CN116730809A - Synthesis method of cyclododecanone - Google Patents

Synthesis method of cyclododecanone Download PDF

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Publication number
CN116730809A
CN116730809A CN202310698659.8A CN202310698659A CN116730809A CN 116730809 A CN116730809 A CN 116730809A CN 202310698659 A CN202310698659 A CN 202310698659A CN 116730809 A CN116730809 A CN 116730809A
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catalyst
cyclododecanone
siloxane
cyclododecanol
modified
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边新建
石达
崔亚宁
卢福广
周建强
李俊平
乔小飞
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a method for synthesizing cyclododecanone. The method takes cyclododecanol as a raw material and prepares cyclododecanone through catalytic dehydrogenation reaction, wherein a modified Cu-Zn catalyst is adopted for catalytic dehydrogenation, and the catalyst comprises a modifier containing pyrrolidine compound and siloxane. The catalyst can effectively prevent toxic and side effects of sulfur and chlorine elements on catalysis, has long service life, high activity and high cyclododecanone selectivity, and can be continuously used for more than 5000h, the cyclododecanol conversion rate is more than or equal to 98%, the cyclododecanone selectivity is more than or equal to 99%, and the selectivity of byproducts cyclododecene is less than 0.2%.

Description

Synthesis method of cyclododecanone
Technical Field
The invention belongs to the fields of catalyst preparation and organic synthesis, and particularly relates to a cyclododecanone synthesis method.
Background
Nylon 12 is mainly obtained by polymerizing nylon 12 monomer-dodecalactam or aminododecanoic acid. The preparation process of the nylon 12 monomer mainly comprises the following steps: the oxidation oximation method, the photonitrosation method, the stonia method, the cyclohexanone amine peroxide method and the like, wherein the oxidation oximation method is the most mature process and is the main method for producing nylon 12 monomers at present.
Cyclododecanone is a very important intermediate in the process of preparing nylon 12 monomer by oxidation oximation. In addition, cyclododecanone belongs to a large ring structure, so that the cyclododecanone has the reaction characteristic of common cyclododecanone and also has special reactivity which is not possessed by small rings and middle rings. Meanwhile, as a petrochemical product which is inexpensive and readily available, it is also a synthetic precursor of many macrocyclic compounds, such as pesticides, macrolide fragrances of fragrances, and musk-like compounds. In addition, it can participate in a number of synthetic reactions, for the synthesis of some compounds of specific structure and for the synthesis of photoactive compounds, many derivatives such as cyclododecanone have received increasing attention for their biological activity.
Cyclododecanone is mainly prepared from Cyclododecatriene (CDT) serving as a raw material, aluminum alkyl and titanium tetrachloride are used as catalysts in the CDT synthesis process, and chloride ions can enter a dehydrogenation reaction system along with CDT products and are enriched on the dehydrogenation catalysts to influence the service life of the catalysts. Meanwhile, in the upstream process of producing cyclododecanol, adsorbents such as sulfonic acid resin and the like can be used, sulfur element in the sulfonic acid resin can be enriched on dehydrogenation catalysis, so that catalyst poisoning is caused, further the activity of the catalyst is influenced, and how to design a catalyst capable of resisting sulfur and chlorine is a difficulty in designing the catalyst.
Copper-based catalysts are generally adopted in industrial secondary alcohol dehydrogenation, and patent CN00133278 reports that Cu-Zn-Al catalysts are adopted in preparation of cyclohexanone by cyclohexanol dehydrogenation, and a small amount of rare earth metal auxiliary agent is additionally added in the catalysts; patent CN150990C reports that cyclohexanol dehydrogenation for cyclohexanone preparation uses a Cu-Zn-Al catalyst with metal oxide added; desoxhlet patent CN110234625A reports that the synthesis process of cyclododecanone is shown in the following formula, cyclododecane is prepared by hydrogenation of cyclododecatriene, cyclododecanol/ketone is prepared by oxidation of cyclododecanol, cyclododecanone is prepared by dehydrogenation of cyclododecanol, and the type of catalyst and the reaction selectivity used for preparing cyclododecanone by dehydrogenation of cyclododecanol are not specifically described.
Patent CN103055880A discloses a catalyst for preparing ketone by cyclododecanol dehydrogenation and a preparation method thereof, the catalyst comprises a main catalyst and an auxiliary agent, wherein the main catalyst is a copper-zinc mixed oxide taking copper element as a main active ingredient and zinc element as a carrier, and the mol ratio of the copper element to the zinc element is 1:3-3:1; the auxiliary agent is a transition metal element with an inactive center and is selected from one of vanadium, chromium, manganese, zirconium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium or yttrium, the catalyst is only evaluated on a laboratory miniature reaction device, and the cyclododecanol conversion rate is only 95%, the cyclododecanone selectivity is only 98% under the conditions that the temperature is 230 ℃ and the space velocity (WHSV) is 0.4, and a large number of side reactions still occur.
Patent CN113181924a reports a high strength dehydrogenation catalyst, its preparation method and application, the catalyst comprises an active component, a reinforcing auxiliary agent and an alkaline auxiliary agent, wherein the active component comprises CuO, znO, zrO 2 And CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the The reinforcing auxiliary agent is silicon dioxide, the content of CuO in the catalyst is 20-50%, the content of ZnO is 25-45%, and the content of ZrO in the catalyst is 2 The content is 10-30%, ceO 2 The content is 0.2-0.5%; the silicon dioxide content is 5% -15%; the content of the alkaline auxiliary agent is 0.4-0.8%. The catalyst is used for dehydrogenation reaction, and the cyclododecanol conversion rate is up to 95%.
In conclusion, the existing method for preparing cyclododecanone still has the problems of low cyclododecanol conversion rate, poor cyclododecanone selectivity, low catalyst life caused by no sulfur resistance and chlorine resistance of the catalyst, and the like.
Disclosure of Invention
The invention aims to provide a method for synthesizing cyclododecanone, which adopts a modified Cu-Zn catalyst, uses cyclododecanol as a raw material and prepares cyclododecanone through dehydrogenation reaction. By adopting the method, the catalyst can be continuously used for more than 5000 hours, the cyclododecanol conversion rate is more than or equal to 98 percent, the cyclododecanone selectivity is more than or equal to 99 percent, and the selectivity of the byproduct cyclododecene is less than 0.2 percent.
In order to achieve the technical effects, the invention adopts the following technical scheme:
a cyclododecanone synthesis method uses cyclododecanol as a raw material, and cyclododecanone is prepared through catalytic dehydrogenation reaction; wherein, the catalytic dehydrogenation adopts a modified Cu-Zn catalyst, which comprises a modifier containing pyrrolidine compound and siloxane.
In the method, a modified Cu-Zn catalyst is filled into a reactor, cyclododecanol is melted and fed, and dehydrogenation reaction is carried out, so that cyclododecanone is prepared.
In the invention, the carrier of the catalyst is a metal and/or nonmetal oxide, preferably one or more of zirconia, magnesia, silica, alumina, lanthanum oxide, titania and thoria, more preferably alumina and/or silica; preferably, the mass ratio of Cu, zn, carrier, pyrrolidine compound and siloxane in the catalyst is 1: (0.1-4): (0.1-10): (0.001-0.1): (0.0001-0.05), preferably 1: (0.3-3): (0.5-5): (0.003-0.06): (0.0003-0.03).
The catalyst disclosed by the invention adopts a combination containing pyrrolidine compound and siloxane as a modifier of the catalyst, the pyrrolidine compound has alkalinity, dehydration under cyclododecanoate condition is prevented to produce cyclododecene, the selectivity of dehydrogenation reaction is improved, nitrogen atoms containing the pyrrolidine compound can coordinate with Cu and Zn metal atoms of a main catalyst, sintering and coalescence of Cu and Zn atoms in the catalyst preparation process are prevented, the specific surface area and activity of the catalyst are improved, meanwhile, the siloxane is introduced into the catalyst, the dispersibility of Cu and Zn in the catalyst can be improved, the specific surface area of the catalyst is improved, the catalytic activity is further improved, the nitrogen atoms containing the pyrrolidine compound and the oxygen atoms of the siloxane can coordinate with Cu and Zn in a coordinated manner, the dispersibility of Cu and Zn is further improved, and sintering of Cu and Zn in a long-time use process is prevented, so that the specific surface area of the catalyst is larger, the activity is higher, and the service life is longer.
In the invention, the preparation method of the catalyst comprises the following steps:
s1: dissolving copper salt, zinc salt and precursor of carrier in water;
s2: adding modifier, stirring, mixing, precipitating metal ions and carrier in the aqueous solution;
s3: filtering the precipitate, drying, roasting and molding to obtain the modified Cu-Zn catalyst.
In the present invention, the copper salt of S1 is a water-soluble copper salt, preferably one or more of nitrate, hydrochloride, sulfate, and phosphate of copper, and more preferably copper nitrate.
In the present invention, the zinc salt in S1 is a water-soluble zinc salt, preferably one or more of nitrate, hydrochloride, sulfate and phosphate of zinc, and more preferably zinc nitrate.
In the invention, the precursor of the carrier in the step S1 is one or more of soluble metal salt, nonmetal salt, metal ester, nonmetal ester, metal oxide and nonmetal oxide, preferably one or more of aluminum nitrate, aluminum hydrochloride, aluminum sulfate, aluminum phosphate, silicate and silica sol, more preferably one or more of aluminum nitrate, tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate.
In the invention, the mass ratio of the copper salt to the water of S1 is 1 (10-50), preferably 1 (20-30).
In the present invention, the pyrrolidine-containing compound in the modifier of S2 is a pyrrolidine substituted with hydrogen on N or C, preferably one or more of N-methylpyrrolidine, 2- (aminomethyl) -1-ethylpyrrolidine, N-Boc-pyrrolidine, 3-aminopyrrolidine, (2S, 4R) -Fmoc-4-tert-butoxycarbonylaminopyrrolidine-2-carboxylic acid and (R) -1-Boc-3-aminopyrrolidine, more preferably N-methylpyrrolidine and/or 3-aminopyrrolidine.
In the present invention, the siloxane in the modifier of S2 is a siloxane containing 2 to 5 silicon, preferably one or more of hexamethyldisiloxane, decamethyl cyclopentasiloxane, tetramethyl diphenyltrisiloxane, ethylsiloxane, propylsiloxane, cyclobutane siloxane, methacryloxypropyl cyclotetrasiloxane, trifluoropropyl methyltrisiloxane, trifluoropropyl cyclotrisiloxane, and more preferably hexamethyldisiloxane and/or decamethyl cyclopentasiloxane.
In the present invention, S2 is added to a precipitant, preferably to an alkali solution, more preferably to one or more of sodium oxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide, cesium hydroxide, ammonium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and an aqueous solution of ammonia.
In the present invention, the firing temperature of S3 is 250 to 600 ℃, preferably 300 to 400 ℃.
In the present invention, the reaction temperature of the process is 170 to 280 ℃, preferably 200 to 250 ℃, and the reaction mass space velocity in terms of cyclododecanol is 0.1 to 2h -1 。
It is another object of the present invention to provide cyclododecanone.
Cyclododecanone is prepared by the method.
It is yet another object of the present invention to provide a modified Cu-Zn catalyst for catalytic dehydrogenation.
A modified Cu-Zn catalyst for catalytic dehydrogenation is prepared by the method.
Compared with the prior art, the invention has the following positive effects:
by adopting the method, the catalyst can be continuously used for more than 5000 hours, the cyclododecanol conversion rate is more than or equal to 98 percent, the cyclododecanone selectivity is more than or equal to 99 percent, and the selectivity of the byproduct cyclododecene is less than 0.2 percent.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention as claimed.
(1) Analysis of reaction conversion
The cyclododecanol conversion and cyclododecanone selectivity were analyzed by gas chromatography.
Instrument model: island GC2010; chromatographic column: DB-5 (30X 0.32X 0.25); column temperature: programmed heating (60 ℃ for 5min, then heating to 120 ℃ at a heating rate of 5 ℃/min, heating to 300 ℃ at a heating rate of 20 ℃/min, and holding for 5 min); sample inlet temperature: 250 ℃; FID temperature: 300 ℃; n (N) 2 Flow rate: 1mL/min; h 2 Flow rate: 40mL/min; spacer purge (N) 2 ) Flow rate: 3mL/min; carrier gas (N) 2 ) Flow rate: 1mL/min; split sample injection, split ratio: 50; feeding inSample amount: 0.03. Mu.L.
(2) Catalyst analysis
The modified Cu-Zn catalyst was analyzed using an instrument of U.S. MicroActive for ASAP 2460, performing standard GB/T19587-2004.
The main raw material manufacturers are as follows:
the main device information is as follows:
example 1
Preparation of modified Cu-Zn catalyst-A:
s1: 20g of copper nitrate and 5.88g of zinc nitrate were dissolved in 200g of deionized water with stirring and mixed with 11.28g of silica sol having a 30wt% silica content;
s2: adding 0.02g N-methylpyrrolidine and 0.002g hexamethyldisiloxane into the reaction solution, stirring and mixing uniformly; adding 10wt% sodium hydroxide aqueous solution into the mixed solution while stirring, and adjusting the pH to 11;
s3: filtering out precipitate, drying the precipitate in a 110 ℃ oven for 4 hours, then transferring the precipitate into a 250 ℃ muffle furnace for roasting for 6 hours, extruding strips and forming to obtain the modified Cu-Zn-Si catalyst-A.
Characterization of the catalyst, catalyst specific surface area 156m 2 /g。
Preparation of cyclododecanone:
loading the modified Cu-Zn catalyst-A into a fixed bed, melting and feeding cyclododecanol at 90 ℃, setting the reaction temperature to 170 ℃, the pressure to 0.1MPa (G), and the mass space velocity of cyclododecanol to 0.1h -1 After the device is stable for 6000 hours, sampling analysis and cyclododecanol conversion are carried outThe conversion rate is 99.17%, the cyclododecanone selectivity is 99.74%, and the selectivity of the byproduct cyclododecene is 0.09%.
Example 2
Preparation of modified Cu-Zn catalyst-B:
s1: 20g of copper nitrate and 58.82g of zinc nitrate are dissolved in 1000g of deionized water with stirring and mixed with 117g of tetraethyl silicate;
s2: adding 0.4g of 3-aminopyrrolidine and 0.2g of decamethyl cyclopentasiloxane into the reaction solution, and stirring and mixing uniformly; adding 5wt% sodium hydroxide aqueous solution into the mixed solution while stirring, and adjusting the pH to 10;
s3: filtering out precipitate, drying the precipitate in a 190 ℃ oven for 10 hours, then transferring the precipitate into a 600 ℃ muffle furnace for roasting for 1 hour, and tabletting and forming to obtain the modified Cu-Zn catalyst-B.
Characterization of the catalyst, the specific surface area of the catalyst was 151m 2 /g。
Preparation of cyclododecanone:
loading the modified Cu-Zn catalyst-B into a fixed bed, melting and feeding cyclododecanol at 95 ℃, setting the reaction temperature to 280 ℃, setting the pressure and the normal pressure, and setting the mass space velocity of cyclododecanol to 2h -1 After the device is stable for 5500 hours, sampling analysis shows that the cyclododecanol conversion rate is 99.24%, the cyclododecanone selectivity is 99.79%, and the byproduct cyclododecene selectivity is 0.10%.
Example 3
Preparation of modified Cu-Zn catalyst-C:
s1: 20g of copper nitrate, 19.61g of zinc nitrate and 28g of aluminum nitrate are stirred and dissolved in 600g of deionized water;
s2: adding 0.1g of 2- (aminomethyl) -1-ethyl pyrrolidine and 0.06g of trifluoropropyl methyl cyclotrisiloxane into the reaction solution, and stirring and mixing uniformly; adding 25wt% ammonia water into the mixed solution while stirring, and adjusting the pH to 9;
s3: filtering out precipitate, drying the precipitate in a baking oven at 150 ℃ for 8 hours, then transferring the dried precipitate into a muffle furnace at 300 ℃ for roasting for 10 hours, extruding strips and forming to obtain the modified Cu-Zn catalyst-C.
Characterization of the catalyst, catalyst specific surface area of 158m 2 /g。
Preparation of cyclododecanone:
loading the modified Cu-Zn catalyst-C into a fixed bed, melting and feeding cyclododecanol at 95 ℃, setting the reaction temperature at 210 ℃ and the pressure at 0.01MPa (G), and setting the mass space velocity of cyclododecanol at 0.7h -1 After the device was run for 7000 hours, the sample was analyzed to show a cyclododecanol conversion of 99.29%, a cyclododecanone selectivity of 99.83% and a byproduct cyclododecene selectivity of 0.08%.
Example 4
Preparation of modified Cu-Zn catalyst-D:
s1: 20g of copper nitrate, 39.21g of zinc nitrate and 45g of aluminum sulfate are stirred and dissolved in 800g of deionized water;
s2: adding 0.2-g N-Boc-pyrrolidine and 0.1g of cyclobutane siloxane into the reaction solution, and uniformly stirring and mixing; adding 25wt% ammonia water into the mixed solution while stirring, and adjusting the pH to 9.5;
s3: filtering out precipitate, drying the precipitate in a 170 ℃ oven for 9 hours, then transferring the precipitate into a 350 ℃ muffle furnace for roasting for 4 hours, extruding strips and forming to obtain the modified Cu-Zn catalyst-D.
Characterization of the catalyst, the specific surface area of the catalyst was 154m 2 /g。
Preparation of cyclododecanone:
loading the modified Cu-Zn catalyst-D into a fixed bed, melting and feeding cyclododecanol at 95 ℃, setting the reaction temperature to 220 ℃, the pressure to 0.05MPa (G), and the mass space velocity of cyclododecanol to 1.3h -1 After the device is stable for 8000h, sampling analysis shows that the cyclododecanol conversion rate is 99.25%, the cyclododecanone selectivity is 99.81%, and the selectivity of byproducts cyclododecene is 0.07%.
Comparative example 1
A Cu-Zn catalyst was prepared as in example 1, except that no silica sol, N-methylpyrrolidine and hexamethyldisiloxane were added, and the catalyst was characterized by having a specific surface area of 73m 2 /g。
Cyclododecanone was prepared in a similar manner to example 1, and after 6000 hours of catalyst use, the sample was taken and analyzed for cyclododecanol conversion 70.43%, cyclododecanone selectivity 86.05% and byproduct cyclododecene selectivity 5.96%.
Comparative example 2
A Cu-Zn catalyst was prepared as in example 1, except that hexamethyldisiloxane was not added, and the catalyst was characterized by having a specific surface area of 97m 2 /g。
Cyclododecanone was prepared in a similar manner to example 1, and after 6000 hours of catalyst use, the sample was analyzed for cyclododecanol conversion 81.01%, cyclododecanone selectivity 88.35% and byproduct cyclododecene selectivity 5.08%.
Comparative example 3
A Cu-Zn catalyst was prepared in a similar manner to example 1, except that N-methylpyrrolidine was not added, the catalyst was characterized and the specific surface area of the catalyst was 84m 2 /g。
Cyclododecanone was prepared in a similar manner to example 1, and after 6000 hours of catalyst use, the sample was analyzed for cyclododecanol conversion 76.13%, cyclododecanone selectivity 87.34% and byproduct cyclododecene selectivity 5.29%.

Claims (10)

1. The method is characterized in that cyclododecanone is prepared by taking cyclododecanol as a raw material through catalytic dehydrogenation;
wherein, the catalytic dehydrogenation adopts a modified Cu-Zn catalyst, which comprises a modifier containing pyrrolidine compound and siloxane.
2. The method according to claim 1, wherein the method comprises charging a modified Cu-Zn catalyst into a reactor, and performing a dehydrogenation reaction on cyclododecanol melt feed to obtain cyclododecanone.
3. A process according to claim 1 or 2, characterized in that the support of the catalyst is a metal and/or non-metal oxide, preferably one or more of zirconia, magnesia, silica, alumina, lanthania, titania, thoria, more preferably alumina and/or silica;
preferably, the mass ratio of Cu, zn, carrier, pyrrolidine compound and siloxane in the catalyst is 1: (0.1-4): (0.1-10): (0.001-0.1): (0.0001-0.05), preferably 1: (0.3-3): (0.5-5): (0.003-0.06): (0.0003-0.03).
4. A process according to any one of claims 1 to 3, wherein the catalyst preparation process comprises the steps of:
s1: dissolving copper salt, zinc salt and precursor of carrier in water;
s2: adding modifier, stirring, mixing, precipitating metal ions and carrier in the aqueous solution;
s3: filtering the precipitate, drying, roasting and molding to obtain the modified Cu-Zn catalyst.
5. The method according to claim 4, characterized in that the copper salt of S1 is a water-soluble copper salt, preferably one or more of the nitrate, hydrochloride, sulfate, phosphate salts of copper, more preferably copper nitrate;
and/or, the zinc salt in S1 is one or more of water-soluble zinc salt, preferably zinc nitrate, hydrochloride, sulfate and phosphate, more preferably zinc nitrate;
and/or, the precursor of the carrier in S1 is one or more of soluble metal salt, non-metal salt, metal ester, non-metal ester, metal oxide and non-metal oxide, preferably one or more of aluminum nitrate, aluminum hydrochloride, aluminum sulfate, aluminum phosphate, silicate and silica sol, more preferably one or more of aluminum nitrate, tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate;
and/or the mass ratio of the copper salt to the water of S1 is 1 (10-50), preferably 1 (20-30).
6. The method according to claim 4, wherein the pyrrolidine-containing compound in the modifier of S2 is one or more of N-or C-substituted pyrrolidine, preferably N-methylpyrrolidine, 2- (aminomethyl) -1-ethylpyrrolidine, N-Boc-pyrrolidine, 3-aminopyrrolidine, (2S, 4R) -Fmoc-4-t-butoxycarbonylaminopyrrolidine-2-carboxylic acid and (R) -1-Boc-3-aminopyrrolidine, more preferably N-methylpyrrolidine and/or 3-aminopyrrolidine;
and/or the siloxane in the modifier in S2 is a siloxane containing 2-5 silicon, preferably one or more of hexamethyldisiloxane, decamethyl cyclopentasiloxane, tetramethyl diphenyl trisiloxane, ethyl siloxane, propyl siloxane, cyclobutane siloxane, methacryloxypropyl cyclotetrasiloxane, trifluoropropyl methyl cyclotrisiloxane, trifluoropropyl cyclotrisiloxane, more preferably hexamethyldisiloxane and/or decamethyl cyclopentasiloxane;
and/or S2 adding a precipitant, preferably adding an alkali liquor, more preferably adding one or more of sodium oxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide, cesium hydroxide, ammonium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and an aqueous solution of ammonia.
7. The method according to claim 4, wherein the firing temperature of S3 is 250-600 ℃, preferably 300-400 ℃.
8. The process according to any one of claims 1 to 7, characterized in that the reaction temperature of the process is 170 to 280 ℃, preferably 200 to 250 ℃, and the reaction mass space velocity in cyclododecanol is 0.1 to 2h -1 。
9. Cyclododecanone prepared by the method of any one of claims 1-8.
10. A modified Cu-Zn catalyst for catalytic dehydrogenation prepared by the method of any one of claims 4-7.
CN202310698659.8A 2023-06-14 2023-06-14 Synthesis method of cyclododecanone Pending CN116730809A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103055880A (en) * 2013-01-18 2013-04-24 苏州瀚海高分子有限公司 Catalyst for preparing ketone via cyclododecanol dehydrogenation and preparation method for same
US20160031784A1 (en) * 2014-08-01 2016-02-04 Evonik Degussa Gmbh Process for preparing cyclododecanone

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