CN114644552A - Method for preparing propionic acid by acrylic acid hydrogenation - Google Patents

Method for preparing propionic acid by acrylic acid hydrogenation Download PDF

Info

Publication number
CN114644552A
CN114644552A CN202210440988.8A CN202210440988A CN114644552A CN 114644552 A CN114644552 A CN 114644552A CN 202210440988 A CN202210440988 A CN 202210440988A CN 114644552 A CN114644552 A CN 114644552A
Authority
CN
China
Prior art keywords
ruthenium
acrylic acid
nano
propionic acid
treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210440988.8A
Other languages
Chinese (zh)
Other versions
CN114644552B (en
Inventor
赵华华
丑凌军
宋焕玲
赵军
杨建�
闫亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanzhou Institute of Chemical Physics LICP of CAS
Original Assignee
Lanzhou Institute of Chemical Physics LICP of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanzhou Institute of Chemical Physics LICP of CAS filed Critical Lanzhou Institute of Chemical Physics LICP of CAS
Priority to CN202210440988.8A priority Critical patent/CN114644552B/en
Publication of CN114644552A publication Critical patent/CN114644552A/en
Application granted granted Critical
Publication of CN114644552B publication Critical patent/CN114644552B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for preparing propionic acid by acrylic acid hydrogenation. The method comprises the following steps: carrying out hydrogenation reaction on a mixed reaction system containing acrylic acid, a nano-load ruthenium-carbon catalyst and a solvent for 2.0-6.0 h under the conditions that the hydrogen pressure is 1.0-7.0 atm and the temperature is 20-65 ℃ to prepare propionic acid; wherein the solvent comprises propionic acid. The invention realizes the synthesis of propionic acid by catalyzing the hydrogenation of acrylic acid through the nano-load ruthenium carbon, does not need product separation, has simple and convenient catalyst composition and preparation method, can be circulated for more than twenty times, and has the advantages of mild reaction conditions, high product yield, low production cost, long catalytic life and the like.

Description

Method for preparing propionic acid by acrylic acid hydrogenation
Technical Field
The invention belongs to the technical field of organic chemistry, and particularly relates to a method for preparing propionic acid by hydrogenating acrylic acid.
Background
Propionic acid is an important fine chemical and basic chemical raw material, and is widely applied to the fields of feed, plastics, food, rubber, paint, spice, pesticide and the like. The demand for propionic acid has increased rapidly in recent years and this trend will continue for the next few years. The 20 th century and the 50 th century developed the synthesis of acetic acid and propionic acid as the by-product by light hydrocarbon compounds, and the 60 th century developed the carbonylation of ethylene, and then developed a variety of technologies such as the oxidation of propionaldehyde, the carbonylation of ethanol, the oxidation of acrylonitrile and the oxidation of n-propanol. The industrialization of the domestic propionic acid production has been already realized, the traditional light hydrocarbon oxidation method is still adopted in the domestic propionic acid preparation technology, and the development of the suitable advanced propionic acid production technology is urgently needed, so that the development of a new propionic acid production method is very necessary.
Acrylic acid is used as an important organic synthetic raw material and a synthetic resin monomer, and the application range of the acrylic acid is gradually expanded. More than 85% of acrylic acid is prepared by adopting an economical propylene oxidation method, and the method is also the first method for large-scale production, and the capability of producing cheap acrylic acid is formed in the world at present. Therefore, the technology for preparing the propionic acid by hydrogenating the acrylic acid is expected to be a cheap technology for producing the propionic acid. At present, few reports relating to the preparation of propionic acid by acrylic acid hydrogenation are reported, and certain progress is made on Pd-based catalysts. For example, Pd/SiO is used2When the catalyst reacts at 200 ℃, the selectivity of the propionic acid can reach 100 percent; the liquid phase reaction is carried out at the reaction temperature of 20-80 ℃ by adopting catalysts such as Pd-Cu, Pd/C and the like, and the conversion rate of acrylic acid can reach 99%. However, the Pd-based catalyst still has the defects of high catalyst cost, poor catalytic stability and acrylic acid under the reaction conditionEasy polymerization, etc. Therefore, it is an urgent problem to provide a low-cost method for preparing propionic acid by hydrogenating acrylic acid.
Disclosure of Invention
The invention mainly aims to provide a method for preparing propionic acid by hydrogenating acrylic acid, which overcomes the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a method for preparing propionic acid by hydrogenating acrylic acid, which comprises the following steps: carrying out hydrogenation reaction on a mixed reaction system containing acrylic acid, a nano-load ruthenium-carbon catalyst and a solvent for 2.0-6.0 h under the conditions that the hydrogen pressure is 1.0-7.0 atm and the temperature is 20-65 ℃ to prepare propionic acid; wherein the solvent comprises propionic acid.
The embodiment of the invention also provides a preparation method of the nano supported ruthenium-carbon catalyst, which comprises the following steps: and (2) putting the activated carbon into a ruthenium salt precursor solution for dipping treatment, then adding an alkaline precipitator for precipitation treatment, and then filtering, drying, roasting and reducing the precipitate to obtain the nano supported ruthenium-carbon catalyst.
The embodiment of the invention also provides the nano supported ruthenium-carbon catalyst prepared by the method, wherein the content of ruthenium in the nano supported ruthenium-carbon catalyst is 2.0-5.0 wt%.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method adopts the nano supported ruthenium-carbon catalyst, can realize the preparation of propionic acid by the hydrogenation of the raw material acrylic acid under mild conditions, ensures that the conversion rate of the raw material acrylic acid and the yield of the product propionic acid both reach more than 99 percent, basically has no generation of polymerization products, and has simple preparation process and high catalytic activity;
(2) the catalyst in the preparation of propionic acid by acrylic acid hydrogenation is simply separated and recycled, can be repeatedly used and has long service life;
(3) the synthetic process of the propionic acid is easy to operate, the product does not need to be separated, and the industrial feasibility is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph of the recycling performance of the nano ruthenium carbon catalyst used in the reaction of preparing propionic acid by hydrogenating acrylic acid in example 1 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Specifically, as an aspect of the technical solution of the present invention, a method for preparing propionic acid by hydrogenating acrylic acid includes: carrying out hydrogenation reaction on a mixed reaction system containing acrylic acid, a nano-load ruthenium-carbon catalyst and a solvent for 2.0-6.0 h under the conditions that the hydrogen pressure is 1.0-7.0 atm and the temperature is 20-65 ℃ to prepare propionic acid; wherein the solvent comprises propionic acid.
In some preferred embodiments, the hydrogen pressure is 1.0 to 4.5 atm.
In some preferred embodiments, the mass ratio of acrylic acid to solvent is from 1: 3 to 3: 1.
In some preferred embodiments, the mass ratio of the catalyst to acrylic acid is 1-10: 100.
In some preferred embodiments, the conversion of acrylic acid in the hydrogenation reaction is above 99%.
In some preferred embodiments, the yield of propionic acid in the hydrogenation reaction is above 99%.
In some preferred embodiments, the ruthenium content of the nano-supported ruthenium carbon catalyst is 2.0 to 5.0 wt%.
In some preferred embodiments, the preparation method of the nano-supported ruthenium carbon catalyst comprises: and (2) putting the activated carbon into a ruthenium salt precursor solution for dipping treatment, then adding an alkaline precipitator for precipitation treatment, and then filtering, drying, roasting and reducing to obtain the nano supported ruthenium-carbon catalyst.
In some preferred embodiments, the precipitation treatment comprises: and adding an alkaline precipitator into the mixed solution formed by the activated carbon and the ruthenium salt precursor solution, and adjusting the pH value to 8-10.
Further, the alkaline precipitant includes any one or a combination of two or more of ammonia water, sodium hydroxide, sodium carbonate, and sodium bicarbonate, and is not limited thereto.
In some preferred embodiments, the firing treatment comprises: and roasting the product obtained by drying treatment at 400-600 ℃ for 2.0-4.0 h under a protective atmosphere.
Further, the protective atmosphere comprises N2。
In some preferred embodiments, the reduction treatment comprises: at H2And reducing the product obtained by roasting treatment at 200-400 ℃ for 2.0-5.0 h under the atmosphere.
In some preferred embodiments, the ruthenium salt in the ruthenium salt precursor solution includes RuCl hydrate3Any one or a combination of two or more of ruthenium acetate, ruthenium acetylacetonate, ammonium hexachlororuthenate and ammonium pentachlororuthenate hydrate, without being limited thereto.
Specifically, the method for preparing propionic acid by hydrogenating acrylic acid comprises the following steps: adopting a nano-load ruthenium-carbon catalyst, taking propionic acid as a reaction solvent, reacting for a certain time at a certain mass ratio of acrylic acid to the catalyst, a certain mass ratio of acrylic acid to propionic acid, a certain reaction temperature and pressure to obtain a propionic acid product, and recycling the catalyst.
In some more specific embodiments, the method for preparing propionic acid by hydrogenating acrylic acid comprises: sequentially adding 0.5-1.5 g of catalyst, 10-30 g of acrylic acid and 30-10 g of propionic acid into a 100mL high-pressure reaction kettle, replacing for 3 times by hydrogen, heating to the required reaction temperature of 20-65 ℃, keeping the reaction pressure of 1.0-4.5 atm, and reacting for 2.0-6.0 h at the reaction speed of 700 r/min. And releasing the pressure after the reaction is finished. Filtering the reaction mixture, analyzing the liquid by a gas chromatography with an FID detector, and recovering the catalyst solid which can be directly reused without drying.
The method realizes the synthesis of the propionic acid by catalyzing the hydrogenation of the acrylic acid by the nano-load ruthenium carbon, does not need product separation, has simple and convenient catalyst preparation, can be circulated for more than twenty times, and has the advantages of mild reaction conditions, high product yield, low production cost, long catalytic life and the like.
Another aspect of an embodiment of the present invention also provides a method for preparing a nano-supported ruthenium carbon catalyst, including: the preparation method comprises the following steps of putting active carbon into ruthenium salt water solution for dipping treatment, then adding alkaline precipitator for precipitation treatment, and then preparing the nano supported ruthenium-carbon catalyst, wherein the preparation method comprises the following steps: filtering, drying, roasting and reducing to obtain the nano supported ruthenium-carbon catalyst.
In some preferred embodiments, the precipitation treatment comprises: and adding an alkaline precipitator into the mixed solution formed by the activated carbon and the ruthenium salt water solution, and adjusting the pH value to 8-10.
In some preferred embodiments, the firing treatment comprises: and roasting the product obtained by drying treatment at 400-600 ℃ for 2.0-4.0 h in a protective atmosphere.
Further, the protective atmosphere comprises N2。
In some preferred embodiments, the reduction treatment comprises: at H2And reducing the product obtained by roasting treatment at 200-400 ℃ for 2.0-5.0 h under the atmosphere.
In some preferred embodiments, the alkaline precipitant includes one or a combination of two or more of ammonia water, sodium hydroxide, sodium carbonate, and sodium bicarbonate, and is not limited thereto.
In some preferred embodiments, the ruthenium salt in the aqueous ruthenium salt solution includes RuCl hydrate3Any one or a combination of two or more of ruthenium acetate, ruthenium acetylacetonate, ammonium hexachlororuthenate and ammonium pentachlororuthenate hydrate, without being limited thereto.
In some more specific embodiments, the method for preparing the nano-supported ruthenium carbon catalyst comprises: in RuCl3(ruthenium content: 37.5%) into the precursor solution, the specific surface area was 950m2·g-1Stirring the activated carbon for 1.0h, then adjusting the pH value to 8-10 by ammonia water, continuously stirring the mixture for 2.0h, filtering the mixture, washing the mixture by water until the mixture is neutral and chloride ions cannot be detected, transferring the mixture to an oven for drying, and drying the mixture in an N atmosphere2Roasting at 400-600 ℃ for 2.0-4.0H in the atmosphere, and roasting in H2Reducing for 2.0-5.0 h at 200-400 ℃ in the atmosphere to obtain the nano supported ruthenium-carbon catalyst. The weight percentage of ruthenium in the catalyst is 2.0-5.0%.
In another aspect of the embodiment of the invention, the nano-supported ruthenium carbon catalyst prepared by the method is provided, and the ruthenium content in the nano-supported ruthenium carbon catalyst is 2.0-5.0 wt%.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
Preparing a catalyst: 0.85g of hydrated RuCl is weighed out3The precursor is stirred and dissolved into 100mL of water, and the specific surface area is added to be 950m2·g-110.00g of activated carbon (2), stirred for 1.0h, and then mixed with 1.0 mol. L-1Adjusting pH to 8 with ammonia water, stirring for 2.0 hr, filtering, washing filter cake with water to neutrality, transferring to oven, drying in N2Roasting at 500 deg.C in atmosphere of 4.0H and at 300 ℃ in H2Reducing in atmosphere to obtain the nanometer load type ruthenium carbon catalyst with the weight percentage of ruthenium of 3.0 percent.
And (3) acrylic acid hydrogenation reaction: 1.5g of catalyst, 30g of acrylic acid and 10g of propionic acid are sequentially added into a 100mL high-pressure reaction kettle, after hydrogen replacement is carried out for 3 times, the temperature is raised to 60 ℃, the reaction pressure is kept at 4.5atm, the reaction speed is 700r/min, and the reaction is carried out for 4.0 h. And releasing the pressure after the reaction is finished. The reacted liquid was collected by filtration and analyzed by gas chromatography with FID detector.
Example 2
Preparing a catalyst: 1.11g of hydrated RuCl was weighed out3The precursor is stirred and dissolved into 100mL of water, and the specific surface area is added to be 950m2·g-110.00g of activated carbon (2), stirred for 1.0h, and then mixed with 1.0 mol. L-1Adjusting pH to 10 with sodium carbonate, stirring for 2.0 hr, filtering, washing filter cake with water to neutrality, transferring to oven, drying, and adding N2Roasting at 400 deg.C for 4.0H under atmosphere, and calcining at 400 deg.C in H2Reducing in atmosphere to obtain the nanometer load type ruthenium carbon catalyst with the ruthenium weight percentage of 4.0 percent.
And (3) acrylic acid hydrogenation reaction: 0.5g of catalyst, 10g of acrylic acid and 30g of propionic acid are sequentially added into a 100mL high-pressure reaction kettle, after hydrogen replacement is carried out for 3 times, the temperature is increased to 80 ℃, the reaction pressure is kept at 6.0atm, the reaction speed is 700r/min, and the reaction lasts for 2.0 hours. And releasing the pressure after the reaction is finished. The reacted liquid was collected by filtration and analyzed by gas chromatography with FID detector.
Example 3
Preparing a catalyst: 0.54g of hydrated RuCl was weighed out3The precursor is stirred and dissolved into 100mL of water, and the specific surface area is added to be 950m2·g-110.00g of activated carbon (2), stirred for 1.0h, and then mixed with 1.0 mol. L-1Adjusting pH to 8 with sodium bicarbonate, stirring for 2.0 hr, filtering, washing filter cake with water to neutrality, transferring to oven for drying, and adding N2Calcining at 500 deg.C for 4.0H in an atmosphere, and calcining at 200 deg.C in H2Reducing in atmosphere to obtain the nanometer load type ruthenium carbon catalyst with the ruthenium weight percentage of 2.0 percent.
And (3) acrylic acid hydrogenation reaction: 1.0g of catalyst, 20g of acrylic acid and 20g of propionic acid are sequentially added into a 100mL high-pressure reaction kettle, after hydrogen replacement is carried out for 3 times, the temperature is raised to 40 ℃, the reaction pressure is kept at 7.0atm, the reaction speed is 700r/min, and the reaction lasts for 2.5 hours. And releasing the pressure after the reaction is finished. The reacted liquid was collected by filtration and analyzed by gas chromatography with FID detector.
Example 4
Preparing a catalyst: 1.40g of hydrated RuCl was weighed3The precursor is stirred and dissolved into 100mL of water, and the specific surface area is added to be 950m2·g-110.00g of activated carbon (1.0 h), and then 1.0 mol. L-1Adjusting pH to 9 with sodium hydroxide, stirring for 2.0 hr, filtering, washing filter cake with water to neutrality, transferring to oven for drying, and adding N2Roasting at 600 deg.C for 2.0H under atmosphere, and calcining at 300 deg.C in H2Reducing in atmosphere to obtain the nanometer load type ruthenium carbon catalyst with the ruthenium weight percentage of 5.0 percent.
And (3) acrylic acid hydrogenation reaction: 0.5g of catalyst, 20g of acrylic acid and 20g of propionic acid are sequentially added into a 100mL high-pressure reaction kettle, after hydrogen replacement is carried out for 3 times, the temperature is raised to 20 ℃, the reaction pressure is kept at 5.0atm, the reaction speed is 700r/min, and the reaction is carried out for 4.0 h. And releasing the pressure after the reaction is finished. The reacted liquid was collected by filtration and analyzed by gas chromatography with FID detector.
Example 5
Preparing a catalyst: 0.85g of hydrated RuCl was weighed3The precursor is stirred and dissolved into 100mL of water, and the specific surface area is added to be 950m2·g-110.00g of activated carbon (2), stirred for 1.0h, and then mixed with 1.0 mol. L-1Adjusting pH to 10 with ammonia water, stirring for 2.0 hr, filtering, washing filter cake with water to neutrality, transferring to oven, drying in N2Calcining at 500 deg.C for 3.0H in the atmosphere, and calcining at 300 deg.C in H2Reducing in atmosphere to obtain the nanometer load type ruthenium carbon catalyst with the ruthenium weight percentage of 3.0 percent.
And (3) acrylic acid hydrogenation reaction: 1.5g of catalyst, 20g of acrylic acid and 20g of propionic acid are sequentially added into a 100mL high-pressure reaction kettle, after hydrogen replacement is carried out for 3 times, the temperature is raised to 65 ℃, the reaction pressure is kept at 1.0atm, the reaction speed is 700r/min, and the reaction lasts for 6.0 hours. And releasing the pressure after the reaction is finished. The reacted liquid was collected by filtration and analyzed by gas chromatography with FID detector.
Comparative example 1
Preparing a catalyst: 0.85g of ruthenium trichloride hydrate is weighed and dissolved in 100mL of ethylene glycol by stirring, and the specific surface area is 950m2·g-110.00g of active carbon, heating to 160 ℃, stirring and refluxing for 6.0 h. Naturally cooling to room temperature, filtering, washing with anhydrous ethanol for 3 times, 50mL each time, washing with water for 6 times, 50mL each time to remove Cl-), draining, and drying in a vacuum drying oven at 80 ℃ overnight to obtain the ruthenium-carbon catalyst with the ruthenium weight percentage of 3.0%.
And (3) acrylic acid hydrogenation reaction: 1.5g of catalyst, 30g of acrylic acid and 10g of propionic acid are sequentially added into a 100mL high-pressure reaction kettle, after hydrogen replacement is carried out for 3 times, the temperature is raised to 60 ℃, the reaction pressure is kept at 6.0atm, the reaction speed is 700r/min, and the reaction is carried out for 4.0 h. And releasing the pressure after the reaction is finished. The reacted liquid was collected by filtration and analyzed by gas chromatography with FID detector.
The results of using the nano-supported ruthenium carbon catalysts prepared by the methods of examples 1 to 5 and comparative example in the reaction for preparing propionic acid by hydrogenating acrylic acid are specifically shown in table 1:
table 1 results of the reaction for preparing propionic acid by hydrogenating acrylic acid in examples 1 to 5
Examples 1 2 3 4 5 Comparative example 1
Acrylic acid conversion% 99.8 99.9 99.9 99.6 99.5 85.5
Propionic acid yield% 99.8 99.9 99.9 99.6 99.5 85.5
The reaction results of twenty times of such recycling are specifically shown in fig. 1, in which the nano-supported ruthenium-carbon catalyst prepared in example 1 is used in the reaction of preparing propionic acid by hydrogenating acrylic acid, and then the catalyst is filtered and directly subjected to the next reaction.
As can be seen from table 1, the ruthenium carbon catalyst prepared using the method of the present invention has higher activity in preparing propionic acid by hydrogenation of acrylic acid than the nano-supported ruthenium carbon catalyst prepared using the liquid phase reduction method, and no formation of polymerization product was detected. As can be seen from FIG. 1, after the catalyst is recycled for 20 times, the yield of the propionic acid is basically maintained and still can reach more than 99 percent, so that the catalyst prepared by the method has good stability.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.

Claims (10)

1. A method for preparing propionic acid by hydrogenating acrylic acid is characterized by comprising the following steps: carrying out hydrogenation reaction on a mixed reaction system containing acrylic acid, a nano-load ruthenium-carbon catalyst and a solvent for 2.0-6.0 h under the conditions that the hydrogen pressure is 1.0-7.0 atm and the temperature is 20-65 ℃ to prepare propionic acid; wherein the solvent comprises propionic acid.
2. The method of claim 1, wherein: the mass ratio of the acrylic acid to the solvent is 1: 3-3: 1;
and/or the mass ratio of the catalyst to the acrylic acid is 1-10: 100.
3. The method of claim 1, wherein: the conversion rate of acrylic acid in the hydrogenation reaction is more than 99 percent;
and/or the yield of propionic acid in the hydrogenation reaction is more than 99%.
4. The method of claim 1, wherein: the content of ruthenium in the nano supported ruthenium-carbon catalyst is 2.0-5.0 wt%.
5. The method of claim 1, wherein the preparation method of the nano-supported ruthenium carbon catalyst comprises: and (2) putting the activated carbon into a ruthenium salt precursor solution for dipping treatment, then adding an alkaline precipitator for precipitation treatment, and then filtering, drying, roasting and reducing to obtain the nano supported ruthenium-carbon catalyst.
6. The method of claim 5, wherein the precipitation treatment comprises: adding an alkaline precipitator into the mixed solution formed by the activated carbon and the ruthenium salt precursor solution, and adjusting the pH value to 8-10; preferably, the alkaline precipitant comprises one or more of ammonia water, sodium hydroxide, sodium carbonate and sodium bicarbonate;
and/or, the roasting treatment comprises: roasting the product obtained by drying treatment at 400-600 ℃ for 2.0-4.0 h in a protective atmosphere;
and/or the reduction treatment comprises the following steps: at H2Reducing the product obtained by roasting treatment at 200-400 ℃ for 2.0-5.0 h under the atmosphere;
and/or the ruthenium salt in the aqueous ruthenium salt solution comprises RuCl hydrate3One or the combination of more than two of ruthenium acetate, ruthenium acetylacetonate, ammonium hexachlororuthenate and ammonium pentachlororutarate hydrate.
7. A preparation method of a nano-load ruthenium-carbon catalyst is characterized by comprising the following steps: and (2) putting the activated carbon into a ruthenium salt precursor solution for dipping treatment, then adding an alkaline precipitator for precipitation treatment, and then filtering, drying, roasting and reducing the precipitate to obtain the nano supported ruthenium-carbon catalyst.
8. The method of claim 7, wherein the precipitation treatment comprises: adding an alkaline precipitator into the mixed solution formed by the activated carbon and the ruthenium salt precursor solution, and adjusting the pH value to 8-10;
the roasting treatment comprises the following steps: roasting the product obtained by drying treatment at 400-600 ℃ for 2.0-4.0 h in a protective atmosphere;
and/or the reduction treatment comprises the following steps: at H2And reducing the product obtained by roasting treatment at 200-400 ℃ for 2.0-5.0 h under the atmosphere.
9. The method of claim 7, wherein: the alkaline precipitator comprises any one or the combination of more than two of ammonia water, sodium hydroxide, sodium carbonate and sodium bicarbonate;
and/or the ruthenium salt in the ruthenium salt precursor solution comprises hydrated RuCl3One or the combination of more than two of ruthenium acetate, ruthenium acetylacetonate, ammonium hexachlororuthenate and ammonium pentachlororuthenate hydrate.
10. The nano-supported ruthenium carbon catalyst prepared by the method of any one of claims 7 to 9, wherein the ruthenium content in the nano-supported ruthenium carbon catalyst is 2.0 to 5.0 wt%.
CN202210440988.8A 2022-04-25 2022-04-25 Method for preparing propionic acid by acrylic acid hydrogenation Active CN114644552B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210440988.8A CN114644552B (en) 2022-04-25 2022-04-25 Method for preparing propionic acid by acrylic acid hydrogenation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210440988.8A CN114644552B (en) 2022-04-25 2022-04-25 Method for preparing propionic acid by acrylic acid hydrogenation

Publications (2)

Publication Number Publication Date
CN114644552A true CN114644552A (en) 2022-06-21
CN114644552B CN114644552B (en) 2023-04-14

Family

ID=81997074

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210440988.8A Active CN114644552B (en) 2022-04-25 2022-04-25 Method for preparing propionic acid by acrylic acid hydrogenation

Country Status (1)

Country Link
CN (1) CN114644552B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1416286A (en) * 1973-03-03 1975-12-03 Hoechst Ag Production of propionic acid
CA1192220A (en) * 1982-11-17 1985-08-20 John F. Knifton Process for preparing acetic and propionic acids and their esters
JP2001157840A (en) * 1999-09-21 2001-06-12 Asahi Kasei Corp Catalyst for hydrogenating carboxylic acid
US20090076303A1 (en) * 2007-09-19 2009-03-19 Scott Han Process for selective reduction of propionic acid from (meth)acrylic acid product streams
CN105384623A (en) * 2015-10-16 2016-03-09 上海交通大学 Preparation method for chiral alpha-substituted propionic acid compounds
CN105498761A (en) * 2015-12-23 2016-04-20 中国科学院兰州化学物理研究所 Preparation method of nano Ru/C supported catalyst
CN112916022A (en) * 2021-01-21 2021-06-08 西南化工研究设计院有限公司 Selective hydrogenation catalyst, preparation method and application thereof
CN113372218A (en) * 2021-07-16 2021-09-10 中国科学院兰州化学物理研究所 Preparation method of methyl methacrylate
CN114230453A (en) * 2021-12-28 2022-03-25 上海玖宜聚合物技术有限公司 Production method for synthesizing propionic acid by one-step hydrogenation

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1416286A (en) * 1973-03-03 1975-12-03 Hoechst Ag Production of propionic acid
CA1192220A (en) * 1982-11-17 1985-08-20 John F. Knifton Process for preparing acetic and propionic acids and their esters
JP2001157840A (en) * 1999-09-21 2001-06-12 Asahi Kasei Corp Catalyst for hydrogenating carboxylic acid
US20090076303A1 (en) * 2007-09-19 2009-03-19 Scott Han Process for selective reduction of propionic acid from (meth)acrylic acid product streams
CN105384623A (en) * 2015-10-16 2016-03-09 上海交通大学 Preparation method for chiral alpha-substituted propionic acid compounds
CN105498761A (en) * 2015-12-23 2016-04-20 中国科学院兰州化学物理研究所 Preparation method of nano Ru/C supported catalyst
CN112916022A (en) * 2021-01-21 2021-06-08 西南化工研究设计院有限公司 Selective hydrogenation catalyst, preparation method and application thereof
CN113372218A (en) * 2021-07-16 2021-09-10 中国科学院兰州化学物理研究所 Preparation method of methyl methacrylate
CN114230453A (en) * 2021-12-28 2022-03-25 上海玖宜聚合物技术有限公司 Production method for synthesizing propionic acid by one-step hydrogenation

Also Published As

Publication number Publication date
CN114644552B (en) 2023-04-14

Similar Documents

Publication Publication Date Title
CN101347737B (en) Selective hydrogenation catalyst of aromatic aldehydes for refinement of terephthalic acid
CN111153768B (en) Synthesis method of isohexide
CN108380208B (en) Pd-Mg/C catalyst for preparing 2, 3-dichloropyridine by catalytic hydrogenation of 2,3, 6-trichloropyridine and preparation method thereof
CN107930647B (en) Catalyst, preparation method thereof and preparation method of 2-ethylhexanal
CN110743544A (en) Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof
CN112371173B (en) Platinum-carbon catalyst applied to hydrogenation of m-nitrobenzenesulfonic acid and preparation method thereof
CN114085136A (en) Method for preparing cyclopentanone by catalyzing furfural
CN114644552B (en) Method for preparing propionic acid by acrylic acid hydrogenation
CN104772141A (en) Preparation method and use of catalyst for glucose hydrogenolysis preparation of low carbon dihydric alcohol
CN113385171A (en) Metal-based catalyst protected by few-layer carbon and application thereof in ethylene oxide carbonylation
CN114522738B (en) Method for preparing 1, 3-propylene glycol by one-step hydrogenation of 3-acetoxy propionaldehyde
CN113134362B (en) Heterogeneous catalyst for preparing lactaldehyde by non-ligand hydroformylation of acetaldehyde and synthesis gas and preparation method and application thereof
CN112452325B (en) Catalyst for preparing 1, 3-butanediol by hydrogenating 3-hydroxybutyraldehyde, and preparation method and application thereof
CN115646498A (en) High-stability copper-based catalyst for ethanol dehydrogenation and preparation method thereof
CN112645900B (en) Synthesis method of accelerant DCBS
CN114308128A (en) Preparation method of M-PCN-224 catalyst and method for hydrogenation esterification reaction
CN114558602A (en) Copper-loaded porous boron nitride nanorod catalyst and preparation method and application thereof
CN116764636B (en) Low-cost metal aerogel catalyst with selective half-hydrogenation capability and preparation and application thereof
CN112121805A (en) Catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation and application thereof
CN111978353A (en) Preparation method of rhodium complex
CN112028728B (en) Method for preparing cyclohexanol and cyclohexane by catalytic hydrogenation of diphenyl ether
CN114011421B (en) Preparation method of hydrogenation catalyst for preparing succinic anhydride from maleic anhydride, and preparation method of succinic anhydride
CN114956956B (en) Method for producing neopentyl glycol
CN107486210A (en) A kind of catalyst for acetic acid one-step method ethanol and preparation method thereof
CN113336624B (en) Method for selectively hydrogenating phenol on Ni-based catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant