CN109939686B - Catalyst for preparing cis-pinane by hydrogenation - Google Patents
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Abstract
A catalyst for preparing cis-pinane by hydrogenation relates to cis-pinane. The catalyst for preparing cis-pinane by hydrogenation comprises a carrier, an active component 1 and an active component 2, wherein the active component 1 is nickel or nickel oxide, and the active component 2 is alkaline earth metal or alkaline earth metal oxide; the content of the active component 1 is 50-500 g/L, and the content of the active component 2 is 0-100 g/L. During preparation, mixing a solution containing a nickel compound and an alkaline earth metal compound with a carrier, adding an aqueous solution of a precipitator, and reacting to obtain a catalyst precursor I; and aging and washing the obtained catalyst precursor I, and then drying and roasting to obtain the catalyst for preparing the cis-pinane through hydrogenation. The catalyst for preparing cis-pinane by hydrogenation can be applied to the reaction of preparing cis-pinane by hydrogenation of alpha-pinene.
Description
Technical Field
The invention relates to cis-pinane, in particular to a catalyst for preparing cis-pinane by hydrogenation.
Background
Pinane is an important intermediate for synthesizing spices such as linalool, citronellol and dihydromyrcenol, the pinane has cis-isomer and trans-isomer, and the cis-pinane has higher activity, so that the industry hopes to obtain the cis-pinane with high content. The method for synthesizing pinane is mainly characterized in that alpha-pinene hydrogenation is adopted to efficiently obtain high-selectivity cis-pinane, and the key point is the selection of an alpha-pinene hydrogenation catalyst.
The catalyst for preparing cis-pinane by hydrogenating alpha-pinene can be divided into noble metal catalyst and non-noble metal catalyst. The noble metal catalysts such as palladium, platinum, rhodium and the like have higher catalytic activity and mild reaction conditions, but the selectivity of the cis-pinane is not high, the production cost is high, and the large-scale industrialization is difficult to realize. The non-noble metal catalyst mainly takes a nickel catalyst as a main component, and comprises raney nickel, nano nickel and the like. Wherein, the Raney nickel catalyst which is commonly used in industry has high hydrogenation pressure, harsh operation conditions and lower cis-pinane content in the product; the nano nickel catalyst has high synthesis cost, complex operation and poor thermal reaction stability and mechanical stability. In recent years, there have been some advances in the research of modified nickel catalysts. For example, chinese patent CN 1191857 provides a novel modified skeletal nickel catalyst, which is used in the reaction of preparing cis-pinane by pinene hydrogenation, wherein the pinene conversion rate is greater than 99%, and the cis-pinane selectivity is 95%. Chinese patent CN1262263 provides an improved process for preparing cis-pinane, which adopts a novel transition metal alloy catalyst, the pinene conversion rate can reach 99%, and the cis-pinane selectivity is greater than 96%. Therefore, how to realize the modification of the nickel catalyst and improve the reaction activity of the catalyst and the cis-selectivity of pinane has important significance in industrial production under mild conditions.
Disclosure of Invention
The first purpose of the invention is to provide a catalyst for preparing cis-pinane by hydrogenation aiming at the problems of low alpha-pinene conversion rate, low cis-pinane selectivity and the like of the catalyst in the prior art.
The second purpose of the invention is to provide a preparation method of the catalyst for preparing the cis-pinane by hydrogenation.
The third purpose of the invention is to provide the application of the catalyst for preparing the cis-pinane by hydrogenation.
The catalyst for preparing the cis-pinane through hydrogenation comprises a carrier, an active component 1 and an active component 2, wherein the active component 1 is nickel or a nickel oxide, and the active component 2 is an alkaline earth metal or an alkaline earth metal oxide; the content of the active component 1 is 50-500 g/L, and the content of the active component 2 is 0-100 g/L.
The content of the active component 2 is preferably more than 0g/L and less than 60g/L, and the active component 1 or the active component 2 has synergistic effect on the aspects of improving the conversion rate of alpha-pinene and the selectivity of cis-pinane.
The carrier can be at least one selected from alumina, silicon dioxide, titanium dioxide, activated carbon and the like, and the BET specific surface area of the carrier can be 80-220 m2A/g, preferably 90 to 150m2(ii)/g; the carrier may have a pore volume of 0.2 to 0.8mL/g, preferably 0.3 to 0.6 mL/g.
The alkaline earth metal may be selected from at least one of Ca, Mg, Sr, Ba, etc., preferably Mg.
The content of the active component 1 can be 100-300 g/L.
The content of the active component 2 can be 5-50 g/L.
The catalyst for preparing cis-pinane through hydrogenation can also comprise an active component 3 besides a carrier, the active component 1 and the active component 2, wherein the active component 3 is Mo or Mo oxide, the content of the active component 3 can be 0.5-50.0 g/L, and at the moment, in the presence of the active component 1, the active component 2 and the active component 3 have a synergistic effect on the aspect of improving the alpha-pinene conversion rate and the cis-pinane selectivity.
The preparation method of the catalyst for preparing the cis-pinane by hydrogenation comprises the following steps:
1) mixing a solution containing a nickel compound and an alkaline earth metal compound with a carrier, adding an aqueous solution of a precipitator, and reacting to obtain a catalyst precursor I;
2) aging and washing the catalyst precursor I obtained in the step 1), and then drying and roasting to obtain the catalyst for preparing the cis-pinane through hydrogenation.
In step 1), the nickel compound may be one selected from nickel chloride, nickel nitrate, nickel sulfate, soluble complex of nickel, and the like; the alkaline earth metal compound can be at least one selected from nitrate, hydrochloride, sulfate, C1-C4 carboxylate and the like; the precipitant can be at least one of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, ammonia water and the like; the reaction temperature can be 30-90 ℃, preferably 40-70 ℃, and the reaction time can be 2-8 h.
In the step 2), the aging temperature can be 30-80 ℃, and the aging time can be 2-10 h; the drying temperature can be 80-120 ℃, and the drying time can be 2-6 h; the roasting atmosphere is not particularly limited, and can achieve comparable technical effects, and an air atmosphere can be adopted for economic consideration; the roasting temperature can be 400-600 ℃, and the roasting time can be 3-8 h.
When the catalyst for preparing cis-pinane by hydrogenation contains an active component 3, the preparation method is better by using a solution of a molybdenum compound or a mixture solution of the molybdenum compound and an alkaline earth metal compound to replace a simple solution of the alkaline earth metal compound in the step 1).
The nickel in the catalyst for preparing the cis-pinane through hydrogenation can be reduced into a simple substance and directly used in the reaction of preparing the cis-pinane through alpha-pinene hydrogenation, or can exist in the form of nickel oxide, so that the catalyst is convenient to store and stably transport, but before use, a reducing agent is required to be used for activation, and the reducing agent used for activation can be hydrogen or a material containing hydrogen.
The catalyst for preparing cis-pinane by hydrogenation can be applied to the reaction of preparing cis-pinane by hydrogenation of alpha-pinene.
The technical key of the invention is the selection of the catalyst, and under the condition of determining the catalyst, the technical personnel of the invention know how to reasonably select the applied process conditions, for example, the specific application method can be as follows:
a method for preparing cis-pinane by hydrogenation, comprising: in an autoclave reactor, a material containing alpha-pinene and hydrogen are used as raw materials and are contacted with a catalyst to react to generate cis-pinane. The pressure of the reaction can be 1.0-3.0 MPa, preferably 1.5-2.5 MPa; the reaction temperature can be 70-120 ℃, and preferably 80-100 ℃; the mass ratio of the catalyst for preparing the cis-pinane by hydrogenation to the material containing the alpha-pinene can be 0.02-0.10, preferably 0.03-0.06; the material containing alpha-pinene contains 92-98% of alpha-pinene and 2-8% of beta-pinene by mass.
The catalyst for preparing cis-pinane by hydrogenation has higher activity and selectivity when being used for preparing the cis-pinane by hydrogenation. The method of the invention is adopted to prepare the cis-pinane, the conversion rate of the alpha-pinene can reach 99.8 percent, the selectivity of the cis-pinane can reach 97.5 percent, and the effect is good.
The invention relates to a catalyst for preparing cis-pinane by hydrogenation, which mainly solves the technical problems of low alpha-pinene conversion rate and low cis-pinane selectivity of the catalyst in the prior art. The invention adopts the catalyst for preparing the cis-pinane by hydrogenation, comprises the carrier and the active component, better solves the technical problem, and can be used for the reaction for preparing the cis-pinane by hydrogenation of alpha-pinene.
The invention has the following outstanding technical effects:
(1) the preparation process of the catalyst is simple and the cost is low;
(2) the catalyst has good hydrogenation activity, mild reaction conditions and high cis-pinane selectivity;
(3) the catalyst has no loss of nickel in the using process and can be repeatedly used for more than 50 times.
Detailed Description
The invention is further illustrated by the following examples.
For convenience, the air atmosphere is adopted in the specific embodiment of the invention.
For convenience of comparison, the nickel in the catalyst of the embodiment of the present invention is in the form of nickel oxide, and is activated for 4 hours at 500 ℃ in a hydrogen atmosphere before use.
Specific examples are given below.
Example 1
1. Catalyst preparation
A powdered alumina carrier (specific surface area of 130 m)20.1L/g, pore volume of 0.50mL/g) is mixed with 0.5L of aqueous solution of nickel nitrate containing 18gNi and magnesium nitrate containing 2g Mg, 0.4L of 10 percent sodium carbonate aqueous solution is dripped at 50 ℃, the reaction lasts for 4h at 50 ℃, the aging lasts for 6h at 50 ℃, then the catalyst is washed by deionized water for 3 times, dried for 4h at 90 ℃ and roasted for 4h at 500 ℃, and the required catalyst (the Ni content is 180g/L, the Mg content is 20g/L) is obtained.
2. Catalyst evaluation
The catalyst is put in a tubular furnace, activated for 4 hours at 500 ℃ under the atmosphere of normal pressure hydrogen, then 3g of the activated catalyst and 100g of the material containing alpha-pinene (containing 97 percent of alpha-pinene and 3 percent of beta-pinene) are put in an autoclave reactor and reacted with hydrogen for 4 hours at 100 ℃ and 2.5 MPa. The composition of the catalyst and the evaluation results are shown in table 1 for convenience of comparison.
Example 2
1. Catalyst preparation
A powdered alumina carrier (specific surface is130m20.1L/g, the pore volume is 0.50mL/g) is mixed with 0.5L of aqueous solution containing 18gNi nickel nitrate and 2gMo molybdenum trioxide, 0.4L of 10 percent sodium carbonate aqueous solution is dripped at 50 ℃, the reaction lasts 4h at 50 ℃, the aging lasts 6h at 50 ℃, then the catalyst is washed by deionized water for 3 times, dried at 90 ℃ for 4h, and roasted at 500 ℃ for 4h, thus obtaining the required catalyst (the Ni content is 180g/L, the Mo content is 20 g/L).
2. Catalyst evaluation
The catalyst evaluation method is shown in example 1. The composition of the catalyst and the evaluation results are shown in table 1 for convenience of comparison.
Example 3
1. Catalyst preparation
A powdered alumina carrier (specific surface area of 130 m)2G, pore volume of 0.50mL/g)0.1L of the catalyst is mixed with 0.5L of an aqueous solution containing 18gNi nickel nitrate, 1.5g of Mg magnesium nitrate and 0.5gMo molybdenum trioxide, 0.4L of a 10% aqueous solution of sodium carbonate is added dropwise at 50 ℃, reacted for 4h at 50 ℃, aged for 6h at 50 ℃, washed for 3 times with deionized water, dried for 4h at 90 ℃ and calcined for 4h at 500 ℃ to obtain the required catalyst (the Ni content is 180g/L, the Mg content is 15g/L and the Mo content is 5 g/L).
2. Catalyst evaluation
The catalyst evaluation method is shown in example 1. The composition of the catalyst and the evaluation results are shown in table 1 for convenience of comparison.
Example 4
1. Catalyst preparation
A powdered alumina carrier (specific surface area of 130 m)20.50mL/g) of 0.1L of the catalyst is mixed with 0.5L of an aqueous solution containing 18gNi nickel nitrate, 1g of Mg magnesium nitrate and 1gMo molybdenum trioxide, 0.4L of a 10 percent sodium carbonate aqueous solution is dropwise added at 50 ℃, the mixture reacts for 4h at 50 ℃, the mixture is aged for 6h at 50 ℃, and then the mixture is washed for 3 times by deionized water, dried for 4h at 90 ℃ and roasted for 4h at 500 ℃, thus obtaining the required catalyst (the Ni content is 180g/L, the Mg content is 10g/L and the Mo content is 10 g/L).
2. Catalyst evaluation
The catalyst evaluation method is shown in example 1. The composition of the catalyst and the evaluation results are shown in table 1 for convenience of comparison.
Example 5
1. Catalyst preparation
A powdered alumina carrier (specific surface area of 130 m)20.50mL/g) of 0.1L of the catalyst is mixed with 0.5L of an aqueous solution containing 18gNi nickel nitrate, 0.5g of Mg magnesium nitrate and 1.5gMo molybdenum trioxide, 0.4L of a 10 percent sodium carbonate aqueous solution is added dropwise at 50 ℃, the mixture reacts for 4h at 50 ℃, the mixture is aged for 6h at 50 ℃, then the mixture is washed for 3 times by deionized water, dried for 4h at 90 ℃ and roasted for 4h at 500 ℃, and the required catalyst (the Ni content is 180g/L, the Mg content is 5g/L and the Mo content is 15g/L) is obtained.
2. Catalyst evaluation
The catalyst evaluation method is shown in example 1. The composition of the catalyst and the evaluation results are shown in table 1 for convenience of comparison.
Example 6
Mixing powdered titanium dioxide carrier (specific surface area 120 m)2G, pore volume of 0.55mL/g)0.1L of the catalyst is mixed with 0.5L of an aqueous solution containing 18gNi nickel nitrate, 1.5g of Mg magnesium nitrate and 0.5gMo molybdenum trioxide, 0.4L of a 10% aqueous solution of sodium carbonate is added dropwise at 50 ℃, reacted for 4h at 50 ℃, aged for 6h at 50 ℃, washed for 3 times with deionized water, dried for 4h at 90 ℃ and calcined for 4h at 500 ℃ to obtain the required catalyst (the Ni content is 180g/L, the Mg content is 15g/L and the Mo content is 5 g/L).
2. Catalyst evaluation
The catalyst evaluation method is shown in example 1. The composition of the catalyst and the evaluation results are shown in table 1 for convenience of comparison.
Example 7
A powdery silica carrier (specific surface area 150 m)2G, pore volume of 0.42mL/g)0.1L of the catalyst is mixed with 0.5L of an aqueous solution containing 18gNi nickel nitrate, 1.5g of Mg magnesium nitrate and 0.5gMo molybdenum trioxide, 0.4L of a 10% aqueous solution of sodium carbonate is added dropwise at 50 ℃, reacted for 4h at 50 ℃, aged for 6h at 50 ℃, washed for 3 times with deionized water, dried for 4h at 90 ℃ and calcined for 4h at 500 ℃ to obtain the required catalyst (the Ni content is 180g/L, the Mg content is 15g/L and the Mo content is 5 g/L).
2. Catalyst evaluation
The catalyst evaluation method is shown in example 1. The composition of the catalyst and the evaluation results are shown in table 1 for convenience of comparison.
Comparative example 1
1. Catalyst preparation
A powdered alumina carrier (specific surface area of 130 m)20.1L/g, the pore volume is 0.50mL/g) is mixed with 0.5L of nickel nitrate aqueous solution containing 20gNi, 0.4L of 10 percent sodium carbonate aqueous solution is dripped at 50 ℃, the reaction is carried out for 4h at 50 ℃, the aging is carried out for 6h at 50 ℃, then the catalyst is washed by deionized water for 3 times, dried for 4h at 90 ℃ and roasted for 4h at 500 ℃, and the required catalyst (the Ni content is 200g/L) is obtained.
2. Catalyst evaluation
The catalyst evaluation method is shown in example 1. The composition of the catalyst and the evaluation results are shown in table 1 for convenience of comparison.
Comparative example 2
1. Catalyst preparation
A powdered alumina carrier (specific surface area of 130 m)20.1L/g, the pore volume is 0.50mL/g) is mixed with 0.5L of magnesium nitrate aqueous solution containing 20g of Mg, 0.4L of 10 percent sodium carbonate aqueous solution is dripped at 50 ℃, the reaction is carried out for 4h at 50 ℃, the aging is carried out for 6h at 50 ℃, then the mixture is washed for 3 times by deionized water, dried for 4h at 90 ℃ and roasted for 4h at 500 ℃, and the required catalyst (the Mg content is 200g/L) is obtained.
2. Catalyst evaluation
The catalyst evaluation method is shown in example 1. The composition of the catalyst and the evaluation results are shown in table 1 for convenience of comparison.
Comparative example 3
1. Catalyst preparation
A powdered alumina carrier (specific surface area of 130 m)2Per g, pore volume of 0.50mL/g)0.1L and 0.5L of molybdenum trioxide aqueous solution containing 20gMo, drying at 90 ℃ for 4h, and calcining at 500 ℃ for 4h to obtain the required catalyst (Mo content of 200 g/L).
2. Catalyst evaluation
The catalyst evaluation method is shown in example 1.
TABLE 1 catalyst compositions and evaluation results for examples 1-7 and comparative examples 1-3
Table 1 shows the compositions and evaluation results of catalysts of examples 1 to 7 and comparative examples 1 to 3.
Claims (10)
1. The catalyst for preparing cis-pinane by hydrogenation is applied to the reaction of preparing cis-pinane by hydrogenation of alpha-pinene, and is characterized in that the catalyst for preparing cis-pinane by hydrogenation comprises a carrier, an active component 1 and an active component 2, wherein the active component 1 is nickel or a nickel oxide, and the active component 2 is an alkaline earth metal or an alkaline earth metal oxide; the content of the active component 1 is 50-500 g/L, and the content of the active component 2 is more than 0g/L and less than 60 g/L;
the carrier is selected from at least one of alumina, silicon dioxide, titanium dioxide and activated carbon, and the BET specific surface area of the carrier is 80-220 m2The pore volume of the carrier is 0.2-0.8 mL/g;
the preparation method of the catalyst for preparing the cis-pinane by hydrogenation comprises the following steps:
1) mixing a solution containing a nickel compound and an alkaline earth metal compound with a carrier, adding an aqueous solution of a precipitator, and reacting to obtain a catalyst precursor I;
2) aging and washing the catalyst precursor I obtained in the step 1), and then drying and roasting to obtain the catalyst for preparing the cis-pinane through hydrogenation.
2. Use according to claim 1, wherein the support has a BET specific surface area of 90 to 150m2(ii)/g; the pore volume of the carrier is 0.3-0.6 mL/g.
3. Use according to claim 1, characterized in that the alkaline earth metal is selected from at least one of Ca, Mg, Sr, Ba.
4. Use according to claim 3, characterized in that the alkaline earth metal is Mg.
5. The use according to claim 1, characterized in that the content of active ingredient 1 is 100 to 300 g/L; the content of the active component 2 is 5-50 g/L.
6. The use according to claim 1, characterized in that the catalyst for preparing cis-pinane by hydrogenation comprises an active component 3 in addition to the carrier, the active component 1 and the active component 2, wherein the active component 3 is Mo or a Mo oxide, and the content of the active component 3 is 0.5-50.0 g/L.
7. Use according to any one of claims 1 to 6, characterized in that the process for the preparation of the catalyst for the hydrogenation of cis-pinane comprises the following steps:
1) mixing a solution containing a nickel compound and an alkaline earth metal compound with a carrier, adding an aqueous solution of a precipitator, and reacting to obtain a catalyst precursor I; the nickel compound is selected from one of nickel chloride, nickel nitrate, nickel sulfate and soluble complex of nickel; the alkaline earth metal compound is selected from at least one of nitrate, hydrochloride, sulfate and C1-C4 carboxylate; the precipitator is at least one selected from potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide and ammonia water; the reaction temperature is 30-90 ℃, and the reaction time is 2-8 h;
2) aging and washing the catalyst precursor I obtained in the step 1), drying and roasting to obtain a catalyst for preparing cis-pinane through hydrogenation; the aging temperature is 30-80 ℃, and the aging time is 2-10 h; the drying temperature is 80-120 ℃, and the drying time is 2-6 h; the roasting atmosphere adopts an air atmosphere; the roasting temperature is 400-600 ℃, and the roasting time is 3-8 h;
when the catalyst for preparing cis-pinane by hydrogenation contains an active component 3, a solution of a molybdenum compound or a mixture solution of the molybdenum compound and an alkaline earth metal compound is used for replacing a simple alkaline earth metal compound solution in the step 1).
8. The use according to claim 7, wherein in step 1), the temperature of the reaction is 40 to 70 ℃.
9. Use according to any one of claims 1 to 6, wherein the use is a process for the preparation of cis-pinane by hydrogenation comprising: in an autoclave reactor, a material containing alpha-pinene and hydrogen are used as raw materials and are contacted with a catalyst to react to generate cis-pinane; the reaction pressure is 1.0-3.0 MPa; the reaction temperature is 70-120 ℃; the mass ratio of the catalyst for preparing the cis-pinane by hydrogenation to the material containing the alpha-pinene is 0.02-0.10; the material containing alpha-pinene contains 92-98% of alpha-pinene and 2-8% of beta-pinene by mass.
10. The use according to claim 9, wherein the pressure of the reaction is 1.5 to 2.5 MPa; the reaction temperature is 80-100 ℃; the mass ratio of the catalyst for preparing the cis-pinane by hydrogenation to the material containing the alpha-pinene is 0.03-0.06.
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| CN104001515A (en) * | 2014-05-04 | 2014-08-27 | 昆明理工大学 | Preparation method and application of loaded-type nickel catalyst |
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