CN114181033A - Method for recovering methane from ethylene waste gas produced in preparation of ethylene through oxidative coupling of methane - Google Patents

Method for recovering methane from ethylene waste gas produced in preparation of ethylene through oxidative coupling of methane Download PDF

Info

Publication number
CN114181033A
CN114181033A CN202010962915.6A CN202010962915A CN114181033A CN 114181033 A CN114181033 A CN 114181033A CN 202010962915 A CN202010962915 A CN 202010962915A CN 114181033 A CN114181033 A CN 114181033A
Authority
CN
China
Prior art keywords
methane
catalyst
cerium
zirconium
salt
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.)
Pending
Application number
CN202010962915.6A
Other languages
Chinese (zh)
Inventor
邵芸
赵清锐
刘红梅
徐向亚
刘东兵
张明森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN202010962915.6A priority Critical patent/CN114181033A/en
Publication of CN114181033A publication Critical patent/CN114181033A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/14808—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with non-metals as element
    • C07C7/14816—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with non-metals as element oxygen; ozone
    • 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
    • B01J23/76—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
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Emergency Medicine (AREA)
  • Water Supply & Treatment (AREA)
  • Biomedical Technology (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a method for recovering methane from ethylene waste gas prepared by oxidative coupling of methane, which comprises the steps of reacting the ethylene waste gas prepared by oxidative coupling of methane with an oxygen source in the presence of a formed catalyst; wherein the shaped catalyst supports CexZr1‑xO2The formed alumina is used as a carrier, x is 0-1, and CuO is used as an active groupAnd (4) dividing. In the method provided by the invention, the catalyst has higher mechanical strength, and can better remove carbon monoxide and hydrogen in the tail gas generated in the reaction of preparing ethylene by demethanization coupling.

Description

Method for recovering methane from ethylene waste gas produced in preparation of ethylene through oxidative coupling of methane
Technical Field
The invention relates to a method for recovering methane from ethylene waste gas produced in the preparation of ethylene through methane oxidative coupling.
Background
The technology for preparing ethylene by Oxidative Coupling of Methane (OCM) has potential application value in the field of petrochemical industry. After a single pass of the feed through the catalyst bed, about 50 wt% of the methane is converted to ethylene, ethane as the main products, and hydrogen, carbon monoxide and carbon dioxide as by-products. After the output material of the reactor is subjected to carbon dioxide removal and ethylene and ethane separation, the main byproducts are unreacted methane, carbon monoxide and hydrogen. In order to improve the utilization efficiency of raw material methane, patent CN 109456139 a carries out processes of quenching and cooling, compressing and boosting, impurity removal, and gas-liquid separation on the OCM reaction product, and adopts a membrane separation technology to separate the methane in the non-condensable gas and return the methane to the OCM reactor for recycling. The patent CN 108137435A adopts an adsorption-desorption method to recycle unreacted methane. The selective catalytic oxidation can also be used for purifying the OCM tail gas, namely the OCM tail gas passes through the catalyst bed layer at a certain temperature, carbon monoxide and hydrogen are oxidized, and methane is not consumed or is consumed a little. After methane is purified, the methane can be fed together with fresh methane, and the utilization efficiency of methane is improved. The powder catalyst can remove carbon monoxide and hydrogen in tail gas.
Having the necessary mechanical strength is one of the properties that industrial heterogeneous catalysts must possess, and therefore catalyst shaping is one of the important steps in the industrial catalyst preparation process. So far, no report is found on the forming mode of the catalyst carrier suitable for OCM exhaust gas purification treatment.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention provides a catalyst with high mechanical strength, which can remove carbon monoxide and hydrogen in the tail gas of ethylene production by demethanization coupling, thereby recovering methane.
The first aspect of the invention provides a method for recovering methane from an ethylene waste gas produced by oxidative coupling of methane, which comprises the steps of reacting the ethylene waste gas produced by oxidative coupling of methane with an oxygen source in the presence of a formed catalyst; wherein the shaped catalyst supports CexZr1-xO2The formed alumina is used as a carrier, x is 0-1, and CuO is used as an active component.
According to some embodiments of the invention, x is 0.1-0.7.
According to some preferred embodiments of the present invention, x is 0.1 to 0.5.
According to some embodiments of the invention, the method comprises separating methane after contacting the ethylene production waste gas from the oxidative coupling of methane with an oxygen source in the presence of the shaped catalyst.
According to some embodiments of the invention, the oxygen source is oxygen gas and/or air.
According to some embodiments of the invention, Ce is present in the shaped catalyst based on the total weight of the supportxZr1-xO2The mass content of (a) is 2 to 15%, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, and any value therebetween.
According to some embodiments of the invention, Ce is present in the shaped catalyst based on the total weight of the supportxZr1-xO2The mass content of (A) is 5-15%.
According to some embodiments of the invention, Ce is present in the shaped catalyst based on the total weight of the supportxZr1-xO2The mass content of (A) is 5-10%.
According to some embodiments of the present invention, the shaped catalyst comprises CuO in an amount of 2 to 15% by mass, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% by mass and any value therebetween, based on the total weight of the support.
According to a preferred embodiment of the present invention, the shaped catalyst has a mass content of CuO of 5 to 10% based on the total weight of the catalyst.
According to some embodiments of the invention, the method of preparing the catalyst comprises loading Ce on a shaped alumina supportxZr1-xO2And then CuO is loaded.
According to the invention, the shaped alumina supports CexZr1-xO2The preparation method is not limited. According to some embodiments of the invention, the Ce-loading is performed by a laserxZr1-xO2Precipitation deposition and/or impregnation may be used.
According to some embodiments of the invention, the Ce-loading is performed by a laserxZr1-xO2Single load or multiple loads.
According to some embodiments of the invention, the supported CuO is impregnated.
According to some embodiments of the invention, the method of forming a catalyst comprises the steps of:
s1: mixing cerium salt water solution, zirconium salt water solution and formed alumina for impregnation, drying and roasting to obtain the loaded CexZr1-xO2The shaped alumina support of (a);
s2: copper salt aqueous solution and the loaded CexZr1-xO2The molded alumina carrier is mixed, impregnated, dried and roasted to obtain the molded catalyst.
According to further embodiments of the present invention, the method of forming a catalyst comprises the steps of:
n1: mixing cerium salt water solution, zirconium salt water solution and formed alumina, adding alkaline solution for precipitation, washing, drying and roasting to obtain the loaded CexZr1-xO2The shaped alumina support of (a);
n2: copper salt aqueous solution and the loaded CexZr1-xO2The molded alumina carrier is mixed, impregnated, dried and roasted to obtain the molded catalyst.
According to some embodiments of the invention, the shaped alumina is spherical alumina.
According to some embodiments of the invention, the cerium salt is a water-soluble cerium salt.
According to some embodiments of the invention, the cerium salt is selected from at least one of cerium nitrate, ammonium cerium nitrate, cerium sulfate and cerium chloride, more preferably from cerium nitrate.
According to some embodiments of the invention, the zirconium salt is a water soluble zirconium salt.
According to some embodiments of the invention, the zirconium salt is selected from at least one of zirconium oxychloride, zirconium chloride, zirconium sulfate and zirconium nitrate, more preferably from zirconium nitrate.
According to some embodiments of the invention, the copper salt is a water soluble copper salt.
According to some embodiments of the invention, the copper salt is selected from at least one of copper nitrate, copper chloride and copper sulfate, more preferably from copper nitrate.
According to some embodiments of the invention, the alkaline solution is selected from an aqueous ammonia and/or sodium carbonate solution.
According to some embodiments of the invention, the temperature of the drying is 60-120 ℃ in step S1 or N1.
According to some embodiments of the invention, the temperature of the calcination in step S1 or N1 is 400-800 ℃.
According to some embodiments of the invention, the time is 2-10h in step S1 or N1.
According to some embodiments of the invention, the temperature of the drying is 60-120 ℃ in step S2 or N2.
According to some embodiments of the invention, the temperature of the calcination in step S2 or N2 is 400-800 ℃.
According to some embodiments of the invention, the time is 2-10h in step S2 or N2.
According to some embodiments of the invention, the waste gas from the oxidative coupling of methane to produce ethylene comprises methane, carbon monoxide and hydrogen.
According to some embodiments of the invention, the volume ratio of methane, carbon monoxide and hydrogen is (12-18): (2-5): 1.
According to a preferred embodiment of the invention, the volume ratio of methane, carbon monoxide and hydrogen is (15-17): (2-4): 1.
According to some embodiments of the invention, the total reaction space velocity of the contacting is from 10 to 200 L.h-1·g-1。
According to a preferred embodiment of the invention, the total reaction space velocity of the contacting is in the range of from 13 to 150 L.h-1·g-1。
According to some embodiments of the invention, the temperature of the contacting is 200-.
According to a preferred embodiment of the invention, the temperature of the contacting is 350-600 ℃.
In a second aspect the invention provides the use of a process according to the first aspect in a reaction for the oxidative coupling of methane to ethylene.
Cerium zirconium oxide Ce according to the inventionxZr1-xO2The spherical alumina loaded CuO is used for OCM tail gas purification treatment.
According to the invention, the tail gas can achieve the effects of carbon monoxide conversion rate of more than 70%, hydrogen conversion rate of more than 70% and methane conversion rate of less than 4.5% by passing through the catalyst bed layer once, and under the optimal operation condition, the effects of carbon monoxide conversion rate of more than 90%, hydrogen conversion rate of more than 85% and methane conversion rate of less than 3% can be achieved, and the obtained methane can be circularly conveyed to the reaction kettle for continuous reaction.
Detailed Description
For easy understanding of the present invention, the present invention will be described in detail with reference to examples, which are provided for illustrative purposes only and are not intended to limit the scope of the present invention.
The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
Example 1
Weighing 0.54g of cerous nitrate hexahydrate and 4.76g of zirconium nitrate pentahydrate, dissolving in 50ml of water, adding 30g of spherical alumina, performing rotary evaporation to dryness, drying at 60 ℃, heating to 450 ℃ at the speed of 5 ℃/min, keeping for 5h, and cooling to room temperature to obtain cerium-zirconium oxide Ce0.1Zr0.9O2Spherical alumina.
Weighing 1.01g of copper nitrate trihydrate, dissolving in 30ml of water, adding cerium zirconium oxide Ce0.1Zr0.9O2Spherical alumina 3.01g, rotary steaming to dry, drying at 80 ℃, heating to 600 ℃ at 5 ℃/min, and keeping for 5h to obtain the shaped catalyst.
A quartz glass tube reactor (inner diameter: 8mm) was charged with 0.21g of the above catalyst, and the catalyst was packed with quartz sand (20 to 40 mesh) on the upper and lower sides. Nitrogen (40ml/min) and oxygen (2.8ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 13 vol%, H)21 vol%, the balance methane, 40ml/min) and oxygen (2.8 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 2
Weighing 0.72g of cerous nitrate hexahydrate and 2.89g of zirconium nitrate pentahydrate, dissolving in 21ml of water, dropwise adding 30g of spherical alumina while stirring, standing for 5h after uniformly stirring, drying at 80 ℃, heating to 600 ℃ at the speed of 5 ℃/min, keeping for 5h, cooling to room temperature, and repeating the above operations twice to obtain cerium-zirconium oxide Ce0.2Zr0.8O2Spherical alumina.
0.48g of copper nitrate trihydrate is weighed and dissolved in 30ml of water, and cerium zirconium oxide Ce is added0.2Zr0.8O22.98g of spherical alumina, drying by rotary evaporation at 60 ℃, heating to 600 ℃ at the speed of 5 ℃/min, and keeping for 5 hours to obtain the shaped catalyst.
In quartz glass tube reactors (inner)Diameter of 8mm), 0.15g of the above catalyst was charged, and quartz sand (20-40 mesh) was filled up and down the catalyst. Nitrogen (100ml/min) and oxygen (7ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 13 vol%, H)21 vol%, the balance methane, 100ml/min) and oxygen (7 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 3
Weighing 0.82g of cerous nitrate hexahydrate and 1.90g of zirconium nitrate pentahydrate, dissolving in 100ml of water, adding 30g of spherical alumina, slowly dropwise adding an ammonia water solution (1mol/L) until the pH value of the solution is 10, continuously stirring for 30min, filtering, washing a filter cake with distilled water, drying at 120 ℃, heating to 800 ℃ at the speed of 5 ℃/min, keeping for 5h, cooling to room temperature, and repeating the operation twice to obtain cerium-zirconium oxide Ce0.3Zr0.7O2Spherical alumina.
0.68g of copper nitrate trihydrate is weighed and dissolved in 30ml of water, and cerium zirconium oxide Ce is added0.3Zr0.7O2Spherical alumina 3.08g, rotary steaming to dry, drying at 120 ℃, heating to 800 ℃ at 5 ℃/min, and keeping for 5h to obtain the formed catalyst.
0.10g of the above catalyst was charged into a quartz glass tube reactor (inner diameter: 8mm), and quartz sand (20 to 40 mesh) was filled up and down with the catalyst. Nitrogen (180ml/min) and oxygen (14ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 13 vol%, H)23 vol%, the balance methane, 180ml/min) and oxygen (14 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 4
Weighing 0.58g of cerous nitrate hexahydrate and 0.58g of zirconium nitrate pentahydrate, dissolving in 100ml of water, adding 30g of spherical alumina, slowly dropwise adding a sodium carbonate solution (1mol/L) until the pH value of the solution is 10, continuously stirring for 30min, filtering, washing a filter cake with distilled water, drying at 100 ℃, heating to 600 ℃ at the rate of 5 ℃/min, and keeping for 5hCooling to room temperature and repeating the operation for three times to obtain cerium zirconium oxide Ce0.5Zr0.5O2Spherical alumina.
0.68g of copper nitrate trihydrate is weighed and dissolved in 30ml of water, and cerium zirconium oxide Ce is added0.5Zr0.5O2Spherical alumina 3.05g, rotary steaming to dry, drying at 80 ℃, heating to 480 ℃ at 5 ℃/min, and keeping for 5h to obtain the formed catalyst.
A quartz glass tube reactor (inner diameter: 8mm) was charged with 0.09g of the above catalyst, and the catalyst was packed with quartz sand (20 to 40 mesh) on the upper and lower sides. Nitrogen (180ml/min) and oxygen (18ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 15 vol%, H)25 vol%, the balance methane, 180ml/min) and oxygen (18 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 5
Weighing 0.54g of cerous nitrate hexahydrate and 4.76g of zirconium nitrate pentahydrate, dissolving in 50ml of water, adding 30g of spherical alumina, performing rotary evaporation to dryness, drying at 80 ℃, heating to 600 ℃ at the speed of 5 ℃/min, keeping for 5h, and cooling to room temperature to obtain cerium-zirconium oxide Ce0.1Zr0.9O2Spherical alumina.
0.28g of copper nitrate trihydrate is weighed and dissolved in 30ml of water, and cerium zirconium oxide Ce is added0.1Zr0.9O2Spherical alumina 3.03g, rotary steaming to dry, drying at 80 ℃, heating to 600 ℃ at 5 ℃/min, and keeping for 5h to obtain the formed catalyst.
A quartz glass tube reactor (inner diameter: 8mm) was charged with 0.21g of the above catalyst, and the catalyst was packed with quartz sand (20 to 40 mesh) on the upper and lower sides. Nitrogen (40ml/min) and oxygen (4ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 15 vol%, H)25 vol%, the remainder being methane, 40ml/min) and oxygen (4 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 6
Weighing 0.32g of cerous nitrate hexahydrate and 2.80g of zirconium nitrate pentahydrate, dissolving in 50ml of water, adding 30g of spherical alumina, performing rotary evaporation to dryness, drying at 80 ℃, heating to 600 ℃ at the speed of 5 ℃/min, keeping for 5h, and cooling to room temperature to obtain cerium-zirconium oxide Ce0.1Zr0.9O2Spherical alumina.
0.48g of copper nitrate trihydrate is weighed and dissolved in 30ml of water, and cerium zirconium oxide Ce is added0.1Zr0.9O2Spherical alumina 3.02g, rotary steaming to dry, drying at 80 ℃, heating to 1000 ℃ at 5 ℃/min, and keeping for 5h to obtain the shaped catalyst.
A quartz glass tube reactor (inner diameter: 8mm) was charged with 0.21g of the above catalyst, and the catalyst was packed with quartz sand (20 to 40 mesh) on the upper and lower sides. Nitrogen (40ml/min) and oxygen (4ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 15 vol%, H)25 vol%, the remainder being methane, 40ml/min) and oxygen (4 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 7
Weighing 1.49g of cerous nitrate hexahydrate and 3.45g of zirconium nitrate pentahydrate, dissolving in 50ml of water, adding 30g of spherical alumina, performing rotary evaporation to dryness, drying at 80 ℃, heating to 600 ℃ at the speed of 5 ℃/min, keeping for 5h, and cooling to room temperature to obtain cerium-zirconium oxide Ce0.3Zr0.7O2Spherical alumina.
Weighing 1.01g of copper nitrate trihydrate, dissolving in 30ml of water, adding cerium zirconium oxide Ce0.3Zr0.7O2Spherical alumina 3.01g, rotary steaming to dry, drying at 80 ℃, heating to 600 ℃ at 5 ℃/min, and keeping for 5h to obtain the shaped catalyst.
A quartz glass tube reactor (inner diameter: 8mm) was charged with 0.21g of the above catalyst, and the catalyst was packed with quartz sand (20 to 40 mesh) on the upper and lower sides. Nitrogen (40ml/min) and oxygen (4ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which contains C)O 15vol％，H25 vol%, the remainder being methane, 40ml/min) and oxygen (4 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 8
Weighing 2.32g of cerous nitrate hexahydrate and 2.30g of zirconium nitrate pentahydrate, dissolving in 50ml of water, adding 30g of spherical alumina, performing rotary evaporation to dryness, drying at 80 ℃, heating to 600 ℃ at the speed of 5 ℃/min, keeping for 5h, and cooling to room temperature to obtain cerium-zirconium oxide Ce0.5Zr0.5O2Spherical alumina.
Weighing 1.01g of copper nitrate trihydrate, dissolving in 30ml of water, adding cerium zirconium oxide Ce0.5Zr0.5O2Spherical alumina 3.01g, rotary steaming to dry, drying at 80 ℃, heating to 600 ℃ at 5 ℃/min, and keeping for 5h to obtain the shaped catalyst.
A quartz glass tube reactor (inner diameter: 8mm) was charged with 0.21g of the above catalyst, and the catalyst was packed with quartz sand (20 to 40 mesh) on the upper and lower sides. Nitrogen (40ml/min) and oxygen (4ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 15 vol%, H)25 vol%, the remainder being methane, 40ml/min) and oxygen (4 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 9
Weighing 3.05g of cerous nitrate hexahydrate and 1.29g of zirconium nitrate pentahydrate, dissolving in 50ml of water, adding 30g of spherical alumina, performing rotary evaporation to dryness, drying at 80 ℃, heating to 600 ℃ at the speed of 5 ℃/min, keeping for 5h, and cooling to room temperature to obtain cerium-zirconium oxide Ce0.7Zr0.3O2Spherical alumina.
Weighing 1.01g of copper nitrate trihydrate, dissolving in 30ml of water, adding cerium zirconium oxide Ce0.7Zr0.3O2Spherical alumina 3.01g, rotary steaming to dry, drying at 80 ℃, heating to 600 ℃ at 5 ℃/min, and keeping for 5h to obtain the shaped catalyst.
In a quartz glass tube reactor (inner diameter of8mm), 0.21g of the above catalyst was charged, and quartz sand (20-40 mesh) was filled up and down with the catalyst. Nitrogen (40ml/min) and oxygen (4ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 15 vol%, H)25 vol%, the remainder being methane, 40ml/min) and oxygen (4 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 10
Weighing 3.98g of cerous nitrate hexahydrate, dissolving in 50ml of water, adding 30g of spherical alumina, performing rotary evaporation to dryness, drying at 80 ℃, heating to 600 ℃ at the speed of 5 ℃/min, keeping for 5h, and cooling to room temperature to obtain cerium-zirconium oxide CeO2Spherical alumina.
Weighing 1.01g of copper nitrate trihydrate, dissolving the copper nitrate trihydrate in 30ml of water, and adding cerium zirconium oxide CeO2Spherical alumina 3.01g, rotary steaming to dry, drying at 80 ℃, heating to 600 ℃ at 5 ℃/min, and keeping for 5h to obtain the shaped catalyst.
A quartz glass tube reactor (inner diameter: 8mm) was charged with 0.21g of the above catalyst, and the catalyst was packed with quartz sand (20 to 40 mesh) on the upper and lower sides. Nitrogen (40ml/min) and oxygen (4ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 15 vol%, H)25 vol%, the remainder being methane, 40ml/min) and oxygen (4 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 11
Weighing 5.51g of pentahydrate zirconium nitrate, dissolving in 50ml of water, adding 30g of spherical alumina, performing rotary evaporation to dryness, drying at 80 ℃, heating to 600 ℃ at the speed of 5 ℃/min, keeping for 5h, and cooling to room temperature to obtain the cerium-zirconium oxide ZrO2Spherical alumina.
1.01g of copper nitrate trihydrate was weighed, dissolved in 30ml of water, and cerium zirconium oxide ZrO was added2Spherical alumina 3.01g, rotary steaming to dry, drying at 80 ℃, heating to 600 ℃ at 5 ℃/min, and keeping for 5h to obtain the shaped catalyst.
A quartz glass tube reactor (inner diameter: 8mm) was charged with 0.21g of the above catalyst, and the catalyst was packed with quartz sand (20 to 40 mesh) on the upper and lower sides. Nitrogen (40ml/min) and oxygen (4ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 15 vol%, H)25 vol%, the remainder being methane, 40ml/min) and oxygen (4 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 12
Weighing 0.54g of cerous nitrate hexahydrate and 4.76g of zirconium nitrate pentahydrate, dissolving in 50ml of water, adding 30g of spherical alumina, performing rotary evaporation to dryness, drying at 80 ℃, heating to 600 ℃ at the speed of 5 ℃/min, keeping for 5h, and cooling to room temperature to obtain cerium-zirconium oxide Ce0.1Zr0.9O2Spherical alumina.
Weighing 1.01g of copper nitrate trihydrate, dissolving in 30ml of water, adding cerium zirconium oxide Ce0.1Zr0.9O2Spherical alumina 3.01g, rotary steaming to dry, drying at 80 ℃, heating to 600 ℃ at 5 ℃/min, and keeping for 5h to obtain the shaped catalyst.
A quartz glass tube reactor (inner diameter: 8mm) was charged with 0.21g of the above catalyst, and the catalyst was packed with quartz sand (20 to 40 mesh) on the upper and lower sides. Nitrogen (40ml/min) and oxygen (4ml/min) were passed through the reactor and the temperature was raised to 400 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 15 vol%, H)25 vol%, the remainder being methane, 40ml/min) and oxygen (4 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 13
Weighing 0.54g of cerous nitrate hexahydrate and 4.76g of zirconium nitrate pentahydrate, dissolving in 50ml of water, adding 30g of spherical alumina, performing rotary evaporation to dryness, drying at 80 ℃, heating to 600 ℃ at the speed of 5 ℃/min, keeping for 5h, and cooling to room temperature to obtain cerium-zirconium oxide Ce0.1Zr0.9O2Spherical alumina.
1.01g of copper nitrate trihydrate are weighed out and dissolved in 30ml of water is added with cerium zirconium oxide Ce0.1Zr0.9O2Spherical alumina 3.01g, rotary steaming to dry, drying at 80 ℃, heating to 600 ℃ at 5 ℃/min, and keeping for 5h to obtain the shaped catalyst.
A quartz glass tube reactor (inner diameter: 8mm) was charged with 0.21g of the above catalyst, and the catalyst was packed with quartz sand (20 to 40 mesh) on the upper and lower sides. Nitrogen (40ml/min) and oxygen (4ml/min) were passed through the reactor and the temperature was raised to 500 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 15 vol%, H)25 vol%, the remainder being methane, 40ml/min) and oxygen (4 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 14
Weighing 0.54g of cerous nitrate hexahydrate and 4.76g of zirconium nitrate pentahydrate, dissolving in 50ml of water, adding 30g of spherical alumina, performing rotary evaporation to dryness, drying at 80 ℃, heating to 600 ℃ at the speed of 5 ℃/min, keeping for 5h, and cooling to room temperature to obtain cerium-zirconium oxide Ce0.1Zr0.9O2Spherical alumina.
Weighing 1.01g of copper nitrate trihydrate, dissolving in 30ml of water, adding cerium zirconium oxide Ce0.1Zr0.9O2Spherical alumina 3.01g, rotary steaming to dry, drying at 80 ℃, heating to 600 ℃ at 5 ℃/min, and keeping for 5h to obtain the shaped catalyst.
A quartz glass tube reactor (inner diameter: 8mm) was charged with 0.21g of the above catalyst, and the catalyst was packed with quartz sand (20 to 40 mesh) on the upper and lower sides. Nitrogen (40ml/min) and oxygen (4ml/min) were passed through the reactor and the temperature was raised to 800 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to a by-product reaction gas (which comprises CO 15 vol%, H)25 vol%, the remainder being methane, 40ml/min) and oxygen (4 ml/min). After 60min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
TABLE 1
Figure BDA0002681164800000111
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A method for recovering methane from the waste gas generated in the preparation of ethylene by oxidative coupling of methane comprises the steps of reacting the waste gas generated in the preparation of ethylene by oxidative coupling of methane with an oxygen source in the presence of a formed catalyst; wherein the shaped catalyst supports CexZr1-xO2The formed alumina is used as a carrier, x is 0-1, and CuO is used as an active component.
2. A method according to claim 1, wherein x is 0.1-0.7, preferably 0.1-0.5.
3. The process according to claim 1 or 2, wherein Ce is present in the shaped catalyst in an amount based on the total weight of the supportxZr1-xO2The mass content of (A) is 2-15%, preferably 5-15%, more preferably 5-10%; and/or
In the formed catalyst, the mass content of the CuO is 2-15%, preferably 5-10% based on the total weight of the formed catalyst.
4. The method of any one of claims 1 to 3, wherein the catalyst is prepared by first loading Ce on a shaped alumina supportxZr1-xO2Then loading CuO; preferably, the first and second electrodes are formed of a metal,
the supported CexZr1-xO2Adopting a precipitation deposition method and/or an impregnation method; and/or
The supported CexZr1-xO2Single load or multiple loads; and/or
The supported CuO adopts an impregnation method.
5. The method for preparing according to any one of claims 1 to 4, wherein the method for forming a catalyst comprises the steps of:
s1: mixing cerium salt water solution, zirconium salt water solution and formed alumina for impregnation, drying and roasting to obtain the loaded CexZr1-xO2The shaped alumina support of (a);
s2: copper salt aqueous solution and the loaded CexZr1-xO2The molded alumina carrier is mixed, impregnated, dried and roasted to obtain the molded catalyst.
6. A method according to any one of claims 1 to 5, wherein the method of shaping a catalyst comprises the steps of:
s1: mixing the aqueous solution of cerium salt and the aqueous solution of zirconium salt with a formed alumina carrier, adding an alkaline solution for precipitation, washing, drying and roasting to obtain the loaded CexZr1-xO2The shaped alumina support of (a);
s2: copper salt aqueous solution and the loaded CexZr1-xO2The molded alumina carrier is mixed, impregnated, dried and roasted to obtain the molded catalyst.
7. The method according to any one of claims 1 to 6, wherein the cerium salt is a water-soluble cerium salt, preferably selected from at least one of cerium nitrate, ammonium cerium nitrate, cerium sulfate and cerium chloride, more preferably from cerium nitrate; and/or
The zirconium salt is a water-soluble zirconium salt, preferably at least one selected from zirconium oxychloride, zirconium chloride, zirconium sulfate and zirconium nitrate, more preferably selected from zirconium nitrate; and/or
The copper salt is a water-soluble copper salt, preferably at least one selected from copper nitrate, copper chloride and copper sulfate, and more preferably selected from copper nitrate; and/or
The alkaline solution is selected from ammonia and/or sodium carbonate solution.
8. The method according to any one of claims 1-7, wherein the off-gas comprises methane, carbon monoxide and hydrogen, wherein the volume ratio of methane, carbon monoxide and hydrogen is (12-18): (2-5):1, more preferably (15-17): (2-4): 1.
9. The process of any one of claims 1 to 8, wherein the contacting is carried out at a total reaction space velocity of from 10 to 200L-h-1·g-1Preferably 13 to 150 L.h-1·g-1(ii) a The contact temperature is 200-700 ℃, preferably 350-600 ℃.
10. Use of a process according to any one of claims 1 to 9 in the oxidative coupling of methane to ethylene.
CN202010962915.6A 2020-09-14 2020-09-14 Method for recovering methane from ethylene waste gas produced in preparation of ethylene through oxidative coupling of methane Pending CN114181033A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010962915.6A CN114181033A (en) 2020-09-14 2020-09-14 Method for recovering methane from ethylene waste gas produced in preparation of ethylene through oxidative coupling of methane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010962915.6A CN114181033A (en) 2020-09-14 2020-09-14 Method for recovering methane from ethylene waste gas produced in preparation of ethylene through oxidative coupling of methane

Publications (1)

Publication Number Publication Date
CN114181033A true CN114181033A (en) 2022-03-15

Family

ID=80539043

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010962915.6A Pending CN114181033A (en) 2020-09-14 2020-09-14 Method for recovering methane from ethylene waste gas produced in preparation of ethylene through oxidative coupling of methane

Country Status (1)

Country Link
CN (1) CN114181033A (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0021736A2 (en) * 1979-06-27 1981-01-07 Imperial Chemical Industries Plc Catalytic process involving carbon monoxide and hydrogen
CN102309965A (en) * 2010-06-25 2012-01-11 中国石油化工股份有限公司 Cu-based catalyst for removing trace gas impurity as well as preparation method and application thereof
DE102012215723A1 (en) * 2012-09-05 2014-05-15 Leibniz-Institut Für Katalyse E.V. An Der Universität Rostock Producing hydrocarbons from methane, comprises reacting methane with oxygen in the presence of a catalyst 1 in a product gas mixture, and contacting the product mixture with hydrogen in the presence of a catalyst 2 without prior separation
CN103949249A (en) * 2014-04-11 2014-07-30 浙江大学 Catalyst used for gas-fired boiler carbon monoxide selective reduction of nitrogen oxides, and preparation method thereof
CN105013484A (en) * 2014-04-15 2015-11-04 中国石化扬子石油化工有限公司 Carbon-alumina supported copper oxide catalyst, preparation method and applications thereof
CN107540511A (en) * 2016-06-24 2018-01-05 中国石油化工股份有限公司 It is a kind of that the method that methane is reclaimed in ethene waste gas is prepared from methane oxidation coupling
CN107540512A (en) * 2016-06-24 2018-01-05 中国石油化工股份有限公司 The method and its application that methane is reclaimed in ethene waste gas are prepared from methane oxidation coupling
CN109675543A (en) * 2018-12-17 2019-04-26 新地能源工程技术有限公司 A kind of sepiolite-alumina composite carrier and the high temperature sintering resistant type methanation catalyst using it
CN109731574A (en) * 2018-06-29 2019-05-10 光大水务（深圳）有限公司 A kind of preparation method of catalyst complex carrier, the catalyst based on the carrier and catalyst

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0021736A2 (en) * 1979-06-27 1981-01-07 Imperial Chemical Industries Plc Catalytic process involving carbon monoxide and hydrogen
CN102309965A (en) * 2010-06-25 2012-01-11 中国石油化工股份有限公司 Cu-based catalyst for removing trace gas impurity as well as preparation method and application thereof
DE102012215723A1 (en) * 2012-09-05 2014-05-15 Leibniz-Institut Für Katalyse E.V. An Der Universität Rostock Producing hydrocarbons from methane, comprises reacting methane with oxygen in the presence of a catalyst 1 in a product gas mixture, and contacting the product mixture with hydrogen in the presence of a catalyst 2 without prior separation
CN103949249A (en) * 2014-04-11 2014-07-30 浙江大学 Catalyst used for gas-fired boiler carbon monoxide selective reduction of nitrogen oxides, and preparation method thereof
CN105013484A (en) * 2014-04-15 2015-11-04 中国石化扬子石油化工有限公司 Carbon-alumina supported copper oxide catalyst, preparation method and applications thereof
CN107540511A (en) * 2016-06-24 2018-01-05 中国石油化工股份有限公司 It is a kind of that the method that methane is reclaimed in ethene waste gas is prepared from methane oxidation coupling
CN107540512A (en) * 2016-06-24 2018-01-05 中国石油化工股份有限公司 The method and its application that methane is reclaimed in ethene waste gas are prepared from methane oxidation coupling
CN109731574A (en) * 2018-06-29 2019-05-10 光大水务（深圳）有限公司 A kind of preparation method of catalyst complex carrier, the catalyst based on the carrier and catalyst
CN109675543A (en) * 2018-12-17 2019-04-26 新地能源工程技术有限公司 A kind of sepiolite-alumina composite carrier and the high temperature sintering resistant type methanation catalyst using it

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
王永刚 等: "《煤化工工艺学》", vol. 1, 30 September 2014, 中国矿业大学出版社, pages: 338 *
肖钢等: "《煤制天然气技术》", vol. 1, 28 February 2017, 武汉大学出版社, pages: 98 *
郑水林 等: "《粉体表面改性的（第四版）》", vol. 4, 30 June 2019, 中国建材工业出版社, pages: 233 - 234 *

Similar Documents

Publication Publication Date Title
JPS62503101A (en) Methods and catalysts for the conversion of methane
CN107540511B (en) Method for recovering methane from ethylene waste gas produced by oxidative coupling of methane
CN107540512B (en) Method for recovering methane from ethylene waste gas produced in preparation of ethylene through oxidative coupling of methane and application of method
CN111229263A (en) Hydroxyapatite-based catalyst, preparation and application thereof
CN111229265B (en) Metal modified hydroxyapatite catalyst and preparation and application thereof
CN109535173B (en) Method for catalytically synthesizing biotin by using high-activity palladium-carbon catalyst
CN107552056B (en) Catalyst for preparing carbon monoxide by carbon dioxide hydrogenation, preparation method and application thereof
CN111204709A (en) Water-gas shift reaction method and catalyst thereof
CN108435171A (en) The preparation method and a kind of method of selective catalytic oxidation glycerine DHA of a kind of bimetallic Pt-Bi catalyst
CN111229266A (en) Supported hydroxyapatite catalyst and preparation and application thereof
CN111282563A (en) Mn-Ce-Zr catalyst and preparation method and application thereof
CN111282576A (en) Fe-Ce-Zr catalyst and preparation method and application thereof
JP2002511017A (en) Use of Ce / Zr mixed oxide phase for the production of styrene by dehydrogenation of ethylbenzene
CN108097286B (en) Catalyst for preparing acrylic acid and methyl acrylate
CN114181033A (en) Method for recovering methane from ethylene waste gas produced in preparation of ethylene through oxidative coupling of methane
US20120259132A1 (en) Process to prepare an ethanol-derivate
CN109926066A (en) Double auxiliary agent nano Pd catalyst Preparation method and uses
CN110801828A (en) Catalyst for preparing olefin by oxidative dehydrogenation of ethane chemical chain and application of catalyst in oxidative dehydrogenation reaction of ethane
CN111036284B (en) Catalyst, preparation method thereof and method for preparing light olefins from synthesis gas
CN114931950A (en) Carrier and preparation method thereof, catalyst and preparation method and application thereof
CN1073891A (en) Methane couple catalyst for making ethylene and process
CN114292167A (en) Preparation method of vanillin
CN111348991B (en) Method for producing vinyl ether
CN109433200B (en) Low-load noble metal catalyst for reducing dilute nitric acid, preparation and application
CN114181031A (en) Method for recovering methane from ethylene waste gas produced by oxidative coupling of methane

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