CN110975916B - Catalyst for selective hydrogenation of olefinic unsaturated carbonyl compounds, preparation method and application thereof - Google Patents

Catalyst for selective hydrogenation of olefinic unsaturated carbonyl compounds, preparation method and application thereof Download PDF

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CN110975916B
CN110975916B CN201911247903.9A CN201911247903A CN110975916B CN 110975916 B CN110975916 B CN 110975916B CN 201911247903 A CN201911247903 A CN 201911247903A CN 110975916 B CN110975916 B CN 110975916B
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catalyst
carbon
nitrogen
roasting
ruthenium
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CN110975916A (en
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王联防
董菁
张永振
黎源
于斌成
苏黎明
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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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
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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Abstract

The invention discloses a catalyst for selectively hydrogenating olefinic unsaturated carbonyl compounds, a preparation method and application thereof. The catalyst comprises 0.05-10 wt% of ruthenium, 0.05-5 wt% of molybdenum and 0.05-5 wt% of iron based on the weight of the carbon carrier; as a preferred embodiment, the ruthenium is nitrogen modified. The catalyst is particularly suitable for preparing citronellal and/or dihydrocitronellal by highly selective hydrogenation of citral, and preparing dihydrocitronellal by highly selective hydrogenation of citronellal. The catalyst can inhibit the formation of aldehyde substance dimerization, obviously reduce the adsorption of CO, strengthen the capability of resisting CO poisoning and obviously improve the stability in the application process.

Description

Catalyst for selective hydrogenation of olefinic unsaturated carbonyl compounds, preparation method and application thereof
Technical Field
The present invention relates to the field of catalysts, in particular to catalysts for the hydrogenation of ethylenically unsaturated carbonyl compounds. More particularly, to a catalyst for selective hydrogenation of citral and/or citronellal.
Background
Ethylenically unsaturated carbonyl compounds, such as acrolein, crotonaldehyde, cinnamaldehyde, citral, 2-methylacrolein, farnesal, and the like, have a very important role in the field of fine chemicals, and not only are themselves important fine chemicals, but also their derivatives are widely used in the fields of flavors and fragrances, medicines, foods, and the like. Among them, the related art in which citral is selectively hydrogenated to obtain citronellal and/or dihydrocitronellal, and citronellal is selectively hydrogenated to obtain dihydrocitronellal is widely reported.
Citronellal is an important isolated perfume with a strong, fresh, green-orange-like, slightly woody aroma. Citronellal is widely used in edible essences, for preparing citrus and cherry essences, as an essence for preparing low-grade soap, as a raw material of other spices, and for synthesizing hydroxycitronellal, menthol and other spices.
The citronellal is derived from two kinds of natural extraction and chemical synthesis. Wherein the citronellal extracted naturally is subject to the change of natural conditions and the like, so that the yield, the quality and the like of the citronellal greatly fluctuate, which is contrary to the stability requirement of the market. The citronellal is synthesized to avoid the above situation, and the main synthetic route comprises: (1) the beta-pinene is used as a raw material and is obtained by pyrolysis, chlorination, hydrolysis, catalytic hydrogenation and air oxidation. The beta-pinene used in the route is also from a natural extract, the supply amount is limited by natural conditions, in addition, the synthesis process is complex, the yield of citronellal is low, and three wastes are more; (2) the citronellal is taken as a raw material, and the citronellal obtained by hydrogenation is a mainstream synthesis route, but the citronellal obtained by hydrogenation with high yield has great technical challenges in view of the special structure of the citral.
CN1234385A discloses a technology for preparing citronellal by selective liquid phase hydrogenation of citral in the presence of powdered rhodium and/or palladium catalyst and in the presence of organic base, with the highest selectivity of the target product being 94%. According to the patent, the laboratory carries out technical verification on example 1 in the patent, and the result shows that the selectivity of citronellal can reach 94%, and the rest products comprise citronellal isomers and excessive hydrogenation product dihydrocitronellal. In addition, experiments show that the catalyst Pd/C can not be mechanically applied under the process condition, and the catalyst loses activity after being used once. The catalyst cannot be recovered by washing with a solvent. Marco Burger et al (Journal of Catalysis 228(2004)152-161) have carried out detailed research on the catalyst deactivation phenomenon of Pd-based catalyst in the process of using it in the hydrogenation of citral, and the research shows that the Pd-based catalyst can cause part of citral to generate carbon monoxide (CO) through aldehyde decomposition, and CO is easy to combine with metal Pd and further causes the Pd to lose the catalytic activity. In summary, the disclosed techniques present a significant technical risk.
Dihydrocitronellal is an important organic synthesis intermediate, and is applied to the field of blending of essences. The method for synthesizing dihydrocitronellal is various and can be obtained by selectively hydrogenating citral or citronellal. For the catalytic hydrogenation of compounds containing a plurality of functional groups that can be reduced, it is difficult to find a catalyst having both high activity and high selectivity. The citral molecule contains two carbon-carbon double bonds and an aldehyde group, and different products can be obtained according to different hydrogenation conditions:
Figure BDA0002308197640000031
it is reported in the literature that hydrogenation occurs at carbon-carbon double bonds and aldehyde groups are not reduced using metallic palladium as a catalyst. Based on this, the catalyst for preparing dihydrocitronellal in the traditional process mostly uses noble metal Pd as an active component, and the product yield of dihydrocitronellal is further improved by adding an auxiliary agent and the like in a phase reaction system.
Houlliban W J (J Org chem,1958,23:689) and the like take 5 percent Pd/C as a catalyst, ethanol is used as a solvent, citral is hydrogenated, the main product is citronellal, the content of dihydrocitronellal is only 6 percent, and the yield of the target product dihydrocitronellal is obviously lower.
Liutianling et al (applied chemistry, 1993, 10(2), 107-108) hydrogenated citral under pressure with 5% Pd/C as catalyst and 1% aqueous sodium carbonate solution as solvent to achieve a yield of 90% dihydrocitronellal. Although the use of alkaline solution significantly improves the product yield of dihydrocitronellal, the aldehyde substance is extremely unstable in alkaline environment and is easy to polymerize and deteriorate to generate acetal and other heavy components, which leads to the reduction of process economy. Meanwhile, the post-treatment process of the process is complicated, and the three wastes are more.
In addition, the selective hydrogenation process of citral or citronellal is accompanied by many side reactions, wherein the polymerization reaction between aldehyde substances is particularly obvious, such as citronellal dimer, citronellal-dihydrocitronellal dimer, etc., and these impurities cause the decrease of process yield and the increase of cost on one hand, and on the other hand, the dimers have large molecular weight (MW > 250) and high viscosity and are easy to adsorb on the surface of the catalyst to cover active sites, which leads to the deactivation of the catalyst and the blockage of a filtration system, etc.
Figure BDA0002308197640000041
Therefore, it is important to develop a low cost, high selectivity, green hydrogenation catalyst system for the preparation of citronellal and/or dihydrocitronellal.
Disclosure of Invention
The present invention provides a catalyst for the selective hydrogenation of olefinically unsaturated carbonyl compounds. The catalyst can prepare citronellal and/or dihydrocitronellal with high selectivity and high yield. The invention also provides a preparation method of the catalyst, which has simple preparation process and low cost.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the present invention provides a catalyst for the selective hydrogenation of olefinically unsaturated carbonyl compounds, i.e. a nitrogen-modified carbon-supported metal catalyst.
The catalyst of the present invention comprises 0.05 to 10% by weight of ruthenium, 0.05 to 5% by weight of molybdenum and 0.05 to 5% by weight of iron, preferably 0.1 to 5% by weight of ruthenium, 0.1 to 1% by weight of molybdenum and 0.1 to 1% by weight of iron, based on the weight of the carbon support.
Preferably, the ruthenium in the catalyst is modified by nitrogen, wherein the molar ratio of nitrogen element to metal ruthenium is 0.01-0.1: 1.
As a preferred embodiment, a method for preparing the catalyst of the present invention comprises the steps of:
1) adding a ruthenium salt aqueous solution into a uniformly dispersed mixture of a carbon carrier and water, then dropwise adding an alkali liquor, stopping dropwise adding the alkali liquor when the pH value of the system reaches 8-10, separating the obtained solid, drying, and roasting to obtain a carbon-supported ruthenium precursor;
2) treating the carbon-supported ruthenium precursor obtained in the step 1) with a nitrogen source substance to obtain a nitrogen-modified carbon-supported ruthenium precursor;
3) performing equal-volume impregnation on the molybdenum salt and iron salt aqueous solution and the nitrogen-modified carbon-supported ruthenium precursor obtained in the step 2), and then roasting to obtain a catalyst precursor;
4) and 3) reducing the catalyst precursor obtained in the step 3) in a hydrogen atmosphere to obtain the catalyst.
In step 1) of the present invention, the carbon support includes, but is not limited to, one or more of graphite, carbon black, and activated carbon, preferably activated carbon.
In the step 1) of the present invention, the ruthenium salt may be ruthenium chloride; the alkali liquor can be 1-15 wt% sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and the like.
In step 1) of the present invention, the atmosphere of the calcination is an inert gas, preferably nitrogen. The roasting temperature is 400-800 ℃, preferably 500-600 ℃, and the roasting time is 2-25 hours, preferably 6-15 hours.
In step 2) of the present invention, the nitrogen source material includes, but is not limited to, one or more of ammonia, methylamine, dimethylamine, trimethylamine, ethylenediamine, isobutyronitrile, hydrazine hydrate and melamine, and preferably trimethylamine.
In the step 2), the space velocity of the nitrogen source substance is 0.01-1 kgNitrogen source/kgExpiration date of ruthenium precursor on carbonPreferably 0.1 to 0.5kgNitrogen source/kgExpiration date of ruthenium precursor on carbon。
In the step 2), the treatment temperature is 600-1000 ℃, preferably 650-750 ℃; the treatment time is 1-30 h, preferably 8-15 h.
In step 3) of the present invention, the molybdenum salt and the iron salt are not particularly limited, and the molybdenum salt may be molybdenum chloride, and the iron salt may be ferric chloride.
In step 3) of the present invention, the atmosphere of the calcination is an inert gas, preferably nitrogen. The roasting temperature is 400-800 ℃, preferably 500-600 ℃, and the roasting time is 5-25 hours, preferably 10-18 hours.
In the step 4), the reduction temperature is 80-400 ℃, preferably 180-300 ℃, and the reduction time is 2-20 hours, preferably 4-10 hours.
Different from the catalyst preparation process in the prior art, the invention carries out two times of modification aiming at the carbon-loaded ruthenium precursor, firstly, the nitrogen source is utilized for modification, the bonding force between the metal ruthenium oxide and the carbon carrier is strengthened, after the subsequent reduction treatment, the bonding force between the metal active component and the carbon carrier is obviously improved, macroscopically, the stability of the catalyst is obviously improved, the metal loss speed is obviously reduced, the bonding force between the metal oxide and the carbon carrier is obviously improved, the active center metal atoms can not generate obvious displacement in the reduction process of the metal oxide under the high-temperature hydrogen atmosphere, the metal atoms are more uniformly dispersed, the invention plays a positive role in improving the reaction performance, and the acid-base property is adjusted through the nitrogen treatment, thereby well inhibiting the formation of aldehyde substance dimerization; then, the metal iron and molybdenum are introduced into the catalyst for further modification, and the metal iron and molybdenum are cooperated with the nitrogen-modified ruthenium oxide, so that the adsorption of CO is remarkably reduced, the CO poisoning resistance is enhanced, the service life of the catalyst is prolonged, and the catalyst still has high activity after being used for many times.
The catalyst of the invention has unexpectedly high selectivity when used for selectively hydrogenating olefinic carbonyl compounds, particularly citral or citronellal, and the selectivity of aldehyde dimerization byproducts is remarkably reduced; meanwhile, the stability of the catalyst in the process of mechanically applying the catalyst is obviously improved, the loss of active components of the catalyst is obviously inhibited, and the result of quantitative element analysis on the catalyst which is mechanically applied for 30 times shows that the loss rate of metal elements is less than 1%.
The catalyst of the present invention can be used as a catalyst for fixed bed and kettle type reactors.
The catalysts of the invention can be used for the selective hydrogenation of olefinically unsaturated carbonyl compounds of the general formula I to give carbonyl compounds, where R1、R2Independently of one another, are monounsaturated and/or polyunsaturated, linear or branched, optionally substituted C1-C20 alkyl groups.
Figure BDA0002308197640000071
Preferably, the ethylenically unsaturated carbonyl compound of the present invention is citral. When citral is used as a raw material for reaction, the product at the end of the reaction is inevitably a mixture of citronellal and dihydrocitronellal, wherein the dihydrocitronellal is obtained by further hydrogenating the product citronellal. From the technical point of view, the citronellal and the dihydrocitronellal can be completely separated by a conventional separation means, such as reduced pressure rectification, so that when the citral is used as a raw material, the citronellal and the dihydrocitronellal are target products and are not to be distinguished.
As another embodiment, in the present invention, the ethylenically unsaturated carbonyl compound is citronellal.
In the hydrogenation reaction, the addition amount of the catalyst is 0.1-5% of the weight of the substrate, and the reaction system can contain a solvent or does not contain a solvent, preferably does not contain a solvent, so that the working procedures such as post-treatment and the like are greatly simplified.
In the invention, the reaction temperature of the hydrogenation is 60-150 ℃, preferably 80-100 ℃, the reaction pressure is 0.1-10 Mpa (G), preferably 1-5 Mpa (G), and the reaction time is 2-24 hours, preferably 4-15 hours.
In the invention, the conversion rate of the hydrogenation reaction is 90-98%, and the selectivity of the target product is more than 99%.
The invention has the remarkable advantages that: the prepared catalyst is used for selectively hydrogenating citral and/or citronellal, the CO poisoning resistance of the catalyst is remarkably improved, the catalyst has high selectivity and stability, no additional auxiliary agent or solvent is added, the process flow is simplified, three wastes are remarkably reduced, and the catalyst has an industrial application prospect.
Detailed Description
The following examples are intended to illustrate the invention without limiting it in any way:
the analysis method comprises the following steps:
a gas chromatograph: agilent7890, chromatography column wax (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: at 150 ℃ for 10min, increasing to 260 ℃ at a rate of 10 ℃/min, for 5min, detector temperature: 280 ℃.
ICP (inductively coupled plasma emission spectrometer): the device is used for metal element detection, and has a focal length of 0.38m, 52.6 echelle grating lines/mm, a 21-degree prism, a charge injection type (CID) detector, a 512 multiplied by 512 detection unit, a wavelength range of 175 nm-1050 nm, a high-frequency generator, a high-frequency power of 2.0KW, 3 turns of a working coil, a frequency of 27.12MHZ, a glass concentric atomizer, a cyclone fog chamber and a built-in 4-channel peristaltic pump. The analysis conditions were as follows: high-frequency power: 1.15KW, plasma gas flow: 15L/min, auxiliary airflow: 0.5L/min, peristaltic pump speed: 100rpm, observation height: 15mm, atomizing gas pressure: 0.22MPa, integration time: the long wave is more than 275nm 15S and the short wave is less than 275nm 25S.
XPS (X-ray photoelectron spectroscopy): for nitrogen detection, X-ray photoelectron spectroscopy (XPS) of samples was obtained on a PHI-1600 type X-ray photoelectron spectrometer. An Al K alpha (1253.6eV) target is adopted, the voltage is 15K V, the power is 250W, and the data acquisition step length is 0.1e V. The sample is subjected to charge correction by taking the binding energy (284.6e V) of the contaminated carbon C1s as a reference, and the binding energy of each energy level is determined.
Citral 98 wt%, pharmaceutical chemical Co., Ltd of Kyoto, Hubei;
citronellal 99 wt%, pharmaceutical chemical company, huge dragon hall, Hubei;
ruthenium chloride 98 wt%, Aladdin reagent, Inc.;
99.6 wt% molybdenum chloride, alatin reagent ltd;
iron chloride 98 wt%, Aladdin reagent, Inc.;
99 wt% sodium hydroxide, Aladdin reagent, Inc.;
activated carbon (coconut shell type, water absorption of 200%), Jiangsu Zhuxi activated carbon, Inc.;
trimethylamine (superior product) > 99.5 wt%, Luxi chemical group, Inc.;
5 wt% Pd/C (50 wt% water), Kingwain Wanfeng catalyst Co.
Example 1
Preparation of carbon-supported ruthenium precursor
a) Fully dispersing 100g of activated carbon in water and keeping a high dispersion state;
b) 62.81g of a 10% wt aqueous solution of ruthenium chloride were added to the mixture obtained in step a);
c) slowly adding 10 wt% NaOH aqueous solution, and stopping dropping alkali liquor when the pH of the mixed solution is stabilized at 8;
d) after the active components are fully precipitated, separating the precipitate from the water phase;
e) and then drying the obtained solid under inert gas, and then roasting at 500 ℃ for 6 hours to obtain the carbon-supported ruthenium precursor.
Preparation of nitrogen-modified carbon-loaded ruthenium precursor
a) Placing the carbon-loaded ruthenium precursor in an alumina reactor, and purging and removing air in the reactor by using argon;
b) after the purging is finished, trimethylamine is introduced at the airspeed of 0.1kgNitrogen source/kgExpiration date of ruthenium precursor on carbon。
c) And (3) carrying out nitrogen modification at the temperature of 650 ℃, treating for 8h, and cooling to room temperature after the treatment is finished to obtain the nitrogen-modified carbon-supported ruthenium precursor.
Preparation of catalyst precursor
a) 0.30g FeCl3、0.29g MoCl5Dissolving in 20g of water, and fully stirring until the solution is completely dissolved to prepare a steeping fluid;
b) dropwise adding the impregnation liquid prepared in the step a) into a nitrogen-modified carbon-supported ruthenium precursor until the dropwise adding is finished, and finishing the equal-volume impregnation of the metal salt solution;
c) roasting the mixture obtained in the step b) at 510 ℃ in a nitrogen atmosphere for 10h, and cooling to room temperature after roasting to obtain a catalyst precursor;
preparation of the catalyst
Weighing 100g of catalyst precursor, filling the catalyst precursor into a reduction reactor, reducing the catalyst precursor at 180 ℃ in hydrogen flow, reducing the catalyst precursor for 10 hours, and then cooling the catalyst to room temperature to obtain the catalyst, wherein the catalyst contains 0.1 wt% of Mo, 0.1 wt% of Fe and 3 wt% of Ru, the weight of the carbon carrier is taken as a reference, the ruthenium is modified by nitrogen, and N/Ru is 0.01 (mol).
Evaluation of reaction Performance
0.1g of catalyst and 100g of citral were added successively to a 500ml hydrogenation autoclave. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, starting heating and stirring, filling hydrogen to 2MPa when the temperature is raised to 100 ℃, and maintaining for 11 hours until the reaction is finished. The reaction results were analyzed by GC and are shown in Table 1.
Example 2
Preparation of carbon-supported ruthenium precursor
a) Fully dispersing 100g of activated carbon in water, and keeping a high dispersion state;
b) 104.68g of a 10% wt aqueous solution of ruthenium chloride are added to the mixture obtained in step a);
c) slowly adding 10 wt% NaOH aqueous solution, and stopping dropping alkali liquor when the pH of the mixed solution is stabilized at 8.5;
d) after the active components are fully precipitated, separating the precipitate from the water phase;
e) and then drying the obtained solid under inert gas, and then roasting at 520 ℃ for 8h to obtain the carbon-supported ruthenium precursor.
Preparation of nitrogen-modified carbon-loaded ruthenium precursor
a) Placing the carbon-loaded ruthenium precursor in an alumina reactor, and purging air in the reactor by using argon;
b) after the purging is finished, trimethylamine is introduced at the airspeed of 0.2kgNitrogen source/kgExpiration date of ruthenium precursor on carbon。
c) And carrying out nitrogen modification at the temperature of 670 ℃, treating for 10h, and cooling to room temperature after the treatment is finished to obtain the nitrogen-modified carbon-loaded ruthenium precursor.
Preparation of catalyst precursor
a) 0.89g of FeCl3、0.57g MoCl5Dissolving in 20g of water, and fully stirring until the solution is completely dissolved to prepare a steeping fluid;
b) dropwise adding the impregnation liquid prepared in the step a) into a nitrogen-modified carbon-supported ruthenium precursor until the dropwise adding is finished, and finishing the equal-volume impregnation of the metal salt solution;
c) roasting the mixture obtained in the step b) at 538 ℃ in a nitrogen atmosphere for 12h, and cooling to room temperature after roasting is finished to obtain a catalyst precursor;
preparation of the catalyst
100g of the catalyst precursor was weighed out and filled into a reduction reactor, reduced at 200 ℃ in a hydrogen stream, reduced for 8 hours and then cooled to room temperature to obtain a catalyst containing 0.2 wt% of Mo, 0.3 wt% of Fe and 5 wt% of Ru, wherein the ruthenium was nitrogen-modified, and N/Ru is 0.07(mol), based on the weight of the carbon support.
Evaluation of reaction Performance
1g of catalyst and 100g of citral were added successively to a 500ml hydrogenation autoclave. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, heating, stirring, charging hydrogen to 4MPa when the temperature is raised to 95 ℃, and maintaining for 7h until the reaction is finished. The reaction results were analyzed by GC and are shown in Table 1.
The catalyst was mechanically used for 30 times, and the ICP analysis of the catalyst components showed that the results are shown in Table 1, and the evaluation of the reaction performance is shown in Table 2.
Example 3
Preparation of carbon-supported ruthenium precursor
a) Fully dispersing 100g of activated carbon in water, and keeping a high dispersion state;
b) adding 2.09g of 10% wt aqueous ruthenium chloride solution to the mixture obtained in step a);
c) slowly adding 10 wt% of NaOH aqueous solution, and stopping dropping alkali liquor when the pH of the mixed solution is stabilized at 9;
d) after the active components are fully precipitated, separating the precipitate from the water phase;
e) and then drying the obtained solid under inert gas, and then roasting at 538 ℃ for 10 hours to obtain the carbon-supported ruthenium precursor.
Preparation of nitrogen-modified carbon-loaded ruthenium precursor
a) Placing the carbon-loaded ruthenium precursor in an alumina reactor, and purging and removing air in the reactor by using argon;
b) after the purging is finished, trimethylamine is introduced at the airspeed of 0.3kgNitrogen source/kgExpiration date of ruthenium precursor on carbon。
c) And (3) carrying out nitrogen modification at the temperature of 690 ℃, treating for 12h, and cooling to room temperature after the treatment is finished to obtain the nitrogen-modified carbon-supported ruthenium precursor.
Preparation of catalyst precursor
a) 1.48g of FeCl3、1.14g MoCl5Dissolving in 20g of water, and fully stirring until the solution is completely dissolved to prepare a steeping fluid;
b) dropwise adding the impregnation liquid prepared in the step a) into a nitrogen-modified carbon-supported ruthenium precursor until the dropwise adding is finished, and finishing the equal-volume impregnation of the metal salt solution;
c) roasting the mixture obtained in the step b) at 500 ℃ in a nitrogen atmosphere for 14h, and cooling to room temperature after roasting to obtain a catalyst precursor;
preparation of the catalyst
Weighing 100g of catalyst precursor, filling the catalyst precursor into a reduction reactor, reducing the catalyst precursor at 240 ℃ in hydrogen flow for 4 hours, and then cooling the catalyst to room temperature to obtain the catalyst, wherein the catalyst contains 0.4 wt% of Mo, 0.5 wt% of Fe and 0.1 wt% of Ru, the weight of the carbon carrier is taken as a reference, ruthenium is modified by nitrogen, and N/Ru is 0.03 (mol).
Evaluation of reaction Performance
2.5g of catalyst and 100g of citral were added successively to a 500ml hydrogenation autoclave. Sealing the pressure kettle, replacing 3 times with nitrogen and hydrogen respectively, heating, stirring, charging hydrogen to 1MPa when the temperature is raised to 90 ℃, and maintaining for 15h until the reaction is finished. The reaction results were analyzed by GC and are shown in Table 1.
Example 4
Preparation of carbon-supported ruthenium precursor
a) Fully dispersing 100g of activated carbon in water and keeping a high dispersion state;
b) 83.74g of a 10% wt aqueous solution of ruthenium chloride were added to the mixture obtained in step a);
c) slowly adding 10 wt% NaOH aqueous solution, and stopping dropping alkali liquor when the pH of the mixed solution is stabilized at 9.4;
d) after the active components are fully precipitated, separating the precipitate from the water phase;
e) and then drying the obtained solid under inert gas, and then roasting at 550 ℃ for 12 hours to obtain the carbon-supported ruthenium precursor.
Preparation of nitrogen-modified carbon-loaded ruthenium precursor
a) Placing the carbon-loaded ruthenium precursor in an alumina reactor, and purging and removing air in the reactor by using argon;
b) after the purging is finished, trimethylamine is introduced at the airspeed of 0.4kgNitrogen source/kgExpiration date with carbon-supported ruthenium precursor。
c) And carrying out nitrogen modification at the temperature of 730 ℃, treating for 13h, and cooling to room temperature after the treatment is finished to obtain the nitrogen-modified carbon-loaded ruthenium precursor.
Preparation of catalyst precursor
a) 2.07g FeCl3、2.29g MoCl5Dissolving in 20g of water, and fully stirring until the solution is completely dissolved to prepare a steeping fluid;
b) dropwise adding the impregnation liquid prepared in the step a) into a nitrogen-modified carbon-supported ruthenium precursor until the dropwise adding is finished, and finishing the equal-volume impregnation of the metal salt solution;
c) roasting the mixture obtained in the step b) at 570 ℃ in a nitrogen atmosphere for 16h, and cooling to room temperature after roasting to obtain a catalyst precursor;
preparation of the catalyst
100g of the catalyst precursor was weighed out and filled into a reduction reactor, reduced at 270 ℃ in a hydrogen stream, and cooled to room temperature after 5 hours of reduction to obtain a catalyst containing 0.8 wt% of Mo, 0.7 wt% of Fe, and 4 wt% of Ru, wherein the ruthenium was nitrogen-modified, and N/Ru was 0.05(mol), based on the weight of the carbon support.
Evaluation of reaction Performance
3g of catalyst and 100g of citronellal are added in sequence into a 500ml hydrogenation pressure kettle. Sealing the pressure kettle, replacing 3 times with nitrogen and hydrogen respectively, heating, stirring, charging hydrogen to 3MPa when the temperature is raised to 85 ℃, and maintaining for 9h until the reaction is finished. The reaction results were analyzed by GC and are shown in Table 1.
Example 5
Preparation of carbon-supported ruthenium precursor
a) Fully dispersing 100g of activated carbon in water, and keeping a high dispersion state;
b) 52.34g of a 10% wt aqueous solution of ruthenium chloride are added to the mixture obtained in step a);
c) slowly adding 10 wt% NaOH aqueous solution, and stopping dropping alkali liquor when the pH of the mixed solution is stabilized at 10;
d) after the active components are fully precipitated, separating the precipitate from the water phase;
e) and then drying the obtained solid under inert gas, and then roasting at 600 ℃ for 15h to obtain the carbon-supported ruthenium precursor.
Preparation of nitrogen-modified carbon-loaded ruthenium precursor
a) Placing the carbon-loaded ruthenium precursor in an alumina reactor, and purging and removing air in the reactor by using argon;
b) after the purging is finished, introducing trimethylamine at the airspeed of 0.5kgNitrogen source/kgExpiration date of ruthenium precursor on carbon。
c) And (3) carrying out nitrogen modification at the temperature of 750 ℃, treating for 15h, and cooling to room temperature after the treatment is finished to obtain the nitrogen-modified carbon-supported ruthenium precursor.
Preparation of catalyst precursor
a) 2.96g of FeCl3、2.86g MoCl5Dissolving in 20g of water, and fully stirring until the solution is completely dissolved to prepare a steeping fluid;
b) dropwise adding the impregnation liquid prepared in the step a) into a nitrogen-modified carbon-supported ruthenium precursor until the dropwise adding is finished, and finishing the equal-volume impregnation of the metal salt solution;
c) roasting the mixture obtained in the step b) at 600 ℃ in a nitrogen atmosphere for 18h, and cooling to room temperature after roasting to obtain a catalyst precursor;
preparation of the catalyst
Weighing 100g of catalyst precursor, filling the catalyst precursor into a reduction reactor, reducing the catalyst precursor at 300 ℃ in hydrogen flow, reducing the catalyst precursor for 7 hours, and then cooling the catalyst to room temperature to obtain the catalyst, wherein the catalyst contains 1 wt% of Mo, 1 wt% of Fe and 2.5 wt% of Ru, the weight of the carbon carrier is taken as a reference, the ruthenium is modified by nitrogen, and N/Ru is 0.1 (mol).
Evaluation of reaction Performance
5g of catalyst and 100g of citronellal are added in sequence into a 500ml hydrogenation pressure kettle. Sealing the pressure kettle, replacing 3 times with nitrogen and hydrogen respectively, heating, stirring, charging hydrogen to 5MPa when the temperature is raised to 80 ℃, and maintaining for 4h until the reaction is finished. The reaction results were analyzed by GC and are shown in Table 1.
Comparative example 1:
comparative catalyst preparation
a) Fully dispersing 100g of activated carbon in water and keeping a high dispersion state;
b) 104.68g of a 10% wt aqueous solution of ruthenium chloride, 11.44g of a 5% wt aqueous solution of molybdenum chloride and 17.73g of a 5% wt aqueous solution of iron chloride were added to the mixture obtained in step a);
c) slowly adding 10 wt% of NaOH aqueous solution, and stopping dropping alkali liquor when the pH value of the mixed solution is stabilized at 9;
d) after the active components are fully precipitated, separating the precipitate from the water phase;
e) drying the obtained solid in inert gas, and then roasting at 538 ℃ for 12 hours to obtain a catalyst precursor;
f) weighing 100g of catalyst precursor, filling the catalyst precursor into a reduction reactor, reducing the catalyst precursor at 200 ℃ in hydrogen flow, reducing the catalyst precursor for 8 hours, and cooling the catalyst to room temperature to obtain the catalyst, wherein the catalyst contains 0.2 wt% of Mo, 0.3 wt% of Fe and 5 wt% of Ru based on the weight of the carbon carrier.
Evaluation of reaction Performance
1g of catalyst and 100g of citral were added successively to a 500ml hydrogenation autoclave. Sealing the pressure kettle, replacing 3 times with nitrogen and hydrogen respectively, heating, stirring, charging hydrogen to 4MPa when the temperature is raised to 95 ℃, and maintaining for 7h until the reaction is finished. The reaction results were analyzed by GC and are shown in Table 1.
The catalyst was mechanically used for 30 times, and the ICP analysis of the catalyst components showed that the results are shown in Table 1 and the evaluation of the reaction performance is shown in Table 2.
Comparative example 2:
nitrogen modified carbon preparation
a) Placing activated carbon in an alumina reactor, and purging and removing air in the reactor by using argon;
b) after the purging is finished, trimethylamine is added, and the space velocity is 0.2kgNitrogen source/kgCarbon value for hour。
c) The nitrogen modification was carried out at a temperature of 670 ℃ for a treatment time of 10h, and after the treatment was completed, the temperature was decreased to room temperature to obtain a nitrogen-modified carbon, wherein N/C was 0.07 (mol).
Comparative catalyst preparation
a) Fully dispersing 100g of nitrogen-modified carbon in water and keeping a high dispersion state;
b) 104.68g of a 10% wt aqueous solution of ruthenium chloride, 11.44g of a 5% wt aqueous solution of molybdenum chloride and 17.73g of a 5% wt aqueous solution of iron chloride were added to the mixture obtained in step a);
c) slowly adding 10 wt% of NaOH aqueous solution, and stopping dropping alkali liquor when the pH value of the mixed solution is stabilized at 9;
d) after the active components are fully precipitated, separating the precipitate from the water phase;
e) then drying the obtained solid under inert gas, and then roasting at 538 ℃ for 12 hours to obtain a catalyst precursor;
f) 100g of the catalyst precursor was weighed and charged into a reduction reactor, reduced at 200 ℃ in a hydrogen stream for 8 hours and then cooled to room temperature to obtain a catalyst containing 0.2 wt% of Mo, 0.3 wt% of Fe and 5 wt% of Ru based on the weight of carbon modified with nitrogen, wherein N/C is 0.07 (mol).
Evaluation of reaction Performance
1g of catalyst and 100g of citral were added successively to a 500ml hydrogenation autoclave. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, heating, stirring, charging hydrogen to 4MPa when the temperature is raised to 95 ℃, and maintaining for 7h until the reaction is finished. The reaction results were analyzed by GC and are shown in Table 1.
Comparative example 3:
preparation of carbon-supported precursor
a) Fully dispersing 100g of activated carbon in water and keeping a high dispersion state;
b) 104.68g of a 10% wt aqueous solution of ruthenium chloride, 11.44g of a 5% wt aqueous solution of molybdenum chloride and 17.73g of a 5% wt aqueous solution of iron chloride were added to the mixture obtained in step a);
c) slowly adding 10 wt% of NaOH aqueous solution, and stopping dropping alkali liquor when the pH value of the mixed solution is stabilized at 9;
d) after the active components are fully precipitated, separating the precipitate from the water phase;
e) drying the obtained solid in inert gas, and then roasting at 538 ℃ for 12 hours to obtain a catalyst precursor;
preparation of the comparative catalyst
a) Placing the catalyst precursor in an alumina reactor, and purging and removing air in the reactor by using argon;
b) after the purging is finished, trimethylamine is added, and the space velocity is 0.2kgNitrogen source/kgReaction time of catalyst precursor。
c) And (3) carrying out nitrogen modification at the temperature of 670 ℃, treating for 10h, and cooling to room temperature after the treatment is finished to obtain the product.
d) Weighing 100g of catalyst precursor, filling the catalyst precursor into a reduction reactor, reducing the catalyst precursor at 200 ℃ in hydrogen flow for 8 hours, and then cooling the catalyst to room temperature to obtain the catalyst, wherein the catalyst comprises 0.2 wt% of Mo, 0.3 wt% of Fe and 5 wt% of Ru, based on the weight of the carbon carrier, the Mo, the Fe and the Ru are modified by nitrogen, and N/(Mo + Fe + Ru) is 0.08 (mol).
Evaluation of reaction Performance
1g of catalyst and 100g of citral were added successively to a 500ml hydrogenation autoclave. Sealing the pressure kettle, replacing 3 times with nitrogen and hydrogen respectively, heating, stirring, charging hydrogen to 4MPa when the temperature is raised to 95 ℃, and maintaining for 7h until the reaction is finished. The reaction results were analyzed by GC and are shown in Table 1.
Comparative example 4
Preparation of carbon-supported iron precursor
a) Fully dispersing 100g of activated carbon in water and keeping a high dispersion state;
b) adding 17.73g of a 5% wt aqueous solution of ferric chloride to the mixture obtained in step a);
c) slowly adding 10 wt% NaOH aqueous solution, and stopping dropping alkali liquor when the pH of the mixed solution is stabilized at 8.5;
d) after the active components are fully precipitated, separating the precipitate from the water phase;
e) and then drying the obtained solid in inert gas, and then roasting at 520 ℃ for 8h to obtain the carbon-supported iron precursor.
Preparation of nitrogen-modified carbon-supported iron precursor
a) Placing the carbon-loaded iron precursor in an alumina reactor, and purging and removing air in the reactor by using argon;
b) after the purging is finished, trimethylamine is introduced at the airspeed of 0.2kgNitrogen source/kgExpiration of carbon-Supported iron precursor。
c) And (3) carrying out nitrogen modification at the temperature of 670 ℃, treating for 10h, and cooling to room temperature after the treatment is finished to obtain the nitrogen-modified carbon-supported iron precursor.
Preparation of catalyst precursor
a) 0.57g of MoCl510.468g of ruthenium chloride is dissolved in 20g of water, and the mixture is fully stirred until the ruthenium chloride is completely dissolved to prepare a steeping liquor;
b) dropwise adding the impregnation liquid prepared in the step a) into the nitrogen modified carbon-supported iron precursor until the dropwise adding is finished, and finishing the equal-volume impregnation of the metal salt solution;
c) roasting the mixture obtained in the step b) at 538 ℃ in a nitrogen atmosphere for 12h, and cooling to room temperature after roasting is finished to obtain a catalyst precursor;
preparation of the catalyst
100g of the catalyst precursor was weighed out and filled into a reduction reactor, reduced at 200 ℃ in a hydrogen stream, and cooled to room temperature after reduction for 8 hours, to obtain a catalyst containing 0.2 wt% of Mo, 0.3 wt% of Fe and 5 wt% of Ru, wherein Fe was nitrogen-modified, and N/Fe is 0.07(mol), based on the weight of the carbon support.
Evaluation of reaction Performance
1g of catalyst and 100g of citral were added successively to a 500ml hydrogenation autoclave. Sealing the autoclave, replacing 3 times with nitrogen and hydrogen respectively, heating, stirring, charging hydrogen to 4MPa when the temperature is raised to 95 ℃, and maintaining for 7h until the reaction is finished. The reaction results were analyzed by GC and are shown in Table 1.
Comparative example 5
Preparation of carbon-loaded molybdenum precursor
a) Fully dispersing 100g of activated carbon in water and keeping a high dispersion state;
b) adding 11.44g of a 5% wt aqueous solution of molybdenum chloride to the mixture obtained in step a);
c) slowly adding 10 wt% NaOH aqueous solution, and stopping dropping alkali liquor when the pH of the mixed solution is stabilized at 8.5;
d) after the active components are fully precipitated, separating the precipitate from the water phase;
e) and then drying the obtained solid under inert gas, and then roasting at 520 ℃ for 8 hours to obtain the carbon-supported molybdenum precursor.
Preparation of nitrogen modified carbon-loaded molybdenum precursor
a) Placing the carbon-loaded molybdenum precursor in an alumina reactor, and purging and removing air in the reactor by using argon;
b) after the purging is finished, trimethylamine is added, and the space velocity is 0.2kgNitrogen source/kgExpiration date of carbon-supported molybdenum precursor。
c) And (3) carrying out nitrogen modification at the temperature of 670 ℃, treating for 10h, and cooling to room temperature after the treatment is finished to obtain the nitrogen-modified carbon-loaded molybdenum precursor.
Preparation of catalyst precursor
a) Dissolving 0.89g of ferric chloride and 10.468g of ruthenium chloride in 20g of water, and fully stirring until the ferric chloride and the 10.468g of ruthenium chloride are completely dissolved to prepare a steeping liquor;
b) dropwise adding the impregnation liquid prepared in the step a) into a nitrogen modified carbon-loaded molybdenum precursor until the dropwise adding is finished, and finishing the equal-volume impregnation of a metal salt solution;
c) roasting the mixture obtained in the step b) at 538 ℃ in a nitrogen atmosphere for 12h, and cooling to room temperature after roasting is finished to obtain a catalyst precursor;
preparation of the catalyst
100g of the catalyst precursor was weighed out and filled into a reduction reactor, reduced at 200 ℃ in a hydrogen stream, and cooled to room temperature after reduction for 8 hours, to obtain a catalyst containing 0.2 wt% of Mo, 0.3 wt% of Fe, and 5 wt% of Ru, based on the weight of the carbon support, wherein Mo was modified with nitrogen, and N/Mo is 0.07 (mol).
Evaluation of reaction Performance
1g of catalyst and 100g of citral were added successively to a 500ml hydrogenation autoclave. Sealing the pressure kettle, replacing 3 times with nitrogen and hydrogen respectively, heating, stirring, charging hydrogen to 4MPa when the temperature is raised to 95 ℃, and maintaining for 7h until the reaction is finished. The reaction results were analyzed by GC and are shown in Table 1.
Comparative example 6
Preparation of carbon-supported ruthenium precursor
a) Fully dispersing 100g of activated carbon in water and keeping a high dispersion state;
b) meanwhile, 104.68g of 10 wt% ruthenium chloride solution is added into the mixed solution obtained in the step a);
c) slowly adding 10 wt% NaOH solution, and stopping dropping alkali liquor when the pH of the mixed solution is stabilized at 8.5;
d) after the active components are fully precipitated, separating the precipitate from the water phase;
e) and then drying the obtained solid under inert gas, and then roasting at 520 ℃ for 8h to obtain the carbon-supported ruthenium precursor.
Preparation of nitrogen-modified carbon-loaded ruthenium precursor
a) Placing the obtained carbon-loaded ruthenium precursor in an alumina reactor, and purging and removing air in the reactor by using argon gas;
b) after the purging is finished, trimethylamine is introduced at the airspeed of 0.2kgNitrogen source/kgExpiration date of ruthenium precursor on carbon。
c) And (3) carrying out nitrogen modification at the temperature of 670 ℃, treating for 10h, and cooling to room temperature after the treatment is finished to obtain the nitrogen-modified carbon-loaded ruthenium precursor.
Preparation of catalyst precursor
a) 0.57g of MoCl5Dissolving in 20g of water, and fully stirring until the solution is completely dissolved to prepare a steeping fluid;
b) dropwise adding the impregnation liquid prepared in the step a) into the nitrogen modified carbon-loaded ruthenium precursor until the dropwise adding is finished, and finishing the equal-volume impregnation of the metal salt solution;
c) roasting the mixture obtained in the step b) at 538 ℃ in a nitrogen atmosphere for 12h, and cooling to room temperature after roasting is finished to obtain a catalyst precursor;
preparation of the catalyst
100g of the catalyst precursor was weighed out and filled into a reduction reactor, reduced at 200 ℃ in a hydrogen stream for 8 hours and then cooled to room temperature to obtain a catalyst containing 0.2 wt% of Mo and 5 wt% of Ru, based on the weight of the carbon support, wherein the ruthenium was nitrogen-modified and N/Ru was 0.07 (mol).
Evaluation of reaction Performance
1g of catalyst and 100g of citral were added successively to a 500ml hydrogenation autoclave. Sealing the pressure kettle, replacing 3 times with nitrogen and hydrogen respectively, heating, stirring, charging hydrogen to 4MPa when the temperature is raised to 95 ℃, and maintaining for 7h until the reaction is finished. The reaction results were analyzed by GC and are shown in Table 1.
Comparative example 7
5 wt% Pd/C2 g followed by 100g citral were added to a 500ml hydrogenation autoclave. Sealing the pressure kettle, replacing 3 times with nitrogen and hydrogen respectively, heating, stirring, charging hydrogen to 4MPa when the temperature is raised to 95 ℃, and maintaining for 7h until the reaction is finished. The reaction results were analyzed by GC and are shown in Table 1.
Comparative example 7-1
The used catalyst in comparative example 7 was subjected to solid-liquid separation and then subjected to mechanical experiments under the same reaction conditions as in comparative example 7, and the results of the thirty-second mechanical reaction were analyzed by GC, and are shown in table 1.
Comparative examples 7 to 2
Adding 5 wt% Pd/C2 g and citral 100g into a 500ml hydrogenation pressure kettle, sealing the pressure kettle, introducing 10ml/min air into the reaction kettle for 10min, heating, stirring, introducing hydrogen to 4MPa when the temperature is raised to 95 deg.C, and maintaining for 7h until the reaction is finished.
The results of the thirty-second reaction were analyzed by GC and are shown in Table 1.
TABLE 1 results of examples and comparative examples
Figure BDA0002308197640000231
Figure BDA0002308197640000241
"-" indicates that the substance was not detected.
The results of the application of example 2 and comparative example 1 are shown in Table 2.
TABLE 2 application results
Figure BDA0002308197640000242

Claims (10)

1. A catalyst for the selective hydrogenation of olefinically unsaturated carbonyl compounds comprising from 0.05 to 10% by weight of ruthenium, from 0.05 to 5% by weight of molybdenum and from 0.05 to 5% by weight of iron, based on the weight of the carbon support; the ruthenium is modified by nitrogen, wherein the molar ratio of nitrogen element to ruthenium is 0.01-0.1: 1; the preparation method of the catalyst comprises the following steps:
1) adding a ruthenium salt aqueous solution into a uniformly dispersed mixture of a carbon carrier and water, then dropwise adding an alkali liquor, stopping dropwise adding the alkali liquor when the pH value of the system reaches 8-10, separating the obtained solid, drying, and roasting to obtain a carbon-supported ruthenium precursor;
2) treating the carbon-supported ruthenium precursor obtained in the step 1) with a nitrogen source substance to obtain a nitrogen-modified carbon-supported ruthenium precursor;
3) performing equal-volume impregnation on the molybdenum salt and iron salt aqueous solution and the nitrogen-modified carbon-loaded ruthenium precursor obtained in the step 2), and then roasting to obtain a catalyst precursor;
4) reducing the catalyst precursor obtained in the step 3) in a hydrogen atmosphere to obtain a catalyst;
in the step 2), the nitrogen source substance comprises one or more of ammonia gas, methylamine, dimethylamine, trimethylamine, ethylenediamine, isobutyronitrile, hydrazine hydrate and melamine; the space velocity of the nitrogen source substance is 0.01-1 kgNitrogen source/kgExpiration date of ruthenium precursor on carbon(ii) a The treatment temperature is 600-1000 ℃; the treatment time is 1-30 h.
2. The catalyst of claim 1, wherein in step 1), the carbon support comprises one or more of graphite, carbon black, and activated carbon.
3. The catalyst according to claim 1, wherein in the step 1), the roasting atmosphere is an inert atmosphere; the roasting temperature is 400-800 ℃, and the roasting time is 2-25 h.
4. The catalyst according to claim 1, wherein in the step 1), the roasting atmosphere is nitrogen; the roasting temperature is 500-600 ℃, and the roasting time is 6-15 h.
5. The catalyst of claim 1, wherein in the step 2), the space velocity of the nitrogen source substance is 0.1-0.5 kgNitrogen source/kgExpiration date of ruthenium precursor on carbon。
6. The catalyst according to claim 1, wherein in the step 2), the temperature of the treatment is 650-750 ℃; the treatment time is 8-15 h.
7. The catalyst according to claim 1, wherein in the step 3), the roasting atmosphere is an inert atmosphere; the roasting temperature is 400-800 ℃, and the roasting time is 5-25 h.
8. The catalyst according to claim 1, wherein in the step 3), the roasting atmosphere is nitrogen; the roasting temperature is 500-600 ℃, and the roasting time is 10-18 h.
9. The catalyst according to claim 1, wherein the catalyst comprises 0.1 to 5 wt% ruthenium, 0.1 to 1 wt% molybdenum, and 0.1 to 1 wt% iron.
10. Use of a catalyst according to any one of claims 1 to 9 for the selective hydrogenation of olefinically unsaturated carbonyl compounds, characterized in that it is used for the highly selective hydrogenation of citral to citronellal and/or dihydrocitronellal, or for the highly selective hydrogenation of citronellal to dihydrocitronellal.
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