CN114588952A - Method for regenerating catalyst - Google Patents
Method for regenerating catalyst Download PDFInfo
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- CN114588952A CN114588952A CN202011437813.9A CN202011437813A CN114588952A CN 114588952 A CN114588952 A CN 114588952A CN 202011437813 A CN202011437813 A CN 202011437813A CN 114588952 A CN114588952 A CN 114588952A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 178
- 238000006243 chemical reaction Methods 0.000 claims abstract description 108
- 239000001257 hydrogen Substances 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 150000001336 alkenes Chemical class 0.000 claims abstract description 34
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 238000011069 regeneration method Methods 0.000 claims description 43
- 230000008929 regeneration Effects 0.000 claims description 40
- 239000002808 molecular sieve Substances 0.000 claims description 27
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- ONWIUHATKXRGRY-UADPMFFRSA-N (2r)-6-amino-2-[[(2r)-2-[[(2r)-2-[[(2r)-2-[[(2r)-2-[[(2r)-2-[[(2r,3s)-2-amino-3-hydroxybutanoyl]amino]propanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-3-phenylpropanoyl]amino]-4-methylpentanoyl]amino]-4-methylpentanoyl]amino]-n-[(2r)-1-[[(2r)-1-[[2-[[ Chemical compound C([C@H](C(=O)N[C@H](CC(C)C)C(=O)N[C@H](CC(C)C)C(=O)N[C@H](CCCCN)C(=O)N[C@H](CC(C)C)C(=O)N[C@H](C)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(N)=O)NC(=O)[C@@H](CC=1C=CC(O)=CC=1)NC(=O)[C@@H](C)NC(=O)[C@H](N)[C@H](C)O)C1=CC=CC=C1 ONWIUHATKXRGRY-UADPMFFRSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 239000003245 coal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- QECJIGNJADOMIG-UHFFFAOYSA-N [C].COC Chemical compound [C].COC QECJIGNJADOMIG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- -1 ethylene, propylene Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 description 1
- JGNPSJMNGPUQIW-UHFFFAOYSA-N [C].CC=C Chemical compound [C].CC=C JGNPSJMNGPUQIW-UHFFFAOYSA-N 0.000 description 1
- QOTAEASRCGCJDN-UHFFFAOYSA-N [C].CO Chemical compound [C].CO QOTAEASRCGCJDN-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of regenerating a catalyst is disclosed, the method comprising: after the catalyst is subjected to a reaction of catalyzing hydrogen for preparing olefin from methanol/dimethyl ether, the catalyst is regenerated in situ at the temperature of 200-600 ℃ and the pressure of 1-9MPa in an atmosphere I containing hydrogen.
Description
Technical Field
The invention relates to a method for in-situ regeneration of a catalyst for preparing olefin from methanol in a high-pressure hydrogen environment, belonging to the field of catalysis.
Background
Low-carbon olefins (ethylene, propylene, etc.) are important chemical products and basic raw materials of a large number of important synthetic materials such as plastics, synthetic resins, fibers, etc. It has been thought that the production of ethylene and propylene requires the consumption of a large amount of petroleum. With the continuous development of society, the demand of China for low-carbon olefins is continuously increased, but petroleum resources are increasingly tense, so that the search for an alternative route for producing olefins has very important significance for chemical production, energy safety and the like in China. In view of the current situation of energy structure of 'rich coal and lean oil' in China, the great development of coal chemical industry routes for preparing aromatic hydrocarbon has very important significance.
The Methanol To Olefin (MTO) technology is a prominent representative of the modern coal chemical technology, and opens up a new way for the clean utilization of coal. Representative techniques include UOP/Hydro MTO developed by using SAPO-34 as a catalyst and MTP (methanol to propylene) process developed by Lurgi company by using ZSM-5 molecular sieve. The DMTO technology is developed by a large chemical and physical research institute in China and is successfully applied to the first coal-to-olefin device in the world in 2010.
However, in the reaction of producing olefins from methanol, the catalyst is easily deactivated by carbon deposition, and therefore, in order to ensure the reaction to be continuously carried out, the deactivated catalyst must be regenerated in time.
At present, the oxidation charring is the most common charring method in industrial production China, the regeneration temperature is usually more than 550 ℃, and the catalyst is easy to cause local temperature runaway so as to damage the catalyst structure; on the other hand, the catalyst can also be subjected to steam regeneration, which can prevent carbon deposition from further thickening and cyclizing, but high-temperature steam easily causes dealumination of the catalyst framework, so that the structural change of the catalyst is caused, and the activity of the catalyst is further influenced. In addition, the temperature of the two regeneration methods is higher than the reaction temperature of the methanol-to-olefin.
In recent years, documents report that the catalyst life can be greatly prolonged when the reaction of producing olefins from methanol/dimethyl ether is carried out in a high-pressure hydrogen atmosphere. However, as the reaction proceeds, the catalyst inevitably loses activity. Due to the high pressure of the system and the presence of large amounts of hydrogen, the two regeneration means mentioned above are difficult to adapt to the requirements of catalyst regeneration thereof.
Disclosure of Invention
According to one aspect of the present application, a method of regenerating a catalyst in situ is provided. The method comprises the following steps: after the catalyst is subjected to a reaction of catalyzing high-pressure hydro-methanol/dimethyl ether to prepare olefin, the catalyst is regenerated in situ at the temperature of 200-600 ℃ and the pressure of 1-9MPa in an atmosphere I containing hydrogen.
In one embodiment, it is preferred that the regeneration of the catalyst is carried out under a pressure condition of 3MPa to 5 MPa.
Optionally, the upper limit of the pressure for regeneration of the catalyst is selected from 3Mpa, 4Mpa, 5Mpa or 9 Mpa; the lower limit is selected from 1MPa, 3MPa, 4MPa or 5 MPa.
In a specific embodiment, in the hydrogen-containing atmosphere I, the volume content of hydrogen in the atmosphere I is 0.05% to 100%; preferably, the volume content of the hydrogen in the atmosphere I is 50% to 100%.
In a specific embodiment, the atmosphere I containing hydrogen may contain other gases, preferably at least one of nitrogen and carbon dioxide. Preferably, the atmosphere I containing hydrogen also comprises an inert gas;
the inert gas includes at least one of nitrogen and carbon dioxide.
In one embodiment, the methanol to olefin reaction is carried out in an atmosphere II containing hydrogen at a temperature of 200 ℃ to 600 ℃.
In one embodiment, it is preferred that the methanol/dimethyl ether to olefin reaction is carried out at a temperature of 300 ℃ to 500 ℃.
Optionally, the upper limit of the temperature of the methanol to olefins reaction is selected from 400 ℃, 430 ℃, 450 ℃, 500 ℃, or 600 ℃; the lower limit is selected from 300 deg.C, 400 deg.C, 430 deg.C, 450 deg.C or 500 deg.C.
In a specific embodiment, in the hydrogen-containing atmosphere II, the volume content of hydrogen in the atmosphere II is 0.05% to 100%;
preferably, the volume content of said hydrogen in said atmosphere II is comprised between 50% and 100%;
preferably, the hydrogen-containing atmosphere II further comprises an inert gas;
the inert gas includes at least one of nitrogen and carbon dioxide.
In one embodiment, the catalyst regeneration temperature is from 300 ℃ to 500 ℃.
Optionally, the upper limit of the regeneration temperature of the catalyst is selected from 400 ℃, 430 ℃, 450 ℃, 500 ℃ or 600 ℃; the lower limit is selected from 300 deg.C, 400 deg.C, 430 deg.C, 450 deg.C or 500 deg.C.
In one embodiment, the regeneration temperature of the catalyst is the same as the reaction temperature for preparing the olefin from the methanol/dimethyl ether.
In one embodiment, the methanol/dimethyl ether to olefin reaction is carried out at a pressure of 1Mpa to 9 Mpa.
In one embodiment, the methanol/dimethyl ether to olefin reaction is preferably carried out under a pressure condition of 3Mpa to 5 Mpa.
Optionally, the upper limit of the pressure of the reaction for preparing the olefin from the methanol/dimethyl ether is selected from 3Mpa, 4Mpa, 5Mpa or 9 Mpa; the lower limit is selected from 1MPa, 3MPa, 4MPa or 5 MPa.
In one embodiment, the regeneration pressure of the catalyst is the same as the methanol/dimethyl ether to olefin reaction pressure.
In one embodiment, the regeneration is for a period of time from 1 hour to 100 hours.
Optionally, the time of regeneration is any time of 1 hour, 10 hours, 20 hours, 30 hours, 40 hours, 50 hours, 60 hours, 70 hours, 80 hours, 90 hours, 100 hours, and a range value between any two values.
In one embodiment, the regeneration is preferably for a period of 10 hours to 40 hours.
In a particular embodiment, the space velocity of the hydrogen-containing atmosphere I in the regeneration is between 500mL/g/h and 20000 mL/g/h.
In one embodiment, it is preferred that the space velocity of the hydrogen-containing atmosphere I during the regeneration is from 5000mL/g/h to 10000 mL/g/h.
In one embodiment, it is preferred that the space velocity of the regeneration is any of 500mL/g/h, 5000mL/g/h, 7000mL/g/h, 7500mL/g/h, 10000mL/g/h, 15000mL/g/h, 20000mL/g/h, and a range between any two values.
In one embodiment, the catalyst comprises an acidic molecular sieve.
In one embodiment, it is preferred that the catalyst comprises at least one of an acidic molecular sieve having RHO, CHA, AEI, MFI, MOR, FAU, configuration.
In one embodiment, it is more preferred that the catalyst comprises at least one of a DNL-6 molecular sieve, a SAPO-34 molecular sieve, a SAPO-18 molecular sieve, a ZSM-5 molecular sieve, or a MOR molecular sieve.
The beneficial effects that this application can produce include:
(1) compared with the prior art, the method provided by the application can regenerate the catalyst in situ under the condition of not changing the reaction pressure and the reaction temperature in the reaction of preparing the olefin from the methanol/dimethyl ether under the high-pressure hydrogen-containing atmosphere, reduces the operation steps and does not need to raise the temperature to reach the regeneration temperature, is beneficial to operation and reduces the energy consumption required by temperature rise and temperature reduction compared with the traditional regeneration method.
(2) Compared with the prior art, the method provided by the application has the advantages that in the reaction of preparing the olefin from the methanol/dimethyl ether under the high-pressure hydrogen-containing atmosphere, the regeneration temperature is lower, and the phenomenon that the catalyst structure is damaged due to local temperature runaway of the catalyst can be avoided compared with the traditional regeneration method.
(3) Compared with the prior art, in the reaction of preparing olefin from methanol/dimethyl ether under the atmosphere of high pressure and hydrogen, the regenerated catalyst eliminates the condensed ring aromatic hydrocarbon but retains the monocyclic aromatic hydrocarbon, which is beneficial to improving the selectivity of the low-carbon olefin.
Detailed Description
The analytical methods and conversion, selectivity in the examples were calculated as follows:
automated analysis was performed using an Agilent7890 gas chromatograph with a gas autosampler, TCD detector connected to a TDX-1 packed column, and FID detector connected to a Plot-Q capillary column.
In some embodiments of the invention, both conversion and selectivity are calculated based on carbon moles:
conversion of methanol or dimethyl ether [ (moles of methanol or dimethyl ether carbon in feed) - (moles of methanol or dimethyl ether carbon in discharge) ]/(moles of methanol carbon in feed) × (100%)
Ethylene selectivity (moles of ethylene carbon in the output) ÷ (moles of all products carbon in the output) × (100%)
Propylene selectivity (moles of propylene carbon in the output) ÷ (moles of all products carbon in the output) × (100%)
C2-C4Selectivity to olefin (C in the discharge)2-C4Carbon mole of (c) ÷ (carbon moles of all products in the discharge) × (100%)
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were purchased commercially, wherein DNL-6 molecular sieves, SAPO-34 molecular sieves, SAPO-18 molecular sieves, ZSM-5 molecular sieves, and MOR molecular sieves were purchased from catalyst factories of southern Kayaku university.
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Catalyst preparation and Performance testing
Example 1
5g of the # 1 catalyst SAPO-34 molecular sieve was packed into a stainless steel reaction tube having an inner diameter of 16mm, activated with 100ml/min of nitrogen at 450 ℃ for 4 hours, and then adjusted to the reaction temperature. Carrying out methanol-to-olefin reaction under a high-pressure hydrogen environment, wherein the reaction conditions are as follows: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 3MPa, and the methanol mass space velocity (WHSV) is 2h-1Hydrogen gas: methanol (H)2MeOH) molar ratio of 10: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1. After the activity of the catalyst is reduced after the reaction is carried out for a period of time, stopping introducing the methanol at the original temperature and pressure, regenerating in a hydrogen environment, introducing the methanol again after the first regeneration is finished, and carrying out the reaction for preparing the olefin by the methanol again. The results of the catalyst reaction and the regeneration results are shown in Table 1.
TABLE 1 results of the catalytic reaction
Example 2
5g of SAPO-34 molecular sieve as the # 1 catalyst is filled into a stainless steel reaction tube with the inner diameter of 16mm, and 100ml of the stainless steel reaction tube is usedPermin Nitrogen was activated at 450 ℃ for 4h and subsequently adjusted to the reaction temperature. The reaction for preparing the olefin from the dimethyl ether is carried out in a high-pressure hydrogen environment, and the reaction conditions are as follows: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 3MPa, and the mass space velocity (WHSV) of the dimethyl ether is 1h-1Hydrogen gas: dimethyl ether (H)2DME) in a molar ratio of 20: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1. After the catalyst activity is reduced after the reaction is carried out for a period of time, the introduction of dimethyl ether is stopped under the original temperature and pressure, the regeneration is carried out in a hydrogen environment, the dimethyl ether is introduced again after the first regeneration is finished, and the reaction for preparing the olefin from the dimethyl ether is carried out again. The results of the catalyst reaction and the regeneration results are shown in Table 2.
TABLE 2 results of the catalytic reaction
Example 3
5g of the # 2 catalyst SAPO-18 molecular sieve was packed into a stainless steel reaction tube having an inner diameter of 16mm, activated with 100ml/min of nitrogen at 450 ℃ for 4 hours, and then adjusted to the reaction temperature. Carrying out methanol-to-olefin reaction under a high-pressure hydrogen environment, wherein the reaction conditions are as follows: the reaction temperature (T) is 430 ℃, the reaction pressure (P) is 4MPa, and the methanol mass space velocity (WHSV) is 2h-1Hydrogen gas: methanol (H)2MeOH) molar ratio of 10: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1. After the activity of the catalyst is reduced after the reaction is carried out for a period of time, stopping introducing the methanol at the original temperature and pressure, regenerating in a hydrogen environment, introducing the methanol again after the first regeneration is finished, and carrying out the reaction for preparing the olefin from the methanol again. The results of the catalyst reaction and the regeneration results are shown in Table 3.
TABLE 3 results of the catalytic reaction
Example 4
Catalyzing 5g of No. 3The agent H-ZSM-5 molecular sieve was filled in a stainless steel reaction tube having an inner diameter of 16mm, activated with 100ml/min of nitrogen at 450 ℃ for 4 hours, and then adjusted to the reaction temperature. Carrying out methanol-to-olefin reaction under a high-pressure hydrogen environment, wherein the reaction conditions are as follows: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 4MPa, and the methanol mass space velocity (WHSV) is 2h-1Hydrogen gas: nitrogen gas: methanol (H)2:N2MeOH) molar ratio of 10: 1. after the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1. After the activity of the catalyst is reduced after the reaction is carried out for a period of time, stopping introducing the methanol at the original temperature and pressure, regenerating in a hydrogen and nitrogen environment, introducing the methanol again after the first regeneration is finished, and carrying out the reaction for preparing the olefin from the methanol again. The results of the catalyst reaction and the regeneration results are shown in Table 4.
TABLE 4 results of catalytic reaction
Example 5
5g of the # 1 catalyst SAPO-34 molecular sieve was packed into a stainless steel reaction tube having an inner diameter of 16mm, activated with 100ml/min of nitrogen at 450 ℃ for 4 hours, and then adjusted to the reaction temperature. Carrying out methanol-to-olefin reaction under a high-pressure hydrogen environment, wherein the reaction conditions are as follows: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 3MPa, and the methanol mass space velocity (WHSV) is 2h-1Hydrogen gas: carbon dioxide: methanol (H)2:CO2MeOH) molar ratio of 10:10: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1. After the activity of the catalyst is reduced after the reaction is carried out for a period of time, stopping introducing the methanol at the original temperature and pressure, regenerating in the presence of hydrogen and carbon dioxide, introducing the methanol again after the first regeneration is finished, and carrying out the reaction for preparing the olefin from the methanol again. The results of the catalyst reaction and the regeneration results are shown in Table 5.
TABLE 5 results of catalytic reaction
Example 6
5g of the # 1 catalyst SAPO-34 molecular sieve was packed into a stainless steel reaction tube having an inner diameter of 16mm, activated with 100ml/min of nitrogen at 450 ℃ for 4 hours, and then adjusted to the reaction temperature. Carrying out methanol-to-olefin reaction under a high-pressure hydrogen environment, wherein the reaction conditions are as follows: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 5MPa, and the methanol mass space velocity (WHSV) is 2h-1Hydrogen gas: methanol (H)2MeOH) molar ratio of 10: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1. After the activity of the catalyst is reduced after the reaction is carried out for a period of time, stopping introducing the methanol at the original temperature and pressure, regenerating in a hydrogen environment, introducing the methanol again after the first regeneration is finished, and carrying out the reaction for preparing the olefin from the methanol again. The results of the catalyst reaction and the regeneration results are shown in Table 6.
TABLE 6 results of catalytic reactions
Example 7
5g of the # 1 catalyst SAPO-34 molecular sieve was packed into a stainless steel reaction tube having an inner diameter of 16mm, activated with 100ml/min of nitrogen at 450 ℃ for 4 hours, and then adjusted to the reaction temperature. Carrying out methanol-to-olefin reaction under a high-pressure hydrogen environment, wherein the reaction conditions are as follows: the reaction temperature (T) is 450 ℃, the reaction pressure (P) is 4MPa, and the methanol mass space velocity (WHSV) is 2h-1Hydrogen gas: methanol (H)2MeOH) molar ratio of 10: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1. After the activity of the catalyst is reduced after the reaction is carried out for a period of time, stopping introducing the methanol at the original temperature and pressure, regenerating in a hydrogen environment, introducing the methanol again after the first regeneration is finished, and carrying out the reaction for preparing the olefin from the methanol again. So circulated, the catalystThe results of the reaction and the regeneration are shown in Table 7.
TABLE 7 results of catalytic reaction
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method of regenerating a catalyst, the method comprising:
after the catalyst is subjected to a reaction for preparing olefin by catalyzing methanol/dimethyl ether, the catalyst is regenerated in situ at the temperature of 200-600 ℃ and the pressure of 1-9MPa in an atmosphere I containing hydrogen.
2. The method according to claim 1, wherein in the hydrogen-containing atmosphere I, the volume content of hydrogen in the atmosphere I is 0.05% to 100%;
preferably, the volume content of said hydrogen in said atmosphere I is comprised between 50% and 100%;
preferably, the atmosphere I containing hydrogen also comprises an inert gas;
the inert gas includes at least one of nitrogen and carbon dioxide.
3. The method according to claim 1, wherein the reaction for preparing olefin from methanol/dimethyl ether is carried out in an atmosphere II containing hydrogen at a temperature of 200 ℃ to 600 ℃;
preferably, the reaction for preparing the olefin from the methanol/dimethyl ether is carried out at the temperature of 300-500 ℃.
4. The method according to claim 3, wherein in the hydrogen-containing atmosphere II, the volume content of hydrogen in the atmosphere II is 0.05-100%;
preferably, the volume content of said hydrogen in said atmosphere II is comprised between 50% and 100%;
preferably, the hydrogen-containing atmosphere II further comprises an inert gas;
the inert gas includes at least one of nitrogen and carbon dioxide.
5. The method of claim 1, wherein the regeneration temperature of the catalyst is the same as the temperature of the methanol/dimethyl ether to olefin reaction.
6. The method of claim 1, wherein the methanol/dimethyl ether to olefin reaction is performed under a pressure of 1Mpa to 9 Mpa;
preferably, the reaction for preparing the olefin from the methanol/dimethyl ether is carried out under the pressure condition of 3MPa to 5 MPa.
7. The method of claim 1, wherein the regeneration pressure of the catalyst is the same as the pressure of the methanol/dimethyl ether to olefin reaction.
8. The method of claim 1, wherein the regeneration is for a period of time of 1 hour to 100 hours;
preferably, the regeneration time is 10 hours to 30 hours.
9. The process according to claim 1, characterized in that in the regeneration, the space velocity of the atmosphere I containing hydrogen is from 500mL/g/h to 20000 mL/g/h;
preferably, the space velocity of the atmosphere I containing hydrogen in the regeneration is 5000mL/g/h to 10000 mL/g/h.
10. The process of claim 1 wherein the catalyst comprises an acidic molecular sieve;
preferably, the catalyst contains at least one of acidic molecular sieves having RHO, CHA, AEI, MFI, MOR, FAU, configuration;
more preferably, the catalyst contains at least one of DNL-6 molecular sieve, SAPO-34 molecular sieve, SAPO-18 molecular sieve, ZSM-5 molecular sieve and MOR molecular sieve.
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