains or mainly consists of the carrier, and the shell contains or mainly consists of the active component.
  • the crude terephthalic acid hydrorefining catalyst has a core-shell structure, in which the core is mainly composed of a carrier, the shell is mainly composed of palladium and ruthenium, and the palladium and ruthenium are evenly distributed in the shell.
  • the shell has a thickness of 10-200, preferably 40-100 microns.
  • the support may be those commonly used in the art for crude terephthalic acid hydrotreating catalysts.
  • the carrier is activated carbon.
  • the activated carbon is at least one of coal-based charcoal, wood charcoal or fruit shell charcoal.
  • the fruit shell charcoal is coconut shell charcoal.
  • the coconut shell charcoal has a specific surface area of 800-1600 m 2 /g, and a pore volume of 0.35-0.80 mL/g.
  • coconut shell charcoal is commercially available in granular form (eg, particles with a particle size of 4-8 mesh).
  • the present invention relates to a method for preparing the above-mentioned crude terephthalic acid hydrorefining catalyst, which includes the following steps:
  • step (2) Mix the catalyst carrier of step (1) with an active metal source and an alkyl amine, and subject the mixture to aging and first heat treatment to obtain a catalyst precursor;
  • step (3) Use a reducing agent to reduce the catalyst precursor in step (2) to obtain the catalyst.
  • step (1) provides the catalyst carrier by pretreating activated carbon to obtain the catalyst carrier.
  • Activated carbon can be pretreated by conventional means in the art to obtain the catalyst carrier.
  • the pretreatment includes washing and drying. In one variation, washing is performed with water, where the volume ratio of water to activated carbon is (2-10):1; and drying is performed at a temperature of 100-130°C for a period of 4-8 hours.
  • the active metal source, alkylamine and solvent before mixing the catalyst support of step (1) with the active metal source and alkylamine, can be mixed.
  • the solvent, alkylamine and active metal source are mixed in a mass ratio of (5000-30000):(20-50):(5-20).
  • the obtained mixture and the catalyst carrier of step (1) may be mixed at a mass ratio of (2-5):1.
  • the solvent can be a conventional organic solvent in this field.
  • the solvent is selected from at least one of diethyl ether, methyl ether, ethanol, isopropanol, and acetone, preferably diethyl ether.
  • step (2) further includes removing solvent before the first heat treatment.
  • the solvent removal includes evaporation and condensation to recover the solvent, wherein the evaporation temperature is preferably 60-90°C.
  • the active metal source includes a palladium source and a ruthenium source.
  • the source of palladium is a palladium salt and the source of ruthenium is a ruthenium salt.
  • the palladium salt suitable for the palladium source is selected from at least one of palladium nitrate, palladium acetate, chloropalladic acid, chloropalladate and dichlorotetraamminepalladium, preferably palladium acetate.
  • the ruthenium salt suitable for the ruthenium source is selected from at least one of ruthenium nitrate, ruthenium acetate, and ruthenium trichloride, with ruthenium acetate being preferred.
  • the alkyl group in the alkylamine is a linear alkyl group, preferably one selected from C3-C20 linear alkyl groups, more preferably one selected from C12-C18 linear alkyl groups. kind.
  • suitable alkylamines include, but are not limited to, dodecylamine, tetradecylamine, cetylamine, and octadecylamine.
  • the aging is carried out for 2-24h, preferably 4-12h.
  • the present invention has no special restrictions on aging conditions, and conventional conditions in the field can be adopted.
  • the aging is carried out in an oxygen-containing atmosphere, for example in air.
  • the first heat treatment includes heat treatment at 150-250°C for 2-8 hours under an inert atmosphere.
  • the inert atmosphere includes nitrogen or an inert gas, preferably nitrogen.
  • the reducing agent is selected from at least one of hydrazine hydrate, formaldehyde formic acid, formaldehyde or formate, preferably hydrazine hydrate.
  • the catalyst precursor of step (2) is reduced using hydrazine hydrate at a mass ratio of hydrazine hydrate to the catalyst precursor of step (2) of 1:(2-10).
  • the reduction is carried out at room temperature (25°C) for 4 to 12 hours, preferably 6 to 9 hours.
  • the resulting catalyst is subjected to a second heat treatment.
  • the second heat treatment includes heat treatment at 100-200°C for 2-8 hours under an inert atmosphere.
  • the inert atmosphere includes nitrogen or an inert gas, preferably nitrogen.
  • the present invention relates to the use of the above crude terephthalic acid hydrorefining catalyst in the hydrorefining reaction of crude terephthalic acid.
  • the crude terephthalic acid is hydrorefined to obtain purified terephthalic acid.
  • the reaction conditions of the hydrorefining reaction of crude terephthalic acid include a reaction temperature of 250-350°C, preferably 270-290°C; and a reaction pressure of 6.5-8.5MPa.
  • 4-CBA is converted and removed to obtain purified terephthalic acid.
  • the 4-CBA conversion rate of the crude terephthalic acid hydrorefining catalyst of the present invention is at least 85%, preferably at least 90%, more preferably 95%, and most preferably 99%.
  • the crude terephthalic acid hydrorefining catalyst of the present invention effectively suppresses the grain growth of palladium in the catalyst at high temperatures (eg, 300°C or higher, 400°C or higher, and 500°C or higher).
  • the crude terephthalic acid hydrorefining catalyst of the present invention has a grain growth rate of palladium in the catalyst at, for example, 300°C, 400°C, or 500°C, of 25% or less, preferably 10% or more. Low, more preferably 5% or less.
  • the grain growth rate is 25%, 20%, 15%, 10%, 5%, 2% or 1%.
  • the grain growth rate of palladium is 10% or less, preferably 5% or less, more preferably 3% or less at 300°C. Low. Hydrorefining is usually carried out under the conditions of reaction pressure of 6.5-8.5MPa and reaction temperature of 250-290°C. Therefore, under conventional hydrorefining conditions, the crude terephthalic acid hydrorefining catalyst of the present invention can well control the grain growth of palladium and has excellent sintering resistance. Therefore, the crude terephthalic acid hydrorefining catalyst of the present invention can enable the hydrorefining reaction of crude terephthalic acid to proceed efficiently and stably.
  • the Pd and Ru contents in the catalysts of the examples and comparative examples of the present invention were measured by ICP-AES.
  • the contents of Ru in different valence states in the catalysts of the examples and comparative examples of the present invention were analyzed by XPS using an ESCA-IAB MK II photoelectron spectrometer.
  • the spectrum of the catalyst was obtained under these conditions, in which 461.5ev(Ru3p3 /2 ) is the characteristic peak corresponding to Ru 0 , and 465.2ev(Ru3p3 /2 ) is the characteristic peak corresponding to Ru +4 .
  • Use xps peakfit4.1 software to fit the Ru3p3 /2 peak and then use the following formula to calculate the percentage content of ruthenium in different valence states.
  • x Ru in the valence state being analyzed
  • I photoelectron peak area
  • n the number of different valence states in Ru being considered
  • S sensitivity factor
  • the catalyst was calcined under N2 protection at 300°C, 400°C and 500°C for 8 hours respectively, and then cooled to room temperature.
  • the calcined catalyst is detected using an X-ray diffractometer (XRD), and the average particle size of the palladium contained therein can be calculated using the Debye-Scherrer formula.
  • XRD X-ray diffractometer
  • Dhkl is the grain diameter along the direction perpendicular to the crystal plane (hkl)
  • k is the Scherrer constant (usually 0.89)
  • ⁇ is the incident X-ray wavelength (Cuka wavelength is 0.15406nm
  • Cuka1 wavelength is 0.15418nm.
  • ⁇ is the Bragg diffraction angle (°)
  • ⁇ is the half-peak width of the diffraction peak (rad).
  • the thermal stability of the catalyst is expressed by the grain growth rate of the active component in the catalyst before and after calcination. The larger this value is, the less stable it is and vice versa.
  • the grain growth rate is calculated according to the following formula:
  • Crystal grain growth rate [(average particle size of Pd after baking - average particle size of Pd in fresh catalyst)/average particle size of Pd in fresh catalyst] ⁇ 100%.
  • Reaction vessel 2L stainless steel autoclave
  • Amount of crude terephthalic acid 30.0g (the content of 4-CBA is 10000ppmw)
  • 4-CBA conversion rate [(4-CBA content of purified terephthalic acid - 4-CBA content of crude terephthalic acid)/4-CBA content of crude terephthalic acid] ⁇ 100%.
  • catalyst carrier 100g of catalyst carrier to the mixture, where the mass ratio of the catalyst carrier to the mixture is 1:4; it is aged for 8 hours, then evaporated and condensed at 80°C to recover diethyl ether, and then the first heat treatment is performed under a nitrogen atmosphere at 180°C 4h. Cool to room temperature to obtain the catalyst precursor. 200 grams of hydrazine hydrate (concentration: 20 wt%) was added to the above catalyst precursor, reduced for 9 hours, and then subjected to a second heat treatment at 180°C for 4 hours in a nitrogen atmosphere, and then cooled to room temperature to obtain a catalyst.
  • catalyst carrier 100g to the mixture, where the mass ratio of the catalyst carrier to the mixture is 1:4; it is aged for 8 hours, then evaporated and condensed at 80°C to recover diethyl ether, and then the first heat treatment is performed under a nitrogen atmosphere at 180°C 4h. Cool to room temperature to obtain the catalyst precursor.
  • hydrazine hydrate concentration: 20 wt% to the above catalyst precursor, reduce it for 6 hours, perform a second heat treatment at 180°C for 4 hours in a nitrogen atmosphere, and cool to room temperature to obtain a catalyst.
  • catalyst carrier 100 g was added to the mixture, where the mass ratio of the catalyst carrier to the mixture was 1:4; it was aged for 8 hours, then evaporated and condensed at 80°C to recover diethyl ether, and cooled to room temperature to obtain the catalyst precursor.
  • the above catalyst precursor was subjected to a second heat treatment at 400°C in a hydrogen atmosphere for 8 hours, and then cooled to room temperature to obtain a catalyst.
  • catalyst carrier 100g to the mixture, where the mass ratio of the catalyst carrier to the mixture is 1:4; it is aged for 8 hours, then evaporated and condensed at 80°C to recover diethyl ether, and then the first heat treatment is performed under a nitrogen atmosphere at 180°C 4h. Cool to room temperature to obtain the catalyst precursor.
  • hydrazine hydrate concentration: 2wt%
  • the active component content, thermal stability and activity of the catalyst were evaluated by the test method mentioned above.
  • the catalyst analysis data are listed in Table 1.
  • catalyst carrier 100g to the mixture, where the mass ratio of the catalyst carrier to the mixture is 1:4; it is aged for 8 hours, then evaporated and condensed at 80°C to recover diethyl ether, and then the first heat treatment is performed under a nitrogen atmosphere at 180°C 4h. Cool to room temperature to obtain the catalyst precursor.
  • hydrazine hydrate concentration: 20 wt%
  • catalyst carrier 100 g was added to the mixture, where the mass ratio of the catalyst carrier to the mixture was 1:4; it was aged for 8 hours, then evaporated and condensed at 80°C to recover diethyl ether, and cooled to room temperature to obtain the catalyst precursor.
  • the above catalyst precursor was subjected to a second heat treatment at 80°C in a hydrogen atmosphere for 8 hours, and then cooled to room temperature to obtain a catalyst.
  • Example 1 of CN102039123A is repeated here.
  • the active ingredient content of Cat 1 is evaluated by the test method described above. It was found that the catalyst was composed of 0-valent palladium and 3-valent ruthenium. Furthermore, the thermal stability and activity of Cat 1 were evaluated through the test methods described above. Relevant analysis data are listed in Table 1.

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Abstract

本发明公开了一种粗对苯二甲酸加氢精制催化剂及其制备方法和应用。所述催化剂包含载体和活性组分；其中，所述活性组分包含钯和钌，其中钯与钌重量之比为(3-10)∶1，以元素计算；其中，钯为Pd0，钌包括Ru0和Ru4+，并且其中Ru4+与Ru0的重量比为0.1-1.0。本发明提供的催化剂具有突出的催化活性和抗烧结性能，特别适用于粗对苯二甲酸的加氢精制反应，本发明催化剂可以使加氢精制反应高效和稳定进行。

Description

粗对苯二甲酸加氢精制催化剂及其制备方法和应用 技术领域
本发明涉及粗对苯二甲酸加氢精制催化剂，具体涉及包含多种活性组分的载体型粗对苯二甲酸加氢精制催化剂及其制备方法和应用。
背景技术
对苯二甲酸(Terephthalic Acid，TA)是一种重要工业原料。其被用于生产聚对苯二甲酸乙二酯(PET)，后者转而被用于生产纤维、瓶、薄膜等产品。对苯二甲酸也可以用于生产聚对苯二甲酸丁二醇酯(PBT)工程塑料等。对苯二甲酸目前主要采用对二甲苯为原料，以醋酸为溶剂，空气为氧化剂，在Co/Mn/Br催化剂体系下，通过液相氧化方法来生产。反应后的既得产品含有副产物和杂质，一般被称为粗对苯二甲酸(Crude Terephthalic Acid，CTA)。副产物包括对甲基苯甲醇(TALC)、对甲基苯甲醛(TALD)、对甲基苯甲酸(p-Toluylic acid)、对羧基苯甲醛(4-CBA)等。在制备聚酯的后续工艺中，4-CBA的存在将负面影响聚酯的色泽和质量。粗对苯二甲酸通常含有高达9000ppm的4-CBA，使得粗对苯二甲酸不能达到用于生产聚酯的标准。已经提出多种方法来去除粗对苯二甲酸中的杂质和副产物，特别是4-CBA，由此将获得精对苯二甲酸(Purified Terephthalic Acid，PTA)。精对苯二甲酸可以泛指比粗对苯二甲酸具有至少更低含量4-CBA的纯化产品。聚合级的精对苯二甲酸可含有25ppm或更低的4-CBA。粗对苯二甲酸中的4-CBA通常可以通过加氢精制而除去，即将其加氢转变为其它的化合物(如对甲基苯甲酸)，随后采用结晶的方法来分离提纯。粗对苯二甲酸的加氢精制通常采用钯/炭催化剂。
钯/炭催化剂采用单一的活性组分。所以，金属钯在载体上的分布状况对催化剂性能的影响非常大。一方面，加氢精制反应是一个一级反应，并且反应速度快。因此，反应过程中反应物分子难以穿透到催化剂颗粒的内部进行反应。这意味着颗粒内部的活性组分由于位阻影响而接触不到反应物分子，从而不能发挥作用。此时，只有外表面的活性组分表现出催化活性。出于充分利用活性组分(钯)的考虑，通常钯/炭催化剂做成蛋壳型(核-壳型)，其中活性组分(钯)主要负载于载体的表面。由于蛋壳型催化剂的活性组分(钯)主要集中在载体表面，其与反应物分子接触的表面积更大，因此比相同量的活性组分被分散分布在整个载体中的催化剂具有更高效的催化能力。另一方面，加氢精制通常在反应压力为6.5-8.5MPa，反应温度为250-290℃条件下进行。这样的反应条件使得活性组分(钯)的晶粒长大不可避免。催化剂的失活主要原因之一就是钯的晶粒长大。失活的商用粗对苯二甲酸加氢精制钯/炭催化剂中，钯晶粒会长大到20nm以上，而相应的新鲜催化剂的钯晶粒在2-5nm之间。钯的晶粒长大的越快，则催化剂的使用寿命则越短，导致重大经济损失。
已经提出多种改善粗对苯二甲酸加氢精制催化剂的寿命的方法，其中包括例如考虑使用多种活性组分。例如，专利US4,892,972公开了采用Pd/C和Rh/C的双层催化剂，Pd与Rh的比例为10∶1。将其用于粗对苯二甲酸加氢精制，结果发现该催化剂的寿命有明显提高。但是，Rh的晶粒不易长大，Rh的价格却是Pd的十倍。因此，该催化剂在实际中不适用。也有建议采用含有Pd和Ru的双金属载体催化剂。在这种催化剂的制备中，Ru源不容易还原成单质Ru。并且，这种催化剂可能需要采用二氧化钛等载体。这类载体耐酸耐碱性能差，不适用于粗对苯二甲酸加氢精制的反应条件。
对于粗对苯二甲酸加氢精制催化剂的活性和热稳定性，现有技术已经实现了一些改进。但是，进一步改进粗对苯二甲酸加氢精制催化剂的活性和热稳定性的需求却是一直存在的。
发明内容
本发明所要解决的技术问题是在粗对苯二甲酸的加氢精制反应的现有技术中存在4-CBA转化率低和催化剂热稳定性差的问题。因此，本发明提供一种新的用于粗对苯二甲酸加氢精制催化剂，其含有多种活性组分。本发明催化剂具有突出的催化活性和抗烧结性能，特别适用于粗对苯二甲酸的加氢精制反应，本发明催化剂可以使加氢精制反应高效和稳定进行。本发明还涉及所述催化剂的制备方法和所述催化剂在粗对苯二甲酸的加氢精制反应中的应用。
在一个方面，本发明提供一种粗对苯二甲酸加氢精制催化剂，其包含载体和活性组分；
其中所述活性组分包含钯和钌；
其中钯与钌的重量比为(3-10)∶1，以元素重量计；
其中，钯为Pd0，并且钌包括Ru0和Ru4+；并且
其中Ru4+与Ru0的重量比为0.1-1.0。
在另一个方面，本发明提供一种制备上述粗对苯二甲酸加氢精制催化剂的方法，其包括以下步骤：
(1)提供催化剂载体；
(2)将步骤(1)的催化剂载体与活性金属源和烷基胺混合，混合物进行陈化和第一热处理，得到催化剂前体；
(3)用还原剂还原步骤(2)的催化剂前体，得到所述的催化剂。
在又一个方面，本发明提供上述粗对苯二甲酸加氢精制催化剂在粗对苯二甲酸的加氢精制反应中的应用。
具体地说，本发明可以体现为以下各项：
1、一种粗对苯二甲酸加氢精制催化剂，所述催化剂包括载体和活性组分；其中，所述活性组分为钯金属和钌金属，所述的钯金属与钌金属重量之比为(3-10)∶1；
其中，所述的钯金属的价态为Pd0，所述钌金属的价态包括Ru0和Ru4+。
2、第1项所述的催化剂，其特征在于，所述催化剂中，Ru4+与Ru0的重量比为0.1-1.0。
3、第1项所述的催化剂，其特征在于，所述载体为活性炭；所述的活性炭优选为煤质炭、木质炭或果壳炭中的至少一种。
4、第1-3项中任一项所述的催化剂的制备方法，包括以下步骤：
(1)将活性炭预处理得到催化剂载体；
(2)将活性金属、烷基胺、溶剂混合，得到催化剂前驱体i；
(3)将步骤(1)的催化剂载体与步骤(2)的催化剂前驱体i混合，陈化、除溶剂、热处理，得到催化剂前体ii；
(4)用还原剂还原步骤(3)的催化剂前体ii，热处理，得到所述的催化剂。
5、第4项所述的方法，其特征在于，步骤(2)所述烷基胺中的烷基选自C3-C20中的一种。
6、第4项所述的方法，其特征在于，步骤(2)中所述活性金属为钯和钌；其中钯源和钌源为钯盐和钌盐；所述钯盐选自硝酸钯、醋酸钯、氯钯酸及其盐、二氯四氨合钯中的至少一种，优选为醋酸钯；所述的钌盐选自硝酸钌、醋酸钌、三氯化钌中至少一种，优选醋酸钌。
7、第4项所述的方法，其特征在于，步骤(2)，所述溶剂、烷基胺和活性金属的质量比为(5000-30000)∶(20-50)∶(5-20)；其中，活性金属中的钯和钌的质量比为(3-6)∶1。
8、第4项所述的方法，其特征在于，步骤(3)所述的步骤(1)的催化剂载体与步骤(2)的催化剂前驱体i的质量之比为1∶(2-5)。
9、第4项所述的方法，其特征在于，步骤(4)中所述还原剂选自氢气、水合肼、甲醛甲酸、甲醛或甲酸盐中的至少一种，优选为水合肼。
10、第1-3项中任一项所述的催化剂在粗对苯二甲酸的加氢精制反应中的应用，在所述催化剂的存在下，粗对苯二甲酸进行加氢精制反应，得到精对苯二甲酸。
与现有技术相比，本发明具有如下优点：
(1)本发明提供的粗对苯二甲酸加氢精制催化剂含有Pd和Ru作为活性组分，特别是通过控制Ru4+与Ru0的重量比在特定的范围(0.1-1.0)内，获得了良好的抗烧结性能。
(2)本发明提供的粗对苯二甲酸加氢精制催化剂的制备方法操作简单。通过对材料和工艺条件的选择，在催化剂中引入了Ru4+与Ru0并实现了对其重量比的有效控制，从而获得了上述粗对苯二甲酸加氢精制催化剂。
(3)本发明的催化剂用于粗对苯二甲酸的加氢精制反应，在保证催化性能的前提下，还具有耐热稳定性高的特点，取得了突出的技术效果。
附图说明
图1为实施例1中制得的催化剂中Pd0在3d区的XPS图谱；
图2为实施例1中制得的催化剂中Ru4+在3p区XPS图谱。
具体实施方式
除了在实施例外，在本文中，参数的所有数值都应理解为在所有情况下均由术语“约”修饰，无论“约”是否实际上出现在该数值之前。
在一个方面，本发明涉及一种粗对苯二甲酸加氢精制催化剂，其包含载体和活性组分；
其中所述活性组分包含钯和钌；
其中钯与钌的重量比为(3-10)∶1，以元素重量计；
其中，钯为Pd0，并且钌包括Ru0和Ru4+；并且
其中Ru4+与Ru0的重量比为0.1-1.0。
本文所用的术语“粗对苯二甲酸”指的是含有较高浓度的对羧基苯甲醛(4-CBA)的对苯二甲酸产品。在一个变型中，粗对苯二甲酸含有例如，至少1000ppm，至少2500ppm，至少5000ppm或至少8000ppm的对羧基苯甲醛。本文所用的术语“粗对苯二甲酸加氢精制”指的是通过使粗对苯二甲酸与氢反应，从而转化并消除对羧基苯甲醛的过程。相应地，将相对于粗对苯二甲酸，对羧基苯甲醛含量降低的产品称为“精对苯二甲酸”。例如，精对苯二甲酸的对羧基苯甲醛含量比粗对苯二甲酸低至少100ppm，至少500ppm，至少1000ppm，至少2500ppm，至少5000ppm或至少8000ppm。在一个变型中，精对苯二甲酸的对羧基苯甲醛含量为25ppm或更低，从而可以直接用作合成聚酯，例如聚对苯二甲酸乙二酯(PET)的原料。
在一个实施方案中，粗对苯二甲酸加氢精制催化剂含有0.3-1wt％的活性组分。活性组分包含钯和钌，其中钯与钌的重量比为(3-10)∶1，优选为(3-6)∶1，以元素重量计。在一个变型中，钯为Pd0，并且钌包括Ru0和Ru4+；并且其中Ru4+与Ru0的重量比为0.1-1.0，优选0.2-0.8.
本发明对活性组分在载体上的分布没有特别限制。在一个实施方案中，至少50％，至少75％，至少90％，或至少95％的活性组分分散在载体表面上。优选，粗对苯二甲酸加氢精制催化剂具有核-壳结构，其中核包含载体或主要由其组成，并且壳包含活性组分或主要由其组成。在一个变型中，粗对苯二甲酸加氢精制催化剂具有核-壳结构，其中核主要由载体组成，壳主要由钯和钌组成，并且钯和钌均匀分布在壳中。优选，壳的厚度为10-200，优选40-100微米。
在一个实施方案中，载体可以为本领域常用的粗对苯二甲酸加氢精制催化剂的那些载体。在一个变型中，载体为活性炭。优选，所述的活性炭为煤质炭、木质炭或果壳炭中的至少一种。优选，所述的果壳炭为椰壳炭。在一个变型中，所述的椰壳炭的比表面积为800-1600m2/g，并且孔容为0.35-0.80mL/g。椰壳炭可以以颗粒形式(例如颗粒尺寸为4-8目的颗粒)商购获得。
在另一个方面，本发明涉及一种制备上述粗对苯二甲酸加氢精制催化剂的方法，其包括以下步骤：
(1)提供催化剂载体；
(2)将步骤(1)的催化剂载体与活性金属源和烷基胺混合，混合物进行陈化和第一热处理，得到催化剂前体；
(3)用还原剂还原步骤(2)的催化剂前体，得到所述的催化剂。
在一个实施方案中，步骤(1)的提供催化剂载体通过预处理活性炭以得到催化剂载体。可以采用本领域常规手段将活性炭预处理以得到催化剂载体。在一个实施方案中，所述预处理包括洗涤和干燥。在一个变型中，洗涤采用水洗，其中水与活性炭体积之比为(2-10)∶1；并且干燥在100-130℃温度下进行4-8h时间。
在一个实施方案中，将步骤(1)的催化剂载体与活性金属源和烷基胺混合前，可以将活性金属源、烷基胺和溶剂混合。在一个变型中，溶剂、烷基胺和活性金属源以(5000-30000)∶(20-50)∶(5-20)的质量比进行混合。并且，所得混合物与步骤(1)的催化剂载体可以以(2-5)∶1的质量比进行混合。
所述溶剂可以采用本领域常规有机溶剂。在一个实施方案中，溶剂选自乙醚、甲醚、乙醇、异丙醇、丙酮中的至少一种，优选为乙醚。
在一个实施方案中，步骤(2)还包括，在第一热处理前进行除溶剂。在一个变型中，所述除溶剂包括蒸发和冷凝以回收溶剂，其中蒸发温度优选60-90℃。
在一个实施方案中，所述活性金属源包含钯源和钌源。在一个变型中，钯源为钯盐，并且钌源为钌盐。适用于钯源的钯盐选自硝酸钯、醋酸钯、氯钯酸、氯钯酸盐和二氯四氨合钯中的至少一种，优选为醋酸钯。适用于钌源的钌盐选自硝酸钌、醋酸钌、三氯化钌中至少一种，优选醋酸钌。
在一个实施方案中，所述烷基胺中的烷基为直链烷基，优选选自C3-C20直链烷基中的一种，更优选选自C12-C18直链烷基中的一种。适用的烷基胺的例子包括但不限于十二烷基胺、十四烷基胺、十六烷基胺和十八烷基胺。
在一个实施方案中，所述陈化进行2-24h，优选4-12h。本发明对陈化条件没有特殊限制，可以采用本领域中的常规条件。在一个变型中，所述陈化在含氧气氛下，例如在空气中进行。
所述第一热处理包括在惰性气氛下在150-250℃热处理2-8h。所述的惰性气氛包含氮气或惰性气体，优选氮气。
在一个实施方案中，所述还原剂选自水合肼、甲醛甲酸、甲醛或甲酸盐中的至少一种，优选为水合肼。在一个变型中，以水合肼与步骤(2)的催化剂前体的质量之比为1∶(2-10)使用水合肼还原步骤(2)的催化剂前体。优选，还原在室温(25℃)下进行4-12小时，优选6-9小时。
在一个实施方案中，在用还原剂还原步骤(2)的催化剂前体后，将得到的催化剂进行第二热处理。所述第二热处理包括在惰性气氛下在100-200℃热处理2-8h。所述的惰性气氛包含氮气或惰性气体，优选氮气。
在又一个方面，本发明涉及上述粗对苯二甲酸加氢精制催化剂在粗对苯二甲酸的加氢精制反应中的应用。在所述催化剂的存在下，粗对苯二甲酸的加氢精制反应得到精对苯二甲酸。在一个变型中，所述粗对苯二甲酸的加氢精制反应的反应条件包括反应温度为250-350℃，优选为270-290℃；并且反应压力为6.5-8.5MPa。在上述粗对苯二甲酸的加氢精制反应中，4-CBA被转化并去除，得到精对苯二甲酸。
本发明的粗对苯二甲酸加氢精制催化剂的4-CBA转化率为至少85％，优选至少90％，更优选95％，最优选99％。本发明的粗对苯二甲酸加氢精制催化剂有效抑制了高温(例如300℃或更高、400℃或更高和500℃或更高)下催化剂中钯的晶粒增长。在一个实施方案中，本发明的粗对苯二甲酸加氢精制催化剂在例如300℃、400℃或500℃下，催化剂中钯的晶粒增长率为25％或更低，优选10％或更低，更优选5％或更低。例如，所述晶粒增长率为25％、20％、15％、10％、5％、2％或1％。在一个变型中，在300℃下，本发明的粗对苯二甲酸加氢精制催化剂中，钯的晶粒增长率为10％或更低，优选5％或更低，更优选3％或更低。加氢精制通常在反应压力为6.5-8.5MPa，反应温度为250-290℃条件下进行。因此，在常规的加氢精制条件下，本发明的粗对苯二甲酸加氢精制催化剂可以很好地控制钯的晶粒增长，具有优异的抗烧结性能。因此，本发明的粗对苯二甲酸加氢精制催化剂可以使粗对苯二甲酸的加氢精制反应高效和稳定进行。
实施例
通过以下实施例使本发明的特点和优点显而易见。实施例旨在描述而非以任何方式限制本发明。
测试方法
本发明实施例和对比例的催化剂中Pd、Ru含量采用ICP-AES测定。
本发明实施例和对比例的催化剂中不同价态Ru的含量，采用ESCA-IAB MK II光电子能谱仪进行XPS分析。分析条件为：激光源采用MgKa射线(hv-1486.6eV)，工作电压10kV，X射线电流20mA采用污染碳C1s(Eb＝284.6eV)作能量校正。此条件下得到催化剂的谱图，其中461.5ev(Ru3p3/2)为Ru0所对应的特征峰，465.2ev(Ru3p3/2)为Ru+4所对应的特征峰。采用xps peakfit4.1软件对Ru3p3/2峰进行拟合分峰然后采用下式计算不同价态钌的百分含量。
其中，x：被分析价态的Ru；I：光电子峰面积；n：被考虑的Ru中不同价态的个数；S：灵敏因子。
本发明实施例和对比例的催化剂热稳定性测定如下：
将催化剂在N2保护下，300℃、400℃和500℃下分别焙烧8小时，然后冷却至室温。用X-射线衍射仪(XRD)检测焙烧后的催化剂，其中所含钯的平均粒径可以用Debye-Scherrer公式计算。
Debye-Scherrer公式：Dhkl＝kλ/βcosθ
其中，Dhkl为沿垂直于晶面(hkl)方向的晶粒直径，k为Scherrer常数(通常为0.89)，λ为入射X射线波长(Cuka波长为0.15406nm，Cuka1波长为0.15418nm。)，θ为布拉格衍射角(°)，β为衍射峰的半高峰宽(rad)。
催化剂的热稳定性用焙烧前后催化剂中活性成分的晶粒增大率表示。此值越大，稳定性越小，反之亦然。晶粒增大率根据下式计算：
晶粒增大率＝[(焙烧后Pd的平均粒径-新鲜催化剂的Pd的平均粒径)/新鲜催化剂的Pd的平均粒径]×100％。
本发明实施例和对比例的催化剂的活性测定如下：
在下表所示条件下，在本发明实施例和对比例的催化剂存在下，在氮气气氛下，将粗对苯二甲酸加氢精制，得到精对苯二甲酸。在用氨水完全溶解后，采用高效液相色谱(HPLC)分析粗对苯二甲酸和精对苯二甲酸以获得其4-CBA的含量，并计算4-CBA转化率，以表征催化剂的活性。
加氢精制条件：
反应容器：           2L不锈钢高压釜
催化剂的用量：       2.0g
粗对苯二甲酸量：     30.0g(其中4-CBA的含量为10000ppmw)
溶剂：               1000mL纯水
反应压力：           7.0MPa
氢气分压：           0.5MPa
反应时间             1.0小时
反应温度：           280℃
4-CBA转化率＝[(精对苯二甲酸的4-CBA含量-粗对苯二甲酸的4-CBA含量)/粗对苯二甲酸的4-CBA含量]×100％。
【实施例1】
称取100克4-8目、片状椰壳活性炭(比表面积为1100m2/g，孔容为0.52mL/g)用纯水洗涤，其中纯水与活性炭体积之比为5∶1，然后在130℃烘干8h；得到催化剂载体。将醋酸钯、醋酸钌、十六烷基胺和乙醚的400克混合物搅拌30min，其中Pd、Ru、十六烷基胺含量分别为1250ppmw、250ppmw、1.0wt％。将100g催化剂载体加入混合物中，其中催化剂载体与混合物的质量之比为1∶4，其陈化放置8h，然后在80℃下蒸发冷凝以回收乙醚，再在180℃氮气气氛下进行第一热处理4h、冷却至室温，得到催化剂前体。向上述催化剂前体中加入200克水合肼(浓度为20wt％)，还原8h，然后在氮气气氛下在180℃进行第二热处理4h，冷却至室温，得到催化剂。
通过如上所述测试方法，对催化剂的活性组分含量、热稳定性和活性进行评价。结果数据列于表1。
【实施例2】
称取100克4-8目、片状椰壳活性炭(比表面积为1100m2/g，孔容为0.52ml/g)用纯水洗涤，其中纯水与活性炭体积之比为5∶1，然后在130℃烘干8h；得到催化剂载体。将醋酸钯、醋酸钌、十六烷基胺、乙醚的400克混合物搅拌30min，其中Pd、Ru、十四烷基胺含量分别为1250ppmw、250ppmw、1.0wt％。将100g催化剂载体加入混合物中，其中催化剂载体与混合物的质量之比为1∶4；其陈化放置8h，然后在80℃下蒸发冷凝回收以乙醚，再在180℃氮气气氛下进行第一热处理4h、冷却至室温，得到催化剂前体。向上述催化剂前体加入200克水合肼(浓度为20wt％)，还原9h，然后在氮气气氛下在180℃进行第二热处理4h，冷却至室温，得到催化剂。
通过如上所述测试方法，对催化剂的活性组分含量、热稳定性和活性进行评价。结果数据列于表1。
【实施例3】
称取100克4-8目、片状椰壳活性炭(比表面积为1100m2/g，孔容为0.52ml/g)用纯水洗涤，其中纯水与活性炭体积之比为5∶1，然后在130℃烘干8h；得到催化剂载体。将醋酸钯、醋酸钌、十六烷基胺、乙醚的400克混合物搅拌30min，其中Pd、Ru、十六烷基胺含量分别为1250ppmw、250ppmw、1.0wt％。将100g催化剂载体加入混合物中，其中催化剂载体与混合物的质量之比为1∶4；其陈化放置8h，然后在80℃下蒸发冷凝回收以乙醚，再在180℃氮气气氛下进行第一热处理4h、冷却至室温得到催化剂前体。向上述催化剂前体加入200克水合肼(浓度为20wt％)，还原7h，在氮气气氛下在180℃下进行第二热处理4h，冷却至室温，得到催化剂。将所得的催化剂在氮气保护下分 别在300℃、400℃、500℃焙烧8小时考察催化剂的热稳定性。
通过如上所述测试方法，对催化剂的活性组分含量、热稳定性和活性进行评价。结果数据列于表1。
【实施例4】
称取100克4-8目、片状椰壳活性炭(比表面积为1100m2/g，孔容为0.52ml/g)用纯水洗涤，其中纯水与活性炭体积之比为5∶1，然后在130℃烘干8h；得到催化剂载体。将醋酸钯、醋酸钌、十六烷基胺、乙醚的400克混合物搅拌30min，其中Pd、Ru、十六烷基胺含量分别为1250ppmw、250ppmw、1.0wt％。将100g催化剂载体加入混合物中，其中催化剂载体与混合物的质量之比为1∶4；其陈化放置8h，然后在80℃下蒸发冷凝回收以乙醚，再在180℃氮气气氛下进行第一热处理4h、冷却至室温，得到催化剂前体。向上述催化剂前体加入200克水合肼(浓度为20wt％)，还原6h，在氮气气氛下在180℃进行第二热处理4h，冷却至室温，得到催化剂。
通过如上所述测试方法，对催化剂的活性组分含量、热稳定性和活性进行评价。结果数据列于表1。
【对比例1】
称取100克4-8目、片状椰壳活性炭(比表面积为1100m2/g，孔容为0.52ml/g)用纯水洗涤，其中纯水与活性炭体积之比为5∶1，然后在130℃烘干8h；得到催化剂载体。将醋酸钯、十六烷基胺、乙醚的400克混合物搅拌30min，其中Pd、十六烷基胺含量分别为1250ppmw、1.0wt％。将100g催化剂载体加入混合物中，其中催化剂载体与混合物的质量之比为1∶4；其陈化放置8h，然后在80℃下蒸发冷凝回收以乙醚，再在180℃氮气气氛下进行第一热处理4h、冷却至室温，得到催化剂前体。向上述催化剂前体加入200克水合肼(浓度为20wt％)，还原8h，在氮气气氛下在180℃进行第二热处理4h，冷却至室温，得到催化剂。通过如上所述测试方法，对催化剂的活性组分含量、热稳定性和活性进行评价。结果数据列于表1。
【对比例2】
称取100克4-8目、片状椰壳活性炭(比表面积为1100m2/g，孔容为0.52ml/g)用纯水洗涤，其中纯水与活性炭体积之比为5∶1，然后在130℃烘干8h；得到催化剂载体。将醋酸钯、醋酸钌、十六烷基胺、乙醚的混合物400克搅拌30min，其中Pd、Ru、十六烷基胺含量分别为1250ppmw、250ppmw、1.0wt％。将100g催化剂载体加入混合物中，其中催化剂载体与混合物的质量之比为1∶4；其陈化放置8h，然后在80℃下蒸发冷凝回收以乙醚，冷却至室温，得到催化剂前体。上述催化剂前体在400℃氢气气氛下进行第二热处理8h，冷却至室温，得到催化剂。
通过如上所述测试方法，对催化剂的活性组分含量、热稳定性和活性进行评价。结果数据列于表1。
【对比例3】
称取100克4-8目、片状椰壳活性炭(比表面积为1100m2/g，孔容为0.52ml/g)用纯水洗涤，其中纯水与活性炭体积之比为5∶1，然后在130℃烘干8h；得到催化剂载体。将醋酸钯、醋酸钌、十六烷基胺、乙醚的400克混合物搅拌30min，其中Pd、Ru、十六烷基胺含量分别为1250ppmw、250ppmw、1.0wt％。将100g催化剂载体加入混合物中，其中催化剂载体与混合物的质量之比为1∶4；其陈化放置8h，然后在80℃下蒸发冷凝回收以乙醚，再在180℃氮气气氛下进行第一热处理4h、冷却至室温，得到催化剂前体。向上述催化剂前体加入200克水合肼(浓度为2wt％)，还原3h，在氮气气氛下在180℃下进行第二热处理4h，冷却至室温，得到催化剂。
通过如上所述测试方法，对催化剂的活性组分含量、热稳定性和活性进行评价，催化剂分析数据列于表1。
【对比例4】
称取100克4-8目、片状椰壳活性炭(比表面积为1100m2/g，孔容为0.52ml/g)用纯水洗涤，其中纯水与活性炭体积之比为5∶1，然后在130℃烘干8h；得到催化剂载体。将醋酸钯、醋酸钌、十六烷基胺、乙醚的400克混合物搅拌30min，其中Pd、Ru、十六烷基胺含量分别为1250ppmw、250ppmw、1.0wt％。将100g催化剂载体加入混合物中，其中催化剂载体与混合物的质量之比为1∶4；其陈化放置8h，然后在80℃下蒸发冷凝回收以乙醚，再在180℃氮气气氛下进行第一热处理4h、冷却至室温，得到催化剂前体。向上述催化剂前体加入200克水合肼(浓度为20wt％)，还原12h，在氮气气氛下在180℃下进行第二热处理4h，冷却至室温，得到催化剂。
通过如上所述测试方法，对催化剂的活性组分含量、热稳定性和活性进行评价。结果数据列于表1。
【对比例5】
称取100克4-8目、片状椰壳活性炭(比表面积为1100m2/g，孔容为0.52ml/g)用纯水洗涤，其中纯水与活性炭体积之比为5∶1，然后在130℃烘干8h；得到催化剂载体。将醋酸钯、醋酸钌、乙醚的混合物400克搅拌30min，其中Pd和Ru含量分别为1250ppmw和250ppmw。将100g催化剂载体加入混合物中，其中催化剂载体与混合物的质量之比为1∶4；其陈化放置8h，然后在80℃下蒸发冷凝回收以乙醚，冷却至室温，得到催化剂前体。上述催化剂前体在80℃氢气气氛下进行第二热处理8h，冷却至室温，得到催化剂。
通过如上所述测试方法，对催化剂的活性组分含量、热稳定性和活性进行评价。结果数据列于表1。
【对比例6】
在此重复CN102039123A的实施例1。
取50g颗粒状椰壳炭载体进行预处理，浸泡在400ml浓度为0.01％的稀硝酸溶液中4小时，然后用去离子水洗涤至中性、沥干，在105℃下干燥24小时，自然冷却至室温。
将氯钯酸、水合三氯化钌、酒石酸溶入20ml去离子水中，添加纯水溶好羟甲基纤维素溶液，用8％碳酸钠调节溶液的PH值为3.0，最后溶液定容至40ml，得到钯胶液，钯胶液各组分的重量组成如下：
Pd(以氯钯酸加入)：0.48％
Ru(以水合三氯化钌加入)：0.02％
酒石酸：0.02％
羟甲基纤维素：0.01％
将载体放入转动的转锅中，5分钟之内将配好的钯胶液喷涂到载体上。放置8小时以上，然后在200℃下，氢气还原6小时，在氢气气氛下自然冷却至室温，最后用纯水洗涤至无Cl-为止，得到对苯二甲酸加氢精制催化剂Cat 1。
通过如上所述测试方法，对Cat 1的活性组分含量进行评价。结果发现催化剂中由0价钯和3价钌构成。并且，通过如上所述测试方法，对Cat 1的热稳定性和活性进行评价。相关分析数据列于表1。
表1各个实施例和对比例的催化剂的测试结果

Claims (12)

  1. 一种粗对苯二甲酸加氢精制催化剂，所述催化剂包含载体和活性组分；其中，所述活性组分包含钯和钌，
    其中钯与钌的重量之比为(3-10)∶1，以元素计；
    其中，钯为Pd0，钌包括Ru0和Ru4+；并且
    其中Ru4+与Ru0的重量比为0.1-1.0。
  2. 根据权利要求1所述的催化剂，其特征在于，所述载体为活性炭；所述的活性炭优选为煤质炭、木质炭或果壳炭中的至少一种。
  3. 根据权利要求1所述的催化剂，其特征在于，其具有核-壳结构，其中核主要由载体组成，并且壳主要由活性组分组成；
    优选，壳的厚度为10-200微米；
    优选，钯和钌均匀分布在壳中。
  4. 根据权利要求1所述的催化剂，其特征在于，在300℃下，钯的晶粒增长率为10％或更低，优选5％或更低，更优选3％或更低。
  5. 权利要求1-4任一项所述的催化剂的制备方法，包括以下步骤：
    (1)提供催化剂载体；
    (2)将步骤(1)的催化剂载体与活性金属源和烷基胺混合，混合物进行陈化和第一热处理，得到催化剂前体；
    (3)用还原剂还原步骤(2)的催化剂前体，得到所述的催化剂。
  6. 根据权利要求5所述的方法，其特征在于，进一步包括步骤：在将步骤(1)的催化剂载体与活性金属源和烷基胺混合前，将活性金属源、烷基胺和溶剂混合；并且
    步骤(2)还包括，在第一热处理前进行除溶剂。
  7. 根据权利要求5所述的方法，其特征在于，进一步包括步骤：在步骤(3)的还原后，进行第二热处理。
  8. 根据权利要求5所述的方法，其特征在于，所述烷基胺中的烷基选自C3-C20烷基中的一种。
  9. 根据权利要求5所述的方法，其特征在于，所述活性金属源包含钯源和钌源；优选包含钯盐和钌盐；所述钯盐选自硝酸钯、醋酸钯、氯钯酸、氯钯酸盐、二氯四氨合钯中的至少一种，优选为醋酸钯；所述的钌盐选自硝酸钌、醋酸钌、三氯化钌中至少一种，优选醋酸钌。
  10. 根据权利要求6所述的方法，其特征在于，步骤(2)，所述溶剂、烷基胺和活性金属的质量比为(5000-30000)∶(20-50)∶(5-20)。
  11. 根据权利要求5所述的方法，其特征在于，所述还原剂选自水合肼、甲醛甲酸、甲醛或甲酸盐中的至少一种，优选为水合肼；
    优选，以水合肼与步骤(2)的催化剂前体的质量之比为1∶(2-10)使用水合肼还原步骤(2)的催化剂前体；
    优选，还原在室温下进行4-12小时，优选6-9小时。
  12. 权利要求1-4任一项所述的催化剂在粗对苯二甲酸的加氢精制反应中的应用。
PCT/CN2023/106209 2022-07-12 2023-07-07 粗对苯二甲酸加氢精制催化剂及其制备方法和应用 WO2024012352A1 (zh)

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CN1785508A (zh) * 2005-11-14 2006-06-14 扬子石油化工股份有限公司 一种用于对苯二甲酸加氢精制的双金属催化剂及其制法
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