CN111138256B

CN111138256B - A kind of preparation method of adipaldehyde

Info

Publication number: CN111138256B
Application number: CN201911296051.2A
Authority: CN
Inventors: 许磊; 袁扬扬; 张晓敏; 陆标; 赵晓炜
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2019-12-16
Filing date: 2019-12-16
Publication date: 2021-07-13
Anticipated expiration: 2039-12-16
Also published as: CN111138256A

Abstract

The application discloses a preparation method of hexanediol, 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 comprise a molecular sieve supported metal oxide as a catalyst. The invention adopts ozone as an oxidant, and a metal oxide loaded by a molecular sieve as a catalyst, and the cyclohexene is oxidized with high selectivity to produce the hexanedial, thereby overcoming the defect that a noble metal complex and sodium periodate are required to be used in the cyclohexene oxidation reaction. Therefore, the invention not only has innovativeness, but also has economic advantages and industrial application prospects.

Description

Preparation method of hexanediol

Technical Field

The application relates to a preparation method of hexanediol, belonging 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. 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%.

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-.

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 hexanediol is provided, and the method adopts a molecular sieve loaded metal oxide as a catalyst, so that the selectivity of hexanediol when cyclohexene is oxidized by using ozone as an oxidant is improved, expensive catalysts such as noble metals and sodium periodate are avoided, and the production cost is reduced.

The preparation method of the hexanediol comprises 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 metal oxide loaded by a molecular sieve.

Optionally, the mixture further comprises:

at least one of oxygen, nitrogen, and 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 140 mg/L, 130 mg/L, 120 mg/L, 110 mg/L, 100mg/L, 90 mg/L, 80 mg/L, 70 mg/L, 60 mg/L, 50 mg/L, 40 mg/L, 30 mg/L or 20 mg/L, and the lower limit is selected from 130 mg/L, 120 mg/L, 110 mg/L, 100mg/L, 90 mg/L, 80 mg/L, 70 mg/L, 60 mg/L, 50 mg/L, 40 mg/L, 30 mg/L, 20 mg/L or 10 mg/L;

optionally, the molecular sieve is a hydrogen-type silicoaluminophosphate molecular sieve; the hydrogen type silicon aluminum molecular sieve comprises at least one of HY, HBeta or HMOR.

Optionally, the metal oxide is a transition metal oxide; the transition metal oxide is at least one selected from the group consisting of an oxide of Fe, an oxide of Co, an oxide of Ni and an oxide of Cu; preferably an oxide of Fe, Co or Ni, more preferably an oxide of Ni and an oxide of Co.

Optionally, in the metal oxide loaded by the molecular sieve, the mass loading amount of the metal is 0.5-10.0%; preferably 0.5 to 5%, more preferably 0.5 to 3%.

Alternatively, the metal has an upper limit of 10.0%, 9.0%, 8.0%, 7.0%, 6.0%, 5.0%, 4.0%, 3.0%, 2.0%, or 1.0% and a lower limit of 9.0%, 8.0%, 7.0%, 6.0%, 5.0%, 4.0%, 3.0%, 2.0%, 1.0%, or 0.5% by mass loading.

Optionally, the preparation method of the molecular sieve supported metal oxide comprises the following steps:

dipping a metal salt solution on a molecular sieve carrier by adopting an isometric dipping method, drying and roasting to obtain the catalyst;

the metal salt in the metal salt solution is selected from at least one of acetate, oxalate, nitrate, sulfate and chloride; the solvent in the metal salt solution is water, deionized water and other conventional solvents capable of dissolving metal salts.

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 0.50-3.00.

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 (0.05-0.30): 1, preferably 0.10: 1.

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 ℃ or 10 ℃, and the lower limit is selected from-70 ℃, 50 ℃, 0 ℃, 10 ℃, 20 ℃, 30 ℃ or 40 ℃.

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 mixed solution further comprises an organic solvent;

the organic solvent is selected from acetonitrile, dichloromethane, acetone, etc.

Optionally, the oxidation reaction is carried out in a tank reactor.

In a specific embodiment, a method for preparing hexanedial by selectively oxidizing cyclohexene adopts ozone as an oxidant and a metal oxide loaded by a molecular sieve as a catalyst, and selectively oxidizes cyclohexene into hexanedial in a tank reactor under the action of an auxiliary agent.

Specifically, cyclohexene, a catalyst, an auxiliary agent and an organic solvent are uniformly mixed, the reaction temperature is-70-50 ℃, and ozone is introduced for reaction for 0.5-2.0 h.

The ozone oxidant adopts air or oxygen as a diluent, and the concentration of ozone is 10-140 mg/L.

The molecular sieve is selected from one of silicon-aluminum molecular sieves such as HY, HBeta, HMOR and the like.

The metal oxide is selected from one of Fe, Co, Ni and Cu.

The preparation method of the transition metal oxide supported molecular sieve catalyst comprises the following steps: the molecular sieve carrier is placed in a metal salt solution and prepared by the steps of soaking in an equal volume, drying, roasting and the like.

Optionally, the drying conditions specifically include:

the drying temperature is 90-110 ℃; the drying time is 10-14 h;

the conditions for calcination include:

the roasting temperature is 300-500 ℃; the roasting time is 3-5 h.

The catalyst is prepared by an isometric impregnation method, and the loading capacity of metal is 0.5-10.0%.

The metal salt in the metal salt solution can be one of acetate, oxalate, nitrate, sulfate and chloride.

The auxiliary agent is methyl pyruvate, and the mass ratio of the methyl pyruvate to the cyclohexene is 0.05-0.3.

The solvent is acetonitrile or dichloromethane.

The beneficial effects that this application can produce include:

1) the invention adopts ozone as an oxidant and metal oxide loaded by a molecular sieve as a 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 required to be used in the cyclohexene oxidation reaction.

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: HY purchased from Nankai catalyst works with a silicon to aluminum (Si/Al) molar ratio of 2.5; HBeta, purchased from Nankai catalyst works, has a silica to alumina molar ratio (Si/Al) of 25.7; HMOR was purchased from a Nankai catalyst plant and had a silica to alumina molar ratio (Si/Al) of 7.8.

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 molecular sieve supported metal oxide catalysts

Dissolving a certain mass of salt solution in water, fixing the volume to 10 m L, taking 10g of molecular sieve, loading metal elements on the molecular sieve by adopting an isometric impregnation method, then placing the molecular sieve in a 100 ℃ oven for drying for 12h, and then roasting in a 500 ℃ muffle furnace for 4 h. 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	Species of metal salt	Mass (g) of metal salt	Mass (g) of molecular sieve
					1	3.0 Fe/HY	Fe(NO3)3·9H2O	2.17	10.00
2	3.0 Co/HY	Co(NO3)2·6H2O	1.48	10.00
					3	3.0 Ni/HY	Ni(NO3)2·2H2O	1.49	10.00
4	3.0 Cu/HY	Cu(NO3)2·3H2O	0.89	10.00
					5	0.5 Co/HBeta	C0(NO3)2·3H2O	0.25	10.00
6	2.0 Co/HBeta	Co(NO3)2·6H2O	0.99	10.00
					7	4.0 Co/HBeta	Co(NO3)2·6H2O	1.98	10.00
8	0.5 Ni/HMOR	Ni(NO3)2·2H2O	0.25	10.00
					9	1.0 Ni/HMOR	Ni(NO3)2·2H2O	0.50	10.00
10	5.0 Ni/HMOR	Ni(NO3)2·2H2O	2.48	10.00

In the catalyst name nA/B, A represents a supported metal element, B represents a molecular sieve, and n represents the mass loading of the metal element A.

Example 11 preparation of hexanedial by Oxidation of cyclohexene

Adding 1.0 g of cyclohexene, 0.10g of methyl pyruvate, 25mL of acetonitrile and 0.10g of 3.0 Fe/HY catalyst into a 250 mL round-bottom flask, heating to 20 ℃, introducing mixed gas with the ozone concentration of 100mg/L, wherein the mixed gas consists of ozone and oxygen, the flow rate of the mixed gas is 60 mL/min, quickly 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 pyruvate was not added, the test results are shown in Table 2.

Example 22

Essentially the same procedure as for the preparation of example 16, except that methyl pyruvate was not added, the results are shown in Table 2.

TABLE 2 Performance of the catalyst for the preparation of adipaldehyde by oxidation of cyclohexene

Practice of Example (b)	Catalyst and process for preparing same	Reaction temperature （℃）	Reaction time （h）	Auxiliary agent (g)	Ozone concentration (mg- L）	Mixed gas flow (mL- min）	Conversion rate of cyclohexene （mol%）	Selectivity to hexanedial （mol%）
									11	3.0 Fe/HY 0.10	20	1	Pyruvic acid methyl ester 0.1 g	100	60	25.4	65.4
12	3.0 Co/HY	-70	0.5	Pyruvic acid methyl ester 0.3 g	140	100	63.2	79.5
									13	3.0 Ni/HY	-50	1	Trifluoro pyruvic acid methyl ester 0.30 g、	160	100	43.5	85.4
14	3.0 Cu/HY	0	1.5	Acetyl methyl pyruvate 0.15 g、	140	100	15.4	45.1
									15	0.5 Co/HBeta	10	2	Acetoacetic acid methyl ester 0.15g	140	100	35.4	83.2
16	2.0 Co/HBeta	10	1	Pyruvic acid methyl ester 0.15g	50	200	46.5	83.5
									17	4.0 Co/HBeta	15	1	Pyruvic acid methyl ester 0.3 g	50	200	85.4	35.8
18	0.5 Ni/HMOR	25	1	Pyruvic acid methyl ester 0.1 g	50	200	26.7	69.4
									19	1.0 Ni/HMOR	40	1	Pyruvic acid methyl ester 0.1 g	80	130	35.6	75.3
20	5.0 Ni/HMOR	50	1	Pyruvic acid methyl ester 0.1 g	100	120	83.2	53.2
									21	3.0 Ni/HY	-50	1	Is free of	160	100	43.8	70.0
22	2.0 Co/HBeta	10	1	Is free of	50	200	46.5	79.2

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 the mass loading of metals in the additive and the catalyst is 0.5-3%, and the metals are Ni and Co, the selectivity of the adipaldehyde can reach more than 69.4%, and can reach 85.4% 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

1. A method for preparing hexanediol is characterized by comprising the following steps:

wherein the catalyst is a metal oxide supported by a molecular sieve;

the metal oxide is a transition metal oxide;

the transition metal oxide is at least one selected from Co oxide and Ni oxide;

the mass loading amount of the metal in the metal oxide loaded by the molecular sieve is 0.5-3%;

the mixed solution also contains an ester auxiliary agent;

the ester auxiliary agent comprises at least one of methyl pyruvate, methyl trifluoropyruvate and methyl acetoacetate.

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 method of claim 1, wherein the molecular sieve is a hydrogen-type silicoaluminophosphate molecular sieve;

the hydrogen type silicon aluminum molecular sieve comprises at least one of HY, HBeta or HMOR.

4. The preparation method according to claim 1, wherein the mass ratio of the catalyst to the cyclohexene is (0.05-0.40): 1.

5. the preparation method according to claim 1, wherein the mass ratio of the ester auxiliary agent to the cyclohexene is (0.05-0.3): 1.

6. the production method according to claim 1, wherein the conditions of the oxidation reaction include:

the reaction temperature is-70-50 ℃;

the reaction time is 0.5-2 h.

7. The method according to claim 1, wherein the mixed solution further contains an organic solvent;

the organic solvent is selected from acetonitrile, dichloromethane or acetone.