CN115069240A - Supported Pd catalyst for hydrogenation of butyronitrile, and preparation method and application thereof - Google Patents

Supported Pd catalyst for hydrogenation of butyronitrile, and preparation method and application thereof Download PDF

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CN115069240A
CN115069240A CN202210654156.6A CN202210654156A CN115069240A CN 115069240 A CN115069240 A CN 115069240A CN 202210654156 A CN202210654156 A CN 202210654156A CN 115069240 A CN115069240 A CN 115069240A
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catalyst
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hydrogenation
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周光远
郭淼
胡雁鸣
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Dalian Institute of Chemical Physics of CAS
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • 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
    • B01J23/44—Palladium
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    • 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
    • B01J23/8906—Iron and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
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Abstract

The invention discloses a novel supported Pd catalyst and a preparation method and application thereof, and the preparation comprises the following steps: 1) dispersing precursors of the oxide A and the oxide B in a solvent, adding a certain amount of alkali, stirring for 0.5-10h at 25-150 ℃, and then calcining the separated solid material in a muffle furnace at 150-550 ℃ for 0.5-10 h; the solvent is one or more of water, ethanol, methanol, acetone, toluene and isopropanol; 2) dispersing the oxide material obtained in the step 1) and Pd salt into a solvent, wherein the molar ratio of the metal oxide to the solvent is 100-3000, and stirring for 0.5-10h at the temperature of 5-60 ℃; adding a reducing agent into the reaction system, continuously stirring for 0.5-10h, wherein the molar ratio of the reducing agent to Pd is 0.1-20, separating, washing and drying to obtain the catalyst; the catalyst has higher C ═ C bond hydrogenation catalytic activity and selectivity in the reaction of preparing HNBR by NBR hydrogenation, and the catalyst has good recycling performance and separation performance with the product HNBR.

Description

Supported Pd catalyst for hydrogenation of butyronitrile, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polymer hydrogenation, and particularly relates to a supported Pd catalyst, a preparation method thereof and application thereof in preparation of hydrogenated butyronitrile through hydrogenation of nitrile rubber.
Background
Hydrogenated nitrile rubber (HNBR) is an elastomeric material prepared by the selective hydrogenation of the C ═ C double bond in nitrile rubber (NBR). The NBR rubber not only keeps the performances of oil resistance, wear resistance and the like of NBR, but also has the weather resistance and chemical properties of heat, oxygen, aging and the like, and is a special rubber with excellent comprehensive performance. HNBR is widely used in the production of synchronous belts and sealing elements in automobiles, oil fields and aerospace. The HNBR has the use temperature of-50-150 ℃, and can replace expensive fluororubber in some aspects. Major manufacturers of HNBR worldwide in 2021 mainly have the Japanese Rui Weng (Zeon), Lansheng in Germany (Lanxess) and the Zanan science and Daien group in China, wherein Rui Weng and Lansheng have absolute leading positions in the HNBR field. Typically, NBR is converted to HNBR in solution by catalytic hydrogenation. To date, various homogeneous and heterogeneous catalysts have been developed and used in NBR hydrogenation processes. The supported heterogeneous metal nanoparticles are concerned by a plurality of researchers due to higher stability and recyclable performance, however, the currently reported heterogeneous NBR hydrogenation catalyst has lower activity, and the stability of the catalyst and the separation performance of the product still have problems.
Many documents and patents describe heterogeneous catalysts for the catalysis of NBR to HNBR, and the properties of the catalysts vary with the type of catalyst and the method of preparation.
Document 1(Luo, et al. int. Eng. chem. Res.2019,28, 1812-containing 1822) describes a Pd/CNTs @ NF catalyst having a high hydrogenation activity on NBR (apparent TOF ═ 240 h) -1 ) However, the hydrogenation degree of NBR is low (-85%).
Document 2(Ai, et al.J.Taiwan Inst.chem.E.2017,77,250- 2 A supported Pd catalyst. The catalyst shows good separation characteristics with a product HNBR in NBR hydrogenation, but the circulation stability of the catalyst is poor.
Disclosure of Invention
The invention aims to provide a novel supported Pd catalyst which has higher C ═ C bond hydrogenation catalytic activity and selectivity in the reaction of preparing HNBR by NBR hydrogenation, and has good recycling performance and separation performance from the product HNBR.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the invention provides a supported Pd catalyst for nitrile rubber hydrogenation, which is characterized in that: the method comprises the following steps:
1) dispersing precursors of the oxide A and the oxide B in a solvent, adding a certain amount of alkali, stirring for 0.5-10h at 25-150 ℃, and then calcining the separated solid material in a muffle furnace at 150-550 ℃ for 0.5-10 h; the solvent is one or more of water, ethanol, methanol, acetone, toluene and isopropanol;
2) dispersing the oxide material obtained in the step 1) and Pd salt into a solvent, wherein the molar ratio of the metal oxide to the solvent is 100-3000, and stirring for 0.5-10h at the temperature of 5-60 ℃; adding a reducing agent into the reaction system, continuously stirring for 0.5-10h, wherein the molar ratio of the reducing agent to Pd is 0.1-20, separating, washing and drying to obtain the catalyst;
in the above technical solution, further, the oxide a in step 1) is SiO 2 、TiO 2 、Al 2 O 3 、ZrO 2 MgO and Fe 3 O 4 Any one or more of; the alkali is one or more of ammonia water, triethylamine and NaOH, and the concentration of the alkali in the system is 0.001-0.1M;
in the above technical solution, further, the precursor of the oxide B in step 1) is any one or more of tetraethyl orthosilicate, sodium silicate, aminopropyltriethoxysilane, n-butyl titanate, titanium tetrachloride, zirconium n-propoxide, and zirconium n-butoxide;
in the above technical solution, further, the Pd salt in step 2) is one or more of acetate, nitrate, chloride, and acetylacetone compound;
in the above technical solution, further, the reducing agent in step 2) is NaBH 4 Hydrazine hydrate, ethanol, formaldehyde and sodium formateOne or more of (a); the concentration of the reducing agent solution is 0.01-2mg mL -1 The solvent used by the reducing agent solution is one or more of water, ethanol and methanol;
in the above technical solution, further, the content of Pd in the catalyst is 0.1-10 wt%.
In the above technical scheme, further, the solvent in step 2) is one or more of water, ethanol and methanol.
The invention provides an application of the supported Pd catalyst, and the catalyst is used for hydrogenation of nitrile rubber to prepare hydrogenated nitrile.
In the above technical scheme, further, the hydrogenation of nitrile rubber to prepare hydrogenated nitrile rubber: adding nitrile rubber and the supported Pd catalyst into a solvent, and reacting at 10-100 ℃ and 0.1-5MPa H 2 Stirring for 0.1-10 h; the solvent is one or more of acetone, tetrahydrofuran, carbon tetrachloride, xylene and chlorobenzene; the molar ratio of C-C in the hydrogenated butyronitrile to the active component Pd in the catalyst is 10-5000: 1; after the reaction system was cooled to room temperature, the remaining hydrogen was removed, and FTIR and NMR analyses were performed after separating the catalyst and the reaction liquid.
In the above technical scheme, further, the acrylonitrile content of the NBR is 18.1-36.5 wt%, and the weight average molecular weight is 264000-360000.
The catalyst is used for preparing HNBR by NBR hydrogenation and has excellent catalytic performance. The catalyst is simple to prepare, and has high catalytic activity, high recycling performance and high separation performance from products.
The invention has the following beneficial effects: the supported Pd catalyst prepared by the invention has high catalytic activity for HNBR (hydrogenated nitrile butadiene rubber) preparation reaction by NBR (nitrile butadiene rubber) hydrogenation, the catalyst selectivity is 99%, the raw material conversion rate is more than 90%, and the supported Pd catalyst has excellent recycling performance and HNBR separation performance.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) photograph of catalyst # 1 obtained in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of catalyst # 2 obtained in example 2;
FIG. 3 is a Transmission Electron Microscope (TEM) photograph of catalyst # 4 obtained in example 4;
FIG. 4 is a Transmission Electron Microscope (TEM) photograph of catalyst # 9 obtained in example 9;
FIG. 5 shows the product obtained in the second cycle of application example 9 1 H NMR results;
FIG. 6 shows the IR results of the product obtained in the second cycle of application example 9.
Detailed Description
The following examples are intended to further illustrate the invention, but are not intended to limit the scope of the invention as defined by the appended claims.
Example 1:
a50 mL single-neck flask was charged with 500mg of commercial SiO 2 (size 600nm) and 400. mu.L of aminopropyltriethoxysilane and 10mL of toluene were refluxed at 110 ℃ for 5h, then washed by centrifugation and dried to give a white solid material. The white solid support obtained was subsequently calcined in a muffle furnace at 150 ℃ for 6 h. 495mg of calcined white solid material and 13.7mg of Na were taken 2 PdCl 4 (5mg Pd) and 2mL of water were stirred at room temperature for 2h, after which NaBH was added 4 The aqueous solution (5.3mg dissolved in 2.5mL deionized water), stirring for 3h, centrifuging, washing with water and ethanol three times, drying in an oven at 100 ℃ to obtain 1 wt% Pd/SiO 2 Catalyst, labeled catalyst # 1.
The Pd nanoparticles are about 2nm and uniformly dispersed on the surface of the carrier according to the analysis of an electron microscope (figure 1).
Example 2:
in a 500mL single-neck flask, 400mg of Fe was added 3 O 4 Nanoparticles (size 200nm), 320mL ethanol, 80mL water and 12mL ammonia were stirred at 40 ℃ for 30min, followed by 1.2mL tetraethyl orthosilicate and 0.3mL aminopropyltriethoxysilane, continued stirring at 40 ℃ for 3h, followed by separation, washing with copious amounts of water and ethanol, and drying at 60 ℃ to give a black solid. 495mg of black solid material and 13.7mg of Na were taken 2 PdCl 4 (5mg Pd) and 2mL of water were stirred at room temperature for 2h, after which NaBH was added 4 (5.3mg in 2)5mL of deionized water), continuously stirring for 3h, then centrifuging, washing with water and ethanol for three times, and drying in an oven at 100 ℃ to obtain 1 wt% of Pd/SiO supported on the solution 2 Catalyst, labeled catalyst # 2.
The Pd nanoparticles are about-2 nm and are uniformly dispersed as shown by electron microscope analysis (figure 2).
Example 3:
this example is essentially the same as example 2, except that 0.3mL of aminopropyltriethoxysilane was changed to 0.3mL of zirconium n-propoxide, resulting in a 1 wt% Pd loading of catalyst # 3.
The Pd nano particles are about 2nm and are uniformly dispersed through electron microscope analysis.
Example 4:
this example is essentially the same as example 3, except that 0.3mL of zirconium n-propoxide was added in an amount of 0.15mL to give a No. 5 catalyst with a 1 wt% Pd loading.
The Pd nanoparticles were found to be about-2 nm and uniformly dispersed by electron microscopy analysis (FIG. 3).
Example 5:
this example is essentially the same as example 4, except that 0.15mL of zirconium n-propoxide was changed to 0.15mL of isopropyl titanate to give catalyst # 5 with 1 wt% Pd loading.
The Pd nano particles are about 2nm and are uniformly dispersed through electron microscope analysis.
Example 6:
this example is essentially the same as example 2, except that Fe was used 3 O 4 Changed into commercial SiO 2 Is P-10 (specific surface 317 m) 2 g -1 Pore size 30nm) and the resulting catalyst was labeled as catalyst # 6.
Example 7:
this example is essentially the same as example 5, except that the Pd salt used is Pd (NO) 3 ) 2 Thus, 7# catalyst with 1 wt% Pd loading was obtained.
The Pd nano-particles are about 2.5nm and are uniformly dispersed through electron microscope analysis.
Example 8:
this example is essentially the same as example 6 except that the loading of Pd is 5 wt%, identified as catalyst # 8.
The Pd nano particles are about 2nm and are uniformly dispersed through electron microscope analysis.
Example 9:
this example is essentially the same as example 8 except that the reducing agent is hydrazine hydrate solution and the resulting catalyst is designated catalyst # 9.
The Pd nanoparticles were found to be about-2 nm and uniformly dispersed by electron microscopy analysis (FIG. 4).
Example 10:
this example is essentially the same as example 8 except that the reducing agent is a sodium formate solution and the resulting catalyst is designated as catalyst # 10.
The Pd nano particles are about 2nm and are uniformly dispersed through electron microscope analysis.
Application example 1:
160mg of No. 1 catalyst, 300mg of nitrile rubber (JSR-230S, Japan, butyronitrile content 35 wt%), 70mL of acetone were charged in a high-pressure reactor, and 2MPa H was charged 2 Stirring for 2h at 60 ℃, cooling the system to room temperature, removing hydrogen, centrifugally separating the catalyst, separating out the product by ethanol, drying, and testing the hydrogenation degree of the product by attenuated total reflection infrared spectroscopy and nuclear magnetic resonance, wherein the catalytic result is shown in table 1.
Application example 2:
the present application example was substantially the same as application example 1, except that 160mg of 2# catalyst was used as the catalyst, the catalyst was separated using a magnet after the reaction, and the degree of hydrogenation of the product, which is (unsaturation degree before hydrogenation-unsaturation degree after hydrogenation)/unsaturation degree before hydrogenation × 100%, was tested by attenuated total reflection infrared spectroscopy and nuclear magnetic resonance after drying. The catalytic results are shown in Table 1.
Application example 3:
the present application example was substantially the same as application example 2 except that 160mg of # 3 catalyst was used, and the catalytic results are shown in Table 1.
Application example 4:
this application example was substantially the same as application example 2 except that 160mg of catalyst # 4 was used, and the catalytic results were shown in Table 1.
Application example 5:
the application example was substantially the same as application example 2 except that 160mg of No. 5 catalyst was used, and the catalytic results are shown in Table 1.
Application example 6:
160mg of No. 6 catalyst, 300mg of nitrile rubber and 70mL of acetone are added into a high-pressure reaction kettle, and 2MPa of H is filled into the high-pressure reaction kettle 2 Stirring for 2h at 60 ℃, cooling the system to room temperature, removing hydrogen, depositing the catalyst, filtering and separating the catalyst, separating the product out by ethanol, drying, testing the hydrogenation degree of the product by attenuated total reflection infrared spectroscopy and nuclear magnetic resonance, and obtaining the catalytic result shown in table 1.
Application example 7:
the application example was substantially the same as application example 2 except that 160mg of No. 7 catalyst was used, and the catalytic results are shown in Table 1.
Application example 8:
this application example was substantially the same as application example 6 except that 32mg of catalyst # 8 was used, and the catalytic results were shown in Table 1.
Application example 9:
this application example was substantially the same as application example 6 except that 160mg of catalyst # 9 was used, and the catalytic results were shown in Table 1.
Application example 10:
this application example was substantially the same as application example 6 except that 160mg of No. 10 catalyst was used, and the catalytic results are shown in Table 1.
Application example 11:
this application example was substantially the same as application example 4, except that the nitrile rubber used was Mw 360000, the nitrile content was 36.5 wt% (No. NBR3604, petrochemical, lang.) and the catalytic results are shown in table 1.
Application example 12:
this application example was substantially the same as application example 6 except that the nitrile rubber used was Mw 360000, the nitrile content was 36.5 wt% (No. NBR3604, petrochemical, lang.) and the catalytic results are shown in table 1.
Comparative example 1:
this comparative example is essentially the same as application example 10, except that the catalyst used was commercial (TCI) Pd/C (5 wt%) 32mg, and the catalytic results are shown in Table 1.
Comparative example 2:
this comparative example is substantially the same as application example 10 except that the catalyst used was commercial (Alfa Aesar) Pd/Al 2 O 3 (5 wt%) 32mg, and the catalytic results are shown in Table 1.
TABLE 1 catalytic results
Figure BDA0003687082340000061
From the results, the degree of hydrogenation of the synthesized catalyst is obviously superior to that of the commercialized Pd/C, and the C ═ C bond hydrogenation selectivity is obviously superior to that of the commercialized Pd/Al 2 O 3 The synthesized catalyst has high catalytic activity and selectivity to C ═ C bonds in nitrile rubber.
Cycle stability study of the catalyst:
the 4#, 8# and Pd/C are separated and dried by the above process, and then the catalytic hydrogenation process is repeated, and the analysis results are shown in Table 2 below.
TABLE 2 hydrogenation results of second catalyzed nitrile rubber with each catalyst
Figure BDA0003687082340000062
As can be seen from the results in the table above, the catalyst synthesized by the invention has excellent recycling performance compared with the commercial Pd/C.
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.

Claims (10)

1. A preparation method of a supported Pd catalyst for nitrile rubber hydrogenation is characterized by comprising the following steps:
1) dispersing the oxide A and the oxide B precursors in a solvent, adding a certain amount of alkali, stirring at 25-150 ℃ for 0.5-10h, and calcining the separated solid material in a muffle furnace at 150-550 ℃ for 0.5-10 h;
the solvent is one or more of water, ethanol, methanol, acetone, toluene and isopropanol;
oxide A is selected from SiO 2 、TiO 2 、Al 2 O 3 、ZrO 2 MgO and Fe 3 O 4 Any one or more of;
the oxide B is selected from oxides of silicon, titanium and zirconium;
2) dispersing the oxide material obtained in the step 1) and Pd salt into a solvent, wherein the molar ratio of the metal oxide to the solvent is 100-3000, and stirring for 0.5-10h at the temperature of 5-60 ℃; adding a reducing agent into the reaction system, continuously stirring for 0.5-10h, wherein the molar ratio of the reducing agent to Pd is 0.1-20, separating, washing and drying to obtain the catalyst.
2. The method for preparing a supported Pd catalyst according to claim 1, characterized in that: in the step 1), the alkali is one or more of ammonia water, triethylamine and NaOH, and the concentration of the alkali in the system is 0.001-0.1M.
3. The method for preparing a supported Pd catalyst according to claim 1, characterized in that: in the step 1), the precursor of the oxide B is any one or more of tetraethyl orthosilicate, sodium silicate, aminopropyltriethoxysilane, n-butyl titanate, isopropyl titanate, zirconium n-propoxide and zirconium n-butoxide.
4. The method for preparing a supported Pd catalyst according to claim 1, characterized in that: in the step 2), the Pd salt is one or more of acetate, nitrate, chloride and acetylacetone compound.
5. The method for preparing a supported Pd catalyst according to claim 1, characterized in that: the reducing agent in the step 2) is NaBH 4 One or more of hydrazine hydrate, ethanol, formaldehyde and sodium formate; the concentration of the reducing agent solution is 0.01-2mg mL -1 The solvent used by the reducing agent solution is one or more of water, ethanol and methanol.
6. The method for preparing a supported Pd catalyst according to claim 1, characterized in that: the Pd content in the catalyst is 0.1-10 wt%.
7. The method for producing a supported Pd catalyst according to claim 1, wherein: the solvent in the step 2) is one or more of water, ethanol and methanol.
8. Use of the supported Pd catalyst obtained by the process according to any one of claims 1 to 7 for the hydrogenation of nitrile rubber to produce hydrogenated nitrile.
9. Use according to claim 8, characterized in that: hydrogenation of nitrile rubber to prepare hydrogenated nitrile rubber, adding nitrile rubber and the supported Pd catalyst into solvent at 10-100 deg.c and 0.1-5MPa H 2 Stirring for 0.1-10 h; the solvent is one or more of acetone, tetrahydrofuran, carbon tetrachloride, xylene and chlorobenzene; the molar ratio of C-C in the hydrogenated butyronitrile to the active component Pd in the catalyst is 10-5000: 1.
10. use according to claim 8, characterized in that: the NBR has an acrylonitrile content of 18.1 to 36.5 wt% and a weight average molecular weight of 264000-360000.
CN202210654156.6A 2022-06-09 2022-06-09 Supported Pd catalyst for hydrogenation of butyronitrile, and preparation method and application thereof Pending CN115069240A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5028665A (en) * 1989-01-09 1991-07-02 The Dow Chemical Company Polymer hydrogenation catalysts
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CN104119478A (en) * 2013-04-27 2014-10-29 蒲城瑞鹰新材料科技有限公司 Novel method for synthesizing hydrogenated nitrile-butadiene rubber by using Pd/TiO2 catalyst
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Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5028665A (en) * 1989-01-09 1991-07-02 The Dow Chemical Company Polymer hydrogenation catalysts
CN104119478A (en) * 2013-04-27 2014-10-29 蒲城瑞鹰新材料科技有限公司 Novel method for synthesizing hydrogenated nitrile-butadiene rubber by using Pd/TiO2 catalyst
CN103537304A (en) * 2013-08-24 2014-01-29 北京化工大学 Preparation of silane coupling agent-modified SiO2 loaded rhodium catalyst and selective hydrogenation application of catalyst to butadiene-acrylonitrile rubber
CN106268735A (en) * 2015-06-08 2017-01-04 中国石油大学(北京) Nitrile butadiene rubber selective heterogeneous hydrogenation catalyst and preparation method and hydrogenation method thereof

Non-Patent Citations (2)

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Title
BINGQING GE ET AL.: "Zirconium promoter effect on catalytic activity of Pd based catalysts for heterogeneous hydrogenation of nitrile butadiene rubber", APPLIED SURFACE SCIENCE, pages 2 *
姚含波: "丁腈橡胶加氢磁性催化剂的制备及应用", 中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑, no. 10, pages 35 *

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