CN110746261B - Cracking gas separation method for gas cracking - Google Patents
Cracking gas separation method for gas cracking Download PDFInfo
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- CN110746261B CN110746261B CN201810812902.3A CN201810812902A CN110746261B CN 110746261 B CN110746261 B CN 110746261B CN 201810812902 A CN201810812902 A CN 201810812902A CN 110746261 B CN110746261 B CN 110746261B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention discloses a pyrolysis gas separation method for gas pyrolysis, which comprises the steps that pyrolysis gas is compressed by a front section of a compressor, then is sequentially subjected to impurity removal and drying treatment, and then enters a deethanizer; separating carbon dioxide and the following light components from carbon three and more heavy components in a deethanizer; the obtained first liquid phase is taken as the reflux of the deethanizer, and the first gas phase enters a second cooling unit; the first gas phase enters a second cooling unit for gradual cooling and gas-liquid separation; the gas phase obtained by the last stage of gas-liquid separation is sent to a hydrogen production unit optionally after cold energy is recovered; the liquid phase obtained by each stage of gas-liquid separation enters a demethanizer; feeding the tower bottom material of the demethanizer into an ethylene rectifying tower for separation, and feeding the gas phase at the tower top into an ethylene recoverer; and the top of the ethylene rectifying tower produces ethylene products. The separation method of the invention does not adopt an expansion machine, reduces the investment and the operation difficulty, and can produce high-pressure and high-purity hydrogen.
Description
Technical Field
The invention belongs to the technical field of hydrocarbon processing, and particularly relates to a pyrolysis gas separation method for gas pyrolysis.
Background
The steam cracking method still dominates the production of ethylene, but the separation process of cracked gas is complex, so that the simplification of the process and the reduction of energy consumption are always the goals pursued by research and designers.
Patent applications CN92100471.0 and CN200910090076.7 both report a front-end deethanization process for separation of cracked gas for steam cracking, the former discloses a process flow employing two-column deethanization and low-pressure demethanization; the latter discloses a process method that a liquid phase material flow at the outlet of a cracking gas condensate dryer is preheated to evaporate a small amount of methane and light carbon components and then sent into cracking gas, and then the liquid phase material flow is continuously heated and sent into a low-pressure deethanizer; although the two methods are somewhat different, they share common features: (1) the cracked gas is compressed to be above 3.6MPaG pressure, and the deethanizer is arranged at the downstream of the last section of the cracked gas compressor; (2) deethanization needs to be accomplished by two columns. Therefore, the method has the problems of complex flow and high investment.
Patent number ZL01132960.2 discloses an improvement of a cryogenic separation method for light hydrocarbon mixture, and specifically discloses a process flow that compressed and cooled light hydrocarbon raw material gas is separated by a gas-liquid separation tank, the gas phase enters a component distribution device, the gas phase at the top of the component distribution device is cooled step by step and then enters a demethanizer, and the demethanizer separates each feed into overhead methane and bottom carbon; the cracking gas separation method disclosed by the method also has the problems of complex flow and high investment, and is suitable for cracking gas separation of liquid cracking. The cold separation process disclosed in patent No. ZL201410455184.0 is simplified but still complicated and does not produce high pressure hydrogen.
Therefore, it is necessary to provide a new method to shorten the flow and to reduce the investment, and to produce high value-added hydrogen.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a pyrolysis gas separation method to shorten the flow and reduce the investment.
In order to achieve the above object, the present invention provides a pyrolysis gas separation method for gas pyrolysis, the pyrolysis gas separation method comprising:
(1) after being compressed by the front section of the compressor, the cracking gas is sequentially subjected to impurity removal and drying treatment, and the cracking gas after the drying treatment enters a deethanizer;
(2) separating carbon dioxide and the following light components from carbon three and more heavy components in a deethanizer; the method comprises the following steps that materials at the top of a deethanizing tower sequentially enter the last section of a compressor, a deethanizing unit and a first cooling unit to obtain a first liquid phase and a first gas phase, wherein the first liquid phase is used as reflux of the deethanizing tower, and the first gas phase enters a second cooling unit;
(3) the first gas phase enters a second cooling unit for gradual cooling and gas-liquid separation; the gas phase obtained by the last stage of gas-liquid separation is sent to a hydrogen production unit optionally after cold energy is recovered, and hydrogen and tail gas are obtained by separation; the liquid phase obtained by each stage of gas-liquid separation enters a demethanizer;
(4) feeding the tower bottom material of the demethanizer into an ethylene rectifying tower for separation, and feeding the gas phase at the tower top into an ethylene recoverer;
(5) the top of the ethylene rectifying tower produces ethylene product, and ethane obtained from the tower bottom is vaporized and returned to the cracking furnace.
The technical scheme of the invention has the following advantages:
(1) in the invention, the deethanizer and the demethanizer are both provided with only one tower, so the investment is low;
(2) in the invention, the operation pressure of the deethanizer is low, and the reflux ratio is reduced;
(3) in the invention, the top gas of the deethanizer is compressed, boosted and then cooled, and the refrigerant grade is not improved;
(4) in the invention, the temperature of the deethanizer is low, so that low-level heat energy can be effectively utilized;
(5) the separation method of the invention does not adopt an expansion machine, thus reducing the investment and the operation difficulty;
(6) the separation method can produce high-pressure and high-purity hydrogen, the pressure can reach 2.0-3.0MPa, and the purity can reach more than 99 mol%.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Fig. 1 shows a schematic apparatus diagram of a pyrolysis gas separation method for gas pyrolysis according to one embodiment of the present invention.
Description of reference numerals:
1. 1-3 sections 2 of a cracked gas compressor, 3 sections of an alkaline washing tower, 4-a deethanizer 5 of a dryer, 4 sections 6 of the cracked gas compressor, 7 a deecetylene unit, 8 a second cooling unit, 9 a demethanizer, 10 an ethylene rectifying tower, 11 an ethylene recoverer, 12 a PSA unit, 13 a first cooling unit, S1 a deethanizer reflux tank, S2 cracked gas from a quenching zone, S3 a material obtained after compression of 1-3 sections of the cracked gas compressor, S4 a dryer feed, S5 dried cracked gas, S6 a gas phase at the top of the deethanizer, S7 a cracked gas at the section outlet of the cracked gas compressor, 4 sections of the cracked gas compressor, and C3 of the deethanizer+Material preparation; s8, a first liquid phase S9, a first gas phase S10, demethanizer bottoms S11, ethylene products S12, recycled ethane S13, demethanizer overhead gas phase S15, low temperature methane S16, hydrogen S17, methane hydrogen tail gas S18, methane rich gas S19, demethanizer first feed S20, demethanizer second feed S21, demethanizer third feed S21
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The invention provides a pyrolysis gas separation method for gas pyrolysis, which comprises the following steps:
(1) after being compressed by the front section of the compressor, the pyrolysis gas is sequentially subjected to impurity removal and drying treatment, and the dried pyrolysis gas enters a deethanizer;
in the present invention, the apparatus for removing impurities comprises an absorption column or an adsorber. The means for removing impurities is preferably a caustic wash tower. And removing acid gas impurities by using an alkaline washing tower.
The raw material of steam cracking generates cracking gas after cracking, the temperature of the cracking gas can be reduced after passing through a quenching system, and the cooled cracking gas enters the front section of the compressor.
(2) Separating carbon dioxide and the following light components from carbon three and more heavy components in a deethanizer; the method comprises the following steps that materials at the top of a deethanizing tower sequentially enter the last section of a compressor, a deethanizing unit and a first cooling unit to obtain a first liquid phase and a first gas phase, wherein the first liquid phase is used as reflux of the deethanizing tower, and the first gas phase enters a second cooling unit;
in the invention, the materials at the bottom of the deethanizer are carbon III and heavy components, and can be directly sent out of the device or further separated to produce propylene.
In the present invention, the deicetylene unit may include: a carbo-hydrogenation reactor or an acetylene selective absorption tower for removing acetylene.
(3) The first gas phase enters a second cooling unit for gradual cooling and gas-liquid separation; wherein, the gas phase obtained by the last stage of gas-liquid separation is sent to a hydrogen production unit optionally after cold energy is recovered, and hydrogen and tail gas are obtained by separation; the liquid phase obtained by each stage of gas-liquid separation enters a demethanizer;
in the present invention, the second cooling unit, the demethanizer and the ethylene column together form a cold separation section. In the step (3), the ethylene content in the gas phase obtained by the last stage of gas-liquid separation is low enough, the gas phase mainly contains hydrogen, methane and carbon monoxide, the process requirements can be met, the gas phase can be sent to a hydrogen production unit after cold energy is recovered, and hydrogen and tail gas are obtained through separation; wherein the hydrogen production unit is preferably a PSA unit.
(4) Feeding the tower bottom material of the demethanizer into an ethylene rectifying tower for separation, and feeding the gas phase at the tower top into an ethylene recoverer;
the material in the bottom of the demethanizer does not contain methane and is sent to an ethylene rectifying tower for further separation. The cold energy of the top condenser of the demethanizer is provided by an ethylene refrigeration system. The condenser in the ethylene recoverer provides cold energy lower than the temperature of the condenser at the top of the demethanizer so that part of components in the gas phase return to the demethanizer after being condensed, and the rest gas phase is rich in methane and is sent out after the cold energy is recovered. The cold energy of the condenser in the ethylene recoverer is provided by a methane refrigeration system.
(5) The top of the ethylene rectifying tower produces ethylene product, and ethane obtained from the tower bottom is vaporized and returned to the cracking furnace.
According to the invention, preferably, in the step (1), the compressor is 4 or 5 sections; when the compressor is 4 sections, the front section of the compressor is 1-3 sections, the deethanizer is positioned between the outlet of the 3 sections of the compressor and the inlet of the 4 sections of the compressor, and the last section of the compressor is the 4 th section; when the compressor is 5 sections, the front section of the compressor is 1-4 sections, the deethanizer is positioned between the outlet of the 4 sections of the compressor and the inlet of the 5 sections of the compressor, and the last section of the compressor is the 5 th section.
According to the invention, preferably, the gas cracking is ethane cracking, propane cracking, or cracking of three or any two mixed materials of ethane, propane and butane.
According to the present invention, preferably, the deethanizer is a single column; the deethanizer is a plate tower or a packed tower; the operating pressure of the deethanizer is 0.7-1.9MPa, preferably 0.9-1.7 MPa.
According to the invention, in step (2), the pressure of the deethanizer overhead material after being pressurized by the last section of the compressor is preferably 2.0-3.4MPa, and preferably 2.8-3.2 MPa.
According to the invention, preferably, the demethanizer is a single column operating at a pressure of 2.0 to 3.2MPa, preferably 2.5 to 3.0 MPa; the temperature at the top of the column is-90 ℃ to-105 ℃.
In the present invention, the overhead temperature of the demethanizer is provided by an ethylene refrigeration or ethane refrigeration system.
According to the present invention, preferably, the ethylene recycler comprises a condenser and optionally a fractionation section, which employs packing or trays; the outlet temperature at the top of the ethylene recoverer is lower than minus 105 ℃;
and the gas phase at the top of the demethanizer enters from the bottom of the ethylene recoverer, part of the materials are condensed by the condenser, the rest gas phase is sent out after cold energy is recovered, and the condensed materials return to the demethanizer.
In the invention, the ethylene recoverer can be directly placed at the top of the reflux tank of the demethanizer or can be placed independently.
According to the invention, preferably, the ethylene rectification column is of the high-pressure column or low-pressure open heat pump type; the operating pressure is 1.6-2.2MPa when the high pressure tower is used, and 0.4-1.2MPa when the low pressure open heat pump type is used.
According to the invention, preferably, the deethanizer and the last stage of the compressor constitute an open heat pump system.
According to the present invention, preferably, the refrigeration required for the separation process is provided by at least one of a propylene or propane refrigeration system, an ethylene or ethane refrigeration system and a methane refrigeration system provided.
The invention is further illustrated by the following examples:
example 1
This example illustrates the use of the present invention in a cracked gas separation process for an 80 million ton/year ethane cracker.
As shown in figure 1, pyrolysis gas S1 from a quenching zone enters a pyrolysis gas compressor 1-3 section 1 to be compressed (the pressure after the compression of the compressor 1-3 section is 1.397MPa), and a material S2 is sent to an alkaline tower 2 to remove CO2And H2S, obtaining dryer feed S3, and then sending the dryer feed S3 into a dryer 3 to remove moisture; the dried cracked gas S4 is sent into a deethanizer 4 after being properly cooled, the gas phase S5 (without carbon, three or more heavy components) at the top of the deethanizer is sent into a compressor 4 section 5 for further compression, and the outlet pressure of the 4 section is 3.020 MPa. The cracked gas (S6) at the section outlet of the cracked gas compressor 4 is sent to a acetylene removal unit 6 for hydrogenation, acetylene in the cracked gas is converted into ethylene, and then the temperature of the ethylene is reduced by refrigerant in a first cooling unit 12. The condensed first liquid phase S8 in the cracked gas is used as reflux of a deethanizer and returns to the top of the deethanizer through a deethanizer reflux tank 13, the first gas phase S9 is sent to a second cooling unit 7 for gradual cooling, and the condensed liquid S19 (first feed of the demethanizer), S20 (second feed of the demethanizer) and S21 (third feed of the demethanizer) after cooling are sent to the demethanizer 8; the gas phase obtained by the last stage of gas-liquid separation of the second cooling unit 7 is a mixture of methane and hydrogen, and the mixture is sent to the PSA unit 11 to produce hydrogen S16 and methane-hydrogen tail gas S17 after cold energy is recovered; demethanizer bottomsS10 contains no methane hydrogen and is sent to an ethylene rectifying tower 9 for separation; the demethanizer overhead vapor S13, which still contains a certain amount of ethylene, is sent to an ethylene recovery unit 10 for further ethylene recovery. The ethylene recovery unit 10 is composed of a lower fractionation section using a filler and an upper condenser. The top gas phase S13 of the demethanizer enters from the bottom of the ethylene recoverer 10, contacts with liquid from an upper condenser in a packing section for mass transfer, and then enters the upper condenser; condensing part of the materials in a condenser by methane refrigerant to provide reflux for the lower part; the residual gas S15 (low-temperature methane) is sent out S18 after cold energy is recovered by the second cooling unit 7, and the condensed material returns to the demethanizer 8. The cold energy required by the ethylene recoverer 10 is provided by a methane refrigeration system. Ethylene products S11 are obtained at the top of the ethylene rectifying tower 9, and ethane S12 obtained at the bottom of the tower is returned to the cracking furnace after being vaporized. Feeding the tower bottom material S7 of the deethanizer 4 into a downstream unit for further separation to obtain products such as propylene, carbon four and the like. Wherein the deethanizer 4 and the last section of the compressor constitute an open heat pump system; the cold energy required by the separation process is provided by a propylene refrigeration system, an ethylene refrigeration system and a methane refrigeration system.
In the embodiment, the cracking gas compressor adopts 4-section compression, and the deethanizer 4 is a plate tower; the operating pressure of the deethanizer is 1.2 MPa; the outlet pressure of the 4 th section 5 of the cracked gas compressor is 3.2 MPa; the operating pressure of the demethanizer is 2.7MPa, the temperature of the top of the tower is-98 ℃, and the temperature of the bottom of the tower is-10 ℃; the outlet temperature at the top of the ethylene recoverer is-111.9 ℃; the ethylene rectifying tower 9 is a high-pressure tower, the pressure at the top of the tower is 1.76MPa, the temperature at the top of the tower is minus 34 ℃, and the temperature at the bottom of the tower is minus 11 ℃.
The parameters of the main streams are shown in tables 1-4:
TABLE 180 million tons/year ethane cracker stream data
TABLE 2
TABLE 3
TABLE 4
By the embodiment, the pyrolysis gas is well separated, and polymer-grade ethylene and pure hydrogen products are obtained. The loss of ethylene in methane hydrogen is only 6.4kmol/h, and the loss rate is 0.14 percent; the recovery rate of pure hydrogen exceeds 86 percent; it can be seen that the method of the present invention has the advantages of simple process and high ethylene and hydrogen recovery rate.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.
Claims (12)
1. A pyrolysis gas separation method for gas pyrolysis is characterized by comprising the following steps:
(1) after being compressed by the front section of the compressor, the pyrolysis gas is sequentially subjected to impurity removal and drying treatment, and the dried pyrolysis gas enters a deethanizer;
(2) separating carbon dioxide and the following light components from carbon three and more heavy components in a deethanizer; feeding the material at the top of the deethanizing tower into the last section of the compressor, a deethanizing unit and a first cooling unit in sequence to obtain a first liquid phase and a first gas phase, wherein the first liquid phase is used as reflux of the deethanizing tower, and the first gas phase is fed into a second cooling unit;
(3) the first gas phase enters a second cooling unit for gradual cooling and gas-liquid separation; wherein, the gas phase obtained by the last stage of gas-liquid separation is sent to a hydrogen production unit optionally after cold energy is recovered; the liquid phase obtained by each stage of gas-liquid separation enters a demethanizer;
(4) feeding the tower bottom material of the demethanizer into an ethylene rectifying tower for separation, and feeding the gas phase at the tower top into an ethylene recoverer;
(5) the top of the ethylene rectifying tower produces ethylene products, and ethane obtained at the tower bottom is vaporized and then returns to the cracking furnace;
the deethanizer and the last section of the compressor form an open heat pump system.
2. The separation method of cracked gas as claimed in claim 1, wherein in the step (1), the compressor is in 4 or 5 stages; when the compressor is 4 sections, the front section of the compressor is 1-3 sections, the deethanizer is positioned between the outlet of the 3 sections of the compressor and the inlet of the 4 sections of the compressor, and the last section of the compressor is the 4 th section; when the compressor is 5 sections, the front section of the compressor is 1-4 sections, the deethanizer is positioned between the outlet of the 4 sections of the compressor and the inlet of the 5 sections of the compressor, and the last section of the compressor is the 5 th section.
3. The separation method of cracked gas as claimed in claim 1, wherein the gas cracking is ethane cracking, propane cracking, or cracking of three or any two mixed materials of ethane, propane and butane.
4. The cracked gas separation process of claim 1, wherein the deethanizer is a single column; the deethanizer is a plate tower or a packed tower; the operating pressure of the deethanizer is 0.7-1.9 MPa.
5. The cracked gas separation method of claim 4, wherein the deethanizer is operated at a pressure of 0.9-1.7 MPa.
6. The pyrolysis gas separation method according to claim 1, wherein in the step (2), the pressure of the deethanizer overhead material after being pressurized by the last stage of the compressor is 2.0-3.4 MPa.
7. The pyrolysis gas separation method according to claim 6, wherein in the step (2), the pressure of the deethanizer overhead material after being pressurized by the last stage of the compressor is 2.8-3.2 MPa.
8. The cracked gas separation method of claim 1, wherein the demethanizer is a single column operating at a pressure of 2.0-3.2 MPa.
9. The cracked gas separation method of claim 8, wherein the operating pressure is 2.5-3.0 MPa.
10. The cracked gas separation process of claim 1, wherein the ethylene recycler comprises a condenser and optionally a fractionation section employing packing or trays; the outlet temperature at the top of the ethylene recoverer is lower than minus 105 ℃;
and the gas phase at the top of the demethanizer enters from the bottom of the ethylene recoverer, part of the materials are condensed by the condenser, the rest gas phase is sent out after cold energy is recovered, and the condensed materials return to the demethanizer.
11. The cracked gas separation method of claim 1, wherein the ethylene rectification column is of the high pressure or low pressure open heat pump type; the operating pressure is 1.6-2.2MPa when the high pressure tower is used, and 0.4-1.2MPa when the low pressure open heat pump type is used.
12. The pyrolysis gas separation method of claim 1, wherein the refrigeration required for the separation process is provided by at least one of a propylene or propane refrigeration system, an ethylene or ethane refrigeration system, and a methane refrigeration system.
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| CN104152173A (en) * | 2013-05-14 | 2014-11-19 | 中国石油天然气股份有限公司大庆石化分公司 | Starting emission reduction method for ethene device |
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| WO1999007655A1 (en) * | 1997-08-05 | 1999-02-18 | David Netzer | A combination process for manufacturing ethylene, ethylbenzene and styrene |
| US7714180B2 (en) * | 2003-04-04 | 2010-05-11 | Exxonmobil Chemical Patents Inc. | Process and apparatus for recovering olefins |
| CN1660722A (en) * | 2004-12-23 | 2005-08-31 | 中国石油化工集团公司 | Method for separating catalytic splitting gas of enriching propylene and propane |
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