CN110975867A - Pd-ZnO/Al2O3Catalyst, preparation method and application thereof - Google Patents
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Abstract
The invention discloses Pd-ZnO/Al2O3The catalyst takes Pd as an active component, ZnO as a cocatalyst and Al as well as a preparation method and application thereof2O3Is a carrier, and comprises the following components in percentage by mass: 0.1-0.25% of Pd, 0.5-2.0% of ZnO, and Al2O397.75% -99.4%. The preparation method comprises the following steps: uniformly mixing and fully grinding a Pd source, a Zn source, an Al source and dicyandiamide, then putting the mixture into a tube furnace, and introducing H2/N2Heating the mixed gas, and performing N treatment after the treatment2Or cooling to room temperature under inert atmosphere to obtain the catalyst. The prepared catalyst is used for polydivinyl acetylene hydrogenation reaction, and the degree of hydrogenation of the polydivinyl acetylene can reach 25.8% under relatively mild reaction conditions.
Description
Technical Field
The invention relates to Pd-ZnO/Al2O3A catalyst, a preparation method and application thereof, belonging to the technical field of catalyst preparation.
Background
Synthetic rubbers are generally classified into general synthetic rubbers and semi-general synthetic rubbers, with chloroprene rubbers being of the semi-general type. Chloroprene rubber has the general properties of most general synthetic rubbers and outstanding properties such as solvent resistance, chemical stability, heat resistance, aging resistance, air tightness and the like, so that the application field is very wide. There are two main processes for producing chloroprene rubber, the acetylene process and the butadiene process. China mainly adopts an acetylene method to produce chloroprene rubber. However, in the production of chloroprene rubber by the acetylene process, Divinylacetylene (DVA) is produced as a by-product.
Formula of acetylene method for producing chloroprene rubber:
equation for the production of divinylacetylene as a by-product:
DVA contains double and triple bonds and is very reactive and therefore very susceptible to polymerization to form polydivinyl acetylene (PDVA). At present, most PDVA concentrated solution is subjected to incineration treatment, only a small part of PDVA concentrated solution is used for waterproof coating and coastal wooden ship anticorrosive paint, but the problems of poor adhesion and easy falling exist, and the application of PDVA concentrated solution is limited. Catalytic hydrogenation of unsaturated polymers is a process for preparing new materials by converting unsaturated polymers into saturated or semi-saturated polymers, thereby changing the properties of the polymers.
The catalyst for catalytic hydrogenation can be divided into two types, namely heterogeneous hydrogenation catalyst and homogeneous hydrogenation catalyst. Wherein the heterogeneous catalyst mainly comprises noble metals such as Pt, Pd, Rh and the like and transition metal elements such as Fe, Co, Ni and the like which are loaded on carriers such as kieselguhr, active carbon, aluminum oxide, calcium carbonate, silicon dioxide and the like. Chemical modification and corrosion resistance research of polydivinyl acetylene in cheschreza [ cheschreza ] university of Chongqing, 2011 ] uses raney nickel and Pd/C catalyst, and researches the reaction conditions with the best hydrogenation effect of PDVA from the aspects of catalyst dosage, polymer concentration, reaction temperature, reaction time, additives and the like. Experiments show that both Raney nickel and Pd/C catalysts can partially hydrogenate polymers, the better conditions of the hydrogenation reaction of the Raney nickel catalyst are that the reaction time is 200-300 min, the reaction temperature is 110 ℃, the reaction pressure is 2 MPa, the catalyst dosage is 8% of the polymer, the polymer concentration is 10-15%, and the polymer hydrogenation degree can reach 10% under the conditions; the preferable conditions of the Pd/C catalyst hydrogenation reaction are that the reaction time is 200-300 min, the reaction temperature is 110 ℃, the reaction pressure is 1.4 MPa, the catalyst dosage is 4% of the polymer, the polymer concentration is 10-15%, and the additive is 5%, and the hydrogenation degree can reach 17% under the conditions.
It is well known that modification by catalytic hydrogenation of polydivinyl acetylene to reduce its unsaturation is an important means to improve its application properties. However, from few literature reports at present, the polydivinyl acetylene hydrogenation modified catalyst still has the defects of harsh reaction conditions, low hydrogenation degree, high noble metal loading in the catalyst and the like. Therefore, it is of great practical significance to design and prepare catalysts with low Pd loading and good catalytic activity.
Disclosure of Invention
The invention aims to provide Pd-ZnO/Al2O3The invention also provides a Pd-ZnO/Al catalyst and a preparation method thereof2O3The application of the catalyst in polydivinyl acetylene hydrogenation.
The invention provides Pd-ZnO/Al2O3The catalyst takes Pd as an active component, ZnO as a cocatalyst and Al2O3Is used as a carrier, and comprises the following components in percentage by mass:
the mass percent of the active component Pd is 0.1-0.25%, the mass percent of ZnO is 0.5-2.0%, and the carrier Al is2O3The mass percentage of the component (A) is 97.75% -99.4%.
Preferably, in the catalyst, the mass percentages of the components are as follows:
an active component Pd: 0.15 to 0.2 percent
And (3) a cocatalyst ZnO: 1.0% -2.0%
Carrier Al2O3：97.8%~98.85%。
The invention provides the Pd-ZnO/Al2O3The preparation method of the catalyst comprises the following steps:
(1) weighing a Pd source, a Zn source, an Al source and dicyandiamide, uniformly mixing and fully grinding, wherein the mass ratio of the Pd salt to the Zn salt to the Al salt to the dicyandiamide is 1: 1.1-43.9: 276.2-4388.6: 100-500;
(2) placing the ground mixed sample in a tube furnace, and introducing H2/N2Slowly heating the mixed gas to 80-90 ℃ for treatment for 3-10 h, and then quickly heating to 300-600 ℃ for treatment for 3-10 h;
(3) after the treatment is finished, H2/N2Switching the mixed gas to N2Or inert gas, and naturally cooling to room temperature to obtain the catalyst.
In the preparation method, the Pd source in the step (1) is one or more of palladium nitrate, palladium chloride and palladium acetate; the Zn source is one or more of zinc nitrate, zinc hydroxide, zinc chloride and zinc acetate; the Al source is one or more of aluminum nitrate, aluminum chloride and aluminum acetate.
The above production process, step (2) said H2/N2The volume ratio of the mixed gas is 1: 1-10, and the flow rate of the mixed gas is 20-100 mL/min; the slow heating rate is 1-3 ℃/min, and the fast heating rate is 5-10 ℃/min.
Further, said H in step (2)2/N2The ratio of the mixed gas is 1: 1-5, and the flow rate is 40-60 mL/min; the slow heating rate is 1-2 ℃/min, the treatment is carried out for 5-8 h at 80-85 ℃, the fast heating rate is 5-8 ℃/min, and the treatment is carried out for 4-6 h at 350-500 ℃.
In the preparation method, the inert gas in the step (3) is one or two of Ar and He, and the flow rate of the inert gas is 20-100 mL/min.
Further, the flow rate of the inert gas is 40-60 mL/min.
The invention also provides the Pd-ZnO/Al2O3The application of the catalyst in polydivinyl acetylene hydrogenation specifically comprises the following steps: PDVA toluene solution and Pd-ZnO/Al2O3Adding catalyst into high-pressure reactor, Pd-ZnO/Al2O3The mass ratio of the catalyst to the PDVA is 1: 30-60, nitrogen is firstly introduced for replacement for three times, then hydrogen is introduced, the reaction pressure is controlled to be 0.1-1.0 MPa, heating and stirring are started, the heating rate is 2-5 ℃/min, the stirring speed is 100-300 rpm, and the temperature is increased to 90-105 ℃ for reaction for 1-3 hours.
Pd-ZnO/Al2O3The catalyst is used in the reaction of catalytic hydrogenation of polydivinyl acetylene, and the hydrogenation degree of the polydivinyl acetylene can reach 25.8%.
The invention has the beneficial effects that:
(1) after the catalyst prepared by the invention is used for the catalytic hydrogenation reaction of polydivinyl acetylene, the unsaturation degree of the polymer can be effectively reduced;
(2) the catalyst has the advantages of mild use condition, high catalytic activity, reusability, low content of noble metal Pd and low cost;
(3) the catalyst has the advantages of simple preparation process, wide raw material source, no harm to human bodies and environment, easy realization of industrial production and good application prospect.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
0.1 g of PdCl is weighed out2，1.76 g Zn(NO3)2·6H2O，35.88 g Al(OH)3And 10 g of dicyandiamide were mixed together and sufficiently ground, and the ground mixed sample was placed in a tube furnace and H was introduced at a flow rate of 50 mL/min2/N2Mixed gas (H)2/N2The volume ratio is 1: 5), the temperature is increased to 80 ℃ at the speed of 1 ℃/min for processing for 8H, then the temperature is increased to 400 ℃ at the speed of 8 ℃/min for processing for 4H, the heating is stopped after the processing is finished, and H is added2/N2The mixed gas is switched to helium with the flow rate of 50 mL/min, and the mixed gas is naturally cooled to the room temperature to obtain the Pd-ZnO/Al2O3CatalysisAnd (3) preparing. Wherein the mass percent of Pd is 0.25wt%, the mass percent of ZnO is 2.0wt%, Al2O3Is 97.75 wt%.
30g of a toluene solution of PDVA (PDVA concentration 20%) and 0.2 g of Pd-ZnO/Al2O3Adding the catalyst into a high-pressure reaction kettle, introducing nitrogen for three times, then introducing hydrogen, controlling the reaction pressure at 1.0 MPa, starting heating and stirring, wherein the heating rate is 2 ℃/min, the stirring speed is 300 rpm, and heating to 105 ℃ for reaction for 3 hours. The unsaturation degree of the PDVA toluene solution and the reacted solution is measured by a bromine number method, so that the hydrogenation degree of the polydivinyl acetylene is calculated to be 25.8%.
Example 2
0.15 g Pd (NO) is weighed3)2·2H2O，1.76 g Zn(NO3)2·6H2O，35.88 g Al(OH)3And 10 g of dicyandiamide by the preparation method of example 1 to obtain Pd-ZnO/Al2O3A catalyst. Wherein the mass percent of Pd is 0.25wt%, the mass percent of ZnO is 2.0wt%, Al2O3Is 97.75 wt%.
Using the reaction conditions and measurement method of example 1, the degree of hydrogenation of polydivinyl acetylene was calculated to be 25.4%.
Example 3
0.05 g of PdCl are weighed out2，0.88 g Zn(NO3)2·6H2O，35.88 g Al(OH)3And 10 g of dicyandiamide by the preparation method of example 1 to obtain Pd-ZnO/Al2O3A catalyst. Wherein the mass percent of Pd is 0.13 wt%, the mass percent of ZnO is 1.02 wt%, Al2O3The mass percentage of (B) is 98.85 wt%.
Using the reaction conditions and measurement method of example 1, the degree of hydrogenation of polydivinyl acetylene was calculated to be 18.7%.
Example 4
0.1 g of PdCl is weighed out2，0.59g Zn(OH)2，35.88 g Al(OH)3And 10 g of dicyandiamide by the preparation method of example 1 to obtain Pd-ZnO/Al2O3A catalyst. Wherein P isd is 0.25wt%, ZnO is 2.0wt%, Al2O3Is 97.75 wt%.
Using the reaction conditions and measurement method of example 1, the degree of hydrogenation of polydivinyl acetylene was calculated to be 25.4%.
Example 5
35.88g of Al (OH) in example 13Changed to 61.38g AlCl3The Pd-ZnO/Al is prepared by the same method under the same other conditions2O3A catalyst. Wherein the mass percent of Pd is 0.25wt%, the mass percent of ZnO is 2.0wt%, Al2O3Is 97.75 wt%.
Using the reaction conditions and measurement method of example 1, the degree of hydrogenation of polydivinyl acetylene was calculated to be 24.9%.
Example 6
The same method is adopted to prepare Pd-ZnO/Al by changing the using amount of dicyandiamide in the example 1 to 30g and keeping other conditions unchanged2O3A catalyst. Wherein the mass percent of Pd is 0.25wt%, the mass percent of ZnO is 2.0wt%, Al2O3Is 97.75 wt%.
Using the reaction conditions and measurement method of example 1, the degree of hydrogenation of polydivinyl acetylene was calculated to be 25.0%.
Example 7
The Pd-ZnO/Al is prepared by the same method by changing the temperature-raising treatment process in the preparation condition of the catalyst in the embodiment 1 into the temperature-raising treatment process of 2 ℃/min to 90 ℃ for 8h, then raising the temperature of 5 ℃/min to 400 ℃ for 4 h, and keeping the other conditions unchanged2O3A catalyst. Wherein the mass percent of Pd is 0.25wt%, the mass percent of ZnO is 2 wt%, and Al2O3Is 97.75 wt%.
Using the reaction conditions and measurement method of example 1, the degree of hydrogenation of polydivinyl acetylene was calculated to be 23.1%.
Example 8
The amount of the PDVA toluene solution used in the reaction conditions of example 1 was changed to 60 g, and the degree of hydrogenation of polydivinyl acetylene was calculated to be 21.6% under the same other conditions.
Example 9
The degree of hydrogenation of polydivinyl acetylene was calculated to be 21.2% by controlling the reaction pressure under the reaction conditions of example 1 to 0.5 MPa and keeping the other conditions unchanged.
Example 10
The stirring speed was changed to 150 rpm under the reaction conditions of example 1, and the degree of hydrogenation of polydivinyl acetylene was calculated to be 24.1% under the other conditions.
Example 11
The reaction temperature in the reaction conditions of example 1 was changed to 95 ℃ and the degree of hydrogenation of polydivinyl acetylene was calculated to be 22.3% under the same conditions.
Example 12
The reaction time in the reaction condition of example 1 was changed to 2 hours, and the degree of hydrogenation of polydivinyl acetylene was calculated to be 24.6% without changing other conditions.
Cycle performance testing of the catalyst:
example 13
The catalyst of example 1 was recovered and labeled as Pd-ZnO/Al2O3-1. Using the evaluation conditions of example 1, the degree of hydrogenation of polydivinyl acetylene was calculated to be 25.2% under the evaluation conditions.
Example 14
The catalyst from example 13 was recovered, labelled Pd-ZnO/Al2O3-2. Using the evaluation conditions of example 1, the degree of hydrogenation of polydivinyl acetylene was calculated to be 24.5% under the evaluation conditions.
Example 15
The catalyst from example 14 was recovered and labeled as Pd-ZnO/Al2O3-3. Using the evaluation conditions of example 1, the degree of hydrogenation of polydivinyl acetylene was calculated to be 24.7% under the evaluation conditions.
Examples 13 to 15 show that the catalyst has good cycle performance and can be reused.
Claims (10)
1. Pd-ZnO/Al2O3A catalyst, characterized by: the catalyst is PdActive component ZnO as cocatalyst, Al2O3Is used as a carrier, and comprises the following components in percentage by mass:
an active component Pd: 0.1 to 0.25 percent
And (3) a cocatalyst ZnO: 0.5% -2.0%
Carrier Al2O3：97.75%~99.4%。
2. The Pd-ZnO/Al alloy according to claim 12O3A catalyst, characterized by: in the catalyst, the mass percent of each component is as follows:
an active component Pd: 0.15 to 0.2 percent
And (3) a cocatalyst ZnO: 1.0% -2.0%
Carrier Al2O3：97.8%~98.85%。
3. The Pd-ZnO/Al alloy as set forth in claim 1 or 22O3The preparation method of the catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) weighing a Pd source, a Zn source, an Al source and dicyandiamide, uniformly mixing and fully grinding, wherein the mass ratio of the Pd salt to the Zn salt to the Al salt to the dicyandiamide is 1: 1.1-43.9: 276.2-4388.6: 100-500;
(2) placing the ground mixed sample in a tube furnace, and introducing H2/N2Slowly heating the mixed gas to 80-90 ℃ for treatment for 3-10 h, and then quickly heating to 300-600 ℃ for treatment for 3-10 h;
(3) after the treatment is finished, H2/N2Switching the mixed gas to N2Or inert gas, and naturally cooling to room temperature to obtain the catalyst.
4. Pd-ZnO/Al according to claim 32O3The preparation method of the catalyst is characterized by comprising the following steps: in the step (1), the Pd source is one or more of palladium nitrate, palladium chloride and palladium acetate; the Zn source is one or more of zinc nitrate, zinc hydroxide, zinc chloride and zinc acetate; the Al source is one or more of aluminum nitrate, aluminum hydroxide, aluminum chloride and aluminum acetate.
5. Pd-ZnO/Al according to claim 32O3The preparation method of the catalyst is characterized by comprising the following steps: said H in step (2)2/N2The volume ratio of the mixed gas is 1: 1-10, and the flow rate of the mixed gas is 20-100 mL/min;
the slow heating rate is 1-3 ℃/min, and the fast heating rate is 5-10 ℃/min.
6. The Pd-ZnO/Al alloy according to claim 52O3The preparation method of the catalyst is characterized by comprising the following steps: said H in step (2)2/N2The ratio of the mixed gas is 1: 1-5, and the flow rate is 40-60 mL/min; the slow heating rate is 1-2 ℃/min, the treatment is carried out for 5-8 h at 80-85 ℃, the fast heating rate is 5-8 ℃/min, and the treatment is carried out for 4-6 h at 350-500 ℃.
7. Pd-ZnO/Al according to claim 32O3The preparation method of the catalyst is characterized by comprising the following steps: in the step (3), the inert gas is one or two of Ar and He, and N2Or the flow rate of the inert gas is 20-100 mL/min.
8. The Pd-ZnO/Al alloy according to claim 72O3The preparation method of the catalyst is characterized by comprising the following steps: the flow rate of the inert gas is 40-60 mL/min.
9. The Pd-ZnO/Al alloy as set forth in claim 1 or 22O3The application of the catalyst is characterized in that: PDVA toluene solution and Pd-ZnO/Al2O3Adding catalyst into high-pressure reactor, Pd-ZnO/Al2O3The mass ratio of the catalyst to the PDVA is 1: 30-60, nitrogen is firstly introduced for replacement for three times, then hydrogen is introduced, the reaction pressure is controlled to be 0.1-1.0 MPa, heating and stirring are started, the heating rate is 2-5 ℃/min, the stirring speed is 100-300 rpm, and the temperature is increased to 90-105 ℃ for reaction for 1-3 hours.
10. Root of herbaceous plantUse according to claim 9, characterized in that: Pd-ZnO/Al2O3The catalyst is used for the catalytic hydrogenation reaction of polydivinyl acetylene, and the hydrogenation degree of the polydivinyl acetylene can reach 25.8%.
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Application publication date: 20200410 |