CN111715238B - Hydrogenation catalyst, preparation method and application thereof - Google Patents

Hydrogenation catalyst, preparation method and application thereof Download PDF

Info

Publication number
CN111715238B
CN111715238B CN202010623101.XA CN202010623101A CN111715238B CN 111715238 B CN111715238 B CN 111715238B CN 202010623101 A CN202010623101 A CN 202010623101A CN 111715238 B CN111715238 B CN 111715238B
Authority
CN
China
Prior art keywords
oxide
hydrogenation catalyst
catalyst
roasting
drying
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010623101.XA
Other languages
Chinese (zh)
Other versions
CN111715238A (en
Inventor
李作金
于海波
詹吉山
沙宇
燕宸
孙康
初乃波
黎源
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202010623101.XA priority Critical patent/CN111715238B/en
Publication of CN111715238A publication Critical patent/CN111715238A/en
Application granted granted Critical
Publication of CN111715238B publication Critical patent/CN111715238B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a catalyst for preparing trimethylolpropane by hydrogenating 2, 2-dimethylolbutyraldehyde and a preparation method thereof, wherein the catalyst comprises the following components: 35-70 wt% of copper oxide, 5-25 wt% of zinc oxide, 5-35 wt% of aluminum oxide, 10-30wt% of silicon dioxide, 0.5-5wt% of alkaline earth metal oxide, 0.05-1.0 wt% of palladium oxide, 0.01-1.0wt% of iridium oxide and 0.01-1.0wt% of tin oxide. When the catalyst is used for preparing trimethylolpropane by a hydrogenation method, the catalyst not only has good activity and selectivity, but also has strong formate conversion capacity and high mechanical stability.

Description

Hydrogenation catalyst, preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysis, relates to a hydrogenation catalyst, a preparation method and application thereof, and particularly relates to a catalyst for preparing trimethylolpropane by hydrogenating 2, 2-dimethylolbutyraldehyde and a preparation method thereof.
Background
Trimethylolpropane (TMP for short), also called trimethylolpropane and 2, 2-dimethylolbutanol, is mainly used for synthesizing high-grade alkyd resin and polyurethane coating, and also can be used for synthesizing plasticizer, aviation lubricating oil, surfactant, wetting agent, textile auxiliary agent, printing ink, various fine chemicals and the like, and has wide market prospect.
There are two main methods for preparing trimethylolpropane at present: disproportionation and catalytic hydrogenation. The disproportionation method is that 2, 2-Dimethylolbutanal (DMB) generated by formaldehyde and n-butyraldehyde continuously performs cross-connazar reaction with formaldehyde under the catalysis of alkali to generate trimethylolpropane and a large amount of sodium formate as a byproduct, and the post-treatment process is complex, the environmental pollution is serious and the production cost is high. The catalytic hydrogenation method is used for carrying out catalytic hydrogenation on the 2, 2-dimethylolbutyraldehyde generated by the formaldehyde and the n-butyraldehyde, and has the advantages of high product yield, few byproducts, short process flow, high product purity, low cost and the like, and has remarkable advantages.
Because the DMB as the raw material has poor thermal stability, the hydrogenation is generally carried out under the conditions of low temperature (generally 80-130 ℃) and liquid phase, so as to avoid the influence of the TMP yield caused by the mass decomposition of DMB, and the requirement on the activity of the hydrogenation catalyst is very high; the DMB solution as the hydrogenation raw material contains a large amount of water, and the hydrogenation catalyst is required to have good liquid resistance and use strength; in addition, the hydrogenation feedstock also contains a large amount of formate, which, if not converted efficiently, affects product purification and adversely affects TMP and downstream product stability and color. Therefore, the 2, 2-dimethylolbutyraldehyde hydrogenation catalyst is required to have the characteristics of high activity and selectivity, good liquid resistance, strong formate conversion capacity and the like.
The 2, 2-dimethylolbutyraldehyde hydrogenation catalyst mainly comprises a nickel-based catalyst, a copper-based catalyst, palladium-based catalyst and other noble metal catalysts, compared with the nickel-based catalyst and the noble metal catalysts, the copper-based catalyst has the advantages of high activity and selectivity, low cost and the like when being used for the 2, 2-dimethylolbutyraldehyde hydrogenation reaction, and the publicly reported 2, 2-dimethylolbutyraldehyde hydrogenation catalyst is mainly a copper-based catalyst.
Catalysts for the hydrogenation of 2, 2-dimethylolbutyraldehyde to trimethylolpropane are reported in many patents.
The patent application WO09407831 adopts a Cu-Cr catalyst, the TMP yield is low (only about 72%), and the Cu-Cr catalyst causes environmental pollution and safety risks in the processes of production, use and post-treatment. EP9804402 discloses a process for the hydrogenation of carbonyl compounds with Raney copper on 45% DMB solutions with TMP selectivity < 92%.
CN102432430B discloses a method for preparing trimethylolpropane by multistage circulation hydrogenation, which improves the yield of trimethylolpropane by hydrogenolysis of trimethylolpropane polymer. CN103274899B discloses a method for preparing trimethylolpropane, which adopts two-stage hydrogenation reactors to improve the yield of trimethylolpropane by hydrogenolysis of trimethylolpropane acetal compounds. CN1041403588 discloses a method for preparing trimethylolpropane by a hydrogenation method, which improves the yield of TMP by hydrogenolysis of DMB formate. CN104892364B discloses a method for preparing trimethylolpropane by adopting a hydrogenation method, and the yield of TMP is improved by hydrogenolysis of trimethylolpropane methyl ether substances.
None of the above reports mention the conversion of formate during hydrogenation.
CN1260193C discloses a method for decomposing ammonium formate in a reaction mixture containing polyhydric alcohol, wherein the temperature of a hydrogenation liquid is increased in another reactor under the action of catalysts such as Co/Cu/Ni to decompose the ammonium formate, the reaction temperature is up to 180 ℃, and the equipment investment and the operation cost are increased.
None of the above reports mentions the mechanical stability of the shaped catalyst when used and the strength after use.
In the prior art, copper catalysts used for hydrogenation reactions are subjected to various internal or external forces from preparation to use, and particularly when the copper catalysts are used for liquid phase reactions, the actual use strength of the catalysts is greatly reduced due to liquid soaking, swelling and the like, so that the catalysts are easy to break and pulverize in a liquid phase hydrogenation system, the stable operation of industrial devices is threatened, and the service life of the catalysts is influenced. Therefore, the improvement of the use strength and stability of the liquid-phase copper hydrogenation catalyst is crucial to the stable operation of an industrial device.
At present, when the catalyst prepared by the prior art is used for preparing trimethylolpropane by hydrogenating 2, 2-dimethylolbutyraldehyde, the problems of poor selectivity caused by insufficient hydrogenation capability of the 2, 2-dimethylolbutyraldehyde, poor formate conversion capability of the catalyst, low product quality caused by poor formate conversion capability of the catalyst, easy pulverization of the catalyst and the like exist. Therefore, the method has great significance for preparing the high-performance 2, 2-dimethylolbutyraldehyde hydrogenation catalyst by improving the dispersion degree of the active component copper and the mass transfer performance of the catalyst to improve the activity and selectivity, enhancing the formate conversion capacity of the catalyst to improve the product quality, and improving the mechanical stability of the catalyst.
Disclosure of Invention
The invention aims to provide a hydrogenation catalyst, in particular to a catalyst for preparing trimethylolpropane by hydrogenating 2, 2-dimethylolbutyraldehyde and a preparation method thereof. The catalyst not only has excellent activity and selectivity, but also has good formate conversion capability and mechanical stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a hydrogenation catalyst, especially a catalyst for preparing trimethylolpropane by hydrogenating 2, 2-dimethylolbutyraldehyde, wherein the total mass of the catalyst is 100 wt% (calculated by inorganic oxides, excluding organic impurities), and the hydrogenation catalyst comprises the following components:
35-70 wt% of copper oxide, such as 40%, 50%, 60%, 65%;
5-25 wt% of zinc oxide, such as 10%, 15%, 20%, 25%;
alumina 5-35 wt%, such as 10%, 20%, 25%, 30%
10-30wt% of silica, such as 10%, 15%, 20%, 25%;
0.5-5wt% of alkaline earth metal oxide, such as 0.5%, 1%, 3%, 4%;
0.05-1.0 wt% of palladium oxide, such as 0.1%, 0.3%, 0.5%, 1.0%;
iridium oxide (Ir) 2 O 3 )0.01-1.0 wt%, such as 0.1%, 0.3%, 0.5%, 1.0%;
0.01-1.0wt% of tin oxide, such as 0.1%, 0.3%, 0.5%, 1.0%.
In a preferred embodiment, the catalyst comprises the following components: 35-65 wt% of copper oxide, 8-25wt% of zinc oxide, 10-30wt% of aluminum oxide, 10-25wt% of silicon dioxide, 0.5-3 wt% of alkaline earth metal oxide, 0.05-0.5 wt% of palladium oxide, 0.01-0.5wt% of iridium oxide and 0.01-0.5wt% of tin oxide.
In a more preferred embodiment, the catalyst comprises the following components: 40-65 wt% of copper oxide, 10-25wt% of zinc oxide, 10-25wt% of aluminum oxide, 10-20 wt% of silicon dioxide, 0.5-2 wt% of alkaline earth metal oxide, 0.05-0.3 wt% of palladium oxide, 0.01-0.3wt% of iridium oxide and 0.01-0.3wt% of tin oxide.
In the catalyst, the alkaline earth metal is at least one selected from Mg, Ca and Ba.
In a preferred embodiment, the molar ratio of Pd, Ir and Sn in the catalyst is 1: 0.25-4: 0.25 to 4, for example, 1:0.3:0.3, 1:0.5:2, 1:1:1, 1:2: 2. The mole ratio of Pd, Ir and Sn is kept in a proper range, which is beneficial to enhancing the formate conversion capability of the catalyst.
In a second aspect of the present invention, there is also provided a method for preparing the hydrogenation catalyst, comprising the steps of, in proportion:
(1) adding deionized water, organic silicon quaternary ammonium salt and organic pore-forming agent into a reaction kettle, and uniformly stirring to obtain a dispersion solution I;
(2) adding a mixed solution I containing a Cu compound, a Zn compound and an Al compound and an alkaline precipitator solution II into the dispersion solution I for precipitation reaction, and heating and aging to obtain aged slurry;
(3) filtering, washing, drying and roasting the aged slurry to obtain composite compound powder;
(4) adding silica sol and a forming assistant into the composite compound powder, fully mixing, extruding, forming, drying and roasting to obtain a carrier;
(5) and dissolving a Pd-containing compound, an Ir-containing compound, a Sn-containing compound and an alkaline earth metal compound in water, soaking the solution on a carrier, drying and roasting to obtain the formed catalyst.
In the preparation method, the addition amount of the organosilicon quaternary ammonium salt in the step (1) is 0.2-2.0% of the total mass sum of the Cu/Zn/Al-containing compounds in the step (2) calculated by oxides; preferably, the organosilicon quaternary ammonium salt is one or more of dimethyldodecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, dimethyltetradecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, dimethylhexadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride and dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride.
Researches find that the organosilicon quaternary ammonium salt can be further matched with an organic pore-forming agent to promote the formation of a hierarchical pore structure and improve the mass transfer performance of the catalyst.
The organic pore-forming agent in the step (1) is selected from one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose and hydroxypropyl methyl cellulose. The dosage of the organic pore-forming agent is 1.0-6.0% of the total mass of the Cu/Zn/Al-containing compounds in the step (2) in terms of oxides. The organic pore-forming agent is added in the preparation process, so that the internal diffusion resistance of the raw materials and the product is reduced, and the activity and the selectivity are effectively improved. The addition amount of the organic pore-forming agent is kept in a proper range, so that the influence on the strength of the catalyst is reduced as much as possible on the premise of obtaining better mass transfer performance; the addition amount of the organic pore-forming agent is too small, so that the effect of improving the catalyst mass transfer performance is not facilitated; too much pore former addition affects the mechanical strength of the catalyst.
As understood by those skilled in the art, in the mixed solution I, each compound is a soluble salt of the corresponding metal; for example:
the Cu-containing compound is selected from one or more of copper nitrate, copper chloride and copper acetate, and copper nitrate is preferably adopted;
the Zn-containing compound is selected from one or more of zinc nitrate, zinc chloride and zinc acetate, and zinc nitrate is preferably adopted;
the Al-containing compound is selected from one or more of aluminum nitrate, aluminum chloride and aluminum acetate, and preferably aluminum nitrate is adopted;
in the mixed solution I in the step (2) of the present invention, the Cu-containing compound is a source of Cu which is an active component of the catalyst.
Preferably, the concentration of the metal ions in the mixed solution I prepared in the step (2) is 0.5-2.0 mol/L.
The alkaline precipitant is one or more selected from sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, ammonium carbonate, ammonium bicarbonate, urea and ammonia water, and preferably sodium carbonate is used. Preferably, the concentration of the alkaline precipitant solution is 10 to 20 wt%.
In the step (2), the alkaline precipitant is generally used in excess (usually 105-115% of the amount theoretically required for completely precipitating the metal particles) to completely precipitate the metal particles, and the amount can be determined by those skilled in the art according to the kind of the alkaline precipitant and the pH value of the reaction system during the precipitation process.
The temperature of the precipitation reaction in the step (2) is 50-90 ℃, and preferably 60-90 ℃; controlling the pH value of the precipitation reaction process to be 6.0-8.0, preferably 6.5-7.5; the precipitation reaction time is 0.5-4h, preferably 1-3 h; the aging temperature is 60-90 deg.C, preferably 75-85 deg.C; the aging time is 2-24h, preferably 2-8 h. The specific reaction to form precipitates and the aging of the precipitates are well known in the art.
In the method of the present invention, in the step (3), deionized water is used for washing. The drying temperature in the step (3) is 100-120 ℃ (for example, 105 ℃, 110 ℃), and the drying time is 4-12h (for example, 5h, 8h, 10 h); the roasting temperature is 250-350 ℃ (such as 260 ℃, 280 ℃ and 320 ℃) and the roasting time is 2-8h (such as 3h, 5h and 7 h). The filtration, washing, drying and calcination processes described in this step are all catalyst treatment processes well known in the art.
In the invention, the silica sol in the step (4) is sodium type silica sol, and SiO in the sodium type silica sol 2 In an amount of 20 to 40 wt.%, e.g., 25 wt.%, 30 wt.%, 35 wt.%; the sodium silica sol has a particle size of 20-40nm, such as 25nm, 30nm, 35 nm; the pH value of the sodium type silica sol is 8.0-10.0.
And (4) the forming aid is sesbania powder. Preferably, the amount of the forming aid is 2-5wt% of the composite compound powder.
In the method of the present invention, the extrusion molding process conditions in step (4) may be: fully kneading various materials used for molding, and performing extrusion molding by adopting an F-26 twin-screw extruder at room temperature; extrusion pressure is 60-200N (e.g., 60N, 100N, 150N), screw speed is 10-50r/min (e.g., 10r/min, 30r/min, 40 r/min).
In the step (4), the drying temperature for drying after extrusion molding is 100-; the roasting temperature is 350-650 ℃ (400 ℃, 450 ℃ and 550 ℃) and the roasting time is 2-8h (3 h, 5h and 7 h). The roasting temperature in the step (4) is obviously higher than that in the step (3), so that the part which is not decomposed during roasting in the step (3) can be fully decomposed during roasting in the step (4), and the pore passages of the catalyst can be more unobstructed and developed. The drying and calcination processes described in this step are all catalyst treatment processes well known in the art.
In the step (5), the palladium-containing compound is palladium nitrate and/or palladium chloride, preferably palladium chloride;
the iridium-containing compound is iridium nitrate and/or iridium chloride, preferably iridium chloride;
the stanniferous compound is stannous acetate and/or stannous chloride, preferably stannous chloride;
in the alkaline earth metal compound, the magnesium-containing compound is one or more of magnesium nitrate, magnesium chloride and magnesium acetate; the calcium-containing compound is one or more of calcium nitrate, calcium chloride and calcium acetate; the barium-containing compound is one or more of barium nitrate, barium chloride and barium acetate; the alkaline earth metal compound preferably employs one or more of magnesium nitrate, calcium nitrate and barium nitrate;
the alkaline earth metal compound is at least one of Mg, Ca and Ba compounds, and the addition of the alkaline earth metal can reduce the acidity of the catalyst and is beneficial to the improvement of reaction selectivity.
The Pd-containing compound, the Ir-containing compound and the Sn-containing compound are added as auxiliaries to improve the formate conversion capability of the catalyst. The addition of the auxiliary Zn effectively improves the dispersion degree of the active component Cu, and can effectively improve the reaction activity and stability of the hydrogenation catalyst.
The impregnation in step (5) is an equal volume impregnation method, which is a catalyst treatment process well known in the art. The drying temperature in the step (5) is 100-; the roasting temperature is 400-550 ℃ (for example, 400 ℃, 450 ℃, 500 ℃) and the roasting time is 2-8h (for example, 2h, 4h, 6 h).
In addition, in the invention, the shaped catalyst in the step (5) is a shaped catalyst, such as a clover, clover or pentafoil type catalyst, and the shaped catalyst has a diameter of 1.5-3.0mm and a length of 2.0-8.0 mm.
In the 2, 2-dimethylolbutyraldehyde hydrogenation catalyst prepared by the invention, the content of organic impurities (such as sesbania powder which is not completely combusted or decomposed and is a forming aid and possibly contains trace carbon) is not more than 1.0wt%, and the content of each component can be ignored in the calculation.
The invention has the beneficial effects that:
the 2, 2-dimethylolbutyraldehyde hydrogenation catalyst prepared by the invention has high dispersion degree of active components, smooth catalyst pore passage and weak acidity, and has excellent activity and selectivity when being used for preparing trimethylolpropane by hydrogenating 2, 2-dimethylolbutyraldehyde, strong formate conversion capability and high mechanical stability.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
< sources of raw materials >
Silica sol, available from Shandong Baite New materials, Inc.;
formaldehyde, n-butyraldehyde, methanol, palladium chloride, iridium chloride, copper nitrate, sodium carbonate, and the like, available from shanghai alading biochemical science and technology, ltd;
hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, and the like are available from Shandong Yousio chemical science and technology, Inc.;
organosilicon quaternary ammonium salts such as dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride and the like are purchased from Wuhananabai pharmaceutical chemical Co., Ltd.
< test methods >
1. Analyzing the composition of a catalyst for preparing Trimethylolpropane (TMP) by hydrogenating 2, 2-Dimethylolbutyraldehyde (DMB) by adopting an X-ray fluorescence spectrometer (XRF);
2. DMB conversion rate (1-moles of DMB remaining in the reaction solution/moles of DMB contained in the raw material) × 100%;
TMP selectivity-100% moles of TMP produced/moles of DMB converted;
formate conversion (1-moles of formate remaining in the reaction solution/moles of formate contained in the feed) 100%
Wherein, the mole number of the 2, 2-dimethylolbutyraldehyde contained in the raw material, the mole number of the generated trimethylolpropane and the mole number of the 2, 2-dimethylolbutyraldehyde remained in the reaction liquid are calculated after being analyzed by an Agilent 7820A gas chromatograph, and the test conditions comprise: adopts DB-5 chromatographic column and FID detector, the vaporizing chamber temperature is 260 deg.C, the detector temperature is 260 deg.C, and the carrier gas is high-purity N 2 The flow rate was 30 ml/min.
The mole number of formate in the raw material and the hydrogenation liquid is calculated after the ion chromatography analysis.
3. The side pressure strength of the catalyst is measured by a particle strength tester
The used catalyst was protected by immersion in a hydrogenation solution to prevent oxidation of the catalyst, and the lateral pressure strength of the 40-grain reacted catalyst was measured and the average value was obtained.
Example 1
(1) 300g of water, 3.0g of dimethyldodecyl [3- (trimethoxysilyl) propyl ] ammonium chloride and 9g of hydroxymethyl cellulose are added into a reaction kettle and stirred uniformly to obtain a dispersion I.
(2) 273.4g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O, 242), 167.1g of zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O, 298) and 163.4g of aluminum nitrate (Al (NO) 3 ) 3 ·9H 2 O, 375) is dissolved in 1471g of water to prepare a mixed salt solution, a sodium carbonate aqueous solution with the concentration of 15 wt% is prepared, the two solutions are respectively heated to 60 ℃ and then are dripped into the reaction kettle in a parallel flow manner, the dripping time is 40min, the temperature of the precipitation process is controlled to be 60 ℃, the pH value of the precipitation process is 7.0 (wherein, the dosage of the sodium carbonate aqueous solution is controlled to be 105% of the theoretical required amount for completely precipitating the metal particles according to the pH value of the precipitation process), and then the mixture is aged at 70 ℃ for 3 h.
(3) And filtering and washing the aged slurry to obtain a filter cake, drying the filter cake at 110 ℃ for 10h, and roasting at 350 ℃ for 4h to obtain the composite compound powder.
(4) 126.7g of sodium silica sol (SiO in silica sol) was added to the above powder 2 Content of 30wt%, SiO 2 The particle diameter of 30nm, the pH value of 9.0) and 6g of sesbania powder are fully kneaded, extruded and formed, dried at the temperature of 110 ℃ for 6 hours and then roasted at the temperature of 550 ℃ for 4 hours to obtain the pentaphyllum carrier with the circumscribed circle diameter of 2.0mm and the length of 3.0-8.0 mm.
(5) And (3) dissolving 19.1g of magnesium nitrate (hexahydrate), 0.72g of palladium chloride, 0.42g of iridium chloride and 0.38g of stannous chloride in water, loading Mg, Pd, Sn and Ir on the carrier obtained in the step (4) by adopting an isometric impregnation method, drying at 120 ℃ for 4h, and roasting at 450 ℃ for 4h to obtain the catalyst A.
Catalyst a (calculated as inorganic oxides) was composed, as analyzed by X-ray fluorescence spectroscopy (XRF): 45.0 wt% of copper oxide, 22.85 wt% of zinc oxide, 11.1 wt% of aluminum oxide, 19.0 wt% of silicon dioxide, 1.5 wt% of magnesium oxide, 0.25 wt% of palladium oxide, 0.15 wt% of iridium oxide and 0.15 wt% of tin oxide.
And (3) catalyst reduction: the Wuyecao type catalyst A is filled in a fixed bed hydrogenation reactor, and the loading amount of the catalyst is 100 ml. Before the catalyst is used, the catalyst is reduced under the mixed gas of nitrogen and hydrogen, and the volume space velocity of the mixed gas is kept for 300h in the reduction process -1 Firstly, the temperature of the reactor is raised to 160 ℃, the temperature is kept constant for 2 hours, the physical water absorbed by the catalyst is removed, and then H with the volume fraction of 5v percent is introduced 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 20 v%, 50 v% and 100%, the temperature of the hot spot of the catalyst bed layer in the process is controlled not to exceed 220 ℃, and finally the temperature is increased to 220 ℃ to reduce for 4h under the pure hydrogen atmosphere.
Evaluation of catalyst Performance:
preparation of condensation liquid: refer to CN104140358B for the preparation of the condensation liquid in example 14.
The starting material was diluted with water and methanol to: 5wt% DMB +0.53 wt% TMP +0.15 wt% DMB formate +44.2 wt% water +50 wt% methanol +0.12 wt% other organics (n-butyraldehyde, etc.). Under the pressure of 4.0MPa, the temperature of 110 ℃ and the pressure of H 2 The mol ratio of DMB/DMB is 10:1, and the liquid hourly space velocity is 2.4h -1 The reaction is carried out under the conditions of (1). The reaction results are shown in Table 1.
Example 2
(1) 300g of water, 2g of dimethyltetradecyl [3- (trimethoxysilyl) propyl ] ammonium chloride and 6g of hydroxyethyl methylcellulose are added into a reaction kettle and stirred uniformly to obtain a dispersion I.
(2) 303.7g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O, 242), 87.4g of zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O, 298) and 348.8g of aluminum nitrate (Al (NO) 3 ) 3 ·9H 2 O, 375) is dissolved in 1661.5g of water to prepare a mixed salt solution, a sodium carbonate aqueous solution with the concentration of 15 wt% is prepared, the two solutions are respectively heated to 65 ℃ and then are dripped into the reaction kettle in a parallel flow manner, the dripping time is 50min, the temperature in the precipitation process is controlled to be 65 ℃, the pH value in the precipitation process is 7.0 (wherein, the dosage of the sodium carbonate aqueous solution is controlled to be 105% of the theoretical required amount for completely precipitating the metal particles according to the pH value in the precipitation process), and then the mixture is aged for 4h at 80 ℃.
(3) And filtering and washing the aged slurry to obtain a filter cake, drying the filter cake at 100 ℃ for 8h, and roasting at 300 ℃ for 4h to obtain the composite compound powder.
(4) To the powder was added 86.7g of sodium type silica sol (SiO in silica sol) 2 30wt% of SiO 2 The particle diameter of 30nm, the pH value of 9.0) and 6g of sesbania powder are fully kneaded, extruded into strips and molded, dried at 100 ℃ for 8 hours and then roasted at 500 ℃ for 8 hours to obtain the clover-type carrier with the circumscribed circle diameter of 2.0mm and the length of 3.0-8.0 mm.
(5) And (3) dissolving 2.7g of barium nitrate, 0.72g of palladium chloride, 0.69g of iridium chloride and 0.20g of stannous chloride in water, loading Ba, Pd, Sn and Ir on the carrier obtained in the step (4) by adopting an isovolumetric impregnation method, drying at 100 ℃ for 8h, and roasting at 500 ℃ for 4h to obtain the catalyst B.
Catalyst B (calculated as inorganic oxide) was composed by X-ray fluorescence spectroscopy (XRF) analysis: 50.0 wt% of copper oxide, 11.9 wt% of zinc oxide, 23.7 wt% of aluminum oxide, 13.0 wt% of silicon dioxide, 0.8 wt% of barium oxide, 0.25 wt% of palladium oxide, 0.25 wt% of iridium oxide and 0.08 wt% of tin oxide.
The reduction of the catalyst and the hydrogenation were carried out under the process conditions and operating conditions referred to in example 1.
Example 3
(1) 300g of water, 1g of dimethylhexadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride and 3g of hydroxyethyl methylcellulose are added into a reaction kettle and stirred uniformly to obtain a dispersion I.
(2) 334.1g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O, 242), 107.8g of zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O, 298) and 161.9g of aluminum nitrate (Al (NO) 3 ) 3 ·9H 2 O, 375) is dissolved in 1661.5g of water to prepare a mixed salt solution, a sodium carbonate aqueous solution with the concentration of 15 wt% is prepared, the two solutions are respectively heated to 65 ℃ and then are dripped into the reaction kettle in a concurrent flow manner, the dripping time is 60min, the temperature in the precipitation process is controlled to be 65 ℃, the pH value in the precipitation process is 7.0 (wherein, the dosage of the sodium carbonate aqueous solution is controlled to be 105% of the theoretical required quantity for completely precipitating the metal particles according to the pH value in the precipitation process), and then the aging is carried out for 4h at 70 ℃.
(3) And filtering and washing the aged slurry to obtain a filter cake, drying the filter cake at 100 ℃ for 8h, and roasting at 320 ℃ for 4h to obtain the composite compound powder.
(4) To the above powder was added 120.7g of sodium type silica sol (SiO in silica sol) 2 30wt% of SiO 2 The particle diameter of 30nm, the pH value of 9.0) and 6g of sesbania powder are fully kneaded, extruded and formed, dried at 110 ℃ for 6 hours and then roasted at 450 ℃ for 8 hours to obtain the clover-shaped carrier with the circumscribed circle diameter of 2.0mm and the length of 3.0-8.0 mm.
(5) And (3) dissolving 3.5g of calcium nitrate, 0.58g of palladium chloride, 0.28g of iridium chloride and 0.63g of stannous chloride in water, loading Ca, Sn, Pd and Ir on the carrier obtained in the step (4) by adopting an isometric impregnation method, drying at 110 ℃ for 8h, and roasting at 400 ℃ for 6h to obtain the catalyst C.
Catalyst C (calculated as inorganic oxide) was composed by X-ray fluorescence spectroscopy (XRF) analysis: 55.0 wt% of copper oxide, 14.75 wt% of zinc oxide, 11 wt% of aluminum oxide, 18.1 wt% of silicon dioxide, 0.6 wt% of calcium oxide, 0.20 wt% of palladium oxide, 0.10 wt% of iridium oxide and 0.25 wt% of tin oxide.
The reduction of the catalyst and the hydrogenation were carried out under the process conditions and operating conditions referred to in example 1.
Example 4
(1) 300g of water, 2g of dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride and 5g of hydroxymethyl cellulose are added into a reaction kettle and stirred uniformly to obtain a dispersion solution I.
(2) 364.5g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O, 242), 73.1g of zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O, 298) and 220.8g of aluminum nitrate (Al (NO) 3 ) 3 ·9H 2 O, 375) is dissolved in 1462.5g of water to prepare a mixed salt solution, a sodium carbonate aqueous solution with the concentration of 15 wt% is prepared, the two solutions are respectively heated to 75 ℃, and then are dripped into the reaction kettle in a parallel flow manner, the dripping time is 90min, the temperature of the precipitation process is controlled to be 75 ℃, the pH value of the precipitation process is 7.0 (wherein, the dosage of the sodium carbonate aqueous solution is controlled to be 105% of the theoretical required amount for completely precipitating the metal particles according to the pH value of the precipitation process), and then the mixture is aged for 2h at 80 ℃.
(3) And filtering and washing the aged slurry to obtain a filter cake, drying the filter cake at 120 ℃ for 4h, and roasting at 280 ℃ for 4h to obtain the composite compound powder.
(4) To the powder was added 93.3g of sodium type silica sol (SiO in silica sol) 2 30wt% of SiO 2 The particle diameter of 30nm, the pH value of 9.0) and 6g of sesbania powder are fully kneaded, extruded and formed, dried at 100 ℃ for 8 hours and then roasted at 500 ℃ for 8 hours to obtain the pentaphyllum carrier with the circumscribed circle diameter of 2.0mm and the length of 3.0-8.0 mm.
(5) And (3) dissolving 6.4g of magnesium nitrate, 0.29g of palladium chloride, 0.69g of iridium chloride and 0.38g of stannous chloride in water, loading Mg, Pd, Sn and Ir on the carrier obtained in the step (4) by adopting an isometric impregnation method, drying at 120 ℃ for 4h, and roasting at 400 ℃ for 6h to obtain the catalyst D.
Catalyst D (calculated as inorganic oxide) was composed by X-ray fluorescence spectroscopy (XRF) analysis: 60.0 wt% of copper oxide, 10.0 wt% of zinc oxide, 15 wt% of aluminum oxide, 14.0 wt% of silicon dioxide, 0.5wt% of magnesium oxide, 0.10 wt% of palladium oxide, 0.25 wt% of iridium oxide and 0.15 wt% of tin oxide.
The reduction of the catalyst and the hydrogenation were carried out under the process conditions and operating conditions referred to in example 1.
Example 5
(1) 300g of water, 2.5g of dimethyldodecyl [3- (trimethoxysilyl) propyl ] ammonium chloride and 8g of hydroxyethyl methylcellulose are added into a reaction kettle and stirred uniformly to obtain a dispersion I.
(2) 273.4g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O, 242), 86.3g of zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O, 298) and 323.8g of aluminum nitrate (Al (NO) 3 ) 3 ·9H 2 O, 375) is dissolved in 1539.3g of water to prepare a mixed salt solution, a sodium carbonate aqueous solution with the concentration of 15 wt% is prepared, the two solutions are respectively heated to 60 ℃ and then are dripped into the reaction kettle in a parallel flow manner, the dripping time is 50min, the temperature in the precipitation process is controlled to be 60 ℃, the pH value in the precipitation process is 7.0 (wherein, the dosage of the sodium carbonate aqueous solution is controlled to be 105% of the theoretical required amount for completely precipitating the metal particles according to the pH value in the precipitation process), and then the mixture is aged for 2h at 70 ℃.
(3) And filtering and washing the aged slurry to obtain a filter cake, drying the filter cake at 120 ℃ for 4h, and roasting at 300 ℃ for 6h to obtain composite compound powder.
(4) 127.7g of sodium silica sol (SiO in silica sol) was added to the above powder 2 30wt% of SiO 2 The particle diameter of 30nm, the pH value of 9.0) and 6g of sesbania powder are fully kneaded, extruded into strips and molded, dried at 120 ℃ for 4 hours and then roasted at 600 ℃ for 4 hours to obtain the clover-type carrier with the circumscribed circle diameter of 2.0mm and the length of 3.0-8.0 mm.
(5) And (3) dissolving 5.1g of barium nitrate, 0.72g of palladium chloride, 0.28g of iridium chloride and 0.50g of stannous chloride in water, loading Ba, Pd, Sn and Ir on the carrier obtained in the step (4) by adopting an isometric impregnation method, drying at 110 ℃ for 10h, and roasting at 450 ℃ for 6h to obtain the catalyst E.
Analysis by X-ray fluorescence spectroscopy (XRF) showed that catalyst E (calculated as inorganic oxides) had a composition of: 45.0 wt% of copper oxide, 11.80 wt% of zinc oxide, 22 wt% of aluminum oxide, 19.15 wt% of silicon dioxide, 1.5 wt% of barium oxide, 0.25 wt% of palladium oxide, 0.10 wt% of iridium oxide and 0.20 wt% of tin oxide.
The reduction of the catalyst and the hydrogenation were carried out under the process conditions and operating conditions referred to in example 1.
Example 6
(1) 300g of water, 1.5g of dimethylhexadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride and 6g of hydroxyethyl methylcellulose are added into a reaction kettle and stirred uniformly to obtain a dispersion I.
(2) 243g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O, 242), 136.9g of zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O, 298) and 342.2g of aluminum nitrate (Al (NO) 3 ) 3 ·9H 2 O, 375) is dissolved in 1607.7g of water to prepare a mixed salt solution, a sodium carbonate aqueous solution with the concentration of 15 wt% is prepared, the two solutions are respectively heated to 70 ℃ and then are dripped into the reaction kettle in a parallel flow manner, the dripping time is 120min, the temperature in the precipitation process is controlled to be 70 ℃, the pH value in the precipitation process is 7.0 (wherein, the dosage of the sodium carbonate aqueous solution is controlled to be 105% of the theoretical required amount for completely precipitating the metal particles according to the pH value in the precipitation process), and then the mixture is aged for 4h at 75 ℃.
(3) And filtering and washing the aged slurry to obtain a filter cake, drying the filter cake at 120 ℃ for 4h, and roasting at 320 ℃ for 4h to obtain the composite compound powder.
(4) To the powder was added 106.7g of sodium type silica sol (SiO in silica sol) 2 30wt% of SiO 2 The particle diameter of 30nm, the pH value of 9.0) and 6g of sesbania powder are fully kneaded, extruded and formed, dried at the temperature of 110 ℃ for 8 hours and then roasted at the temperature of 550 ℃ for 4 hours to obtain the clover-shaped carrier with the circumscribed circle diameter of 2.0mm and the length of 3.0-8.0 mm.
(5) And (3) dissolving 8.8g of calcium nitrate, 0.58g of palladium chloride, 0.14g of iridium chloride and 0.70g of stannous chloride in water, loading Ca, Sn, Pd and Ir on the carrier obtained in the step (4) by adopting an isovolumetric impregnation method, drying at 110 ℃ for 8 hours, and roasting at 400 ℃ for 4 hours to obtain the catalyst F.
Analysis by X-ray fluorescence spectroscopy (XRF) of catalyst F (calculated as inorganic oxide) had the composition: 40.0 wt% of copper oxide, 18.72 wt% of zinc oxide, 23.25 wt% of aluminum oxide, 16.0 wt% of silicon dioxide, 1.5 wt% of calcium oxide, 0.20 wt% of palladium oxide, 0.05 wt% of iridium oxide and 0.28 wt% of tin oxide.
The reduction of the catalyst and the hydrogenation were carried out under the process conditions and operating conditions referred to in example 1.
Comparative example 1
The procedure for preparing a pentafoil type 2, 2-dimethylolbutyraldehyde hydrogenation catalyst was the same as in example 1, except that no Pd, Ir, or Sn was impregnated after extrusion molding to prepare catalyst G.
The reduction of the catalyst and the hydrogenation were carried out under the process conditions and operating conditions referred to in example 1.
Comparative example 2
The procedure for preparing a clover-type 2, 2-dimethylolbutyraldehyde hydrogenation catalyst was the same as in example 2, except that dimethyltetradecyl [3- (trimethoxysilyl) propyl ] ammonium chloride and hydroxyethylmethylcellulose were not added to the reactor, and the procedure of example 2 was otherwise the same as that for preparing catalyst H.
The reduction of the catalyst and the hydrogenation were carried out under the process conditions and operating conditions referred to in example 1.
Comparative example 3
The procedure for preparing a Trifolium type 2, 2-dimethylolbutyraldehyde hydrogenation catalyst was the same as in example 3, except that in the step (4), 36.2g of gas phase SiO was added instead of silica sol and sesbania powder 2 And 3g of graphite, and pressing the mixture into cylindrical tablets with the diameter of 3mm and the height of 3mm after fully mixing to prepare the catalyst I.
The reduction of the catalyst and the hydrogenation were carried out under the process conditions and operating conditions referred to in example 1.
TABLE 1 evaluation results of catalysts
DMB conversion% TMP selectivity% Formate conversion%
Catalyst A 97.9 98.4 78.2
Catalyst B 98.1 98.6 77.6
Catalyst C 98.5 98.4 74.3
Catalyst D 97.8 98.5 75.9
Catalyst E 98.3 99.1 78.5
Catalyst F 98.6 98.5 73.8
Catalyst G 92.6 96.5 23.1
Catalyst H 91.2 94.6 53.6
Catalyst I 89.6 95.3 50.2
TABLE 2 catalyst Strength and State before and after reaction
Figure BDA0002563751050000181
N/pellet is the unit of catalyst strength, force applied even if 1 pellet of catalyst breaks
As can be seen from tables 1 and 2, catalysts a to F have good activity and selectivity, while the catalysts of comparative examples 1 to 3 have either low activity or poor selectivity.
By comparing example 1 with comparative example 1, it is shown that the addition of Pd, Sn and Ir significantly improves the formate conversion capability of the catalyst.
By comparing example 2 with comparative example 2, it is shown that the addition of dimethyltetradecyl [3- (trimethoxysilyl) propyl ] ammonium chloride and 6g of hydroxyethyl methylcellulose can improve the mass transfer performance of the catalyst, effectively increasing the reaction activity and selectivity.
The comparison between example 3 and comparative example 3 shows that the extruded catalyst has excellent activity, selectivity and mechanical strength, the tabletted catalyst has poor adhesion, and the catalyst is broken and has obviously lowered strength after reaction.
The results show that the catalyst prepared by the method has high active component dispersity and good mass transfer performance, and has good activity and selectivity, strong formate conversion capacity and high mechanical stability when being used for preparing TMP by DMB hydrogenation.

Claims (11)

1. A hydrogenation catalyst, which is characterized in that the hydrogenation catalyst comprises the following components by weight percent based on 100 wt% of the total mass of the hydrogenation catalyst:
35-70 wt% of copper oxide, 5-25 wt% of zinc oxide, 5-35 wt% of aluminum oxide, 10-30wt% of silicon dioxide, 0.5-5wt% of alkaline earth metal oxide, 0.05-1.0 wt% of palladium oxide, 0.01-1.0wt% of iridium oxide and 0.01-1.0wt% of tin oxide;
the molar ratio of Pd, Ir and Sn in the hydrogenation catalyst is 1: 0.25-4: 0.25 to 4;
the preparation method of the hydrogenation catalyst comprises the following steps in proportion:
(a) adding deionized water, organic silicon quaternary ammonium salt and organic pore-forming agent into a reaction kettle, and uniformly stirring to obtain a dispersion solution I;
(b) adding a mixed solution I containing a Cu compound, a Zn compound and an Al compound and an alkaline precipitator solution II into the dispersion solution I for precipitation reaction, and heating and aging to obtain aged slurry;
(c) filtering, washing, drying and roasting the aged slurry to obtain composite compound powder;
(d) adding silica sol and a forming assistant into the composite compound powder, fully mixing, extruding, forming, drying and roasting to obtain a carrier;
(e) and dissolving a Pd-containing compound, an Ir-containing compound, a Sn-containing compound and an alkaline earth metal compound in water, soaking the solution on a carrier, drying and roasting to obtain the catalyst.
2. The hydrogenation catalyst of claim 1 wherein the hydrogenation catalyst comprises, based upon the total mass of hydrogenation catalyst being 100 wt%: 35-65 wt% of copper oxide, 8-25wt% of zinc oxide, 10-30wt% of aluminum oxide, 10-25wt% of silicon dioxide, 0.5-3 wt% of alkaline earth metal oxide, 0.05-0.5 wt% of palladium oxide, 0.01-0.5wt% of iridium oxide and 0.01-0.5wt% of tin oxide.
3. The hydrogenation catalyst of claim 2, wherein the hydrogenation catalyst comprises, based on 100 wt% of the total mass of the hydrogenation catalyst: 40-65 wt% of copper oxide, 10-25wt% of zinc oxide, 10-25wt% of aluminum oxide, 10-20 wt% of silicon dioxide, 0.5-2 wt% of alkaline earth metal oxide, 0.05-0.3 wt% of palladium oxide, 0.01-0.3wt% of iridium oxide and 0.01-0.3wt% of tin oxide.
4. The hydrogenation catalyst according to claim 1, wherein the organosilicon quaternary ammonium salt is added in an amount of 0.2 to 2.0% of the total mass of the Cu/Zn/Al-containing compounds in step (b) in terms of oxides.
5. The hydrogenation catalyst of claim 4 wherein said organosilicon quaternary ammonium salt is one or more of dimethyldodecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, dimethyltetradecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, dimethylhexadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, and dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride.
6. The hydrogenation catalyst of claim 1, wherein the organic pore former is selected from one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose and hydroxypropyl methyl cellulose; the dosage of the organic pore-forming agent is 1.0-6.0% of the total mass of the Cu/Zn/Al-containing compounds in the step (b) calculated by oxides.
7. The hydrogenation catalyst according to any one of claims 1 to 6, wherein the temperature of the precipitation reaction in step (b) is 50 to 90 ℃, the pH value during precipitation is 6.0 to 8.0, and the precipitation reaction time is 0.5 to 4 hours; the aging temperature is 60-90 ℃, and the aging time is 2-24 h.
8. The hydrogenation catalyst as claimed in claim 1, wherein the drying temperature in step (c) is 100-120 ℃ and the drying time is 4-12 h; the roasting temperature is 250-350 ℃, and the roasting time is 2-8 h.
9. The hydrogenation catalyst according to claim 1, wherein the silica sol of step (d) is a sodium-type silica sol, and SiO is contained in the silica sol 2 The content is 20-40%, the particle size of the silica sol is 20-40nm, and the pH value of the silica sol is 8.0-10.0; and/or:
the forming auxiliary agent is sesbania powder, and the using amount of the forming auxiliary agent is 2-5wt% of the composite compound powder; and/or:
the drying temperature is 100-120 ℃, and the drying time is 4-12 h; the roasting temperature is 350-650 ℃, and the roasting time is 2-8 h.
10. The hydrogenation catalyst as claimed in claim 1, wherein the drying temperature in step (e) is 100-120 ℃ and the drying time is 4-12 h; the roasting temperature is 400-550 ℃, and the roasting time is 2-8 h.
11. Use of a hydrogenation catalyst according to any one of claims 1 to 10 for the hydrogenation of 2, 2-dimethylolbutyraldehyde to produce trimethylolpropane.
CN202010623101.XA 2020-07-01 2020-07-01 Hydrogenation catalyst, preparation method and application thereof Active CN111715238B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010623101.XA CN111715238B (en) 2020-07-01 2020-07-01 Hydrogenation catalyst, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010623101.XA CN111715238B (en) 2020-07-01 2020-07-01 Hydrogenation catalyst, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111715238A CN111715238A (en) 2020-09-29
CN111715238B true CN111715238B (en) 2022-08-05

Family

ID=72571007

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010623101.XA Active CN111715238B (en) 2020-07-01 2020-07-01 Hydrogenation catalyst, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111715238B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112517018B (en) * 2020-11-30 2022-08-05 万华化学集团股份有限公司 Catalyst for preparing trimethylolpropane by hydrogenating 2, 2-dimethylolbutyraldehyde and preparation method and application thereof
CN113278995B (en) * 2021-05-14 2023-06-02 中国科学院山西煤炭化学研究所 Method for preparing oxalic acid by carbon dioxide or bicarbonate or carbonate

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101176848A (en) * 2007-11-12 2008-05-14 青岛科技大学 Catalyzer for preparing 1, 3-trimethylene glycol from 3-hydracrylic acid ester through hydrogenation and preparation method thereof
CN102712559A (en) * 2009-11-17 2012-10-03 巴斯夫欧洲公司 Method for producing a supported hydrogenation catalyst having increased hydrogenation activity
CN103254034A (en) * 2013-05-22 2013-08-21 烟台万华聚氨酯股份有限公司 Trimethylolpropane preparation method
CN103274899A (en) * 2013-05-22 2013-09-04 烟台万华聚氨酯股份有限公司 Preparation method of trimethylolpropane
CN104140358A (en) * 2014-07-28 2014-11-12 万华化学集团股份有限公司 Method for preparing trimethylolpropane through hydrogenation
CN104892364A (en) * 2015-06-02 2015-09-09 万华化学集团股份有限公司 Method for preparing trimethylolpropane by adopting hydrogenation method
CN108772073A (en) * 2018-05-21 2018-11-09 河南省化工研究所有限责任公司 A kind of hydrogenation catalyst and its preparation method and application that trimethylolpropane preparation process uses
CN110075857A (en) * 2019-05-09 2019-08-02 万华化学集团股份有限公司 A kind of dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method thereof
CN110121486A (en) * 2017-10-23 2019-08-13 Lg化学株式会社 The preparation method of trimethylolpropane

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101176848A (en) * 2007-11-12 2008-05-14 青岛科技大学 Catalyzer for preparing 1, 3-trimethylene glycol from 3-hydracrylic acid ester through hydrogenation and preparation method thereof
CN102712559A (en) * 2009-11-17 2012-10-03 巴斯夫欧洲公司 Method for producing a supported hydrogenation catalyst having increased hydrogenation activity
CN103254034A (en) * 2013-05-22 2013-08-21 烟台万华聚氨酯股份有限公司 Trimethylolpropane preparation method
CN103274899A (en) * 2013-05-22 2013-09-04 烟台万华聚氨酯股份有限公司 Preparation method of trimethylolpropane
CN104140358A (en) * 2014-07-28 2014-11-12 万华化学集团股份有限公司 Method for preparing trimethylolpropane through hydrogenation
CN104892364A (en) * 2015-06-02 2015-09-09 万华化学集团股份有限公司 Method for preparing trimethylolpropane by adopting hydrogenation method
CN110121486A (en) * 2017-10-23 2019-08-13 Lg化学株式会社 The preparation method of trimethylolpropane
EP3539941A1 (en) * 2017-10-23 2019-09-18 LG Chem, Ltd. Method for preparing trimethylolpropane
CN108772073A (en) * 2018-05-21 2018-11-09 河南省化工研究所有限责任公司 A kind of hydrogenation catalyst and its preparation method and application that trimethylolpropane preparation process uses
CN110075857A (en) * 2019-05-09 2019-08-02 万华化学集团股份有限公司 A kind of dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method thereof

Also Published As

Publication number Publication date
CN111715238A (en) 2020-09-29

Similar Documents

Publication Publication Date Title
JP7019813B2 (en) Catalyst for producing α-phenylethanol by hydrogenation of acetophenone, its production method and application
CN110075857B (en) Dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method thereof
EP2650048A2 (en) Non-chrome catalysts for Cu/Cr catalyst applications
CN111715238B (en) Hydrogenation catalyst, preparation method and application thereof
CN108025292B (en) Improved copper-containing multi-metal catalyst and method for preparing bio-based 1, 2-propylene glycol using the same
CN101347737B (en) Selective hydrogenation catalyst of aromatic aldehydes for refinement of terephthalic acid
CN111233626A (en) Method for preparing benzhydryl alcohol by hydrogenation of benzophenone
EP1000658A2 (en) A copper-containing catalyst, a process for the preparation and use thereof
CN109529870B (en) Acetophenone hydrogenation catalyst and preparation method thereof
CN102432565A (en) Method for preparing 2-hydroxyethylpiperazine
CN112517059B (en) Dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method thereof
CN112010802B (en) Continuous preparation method of 3-methylpyridine
CN114797882A (en) Catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation and preparation method and application thereof
CN103331160B (en) Preparation method of high-dispersion copper-based catalyst based on non-precious metal
CN104399474A (en) Catalyst for synthesizing methoxy acetone through alcohol dehydrogenization, preparation method and application of catalyst
WO2023134779A1 (en) Hydrogenation catalyst and preparation method therefor, and method for preparing isohexanediol and methyl isobutyl carbinol
CN114192162A (en) Dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method and application thereof
CN113101928B (en) Catalyst for preparing 1, 4-butenediol from 1, 4-butynediol and preparation method and application thereof
CN115121270A (en) Catalyst for synthesizing 2-ethylhexanal by selective hydrogenation and application method thereof
CN112264026A (en) Preparation method of high-activity high-selectivity methanol synthesis catalyst
CN114073990A (en) Preparation method of copper-based hydrogenation catalyst without roasting
CN113731442B (en) Catalyst for dimethyl maleate hydrogenation reaction and preparation method and application thereof
CN1226089C (en) Catalyst for preparing 2-ethylhexanol by gas-sphase hydrogenation of octylene aldehyde and its preparing process
CN1669651A (en) Catalyst for preparing gamma-butyrolactone by normal pressure gas phase hydrogenation of maleic-anhydride and preparation process thereof
EP0909214A1 (en) Catalyst for dehydrogenation of cyclohexanol, process for the preparation of said catalyst and use thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant