CN107935836B - CO selective oxidation removal method, method and system for preparing acrylic acid by one-step oxidation of propane - Google Patents

CO selective oxidation removal method, method and system for preparing acrylic acid by one-step oxidation of propane Download PDF

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CN107935836B
CN107935836B CN201610894192.4A CN201610894192A CN107935836B CN 107935836 B CN107935836 B CN 107935836B CN 201610894192 A CN201610894192 A CN 201610894192A CN 107935836 B CN107935836 B CN 107935836B
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propane
tail gas
catalyst
component
acrylic acid
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CN107935836A (en
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杨维慎
李军
楚文玲
张浩文
王红心
田金光
杨开研
李铖
刘长庆
李鸿雄
张�荣
刘进平
陈景润
刘俊霞
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Shaanxi Yanchang Petroleum Group Refining & Petrochemical Co
Dalian Institute of Chemical Physics of CAS
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Shaanxi Yanchang Petroleum Group Refining & Petrochemical Co
Dalian Institute of Chemical Physics of CAS
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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

Abstract

The method for removing CO by selective oxidation and the method and system for preparing acrylic acid by one-step oxidation of propane are adopted, and CuO and CeO are selected as the removing method2、Co3O4、FeOx、NiO、MnOx、VOx、ZnO、La2O3And MoOxAt least two of the composite oxides are used as catalyst, and the catalyst contains CO and O2And at least one hydrocarbon mixed gas to remove CO. The method for preparing the acrylic acid by the one-step oxidation of the propane comprises a propane selective oxidation reaction process, a crude acrylic acid separation process and a tail gas treatment process, wherein the tail gas treatment process comprises the step of circularly using the tail gas in the propane selective oxidation process after dehydrating and selectively removing CO. The system includes a tail gas treatment assembly that connects a product separation assembly with a feedstock premixing assembly. The method selectively removes CO with larger explosion risk in the tail gas, retains propane and propylene in the tail gas, effectively treats and recycles the tail gas with high CO content generated in the process, and is favorable for realizing industrialization of preparing acrylic acid by one-step oxidation of propane.

Description

CO selective oxidation removal method, method and system for preparing acrylic acid by one-step oxidation of propane
Technical Field
The invention relates to a method for selectively removing CO, a system and a process for continuously producing high-added-value product acrylic acid by one-step oxidation of propane, in particular to a method and a system for treating and recycling tail gas, and belongs to the technical field of petrochemical industry.
Background
Acrylic acid is an important petrochemical, light industrial, and pharmaceutical raw material, and can be used for producing adsorbents, purifiers, fibers, pulp additives, adhesives, plastics, paints, and the like, and their new uses are being expanded.
The method widely used in industry at present is a two-step catalyst using propylene as raw materialOxidation by oxidation, for example EP-A575897. The price of propylene is higher than that of propane in terms of raw material cost, and as the use of propylene expands, the price of propylene rises, and this difference in price increases further. If the industrialization of the process for preparing the acrylic acid by taking the propane as the raw material is realized by replacing the propylene, the cost of the raw material is greatly reduced. Therefore, the direct oxidation of propane instead of propylene, which is cheap and easily available, to prepare acrylic acid, becomes one of the research hotspots for the development and utilization of light alkanes. Meanwhile, propane is rich in source and is the main component in oil field gas, natural gas and refinery gas. In China, the completion of the west-east gas transportation project will lead C originally used as liquefied gas3-C4The alkanes are in large excess, and therefore, how to utilize these inexpensive alkanes has significant economic and practical significance.
Since the selective oxidation of propane to acrylic acid is a strongly exothermic reaction, in order to effectively control the amount of heat released during the reaction, the propane conversion rate is generally controlled in industrial applications under conditions that ensure high product selectivity. In order to save cost, unreacted raw material propane in the reaction tail gas needs to be recycled. One problem is that potential safety hazards (the explosion limit of CO is 12-74%) exist in the gradual accumulation of CO components in the recycling process of reaction tail gas, therefore, the CO components in the reaction tail gas for preparing acrylic acid by propane one-step oxidation must be selectively oxidized and removed before the reaction tail gas is recycled, and hydrocarbon components such as ethane, ethylene, propane and propylene in the reaction tail gas must be completely reserved for recycling. We have now successfully developed a high activity, high selectivity mixed metal oxide catalyst for the production of acrylic acid by the one-step oxidation of propane. With the development of a novel and efficient catalyst for one-step oxidation of propane, it is necessary to develop a catalyst for selective oxidation removal of CO in the circulating tail gas of one-step oxidation reaction of propane to ensure the continuity of the process flow of producing acrylic acid from propane, so as to realize industrialization of preparing acrylic acid by selective oxidation of propane.
Disclosure of Invention
In order to solve the problem of removing CO from the circulating tail gas in the reaction for preparing acrylic acid by one-step oxidation of propane in the prior art, the invention provides a method for selectively removing CO by oxidation, which adopts non-noble metal composite oxide as a catalyst to achieve the aim of removing CO and further provides a method and a system for preparing acrylic acid by one-step oxidation of propane.
The technical purpose of the first aspect of the invention is to provide a method for selective oxidative removal of CO, which adopts a material selected from CuO and CeO2、Co3O4、FeOx、NiO、MnOx、VOx、ZnO、La2O3And MoOxA composite oxide of at least two of them is used as a catalyst, and the catalyst contains CO and O2And at least one hydrocarbon mixed gas to remove CO.
The technical object of the second aspect of the present invention is to provide a method for preparing acrylic acid by one-step oxidation of propane, comprising a propane selective oxidation reaction step, a crude acrylic acid separation step and a tail gas treatment step, wherein the tail gas treatment step comprises: after the tail gas is dehydrated and the carbon monoxide is selectively removed, the tail gas is circularly used for the propane selective oxidation process; the method for selectively removing carbon monoxide from the tail gas comprises the following steps: to be selected from CuO and CeO2、Co3O4、FeOx、NiO、MnOx、VOx、ZnO、La2O3And MoOxThe composite oxide of at least two components in the catalyst is used as a catalyst and is in contact reaction with tail gas to remove CO.
The technical purpose of the third aspect of the invention is to provide a system for preparing acrylic acid by propane one-step oxidation, which comprises a raw material premixing component, a propane selective oxidation reaction component, a product separation component and a tail gas treatment component, wherein the tail gas treatment component is connected with the product separation component and the raw material premixing component and comprises a tail gas dehydration tank, a CO removal reactor and a compressor which are sequentially arranged.
According to the method for selectively oxidizing and removing CO, the method and the system for preparing the acrylic acid by the one-step oxidation of the propane, which are provided by the invention, through the system and the process flow design, the CO with a larger explosion risk in the tail gas is selectively removed, and the unreacted propane and the gas-phase product propylene are reserved and recycled to the production process, the tail gas with high carbon monoxide content generated in the process of preparing the acrylic acid by the one-step oxidation of the propane is effectively treated and recycled, and the industrial production of preparing the acrylic acid by the selective oxidation of the propane is favorably realized.
Drawings
FIG. 1 is a schematic diagram of a system for producing acrylic acid by one-step oxidation of propane according to the present invention, wherein:
r-101, a propane selective oxidation reactor; r-102, a CO removal reactor; m-101, a premixer; m-102, a feed mixer; e-102, propane superheater; e-103, a cooling section; v-104, a quencher; c-110, an absorption tower; v-103, a tail gas dehydration tank; k-101, a compressor;
FIG. 2 shows the performance of catalyst M1 in a system for preparing acrylic acid by one-step oxidation of propane, which runs for 200 h;
FIG. 3 is a graph showing the trend of the performance of catalyst M1 loaded in a system for preparing acrylic acid by one-step oxidation of propane at different temperatures;
FIG. 4 is a graph showing the trend of the performance of a system for preparing acrylic acid by one-step oxidation of propane, in which (a) is CO in the tail gas treatment process, when a catalyst M2 is filled in the system2And O2The concentration change curve of (a), (b) is the change curve of the conversion rate and the selectivity of CO at different temperatures;
FIG. 5 is a graph showing the trend of the performance of a system for preparing acrylic acid by one-step oxidation of propane, in which (a) is CO in the tail gas treatment process, when a catalyst M3 is filled in the system2And O2The concentration change curve of (a) and (b) the change curves of the conversion rate and the selectivity of CO at different temperatures.
Detailed Description
The following detailed description of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
One of the technical objects of the present invention is to provide a method for selective oxidation removal of CO, which uses a catalyst selected from CuO and CeO2、Co3O4、FeOx、NiO、MnOx、VOx、ZnO、La2O3And MoOxA composite oxide of at least two of them is used as a catalyst, and the catalyst contains CO and O2And at least one hydrocarbon mixed gas to remove CO.
In the method of the present invention, the specific conditions of the selective oxidation CO removal reaction are as follows: the reaction temperature is 50-200 ℃, preferably 120-200 ℃, more preferably 150-180 ℃, the pressure is 0.1-0.5 MPa, and the reaction space velocity is 5000-35000 L.Kg-1·h-1The reaction is carried out in a fixed bed reactor.
In one specific embodiment of the above method of the present invention, the catalyst is selected from the group consisting of CuO and CeO2And Co3O4A composite oxide composed of two or three of (1); further, CuO-CeO may be exemplified but not limited thereto2-Co3O4、CuO-Co3O4、CuO-CeO2And the proportions of the components in the catalyst are as follows by mole: cu: ce: co 1: 0.5-10: 0.5-10, Cu: co 1: 0.5-10, Cu: ce ═ 1: 0.5 to 10.
In the above-described process of the present invention, it will be understood by those skilled in the art that the catalyst may further comprise conventional additives to prepare a shaped catalyst according to the following ratio of the composite oxide: diluent 100: 0.1-200 of alpha-Al2O3、γ-Al2O3Or SiO2Etc. as diluents, or according to the complex oxide: lubricant 100: graphite and/or talcum powder is added in a proportion of 0.1-5 to serve as a lubricant, and the mixture is pressed into cylindrical, flaky, annular cylindrical, spherical and other molded catalysts.
In the above-mentioned method of the present invention, the catalyst is prepared by the following method: according to the appointed proportion, soluble salt of metal element or lanthanide in the composite oxide is dissolved in deionized water to form precursor salt mixed solution, alkaline solution is added to carry out coprecipitation reaction to obtain catalyst precursor, and the catalyst is obtained by roasting.
In the above method of the present invention, the soluble salt of the metal element or lanthanide in the catalyst preparation method is selected from one or more of chloride, nitrate, carbonate or sulfate; the alkaline solution is NaOH, KOH or ammonia water; the specific roasting conditions are as follows: roasting for 2-10 hours at 400-1000 ℃ in air atmosphere, wherein the heating rate is 0.5-10 ℃/min.
In the above-mentioned process of the present invention, the catalyst contains CO and O2And the at least one hydrocarbon further comprises any one or more of the following gases: steam, N2Ethane, ethylene, propane, CO2And propylene.
In the above-mentioned method of the present invention, the mentioned compound contains CO and O2And the mixed gas of at least one hydrocarbon is the circulating tail gas of the acrylic acid prepared by one-step oxidation of propane, and the circulating tail gas comprises the following components in percentage by volume: h2O3.5～10.0％；N245.0～65.0％；O25.0-10.0%; 0.01 to 0.05 percent of ethane; 0.01-0.05% of ethylene; 10.0-15.0% of propane and 2.0-10.0% of CO; CO222.0-10.0%; 1.5 to 5.0 percent of propylene.
The method of the invention is adopted to carry out selective oxidation removal of CO, the mole (volume) percentage content of carbon monoxide after treatment is not more than 0.05%, and other alkane (ethane, propane) and alkene (ethylene, propylene) components are not changed.
The invention also provides a method for preparing acrylic acid by one-step oxidation of propane, which comprises a propane selective oxidation reaction process, a crude acrylic acid separation process and a tail gas treatment process, wherein the tail gas treatment process comprises the following steps: after the tail gas is dehydrated and the carbon monoxide is selectively removed, the tail gas is circularly used for the propane selective oxidation process; wherein, the method for removing carbon monoxide from tail gas adopts the method for selectively oxidizing and removing CO.
In the method for preparing acrylic acid by one-step oxidation of propane, the volume percentage of CO in tail gas is not more than 0.05 percent after the tail gas is treated.
In another specific embodiment of the above method for producing acrylic acid by one-step oxidation of propane, the selective oxidation reaction of propane is carried out in the presence of a mixed metal oxide catalyst containing any 4 or more elements of Mo, V, Sb, Te, Nb, Al, W, K, Co. More specifically, the mixed metal oxide catalyst may be exemplified by, but not limited to, a mixed metal oxide catalyst of Mo-V-Te-Nb-O, Mo-V-Sb-Nb-O, Mo-K-V-Te-Nb-O or Mo-V-Al-W-Nb-O. The mixed metal oxide catalyst is in the shape of a ring column, a sphere or a cylinder. Preference is given to catalysts in the form of a ring column. Examples of the catalyst include, but are not limited to, a ring-column catalyst widely used in the art, having an inner diameter of 1.5 to 3.0mm, an outer diameter of 4.0 to 6.0mm, and a height of 3.0 to 5.0 mm.
In the method for preparing acrylic acid by propane one-step oxidation, the raw material gas in the propane selective oxidation reaction step is composed of water vapor and O from a battery limit zone2、N2The propane and the tail gas for circulation obtained after the tail gas treatment process comprise the following components in percentage by mass: h2O 10.0～28.0％；N240.0～50.0％；O210.0-18.0%; 10.0-15.0% of propane; CO 0-0.01%; CO222.0-8.0% and 1.5-5.0% of propylene.
In the above method for preparing acrylic acid by propane one-step oxidation, the selective oxidation reaction of propane preferably adopts a tubular fixed bed reactor, and the reaction control conditions include: the operation temperature is 300-500 ℃, the operation pressure is 0.1-0.5 MPa, and the reaction space velocity is 2000-5000 L.Kg-1·h-1. Those skilled in the art can select the catalyst and the raw material ratio according to the specification.
The other purpose of the invention is to provide a system for preparing acrylic acid by one-step oxidation of propane, which comprises a raw material premixing component, a propane selective oxidation reaction component, a product separation component and a tail gas treatment component, wherein the tail gas treatment component is connected with the product separation component and the raw material premixing component and comprises a tail gas dehydration tank V-103, a CO removal reactor R-102 and a compressor K-101 which are sequentially arranged, the CO removal reactor R-102 is filled with a catalyst, and the catalyst is selected from CuO and CeO2、Co3O4、FeOx、NiO、MnOx、VOx、ZnO、La2O3And MoOxA composite oxide of at least two of the above.
In one specific embodiment of the system of the present invention, the catalyst filled in the CO reactor R-102 is selected from CuO and CeO2And Co3O4A composite oxide composed of two or three of (1); further, CuO-CeO may be exemplified but not limited thereto2-Co3O4、CuO-Co3O4、CuO-CeO2And the proportions of the components in the catalyst are as follows by mole: cu: ce: co 1: 0.5-10: 0.5-10, Cu: co 1: 0.5-10, Cu: ce ═ 1: 0.5 to 10.
In the system of the present invention described above, it will be understood by those skilled in the art that the catalyst also includes additives commonly used in the art to prepare a shaped catalyst according to the following ratio of composite oxide: diluent 100: 0.1-200 of alpha-Al2O3、γ-Al2O3Or SiO2Etc. as diluents, or according to the complex oxide: lubricant 100: graphite and/or talcum powder is added in a proportion of 0.1-5 to serve as a lubricant, and the mixture is pressed into cylindrical, flaky, annular cylindrical, spherical and other molded catalysts.
In the system of the invention, the catalyst is prepared by the following method: according to the appointed proportion, soluble salt of metal element or lanthanide in the composite oxide is dissolved in deionized water to form precursor salt mixed solution, alkaline solution is added to carry out coprecipitation reaction to obtain catalyst precursor, and the catalyst is obtained by roasting.
In the above system of the present invention, the soluble salt of the metal element or lanthanide in the catalyst preparation method is selected from one or more of chloride, nitrate, carbonate or sulfate; the alkaline solution is NaOH, KOH or ammonia water; the specific roasting conditions are as follows: roasting for 2-10 hours at 400-1000 ℃ in air atmosphere, wherein the heating rate is 0.5-10 ℃/min.
In a more specific embodiment, the above-mentioned system for preparing acrylic acid by one-step oxidation of propane according to the present invention comprises:
a raw material premixing component comprising a feed mixer M-102 for receiving and mixing propane and O from a battery compartment2、N2The mixed raw material gas is conveyed to the propane selective oxidation reaction component;
the propane selective oxidation reaction component is used for receiving mixed feed gas from the feed mixer M-102 and catalyzing propane selective oxidation reaction to be carried out, and comprises a propane selective oxidation reactor R-101 with a cooling section E-103;
the product separation component is used for receiving the reaction product from the propane selective oxidation reaction component, separating crude acrylic acid and outputting tail gas to the tail gas treatment component, and comprises a quencher V-104 and an absorption tower C-110 which are connected in sequence;
the tail gas treatment component is connected with the product separation component and the raw material premixing component and is used for receiving tail gas from the product separation component and inputting the cycle tail gas subjected to dehydration and carbon monoxide (CO) removal treatment to the raw material premixing component; the tail gas treatment component comprises a tail gas dehydration tank V-103, a CO removal reactor R-102 and a compressor K-101 which are sequentially connected between an absorption tower C-110 and a feed mixer M-102.
In the system of the invention, the raw material premixing component comprises a feed mixer M-102, a propane superheater E-102 and a premixer M-101 which are connected with the feed mixer M-102; the propane superheater E-102 is used for receiving and heating vaporized propane and delivering the vaporized propane to a feed mixer M-102; the premixer M-101 is used for receiving and mixing the input O of the battery limits2、N2Water vapor and recycled tail gas from the tail gas treatment component and delivered to the feed mixer M-102.
In the system of the present invention, the propane selective oxidation reactor R-101 is filled with a mixed metal oxide catalyst containing any 4 or more elements of Mo, V, Sb, Te, Nb, Al, W, K, and Co. Specifically, but not limited to, a mixed metal oxide catalyst of Mo-V-Te-Nb-O, Mo-V-Sb-Nb-O, Mo-K-V-Te-Nb-O or Mo-V-Al-W-Nb-O can be exemplified. Preferably, the mixed metal oxide catalyst is selected from a ring column, sphere or cylinder, and most preferably, the mixed metal oxide catalyst is a ring column catalyst. Examples of the catalyst include, but are not limited to, a ring-column catalyst widely used in the art, having an inner diameter of 1.5 to 3.0mm, an outer diameter of 4.0 to 6.0mm, and a height of 3.0 to 5.0 mm.
In still another aspect, the present invention also includes a method for the integrated production of acrylic acid by using the system for preparing acrylic acid by one-step oxidation of propane according to the present invention. Any of the preferred embodiments described above in relation to the system in the present invention are of course also applicable to the production carried out with the system.
The following specific examples are presented to further illustrate the invention and should not be construed as limiting the invention in any way.
Example 1
A system for preparing acrylic acid by one-step oxidation of propane is shown in attached figure 1.
The system consists of a raw material premixing component, a propane selective oxidation reaction component, a product separation component and a tail gas treatment component. Wherein:
the raw material premixing component comprises a feed mixer M-102, a propane superheater E-102 and a premixer M-101 which are connected with the feed mixer M-102; the propane superheater E-102 is used for receiving and heating vaporized propane and delivering the vaporized propane to a feed mixer M-102; the premixer M-101 is used for receiving and mixing the input O of the battery limits2、N2Water vapor and recycled tail gas from the tail gas treatment component and conveying the same to a feed mixer M-102;
the propane selective oxidation reaction component is used for receiving mixed raw material gas from a feed mixer M-102 and catalyzing propane selective oxidation reaction to be carried out, and comprises a main equipment unit of a propane selective oxidation reactor R-101 with a cooling section E-103;
the product separation component is used for receiving the reaction product from the propane selective oxidation reaction component, separating crude acrylic acid and outputting tail gas to the tail gas treatment component, and comprises a quencher V-104 and an absorption tower C-110 which are connected in sequence;
the tail gas treatment component is connected with the product separation component and the raw material premixing component and is used for receiving tail gas from the product separation component and inputting the cycle tail gas subjected to dehydration and carbon monoxide (CO) removal treatment to the raw material premixing component; the tail gas treatment component comprises a tail gas dehydration tank V-103, a CO removal reactor R-102 and a compressor K-101 which are sequentially connected between an absorption tower C-110 and a feed mixer M-102.
The process for producing acrylic acid by using the system for preparing acrylic acid by propane one-step oxidation of the embodiment can be described as follows: raw material propane is sent into a device from a boundary area, enters a propane vaporizer for vaporization, is superheated by a propane superheater E-102 and then enters a feed mixer M-102. Oxygen and nitrogen are respectively sent into a premixer M-101 from a boundary zone, are fully mixed with water vapor from the boundary zone and circulating tail gas from the top of an absorption tower C-110, then enter a feed mixer M-102, are fully mixed with superheated propane, and then are sent into a propane selective oxidation reactor R-101. The mixed gas is catalyzed by a catalyst filled in the reactor to generate a gas flow containing acrylic acid, the gas flow enters a quencher V-104 after heat exchange of a cooling section E-103 at the bottom end of R-101, and enters an absorption tower C-110 after being sprayed and quenched by acrylic acid aqueous solution from the absorption tower C-110. The components such as acrylic acid in the absorption gas are washed by desalted water from the top of the tower in the tower, and a crude acrylic acid product is obtained by separation at the bottom of the tower. And (2) discharging a part of reaction tail gas discharged from the top of the absorption tower C-110 into a waste gas incinerator for incineration, feeding a part of reaction tail gas into a tail gas dehydration tank V-103 for dehydration, sending the part of reaction tail gas into a CO removal reactor R-102, selectively removing CO in the reaction tail gas through a catalyst oxidation reaction, compressing the reaction tail gas by a circulating compressor K-101, returning to M-101, fully mixing the reaction tail gas by M-102, and then feeding into R-101 to continuously participate in a propane one-step oxidation reaction, thereby realizing the continuity of preparing acrylic acid through propane one-step oxidation.
Example 2
Preparation of selective oxidative CO removal catalyst M1: adding Cu (NO)3)2·3H2O、CoCl2·6H2O and Ce (NO)3)3·6H2O is according to Cu: co: the Ce molar ratio is 1: 5: 5 in deionized water, weighing a certain amount of NaOH, adding the NaOH into the mixed solution to ensure that the pH of the solution is 10.5, and stirring the solution to 1 toAfter 10 hours, filtering and washing with deionized water for 3-5 times. Drying, placing the mixture in a muffle furnace in air atmosphere, raising the temperature to 400-1000 ℃ at a heating rate of 0.5-10 ℃/min, and keeping the temperature for 2-10 hours; sieving to 20-30 meshes to prepare CuO-CeO2-Co3O4Three-way catalyst M1.
Example 3
Preparation of selective oxidative CO removal catalyst M2: catalyst M1 prepared in example 2 was taken together with alpha-Al2O3Mixing the components according to the mass ratio of 1:1 to prepare a molded catalyst M2.
Example 4
Preparation of selective oxidative CO removal catalyst M3: the catalyst M1 prepared in example 2 was mixed with graphite in a mass ratio of 100:5 to prepare a molded catalyst M3.
Example 5
Preparation of selective oxidative CO removal catalyst M4: adding Cu (NO)3)2·3H2O、CoCl2·6H2O is according to Cu: the molar ratio of Co is 1: dissolving 10 in deionized water, weighing a certain amount of NaOH, adding the NaOH into the mixed solution to ensure that the pH value of the solution is 10.5, stirring for 1-10 hours, filtering, and washing with deionized water for 3-5 times. And (3) drying, placing the mixture in a muffle furnace in an air atmosphere, raising the temperature to 400-1000 ℃ at a heating rate of 0.5-10 ℃/min, and keeping the temperature for 2-10 hours. Sieving to 20-30 meshes to prepare CuO-Co3O4Binary catalyst M4.
Example 6
Preparation of selective oxidative CO removal catalyst M5: adding Cu (NO)3)2·3H2O、Ce(NO3)3·6H2O is according to Cu: the Ce molar ratio is 1: dissolving 10 in deionized water, weighing a certain amount of NaOH, adding the NaOH into the mixed solution to ensure that the pH value of the solution is 10.5, stirring for 1-10 hours, filtering, and washing with deionized water for 3-5 times. And (3) drying, placing the mixture in a muffle furnace in an air atmosphere, raising the temperature to 400-1000 ℃ at a heating rate of 0.5-10 ℃/min, and keeping the temperature for 2-10 hours. Sieving to 20-30 meshes to prepare CuO-CeO2Binary catalyst M5.
Example 7
Catalysts M1-M5 were applied to the system for producing acrylic acid by one-step oxidation of propane in example 1, and were filled in the CO removal reactor R-102, and the composition of the tail gas entering the CO removal reactor R-102 in the measurement system was: CO22：C2H4：C2H6：O2：N2：CO：C3H6：C3H81.51: 0.0211: 0.0198: 8.11: 79.22: 1.5: 0.411: 9.21, the specific reaction conditions are shown in Table 1, and the results of selectivity and conversion in the CO removal reaction of catalysts M1-M5 are shown in Table 1.
TABLE 1
Figure BDA0001130231610000101
Wherein the catalyst M1 has a space velocity of 4500 L.Kg at 0.1MPa and 150 deg.C-1·h-1The operation was continued for 200h, and the CO conversion and the volume fraction of the components in the off-gas are shown in fig. 2.
The catalyst M1 has a space velocity of 4500, 15000, 32000L & Kg at 0.1MPa, 100-180 deg.C-1·h-1Under the conditions, the change trend of the conversion rate of CO is shown in figure 3, and the graph shows that the conversion rate and the selectivity of CO are close to 100% in the reaction temperature of 150-180 ℃.
Catalyst M1 at 0.1MPa, space velocity 15000 L.Kg-1·h-1Under the condition, deflagration occurs at 220-230 ℃, oxidation reaction occurs on part of propylene and ethylene, the temperature of a catalyst bed layer is sharply increased by about 80-90 ℃, and heat release is difficult to control in the reaction process. Therefore, in order to prevent the occurrence of the deflagration phenomenon during the reaction, the reaction temperature must be strictly controlled below 200 ℃.
Catalyst M2 at 0.1MPa, 5000 L.Kg-1·h-1CO and O in tail gas at the reaction temperature of 50-300 ℃ at airspeed2The concentration of (2) and the conversion rate and selectivity of CO are shown in figure 4, and it can be seen from the figure that the conversion rate and selectivity of CO are close to 100% in the temperature range of 150-180 ℃.
Catalyst M3 in0.1MPa、5000L·Kg-1·h-1CO and O in tail gas at the reaction temperature of 50-300 ℃ at airspeed2The concentration of (2) and the conversion rate and selectivity of CO are shown in figure 5, and it can be seen from the figure that the conversion rate and selectivity of CO are close to 100% in the temperature range of 150-180 ℃.

Claims (13)

  1. A selective oxidation removal method of CO is characterized in that CuO-CeO is adopted2、Co3O4-CeO2Or CuO-CeO2-Co3O4The composite oxide is used as a catalyst and contains CO and O2And the CO is removed by contact reaction with at least one hydrocarbon mixed gas, and the reaction temperature is 50-200 ℃.
  2. 2. The method according to claim 1, wherein the specific conditions of the selective oxidative CO removal reaction are as follows: the pressure is 0.1-0.5 MPa, and the reaction space velocity is 5000-35000 L.Kg-1·h-1The reaction is carried out in a fixed bed reactor.
  3. 3. The method of claim 1, wherein the catalyst is CuO-CeO2-Co3O4、CuO-CeO2The composite oxide comprises the following components in proportion by mole: cu: ce: co = 1: 0.5-10: 0.5 to 10; cu: ce = 1: 0.5 to 10.
  4. 4. The method of claim 1 or 2, wherein the catalyst further comprises a shaped catalyst that is present as a composite oxide: diluent = 100: 0.1-200 of alpha-Al2O3、γ-Al2O3Or SiO2As a diluent, or according to the composite oxide: lubricant = 100: graphite and/or talcum powder is added in a proportion of 0.1-5 to serve as a lubricant, and the mixture is pressed into cylindrical, flaky, annular cylindrical and spherical molded catalysts.
  5. 5. The method of claim 1, wherein the catalyst is prepared by: according to the appointed proportion, soluble salts of metal elements in the composite oxide are dissolved in deionized water to form precursor salt mixed solution, alkaline solution is added to carry out coprecipitation reaction to obtain a catalyst precursor, and the catalyst is obtained by roasting.
  6. 6. The method of claim 1, wherein the gas containing CO and O2And the at least one hydrocarbon further comprises any one or more of the following gases: steam, N2Ethane, ethylene, propane, CO2And propylene.
  7. 7. The method of claim 6, wherein the gas containing CO and O2And the mixed gas of at least one hydrocarbon is the circulating tail gas of the acrylic acid prepared by one-step oxidation of propane, and the tail gas comprises the following components in percentage by volume: h2O3.5~10.0%；N245.0~65.0%；O25.0-10.0%; 0.01 to 0.05 percent of ethane; 0.01-0.05% of ethylene; 10.0-15.0% of propane and 2.0-10.0% of CO; CO222.0-10.0%; 1.5 to 5.0 percent of propylene.
  8. 8. The method for preparing acrylic acid by one-step oxidation of propane comprises a propane selective oxidation reaction process, a crude acrylic acid separation process and a tail gas treatment process, wherein the tail gas treatment process comprises the following steps: after the tail gas is dehydrated and the carbon monoxide is selectively removed, the tail gas is circularly used for the propane selective oxidation process; the method for selectively removing carbon monoxide from the tail gas adopts the method of any one of claims 1 to 7.
  9. 9. The method of claim 8, wherein the selective oxidation of propane is carried out in the presence of a mixed metal oxide catalyst comprising any 4 or more of Mo, V, Sb, Te, Nb, Al, W, K, Co.
  10. 10. System for preparing acrylic acid by one-step oxidation of propaneThe device comprises a raw material premixing component, a propane selective oxidation reaction component, a product separation component and a tail gas treatment component, and is characterized in that the tail gas treatment component is connected with the product separation component and the raw material premixing component and comprises a tail gas dehydration tank (V-103), a CO removal reactor (R-102) and a compressor (K-101) which are sequentially arranged, wherein a catalyst is filled in the CO removal reactor (R-102), and the catalyst is CuO-CeO2、Co3O4-CeO2Or CuO-CeO2-Co3O4A composite oxide.
  11. 11. The system according to claim 10, characterized in that it comprises in particular:
    a raw material premixing assembly including a feed mixer (M-102) for receiving and mixing propane, O from a battery limits2、N2The mixed raw material gas is conveyed to the propane selective oxidation reaction component;
    a propane selective oxidation reaction assembly for receiving mixed feed gas from the feed mixer (M-102) and catalyzing the propane selective oxidation reaction to proceed, comprising a propane selective oxidation reactor (R-101) comprising a cooling section (E-103);
    the product separation component is used for receiving the reaction product from the propane selective oxidation reaction component, separating crude acrylic acid and outputting tail gas to the tail gas treatment component, and comprises a quencher (V-104) and an absorption tower (C-110) which are connected in sequence;
    the tail gas treatment component is connected with the product separation component and the raw material premixing component and is used for receiving tail gas from the product separation component and inputting the circulating tail gas subjected to dehydration and carbon monoxide removal treatment to the raw material premixing component; the tail gas treatment component comprises a tail gas dehydration tank (V-103), a CO removal reactor (R-102) and a compressor (K-101) which are sequentially connected between an absorption tower (C-110) and a feed mixer (M-102).
  12. 12. System according to claim 10 or 11, characterized in thatThe raw material premixing component comprises a feed mixer (M-102) and a propane superheater (E-102) and a premixer (M-101) which are connected with the feed mixer; the propane superheater (E-102) is used for receiving and heating the vaporized propane and delivering the vaporized propane to the feed mixer (M-102); the premixer (M-101) is used for receiving and mixing O input from the battery limits2、N2Water vapor and recycled tail gas from the tail gas treatment component and delivered to a feed mixer (M-102).
  13. 13. The system of claim 10, wherein the propane selective oxidation reactor (R-101) is packed with a mixed metal oxide catalyst comprising any 4 or more of Mo, V, Sb, Te, Nb, Al, W, K, Co.
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CN112439419A (en) * 2019-08-30 2021-03-05 中国科学院大连化学物理研究所 Application of supported catalyst in selective CO removal in tail gas generated in preparation of acrylic acid by one-step oxidation of propane
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