CN111068668A - Bimetallic catalyst and method for preparing tertiary alcohol structure-containing carbonyl compound by using bimetallic catalyst - Google Patents

Bimetallic catalyst and method for preparing tertiary alcohol structure-containing carbonyl compound by using bimetallic catalyst Download PDF

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CN111068668A
CN111068668A CN201911380264.3A CN201911380264A CN111068668A CN 111068668 A CN111068668 A CN 111068668A CN 201911380264 A CN201911380264 A CN 201911380264A CN 111068668 A CN111068668 A CN 111068668A
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catalyst
tertiary alcohol
palladium
bimetallic catalyst
alcohol structure
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CN111068668B (en
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吴昊
冯传密
王聪
刘新伟
杨克俭
王元平
霍瑜姝
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China Tianchen Engineering Corp
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
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    • 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
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    • 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
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract

The invention relates to a bimetallic catalyst and application thereof. The bimetallic catalyst consists of metal palladium and an active auxiliary agent. The catalyst can be used for preparing carbonyl compounds containing tertiary alcohol structures. The preparation process is that the bimetallic catalyst is used for catalyzing the oxidative dehydrogenation reaction of alcohol containing tertiary alcohol structure in oxygen-containing atmosphere. The bimetallic catalyst disclosed by the invention is mild in preparation condition, and the problems of complex preparation process, harsh conditions, pollution in the preparation process and the like of the traditional catalyst are solved. The addition amounts of the metal palladium and the active additive are small, but the catalytic activity is high, the catalytic life is over 2000h, the oxidative dehydrogenation selectivity is stabilized at 98.5%, the conversion rate is 96.6%, and the yield is 95.1%. Compared with the prior art, the method for preparing the tertiary alcohol structure-containing carbonyl compound by using the bimetallic catalyst has the advantages of milder reaction conditions and is particularly suitable for preparing the tertiary alcohol structure-containing carbonyl compound sensitive to high temperature.

Description

Bimetallic catalyst and method for preparing tertiary alcohol structure-containing carbonyl compound by using bimetallic catalyst
Technical Field
The invention relates to the field of fine chemical synthesis, in particular to a bimetallic catalyst and a method for preparing a carbonyl compound containing a tertiary alcohol structure by using the bimetallic catalyst.
Background
A widely used method in industry for preparing aldehydes or ketones is to catalyze oxidative dehydrogenation of corresponding primary or secondary alcohols. For example, formaldehyde or acetaldehyde is prepared in industry, methanol or ethanol vapor is mixed with air, and the mixture is passed through a silver wire mesh or a fluffy crystallized silver catalyst at the temperature of 400-600 ℃. The preparation of the caprolactam intermediate cyclohexanone is obtained by oxidative dehydrogenation of cyclohexanol at the temperature of 200-400 ℃ under a copper catalyst. US4165342 discloses the preparation of unsaturated carbonyl compounds in a tubular reactor by mixing unsaturated alcohol vapor with air at 320-650 c through silver and copper wire meshes of different thicknesses. The above-disclosed techniques all provide higher yields of carbonyl compounds, but such processes have difficulty achieving desirable results for the oxidative dehydrogenation of primary/secondary alcohols having tertiary alcohol structural characteristics. Because the temperature required for oxidative dehydrogenation of primary alcohol or secondary alcohol containing tertiary alcohol structure is usually above 200 ℃, the tertiary alcohol group dehydration reaction is very easy to occur under the condition, and some of such reactants and products thereof sensitive to acid, alkali and high temperature also undergo side reactions such as decomposition, polymerization and the like at high temperature, so that the selectivity and yield of the reaction are reduced.
Patent US3940446 describes that copper oxide is used as a catalyst, and a primary alcohol raw material with a tertiary alcohol structure is fed semi-continuously after high-temperature vaporization, wherein the reaction temperature is 200-350 ℃, and the vacuum degree of a reaction system is 12-20 kPa. In order to improve the reaction selectivity, a large amount of high boiling point solvent with normal pressure boiling point of 450-550 ℃ is added into the reaction system, and finally, the conversion rate of 55.6 percent and the yield of 88.5 percent are obtained. Wherein, the catalyst can be used only 16 times. The method belongs to semi-continuous operation, the product can not be removed in time, which causes the decomposition or polymerization of the heat-sensitive raw material and the product thereof at high temperature, the generated high polymer is easy to be enriched in a reaction system, and the activity of the catalyst is inhibited or poisoned, which causes the rapid reduction of the service life of the catalyst. In addition, in order to prevent the decomposition of sensitive reactants and products, a large amount of high-boiling-point solvent is added in the reaction process and vacuum operation is adopted, so that the complexity of post-treatment is greatly increased, and higher energy consumption is generated.
Patent CN108892607A discloses that hydroxyl citronellol is vaporized by using CuO/ZnO/NiO/alkali metal oxide loaded by zeolite as a catalyst and then continuously enters a fixed bed reactor for oxidative dehydrogenation at the temperature of 150 ℃ and 220 ℃ and the vacuum degree of a reaction system of 5-20kPa to obtain the unequal conversion rate of 15-97% and the selectivity of 86-99%. The catalyst adopted by the method is complex to prepare and has large filling amount.
Disclosure of Invention
In view of the above, the present invention aims to provide a bimetallic catalyst and a preparation method thereof, wherein the bimetallic catalyst is used for preparing carbonyl compounds containing tertiary alcohol structures; so as to overcome the problems of short service life and easy deactivation of the catalyst in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the bimetallic catalyst is a supported bimetallic catalyst, and the active component of the catalyst is metal palladium; the active auxiliary agent is at least one of gold, platinum, iridium, rhodium, ruthenium and osmium, preferably gold or platinum; the carrier of the supported bimetallic catalyst is selected from gamma-alumina, activated carbon, silica, calcium carbonate, an all-silicon molecular sieve, a titanium-silicon molecular sieve TS-1, a ZSM-5 molecular sieve, hydrotalcite and kaolin, and preferably gamma-alumina and silica. The weight ratio of the metal palladium to the carrier is (0.001-0.05): 1, preferably in the ratio of (0.003-0.03): 1; the weight ratio of the metal auxiliary agent to the metal palladium is (0.001-1): 1, preferably in a ratio of (0.05-0.1): 1.
the preparation method of the bimetallic catalyst comprises the following specific steps:
(1) the solution or suspension containing metallic palladium is dissolved in purified water in proportion and heated to 30-100 ℃, preferably to 40-80 ℃. The metal palladium salt is selected from soluble palladium salts such as palladium chloride, palladium nitrate, palladium sulfate and the like or complexes thereof.
(2) Adding the catalyst carrier into the solution or suspension obtained in the step (1) for soaking and adsorbing for 0.5-24 hours, preferably 1-3 hours.
(3) Washing the catalyst carrier adsorbed with the palladium compound in the step (2) for 3 times by using purified water, and then burning at the temperature of 100-500 ℃, wherein the heat treatment time is 0.5-5 hours, preferably 1-3 hours; further, the burning temperature is preferably 150-.
(4) Dissolving the solution or suspension containing metal adjuvant in purified water at a certain proportion, and heating the resultant water solution to 30-100 deg.C, preferably 40-80 deg.C. The metal auxiliary agent is selected from corresponding soluble salts or complexes thereof.
(5) Adding the burned carrier obtained in the step (3) into the solution obtained in the step (4) for soaking and adsorbing for 0.5-24 hours, preferably for 1-3 hours.
(6) Washing the carrier which is obtained in the step (5) and is adsorbed with palladium and a metal additive by using purified water for 3 times, and then burning at the temperature of 100-500 ℃, wherein the burning time is 0.5-5 hours, preferably 1-3 hours; further, the burning temperature is preferably 150-.
(7) And (4) carrying out reduction reaction on the catalyst obtained in the step (6) in a hydrogen atmosphere, wherein both palladium and a metal auxiliary agent exist in the form of a metal simple substance. The reduction temperature is 30-300 ℃, preferably 150-250 ℃, more preferably 180-220 ℃; the reduction time is from 0.5 to 24 hours, preferably from 1 to 3 hours.
The invention also aims to provide a method for preparing a carbonyl compound containing a tertiary alcohol structure by using the bimetallic catalyst, which overcomes the problems of high reaction temperature, addition of a large amount of high-boiling-point solvent in the reaction process, low reaction selectivity and yield and large catalyst filling amount in the prior art for preparing the carbonyl compound containing the tertiary alcohol structure.
The specific preparation process comprises the following steps: the bimetallic catalyst is used for catalyzing the oxidative dehydrogenation reaction of alcohol containing a tertiary alcohol structure in oxygen-containing atmosphere to prepare a corresponding carbonyl compound containing the tertiary alcohol structure. The structural general formula of the alcohol containing the tertiary alcohol structure is shown as a formula I, and the structural general formula of the carbonyl compound containing the tertiary alcohol structure is shown as a formula II.
Figure RE-GDA0002406353870000041
Figure RE-GDA0002406353870000042
Wherein R is1And R2Are respectively selected from C1-C18Alkyl, optionally substituted C5-C18Cycloalkyl or optionally substituted C6-C18Aryl, wherein said C5-C18Cycloalkyl and C6-C18The ring atoms of the aryl group may be substituted with a heteroatom selected from N, O and S. R3、R4And R5Are respectively selected from hydrogen and C1-C18Alkyl, optionally substituted C5-C18Cycloalkyl or optionally substituted C6-C18Aryl, wherein said C5-C18Cycloalkyl and C6-C18The ring atoms of the aryl group may be substituted with a heteroatom selected from N, O and S. And n is an integer of 0-20.
The alcohol containing tertiary alcohol structure shown in the general formula I comprises 3, 3-diphenyl-3-hydroxy propanol, 3-diphenyl-3-hydroxy-2-methyl propanol, 2-methyl-2-hydroxy-propanol, 2-hydroxy-1, 2-dimethyl propanol, 4-diphenyl-4-hydroxy butanol, 3-methyl-3-hydroxy butanol, 3-hydroxy-1, 3-dimethyl butanol, 4-hydroxy-4-methyl-pentanol, 6-hydroxy-3, 5, 6-trimethyl heptanol, 6-hydroxy-1, 3,5, 6-tetramethyl heptanol, 7-hydroxy-3, 6-7-trimethyl octanol, 7-hydroxy-3, 7-dimethyloctanol. As a typical example, the alcohol having a tertiary alcohol structure may be any one of 6-hydroxy-3, 5, 6-trimethylheptanol, 6-hydroxy-1, 3,5, 6-tetramethylheptanol, 7-hydroxy-3, 6-7-trimethyloctanol, and 7-hydroxy-3, 7-dimethyloctanol is particularly preferable.
The specific preparation method of the carbonyl compound containing the tertiary alcohol structure comprises the following steps: and (3) enabling the alcohol containing the tertiary alcohol structure to pass through a catalyst bed layer to perform oxidative dehydrogenation. Cooling and separating the reaction product to obtain the corresponding carbonyl compound containing the tertiary alcohol structure.
The oxidative dehydrogenation can be carried out under normal pressure, reduced pressure or increased pressure, and the reaction pressure is usually 0.01 to 5MPa, preferably 0.1 to 5MPa, particularly preferably 0.1 to 2 MPa.
The oxidative dehydrogenation is carried out at a temperature in the range from 50 to 200 deg.C, preferably from 60 to 180 deg.C, particularly preferably from 80 to 150 deg.C.
The starting material for the oxidative dehydrogenation of the alcohol of the general formula I can be fed in the liquid phase or in the gas phase. For alcohols of the formula I which boil above 200 ℃ at normal pressure or are unstable at elevated temperatures, preference is given to using the liquid-phase feed; for alcohols of the formula I which have a boiling point below 200 ℃ at normal pressure or are relatively stable at elevated temperatures, preference is given to using a gas-phase feed. When gas phase feeding is adopted, the alcohol of the general formula I can be preheated and vaporized by adopting a heater in any form, and then mixed with an oxidant to enter the oxidative dehydrogenation reactor.
The oxidant of the oxidative dehydrogenation reaction is oxygen-containing gas, and air is the best. The oxygen content of the oxygen-containing gas is 5 to 100 vol%, preferably 9 to 25 vol%.
The oxidant may be injected before the oxidative dehydrogenation reaction, in a single injection at the beginning of the reaction, repeatedly during the reaction, or continuously throughout the reaction, with continuous injection of the oxidant throughout the reaction being preferred. The flow rate of the oxidant is 1-100 L.h-1V (100g of the alcohol of the formula I), preferably from 2 to 80 l.h-1/(100g of an alcohol of the formula I)) More preferably 5 to 50 L.h-1/(100g of alcohol of the formula I).
The oxidative dehydrogenation reaction can be carried out using a batch process or a continuous process, and is preferably carried out as a continuous process. When the continuous method is used for production, the mass space velocity of the alcohol with the general formula I is 1-50h-1Preferably 2 to 30h-1More preferably 5-20 h-1。
The oxidative dehydrogenation reaction can be carried out in the presence or absence of an added solvent, preferably without the addition of an external solvent. When carried out in the presence of added solvent, solvents which are inert under the conditions of the oxidative dehydrogenation reaction are preferred.
In order to further improve the stability of certain heat-sensitive alcohols of the general formula I or aldehydes of the general formula II under the oxidative dehydrogenation reaction conditions, reduce side reactions such as thermal decomposition, polymerization, cyclization of raw materials and products, and improve the reaction selectivity and yield, stabilizers such as hydroquinone and 2, 6-di-tert-butyl-p-methylphenol are preferably added. The amount of the stabilizer added is 0.01 to 1%, preferably 0.05 to 0.5% by weight of the alcohol of the formula I.
For liquid phase feeds of alcohols of formula I, the oxidative dehydrogenation reactor may be selected from bubble-packed reactors, trickle-bed reactors. For gas phase feeds of alcohols of formula I, the oxidative dehydrogenation reactor may be selected from fixed bed reactors, stirred tank reactors. The oxidative dehydrogenation reaction is preferably carried out in 2 to 5 reactors, which may be connected in series.
As an example of an apparatus for the oxidative dehydrogenation, the components of the oxidative dehydrogenation can be introduced into the reactor cocurrently in a bubble-packed reactor, preferably on the same side of the reactor, i.e.at the bottom of the reactor, the alcohol of formula I and the oxygen-containing gas mixture in liquid phase being introduced into the reactor. Or the components of said oxidative dehydrogenation reaction are introduced counter-currently into the reactor, preferably on the opposite side of the reactor, i.e. at the bottom of the reactor, the alcohol of formula I in liquid phase is introduced into the reactor, the oxygen-containing gas mixture being introduced at the top of the reactor; or the alcohol of the formula I in liquid phase is introduced into the reactor at the top and the oxygen-containing gas mixture is introduced at the bottom.
As an example of an oxidative dehydrogenation reactor, the components of the oxidative dehydrogenation reaction can be introduced cocurrently into the trickle bed reactor in a trickle bed reactor, preferably at the same side of the reactor, i.e. at the top of the reactor, the alcohol of the formula I and the oxygen-containing gas mixture in liquid phase are introduced into the reactor.
As an example of an oxidative dehydrogenation reactor, the alcohol vapor of the formula I is introduced into the reactor cocurrently with the oxygen-containing gas mixture in a fixed-bed reactor, preferably on the same side of the reactor, i.e.at the top or bottom of the reactor.
As an example of an oxidative dehydrogenation reactor, a continuous stirred tank reactor is used, into which a liquid phase mixture of the alcohol of the formula I and an excess of oxygen-containing gas is continuously fed, after which the offgas is continuously discharged and the liquid reaction product is continuously withdrawn via a filter in order to ensure that the catalyst remains in the reactor at all times.
Furthermore, the crude product of the carbonyl compound of the general formula II obtained in the oxidative dehydrogenation is subjected to purification measures, including rectification, chromatography or integration measures. The rectification apparatus for the purification comprises optionally equipped rectification columns, bubble columns, plate columns or evaporators, such as thin-film evaporators, falling-film evaporators, forced circulation evaporators, wiped-film evaporators and combinations thereof.
Compared with the prior art, the bimetallic catalyst and the method for preparing the carbonyl compound containing the tertiary alcohol structure by using the bimetallic catalyst have the following advantages:
1. the bimetallic catalyst disclosed by the invention is mild in preparation condition, and the problems of complex preparation process, harsh conditions, pollution in the preparation process and the like of the traditional catalyst are solved. The addition amounts of the metal palladium and the active additive are small, but the catalytic activity is high, the long-period continuous stable operation can be realized, the catalytic life is over 2000h, the oxidative dehydrogenation selectivity is stable at 98.5%, the conversion rate is 96.6%, and the yield is 95.1%.
2. Compared with the prior art, the method for preparing the carbonyl compound containing the tertiary alcohol structure by using the bimetallic catalyst has the advantages of milder reaction conditions and is particularly suitable for preparing the carbonyl compound containing the tertiary alcohol structure sensitive to high temperature. The reaction temperature for preparing the carbonyl compound containing the tertiary alcohol structure is 50-200 ℃, the problems that the tertiary alcohol group is dehydrated and cyclized to generate the isopulegol under the high-temperature reaction condition of more than 200 ℃ in the prior art, the raw materials and the product are further oxidized, decomposed, polymerized and have side reactions and the like under the high temperature are solved, and the carbonyl compound containing the tertiary alcohol structure is continuously prepared with high selectivity and high yield.
3. According to the method for preparing the carbonyl compound containing the tertiary alcohol structure, no solvent is added in the reaction process, the energy consumption required by the reaction is low, three wastes are hardly discharged, and the method is particularly suitable for industrial production of bulk chemicals.
Drawings
FIG. 1 is a plot comparing the conversion and selectivity of the catalysts of example 1 and comparative example 1 for the oxidative dehydrogenation of 7-hydroxy-3, 7-dimethyloctanal.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
In the following examples, the catalyst was prepared as follows:
(1) the palladium chloride is added into the carrier according to the weight ratio of the metal palladium to the carrier of (0.001-0.05): 1 is dissolved in purified water and heated to 30-100 ℃.
(2) The catalyst carrier is soaked and adsorbed in palladium chloride solution for 0.5-24 hr.
(3) Washing the catalyst carrier adsorbed with palladium chloride with purified water for 3 times, and burning in air at 100-700 deg.c for 0.5-5 hr.
(4) According to the weight ratio of the active assistant metal to the metal palladium (0.001-1): 1, dissolving soluble salt containing the assistant metal in purified water, and heating the formed aqueous solution to 30-100 ℃.
(5) And (4) adding the catalyst carrier obtained in the step (3) into the assistant metal salt aqueous solution obtained in the step (4) for soaking and adsorbing for 0.5-24 hours.
(6) Washing the catalyst carrier obtained in the step (5) for 3 times by using purified water, and then burning for 0.5-24 hours at the temperature of 100-500 ℃.
(7) And (4) reducing the catalyst obtained in the step (6) in a hydrogen atmosphere, wherein the reduction temperature is 30-300 ℃, and the reduction time is 0.5-24 hours.
In the following examples, the analysis of each component in the reaction system by gas chromatography and the quantification by the calibration and normalization method were carried out with reference to the prior art, and the conversion of the reactant, the selectivity of the product and the yield were calculated on the basis thereof. The gas chromatographic conditions were as follows:
a chromatographic column: agilent DB-Wax (specification of 30m × 0.32mm × 0.25 mm); sample inlet temperature: 300 ℃; the split ratio is as follows: 30: 1; column flow rate: 1.5 mL/min; column temperature: 0.5min at 100 ℃; temperature rising procedure: raising the temperature to 300 ℃ at a speed of 15 ℃/min, and keeping the temperature for 8 min; detector temperature: 300 ℃, hydrogen flow: 35mL/min, air flow: 350 mL/min.
Example 1: preparation of Supported bimetallic catalyst A (0.5% Pd-0.025% Au/gamma-Al)2O3)
Dissolving 0.84g palladium chloride (palladium content is 0.50g) in 100mL purified water, heating to 80 deg.C, and collecting 100g gamma-Al2O3Adding carrier (10-30 mesh), soaking and adsorbing for 3 hr, washing with purified water for 3 times, and burning at 400 deg.C for 3 hr. Dissolving 0.038g of gold trichloride (with gold content of 0.025g) containing active assistant gold in 100mL of purified water, heating to 95 ℃, soaking and adsorbing the burned and cooled palladium-containing carrier again for 0.5 hour, washing with purified water for 3 times, and burning at 400 ℃ for 5 hours. The obtained catalyst carrier was reduced at 200 ℃ for 3 hours in a hydrogen atmosphere to obtain catalyst a.
Example 2: preparation of Supported bimetallic catalyst B (1% Pd-0.1% Au/SiO)2)
Dissolving 2.16g palladium nitrate (palladium content is 1.0g) in 100mL purified water, heating to 35 deg.C, and collecting 100g SiO2Adding carrier (100 mesh), soaking and adsorbing for 24 hr, washing with purified water for 3 times, and burning at 495 deg.C for 0.5 hr. Get and containDissolving 0.15g of gold trichloride (gold content is 0.1g) with active auxiliary agent gold in 100mL of purified water, heating to 40 ℃, and burning and cooling the SiO containing palladium2The carrier is soaked and adsorbed for 3 hours again, washed by purified water for 3 times and then burned for 3 hours at the temperature of 300 ℃. The obtained SiO2And reducing the carrier at 35 ℃ for 24 hours in a hydrogen atmosphere to obtain a catalyst B.
Example 3: preparation of Supported bimetallic catalyst C (0.1% Pd-0.05% Pt/activated carbon)
Dissolving 0.22g of palladium nitrate (the palladium content is 0.1g) in 100mL of purified water, heating to 60 ℃, adding 100g of activated carbon carrier (80-100 meshes) into the solution, soaking and adsorbing for 1 hour, washing for 3 times by using purified water, and then burning for 2 hours at 300 ℃. Dissolving platinum chloride (platinum content is 0.05g) 0.086g containing active auxiliary agent platinum in 100mL of purified water, heating to 80 ℃, soaking and adsorbing the burned and cooled palladium-containing carrier for 1 hour again, washing with purified water for 3 times, and burning for 1 hour at 450 ℃. The obtained catalyst carrier was reduced at 300 ℃ for 0.5 hour in a hydrogen atmosphere to obtain catalyst C.
Example 4: preparation of Supported bimetallic catalyst D (3% Pd-0.006% Ir/all-silica molecular sieves)
Dissolving 6.49g of palladium nitrate (the palladium content is 3g) in 100mL of purified water, heating to 95 ℃, adding 100g of all-silicon molecular sieve carrier (80-100 meshes) into the solution, soaking and adsorbing for 0.5 hour, washing for 3 times by using purified water, and then burning for 5 hours at 100 ℃. Dissolving 0.013g of chloroiridic acid (iridium content is 0.006g) containing active assistant metal iridium in 100mL of purified water, heating to 60 ℃, soaking and adsorbing the burned and cooled palladium-containing carrier again for 5 hours, washing with purified water for 3 times, and burning at 500 ℃ for 2 hours. The obtained catalyst carrier was reduced at 150 ℃ for 5 hours in a hydrogen atmosphere to obtain catalyst D.
Example 5: preparation of Supported bimetallic catalyst E (5% Pd-5% Rh/titanium silicalite TS-1)
Dissolving 9.5g of palladium sulfate (the palladium content is 5g) in 100mL of purified water, heating to 30 ℃, adding 100g of titanium silicalite TS-1 carrier (40-60 meshes) into the solution, soaking and adsorbing for 10 hours, washing for 3 times by using purified water, and then burning for 1 hour at 200 ℃. 10.16g of rhodium trichloride (the rhodium content is 5g) containing active assistant metal rhodium is dissolved in 100mL of purified water, the temperature is raised to 30 ℃, the burned and cooled palladium-containing carrier is soaked and adsorbed again for 24 hours, and the palladium-containing carrier is burned for 5 hours at the temperature of 110 ℃ after being washed for 3 times by the purified water. The obtained catalyst carrier was reduced at 250 ℃ for 10 hours in a hydrogen atmosphere to obtain catalyst E.
Example 6: preparation of Supported bimetallic catalyst F (0.8% Pd-0.064% Ru/ZSM-5 molecular sieves)
Dissolving 1.33g palladium chloride (palladium content is 0.80g) in 100mL purified water, heating to 70 deg.C, adding 100g ZSM-5 molecular sieve (80-100 mesh), soaking and adsorbing for 5 hr, washing with purified water for 3 times, and igniting at 350 deg.C for 2 hr. Dissolving 0.13g of ruthenium trichloride (the ruthenium content is 0.064g) containing active assistant metal ruthenium in 100mL of purified water, heating to 50 ℃, soaking and adsorbing the burned and cooled palladium-containing carrier for 2 hours again, washing with purified water for 3 times, and burning for 5 hours at 200 ℃. The obtained catalyst carrier was reduced at 220 ℃ for 2 hours in a hydrogen atmosphere to obtain a catalyst F.
Example 7: preparation of Supported bimetallic catalyst G (0.3% Pd-0.018% Os/hydrotalcite)
Dissolving 0.5g palladium chloride (palladium content is 0.30g) in 100mL of purified water, heating to 50 ℃, adding 100g hydrotalcite (80-100 meshes) into the solution, soaking and adsorbing for 8 hours, washing for 3 times by using purified water, and then burning for 5 hours at 250 ℃. 0.028g of osmium trichloride (the osmium content is 0.018g) containing the metal osmium as the active assistant is dissolved in 100mL of purified water, the temperature is raised to 75 ℃, the palladium-containing carrier after burning and cooling is soaked and adsorbed again for 8 hours, and the carrier is washed for 3 times by the purified water and burned for 1 hour at 350 ℃. The obtained catalyst carrier was reduced at 180 ℃ for 3 hours in a hydrogen atmosphere to obtain a catalyst G.
Example 8: preparation of Supported bimetallic catalyst H (0.015% Pd-0.045% Pt/Kaolin)
Dissolving 3.24g of palladium nitrate (the palladium content is 1.5g) in 100mL of purified water, heating to 40 ℃, adding 100g of kaolin carrier (80-100 meshes) into the solution, soaking and adsorbing for 12 hours, washing for 3 times by using purified water, and then burning for 3 hours at 350 ℃. Dissolving platinum chloride (platinum content is 0.045g) 0.078g containing active assistant metal platinum in 100mL of purified water, heating to 65 ℃, soaking and adsorbing the burned and cooled palladium-containing carrier for 4 hours again, washing with purified water for 3 times, and burning for 2 hours at 330 ℃. The obtained catalyst carrier was reduced at 240 ℃ for 0.5 hour in a hydrogen atmosphere to obtain catalyst H.
Example 9: liquid phase feeding preparation of 7-hydroxy-3, 7-dimethyl octanal
And respectively filling the catalysts A to H into a bubbling filling reactor provided with a heating and heat-preserving device, wherein the tube diameter of the reactor is 20mm, the tube diameter is 2000mm, and the filling height of the catalyst is 200 mm. Before the reaction, the reactor was purged three times with air. After the reaction, air was introduced from the bottom of the reactor under the control of a gas flow meter, the gas flow rate was controlled to 1 to 100L/h/(100g of raw material alcohol), and simultaneously, raw material 7-hydroxy-3, 7-dimethyloctanol, in which 0.01 to 0.1%/(100 g of raw material alcohol) 2, 6-di-t-butyl-p-methylphenol stabilizer was dissolved in advance, was fed from the bottom of the reactor by a plunger pump. The reaction temperature is controlled at 50-150 ℃, the system pressure is controlled at 0.01-5MPa, and the retention time is controlled by mass space velocity, namely, 1-50 g of raw material alcohol/g of catalytic active metal/h. The equipment is continuously operated for 100h, reaction liquid is extracted from the top of the reactor, and a crude product is obtained after multi-stage cooling. The results of the oxidative dehydrogenation reactions obtained after gas chromatography detection and quantification by calibrated normalization are shown in table 1.
TABLE 1 bimetallic catalyst for catalytic oxidative dehydrogenation of 7-hydroxy-3, 7-dimethyloctanal
Figure RE-GDA0002406353870000121
Figure RE-GDA0002406353870000131
Example 10: preparation of 2-methyl-2-hydroxypropanal by gas phase feeding
The catalyst A, B or C is filled into a fixed bed reactor equipped with a heating and heat-insulating device, the tube diameter of the reactor is 20mm,the pipe diameter is 2000mm, and the catalyst filling height is 200 mm. Before the reaction, the reactor was purged three times with air. After the reaction, air is introduced from the bottom of the reactor under the control of a gas flow meter, and the gas flow is controlled to be 20-30 L.h-1(100g of the starting alcohol), while the starting 2-methyl-2-hydroxy-propanol was pumped by means of a plunger pump into a preheater at a preheating temperature of 176 ℃ and 180 ℃ for vaporization, and then mixed with air and introduced into the fixed-bed reactor cocurrently from the top of the reactor. The reaction temperature is controlled at 180 ℃ and 200 ℃, the system pressure is controlled at 0.2-0.3MPa, and the retention time is controlled by mass space velocity, namely 10-20 g of raw material alcohol/g of catalytically active metal/h. The equipment is continuously operated for 100h, reaction liquid is extracted from the top of the reactor, and a crude product is obtained after multi-stage cooling. The results of the oxidative dehydrogenation reactions obtained after gas chromatography detection and quantification by calibrated normalization are shown in table 2.
TABLE 2 bimetallic catalyst for catalytic oxidative dehydrogenation to 2-methyl-2-hydroxypropanal
Figure RE-GDA0002406353870000141
Comparative example 1: verification of the synergistic catalytic action of the Supported bimetallic catalyst
1. Preparation of Supported monometallic catalyst I (0.5% Pd/. gamma. -Al)2O3)
No auxiliary metal is added, only metal palladium is added, and other preparation processes are the same as those of the example 1.
Dissolving 0.84g palladium chloride (palladium content is 0.50g) in 100mL purified water, heating to 80 deg.C, and collecting 100g gamma-Al2O3Adding carrier (10-30 mesh), soaking and adsorbing for 3 hr, washing with purified water for 3 times, and burning at 400 deg.C for 3 hr. And reducing the obtained catalyst carrier for 3 hours at 200 ℃ in a hydrogen atmosphere to obtain the catalyst I.
2. Preparation of Supported monometallic catalyst J (0.5% Au/. gamma. -Al)2O3)
No metal palladium is added, only the metal gold is added, and the other preparation processes are the same as those of the example 1.
0.77g of trisDissolving gold chloride (gold content 0.50g) in 100mL of purified water, heating to 80 deg.C, and collecting 100g of gamma-Al2O3Adding carrier (10-30 mesh), soaking and adsorbing for 3 hr, washing with purified water for 3 times, and burning at 400 deg.C for 3 hr. The obtained catalyst carrier is reduced for 3 hours at 200 ℃ in a hydrogen atmosphere to prepare a catalyst J.
The catalyst A, I, J is respectively filled into a bubbling filling reactor provided with a heating and heat-preserving device, the diameter of the reactor is 20mm, the diameter of the reactor is 2000mm, and the filling height of the catalyst is 200 mm. Before the reaction, the reactor was purged three times with air. After the reaction, air is introduced from the bottom of the reactor under the control of a gas flow meter, and the gas flow is controlled to be 20-30 L.h-1(100g of raw alcohol), while 7-hydroxy-3, 7-dimethyloctanol as a raw material, in which 1%/(100 g of raw alcohol) 2, 6-di-tert-butyl-p-methylphenol stabilizer was dissolved in advance, was fed from the bottom of the reactor by a plunger pump. The reaction temperature is controlled at 90-100 ℃, the system pressure is controlled at 0.2-0.3MPa, and the retention time is controlled by mass space velocity, namely 5g of raw material alcohol/g of catalytic active metal/h. The equipment is continuously operated, reaction liquid is extracted from the top of the reactor every 5 hours, and a crude product is obtained after multi-stage cooling. The results of the oxidative dehydrogenation reactions obtained after gas chromatography detection and quantification by the calibrated normalization method are shown in fig. 1.
As can be seen from FIG. 1, the supported single metal catalyst I (0.5% Pd/. gamma. -Al)2O3) And supported single metal catalyst J (0.5% Au/gamma-Al)2O3) Better conversion rate and selectivity can be obtained in the initial stage of oxidative dehydrogenation reaction, but as the reaction time is prolonged, the catalytic activity of the catalyst I is slowly reduced, and the catalytic activity of the catalyst J is rapidly reduced, so that the conversion rate and the selectivity of the reaction are seriously slipped, and the supported bimetallic catalyst A (0.5 percent of Pd-0.025 percent of Au/gamma-Al) in the example 12O3) But can maintain the catalytic activity for a long time, and the conversion rate and the selectivity of the oxidative dehydrogenation reaction slightly fluctuate under the condition of keeping a high level. The existence of the metal palladium and the active promoter such as gold or platinum in the catalyst is proved to have the synergistic catalytic action.
And (3) carrying out long-period operation for 2000h on the oxidative dehydrogenation reaction catalyzed by the catalyst A in the comparative example 1, extracting reaction liquid from the top of the reactor, and carrying out multi-stage cooling to obtain a crude product. After gas chromatography detection and quantification by a calibration normalization method, the result of the oxidative dehydrogenation reaction is obtained: the reaction conversion rate is stabilized at 96.6%, the selectivity is 98.5%, the yield is 95.1%, and the reaction is obviously superior to the results in the prior art.
Compared with the mechanism that the silver or copper catalyst oxidizes the raw material alcohol through the oxidation state and realizes catalytic circulation per se, the metal palladium has higher reaction activity due to the extra-nuclear electron arrangement characteristic of the atomic structure, obtains a Pd-alcoholate intermediate through oxidation addition with alcoholic hydroxyl, and then obtains a corresponding carbonyl compound and Pd after β -eliminationII-a hydrogen intermediate. PdIIPd is released by the action of the hydrogen intermediate and oxygen0And the catalytic circulation of Pd is realized. The co-promoter metal, gold or platinum, forms the core of the catalyst particle during calcination of the catalyst, while the palladium is distributed on the shell of the catalyst. Gold or platinum can be used as an electronic stabilizing modifier of palladium to further stabilize a palladium ion intermediate, reduce the reaction degree of the catalyst for absorbing alcohol, avoid the catalyst from being obviously inactivated and further prolong the service life of the catalyst. Meanwhile, the active auxiliary agents such as gold and platinum can improve the dispersion degree of palladium on the surface of catalyst particles, and effectively improve the selectivity of catalytic oxidative dehydrogenation of palladium (see example 1 and comparative example 1). The use of palladium in combination with other noble metals, based on the above synergistic catalytic action of palladium metal with a co-agent such as gold or platinum, allows the oxidative dehydrogenation reaction to be carried out at lower temperatures, in particular temperatures below 150 ℃ in the case of the preferred preparation of 7-hydroxy-3, 7-dimethyloctanal, which is very advantageous for product quality and suppression of unwanted side reactions. Meanwhile, the lower reaction temperature is matched with the electron stabilization modification effect of the assistant metal to react on the catalyst, so that the catalyst is prevented from being poisoned by-products generated at high temperature, generating coking and carbon deposition and the like, the service life of the catalyst is greatly prolonged, and the rapid inactivation is avoided.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. A bimetallic catalyst characterized by: the bimetallic catalyst is a supported bimetallic catalyst, and the active component of the catalyst is metal palladium; the active auxiliary agent of the catalyst is at least one of gold, platinum, iridium, rhodium, ruthenium and osmium; the carrier of the bimetallic catalyst is selected from gamma-Al2O3The composite material comprises activated carbon, silicon dioxide, calcium carbonate, an all-silicon molecular sieve, a titanium-silicon molecular sieve TS-1, a ZSM-5 molecular sieve, hydrotalcite and kaolin.
2. The bimetallic catalyst of claim 1, wherein: the weight ratio of the metal palladium to the carrier is (0.001-0.05): 1; the weight ratio of the metal auxiliary agent to the metal palladium is (0.001-1): 1.
3. preparing the bimetallic catalyst of claims 1 or 2, characterized in that: the preparation method comprises the following specific steps of,
(1) dissolving solution or suspension containing metal palladium in purified water in proportion, and heating to 30-100 ℃; the metal palladium salt is selected from soluble palladium salts such as palladium chloride, palladium nitrate, palladium sulfate and the like or complexes thereof;
(2) adding a catalyst carrier into the solution or suspension obtained in the step (1) for soaking and adsorbing for 0.5-24 hours;
(3) washing the catalyst carrier adsorbed with the palladium compound in the step (2) by using purified water, and then burning at the temperature of 100-500 ℃, wherein the burning time is 0.5-5 hours;
(4) dissolving a solution or suspension containing a metal auxiliary agent in purified water according to a proportion, and heating the formed water solution to 30-100 ℃;
(5) adding the burned carrier obtained in the step (3) into the solution obtained in the step (4) for soaking and adsorbing for 0.5-24 hours;
(6) washing the carrier which is obtained in the step (5) and is adsorbed with palladium and a metal auxiliary agent by using purified water, and then burning at the temperature of 100-500 ℃, wherein the burning time is 0.5-5 hours, preferably 1-3 hours;
(7) carrying out reduction reaction on the catalyst obtained in the step (6) in a hydrogen atmosphere, wherein the reduction temperature is 30-300 ℃; the reduction time is 0.5-24 hours.
4. A process for producing a carbonyl compound containing a tertiary alcohol structure using the bimetallic catalyst as claimed in claim 1 or 2, characterized in that: the carbonyl compound containing the tertiary alcohol structure takes corresponding alcohol containing the tertiary alcohol structure as a raw material, the structural general formula of the alcohol containing the tertiary alcohol structure is shown as a formula I, and the structural general formula of the corresponding carbonyl compound containing the tertiary alcohol structure is shown as a formula II;
Figure FDA0002342072900000021
wherein R is1And R2Are respectively selected from C1-C18Alkyl, optionally substituted C5-C18Cycloalkyl or optionally substituted C6-C18Aryl, wherein said C5-C18Cycloalkyl and C6-C18The ring atoms of the aryl group may be substituted with a heteroatom selected from N, O and S; r3、R4And R5Are respectively selected from hydrogen and C1-C18Alkyl, optionally substituted C5-C18Cycloalkyl or optionally substituted C6-C18Aryl, wherein said C5-C18Cycloalkyl and C6-C18The ring atoms of the aryl group may be substituted with a heteroatom selected from N, O and S; n is an integer of 0 to 20;
the specific preparation method of the carbonyl compound containing the tertiary alcohol structure comprises the following steps: the alcohol containing tertiary alcohol structure passes through a catalyst bed layer, and is subjected to oxidative dehydrogenation reaction under the action of an oxidant, and the reaction is carried out at the temperature of 50-200 ℃;
the oxidant of the oxidative dehydrogenation reaction is selected from oxygen-containing gases.
5. A process for the preparation of a carbonyl compound containing a tertiary alcohol structure as claimed in claim 4, characterized in that: the oxidant of the oxidative dehydrogenation reaction is air.
6. A process for the preparation of a carbonyl compound containing a tertiary alcohol structure as claimed in claim 4, characterized in that: adding a stabilizer into the alcohol containing tertiary alcohol structure in the raw material; the addition amount of the stabilizer is 0.01-1% of the weight of the alcohol containing the tertiary alcohol structure.
7. A process for the preparation of a carbonyl compound containing a tertiary alcohol structure as claimed in claim 4, characterized in that: continuously injecting the oxidant in the whole reaction process, wherein the flow rate of the oxidant is 1-100 L.h-1/(100g of alcohol of the formula I).
8. A process for the preparation of a carbonyl compound containing a tertiary alcohol structure as claimed in claim 4, characterized in that: the oxidative dehydrogenation reaction is carried out by adopting a continuous method, and the mass space velocity of the alcohol shown as the general formula I is 1-50h-1。
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