CN116493022A - Catalyst for preparing 1, 6-hexanediol by adipic acid reduction and preparation method thereof - Google Patents

Catalyst for preparing 1, 6-hexanediol by adipic acid reduction and preparation method thereof Download PDF

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Publication number
CN116493022A
CN116493022A CN202310456712.3A CN202310456712A CN116493022A CN 116493022 A CN116493022 A CN 116493022A CN 202310456712 A CN202310456712 A CN 202310456712A CN 116493022 A CN116493022 A CN 116493022A
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catalyst
solution
hexanediol
adipic acid
preparing
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巩伟
王辉
王许云
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Qingdao University of Technology
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Qingdao University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a catalyst for preparing 1, 6-hexanediol by adipic acid one-step method and a preparation method thereof, wherein the catalyst comprises an active component, transition metal and Cu 2 An O carrier, wherein the active component is Ru, the transition metal is at least one of Co, cu, ni, fe, mo and Zn, and the carrier is of a spherical nano-sphere structure, such as Cu 2 O, etc. Respectively selecting and firstly respectively preparing solution 1: cu with a certain concentration 2 O carrier solution, solution 2: a mixed solution containing a soluble salt of any one of the above transition metals and a Ru salt; then rapidly adding the solution 2 into the solution 1, and slowly dripping NaBH with a certain concentration into the mixed solution 4 A solution; reacting for a period of time, washing with water to neutralityFiltering, drying to obtain Ru/XB/Cu 2 O (x=co, cu, ni, fe, mo or Zn). The catalyst has low cost, simple preparation process, high adipic acid conversion rate up to 85%, high 1, 6-hexanediol yield up to 92%, good technical effect and good industrialization prospect.

Description

Catalyst for preparing 1, 6-hexanediol by adipic acid reduction and preparation method thereof
Technical field:
the invention relates to the technical field of catalyst preparation, in particular to a method for preparing a catalyst with a strong acid site and a large number of acid sites, which can synthesize 1, 6-hexanediol by a one-step method from adipic acid.
The background technology is as follows:
1, 6-Hexanediol (HDOL) is an environment-friendly chemical raw material which has no pollution to the environment, is widely applied to the synthesis of polyester, polyurethane, paint and the like, and is known as a new foundation stone for the organic synthesis at present. Related data show that the current domestic market demand speed increase of the product is over 20% per year, and the product has an increasing trend year by year. At present, the industrial production of HDOL mostly adopts an adipic acid esterification hydrogenation reaction path, the reaction condition of the path is mild, but the reaction yield is generally not high, so that the selection and rational design of the catalyst are key to improving the yield of HDO.
The process route for synthesizing 1, 6-hexanediol from adipic acid mainly comprises the following steps: direct hydrogenation of adipic acid, hydrogenation of adipic acid ester derivatives, catalytic hydrogenation of ester mixtures and preparation of 1, 6-hexanediol by using olefins. At present, the most potential process route is the direct hydrogenation process of adipic acid. The synthesis of 1, 6-hexanediol from adipic acid can be summarized as a one-step process and a two-step process. The one-step method is to hydrogenate 1, 6-hexanediol by adipic acid one-step method; the two-step method is to esterify adipic acid and methanol into adipic acid dimethyl ester, and then further hydrogenate adipic acid dimethyl ester into 1, 6-hexanediol. Compared with the two methods, the method for synthesizing the 1, 6-hexanediol by one-step hydrogenation of adipic acid has low energy consumption, low cost and more economic benefit due to easy operation under low reaction conditions, so that the one-step hydrogenation of adipic acid for preparing the 1, 6-hexanediol has the technical potential of replacing the two-step method.
In recent years, the preparation and hydrogenation tests of catalysts for synthesizing 1, 6-hexanediol by a one-step method are reported in the literature. However, the catalyst noble metal catalyst has the defects of high specific weight, high cost, complex preparation process, low selectivity to target product 1, 6-hexanediol and the like.
Therefore, the invention surrounds the problems of hydrogenation activity and stability of the Cu-based catalyst, prepares Cu which takes noble metal Ru as a main catalyst component, transition metal and nano-spheres 2 O is compounded to obtain Ru/CoB/Cu with low price and good effect 2 O, which can effectively treatThe conversion rate of diacid to 1, 6-hexanediol is as high as 85%, and the yield of 1, 6-hexanediol can reach 92%.
The invention comprises the following steps:
the invention aims to seek a catalyst for preparing 1, 6-hexanediol by adipic acid reduction and a preparation method thereof, which solve the problems of higher preparation cost, unsatisfactory yield and the like of the existing catalyst for preparing 1, 6-hexanediol by adipic acid reduction.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the catalyst for preparing 1, 6-hexanediol by adipic acid reduction comprises active components Ru, transition metal and nanospheres, wherein the transition metal is at least one of Co, cu, ni, fe, mo and Zn, and the nanospheres are Cu 2 O、γ-Al 2 O 3 Or diatomaceous earth, ru: transition metal simple substance: the mass ratio of the nanospheres is 0.0370:0.0520: (0.01-0.08).
Preferably, the nanospheres are Cu 2 O, transition metal is Co, ru: co: cu (Cu) 2 The mass ratio of O is 0.0370:0.0520: (0.045-0.08).
The preparation method of the catalyst for preparing the 1, 6-hexanediol by reducing adipic acid specifically comprises the following steps:
(1) Preparing a nanosphere solution;
(2) Preparing a mixed solution of a transition metal soluble salt and Ru salt;
(3) Transferring the mixed solution to the nanosphere solution rapidly, uniformly mixing, and slowly dripping NaBH with a certain concentration into the mixed solution 4 A solution;
(4) And (3) reacting for a period of time, washing with water to be neutral, filtering, and drying to obtain the catalyst.
The transition metal salts include, but are not limited to, coCl 2 ·6H 2 O、CuCl 2 ·6H 2 O、NiCl 2 ·6H 2 O、FeCl 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、ZnCl 2 And soluble salts of transition metals such as Co, cu, ni, fe, mo and Zn.
NaBH in step (3) of the present invention 4 The metal in the transition metal salt and the Ru salt is reduced.
The method for preparing 1, 6-hexanediol by adipic acid reduction uses water as solvent, and under the catalysis of the catalyst, adipic acid reacts with hydrogen for 4-11h under the reaction condition of 6mpa and 200 ℃ to generate 1, 6-hexanediol. In the process, the catalyst comprises the following components: adipic acid: water= (0.05 to 0.1): 1: (2-15).
Compared with the prior art, the invention has the advantages that: (1) The transition metal is used as a raw material, and a small amount of noble metal Ru is used for preparing the catalyst, so that the preparation cost of the catalyst is reduced; (2) The nanosphere not only can be used as a carrier to provide more active sites, but also has certain catalytic activity by NaBH 4 After the noble metal Ru is reduced, an alloy catalyst is formed with the noble metal Ru; (3) The conversion rate of adipic acid is as high as 85%, the yield of 1, 6-hexanediol can reach 92%, a better technical effect is achieved, and the method has a better industrialization prospect.
Description of the drawings:
FIG. 1 is Cu 2 SEM image of O nanospheres.
FIG. 2 is Cu 2 O，Ru/Cu 2 O，Co/Cu 2 O and RuCoB/Cu 2 H of O 2 -TPR。
The specific embodiment is as follows:
the invention will be further described with reference to specific examples and figures of the specification.
Example 1
The embodiment relates to a preparation method of a catalyst for preparing 1, 6-hexanediol by adipic acid reduction, which specifically comprises the following steps:
(1) Will be 0.5mL of 20mg.mL -1 RuCl 3 ·nH 2 O and 207mgCoCl 2 ·6H 2 O is dissolved in 50mL of water;
(2) 45mg of Cu prepared by the method of comparative example 1 was then added to the solution of step (1) 2 O nanospheres, 20mL of 0.2mol.L -1 Reducing agent NaBH 4 Slowly adding dropwise into the above solution, reacting for about 0.5 hr, washing with water to neutrality, drying overnight, filtering, and drying to obtain Ru/Co/B/Cu 2 And (3) an O catalyst.
Examples 2 to 6
Examples 2-6 the catalyst preparation procedure was the same as in example 1 except that the transition metal salt (see Table 1) was different from example 1.
To study Cu 2 O，Ru/Cu 2 O，Co/Cu 2 O and RuCoB/Cu 2 The acidity and acidity center of the O catalyst were H 2- TPR, results are shown in FIG. 2. As shown in fig. 2, three major peaks are observed; the peak at 150 to 200℃is Ru reduction, and the peak at 400 to 450℃is Co (+2) reduction to Co (0). The peak area decreases with increasing Co component content. This phenomenon may occur because cobalt oxide appears, increasing the distance between adjacent Ru atoms, resulting in a decrease in hydrogen absorption capacity.
Example 7
The embodiment relates to a preparation method of a catalyst for preparing 1, 6-hexanediol by adipic acid reduction, which specifically comprises the following steps:
(1) Will be 0.5mL of 20mg.mL -1 RuCl 3 ·nH 2 O and 207mgCoCl 2 ·6H 2 O is dissolved in 50mL of water;
(2) 45mg of gamma-Al are then added to the solution of step (1) 2 O 3 (gamma-phase nanoscale, nanjing Baoket New Material Co., ltd.) 20mL of 0.2 mol.L -1 Reducing agent NaBH 4 Slowly adding dropwise into the above solution, reacting for about 0.5 hr, washing with water to neutrality, drying overnight, filtering, and drying to obtain Ru/Co/B/gamma-Al 2 O 3 A catalyst.
Example 8
The embodiment relates to a preparation method of a catalyst for preparing 1, 6-hexanediol by adipic acid reduction, which specifically comprises the following steps:
(1) Will be 0.5mL of 20mg.mL -1 RuCl 3 ·nH 2 O and 207mgCoCl 2 ·6H 2 O is dissolved in 50mL of water;
(2) Subsequently, 45mg of diatomaceous earth (white diatomaceous earth, yixing city Junli diatomaceous earth Co., ltd.) was added to the solution of step (1), 20mL of 0.2 mol.L -1 Reducing agent NaBH 4 Slowly adding the mixture into the solution dropwise, reacting 0And about 5h, washing with water to be neutral, drying overnight, filtering, and drying to obtain the Ru/Co/B/diatomite catalyst.
Comparative example 1
This comparative example relates to Cu 2 The preparation method of the O nanospheres comprises the following steps:
399mg of Cu (CH 3 COO) was first added 2 ·H 2 O was dissolved in 25mL of LDMF (N, N-dimethylformamide) containing 0.3mL of deionized water and magnetically stirred for 15 minutes, and then sonicated for 3 minutes. The above solution was kept at 85 ℃ for 10 minutes under magnetic stirring, and then aged at room temperature for 2 hours. The product obtained is washed thoroughly with ethanol, collected by centrifugation and dried at 40 ℃. Subsequently, the obtained Cu 2 O nanospheres (25 mg) were introduced into 15mL of ultrapure water and sonicated for 10 minutes.
Cu is shown in FIG. 1 2 SEM images of O nanospheres are surface structure drawings of the support itself and the supported catalyst of example 1.
Comparative example 2
(1) 207mgCoCl 2 ·6H 2 O is dissolved in 50mL of water to form a mixed aqueous solution;
(2) 48mg of Cu prepared by the method of comparative example 1 was then added to the solution of step (1) 2 O nanospheres, 20mL of 0.2mol.L -1 Reducing agent NaBH 4 Slowly adding the solution dropwise, reacting for 1-12 h, washing with water to neutrality, drying overnight, filtering, and drying to obtain Co/B/Cu 2 And (3) an O catalyst.
Comparative example 3
(1) Will be 0.5mL of 20mg.mL -1 RuCl 3 ·nH 2 O is dissolved in 50mL of water;
(2) 96.3mg of Cu prepared by the method of comparative example 1 was then added to the solution of step (1) 2 O nanospheres, 20mL of 0.2mol.L -1 Reducing agent NaBH 4 Slowly adding the mixture into the solution dropwise, reacting for about 1h, continuously reacting for 2-12 h, washing with water to be neutral, drying overnight, filtering, and drying to obtain Ru/Cu 2 And (3) an O catalyst.
Application instance
The catalysts prepared in examples 1-5 and comparative examples 1-5 were evaluated using the following methods:
into a batch reactor, 0.2g of adipic acid solid, 70mL of a solvent (e.g., methanol, dioxane, water, etc., see Table 1 for details) and 0.1g of the catalyst described above were charged, and the reactor was sealed. Firstly, N is introduced into 2 The residual air in the reactor is discharged and repeatedly operated for three times, and then H is introduced 2 Purging three times. Then through H 2 The reactor was pressurized to about 6.5MPa and stirring was turned on once the system reached the set temperature of 240 ℃. This point was set to start (t=0) and the stirring system was started at a stirring rate of 400rpm, and the reaction was continued for 5h. After the reaction, the catalyst was cooled, depressurized and filtered, and the reaction product was analyzed by gas chromatography, and the specific results are shown in table 1.
TABLE 1

Claims (4)

1. The catalyst for preparing 1, 6-hexanediol by adipic acid reduction is characterized by comprising active components Ru, transition metal and nanospheres, wherein the transition metal is at least one of Co, cu, ni, fe, mo and Zn, and the nanospheres are Cu 2 O、γ-Al 2 O 3 Or diatomaceous earth, ru: transition metal simple substance: the mass ratio of the nanospheres is 0.0370:0.0520: (0.01-0.08).
2. The catalyst for preparing 1, 6-hexanediol by reducing adipic acid according to claim 1, wherein the nanospheres are Cu 2 O, transition metal is Co, ru: co: cu (Cu) 2 The mass ratio of O is 0.0370:0.0520: (0.045-0.08).
3. The method for preparing the 1, 6-hexanediol catalyst by reducing adipic acid as claimed in claim 1, which is characterized by comprising the following steps:
(1) Preparing a nanosphere solution;
(2) Preparing a mixed solution of a transition metal soluble salt and Ru salt;
(3) Transferring the mixed solution to the nanosphere solution rapidly, uniformly mixing, and slowly dripping NaBH with a certain concentration into the mixed solution 4 A solution;
(4) And (3) reacting for a period of time, washing with water to be neutral, filtering, and drying to obtain the catalyst.
4. The method for preparing a 1, 6-hexanediol catalyst by reducing adipic acid according to claim 3, wherein the transition metal salt is CoCl 2 ·6H 2 O、CuCl 2 ·6H 2 O、NiCl 2 ·6H 2 O、FeCl 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O or ZnCl 2 。
CN202310456712.3A 2023-04-26 2023-04-26 Catalyst for preparing 1, 6-hexanediol by adipic acid reduction and preparation method thereof Pending CN116493022A (en)

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CN116493022A true CN116493022A (en) 2023-07-28

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