CN114425277A - Reactor and application thereof in preparation of carbon dioxide hydrocarbon by oxidative coupling of methane - Google Patents

Reactor and application thereof in preparation of carbon dioxide hydrocarbon by oxidative coupling of methane Download PDF

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CN114425277A
CN114425277A CN202010942380.6A CN202010942380A CN114425277A CN 114425277 A CN114425277 A CN 114425277A CN 202010942380 A CN202010942380 A CN 202010942380A CN 114425277 A CN114425277 A CN 114425277A
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reaction
carrier
reaction cavity
reactor
methane
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CN114425277B (en
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赵清锐
韦力
王雪
武洁花
邵芸
张明森
刘东兵
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to the field of catalysis, and discloses a reactor and application thereof in preparing carbon dioxide hydrocarbon by methane oxidative coupling, wherein the reactor comprises a reaction cavity and a catalyst filled in the reaction cavity, the reaction cavity is made of alumina, and the roughness of the inner surface of the reaction cavity is 0.5-1 micron; the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal. The reactor has high mechanical strength, high temperature resistance, good falling resistance and good stability, is used for methane oxidative coupling reaction, has high raw material conversion rate, less side reaction, high selectivity and yield of the carbon dioxide hydrocarbon, and is easy for large-scale production and application.

Description

Reactor and application thereof in preparation of carbon dioxide hydrocarbon by oxidative coupling of methane
Technical Field
The invention relates to the field of catalysis, in particular to a reactor and application thereof in preparing carbo-dihydrocarb through methane oxidative coupling.
Background
At present, in the world industry, ethylene is still mainly obtained through two ways, one is obtained by directly cracking crude oil at high temperature, and the other is obtained by further cracking naphtha obtained by refining crude oil, so that the raw materials of ethylene are petroleum at present, however, in recent years, with continuous breakthrough of natural gas exploration technologies such as shale gas, combustible ice and the like, a batch of large and medium-sized gas fields are continuously brought forward, the proven reserves and the output are rapidly increased, the proportion of natural gas in primary energy is gradually increased, and the natural gas chemical industry gradually becomes one of the development directions of the petrochemical industry. Natural gas, as one of three major energy sources (coal, petroleum and natural gas) in modern industry, has the advantages of high quality, cleanness and abundant reserves, and occupies a very important position. Therefore, the preparation of ethylene by natural gas instead of petroleum becomes the focus of research in various countries.
The main component of natural gas is methane. The technology for preparing ethylene by oxidative coupling of methane is the most direct and effective way for chemical utilization of methane, and although research has been carried out for more than 30 years, the technology level of the technology for preparing ethylene does not reach the level of economic operation, and industrial production is not formed yet. Especially the form and material of the reactor are a difficulty of the technology. The oxidative coupling of methane reported at present is carried out on quartz reactors, which have certain disadvantages in terms of mechanical strength, since stainless steel reactor walls produce major side reactions.
Therefore, the existing reactor for methane oxidation coupling needs to be further improved.
Disclosure of Invention
The invention aims to overcome the technical problems of more side reactions and poor mechanical strength of the existing reactor for carrying out the methane oxidative coupling reaction, and provides a reactor and application thereof in preparing carbon-dioxide hydrocarbon by methane oxidative coupling.
In order to achieve the above object, one aspect of the present invention provides a reactor, which includes a reaction chamber and a catalyst filled in the reaction chamber, wherein the reaction chamber is made of alumina, and the roughness of the inner surface of the reaction chamber is 0.5 to 1 μm;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal.
The reactor provided by the invention has the advantages of high mechanical strength, high temperature resistance, drop resistance and good stability, is used for methane oxidative coupling reaction, has high raw material conversion rate, less side reaction and high selectivity and yield of the carbon dioxide hydrocarbon, and is easy for large-scale production and application.
In a second aspect the present invention provides a process for the oxidative coupling of methane to produce a carbo-carburis, which process comprises:
(1) filling a catalyst in a reaction cavity of the reactor, wherein the reaction cavity is made of alumina, and the roughness of the inner surface of the reaction cavity is 0.5-1 micron;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal;
(2) introducing methane and oxygen into the alumina reaction cavity to contact with the catalyst for catalytic reaction.
The method for preparing the carbo-dydrocarbon by oxidative coupling of the methane has the advantages of high conversion rate of raw materials of catalytic reaction, less side reaction, high selectivity and yield of the carbo-dydrocarbon and easy large-scale production and application.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a reactor, which comprises a reaction cavity and a catalyst filled in the reaction cavity, wherein the reaction cavity is made of alumina, and the roughness of the inner surface of the reaction cavity is 0.5-1 micron;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal.
In some embodiments of the present invention, the roughness of the inner surface of the reaction chamber is preferably 0.6 to 0.8 μm. Roughness refers to the small pitch and small peak-to-valley unevenness of the machined surface, as measured by the needle drawing method. In particular, the roughness of the inner surface of the cavity is large, and the wall of the cavity can generate more side reactions.
In some embodiments of the invention, the ratio of the thickness of the reaction chamber to the inner diameter of the reaction chamber is preferably 0.2 to 0.3: 1.
in some embodiments of the invention, the material of the reactor is a commercially available common alumina product, preferably α -Al2O3。
In some embodiments of the invention, the reactor further comprises a stainless steel support sleeve disposed around the reaction chamber along an outer wall thereof. In the invention, no gap is left between the stainless steel support sleeve and the alumina reaction cavity, and the stainless steel support sleeve and the alumina reaction cavity are tightly attached.
In some embodiments of the present invention, preferably, the catalyst further contains an auxiliary, preferably at least one selected from oxides of Sr, La, Y and Sm. More preferably, the content of the auxiliary is 1 to 8g, and still more preferably 2 to 4g, based on 100g of the carrier.
In some embodiments of the present invention, the active component is preferably at least one of an oxide of Li, an oxide of Na, an oxide of K, and an oxide of Rb.
In some embodiments of the invention, the active ingredient is present in an amount of 1 to 25g, preferably 3 to 20g, based on 100g of the carrier.
In some embodiments of the invention, the catalyst used is commercially available or prepared by methods known in the art.
According to a preferred embodiment of the present invention, the catalyst without promoter is prepared by: adding a precursor of the active component into deionized water, adding a carrier, stirring for 1-3 hours, drying at 100-120 ℃ for 20-24 hours, and roasting at 700-750 ℃ for 4-6 hours to obtain the catalyst.
According to another preferred embodiment of the present invention, the promoted catalyst is prepared by: adding a precursor of an active component into deionized water, adding a carrier, stirring for 1-3 hours, and then drying at 100-120 ℃ for 20-24 hours to obtain a solid A; then dissolving the precursor of the auxiliary agent in deionized water, adding the solid A, stirring for 1-3 hours, drying for 20-24 hours at 100-120 ℃, and roasting for 4-6 hours at 700-750 ℃ to obtain the catalyst of the invention.
In a second aspect the present invention provides a process for the oxidative coupling of methane to produce a carbo-carburis, which process comprises:
(1) filling a catalyst in a reaction cavity of the reactor, wherein the reaction cavity is made of alumina, and the roughness of the inner surface of the reaction cavity is 0.5-1 micron;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal;
(2) introducing methane and oxygen into the alumina reaction cavity to contact with the catalyst for catalytic reaction.
In some embodiments of the present invention, the roughness of the inner surface of the reaction chamber is preferably 0.6 to 0.8 μm.
In the present invention, the description of the structure of the reactor, as mentioned above, will not be repeated herein.
In some embodiments of the present invention, preferably, the catalyst further contains an auxiliary, preferably at least one selected from oxides of Sr, La, Y and Sm. More preferably, the content of the auxiliary is 1 to 8g, and still more preferably 2 to 4g, based on 100g of the carrier.
In some embodiments of the present invention, the active component is preferably at least one of an oxide of Li, an oxide of Na, an oxide of K, and an oxide of Rb.
In some embodiments of the invention, the active ingredient is present in an amount of 1 to 25g, preferably 3 to 20g, based on 100g of the carrier.
In some embodiments of the invention, the volume ratio of methane to oxygen is preferably 2-10: 1, more preferably 2.2 to 4: 1.
in some embodiments of the invention, the conditions of the catalytic reaction include: the reaction temperature is preferably 700 to 780 ℃ and more preferably 700 to 750 ℃. The reaction pressure of the catalytic reaction is preferably 0.001-0.02MPa, and the reaction time of the catalytic reaction is preferably 0.5-20 h. The hourly space velocity of the reaction gas, in terms of methane and oxygen, is preferably from 5000 to 35000 mL/(g.h).
In the invention, the fillers at the two ends of the catalyst are inert materials which only play a role of supporting the catalyst and do not participate in the reaction. Preferably, the inert material is silica and/or alumina, the silica being derived from quartz sand.
In the present invention, the unit "mL/(g.h)" is the amount (mL) of the total gas of methane and oxygen used at a time of 1 hour, relative to 1g of the catalyst by mass.
In the present invention, the pressure means gauge pressure.
In the present invention, the carbo-hydrocarbon may be ethane and/or ethylene.
The present invention will be described in detail below by way of examples. In the examples and comparative examples, the reagents used were all commercially available analytical reagents. SiO 22Is derived from quartz sand, and the quartz sand is purchased from Qingdao ocean chemical industry Co. Alumina is available from nodulizer fillers, ltd. The method for measuring the element composition of the catalyst is an X-ray fluorescence method, and the specific detection refers to GB/T30905-2014.
Preparation example 1
The preparation method of the catalyst without the auxiliary agent comprises the following steps: adding a precursor of the active component into deionized water with the temperature of 50 ℃ and the weight of 25g, adding a carrier, stirring for 2 hours, drying for 24 hours at the temperature of 120 ℃, and then roasting for 6 hours at the temperature of 750 ℃ to obtain the catalyst used in the embodiment.
Preparation example 2
The preparation method of the catalyst with the auxiliary agent comprises the following steps: adding a precursor of the active component into deionized water at 50 ℃ and 25g, adding a carrier, stirring for 2 hours, and drying at 120 ℃ for 24 hours to obtain a solid A; then dissolving the precursor of the auxiliary agent in deionized water at 50 ℃ and 25g, adding the solid A, stirring for 2 hours, drying at 120 ℃ for 24 hours, and then roasting at 750 ℃ for 6 hours to obtain the catalyst used in the examples or the comparative examples.
In the preparation examples, the precursor of the active component and the precursor of the auxiliary agent both refer to nitrate, and the usage amount of each component is such that the content of the active component and the auxiliary agent in the catalyst is shown in table 1:
TABLE 1
Figure BDA0002674068200000061
Note: the contents of the components in the catalyst are relative contents calculated on the basis of 100g of the carrier;
"/" indicates no promoter is present in the catalyst.
Example 1
The reactor is alpha-Al with the inner diameter of 10mm and the length of 530mm2O3A reaction tube, the loading of the catalyst was 0.2g, the thickness of the reaction tube was 2mm, the roughness of the inner surface of the reaction tube was 0.6 μm, the reaction pressure was a pressure generated by the raw material itself, i.e., 0.014MPa, the reaction temperature was 750 ℃, and the volume ratio of methane to oxygen was 2.2: 1, the hourly space velocity of reaction gas in terms of methane and oxygen is 12000 mL/(g.h), and reaction products are collected after 1 hour of reaction.
Example 2
The reactor is alpha-Al with the inner diameter of 12mm and the length of 530mm2O3The loading of the catalyst in the reaction tube was 0.2g, the thickness of the reaction tube was 3.5mm, the roughness of the inner surface of the reaction tube was 0.7 μm, the reaction pressure was the pressure generated by the raw material itself, i.e., 0.006MPa, the reaction temperature was 700 ℃, and the volume ratio of methane to oxygen was 3: 1, the hourly space velocity of reaction gas measured by methane and oxygen is 5000 mL/(g.h), and reaction products are collected after 1 hour of reaction.
Example 3
The reactor is alpha-Al with the inner diameter of 10mm and the length of 530mm2O3The loading of the catalyst in the reaction tube was 0.2g, the thickness of the reaction tube was 2.5mm, the roughness of the inner surface of the reaction tube was 0.8 μm, the reaction pressure was the pressure generated by the raw material itself, i.e., 0.018MPa, the reaction temperature was 780 ℃, and the volume ratio of methane to oxygen was 4: 1, the hourly space velocity of reaction gas measured by methane and oxygen is 35000 mL/(g.h), and reaction products are collected after 1 hour of reaction.
Example 4
The reactor is alpha-Al with the inner diameter of 10mm and the length of 530mm2O3The loading of the catalyst in the reaction tube was 0.2g, the thickness of the reaction tube was 2mm, the roughness of the inner surface of the reaction tube was 1 μm, the reaction pressure was the pressure generated by the raw material itself, i.e., 0.009MPa, the reaction temperature was 780 ℃, and the volume ratio of methane to oxygen was 6: 1, the hourly space velocity of reaction gas measured by methane and oxygen is 8000 mL/(g.h), and reaction products are collected after 1 hour of reaction.
Example 5
The reactor is alpha-Al with the inner diameter of 10mm and the length of 530mm2O3The loading of the catalyst in the reaction tube was 0.2g, the thickness of the reaction tube was 2mm, and the inner surface of the reaction tube was roughThe temperature is 0.5 micron, the reaction pressure is the pressure generated by the raw materials, namely 0.015MPa, the reaction temperature is 730 ℃, and the volume ratio of methane to oxygen is 10: 1, the hourly space velocity of reaction gas in terms of methane and oxygen is 15000 mL/(g.h), and reaction products are collected after 1 hour of reaction.
Comparative example 1
A reaction for producing a hydrocarbon by oxidative coupling of methane was carried out in the same manner as in example 1, except that 314L stainless steel was used as the material of the reactor.
Comparative example 2
The reaction for producing hydrocarbons by oxidative coupling of methane was carried out in the same manner as in example 1, except that the material of the reactor was quartz.
Comparative example 3
The reaction for producing a hydrocarbon by oxidative coupling of methane was carried out in the same manner as in example 1, except that the catalyst was replaced with the catalyst shown in comparative example 3 in Table 1.
Comparative example 4
The reaction for producing a hydrocarbon by oxidative coupling of methane was carried out in the same manner as in example 1, except that the roughness of the inner surface of the reactor was 2.5 μm.
Comparative example 5
The reaction for producing a hydrocarbon by oxidative coupling of methane was carried out in the same manner as in comparative example 1, except that the catalyst used in comparative example 3 was used.
Test example 1
The reaction product components obtained in the examples and comparative examples were measured on a gas chromatograph available from Agilent under the model number 7890A. The product is measured by a double detection channel triple valve four-column system, wherein the FID detector is connected with an alumina column and is used for analyzing CH4、C2H6、C2H4、C3H8、C3H6、C4H10、C4H8、CnHmEqual-component TCD detector mainly used for detecting CO and CO2、N2、O2、CH4。
The methane conversion and the like are calculated as follows:
methane conversion ═ amount of methane consumed by the reaction/initial amount of methane × 100%
Ethylene selectivity is the amount of methane consumed by ethylene produced/total consumption of methane × 100%
Ethane selectivity is the amount of methane consumed by ethane produced/total consumption of methane × 100%
Carbo-carb selectivity ═ ethane selectivity + ethylene selectivity
COx(CO+CO2) Selectivity to CO and CO formed2The amount of co-consumed methane/total consumption of methane X100%
Yield of carbo-carb ═ methane conversion x (ethane selectivity + ethylene selectivity)
The results obtained are shown in Table 2.
TABLE 2
Numbering Methane conversion/% Selectivity for carbon dioxide/%) COxSelectivity/%) Yield of carbo-dydrocarbon/%)
Example 1 23.5 70.6 27.3 16.6
Example 2 23.3 70.1 27.8 16.3
Example 3 23 69.5 28.1 16
Example 4 22.6 69.1 28.5 15.6
Example 5 22.2 69 28.8 15.3
Comparative example 1 12.4 43.5 52.5 5.4
Comparative example 2 22.9 70 27.4 16
Comparative example 3 17.8 51.8 45.2 9.2
Comparative example 4 20.1 55.7 41.3 11.2
Comparative example 5 16.9 41.2 54.6 7
As is clear from the test results in Table 2, examples 1 to 5 have higher selectivity of the carbo-hydride, higher yield of the carbo-hydride, and CO, relative to comparative example 1xThe selectivity is relatively low, which indicates that the deep oxidation of methane is inhibited and the occurrence of side reactions is reduced when the reactor is used for preparing the carbon dioxide hydrocarbon by oxidative coupling of the methane. In example 1, the maximum temperature of the quartz tube used in comparative example 2 used in a short time was about 1400 c, while the maximum temperature of the alumina tube used in example 1 was 1700 c, as compared with comparative example 2. The oxidative coupling of methane is a high-temperature strong exothermic reaction, the reaction temperature is generally higher than 750 ℃, the reaction heat reaches 83kcal/mol, an obvious hot zone exists in the reactor, the bed temperature can even rise to 1200 ℃, and the reaction cannot be borne by a quartz reactor. In addition, compared with a quartz tube, the alumina reaction tube has high strength, good stability and high temperature resistance. Therefore, for the high temperature strongly exothermic reaction of methane oxidative coupling, the alumina reaction tube is more suitable for large-scale use. The higher selectivity and yield of the carbo-carbyls of examples 1-5 relative to comparative examples 3-5 indicate that superior catalytic performance can only be achieved with this approach for a particular catalyst.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A reactor is characterized by comprising a reaction cavity and a catalyst filled in the reaction cavity, wherein the reaction cavity is made of alumina, and the roughness of the inner surface of the reaction cavity is 0.5-1 micron;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal.
2. The reactor of claim 1, wherein the roughness of the inner surface of the reaction chamber is 0.6-0.8 microns;
and/or the ratio of the thickness of the reaction cavity to the inner diameter of the reaction cavity is 0.2-0.3: 1;
and/or the reaction cavity is made of alpha-Al2O3；
And/or the reactor also comprises a stainless steel support sleeve which is fixedly arranged along the outer wall of the reaction cavity in a surrounding way.
3. The reactor according to claim 1 or 2, wherein the catalyst further contains a promoter, preferably at least one selected from oxides of Sr, La, Y and Sm;
preferably, the content of the auxiliary agent is 1 to 8g, preferably 2 to 4g, based on 100g of the carrier.
4. The reactor according to any one of claims 1-3, wherein the active component is at least one of an oxide of Li, an oxide of Na, an oxide of K and an oxide of Rb;
and/or the content of the active component is 1 to 25g, preferably 3 to 20g based on 100g of the carrier.
5. A method for preparing a carbo-hydrocarbon by oxidative coupling of methane, the method comprising:
(1) filling a catalyst in a reaction cavity of the reactor, wherein the reaction cavity is made of alumina, and the roughness of the inner surface of the reaction cavity is 0.5-1 micron;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal;
(2) introducing methane and oxygen into the alumina reaction cavity to contact with the catalyst for catalytic reaction.
6. The method of claim 5, wherein the roughness of the inner surface of the reaction chamber is 0.6-0.8 microns;
and/or the ratio of the thickness of the reaction cavity to the inner diameter of the reaction cavity is 0.2-0.3: 1;
and/or the reaction cavity is made of alpha-Al2O3；
And/or the reactor also comprises a stainless steel support sleeve which is fixedly arranged along the outer wall of the reaction cavity in a surrounding way.
7. The process according to claim 5 or 6, wherein the catalyst further contains a promoter, preferably at least one selected from the group consisting of oxides of Sr, La, Y and Sm;
preferably, the content of the auxiliary agent is 1 to 8g, preferably 2 to 4g, based on 100g of the carrier.
8. The method of any one of claims 5-7, wherein the active component is at least one of an oxide of Li, an oxide of Na, an oxide of K, and an oxide of Rb;
and/or the content of the active component is 1 to 25g, preferably 3 to 20g based on 100g of the carrier.
9. The method of any one of claims 5-8, wherein the volume ratio of methane to oxygen is 2-10: 1, preferably 2.2 to 4: 1.
10. the method of claim 5, wherein the conditions of the catalytic reaction comprise: the reaction temperature is 700-780 ℃, preferably 700-750 ℃, the reaction pressure is 0.001-0.02MPa, the reaction time is 0.5-20h, and the hourly space velocity of the reaction gas calculated by methane and oxygen is 5000-35000 mL/(g.h).
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