CN106944103B - Hydrothermal activation method for preparing acrylic acid catalyst by oxidizing propane and application - Google Patents
Hydrothermal activation method for preparing acrylic acid catalyst by oxidizing propane and application Download PDFInfo
- Publication number
- CN106944103B CN106944103B CN201710253259.0A CN201710253259A CN106944103B CN 106944103 B CN106944103 B CN 106944103B CN 201710253259 A CN201710253259 A CN 201710253259A CN 106944103 B CN106944103 B CN 106944103B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- propane
- acrylic acid
- reaction
- hydrothermal
- 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.)
- Active
Links
Classifications
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
Abstract
The invention discloses a hydrothermal activation method for preparing an acrylic acid catalyst by propane oxidation and application thereof, wherein water vapor, a small amount of propane and oxygen are merged, preheated at 170-230 ℃ in a preheating furnace, then enter a reactor to contact with a pre-loaded catalyst bed layer which takes Mo, V, Te, Nb and O elements as main active components, and are subjected to activation treatment for 2.0-10.0 hours at 320-400 ℃. In the preparation method of the catalyst provided by the invention, the dispersing agent is added to reduce the agglomeration degree among composite oxide particles, the surface activity of the catalyst is improved by adopting a pre-activation method, and performance evaluation shows that the conversion rate of propane, the selectivity of acrylic acid and the yield are obviously improved.
Description
Technical Field
The invention belongs to the field of petrochemical industry, relates to a preparation technology of a catalyst for generating acrylic acid through oxidation reaction of propane and oxygen, and particularly provides a catalyst hydrothermal activation method for improving catalytic performance.
Background
Propane is a low-chain saturated alkane, is one of the main components of natural gas, liquefied petroleum gas and coal bed gas, and is relatively rich in the earth. However, most of the natural gas resources which are exploited currently are mainly utilized as fuel, while the natural gas resources for chemical conversion into high-value-added compounds are relatively few and are not fully utilized.
Acrylic acid is unsaturated fatty acid, is an important organic chemical product, and is widely used for producing water-soluble coatings, super absorbent resins and comonomers of butyl acrylate and ethyl acrylate for adhesives.
The acrylic acid produced in industry at present is mainly prepared by two-step oxidation of propylene, and the total yield of the acrylic acid is over 80 percent. Because the cost of propylene is high and is about 2 times of the price of propane, the method for preparing acrylic acid by directly oxidizing propylene by using cheap and easily available propane instead of propylene becomes one of the research hotspots for developing and utilizing low-carbon alkane, the process route is short, the energy consumption is low, and the method not only can bring huge economic benefits, but also is more environment-friendly.
The acrylic acid industrial production goes through the technological processes of a Reppe method, an acrylonitrile hydrolysis method, a cyanoethanol method, a propylene oxidation method and the like which take acetylene and CO as raw materials, the first three methods have certain toxicity and higher cost and are gradually replaced by a propylene direct oxidation method, and the propylene gas phase two-step oxidation method is the only way for producing acrylic acid at present. However, the main sources of propylene are the by-product of ethylene production by petroleum cracking and the by-product of catalytic cracking gasoline, and the supply is increasingly tense due to multiple purposes, and the price is far higher than that of propane. If cheap and easily available propane is used as a raw material to replace propylene, the cost of the raw material is greatly reduced if acrylic acid is generated in one step by catalytic oxidation of the propane. Therefore, the selective oxidation of propane to produce acrylic acid would produce great economic benefits.
Some basic researches report on the preparation of acrylic acid by one-step oxidation of propane, and the adopted catalyst mainly comprises three systems of vanadium phosphorus oxide (V-P-O), heteropoly acid and salt thereof (HPCs), composite metal oxide (MMO) and the like. When a V-P-O catalyst system for preparing maleic anhydride by butane oxidation for industrial production is used for preparing acrylic acid by selective oxidation of propane, the effect is not ideal, and the once-through yield is not more than 19%; although heteropoly acid and its salt have the advantage of controllable structure, because it does not roast in the preparation process, the catalyst structure is not stable enough, it is easy to be deactivated by structure collapse under the operation temperature higher than 400 deg.C, and its effect on preparing acrylic acid by propane one-step oxidation is not ideal, the highest yield of acrylic acid is only 13%. Since 1991, mixed metal oxide catalyst systems represented by Mo-V based catalysts have been extensively studied, and have also achieved good catalytic effects in the reaction of selective oxidation of propane to acrylic acid. However, in the reported patents or documents, the selectivity and the single-pass yield of acrylic acid are low, which limits the application of the composite metal oxide in industrial production. In order to improve the selectivity and once-through yield of acrylic acid, no report has been found on a method for improving the activity of a catalyst obtained by performing hydrothermal pretreatment on a catalyst for producing acrylic acid by oxidizing propane.
Disclosure of Invention
The invention aims to solve the problems of low activity and poor product selectivity of acrylic acid generated by the reaction of propane and oxygen, and the catalyst for preparing acrylic acid by oxidizing propane is subjected to hydrothermal activation before the reaction, so that the selectivity of acrylic acid can be obviously improved on the premise of ensuring the good activity of the catalyst.
The invention provides a hydrothermal activation method of a molybdenum vanadium tellurium niobium composite metal catalyst for a reaction of preparing acrylic acid by selective oxidation of propane, which is characterized by comprising the following steps: the steam, a small amount of propane and oxygen are merged and preheated by a preheating furnace at 170-230 ℃, and then enter a reactor to contact with a pre-installed catalyst bed layer for activation treatment. Wherein the activation temperature is 320-400 ℃, the flow rate of water vapor is 20-48 ml/h, the flow rate of propane/oxygen mixed gas (volume ratio is 0.3-0.6) is 2.0-5.0 ml/h, the operation pressure is 0.1-0.5 MPa, and the hydrothermal activation time is 2.0-10.0 h. The catalyst used for preparing acrylic acid by the propane selective oxidation method is non-supported multi-component metal oxide particles with the size of 20-40 meshes, and the general formula of the catalyst is MoxVyTezNbmOnWherein Mo, V, Te and Nb are active components, and the atomic molar ratios of the four metal elements and oxygen thereof are respectively x: y: z: m: n is 1: (0.1-0.5): (0.1-0.5): (0.1-0.8): (3.0-6.5).
The preparation method of the composite metal oxide catalyst is characterized by comprising the following steps: mixing ammonium paramolybdate, ammonium metavanadate, telluric acid and deionized water in a water bath at 50-80 ℃ for rotary mixing, adding a dispersing agent for full dissolution, then adding a niobium oxalate solution for rotary mixing to obtain 250-350 g/L mixed slurry, continuously rotary mixing for 1-3 hours, cooling to room temperature, vacuumizing, rotary evaporating, roasting at 200-400 ℃ for 2-4 hours in an air atmosphere, and roasting at 550-650 ℃ for 2-4 hours in an inert atmosphere to obtain a catalyst solid.
The dispersant in the preparation process of the catalyst is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, N-dimethylformamide, polyethylene glycol-600, polyethylene glycol-1000, Tween-20, polyethylene glycol octyl phenyl ether and dodecyl dimethyl tertiary amine.
The addition amount of the dispersing agent is 0.2-0.5 wt% of the solid mass of the composite oxide catalyst.
The composite oxide activated by the catalyst prepared by the method is used for the reaction of synthesizing acrylic acid by oxidizing propane.
The catalyst prepared by the invention is used for reaction in a continuous fixed bed reactor, and the molar ratio of the raw reaction gas is n (propane): n (oxygen): n (nitrogen gas): n (steam) ═ 1.0: 1.5-3.0: 0.1-2.0: 2.0-3.0, the reaction temperature is 380-450 ℃, the reaction pressure is 0.1-0.5 MPa, and the reaction space velocity is 1000-2500 ml/(g.h).
The preparation method of the catalyst of the invention introduces the surfactant as the dispersant, overcomes many defects in a liquid phase reaction method, can reduce the agglomeration phenomenon of ultrafine nano-particles formed by the composite oxide, improves the dispersion degree of active components of the catalyst and increases the activity of the catalyst.
The invention provides a simple and effective activation method for preparing an acrylic acid composite metal catalyst by selective oxidation of propane, and the catalyst after hydrothermal activation has high catalytic activity, propane conversion rate and acrylic acid one-way yield, and is simple in process and convenient to operate.
Detailed Description
The embodiments and the effects of the present invention are further illustrated by the examples and comparative examples, but the scope of the present invention is not limited to the contents listed in the examples.
Examples 1 to 15
Adding ammonium paramolybdate, ammonium metavanadate and telluric acid into a rotary flask, adding deionized water, carrying out rotary mixing in a water bath at 60 ℃ for 120min, adding a dispersing agent, fully dissolving, and then cooling to 40 ℃ to obtain a dark red Mo-V-Te solution; adding niobium oxalate solution into the mixture, carrying out rotary mixing to obtain 250-350 g/L mixed slurry, continuously carrying out rotary mixing for 120min, cooling to room temperature, vacuumizing, and carrying out rotary evaporation to dryness to obtain tawny MoxVyTezNbmOnCalcining the catalyst precursor at 300 ℃ for 120min in air atmosphere, naturally cooling to room temperature, and then carrying out N2Roasting for 2 hours at 600 ℃ in the atmosphere to obtain black catalyst solid. The addition amount of the dispersing agent is 0.2-0.5 wt% of the solid mass of the composite oxide catalyst. Fully grinding the catalyst solid, tabletting and forming, sieving into 20-40 mesh catalyst particles, placing the catalyst particles in a reactor for hydrothermal activation treatment, wherein the names of the prepared catalysts, the molar ratios of Mo, V, Te, Nb and O, the proportion and the types of the added dispersing agents are shown in table 1, and the hydrothermal activation conditions are shown in table 2.
TABLE 1
TABLE 2
Comparative example 1
The procedure of example 1 was followed, except that the composite oxide catalyst initially prepared was not subjected to hydrothermal activation treatment, and the resulting catalyst was designated as VS-1.
Comparative example 2
The procedure of example 2 was followed, except that the composite oxide catalyst initially prepared was not subjected to hydrothermal activation, and the resulting catalyst was designated as VS-2.
Examples 16 to 29
Effect of different hydrothermal activation temperatures on catalytic reaction Performance
The hydrothermally activated composite oxide catalyst (20-40 mesh) particles obtained in examples 1-10 and comparative examples 1-2 were loaded into a reaction tube for propane oxidation to prepare acrylic acid, the molar ratio composition of the reaction raw materials, the reaction temperature, the reaction pressure and the reaction space velocity are shown in table 3, the product after the reaction was subjected to online agilent GC7820A chromatographic analysis, the gas product was subjected to TCD detection, the liquid product was subjected to FID detection, and the calculated propane conversion rate, acrylic acid selectivity and yield are shown in table 3.
TABLE 3
From the evaluation results of the catalysts prepared by the invention after hydrothermal activation obtained in table 3, it can be found that the catalyst provided by the invention catalyzes the reaction by propane, the conversion rate of propane is greater than 55%, the selectivity of the target product, namely acrylic acid is greater than 79%, and the yield of acrylic acid is greater than 45%, which is obviously improved compared with the catalytic performance of the comparative catalyst which is not subjected to hydrothermal activation treatment.
The embodiments are only for illustrating the technical concept and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (5)
1. A hydrothermal activation method of a catalyst for preparing acrylic acid by propane oxidation is characterized in that: the steam, a small amount of propane and oxygen are merged, preheated by a preheating furnace at 170-230 ℃, and then enter a reactor to contact with a pre-installed catalyst bed layer for activation treatment; wherein the activation temperature is 320-390 ℃, the flow rate of water vapor is 20-48 ml/h, the flow rate of a propane/oxygen mixed gas with a volume ratio of 0.3-0.6 is 2.0-5.0 ml/h, the operation pressure is 0.1-0.5 MPa, and the hydrothermal activation time is 2.0-10.0 h;
the catalyst is 20-40 mesh non-supported multi-component metal oxide particles, and the general formula of the catalyst is MoxVyTezNbmOnWherein Mo, V, Te and Nb are active components, and the atomic molar ratios of the four metal elements and oxygen thereof are respectively x: y: z: m: n is 1: 0.1-0.5: 0.1-0.5: 0.1-0.8: 3.0 to 6.5;
the preparation method of the catalyst comprises the steps of mixing ammonium paramolybdate, ammonium metavanadate, telluric acid and deionized water in a water bath at 50-80 ℃ for rotary mixing, adding a dispersing agent for full dissolution, adding a niobium oxalate solution for rotary mixing to obtain 250-350 g/L mixed slurry, continuously rotary mixing for 1-3 hours, cooling to room temperature, vacuumizing, rotary evaporating to dryness, roasting at 200-400 ℃ for 2-4 hours in an air atmosphere, and roasting at 550-650 ℃ for 2-4 hours in an inert atmosphere to obtain a catalyst solid.
2. The hydrothermal activation method of claim 1, wherein: the dispersing agent is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, N-dimethylformamide, polyethylene glycol-600, polyethylene glycol-1000, Tween-20, polyethylene glycol octyl phenyl ether and dodecyl dimethyl tertiary amine.
3. The hydrothermal activation method of claim 1, wherein: the addition amount of the dispersing agent is 0.2-0.5 wt% of the solid mass of the composite oxide catalyst.
4. The use of the catalyst activated by the hydrothermal activation method according to claim 1 for catalyzing the reaction of synthesizing acrylic acid by oxidizing propane.
5. Use according to claim 4, characterized in that: reacting in a continuous fixed bed reactor, wherein the molar ratio of reaction raw material gas is n propane: n oxygen: n nitrogen gas: n-steam 1.0: 1.5-3.0: 0.1-2.0: 2.0-3.0, the reaction temperature is 380-450 ℃, the reaction pressure is 0.1-0.5 MPa, and the reaction space velocity is 1000-2500 ml/(g.h).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710253259.0A CN106944103B (en) | 2017-04-18 | 2017-04-18 | Hydrothermal activation method for preparing acrylic acid catalyst by oxidizing propane and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710253259.0A CN106944103B (en) | 2017-04-18 | 2017-04-18 | Hydrothermal activation method for preparing acrylic acid catalyst by oxidizing propane and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106944103A CN106944103A (en) | 2017-07-14 |
| CN106944103B true CN106944103B (en) | 2020-04-24 |
Family
ID=59476317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710253259.0A Active CN106944103B (en) | 2017-04-18 | 2017-04-18 | Hydrothermal activation method for preparing acrylic acid catalyst by oxidizing propane and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106944103B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114534714B (en) * | 2020-11-26 | 2023-08-22 | 中国科学院大连化学物理研究所 | Molybdenum vanadium antimony oxide catalyst for coproducing propylene and acrylic acid by propane oxidation and preparation method thereof |
| CN115739130B (en) * | 2022-12-05 | 2023-09-08 | 山东玉皇化工有限公司 | Forming method of MoVTeNb catalyst, formed catalyst and industrial application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1795987A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院大连化学物理研究所 | Catalyst of Mo, V, Te, Nb in use for reaction of producing crylic acid by selective oxidation of propane |
| CN105363431A (en) * | 2014-08-29 | 2016-03-02 | 中国科学院大连化学物理研究所 | High-active-crystal-exposure-ratio Mo-V-Te-Nb-O catalyst and preparation and application thereof |
-
2017
- 2017-04-18 CN CN201710253259.0A patent/CN106944103B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1795987A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院大连化学物理研究所 | Catalyst of Mo, V, Te, Nb in use for reaction of producing crylic acid by selective oxidation of propane |
| CN105363431A (en) * | 2014-08-29 | 2016-03-02 | 中国科学院大连化学物理研究所 | High-active-crystal-exposure-ratio Mo-V-Te-Nb-O catalyst and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "TeO2为碲源制备 MoVTeNbO催化剂的研究";李安莲;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120415(第04期);第2.2.2节、2.2.3节、2.2.4节、3.4.2节、3.2.5节、3.6节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106944103A (en) | 2017-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100415370C (en) | Catalyst for partial oxidation and preparation method thereof | |
| CN101757930A (en) | The complex oxide catalyst of bi/mo/fe for the oxidative dehydrogenation of 1-butene to 1,3-butadiene and process thereof | |
| CN109939693B (en) | CoMn2O4Bimetallic oxide catalyst, preparation method and application | |
| CN105080596A (en) | Isobutane oxidation dehydrogenation catalyst and preparation method and application method thereof | |
| CN106944103B (en) | Hydrothermal activation method for preparing acrylic acid catalyst by oxidizing propane and application | |
| CN101439292A (en) | Solid catalyst for producing isobutene from oxidative dehydrogenation of isobutane and preparation method thereof | |
| CN102631914A (en) | Vanadium pentoxide catalyst taking mesoporous carbon as carrier, and preparation method thereof | |
| CN108409692A (en) | A kind of method that the carbon material supported ruthenium catalyst catalysis levulic acid Hydrogenation of sulfur doping takes gamma-valerolactone | |
| CN104837799A (en) | Catalytic conversion of bio-mass derivable aliphatic alcohols to valuable alkenes or oxygenates | |
| CN101993362B (en) | Method for producing oxalic ester through coupling CO | |
| CN100333834C (en) | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof | |
| CN108503529B (en) | Method for preparing acrylic acid from propane | |
| CN104437456A (en) | Catalyst for preparing isobutene by isobutane dehydrogenation and preparation method and application of catalyst | |
| Ai | A Study of the Catalytic Partial Oxidation of Hydrocarbons. VI. The Effect of Molybdenum Addition to the Vanadium Oxide Catalyst on the Oxidation of Butene to Maleic Anhydride | |
| CN103285890A (en) | Cr-doped catalyst for preparing acrylic acid by catalytically oxidizing propane and preparation method of Cr-doped catalyst | |
| CN104549293A (en) | Method for preparing olefin compound based on catalyst obtained by compounding carbon tubes and transition metals | |
| CN113842934B (en) | Oxidation catalyst and preparation method and application thereof | |
| CN113877613A (en) | CO (carbon monoxide)2Hydrogenated biomass charcoal-based transition metal catalyst and preparation method thereof | |
| CN104284721A (en) | Oxidation catalyst for preparing butadiene and method for preparing same | |
| CN105013481B (en) | A kind of C SiC itself and preparation method and application of load type platinum based catalyst again | |
| EP1027929A1 (en) | Catalyst for the production of acrylonitrile | |
| CN105521803B (en) | Multiple active components catalyst for preparing propene by oxidative dehydrogenation of propane and the preparation method and application thereof | |
| CN109621996B (en) | Catalyst for directly preparing aromatic hydrocarbon by carbon dioxide hydrogenation and preparation method and application thereof | |
| CN117339607A (en) | Catalyst for preparing acrylic acid by catalyzing propane and application thereof | |
| CN115090308B (en) | Metal-doped sodium super-ionic catalyst and preparation method and application thereof |
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 |