CN110975901A - Catalyst and method for preparing geraniol by hydrogenating citral by using same - Google Patents
Catalyst and method for preparing geraniol by hydrogenating citral by using same Download PDFInfo
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- CN110975901A CN110975901A CN201911201950.XA CN201911201950A CN110975901A CN 110975901 A CN110975901 A CN 110975901A CN 201911201950 A CN201911201950 A CN 201911201950A CN 110975901 A CN110975901 A CN 110975901A
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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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
- B01J29/00—Catalysts comprising molecular sieves
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- 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
- C07C29/14—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 a —CHO group
- C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The invention discloses a catalyst and a method for preparing geraniol by hydrogenating citral, wherein the novel catalyst is used for realizing the purpose of preparing high-purity geraniol by one-step hydrogenation of citral. The method not only reduces the step of separating citral, but also saves the difficulty of separating the later-stage product, simplifies the process operation flow, and ensures that the yield of the geraniol reaches more than 98 percent.
Description
Technical Field
The invention relates to the technical field of citral hydrogenation, in particular to a catalyst and a method for preparing geraniol by using the catalyst for citral hydrogenation.
Background
Geraniol (chemical name is trans-3, 7-dimethyl-octadien-1-ol) is a rare spice, has mild and sweet rose smell, and tastes bitter. It can be widely used in flower fragrance type essence for daily use, fruit fragrance type edible essence such as apple, strawberry, etc., and fragrance type edible essence such as cinnamon, ginger, etc., or ester type essence, and can be used for resisting bacteria and expelling parasites.
In citral, neral and geranial can be easily interconverted, thereby making it difficult to obtain a single component.
In industrial production, the purification of a substrate by a rectification method is a commonly adopted method, but the separation process is very difficult due to the existence of reactions such as interconversion between neral and geranial, citral isomerization and mutual polymerization, and reports on high purification of a certain component in citral are not common.
At present, the demands of the perfume market on nerol and geraniol products have the characteristic of diversity, the price of geraniol is higher than that of nerol, meanwhile, the perfume market has certain complexity, and the prices of different perfumes are influenced by the market and have certain fluctuation. However, in the known prior art, the process for preparing nerol or geraniol cannot be prepared from citral in one step. Generally, the method is obtained through two steps, and the obtained product has low purity, complex process and poor market-changing capability.
Patent CN101747152 uses iron oxide loaded with platinum as catalyst, and synthesizes nerol and geraniol by selective hydrogenation of citral. When the conversion of citral was 14.2%, the total selectivity of geraniol and nerol was 58.9%.
Patent US4100180 describes a batch process for the hydrogenation of unsaturated aldehydes to give unsaturated alcohols under the action of PtO/Zn/Fe catalysts, with a total selectivity of geraniol and nerol of 85.5% when the conversion of citral reaches 70%.
Cn02155367.x describes a process for the preparation of iron doped ruthenium catalysts involving carbon loading and their use in the selective liquid phase hydrogenation of citral to produce geraniol or nerol. When the citral conversion was 95.61%, the overall selectivity for nerol and geraniol was 95.22%.
The above methods have poor product selectivity, cannot obtain a single product at one time, and have complex process and poor economic benefit.
Disclosure of Invention
The invention aims to develop a method for preparing a single product geraniol by using citral as a raw material through a one-step reaction, aiming at the problems that the high-purity geraniol cannot be prepared from citral in one step in the prior art, and the problems of poor selectivity, complex process, poor economic benefit and the like are solved. The method has the advantages of simple operation, high product yield, high economic value, less three wastes and the like, has simple requirements on equipment, is suitable for industrial production and application, and has better industrial prospect.
According to a first embodiment of the present invention, there is provided a catalyst for the hydrogenation of citral to geraniol, comprising a catalytically active center iodine, phosphorus and any one or more selected from nickel, cobalt and copper, supported on a carrier.
Further, iodine accounts for 1-5 wt%, preferably 2-3 wt%, phosphorus accounts for 1-5 wt%, preferably 2-3 wt%, and any one or more selected from nickel, cobalt and copper accounts for 1-5 wt%, preferably 2-4 wt%, of the carrier, calculated on the element basis, based on the total mass of the carrier.
Furthermore, one or more than two of nickel, cobalt and copper are loaded on the carrier in a mixed way, and the loading amount of each element is more than or equal to 20 wt% of the total mixed loading amount of the metal elements, preferably more than or equal to 30 wt%.
Iodine, phosphorus, nickel, cobalt and copper are respectively loaded on the carrier in the form of oxides.
Further, the carrier is any one or more of carriers with rich pore channel structures, such as a molecular sieve, an alumina pellet, activated carbon, a ceramic pellet and the like, and the molecular sieve is preferred. In the catalyst of the invention, iodine (I) plays a crucial role in isomerization reaction, and phosphorus (P) and oxygen atom form weak coordination, which is beneficial to capturing a substrate. The Ni/Co/Cu catalytic hydrogenation reaction is advantageously carried out by selecting one or more of the Ni/Co/Cu catalytic hydrogenation reactions for mixed loading.
According to a second embodiment of the present invention, there is provided a method for preparing the above catalyst, which comprises: the carrier is added into a solution (general aqueous solution) containing an iodine compound, a phosphorus compound, and a soluble salt (the solubility in water is more than 0.1 wt%) selected from any one or more of nickel, cobalt, and copper, and is impregnated, or the carrier is added into a solution of an iodine compound, a solution of a phosphorus compound, and a solution of a soluble salt selected from any one or more of nickel, cobalt, and copper, and is impregnated in steps (the order may not be limited), filtered, dried, and finally calcined to obtain a shaped catalyst.
Further, the iodine compound may be selected from any one or more of potassium iodide, sodium iodide, ethyl iodide, 1, 2-diiodoethane, 1, 3-diiodopropane, etc., preferably potassium iodide and sodium iodide, and the phosphorus compound may be selected from any one or more of diammonium hydrogen phosphate, phosphoric acid, dipotassium hydrogen phosphate, trisodium phosphate, disodium hydrogen phosphate, etc., preferably diammonium hydrogen phosphate, the soluble salt is one or more of soluble nickel salt, soluble cobalt salt and soluble copper salt, the soluble nickel salt can be selected from any one or more of nickel chloride, nickel sulfate and nickel nitrate, preferably nickel chloride, the soluble cobalt salt may be selected from any one or more of cobalt chloride, cobalt sulphate, cobalt nitrate, preferably cobalt chloride, the soluble copper salt can be selected from any one or more of copper chloride, copper sulfate and copper nitrate, and is preferably copper chloride.
Further, the concentration of the iodine compound solution is 0.1 to 2.0 wt%, preferably 0.5 to 1.5 wt%, the concentration of the phosphorus compound solution is 0.1 to 3.0 wt%, preferably 0.5 to 2.0 wt%, the concentration of the soluble nickel salt solution is 0.1 to 2.0 wt%, preferably 0.5 to 1.0 wt%, the concentration of the soluble cobalt salt solution is 0.1 to 3.0 wt%, preferably 0.5 to 1.5 wt%, and the concentration of the soluble copper salt solution is 0.1 to 2.5 wt%, preferably 0.5 to 2.0 wt%.
Further, when the soluble metal salt solution is a mixture of two or more soluble metal salts, the proportion of each soluble metal salt to the total mass of the soluble metal salts is preferably such that the amount of each element supported is 20 wt% or more, preferably 30 wt% or more of the total amount of the mixed load of the metal elements.
The loading method adopted in the invention is a room temperature static impregnation method, and the impregnation can be carried out step by step or simultaneously, preferably simultaneously, the impregnation time is, for example, 8-36h, preferably 10-15h, the catalyst is dried after the impregnation is finished, the drying temperature is, for example, 70-110 ℃, preferably 80-100 ℃, the drying time is, for example, 4-10h, preferably 5-8h, in order to avoid the loss of active centers during the use process, the catalyst is dried (for example, in the air atmosphere), the calcination temperature is, for example, 150-.
In the above method, the carrier is preferably a carrier having a rich pore structure, such as a molecular sieve, alumina beads, activated carbon, ceramic beads, and the like, and more preferably a molecular sieve.
According to a third embodiment of the present invention, there is provided a process for producing geraniol using the above-mentioned catalyst, which comprises: the citral is subjected to a hydrogenation reaction in a reactor (e.g., a hydrogenation autoclave) containing the above-described catalyst under the introduction of hydrogen.
Further, the input amount of the catalyst can be 0.1-5 wt%, preferably 0.5-2 wt% of the substrate citral, the reaction pressure (pressure of filling hydrogen) is, for example, 1-7MPa, preferably 3-5MPa, the reaction temperature is, for example, 0-100 ℃, preferably 30-60 ℃, and the reaction time is, for example, 2-10h, preferably 4-8 h.
The invention has the beneficial effects that:
the novel catalyst adopted by the invention realizes the purpose of preparing high-purity geraniol by one-step hydrogenation of citral, and meanwhile, the selectivity of the target product geraniol is up to more than 98%, so that the steps of separating citral are reduced, the separation difficulty of later-stage products is also saved, and the process operation flow is simplified.
Detailed Description
The method according to the invention will be further illustrated by the following examples, but the invention is not limited to the examples listed, but also encompasses any other known modification within the scope of the claims of the invention.
The analysis method comprises the following steps: gas chromatograph: agilent7890, column DB-5 (conversion, selectivity determination), injection port temperature: 300 ℃; the split ratio is 50: 1; the carrier gas flow is 52.8 ml/min; temperature rising procedure: holding at 120 ℃ for 15min, increasing to 250 ℃ at a rate of 10 ℃/min, holding for 10min, detector temperature: 280 ℃.
The use of the medicine:
citral is more than or equal to 98%, and is produced by Hubei Julongtang pharmaceutical chemical Co., Ltd;
potassium iodide is more than or equal to 98.5 percent, Aladdin reagent Co., Ltd;
diammonium phosphate is more than or equal to 98.5%, Aladdin reagent, Inc.;
nickel chloride is more than or equal to 99.5 percent, Aladdin reagent Co., Ltd;
cobalt chloride is more than or equal to 99.5 percent, Aladdin reagent Co., Ltd;
copper chloride is more than or equal to 99.5 percent, and Aladdin reagent Co.
Catalyst preparation
The method comprises the following steps of taking a molecular sieve as a carrier, taking iodine, phosphorus, nickel, cobalt and copper as active components, taking potassium iodide as an iodine source, taking diammonium hydrogen phosphate as a phosphorus source, taking nickel chloride as a nickel source, taking cobalt chloride as a cobalt source and taking copper chloride as a copper source. According to the loading capacity of each element in the catalyst composition table, potassium iodide, diammonium hydrogen phosphate, nickel chloride, cobalt chloride and copper chloride are respectively prepared into impregnation liquid in a required proportion, and then the molecular sieve carrier is placed in the impregnation liquid by an isometric impregnation method and is uniformly stirred. Standing for 10-15 hours, drying at 80 ℃ for 5 hours, and roasting in air to obtain the catalyst. The roasting temperature is controlled to be 300 ℃, the roasting time is controlled to be 3 hours, and the formed catalyst can be obtained for use after the process.
The catalyst comprises the following components:
| iodine/wt% | Phosphorus/wt.% | Nickel/wt.% | Cobalt/wt.% | Copper/wt% | Carrier | |
| Catalyst 1 | 2 | 2.5 | 3 | 3 | 3 | Molecular sieves |
| Catalyst 2 | 2.5 | 2.5 | 3 | 3 | 3 | Molecular sieves |
| Catalyst 3 | 3 | 2.5 | 3 | 3 | 3 | Molecular sieves |
| Catalyst 4 | 2.5 | 2 | 3 | 3 | 3 | Molecular sieves |
| Catalyst 5 | 2.5 | 3 | 3 | 3 | 3 | Molecular sieves |
| Catalyst 6 | 2.5 | 2.5 | 2 | 3 | 3 | Molecular sieves |
| Catalyst 7 | 2.5 | 2.5 | 4 | 3 | 3 | Molecular sieves |
| Catalyst 8 | 2.5 | 2.5 | 3 | 2 | 3 | Molecular sieves |
| Catalyst 9 | 2.5 | 2.5 | 3 | 4 | 3 | Molecular sieves |
| Catalyst 10 | 2.5 | 2.5 | 3 | 3 | 2 | Molecular sieves |
| Catalyst 11 | 2.5 | 2.5 | 3 | 3 | 4 | Molecular sieves |
| Catalyst 12 | 2.5 | 2.5 | 3 | 3 | 0 | Molecular sieves |
| Catalyst 13 | 2.5 | 2.5 | 3 | 0 | 3 | Molecular sieves |
| Catalyst 14 | 2.5 | 2.5 | 0 | 3 | 3 | Molecular sieves |
| Catalyst 15 | 2.5 | 2.5 | 3 | 0 | 0 | Molecular sieves |
| Catalyst 16 | 2.5 | 2.5 | 0 | 3 | 0 | Molecular sieves |
| Catalyst 17 | 2.5 | 2.5 | 0 | 0 | 3 | Molecular sieves |
Example 1
Adding catalyst 1 and substrate citral into a 500ml hydrogenation pressure kettle in sequence, wherein the dosage of catalyst 1 is 1.0 wt% of substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 2
The catalyst 2 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 2 is 1.0 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 3
The catalyst 3 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 3 is 1.0 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 4
Catalyst 4 and substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of catalyst 4 is 0.5 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 5
The catalyst 5 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 5 is 0.5 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 6
The catalyst 6 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 6 is 2 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 7
The catalyst 7 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 7 is 2 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 8
The catalyst 8 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 8 is 1.5 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 9
The catalyst 9 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 9 is 1.5 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 10
The catalyst 10 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 10 is 1.0 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 11
The catalyst 11 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 11 is 1.0 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 12
The catalyst 12 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 12 is 1.0 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 13
The catalyst 13 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 13 is 1.0 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 14
The catalyst 14 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 14 is 1.0 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 15
The catalyst 15 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 15 is 1.0 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 16
The catalyst 16 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst 16 is 1.5 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Example 17
The catalyst 17 and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the dosage of the catalyst 17 is 1.5 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
TABLE 1 results of the reaction
Comparative example 1
Weighing 0.63g of nickel chloride, 0.66g of cobalt chloride, 0.66g of copper chloride and 10g of molecular sieve carrier, uniformly stirring, dropwise adding deionized water into the mixture until the liquid level just exceeds the solid surface, standing for 15 hours, drying at 80 ℃ for 5 hours, and roasting to obtain the catalyst. The roasting temperature is controlled to be 300 ℃, and the roasting time is controlled to be 3 hours, so that the catalyst is prepared.
The catalyst and the substrate citral are added into a 500ml hydrogenation pressure kettle in sequence, and the input amount of the catalyst is 1.0 wt% of the substrate citral. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, charging hydrogen to 2.0Mpa, heating, stirring, controlling reaction temperature at 50 deg.C for 5h, and maintaining hydrogen pressure at 3.0Mpa by supplementing. The samples were analyzed and the results are shown in Table 1.
Claims (9)
1. A catalyst for preparing geraniol by hydrogenating citral comprises a catalytic active center iodine, phosphorus and any one or more selected from nickel, cobalt and copper which are loaded on a carrier.
2. The catalyst according to claim 1, wherein iodine comprises 1-5 wt%, preferably 2-3 wt%, phosphorus comprises 1-5 wt%, preferably 2-3 wt%, of the carrier, and any one or more selected from nickel, cobalt, and copper comprises 1-5 wt%, preferably 2-4 wt%, of the carrier, calculated as element, based on the total mass of the carrier.
3. The catalyst according to claim 1 or 2, wherein one or more of nickel, cobalt and copper are supported on the carrier in a mixed manner, and the amount of each element is greater than or equal to 20 wt%, preferably greater than or equal to 30 wt% of the total mixed load of the metal elements.
4. A catalyst according to any one of claims 1 to 3, wherein the support is a support with a rich pore structure, preferably selected from any one or more of molecular sieves, alumina beads, activated carbon, ceramic beads, more preferably molecular sieves.
5. A method of preparing the catalyst of any one of claims 1-4, comprising: adding the carrier into a solution containing an iodine compound, a phosphorus compound and one or more soluble salts selected from nickel, cobalt and copper for impregnation, or adding the carrier into the solution containing the iodine compound, the solution containing the phosphorus compound and the solution containing one or more soluble salts selected from nickel, cobalt and copper for stepwise impregnation, filtering, drying and finally roasting to obtain the formed catalyst.
6. The process according to claim 5, wherein the iodine compound is selected from any one or more of potassium iodide, sodium iodide, ethyl iodide, 1, 2-diiodoethane, 1, 3-diiodopropane, preferably potassium iodide or sodium iodide,
the phosphorus compound is selected from one or more of diammonium hydrogen phosphate, phosphoric acid, dipotassium hydrogen phosphate, trisodium phosphate and disodium hydrogen phosphate, preferably diammonium hydrogen phosphate,
the soluble salt is one or more of soluble nickel salt, soluble cobalt salt and soluble copper salt, wherein the soluble nickel salt is selected from any one or more of nickel chloride, nickel sulfate and nickel nitrate, preferably nickel chloride, the soluble cobalt salt is selected from any one or more of cobalt chloride, cobalt sulfate and cobalt nitrate, preferably cobalt chloride, and the soluble copper salt is selected from any one or more of copper chloride, copper sulfate and copper nitrate, preferably copper chloride.
7. The method according to claim 5 or 6, wherein the immersion time is 8-36h, preferably 10-15h, and/or
Drying at 70-110 deg.C, preferably 80-100 deg.C for 4-10 hr, preferably 5-8 hr, and/or
The catalyst is baked in a vacuum environment after being dried, the baking temperature is set to be 150-.
8. A process for the preparation of geraniol using the catalyst of any one of claims 1-4 or obtained by the process of any one of claims 5-7, the process comprising: under the condition of introducing hydrogen, citral is subjected to hydrogenation reaction in a reactor filled with the catalyst.
9. The method according to claim 8, wherein the catalyst input amount is 0.1-5 wt%, preferably 0.5-2 wt% of the substrate citral; and/or
The reaction pressure is 1-7MPa, preferably 3-5MPa, the reaction temperature is 0-100 ℃, preferably 30-60 ℃, and the reaction time is 2-10h, preferably 4-8 h.
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| WO2007013156A1 (en) * | 2005-07-27 | 2007-02-01 | National Institute Of Advanced Industrial Science And Technology | Method for producing citral hydride |
| US20120071700A1 (en) * | 2010-09-21 | 2012-03-22 | Long Huang | Catalysts for hydrogenation of unsaturated hydrocarbons and preparations and uses thereof |
| CN102408304A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Method for preparing alcohols by selectively hydrogenating aldehydes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE700530A (en) * | 1966-06-25 | 1967-12-27 | ||
| EP0422968A1 (en) * | 1989-10-13 | 1991-04-17 | Institut Français du Pétrole | Hydrogenation of citral |
| WO2007013156A1 (en) * | 2005-07-27 | 2007-02-01 | National Institute Of Advanced Industrial Science And Technology | Method for producing citral hydride |
| US20120071700A1 (en) * | 2010-09-21 | 2012-03-22 | Long Huang | Catalysts for hydrogenation of unsaturated hydrocarbons and preparations and uses thereof |
| CN102408304A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Method for preparing alcohols by selectively hydrogenating aldehydes |
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