CN112705042A - Method for removing acetylene and ethylene in natural gas cracking tail gas - Google Patents
Method for removing acetylene and ethylene in natural gas cracking tail gas Download PDFInfo
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- 239000005977 Ethylene Substances 0.000 title claims abstract description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000003345 natural gas Substances 0.000 title claims abstract description 25
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- 239000002131 composite material Substances 0.000 claims abstract description 42
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
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- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 238000007872 degassing Methods 0.000 claims description 11
- 238000005070 sampling Methods 0.000 claims description 9
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- 239000002245 particle Substances 0.000 claims description 7
- 239000012798 spherical particle Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 238000001514 detection method Methods 0.000 abstract description 3
- 230000009972 noncorrosive effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
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- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 6
- 238000005273 aeration Methods 0.000 description 5
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 239000010742 number 1 fuel oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
Abstract
The invention provides a method for removing acetylene and ethylene in natural gas cracking tail gas, which comprises the following steps: the airspeed is 3000-6000h‑1Preheating the tail gas to 140-180 ℃, introducing the tail gas into a composite bed hydrogenation reactor, and removing acetylene and ethylene in the composite bed hydrogenation reactor by using a palladium or copper catalyst as a hydrogenation catalyst. The method has simple process flow, convenient operation and basically no three-waste discharge; the catalyst adopted by the method is non-toxic and non-corrosive, and can be recycled; the method has good effect of removing trace acetylene and ethylene in the acetylene tail gas, the content of acetylene at the outlet of the hydrogenation reactor of the composite bed after hydroconversion is less than or equal to 5ppm, and the content of ethylene is less than or equal to 100ppm, thereby conforming to the process technologyThe indexes are required, particularly in the 8 th to 10 th days of the initial removal period, the contents of acetylene and ethylene at the outlet of the reactor are both lower than the detection lower limit value, and the contents of acetylene and ethylene are both less than 1 ppm.
Description
Technical Field
The invention belongs to the technology for preparing acetylene by natural gas cracking, and particularly relates to a method for removing acetylene and ethylene in natural gas cracking tail gas.
Background
In the process of producing acetylene by using natural gas as a raw material and adopting a partial oxidation method, a large amount of CO and H can be generated2The tail gas (natural gas cracking tail gas) is a high-quality raw material for synthesizing methanol, but contains a small amount of unsaturated hydrocarbons such as acetylene, ethylene and the like, and needs to be removed in advance, otherwise the unsaturated hydrocarbons are easy to generate polymers in subsequent reactions and deposit on the surface of the catalyst, so that the catalyst is inactivated.
At present, trace amounts of ethylene, acetylene and oxygen in natural gas cracking tail gas are converted into carbon dioxide and water through partial oxidation and then enter a synthesis system to synthesize methanol, and are converted into ethane through hydrogenation and then enter a synthesis reaction system to synthesize methanol. However, the method for removing trace acetylene ethylene by using palladium-containing and copper-containing catalysts through the first hydrogenation reactor and the second hydrogenation reactor at home and abroad only has a good effect on removing trace acetylene (the acetylene content in the tail gas can reach an index less than 5 ppm) and has a poor effect on removing ethylene, although the ethylene content in the tail gas at the initial removal stage (within one month) can reach 20ppm, the ethylene content in the tail gas gradually increases to 1000ppm after three months along with the prolonging of the service life, the ethylene cannot be removed basically after one year, and the ethylene content reaches about 2500 ppm.
In addition, document CN102218323B discloses an application of an unsaturated hydrocarbon hydrogenation catalyst, which includes a carrier, an active component and an auxiliary agent, wherein the active component is a mixture of nickel oxide and other metal oxides, the auxiliary agent is at least two of magnesium oxide, lanthanum oxide and cerium oxide, the weight percentage content of nickel oxide in the unsaturated hydrocarbon hydrogenation catalyst is 5% to 15%, the weight percentage content of other metal oxides is 1% to 10%, the weight percentage content of the auxiliary agent is 1% to 10%, and the balance is the carrier; the other metal oxide is one or more of molybdenum oxide, cobalt oxide and iron oxide, and the application is the application of an unsaturated hydrocarbon hydrogenation catalyst in hydrogenating unsaturated hydrocarbons in tail gas of the indirect coal oil industry into saturated hydrocarbons in the indirect coal oil industry. However, its effect on trace ethylene removal is still not good enough.
Disclosure of Invention
The invention aims to provide a method for removing acetylene and ethylene in natural gas cracking tail gas, which has a good removing effect on trace acetylene and ethylene in the natural gas cracking tail gas.
In order to achieve the above object, the present invention adopts the following technical solutions.
The method for removing the ethylene in the natural gas cracking tail gas comprises the following steps: the airspeed is 3000-6000h-1Preheating the tail gas to 140-180 ℃, introducing the tail gas into a composite bed hydrogenation reactor, and removing acetylene and ethylene in the composite bed hydrogenation reactor by using a palladium or copper catalyst as a hydrogenation catalyst.
The method for removing acetylene and ethylene in natural gas cracking tail gas comprises the following steps: the airspeed is 3000-6000h-1Preheating the tail gas to 140-180 ℃, introducing the tail gas into a composite bed hydrogenation reactor, and removing acetylene and ethylene in the composite bed hydrogenation reactor by using a palladium and/or copper catalyst as a hydrogenation catalyst.
Preferably, the space velocity of the tail gas is controlled to be 4000-5000 h-1。
Preferably, the temperature of the tail gas introduced into the hydrogenation reactor of the composite bed is controlled to be 150-170 ℃.
Preferably, the flow rate of the tail gas is controlled to be 30-60m3/h。
In order to further improve the removal effect of acetylene ethylene in tail gas, the components of the palladium catalyst comprise an alumina carrier and an active component palladium (Pd), wherein the mass ratio of the active component palladium is 0.04-0.08 percent of the total amount of the hydrogenation catalyst, and the balance is the alumina carrier; the copper catalyst comprises copper oxide, zinc oxide and an alumina carrier, wherein the mass ratio of the copper oxide is not less than 50% of the total amount of the hydrogenation catalyst, the mass ratio of the zinc oxide is not less than 20% of the total amount of the hydrogenation catalyst, and the balance is the alumina carrier.
Preferably, the hydrogenation catalyst is spherical particles with the particle size of phi 3-5mm and the bulk density of 0.8 +/-0.05 Kg/L.
As a preferred scheme of the invention, the method for removing acetylene and ethylene in the natural gas cracking tail gas comprises the following steps:
closing the steam pipeline, opening the tail gas pipeline, and regulating the flow of the tail gas introduced into the heater to 30-60m3The air speed of the exhaust gas is adjusted to 3000-6000h-1；
Then opening a steam pipeline, introducing steam into a heater to heat the tail gas, and controlling the temperature of the tail gas entering the composite reactor to be 140-180 ℃; the tail gas is subjected to hydrogenation catalytic reaction in the composite reactor to remove acetylene and ethylene.
In order to simplify the process flow and the operation flow, the method for removing acetylene and ethylene in the natural gas cracking tail gas is carried out by adopting a degassing system, and the degassing system comprises: the inlet of the heater is connected with a steam pipeline and a tail gas pipeline, the outlet of the heater is connected with the inlet of the composite bed hydrogenation reactor through a pipeline, and the outlet of the composite bed hydrogenation reactor is connected with a methanol synthesis system through a pipeline; the steam pipeline and the tail gas pipeline are respectively provided with a shutoff valve, a pipeline between the heater and the composite bed hydrogenation reactor is provided with a temperature regulating valve, a flow regulating valve, a pressure gauge, a raw material gas sampling port and a shutoff valve, and a pipeline at the outlet of the composite bed hydrogenation reactor is provided with a purified gas sampling port and a low discharge port.
Has the advantages that: the method has simple process flow, convenient operation and basically no three-waste discharge; the catalyst adopted by the method is non-toxic and non-corrosive, and can be recycled; the method has good removal effect on trace acetylene and ethylene in the acetylene tail gas, the content of acetylene at the outlet of the hydrogenation reactor of the composite bed after hydroconversion is less than or equal to 5ppm, the content of ethylene is less than or equal to 100ppm, the method meets the technical index requirements of the process, and particularly, the content of acetylene and ethylene at the outlet of the reactor is lower than the lower detection limit value and the content of acetylene and ethylene is less than 1ppm in the 8 th to 10 th days of the initial removal period.
Drawings
FIG. 1 is a schematic diagram of an apparatus for removing trace acetylene and ethylene from a natural gas cracking tail gas in an embodiment.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific embodiments, but the following embodiments are only used for understanding the principle of the present invention and the core idea thereof, and do not limit the scope of the present invention. It should be noted that modifications to the invention as described herein, which do not depart from the principles of the invention, are intended to be within the scope of the claims which follow.
Example 1
The method for removing acetylene and ethylene in natural gas cracking tail gas is carried out by adopting a degassing system, and the degassing system is shown in figure 1 and comprises the following steps: the inlet of the heater 5 is connected with the steam pipeline 3 and the tail gas pipeline 1, the outlet of the heater 5 is connected with the inlet of the composite bed hydrogenation reactor 12 through a pipeline, and the outlet of the composite bed hydrogenation reactor 12 is connected with the methanol synthesis system through a pipeline; the steam pipeline 3 is provided with a shut-off valve 4, the tail gas pipeline 1 is provided with a shut-off valve 2, a pipeline between the heater 5 and the composite bed hydrogenation reactor 12 is provided with a temperature regulating valve 7, a flow regulating valve 8, a pressure gauge 6, a raw material gas sampling pipe 10 and a shut-off valve 11, the raw material gas sampling pipe 10 is provided with a valve 9, a pipeline 18 at the outlet of the composite bed hydrogenation reactor 12 is provided with a purified gas sampling pipe 16 and a low discharge port, the purified gas sampling pipe 16 is provided with a valve 15, the low discharge port is connected with a short pipe 14 of the valve 13, and the pipeline 18 at the outlet of the composite bed hydrogenation reactor 12 is also provided with a shut-off valve 17.
In the embodiment, acetylene in the natural gas cracking tail gas is removed,The method for preparing the ethylene comprises the following steps: before aeration, 10L of hydrogenation catalyst is added into a composite bed hydrogenation reactor 12 (the mass of an active component palladium (Pd) of the hydrogenation catalyst accounts for 0.04-0.08%, specifically, the mass of the active component palladium (Pd) accounts for the total mass of the hydrogenation catalyst, the balance is an alumina carrier, the hydrogen catalyst is spherical particles, the particle size of the hydrogen catalyst is phi 3-5mm, and the bulk density is 0.8 +/-0.05 Kg/L); firstly, the valve 4 on the steam pipeline 3 is closed, the valve 2, the valve 11 and the valve 13 on the tail gas pipeline 1 are opened, and the flow of the tail gas introduced into the heater 5 is adjusted to be 30m3The space velocity is 3000h-1(ii) a Then opening a valve 4 of a steam inlet pipeline 3, introducing steam into a heater 5 to heat the tail gas, and adjusting the tail gas at the outlet of the heater 5 to ensure that the temperature of the tail gas entering a composite bed hydrogenation reactor 12 is 130 ℃; and increased by 10 ℃ every 2 days.
Example 2
The method for removing acetylene and ethylene in the natural gas cracking tail gas in the embodiment adopts the degassing system in the embodiment 1, and comprises the following steps: before aeration, adding 10L of hydrogenation catalyst (the active component of the hydrogenation catalyst is palladium (Pd) with the mass ratio of 0.04-0.08%, the rest is alumina carrier, the hydrogen catalyst is spherical particles with the particle size of phi 3-5mm and the bulk density of 0.8 +/-0.05 Kg/L) into a composite bed hydrogenation reactor 12; firstly, the valve 4 on the steam pipeline 3 is closed, the valve 2, the valve 11 and the valve 13 on the tail gas pipeline 1 are opened, and the flow of the tail gas introduced into the heater 5 is adjusted to be 40m3The space velocity is 4000h-1(ii) a Then opening a valve 4 of a steam inlet pipeline 3, introducing steam into a heater 5 to heat the tail gas, and adjusting the tail gas at the outlet of the heater 5 to ensure that the temperature of the tail gas entering a composite bed hydrogenation reactor 12 is 130 ℃; and increased by 10 ℃ every 2 days.
Example 3
The method for removing acetylene and ethylene in the natural gas cracking tail gas in the embodiment adopts the degassing system in the embodiment 1, and comprises the following steps: before aeration, 10L of hydrogenation catalyst (the active component of the hydrogenation catalyst is palladium (Pd) with the mass ratio of 0.04-0.08%, the rest is alumina carrier, the hydrogen catalyst is spherical particles with the particle size of phi 3-5mm and the bulk density of 0.8 +/-0.05 Kg/L) is added into a composite bed hydrogenation reactor 12; the valve 4 on the steam pipeline 3 is closed and openedA valve 2, a valve 11 and a valve 13 are arranged on the tail gas pipeline 1, and the flow of the tail gas introduced into the heater 5 is adjusted to be 50m3The space velocity is 5000h-1(ii) a Then opening a valve 4 of a steam inlet pipeline 3, introducing steam into a heater 5 to heat the tail gas, and adjusting the tail gas at the outlet of the heater 5 to ensure that the temperature of the tail gas entering a composite bed hydrogenation reactor 12 is 130 ℃; and increased by 10 ℃ every 2 days.
Example 4
The method for removing acetylene and ethylene in the natural gas cracking tail gas in the embodiment adopts the degassing system in the embodiment 1, and comprises the following steps: before aeration, 10L of hydrogenation catalyst (the active component palladium (Pd) of the hydrogenation catalyst accounts for 0.04-0.08% by mass, the balance is alumina carrier, the hydrogen catalyst is spherical particles, the particle size is phi 3-5mm, and the bulk density is 0.8 +/-0.05 Kg/L) is added into a composite bed hydrogenation reactor 12; firstly, the valve 4 on the steam pipeline 3 is closed, the valve 2, the valve 11 and the valve 13 on the tail gas pipeline 1 are opened, and the flow of the tail gas introduced into the heater 5 is adjusted to be 60m3The space velocity is 6000h-1(ii) a Then opening a valve 4 of a steam inlet pipeline 3, introducing steam into a heater 5 to heat the tail gas, and adjusting the tail gas at the outlet of the heater 5 to ensure that the temperature of the tail gas entering a composite bed hydrogenation reactor 12 is 130 ℃; and increased by 10 ℃ every 2 days.
Example 5
In this embodiment, the method for removing ethylene from natural gas cracking tail gas is performed by using the degassing system in embodiment 1, and includes the steps of: before aeration, 10L of hydrogenation catalyst (the active component of the hydrogenation catalyst is palladium (Pd) with the mass ratio of 0.04-0.08%, the rest is alumina carrier, the hydrogen catalyst is spherical particles with the particle size of phi 3-5mm and the bulk density of 0.8 +/-0.05 Kg/L) is added into a composite bed hydrogenation reactor 12; firstly, closing the valve 4 on the steam pipeline 3, opening the valve 2, the valve 11 and the valve 13 on the tail gas pipeline 1, and adjusting the flow of the tail gas introduced into the heater 5 to be 30-60m3The air speed is 3000-6000h-1(ii) a Then opening a valve 4 of a steam inlet pipeline 3, introducing steam into a heater 5 to heat the tail gas, and adjusting the tail gas at the outlet of the heater 5 to ensure that the temperature of the tail gas entering a composite bed hydrogenation reactor 12 is 130 ℃; and increased by 10 ℃ every 2 days.
In the process of removing acetylene and ethylene from the natural gas cracking tail gas, the contents of acetylene and ethylene at the inlet and the outlet of the hydrogenation reactor of the composite bed were sampled and analyzed from the sampling ports of the degassing system in example 1 and example 4, and the results are shown in table 1. The method for measuring the content of trace acetylene ethylene in the tail gas adopts a gas chromatography, and specifically comprises the following steps: the instrument adopts a GC-14B gas chromatograph or other instruments with the same performance, the detector is a hydrogen flame ionization detector, the chromatographic column is a Porapak N column, and the size and the material of a column tube are
Stainless steel; the operating conditions were: the temperature of the vaporizing chamber is 125 ℃, the temperature of the column box is 100 ℃, the temperature of the detector is 130 ℃ and the carrier gas (N)2) The flow rate is 40mL/min, the hydrogen flow rate is 40mL/min, the air flow rate is 400mL/min, and the sample injection amount is 1.5 mL; the gas chromatography quantitative method adopts an external standard method, and the measuring method of the correction factor comprises the following steps: after the operation conditions of each instrument are stable, feeding samples respectively, saturating the chromatographic column by feeding the samples for the first time, continuously feeding the samples for two times, measuring peak areas, calculating an average value, and calculating a correction factor.
TABLE 1 ethylene and acetylene content measurement results
As can be seen from table 1, the method of the present invention can remove trace amounts of acetylene and ethylene from the natural gas cracking tail gas, and the method of examples 1 to 4 is adopted to remove trace amounts of acetylene and ethylene from the tail gas, so that the removal effect is good, the acetylene content at the outlet of the composite bed hydrogenation reactor after hydroconversion is less than or equal to 5ppm, and the ethylene content is less than or equal to 100ppm, which meet the requirements of technical indexes of the process, and especially in the 8 th to 10 th days of the initial removal period, the acetylene and ethylene contents at the outlet of the reactor are both lower than the lower detection limit, and the acetylene and ethylene contents are both less than 1.
Claims (10)
1. The method for removing ethylene in natural gas cracking tail gas is characterized by comprising the following steps: the airspeed is 3000-6000h-1Preheating the tail gas to 140-180 ℃ and then introducing the tail gasIn the composite bed hydrogenation reactor, palladium or copper catalyst is used as hydrogenation catalyst to remove acetylene and ethylene.
2. The method for removing acetylene and ethylene in natural gas cracking tail gas is characterized by comprising the following steps: the airspeed is 3000-6000h-1Preheating the tail gas to 140-180 ℃, introducing the tail gas into a composite bed hydrogenation reactor, and removing acetylene and ethylene in the composite bed hydrogenation reactor by using a palladium or copper catalyst as a hydrogenation catalyst.
3. The method according to claim 1 or 2, characterized in that: the space velocity of the tail gas is controlled to be 4000-5000 h-1。
4. The method of claim 3, wherein: the temperature of the tail gas introduced into the hydrogenation reactor of the composite bed is controlled to be 150-170 ℃.
5. The method of claim 4, wherein: the flow rate of the tail gas is controlled to be 30-60m3/h。
6. The method of claim 5, wherein: the components of the palladium catalyst comprise an alumina carrier and an active component palladium, wherein the mass ratio of the active component palladium is 0.04-0.08 percent of the total amount of the hydrogenation catalyst, and the balance is the alumina carrier.
7. The method of claim 6, wherein: the hydrogenation catalyst is spherical particles with the particle size of phi 3-5mm and the bulk density of 0.8 plus or minus 0.05 Kg/L.
8. The method of claim 7, wherein the steps comprise:
closing the steam pipeline, opening the tail gas pipeline, and regulating the flow of the tail gas introduced into the heater to 30-60m3The air speed of the exhaust gas is adjusted to 3000-6000h-1；
Then opening a steam pipeline, introducing steam into a heater to heat the tail gas, and controlling the temperature of the tail gas entering the composite reactor to be 140-180 ℃; the tail gas is subjected to hydrogenation catalytic reaction in the composite reactor to remove acetylene and ethylene.
9. The method of claim 8, wherein: a degassing system is adopted, the degassing system comprises a heater, and the outlet of the composite bed hydrogenation reactor is connected with a methanol synthesis system through a pipeline; the inlet of the heater is connected with a steam pipeline and a tail gas pipeline, the outlet of the heater is connected with the inlet of the composite bed hydrogenation reactor through a pipeline, the steam pipeline and the tail gas pipeline are respectively provided with a shutoff valve, a pipeline between the heater and the composite bed hydrogenation reactor is provided with a temperature regulating valve, a flow regulating valve, a pressure gauge, a raw material gas sampling port and a shutoff valve, and the pipeline at the outlet of the composite bed hydrogenation reactor is provided with a purified gas sampling port and a low exhaust port.
10. The method of claim 5, wherein: the copper catalyst comprises copper oxide, zinc oxide and an alumina carrier, wherein the mass ratio of the copper oxide is not less than 50% of the total amount of the hydrogenation catalyst, the mass ratio of the zinc oxide is not less than 20% of the total amount of the hydrogenation catalyst, and the balance is the alumina carrier.
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