CN111138257B - Method for preparing hexanedial - Google Patents
Method for preparing hexanedial Download PDFInfo
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- CN111138257B CN111138257B CN201911296052.7A CN201911296052A CN111138257B CN 111138257 B CN111138257 B CN 111138257B CN 201911296052 A CN201911296052 A CN 201911296052A CN 111138257 B CN111138257 B CN 111138257B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
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- C—CHEMISTRY; METALLURGY
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- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/30—Tungsten
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Abstract
The application discloses a method for preparing hexanedial, which comprises the following steps: carrying out oxidation reaction on the mixed solution containing cyclohexene and the mixed gas containing ozone under the reaction condition to obtain adipic dialdehyde; wherein the reaction conditions include a supported metal oxide as a catalyst, the metal oxide consisting of W oxide and Mo oxide. The invention adopts the supported W, Mo bimetal oxide as the catalyst, and the cyclohexene is oxidized with high selectivity to produce the hexanedial, thereby overcoming the defect that noble metal complex and sodium periodate are needed in the cyclohexene oxidation reaction.
Description
Technical Field
The application relates to a method for preparing hexanedial, which belongs to the field of chemistry and chemical engineering.
Background
The 1, 6-hexanedial is an important fine chemical product, is a quick-acting broad-spectrum chemical sterilizing agent, can quickly and efficiently kill most bacteria, bacteria propagules, fungi, spores, viruses and the like, does not corrode metal instruments, glass and plastic products, and can be widely used for disinfection and sterilization of medical instruments, food appliances and the like because of no harm to human bodies. In addition, the adipaldehyde is also used for petroleum exploitation and has the effect of inhibiting sulfate reducing bacteria to increase the sulfur content of crude oil. In addition, the 1, 6-hexanedial is used as a cross-linking agent, has the characteristics of high activity, quick reaction, large binding capacity, stable product, strong resistance to acid, water and enzyme and the like, and can be used for adhering and repairing biological tissues and human organs. The leather tanning effect of the 1, 6-hexanedial is good, the grain surface of the tanned leather is fine, the suede is uniform, the dyeing is bright, and the leather has high perspiration resistance, heat resistance and soaping resistance.
The trans-1, 2-cyclohexanediol is prepared by oxidizing cyclohexene with a sodium periodate/silica gel system, and the 1, 6-hexanedial (perfume and essence cosmetics, 2006(6): 17-20) can be prepared with high selectivity. Periodate, though effective, has the drawback of being expensive, not easy to handle and store, for which many companies are constantly seeking processes which are simple to prepare, stable in nature, inexpensive and readily available, combining carbonation chemicals and plastics technology companies (US 5312996 and CN 1087078A) reacting butadiene with hydrogen and carbon monoxide in the presence of a catalyst rhodium which complexes with certain polyphosphites to produce 1, 6-hexanedial in high conversion. At 110 ℃ and 900psig, the conversion was 99% and the selectivity to adipaldehyde was 30%.
The literature prepares novel Ru (II) -TSC complexes [ RuH (TSC) (CO) (PPh)3)2]The catalyst is applied to the oxidation cracking reaction of olefin, and has effect on the oxidation reaction of a row of olefin. In the presence of sodium periodate, the yield can reach 99% at most by oxidizing in acetonitrile/water solution at room temperature (Chemistry Select, 2018,3(11): 3036-3041). The literature studies [ Ru (COD) (L1) Br coordinated by naphthyridine functionalized N-heterocyclic carbene ligand2]And NaIO4Performance of the catalyst in olefin oxidative cracking reactions. In methyl acetate/acetonitrile/water solvent, the catalyst has good selectivity for olefin selective oxidative cracking. When cyclohexene is oxidized, the yield of adipaldehyde can reach 100% (Journal of the American Chemical Society, 2014,136, 13987-. Cyclohexene is taken as raw material, RuCl is adopted3-NaIO4The catalyst was used to synthesize 1, 6-hexanedial by oxidizing cyclohexene in 1, 2-dichloroethane-water solution in a yield of 70% (Journal of Organic Chemistry,2001,66(14): 48144818). Hydroxyapatite-loaded Ru nanoparticles and NaIO4The catalyst is used in the cyclohexene oxidation cracking reaction, and is oxidized in dichloroethane/water solvent for 3 hours at room temperature, and the selectivity of the hexanedial is 51 percent. (Angew. chem. int. Ed.,2004,43, 3303-.
CN109369356A discloses a method for preparing 1, 6-hexanedial by selective oxidation of cyclohexene with a cobalt complex of an isosteryl alcohol derivative. The literature reports that the yield of glutaraldehyde obtained by oxidizing cyclopentene with 50% hydrogen peroxide by using peroxyniobic acid as a catalyst and ethanol as a solvent is as high as 72%, which indicates that the peroxyniobic acid is an excellent catalyst with good activity and selectivity for preparing glutaraldehyde by oxidizing cyclopentene through ring opening. While the cyclohexene oxide is used for preparing 1, 6-hexanedial, the cyclohexene conversion rate is 100%, but the selectivity of the 1, 6-hexanedial is only 40% (the Redding university (Nature science edition), 2002, 41(3): 317-.
CN102746127A discloses that cyclohexene is used as a raw material, ozone is used as an oxidant, an organic solvent and glacial acetic acid are used as a mixed solvent, an ozonization reaction is carried out at a reaction temperature of-20-10 ℃ to obtain ozonization reaction liquid, and ozonides are directly subjected to a reduction reaction without separation; the method for preparing the 1, 6-hexanedial comprises the steps of carrying out reduction decomposition on the 1, 6-hexanedial by using zinc powder, and reacting at room temperature for 0.5-1.5 h under the protection of nitrogen, wherein the yield of the 1, 6-hexanedial in the method is up to 60%.
In conclusion, in the reaction for preparing the hexanedial by oxidizing the cyclohexene, a metal complex-NaIO is mostly adopted4The catalyst system and the preparation method of the catalyst are complex and expensive. The problem of over-oxidation exists when cyclohexene is oxidized by adopting high-concentration hydrogen peroxide as an oxidant, high selectivity of the hexanedial is difficult to obtain, and further industrial application of the process is hindered.
Disclosure of Invention
According to one aspect of the application, a method for preparing hexanedial is provided, the method adopts a supported bimetallic oxide as a catalyst, so that the selectivity of the hexanedial is improved when cyclohexene is oxidized by using ozone as an oxidant, expensive catalysts such as noble metal and sodium periodate are avoided, and the production cost is reduced.
A method of preparing adipaldehyde, the method comprising:
carrying out oxidation reaction on mixed liquor containing cyclohexene and mixed gas containing ozone in the presence of a catalyst to obtain adipic dialdehyde;
wherein the catalyst is a supported metal oxide, and the metal oxide consists of W oxide and Mo oxide.
Optionally, the mixture further comprises:
oxygen, air, inert gas;
the concentration of ozone in the mixed gas is 10-140 mg/L.
Optionally, the upper limit of the concentration of ozone in the mixed gas is selected from 140mg/L, 130mg/L, 120mg/L, 110mg/L, 100mg/L, 90mg/L, 80mg/L, 70mg/L, 60mg/L, 50mg/L, 40mg/L, 30mg/L or 20mg/L, and the lower limit is selected from 130mg/L, 120mg/L, 110mg/L, 100mg/L, 90mg/L, 80mg/L, 70mg/L, 60mg/L, 50mg/L, 40mg/L, 30mg/L, 20mg/L or 10 mg/L;
optionally, the carrier in the supported metal oxide is a mesoporous material; the mesoporous material is at least one of mesoporous molecular sieve, mesoporous alumina and mesoporous silica; the mesoporous molecular sieve is selected from at least one of MCM-41 or SBA-15.
Optionally, in the supported metal oxide, the mass loading amount of the metal W is 0.5-5.0%, and the mass loading amount of the metal Mo is 0.02-2.0%;
preferably, the mass loading amount of the metal W is 2-3%, and the mass loading amount of the metal Mo is 1-2%.
Alternatively, the upper limit of the mass loading of the metal W may be selected from 5.0%, 4.0%, 3.0%, 2.0% or 1.0%, and the lower limit may be selected from 4.0%, 3.0%, 2.0%, 1.0% or 0.5%; the upper limit of the mass loading of the metal Mo can be selected from 2.0%, 1.5%, 1.0%, 0.5% or 0.1%, and the lower limit can be selected from 1.5%, 1.0%, 0.5%, 0.1% or 0.02%.
Optionally, the preparation method of the supported metal oxide comprises the following steps:
soaking a metal salt solution into the carrier by adopting an isometric soaking method, and drying and roasting to obtain a catalyst;
the metal salt in the metal salt solution is ammonium tungstate and ammonium molybdate;
optionally, the drying conditions specifically include:
the drying temperature is 80-110 ℃; the drying time is 10-14 h;
the conditions for calcination include:
the roasting temperature is 480-520 ℃; the roasting time is 3-5 h.
Optionally, the oxidizing reaction of the mixed solution containing cyclohexene and the mixed gas containing ozone under the reaction conditions includes:
firstly, heating the mixed liquid containing cyclohexene in the reactor to the reaction temperature, and then introducing the mixed gas containing ozone into the reactor for oxidation reaction.
Optionally, the oxidation reaction conditions further comprise:
the reaction temperature is-70-50 ℃;
the reaction time is 0.5-2 h.
Optionally, the upper limit of the reaction temperature is selected from 50 ℃, 40 ℃, 30 ℃,20 ℃, 10 ℃ or 0 ℃, and the lower limit is selected from-70 ℃, 50 ℃, 10 ℃, 0 ℃, 40 ℃, 30 ℃ or 20 ℃.
Optionally, the upper limit of the reaction time is 2h, 1.5h or 1h, and the lower limit is 1.5h, 1h or 0.5 h.
Optionally, the mass ratio of the catalyst to the cyclohexene is (0.05-0.40): 1, preferably (0.05-0.20): 1.
Optionally, the molar ratio of the ozone to the cyclohexene is 0.50-2.00.
Optionally, the mixed solution further contains an ester auxiliary agent; the ester auxiliary agent comprises at least one of methyl pyruvate, methyl trifluoropyruvate, methyl acetylacetonate and methyl acetoacetate; methyl pyruvate is preferred.
By adding methyl pyruvate, cyclohexene forms a stable intermediate transition state in the reaction process, the cyclohexene is prevented from being excessively oxidized to generate acid, and the selectivity of the hexanedial is effectively improved.
Optionally, the molar ratio of the ester auxiliary agent to the cyclohexene is (0.05-0.5): 1, preferably (0.05 to 0.30): 1, more preferably 0.10: 1.
Optionally, the mixed solution further comprises an organic solvent;
the organic solvent is selected from acetonitrile, acetone or dichloromethane.
Optionally, the oxidation reaction is carried out in a tank reactor.
In a specific embodiment, a method for preparing hexanedial by selectively oxidizing cyclohexene, which adopts a supported W, Mo bimetallic oxide as a catalyst and ozone as an oxidant to selectively oxidize cyclohexene into hexanedial.
Specifically, after the cyclohexene, the catalyst, the auxiliary agent and the organic solvent are uniformly mixed, ozone is introduced for reaction at the reaction temperature of-70-50 ℃, and the reaction lasts for 0.5-2.0 hours.
The supported catalyst carrier is MCM-41, SBA-15, mesoporous alumina and mesoporous SiO2Etc. have a large specific surface area.
The catalyst support was calcined at 550 ℃ for 4h in a nitrogen atmosphere to remove adsorbed species in the channels prior to use.
The supported catalyst is prepared by soaking a carrier in a metal salt solution, soaking for 24 hours at room temperature by volume, drying at 110 ℃, and roasting at 500 ℃.
The load capacity of the supported catalyst W is 0.5-5.0%, and the load capacity of Mo is 0.02-2.0%.
The metal salt is ammonium tungstate and ammonium molybdate.
The auxiliary agent is methyl pyruvate, and the molar ratio of the methyl pyruvate to cyclohexene is 0.1-0.5, preferably 0.1-0.3.
The solvent is acetonitrile, acetone or dichloromethane.
The beneficial effects that this application can produce include:
1) the supported W, Mo bimetal oxide is used as a catalyst, cyclohexene is oxidized with high selectivity to produce the hexanedial, the defect that noble metal complexes and sodium periodate are needed in cyclohexene oxidation reaction is overcome, the ozone is used as an oxidant, the cyclohexene is selectively oxidized into the hexanedial, and the product selectivity is high;
2) the preparation method provided by the invention can prepare the product through one-step oxidation, is simple to operate, and is an environment-friendly process without generating three wastes;
3) therefore, the invention not only has innovativeness, but also has economic advantages and industrial application prospects.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
The raw materials in the examples of the present invention were all purchased from commercial sources unless otherwise specified.
Wherein:
MCM-41 was purchased from a southern catalyst plant; SBA-15 purchased from Nanjing Mr. PioneerRice; mesoporous SiO2Purchased from Qingdao ocean chemical Co.
The analytical methods and conversion, selectivity in the examples were calculated as follows:
the analytical methods and conversion, selectivity in the examples were calculated as follows:
automated analysis was performed using an Agilent7890 gas chromatograph with an autosampler. Adding n-dodecane into the reaction solution after the reaction as an internal standard, and quantifying by adopting an internal standard method.
In some embodiments of the invention, both conversion and selectivity are calculated based on carbon moles:
cyclohexene conversion (mol) = [ (cyclohexene amount in feed) - (cyclohexene amount in discharge) ]/(cyclohexene amount in feed) × 100%
Adipaldehyde selectivity (mol) = (amount of adipaldehyde in discharge) ÷ (amount of cyclohexene converted) × 100%.
Examples 1-10 preparation of Supported W, Mo catalysts
First, the support was calcined at 550 ℃ for 4h in a nitrogen atmosphere to remove adsorbed species in the pores. Dissolving ammonium tungstate and ammonium molybdate in water in certain mass, fixing the volume according to the saturated water absorption capacity of the carrier (when MCM-41 is adopted, the volume is 50ml, when SBA-15 is adopted, the volume is 30 ml, and when mesoporous silica is adopted, the volume is 20 ml), loading 10g of the carrier on the carrier by adopting an isometric impregnation method to load a metal salt solution, then placing the carrier in an oven at 100 ℃ for drying for 12h, and roasting in a muffle furnace at 500 ℃ for 4h to obtain the catalyst. The types and the masses of the carrier and the metal salt are shown in Table 1.
TABLE 1 preparation parameters of the catalysts
| Examples | Catalyst and process for preparing same | Mass (g) of ammonium tungstate | Quality of ammonium molybdate (g) | Mass of carrier (g) |
| 1 | 0.5 W-1.0Mo/MCM-41 | 0.07 | 0.18 | 10.00 |
| 2 | 1.0 W-1.0Mo/MCM-41 | 0.14 | 0.18 | 10.00 |
| 3 | 2.0 W-1.0Mo/MCM-41 | 0.28 | 0.18 | 10.00 |
| 4 | 3.0 W-1.0Mo/MCM-41 | 0.42 | 0.18 | 10.00 |
| 5 | 5.0 W-1.0Mo/MCM-41 | 0.69 | 0.18 | 10.00 |
| 6 | 5.0 W-2.0Mo/MCM-41 | 0.69 | 0.37 | 10.00 |
| 7 | 3.0 W-1.0Mo/SBA-15 | 0.42 | 0.18 | 10.00 |
| 8 | 3.0 W-2.0Mo/SBA-15 | 0.42 | 0.37 | 10.00 |
| 9 | 3.0 W-0.5Mo/SiO2 | 0.42 | 0.09 | 10.00 |
| 10 | 3.0 W-0.02Mo/SBA-15 | 0.42 | 0.037 | 10.00 |
In the catalyst name aW-bMo/X, a represents the mass loading amount of the metal W element, b represents the mass loading amount of the metal Mo element, and X represents the carrier.
Example 11 preparation of hexanedial by Oxidation of cyclohexene
Adding 1.0 g of cyclohexene, 0.10g of methyl pyruvate, 25mL of acetonitrile and 0.5W-1.0Mo/MCM-41 catalyst (0.10 g) into a 250mL round-bottom flask, raising the temperature to 20 ℃, introducing a mixed gas with the ozone concentration of 100mg/L, wherein the mixed gas consists of ozone and oxygen, the flow of the mixed gas is 80 mL/min, rapidly cooling to room temperature after reacting for 1h, and analyzing the composition of a product by using a gas chromatograph.
Examples 12-20 Oxidation of cyclohexene to adipaldehyde
Cyclohexene oxidation was carried out in the same manner as in example 11 except for the specific differences in reaction conditions and the results shown in Table 2.
Example 21
Essentially the same procedure as for the preparation of example 13, except that methyl trifluoropyruvate was not added, the test results are shown in Table 2.
Example 22
Essentially the same procedure as for the preparation of example 14, except that methyl acetylacetonate was not added, the results of the tests are shown in Table 2.
Example 23
Essentially the same procedure as for the preparation of example 17, except that methyl pyruvate was not added, the results are shown in Table 2.
Example 24
Essentially the same procedure as in example 18 was followed, except that methyl pyruvate was not added and the results are shown in Table 2.
TABLE 2 Performance of the catalyst for the preparation of adipaldehyde by oxidation of cyclohexene
| Fruit of Chinese wolfberry Applying (a) to Example (b) | Catalyst and process for preparing same | Reaction of Temperature of （℃） | Reaction of Time （h） | Auxiliary agent (g) | Concentration of ozone Degree (mg- L） | Mixed gas flow Volume (mL- min） | Cyclohexene oxide Chemical conversion rate （mol%） | Selection of hexanedial Selectivity is （mol%） |
| 11 | 0.5 W- 1.0Mo/ MCM-41 | 20 | 1 | Pyruvic acid A Ester 0.1 g | 100 | 80 | 36.5 | 43.5 |
| 12 | 1.0 W- 1.0Mo/ MCM-41 | -30 | 0.5 | Pyruvic acid A Ester 0.25 g | 140 | 100 | 46.3 | 56.7 |
| 13 | 2.0 W- 1.0Mo/ MCM-41 | -50 | 1 | Trifluoroacetone Acid methyl ester 0.35g | 160 | 80 | 56.2 | 73.5 |
| 14 | 3.0 W- 1.0Mo/ MCM-41 | 0 | 1.5 | Acetylacetone Acid methyl ester 0.15 g | 130 | 100 | 68.2 | 84.3 |
| 15 | 5.0 W- 1.0Mo/ MCM-41 | 10 | 2 | Acetoacetic acid Methyl ester 0.15 g | 140 | 100 | 64.3 | 65.32 |
| 16 | 5.0 W- 2.0Mo/ MCM-41 | 10 | 1 | Pyruvic acid A Ester 0.15g | 50 | 200 | 56.4 | 45.2 |
| 17 | 3.0 W- 1.0Mo/ SBA-15 | 30 | 1 | Pyruvic acid A Ester 0.3 g | 50 | 200 | 35.6 | 75.3 |
| 18 | 3.0 W- 2.0Mo/ SBA-15 | 25 | 1 | Pyruvic acid A Ester 0.1 g | 50 | 200 | 41.2 | 71.5 |
| 19 | 3.0 W- 0.5Mo/ SiO2 | 40 | 1 | Acetoacetic acid Methyl ester 0.15 g | 80 | 130 | 29.7 | 43.2 |
| 20 | 3.0 W- 0.02Mo/ SBA-15 | 50 | 1 | Pyruvic acid A Ester 0.15g | 120 | 120 | 29.3 | 63.5 |
| 21 | 2.0 W- 1.0Mo/ MCM-41 | -50 | 1 | Is free of | 160 | 80 | 53.8 | 69.8 |
| 22 | 3.0 W- 1.0Mo/ MCM-41 | 0 | 1.5 | Is free of | 130 | 100 | 67.5 | 81.5 |
| 23 | 3.0 W- 1.0Mo/ SBA-15 | 30 | 1 | Is free of | 50 | 200 | 41.6 | 71.2 |
| 24 | 3.0 W- 2.0Mo/ SBA-15 | 25 | 1 | Is free of | 50 | 200 | 39.5 | 68.2 |
As can be seen from table 2, the adipaldehyde prepared by the preparation method provided by the application generally has high selectivity, and particularly when an auxiliary agent is used, the mass loading of metal W in the catalyst is 2-3%, and the mass loading of metal Mo is 1-2%, the adipaldehyde selectivity can reach more than 71.5%, and can reach 84.3% at most; the examples using the adjuvant had a higher selectivity for adipaldehyde than the examples not used.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for preparing hexanediol is characterized by comprising the following steps:
carrying out oxidation reaction on mixed liquor containing cyclohexene and mixed gas containing ozone in the presence of a catalyst to obtain adipic dialdehyde;
wherein the catalyst is a supported metal oxide, and the metal oxide consists of W oxide and Mo oxide;
in the supported metal oxide, the mass loading capacity of metal W is 2-3%, and the mass loading capacity of metal Mo is 1-2%;
the reaction temperature is-70-30 ℃.
2. The method according to claim 1, wherein the mixed gas further comprises:
at least one of oxygen, air, and inert gas;
the concentration of ozone in the mixed gas is 10-140 mg/L.
3. The preparation method according to claim 1, wherein the carrier in the supported metal oxide is a mesoporous material; the mesoporous material is at least one of mesoporous molecular sieve, mesoporous alumina and mesoporous silica; the mesoporous molecular sieve is selected from at least one of MCM-41 or SBA-15.
4. The method according to claim 1, wherein the oxidizing reaction of the mixed solution containing cyclohexene and the mixed gas containing ozone under the reaction conditions comprises:
firstly, heating the mixed solution containing cyclohexene in the reactor to the reaction temperature, and then introducing the mixed gas containing ozone into the reactor to carry out oxidation reaction.
5. The preparation method according to claim 1, wherein the mass ratio of the catalyst to the cyclohexene is (0.05-0.40): 1.
6. the production method according to claim 1, wherein the conditions of the oxidation reaction include:
the reaction time is 0.5-2 h.
7. The method of claim 1, wherein: the mixed solution also contains an ester auxiliary agent; the ester auxiliary agent comprises at least one of methyl pyruvate, methyl trifluoropyruvate, methyl acetylacetonate and methyl acetoacetate.
8. The method of claim 7, wherein: the mass ratio of the ester auxiliary agent to the cyclohexene is (0.05-0.5): 1.
9. the preparation method of the cyclohexene, wherein the mass ratio of the ester auxiliary agent to the cyclohexene is (0.1-0.3): 1.
10. The method according to claim 1, wherein the mixed solution further contains an organic solvent;
the organic solvent is selected from acetonitrile, acetone or dichloromethane.
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| CN109369356B (en) * | 2018-12-29 | 2021-08-10 | 郑州大学 | Method for preparing 1, 6-hexanedial by selectively oxidizing cyclohexene |
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