CN115710155A - System and method for preparing polymerization-grade olefin by DCC reaction oil gas - Google Patents
System and method for preparing polymerization-grade olefin by DCC reaction oil gas Download PDFInfo
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- CN115710155A CN115710155A CN202110970726.8A CN202110970726A CN115710155A CN 115710155 A CN115710155 A CN 115710155A CN 202110970726 A CN202110970726 A CN 202110970726A CN 115710155 A CN115710155 A CN 115710155A
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Abstract
The invention belongs to the field of olefin production, and discloses a system and a method for preparing polymerization-grade olefin by DCC reaction oil gas. The system comprises a DCC device, a fractionation unit, a compression impurity removal unit, a cryogenic separation unit and a steam cracking unit; outlets of the DCC device and the steam cracking unit are both connected with a fractionation unit, and the fractionation unit is sequentially connected with a compression impurity removal unit and a cryogenic separation unit; an outlet of the cryogenic separation unit is connected to an inlet of the steam cracking unit via a saturated alkane recycle line. The invention takes DCC and light hydrocarbon steam cracking as the two ends of the raw material cracking, can prepare olefin from the raw material to the utmost extent, meets the requirement of 'eating dry pressing clean', and can obtain polymer grade ethylene and polymer grade propylene products at the same time.
Description
Technical Field
The invention belongs to the field of olefin production, and particularly relates to a system and a method for preparing polymerization-grade olefin by DCC reaction oil gas.
Background
In the traditional separation process flow of DCC (deep catalytic cracking), heavy oil such as raw material hydrogenated wax oil and hydrogenated heavy oil is subjected to catalytic cracking to obtain reaction oil gas; the reaction oil gas is subjected to fractionation, absorption and stabilization, and heavy components such as coke, slurry oil, diesel oil, gasoline and the like are removed to obtain light gas and liquid phases; the LPG and the dry gas are subjected to double-desorption to obtain desulfurized LPG and desulfurized dry gas (i.e. the dry gas and the liquefied gas are subjected to inorganic sulfur removal, and the liquefied gas and the gasoline are subjected to organic sulfur removal); carrying out gas separation on the desulfurized liquefied gas to obtain propylene, propane and mixed C4, and further refining the propylene gas to obtain a polymer-grade propylene product; removing methane/hydrogen tail gas from the desulfurized dry gas through dry gas recovery treatment (namely oil absorption or PSA) to obtain concentrated mixed carbon dioxide dry gas; the concentrated mixed carbon dioxide dry gas is subjected to cryogenic separation to obtain a polymer grade ethylene product, and the separated saturated alkane is subjected to a light hydrocarbon steam cracking process to prepare olefin. See fig. 1.
The process has the characteristics that: the DCC (deep catalytic cracking) device and the steam cracking device are required to be arranged at the same time to obtain a polymer grade ethylene product and a polymer grade propylene product, and meanwhile, the dry gas recovery processing unit has different process routes, namely oil absorption or PSA, the loss rate of the carbon two components is 8-17%, so that the recovery rate of the polymer grade olefin in the whole process is low. Therefore, the existing scheme has long flow, low recovery rate of polymerization-grade olefin, repeated arrangement of partial separation units or equipment and high investment.
Therefore, a new system and method for preparing polymer grade olefin by DCC reaction oil gas is needed.
Disclosure of Invention
The invention aims to provide a system and a method for preparing polymerization-grade olefin by DCC reaction oil gas aiming at the defects of the prior art. The present invention uses DCC and light hydrocarbon steam cracking as the two ends of raw material cracking, and the produced reaction oil gas and cracking gas are passed through the operation units of fractionation, compression, impurity-removing and separation to separate the products of polymerization-grade ethylene and polymerization-grade propylene, so that it can maximally prepare olefin from the raw material.
In order to achieve the above object, the present invention provides a system for preparing polymer grade olefin by DCC reaction oil gas, which comprises a DCC device, a fractionation unit, a compression impurity removal unit, a cryogenic separation unit and a steam cracking unit;
outlets of the DCC device and the steam cracking unit are both connected with a fractionation unit, and the fractionation unit is sequentially connected with a compression impurity removal unit and a cryogenic separation unit;
an outlet of the cryogenic separation unit is connected to an inlet of the steam cracking unit via a saturated alkane recycle line.
In another aspect, the present invention provides a method for preparing polymer grade olefin by DCC reaction oil gas, which is performed in the system, and comprises the following steps:
s1: feeding the reaction oil gas produced by the DCC device and the pyrolysis gas from the steam cracking unit into the fractionation unit and the compression impurity removal unit in sequence for fractionation and compression impurity removal treatment to obtain impurity-removed process gas;
s2: feeding the process gas after impurity removal into the cryogenic separation unit for cryogenic step-by-step separation treatment to obtain polymer-grade ethylene, polymer-grade propylene products, hydrogen-rich gas, methane tail gas, mixed C4 and saturated alkane;
s3: and sending the saturated alkane into the steam cracking unit for treatment to obtain the cracked gas, and sending the cracked gas into the fractionation unit.
The technical scheme of the invention has the following beneficial effects:
(1) The system and the method of the invention take DCC (deep catalytic cracking) and light hydrocarbon steam cracking as the two ends of the raw material cracking, can prepare olefin from the raw material to the utmost extent, meet the requirement of 'dry eating and clean pressing', and can simultaneously obtain polymer-grade ethylene and polymer-grade propylene products, and byproducts such as hydrogen-rich gas, methane tail gas, mixed C4, cracked gasoline and the like.
(2) The system and the method optimize impurity removal and separation processes, avoid the loss of carbon two components in the dry gas recovery process, circulate the saturated alkane (ethane/propane) separated by the cryogenic separation unit as a raw material to the steam cracking unit to increase the yield of olefin, improve the separation efficiency (namely the recovery rate of polymer grade olefin and the yield of diene), form a DCC reaction oil gas recovery technology of 'two ends and one tail', greatly simplify the process of preparing ethylene by DCC (deep catalytic cracking) reaction oil gas, and simultaneously improve the recovery rate of polymer grade ethylene from 83-92% to more than 99.6%.
(3) The invention provides a 'one-tail' separation process by simplifying the process, can save a set of equipment of units of quenching/fractionation, stable absorption, gas separation, dry gas recovery and the like, and simplifies two-line desulfurization into one-line impurity removal, thereby forming a 'one-tail' process of fractionation, compression, impurity removal and separation. Therefore, the number of the devices is reduced, the investment and the occupied area are correspondingly reduced, the complexity of the operation of the device is also reduced, and the operation stability of the device is improved.
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.
Figure 1 shows a process flow diagram of one prior art DCC reaction oil and gas to polymer grade olefins.
Figure 2 shows a process flow diagram for preparing polymer grade olefin by DCC reaction oil gas provided by embodiment 2 of the invention.
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 system for preparing polymerization-grade olefin by DCC reaction oil gas, which comprises a DCC device, a fractionation unit, a compression impurity removal unit, a cryogenic separation unit and a steam cracking unit;
outlets of the DCC device and the steam cracking unit are both connected with a fractionation unit, and the fractionation unit is sequentially connected with a compression impurity removal unit and a cryogenic separation unit;
an outlet of the cryogenic separation unit is connected to an inlet of the steam cracking unit via a saturated alkane recycle line.
In the invention, because the DCC (deep catalytic cracking) raw material is heavy oil such as hydrogenated wax oil and/or hydrogenated heavy oil, saturated alkane (ethane/propane) contained in the cracked reaction oil gas can not be used as the raw material of catalytic cracking after final separation, and olefin is prepared by further cracking through a steam cracking unit.
The system and method of the present invention avoids the loss of the carbon dioxide component of the dry gas recovery unit. In the existing process, in order to recover ethylene in dry gas, methane hydrogen tail gas needs to be removed through a dry gas recovery unit to obtain concentrated mixed carbon dioxide dry gas, the process usually adopts oil absorption or PSA and other modes, and 8-17% of carbon dioxide components are mixed in the methane tail gas and cannot be recovered. The cryogenic separation rectification operation can well control the separation index of the rectification tower at a lower operation temperature, improve the recovery rate of polymer-grade ethylene and polymer-grade propylene while obtaining the polymer-grade ethylene and the polymer-grade propylene, reduce the loss of saturated alkane such as ethane/propane and the like, and greatly improve the diene yield of the device.
According to the present invention, preferably, the inlet of the steam cracking unit is further connected to a refinery propane feed line; and the inlet of the compression impurity removal unit is also connected with a mixed dry gas feeding pipeline.
According to the invention, preferably, the cryogenic separation unit is further connected with a hydrogen-rich gas output line, a methane tail gas output line, a polymerization stage ethylene output line, a polymerization stage propylene output line and a mixed carbon four output line.
According to the present invention, preferably, the compression and impurity removal unit includes at least one of a compressor, an amine wash/caustic wash tower and a impurity removal adsorption bed.
According to the present invention, preferably, the cryogenic separation unit comprises at least one of a cold box, a demethanizer, a deethanizer, an ethylene rectifier, a depropanizer, a propylene rectifier, a debutanizer, an ethylene machine and a propylene machine.
In another aspect of the present invention, there is provided a method for preparing polymer grade olefin by DCC reaction oil gas, the method is carried out in the system, and comprises the following steps:
s1: the reaction oil gas produced by the DCC device and the pyrolysis gas from the steam cracking unit are sequentially sent to the fractionation unit and the compression impurity removal unit for fractionation and compression impurity removal treatment to obtain process gas after impurity removal;
s2: feeding the process gas after impurity removal into the cryogenic separation unit for cryogenic step-by-step separation treatment to obtain polymer-grade ethylene, polymer-grade propylene products, hydrogen-rich gas, methane tail gas, mixed C4 and saturated alkane;
s3: and sending the saturated alkane into the steam cracking unit for processing to obtain the cracked gas, and sending the cracked gas into the fractionation unit.
The system and the method of the invention simplify the separation process and reduce the investment of the device. In the existing process, two separation processes are needed, one separation process is used for separating DCC reaction oil gas, light gas/liquid phases are obtained through oil absorption processes such as fractionation, stable absorption and the like, and LPG and dry gas are obtained after organic sulfur and inorganic sulfur are removed through double removal. LPG is subjected to gas separation to obtain propylene, and the propylene is required by a downstream deviceFurther purification is sometimes required; the dry gas can be subjected to cryogenic separation after being pretreated by dry gas recovery and the like, so that a polymer-grade ethylene product is obtained. After ethane/propane is circulated to a cracking furnace for cracking, the ethane/propane is subjected to quenching and compression and also subjected to cryogenic separation, so that the ethane/propane can be eaten and squeezed completely. By adopting the 'one-tail' separation process, the reaction oil gas cracked by DCC and the cracked gas cracked by light hydrocarbon steam are sent into the fractionating unit together, after heavy components such as diesel oil, cracked gasoline and the like are removed, CO is removed after the heavy components are pressurized by the compressor 2 、H 2 S、NO x And impurities such as organic sulfur, arsenic and mercury are separated step by step in a cryogenic separation unit to obtain polymer-grade ethylene and polymer-grade propylene products, saturated alkanes such as ethane/propane and the like are directly circulated to light hydrocarbon cracking furnaces (steam cracking units) in two ends for cracking, so that the separation process is greatly simplified, and meanwhile, on the purity of the product, no further refining is needed, and the product can be directly used as raw materials for devices such as a downstream polyolefin device and EOEG.
According to the present invention, preferably, the feedstock in the DCC device is hydrogenated wax oil and/or hydrogenated heavy oil.
According to the invention, preferably, substances removed by the gas in the fractionating unit after the fractionating treatment are heavy components with the distillation range of more than or equal to 150 ℃, and preferably, the substances removed by the fractionating unit comprise coke, oil slurry, diesel oil and pyrolysis gasoline.
According to the invention, preferably, after the gas in the compression impurity removal unit is subjected to the compression impurity removal treatment, the removed impurities comprise CO 2 、H 2 S、NO x Organic sulfur, arsenic and mercury.
According to the invention, preferably, the content of impurities in the gas treated by the compression impurity removal unit is less than or equal to 1ppm.
According to the present invention, it is preferable that the operating pressure of the compressor in the compression impurity removing unit is 1.5 to 4MPaG.
According to the invention, preferably, the refrigeration capacity of the cryogenic separation unit is provided by the cascade refrigeration of an ethylene machine and a propylene machine.
According to the present invention, preferably, the methane/hydrogen tail gas in the cryogenic separation unit is separated at a temperature of-160 to-165 ℃ to obtain the hydrogen-rich gas and a portion of the methane tail gas in the methane tail gas.
According to the present invention, preferably, the remaining methane tail gas of the methane tail gas is from the demethanizer overhead gas phase.
According to the present invention, preferably, the hydrogen-rich gas contains H 2 /N 2 The purity is 94-96mol%.
In the cryogenic separation unit of the invention, as a preferable scheme, the methane-hydrogen tail gas is separated from the hydrogen-rich gas at-163 ℃, so that the hydrogen-rich gas with higher added value, namely H, is obtained 2 /N 2 95mol percent, compared with the prior process, the method can recover the hydrogen to the maximum extent without Pressure Swing Adsorption (PSA), and reduce a large amount of hydrogen lost along with methane hydrogen tail gas in a dry gas recovery unit.
According to the present invention, preferably, the recovery of polymer grade olefins is above 99.6%; the yield of the diene reaches more than 28 percent.
The present invention is specifically illustrated by the following examples.
Example 1
The embodiment provides a system for preparing polymerization-grade olefin by DCC reaction oil gas, which comprises a DCC device, a fractionation unit, a compression impurity removal unit, a cryogenic separation unit and a steam cracking unit, as shown in the process flow of FIG. 2;
outlets of the DCC device and the steam cracking unit are both connected with a fractionation unit, and the fractionation unit is sequentially connected with a compression impurity removal unit and a cryogenic separation unit;
an outlet of the cryogenic separation unit is connected to an inlet of the steam cracking unit via a saturated alkane recycle line. The cryogenic separation unit is also provided with other outlets which are respectively connected with a hydrogen-rich gas output pipeline, a methane tail gas output pipeline, a polymerization stage ethylene output pipeline, a polymerization stage propylene output pipeline and a mixed carbon four output pipeline.
The compression impurity removal unit includes a compressor, an amine wash/caustic wash tower, and a de-impurity adsorption bed (not shown).
The cryogenic separation unit comprises a cold box, a demethanizer, a deethanizer, an ethylene rectifier, a depropanizer, a propylene rectifier, a debutanizer, an ethylene machine and a propylene machine (not shown).
The method for preparing polymerization-grade olefin by DCC reaction oil gas in the system comprises the following steps:
s1: hydrogenated heavy oil is used as a raw material of the DCC device, reaction oil gas produced by the DCC device and pyrolysis gas from the steam cracking unit are sequentially sent to the fractionating unit and the compression impurity removal unit for fractionation and compression impurity removal treatment, and heavy components such as coke, slurry oil, diesel oil and pyrolysis gasoline and CO are sequentially removed 2 、H 2 S、NO x Organic sulfur, arsenic, mercury and other impurities to obtain process gas after impurity removal; the content of impurities in the gas treated by the compression impurity removal unit is less than or equal to 1ppm;
s2: feeding the process gas after impurity removal into the cryogenic separation unit for cryogenic step-by-step separation treatment to obtain polymer-grade ethylene, polymer-grade propylene products, hydrogen-rich gas, methane tail gas, mixed C4 and saturated alkane; wherein, the cold energy of the cryogenic separation unit is provided by the cascade refrigeration of an ethylene machine and a propylene machine; separating methane tail gas and hydrogen-rich gas from methane-hydrogen tail gas at-163 deg.C to obtain hydrogen-rich gas with high added value, i.e. H 2 /N 2 95mol%, and a portion of the methane tail gas in the methane tail gas, the remaining methane tail gas being from the demethanizer overhead gas phase.
S3: and sending the saturated alkane into the steam cracking unit for processing to obtain the cracked gas, and sending the cracked gas into the fractionation unit.
The recovery rate of polymer-grade ethylene, the recovery rate of polymer-grade propylene and the diene obtained by the system and the method of the embodiment are respectively more than 99.6%, more than 99.95% and more than 28%.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A DCC reaction oil gas preparation polymerization grade alkene system, wherein the system includes DCC device, fractionation unit, compression edulcoration unit, cryogenic separation unit and steam cracking unit;
outlets of the DCC device and the steam cracking unit are both connected with a fractionation unit, and the fractionation unit is sequentially connected with a compression impurity removal unit and a cryogenic separation unit;
an outlet of the cryogenic separation unit is connected to an inlet of the steam cracking unit via a saturated alkane recycle line.
2. The system for DCC reaction of oil and gas to produce polymer grade olefins according to claim 1, wherein,
the inlet of the steam cracking unit is also connected with a refinery propane feeding pipeline;
and the inlet of the compression impurity removal unit is also connected with a mixed dry gas feeding pipeline.
3. The system for DCC reaction oil and gas preparation of polymer grade olefins according to claim 1 or 2, wherein the cryogenic separation unit is further connected with a hydrogen-rich gas output line, a methane tail gas output line, a polymer grade ethylene output line, a polymer grade propylene output line and a mixed carbon four output line.
4. The system for DCC reaction oil and gas preparation of polymer grade olefins according to claim 1 or 2, wherein the compression impurity removal unit comprises at least one of a compressor, an amine wash/caustic wash tower and a de-impurity adsorption bed.
5. The system for DCC reaction oil and gas preparation of polymer grade olefins according to claim 1 or 2, wherein the cryogenic separation unit comprises at least one of a cold box, a demethanizer, a deethanizer, an ethylene rectifier, a depropanizer, a propylene rectifier, a debutanizer, an ethylene machine, and a propylene machine.
6. A method for preparing polymer grade olefin by DCC reaction oil gas, which is characterized in that the method is carried out in the system of any one of claims 1 to 5, and comprises the following steps:
s1: feeding the reaction oil gas produced by the DCC device and the pyrolysis gas from the steam cracking unit into the fractionation unit and the compression impurity removal unit in sequence for fractionation and compression impurity removal treatment to obtain impurity-removed process gas;
s2: sending the process gas subjected to impurity removal into the cryogenic separation unit for cryogenic step-by-step separation treatment to obtain polymer-grade ethylene, a polymer-grade propylene product, hydrogen-rich gas, methane tail gas, mixed C4 and saturated alkane;
s3: and sending the saturated alkane into the steam cracking unit for processing to obtain the cracked gas, and sending the cracked gas into the fractionation unit.
7. The method for preparing polymer grade olefin by DCC reaction oil gas according to claim 6, wherein the raw material in the DCC device is hydrogenated wax oil and/or hydrogenated heavy oil.
8. The method for DCC reacting oil and gas to produce polymer grade olefins according to claim 6, wherein,
after the gas in the fractionating unit is subjected to the fractionating treatment, the removed substances are heavy components with the distillation range of more than or equal to 150 ℃, and preferably, the substances removed by the fractionating unit comprise coke, slurry oil, diesel oil and pyrolysis gasoline;
after the gas in the compression impurity removal unit is subjected to compression impurity removal treatment, the removed impurities comprise CO 2 、H 2 S、NO x Organic sulfur, arsenic and mercury; the content of impurities in the gas treated by the compression impurity removal unit is less than or equal to 1ppm;
the working pressure of a compressor in the compression impurity removal unit is 1.5-4MPaG.
9. The method for producing polymer grade olefins by DCC reaction oil gas according to claim 6, wherein the refrigeration capacity of the cryogenic separation unit is provided by the cascade refrigeration of an ethylene machine and a propylene machine;
separating the methane/hydrogen tail gas in the cryogenic separation unit at the temperature of-160 to-165 ℃ to obtain the hydrogen-rich gas and a part of methane tail gas in the methane tail gas;
h in the hydrogen-rich gas 2 /N 2 The purity is 94-96mol%;
the remaining methane tail gas in the methane tail gas is from the demethanizer overhead gas phase.
10. The method for preparing polymer grade olefin by DCC reaction oil gas according to any one of claims 6 to 9, wherein the recovery rate of the polymer grade olefin is more than 99.6%; the yield of the diene reaches over 28 percent.
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