CN116240050B - Combined processing method for producing basic organic chemical raw materials from crude oil - Google Patents
Combined processing method for producing basic organic chemical raw materials from crude oil Download PDFInfo
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- CN116240050B CN116240050B CN202111493683.5A CN202111493683A CN116240050B CN 116240050 B CN116240050 B CN 116240050B CN 202111493683 A CN202111493683 A CN 202111493683A CN 116240050 B CN116240050 B CN 116240050B
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- 239000010779 crude oil Substances 0.000 title claims abstract description 92
- 239000002994 raw material Substances 0.000 title claims abstract description 43
- 239000000126 substance Substances 0.000 title claims abstract description 25
- 238000003672 processing method Methods 0.000 title claims abstract description 17
- 239000003921 oil Substances 0.000 claims abstract description 256
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 129
- 238000000926 separation method Methods 0.000 claims abstract description 83
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 77
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000295 fuel oil Substances 0.000 claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 55
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 39
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- 238000004230 steam cracking Methods 0.000 description 11
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- 239000008096 xylene Substances 0.000 description 9
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- 125000003118 aryl group Chemical group 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
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- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- 229910052772 Samarium Inorganic materials 0.000 description 1
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- 229910052788 barium Inorganic materials 0.000 description 1
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- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
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- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
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- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
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- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
- C07C4/10—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from acyclic hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A combined processing method for producing basic organic chemical raw materials from crude oil uses whole crude oil as raw materials, and includes such steps as desalting and dewatering pretreatment, heat exchange with high-temp heat exchange medium, flash separation to obtain light naphtha and heavy fraction oil, catalytic cracking unit for heavy oil, catalytic cracking unit for light oil, hydrocracking and product separation unit, and features high match between the nature composition of raw materials and low-carbon olefin and light arene, and high yield of light and heavy aromatics.
Description
Technical Field
The invention relates to the field of petroleum processing, in particular to a combined processing method for producing basic organic chemical raw materials from crude oil.
Background
The demands of light aromatic hydrocarbon which mainly comprises low-carbon olefin and benzene, toluene and xylene and mainly comprises ethylene, propylene and butylene are important basic organic chemical raw materials, and the demands of the light aromatic hydrocarbon are always kept to be high-speed growing. Therefore, the production of low-carbon olefin and light aromatic hydrocarbon from crude oil becomes a main development trend of transformation upgrading, quality improvement and efficiency enhancement of petroleum refining enterprises.
The traditional refinery processing flow mainly comprises devices such as atmospheric and vacuum pressure, catalytic cracking, delayed coking, gasoline and diesel hydrogenation, and the like, has small processing depth and breadth for crude oil, and mainly comprises fuel oil such as gasoline, kerosene, diesel oil and the like. The yield of the basic chemical raw materials such as low-carbon olefin, light aromatic hydrocarbon and the like of the fuel type refinery is about 10 percent by adopting the traditional petroleum processing process flow, and the yield of the basic chemical raw materials directly prepared from crude oil is more than 40 percent, thereby bringing great economic benefit and strong enterprise competitiveness.
CN101253254a discloses a process for producing olefins using whole crude oil feedstock, which is mainly directed to using whole crude oil as feedstock for a steam cracker, preheating crude oil and separating light and heavy petroleum fractions in a conventional steam cracker with little or no coke formation, steam cracking the light fraction to produce light olefins, and discharging the heavy fraction from the cracker together with residuum produced by the cracking.
CN111116286a discloses a method and apparatus for preparing low-carbon olefin from petroleum hydrocarbon, which is mainly optimized for the feeding of steam cracking apparatus, the method includes using a cyclone separating apparatus to separate gasified petroleum hydrocarbon into vapor phase and liquid phase under reduced pressure, the vapor phase entering the steam cracking apparatus to produce low-carbon olefin, thereby realizing improvement of cracking efficiency of petroleum hydrocarbon raw material and reduction of coking of heavy raw material in cracking furnace.
CN111196936a discloses a combined method and device for directly producing olefin from crude oil, firstly adopting pretreatment such as desalting and dewatering to remove water, metal and non-metal impurities in the feed, then sending the improved crude oil into a pyrolysis furnace convection section of a steam pyrolysis device to heat and enter a gas-liquid separator to separate light fraction from heavy fraction, wherein diesel oil and lighter petroleum fraction are sent into the pyrolysis furnace to make steam pyrolysis reaction to produce low-carbon olefin, the liquid heavy fraction separated by the gas-liquid separator is sent into a hydrogenation unit to be further cracked, and hydrogenated tail oil and light petroleum oil produced by cracking are further sent into the pyrolysis furnace to make steam pyrolysis reaction to produce low-carbon olefin. The combined method of steam cracking and hydrocracking can maximally produce low-carbon olefin.
The method has the greatest characteristics that oil refining devices such as atmospheric and vacuum distillation and the like of a traditional refinery are omitted, crude oil is directly supplied to a steam cracking device, components of crude oil and gas are separated, gaseous light fraction enters a steam cracking radiation section for cracking, and liquid heavy fraction is used as raw material of other devices of the refinery, so that the method has the advantages of simplifying process flow, saving construction investment and reducing raw material cost to a certain extent. However, the patent methods have higher requirements on the quality of crude oil, require that the crude oil contains more light fractions, and easily coke on the inner wall of a pipeline and a gas-liquid separator when the heavy fractions are too much; the cracking temperature of the steam cracking device is up to more than 800 ℃, and the heating and cracking of crude oil by using the preheating section and the radiation section lead to high energy consumption of the unit. In addition, the steam cracking device takes light alkane, naphtha, light oil and other petroleum hydrocarbons as raw materials, the temperature is above 800 ℃ (generally not more than 950 ℃), and in the presence of steam, molecular fracture and dehydrogenation reactions occur by utilizing high-temperature pyrolysis reaction, and the steam cracking device takes a free radical reaction mechanism as the main part.
In order to improve the yield of the low-carbon olefin in the traditional refinery, china petrochemical industry develops a series of heavy oil catalytic cracking technologies, such as processes of DCC (CN 1004878, CN 1034586), CPP (CN 1030326, CN 1159416), HCC (CN 1030313, CN 1215041) and the like, and can process heavy distillate oil obtained by atmospheric and vacuum distillation of crude oil. The reaction temperature of the heavy oil catalytic cracking process is 150-200 ℃ lower than the steam cracking temperature, the energy consumption is lower than that of steam cracking, and the catalyst used by the process has double catalytic activities of a positive carbon ion reaction mechanism and a free radical reaction mechanism, and has higher low-carbon olefin yield. However, because the heavy oil obtained by the atmospheric and vacuum distillation unit is used as a processing raw material, when the heavy oil conversion rate in the DCC process is high, the low-value dry gas and coke yield is also high; CPP technology has the problem that the yield of ethylene and low-value product methane are increased simultaneously; the HCC reaction mechanism is mainly a free radical mechanism, the reaction temperature is higher, the heat balance requirement is difficult to meet only by burning the regenerated catalyst, and the energy consumption is higher than that of a common catalytic cracking process. Therefore, in order to further increase the low-carbon olefins, it is necessary to change the current state of the catalytic cracking process, which is currently mainly processing heavy oil raw materials.
The high-energy consumption devices such as atmospheric and vacuum distillation and the like can be omitted from directly preparing the basic chemical raw materials from crude oil, so that the whole refinery process is short, the energy consumption is low, the construction investment can be saved, and the raw material cost can be reduced; the challenges faced in directly processing crude oil are that heavy fraction in crude oil is difficult to vaporize, fuel oil yield in primary cracking products is high, catalyst deactivation is fast, and dry gas and coke yield is high. The current refinery product mode is changed from the main production of distillate products such as gasoline, aviation kerosene and diesel oil to the main production of molecular products such as light olefins and light aromatics, when the main products are changed, the crude oil atmospheric and vacuum distillation unit for the distillate products are required to be simplified, the separation unit for the molecular products is required to be emphasized, more raw materials suitable for cracking are selected to increase the reaction conversion depth, the fuel yield is reduced, the yields of the light olefins and the light aromatics are increased at the same time, and the existing public patents show that the patents for directly producing the light olefins and the light aromatics from the crude oil are fewer, and no suitable processing combination technology exists at present.
Disclosure of Invention
The invention aims to provide a method for producing basic organic chemical raw materials from crude oil, which solves the problems that heavy fraction in crude oil is difficult to vaporize, fuel oil yield in a primary cracking product is high, catalyst deactivation is fast, dry gas and coke yield are high and the like when crude oil is directly processed in the prior art.
In order to achieve the above object, the present invention provides a combined processing method for producing a basic organic chemical raw material from crude oil, comprising the steps of:
Step one: crude oil enters a desalting and dewatering pretreatment unit and exchanges heat with a high-temperature heat exchange medium after being desalted and dewatered;
step two: the crude oil enters a flash evaporation unit to be separated into light naphtha and heavy distillate after heat exchange and temperature rise;
step three: sending the light naphtha obtained after flash evaporation in the second step into a light oil catalytic cracking unit, sending the light naphtha into a light oil cracking reactor for cracking reaction, and sending the reacted oil gas into a first oil gas fractionation device of the light oil catalytic cracking unit for separation into dry gas, liquefied gas, cracked gasoline, recycle oil and slurry oil;
Step four: sending the heavy fraction oil obtained after flash evaporation in the second step into a heavy oil catalytic cracking unit, sending the heavy fraction oil into a heavy oil cracking reactor for cracking reaction, and sending the reacted oil gas into a second oil gas fractionation device of the heavy oil catalytic cracking unit for separation into dry gas, liquefied gas, pyrolysis gasoline, recycle oil and slurry oil;
step five: separating main product ethylene and byproduct hydrogen, methane and ethane from the dry gas obtained in the third step and the fourth step through a dry gas separation unit;
Step six: separating the liquefied gas obtained in the third step and the fourth step into main products of propylene, butylene and byproducts of propane and butane through a liquefied gas separation unit, and further sending the butylene and the butane back to a light oil cracking reactor of a light oil catalytic cracking unit for reaction to produce low-carbon olefin;
Step seven: separating the main product light aromatic hydrocarbon, the alkane-rich gasoline and the olefin-rich gasoline from the pyrolysis gasoline obtained in the third step and the fourth step through a gasoline separation unit, and further returning the alkane-rich gasoline and the olefin-rich gasoline to a light oil catalytic pyrolysis unit light oil pyrolysis reactor for reaction to produce light olefins and light aromatic hydrocarbon;
Step eight: separating saturated hydrocarbon-rich distillate and aromatic hydrocarbon-rich distillate from the cycle oil obtained in the third and fourth steps through a cycle oil separation unit; the saturated hydrocarbon-rich distillate oil is further sent back to the heavy oil catalytic cracking unit to enter a heavy oil cracking reactor for reaction to produce low-carbon olefin and light aromatic hydrocarbon, and the aromatic hydrocarbon-rich distillate oil enters a hydrocracking unit to be subjected to hydrocracking conversion to produce light aromatic hydrocarbon, and a small part of byproduct dry gas and liquefied gas are produced.
The combined processing method for producing the basic organic chemical raw material from the crude oil, disclosed by the invention, has the characteristic factor of 11.5-13.0, preferably 12.0-12.7, and the mass of the fraction of the crude oil at the temperature of less than 200 ℃ is more than 15wt%.
The combined processing method for producing the basic organic chemical raw material from the crude oil, disclosed by the invention, comprises the steps of desalting and dehydrating the crude oil, wherein the water content of the crude oil is less than 0.5wt% and the salt content is less than 0.3mg/L.
The combined processing method for producing basic organic chemical raw materials from crude oil, disclosed by the invention, comprises the steps of desalting and dehydrating crude oil, and carrying out heat exchange on the desalted and dehydrated crude oil by a heat exchange medium to reach 220-300 ℃.
The invention relates to a combined processing method for producing basic organic chemical raw materials from crude oil, wherein the heat exchange medium is high-temperature pyrolysis oil gas of a catalytic pyrolysis unit.
The invention relates to a combined processing method for producing basic organic chemical raw materials from crude oil, wherein the distillation range of light naphtha obtained after flash evaporation is from an initial distillation point to 240 ℃, and the distillation range of heavy distillate oil obtained is more than 240 ℃.
According to the combined processing method of the basic organic chemical raw materials for crude oil production, light naphtha obtained after flash evaporation enters a light oil catalytic cracking unit and a light oil cracking reactor bottom to carry out cracking reaction in the presence of a cracking catalyst to obtain cracked oil gas; the heavy fraction oil obtained after flash evaporation enters a heavy oil cracking reactor of a heavy oil catalytic cracking unit to carry out cracking reaction in the presence of a cracking catalyst to obtain cracked oil gas; the cracking catalyst is a composite catalyst formed by mixing a metal modified FAU type molecular sieve, an MFI molecular sieve and an MTT molecular sieve.
The silicon-aluminum molar ratio of the FAU type molecular sieve is 6-12; the silicon-aluminum molar ratio of the MFI molecular sieve is 30-200; the molar ratio of molecular sieve to silicon to aluminum of MTT is 30-100. The mass ratio of the FAU molecular sieve to the MFI molecular sieve to the MTT molecular sieve in the composite catalyst is (1-2): 10: (0-3).
The metal used for the FAU type molecular sieve modification is a rare earth element conventionally added in the art, and specifically can be, for example, lanthanoid elements, specifically can be, for example, selected from La (lanthanum), ce (cerium), pr (praseodymium), nd (neodymium), pm (promethium), sm (samarium), and Eu (europium); preferably, the rare earth in the composite catalyst is selected from lanthanum.
The elements used for modifying the MFI type molecular sieve are nonmetallic elements, alkaline earth elements and transition metal elements which are added conventionally in the field, wherein the nonmetallic elements can be phosphorus elements; the alkaline earth element may Be selected from Be (beryllium), mg (magnesium), ca (calcium), sr (strontium), ba (barium), for example, preferably the alkaline earth element in the composite catalyst is selected from Mg; the transition metal element may be a group ib, iib, ivb, viib, or viib element, and may specifically be selected from Ti (titanium), mn (manganese), fe (iron), co (cobalt), ni (nickel), cu (copper), zn (zinc), for example, and preferably, the transition metal element in the composite catalyst is selected from one or two of the above transition metals.
The elements used for modifying the MTT type molecular sieve are nonmetallic elements and transition metal elements which are added conventionally in the field, wherein the nonmetallic elements can be phosphorus elements; the transition metal element may be a group ib, iib, ivb, viib, or viib element, and may specifically be selected from Ti (titanium), mn (manganese), fe (iron), co (cobalt), ni (nickel), cu (copper), zn (zinc), for example, and preferably, the transition metal element in the composite catalyst is selected from one or two of the above transition metals.
The cracking catalyst is fluidized and circulated back and forth between the cracking reactor and the catalyst regenerator, participates in the reaction in the cracking reactor, and enters the catalyst regenerator to be burnt for recovering the activity after the activity is reduced.
The invention relates to a combined processing method for producing basic organic chemical raw materials from crude oil, wherein, a light oil catalytic cracking unit and a heavy oil catalytic cracking unit are continuous reaction-regeneration catalytic cracking devices, and the light oil catalytic cracking unit comprises a light oil cracking reactor, a first catalyst regenerator and a first oil gas fractionation device; the heavy oil catalytic cracking unit comprises a heavy oil cracking reactor, a second catalyst regenerator and a second oil gas fractionation device; the light oil cracking reactor and the heavy oil cracking reactor are both gas-solid fluidization type reactors with a combination of a conveying bed and a fast bed or a turbulent bed.
The invention relates to a combined processing method for producing basic organic chemical raw materials from crude oil, wherein the reaction conditions of a light oil cracking reactor comprise: the reaction temperature is 550-720 ℃, the catalyst-oil ratio is 10-40, the water-oil ratio is 0.2-0.5, the reaction time is 1.0-6.0 s, and the reaction pressure is 0.1-0.25 MPa.
The invention relates to a combined processing method for producing basic organic chemical raw materials from crude oil, wherein the reaction conditions of a heavy oil cracking reactor comprise: the reaction temperature is 530-650 ℃, the catalyst-oil ratio is 10-40, the water-oil ratio is 0.2-0.4, the reaction time is 2-8 s, and the reaction pressure is 0.1-0.25 MPa.
The invention relates to a combined processing method for producing basic organic chemical raw materials from crude oil, wherein the reaction conditions of a hydrocracking unit comprise: the reaction temperature is 300-450 ℃, the hydrogen-oil volume ratio is 700-1500, the weight hourly space velocity is 0.6-2.0 h -1, and the reaction pressure is 3.0-10.0 MPa.
The beneficial effects of the invention are as follows:
The method takes whole crude oil as raw material, carries out desalting and dewatering pretreatment, carries out flash evaporation separation to obtain light naphtha and heavy distillate oil after heat exchange with a high-temperature heat exchange medium, utilizes a heavy oil catalytic cracking unit, a light oil catalytic cracking unit, a hydrocracking and product separation unit, and preferentially selects raw materials suitable for cracking and cracking, and highly matches the property composition of the cracking and cracking raw materials with products such as low-carbon olefin, light aromatic hydrocarbon and the like in molecular structure, thereby realizing deep cracking and cracking conversion of the light and heavy distillate, and achieving the aims of low processing cost and high yield of the low-carbon olefin and the light aromatic hydrocarbon.
(1) The simple flash evaporation unit is used for replacing a complex and high-energy-consumption atmospheric and vacuum distillation unit of a conventional refinery, so that the whole crude oil processing flow is short, the energy consumption is low, and the construction investment is saved.
(2) The light oil and heavy oil catalytic cracking unit with the circulating fluidization type reactor has strong adaptability to raw materials, high catalytic activity, low operation cost and high low-carbon olefin yield, and can efficiently crack petroleum hydrocarbon.
(3) The method utilizes product separation units such as dry gas, liquefied gas, pyrolysis gasoline, recycle oil and the like to realize the accurate separation of molecular products such as low-carbon olefin, light aromatic hydrocarbon and the like, separates further convertible hydrocarbon according to a molecular structure, and sends the separated hydrocarbon into a proper processing unit for deep pyrolysis and cracking conversion, thereby improving the yields of the low-carbon olefin and the light aromatic hydrocarbon.
(4) The light oil catalytic cracking unit is utilized to carry out deep conversion on butane, butene, alkane-rich gasoline and olefin-rich gasoline which are sent out by the separation unit and have high molecular bond energy and are difficult to crack, so that the aim of producing low-carbon olefin by taking small-molecular hydrocarbon as a raw material is fulfilled.
(5) And (3) carrying out recycling conversion on the saturated hydrocarbon-rich fraction in the recycling oil sent out by the separation unit by utilizing the heavy oil catalytic cracking unit, so as to improve the conversion rate of crude oil and increase the yields of low-carbon olefin and light aromatic hydrocarbon.
(6) The hydrocracking unit is utilized to carry out hydroconversion on aromatic hydrocarbon in the recycle oil, the hydrogenation depth is controlled, and the aim of producing light aromatic hydrocarbon by taking polycyclic aromatic hydrocarbon as a raw material is fulfilled.
(7) The three reaction process units are separated and combined with products, so that the maximum production of basic chemical raw materials such as low-carbon olefin, light aromatic hydrocarbon and the like of crude oil can be realized, 40-65wt% of low-carbon olefin (ethylene+propylene+butylene) and 8-25wt% of light aromatic hydrocarbon (benzene+toluene+xylene) can be obtained through the processing of the combined process, and a conventional refinery can only produce about 20wt% of basic chemical raw materials such as low-carbon olefin, light aromatic hydrocarbon and the like.
Drawings
Fig. 1 is a schematic process flow diagram of embodiment 1 of the present invention.
Wherein, the reference numerals:
1. 36, 8, 9, 11, 13, 14, 15, 17, 18, 19, 20, 22, 24, 27, 28, 30, 31, 32, 33, 34, 35 pipeline
2. Desalination and dehydration pretreatment unit
4. Heat exchange unit
5. Heavy oil cracking reactor
7. Second oil gas fractionation device
10. Dry gas separation unit
12. Liquefied gas separation unit
16. Gasoline separation unit
21. Recycle oil separation unit
23. Hydrocracking unit
25. Flash unit
26. Light oil cracking reactor
29. First oil gas fractionation device
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
A combined processing method for producing basic organic chemical raw materials from crude oil, comprising: crude oil firstly enters a desalting and dewatering unit for pretreatment, then enters a heat exchange unit for heat exchange with a heat exchange medium for heating, and then enters a flash evaporation unit for separation into light naphtha and heavy distillate; the light naphtha obtained after flash evaporation is sent to the bottom of a cracking reactor of a light oil catalytic cracking unit for reaction; sending the heavy distillate oil obtained after flash evaporation into a heavy oil catalytic cracking unit for cracking reaction; the reacted oil gas respectively enters an oil gas fractionation device of a catalytic cracking unit and is separated into dry gas, liquefied gas, pyrolysis gasoline, recycle oil and slurry oil; the dry gas is separated into main product ethylene, byproduct hydrogen, methane and ethane through a dry gas separation unit; the liquefied gas passes through a liquefied gas separation unit to separate main products of propylene, butylene and byproducts of propane and butane, the butane is further sent to the bottom of a light oil catalytic cracking unit cracking reactor to react to produce light olefins, and the butylene is further sent to the lower part of the light oil catalytic cracking unit cracking reactor to react to produce ethylene and propylene; the pyrolysis gasoline passes through a gasoline separation unit to separate main products of light aromatic hydrocarbon, alkane-rich gasoline and olefin-rich gasoline, the alkane-rich gasoline is further sent to the bottom of a pyrolysis reactor of a light oil catalytic pyrolysis unit to react to produce low-carbon olefin and light aromatic hydrocarbon, and the olefin-rich gasoline is further sent back to the lower part of the pyrolysis reactor of the light oil catalytic pyrolysis unit to react to produce low-carbon olefin and light aromatic hydrocarbon; the recycle oil is subjected to a recycle oil separation unit to separate saturated hydrocarbon-rich distillate and aromatic hydrocarbon-rich distillate; the saturated hydrocarbon-rich distillate oil is further sent back to a cracking reactor of a heavy oil catalytic cracking unit for reaction to produce low-carbon olefin and light aromatic hydrocarbon, and the aromatic hydrocarbon-rich distillate oil enters a hydrocracking unit for hydrocracking and conversion to produce light aromatic hydrocarbon, and a small part of byproduct dry gas and liquefied gas are produced. For crude oil with characteristic factors of 11.5-13.0 (preferably 12.0-12.7), 40-65wt% of low-carbon olefin (ethylene, propylene and butylene) and 8-25wt% of light aromatic hydrocarbon (benzene, toluene and xylene) can be obtained through the processing of the combined process, so that the maximum production of basic organic chemical raw materials is realized.
More specifically, the method comprises the steps of:
(1) The crude oil enters a desalting and dewatering pretreatment unit, the water content of the desalted and dewatered crude oil is less than 0.5wt percent, the salt content is less than 0.3mg/L, and the crude oil is sent to a heat exchange unit;
(2) The desalted and dehydrated crude oil enters a heat exchange unit to exchange heat with high-temperature pyrolysis oil gas serving as a heat exchange medium of a catalytic cracking unit, and the temperature reaches 220-300 ℃ after heat exchange;
(3) The crude oil enters a flash evaporation unit to be separated into light naphtha and heavy distillate after heat exchange and temperature rise;
(4) The light naphtha obtained after flash evaporation is further sent to the bottom of a cracking reactor of a light oil catalytic cracking unit for reaction, and the reaction conditions of the cracking reactor include: the reaction temperature is 550-720 ℃ (preferably 600-680 ℃), the catalyst-oil ratio is 10-40 (preferably 15-30), the water-oil ratio is 0.2-0.5 (preferably 0.2-0.4), the reaction time is 1.0-6.0 s (preferably 1.5-3.0 s), and the reaction pressure is 0.1-0.25 MPa (preferably 0.15-0.20 MPa);
(2) And sending the heavy distillate oil obtained after flash evaporation into a cracking reactor of a heavy oil catalytic cracking unit for reaction, wherein the reaction conditions of the cracking reactor include: the reaction temperature is 530-650 ℃ (preferably 550-600 ℃), the catalyst-oil ratio is 10-40 (preferably 10-20), the water-oil ratio is 0.2-0.4 (preferably 0.3-0.4), the reaction time is 2-8 s (preferably 4-6 s), the reaction pressure is 0.1-0.25 MPa (preferably 0.12-0.20 MPa), and the oil gas after the cracking reaction enters an oil gas fractionation device of a catalytic cracking unit and is separated into dry gas, liquefied gas, cracked gasoline, recycle oil and slurry oil;
(3) Dry gas from the oil gas fractionation device of the catalytic cracking unit enters a dry gas separation unit to separate main product ethylene and byproducts hydrogen, methane and ethane;
(4) Liquefied gas from an oil gas fractionation device of the catalytic cracking unit passes through a liquefied gas separation unit to separate main products of propylene, butylene and byproducts of propane and butane, the butane is further sent to the bottom of a cracking reactor of the light oil catalytic cracking unit for reaction, the butylene is further sent to the lower part of the cracking reactor of the light oil catalytic cracking unit for reaction, and the reaction conditions of the cracking reactor comprise: the reaction temperature is 550-720 ℃ (preferably 600-680 ℃), the catalyst-oil ratio is 10-40 (preferably 15-30), the water-oil ratio is 0.2-0.5 (preferably 0.2-0.4), the reaction time is 1.0-6.0 s (preferably 1.5-3.0 s), and the reaction pressure is 0.1-0.25 MPa (preferably 0.15-0.20 MPa);
(5) The pyrolysis gasoline from the oil gas fractionation device of the catalytic pyrolysis unit passes through a gasoline separation unit to separate main products, namely light aromatic hydrocarbon, alkane-rich gasoline and olefin-rich gasoline; the alkane-rich gasoline is further sent to the bottom of the light oil catalytic cracking unit cracking reactor for reaction, the alkene-rich gasoline is further sent to the lower part of the light oil catalytic cracking unit cracking reactor for reaction, and the reaction conditions of the cracking reactor include: the reaction temperature is 550-720 ℃ (preferably 600-680 ℃), the catalyst-oil ratio is 10-40 (preferably 15-30), the water-oil ratio is 0.2-0.5 (preferably 0.2-0.4), the reaction time is 1.0-6.0 s (preferably 1.5-3.0 s), and the reaction pressure is 0.1-0.25 MPa (preferably 0.15-0.20 MPa);
(6) The recycle oil from the oil gas fractionation device of the catalytic cracking unit passes through a recycle oil separation unit, the separated saturated hydrocarbon-rich fraction and aromatic hydrocarbon-rich fraction are further returned to a cracking reactor of the heavy oil catalytic cracking unit for reaction, and the reaction conditions of the cracking reactor comprise: the reaction temperature is 530-650 ℃ (preferably 550-600 ℃), the catalyst-oil ratio is 10-40 (preferably 10-20), the water-oil ratio is 0.2-0.4 (preferably 0.3-0.4), the reaction time is 2-8 s (preferably 4-6 s), and the reaction pressure is 0.1-0.25 MPa (preferably 0.12-0.20 MPa);
(7) The aromatic-rich fraction obtained by the recycle oil separation unit enters a hydrocracking unit for hydrocracking and converting to produce light aromatic, and a small part of byproduct dry gas and liquefied gas are produced; the reaction conditions of the hydrocracking unit include: the reaction temperature is 300-450 ℃ (preferably 340-400 ℃), the hydrogen-oil volume ratio is 700-1500 (preferably 800-1200), the weight hourly space velocity is 0.6-2.0 h -1 (preferably 0.8-1.5 h -1), and the reaction pressure is 3.0-10.0 MPa (preferably 4-8 MPa).
Example 1
The crude oil enters a desalting and dewatering pretreatment unit 2 through a pipeline 1, the water content after desalting and dewatering is less than 0.5wt%, the salt content is less than 0.3mg/L, the crude oil enters a heat exchange unit 4 through a pipeline 3 to exchange heat with a heat exchange medium, the temperature reaches 220-300 ℃ after heat exchange, and the crude oil enters a flash evaporation unit 25 to be separated into light naphtha (initial distillation point-240 ℃) and heavy distillate oil (> 240 ℃); the light naphtha obtained after flash evaporation is further sent to the bottom cracking reaction of the light oil cracking reactor 26 of the light oil catalytic cracking unit through a pipeline 35, the reacted oil gas enters the first oil gas fractionation device 29 of the light oil catalytic cracking unit through a pipeline 27 and is separated into dry gas, liquefied gas, pyrolysis gasoline, recycle oil and slurry oil, the slurry oil is sent out of the device through a pipeline 28, and the dry gas, the liquefied gas, the pyrolysis gasoline and the recycle oil are respectively sent to the dry gas separation unit 10, the liquefied gas separation unit 12, the gasoline separation unit 16 and the recycle oil separation unit 21 through a pipeline 30, a pipeline 31, a pipeline 32 and a pipeline 33; the heavy fraction oil obtained after passing through the flash evaporation unit 25 enters a heavy oil cracking reactor 5 of a heavy oil catalytic cracking unit through a pipeline 34 for cracking reaction, the reacted oil gas enters a second oil gas fractionation device 7 of the catalytic cracking unit through a pipeline 6 and is separated into dry gas, liquefied gas, pyrolysis gasoline, recycle oil and slurry oil, the slurry oil is sent out of the device through a pipeline 8, and the dry gas, the liquefied gas, the pyrolysis gasoline and the recycle oil are respectively sent into a dry gas separation unit 10, a liquefied gas separation unit 12, a gasoline separation unit 16 and a recycle oil separation unit 21 through a pipeline 9, a pipeline 11, a pipeline 15 and a pipeline 20. After the dry gas of the light and heavy catalytic cracking units enters the dry gas separation unit 10, main products ethylene and byproducts hydrogen, methane and ethane are separated; after liquefied gas of the light and heavy catalytic cracking units enters the liquefied gas separation unit 12, main products propylene, butylene, byproducts propane and butane are separated, the butane is further sent to the bottom of the light oil cracking reactor 26 of the light oil catalytic cracking unit through a pipeline 13 for reaction, and the butylene is further sent to the lower part of the light oil cracking reactor 26 of the light oil catalytic cracking unit through a pipeline 14 for reaction; after the pyrolysis gasoline of the light and heavy catalytic pyrolysis units enters the gasoline separation unit 16, main products of light aromatic hydrocarbon, alkane-rich gasoline and olefin-rich gasoline are separated, the light aromatic hydrocarbon is sent out of the device through a pipeline 19, the alkane-rich gasoline is further sent into the bottom of the light oil catalytic pyrolysis unit light oil pyrolysis reactor 26 through a pipeline 17 for reaction, and the olefin-rich gasoline is further sent back to the lower part of the light oil catalytic pyrolysis unit light oil pyrolysis reactor 26 through a pipeline 18 for reaction; after the recycle oil of the light and heavy catalytic cracking unit enters a recycle oil separation unit 21, separating saturated hydrocarbon-rich distillate and aromatic hydrocarbon-rich distillate; the saturated hydrocarbon-rich distillate oil is further sent back to the heavy oil catalytic cracking unit through a pipeline 24 and is mixed with the heavy distillate oil to enter a heavy oil cracking reactor 5 for reaction to produce light olefins and light aromatics, and the aromatic hydrocarbon-rich distillate oil enters a hydrocracking unit 23 through a pipeline 22 for hydrocracking conversion to produce light aromatics, and a small part of byproduct dry gas and liquefied gas are produced.
The feedstock used in this example was crude oil with a characteristic factor K of 13.0, the properties of which are shown in table 1.1.
The catalyst for the cleavage reaction of this example (catalyst grade: LPS-67C, purchased from Petroleum Rana catalyst division, china) was: FAU type molecular sieve with 1wt% lanthanum, MFI type molecular sieve with 4wt% phosphorus, 0.5wt% magnesium, 3wt% iron and 0.1wt% titanium, and MTT type molecular sieve with 2wt% phosphorus and 1wt% zinc; the mass ratio of the FAU type molecular sieve to the MFI type molecular sieve to the MTT type molecular sieve in the composite catalyst is 1:10:3, the silicon-aluminum molar ratio of the MFI type molecular sieve is 30, and the silicon-aluminum molar ratio of the MTT type molecular sieve is 60.
TABLE 1.1 raw oil Properties
Taking crude oil as a reference, enabling 68.09wt% of heavy distillate oil obtained after flash evaporation to enter a cracking reactor of a heavy oil catalytic cracking unit for cracking reaction, wherein the process operation conditions of the cracking reactor of the heavy oil catalytic cracking unit are shown in table 1.2, and the product distribution of the heavy oil catalytic cracking unit is shown in table 1.3. The 31.91wt% light naphtha obtained after flash evaporation enters the bottom of a cracking reactor of a light oil catalytic cracking unit to carry out cracking reaction (the process operation conditions and the main product distribution are shown in tables 1.7 and 1.8).
TABLE 1.2 Process operating conditions for a heavy oil catalytic cracking unit cracking reactor
TABLE 1.3 product distribution/wt% of heavy oil catalytic cracking units (based on unit weight heavy distillate)
The yield of the catalytic cracking dry gas from the oil gas fractionation device of the heavy oil catalytic cracking unit is 11.60 weight percent based on the unit weight of heavy distillate oil, wherein the yield of ethylene is 7.61 weight percent (see table 1.3); wherein the catalytic cracking liquefied gas yield is 50.18wt%, the propylene yield is 23.26wt%, the butene yield is 12.74wt%, and the butane yield is 10.01wt% (see table 1.3); the composition of the dry gas entering the dry gas separation unit is shown in table 1.4, and the separated dry gas is used as hydrogen, methane, ethane and ethylene products respectively.
TABLE 1.4 composition of dry gas entering the dry gas separation unit/wt%
The composition of the liquefied gas entering the liquefied gas separation unit is shown in table 1.5, main products of propylene, butylene and byproducts of propane and butane are obtained after separation, the separated butane enters the bottom of a light oil catalytic cracking unit cracking reactor to react to produce low-carbon olefin, and a small part of byproduct dry gas (the process operation conditions and the main product distribution are shown in table 1.7 and table 1.8) enters the lower part of the light oil catalytic cracking unit cracking reactor to react to produce ethylene and propylene (the process operation conditions and the main product distribution are shown in table 1.7 and table 1.8).
TABLE 1.5 composition of liquefied gas entering the liquefied gas separation unit/wt%
The yield of the catalytic pyrolysis gasoline from the oil-gas fractionation device of the catalytic pyrolysis unit is 16.41wt% (calculated in tables 1.1, 1.3 and 1.8) based on the unit mass of crude oil, the composition of the gasoline entering the gasoline separation unit and the composition of the separated alkane-rich gasoline and the separated alkene-rich gasoline are shown in table 1.6, the separated alkane-rich gasoline enters the bottom of the cracking reactor of the light oil catalytic pyrolysis unit to react (the process operation conditions and the main product distribution are shown in tables 1.7 and 1.8), and the separated alkene-rich gasoline is returned to the lower part of the cracking reactor of the light oil catalytic pyrolysis unit to react (the process operation conditions and the main product distribution are shown in tables 1.7 and 1.8).
TABLE 1.6 composition of gasoline entering separation unit and composition of separated alkane-rich, olefin-rich gasoline and light aromatic hydrocarbon/wt%
Table 1.7 shows the process conditions of the pyrolysis reactor of the light oil catalytic pyrolysis unit, and Table 1.8 shows the main product distribution of the light oil catalytic pyrolysis unit.
TABLE 1.7 Process operating conditions for light oil catalytic cracking Unit cracking reactor
TABLE 1.8 distribution of light oil catalytic cracking Unit products/wt% (based on unit mass of light oil catalytic cracking Unit feed)
The yield of the catalytic cracking dry gas from the oil gas fractionation device of the light oil catalytic cracking unit is 38.98wt percent based on the unit mass of the light oil catalytic cracking unit feed, wherein the yield of ethylene is 35.67wt percent (see table 1.8); wherein the catalytic cracking liquefied gas yield is 49.32wt%, the propylene yield is 32.83wt%, the butene yield is 6.77wt%, and the butane yield is 8.45wt% (see table 1.8); the composition of the dry gas entering the dry gas separation unit is shown in table 1.4, the composition of the liquefied gas entering the liquefied gas separation unit is shown in table 1.5, and the composition of the gasoline entering the gasoline separation unit and the composition of the separated alkane-rich gasoline and olefin-rich gasoline are shown in table 1.6.
The yield of the catalytic cracking cycle oil from the oil and gas fractionation device of the catalytic cracking unit was 4.36wt% (calculated in tables 1.1, 1.3 and 1.8) based on the unit mass of crude oil, and the composition of the cycle oil entering the cycle oil separation unit and the composition of the separated saturated hydrocarbon-rich fraction oil and aromatic hydrocarbon-rich fraction oil are shown in table 1.9. The separated saturated hydrocarbon-rich distillate oil is further sent back to the heavy oil catalytic cracking unit and mixed with the heavy distillate oil to enter a cracking reactor for reaction to produce light olefins and light aromatics (the process operating conditions and the main product distribution are shown in tables 1.2 and 1.3), the aromatic hydrocarbon-rich distillate oil enters a hydrocracking unit for hydrocracking and conversion to produce light aromatics, and a small part of byproduct dry gas and liquefied gas are produced.
TABLE 1.9 composition of cycle oil and composition of saturated hydrocarbon-rich fraction and aromatic hydrocarbon-rich fraction after separation/wt%
Table 1.10 shows the process conditions for the reaction of the aromatic-rich distillate into the hydrocracking unit, and Table 1.11 shows the main product distribution of the hydrocracking unit.
TABLE 1.10 Process operating conditions for hydrocracking Unit reactions of aromatic-rich distillate
TABLE 1.11 Main product distribution/wt% of hydrocracking Unit
The yields of the low-carbon olefin (ethylene+propylene+butylene, ethylene+propylene) and the light aromatic hydrocarbon (benzene+toluene+xylene) in the cracking and cracking processes are shown in table 1.12, the heavy oil is catalytically cracked to obtain 36.23wt% of the low-carbon olefin (ethylene+propylene+butylene) and 10.85wt% of the light aromatic hydrocarbon based on the unit mass of crude oil, the light oil is catalytically cracked to obtain 38.72wt% of the low-carbon olefin (ethylene+propylene+butylene) and 4.78wt% of the light aromatic hydrocarbon, and the hydrocracking is performed to obtain 2.41wt% of the light aromatic hydrocarbon.
TABLE 1.12 yields of light olefins and aromatics for cracking and cracking processes (based on crude oil unit mass)
The yield of the low-carbon olefin (ethylene+propylene+butylene, ethylene+propylene) and the yield of the light aromatic hydrocarbon (benzene+toluene+xylene) obtained by adopting the combined process are shown in table 1.13, compared with the yield of the low-carbon olefin and the yield of the light aromatic hydrocarbon in the existing refining integrated refinery (constant force petrochemical 20Mt/a refining integrated project is comprehensively put into production, china petrochemical organic raw material science and technology center station, petrochemical technology and economy, 2019, 35 (04): 37. Anti-epidemic situation acts as constant force petrochemical 150 ten thousand t/a ethylene project to produce qualified products, petrochemical design 2020, 37 (01): 14.) the yield of the low-carbon olefin (ethylene+propylene+butylene) is increased by 49.10 percent, the yield of the ethylene+propylene is increased by 46.74 percent, and the yield of the low-carbon olefin and the light aromatic hydrocarbon is increased by 44.44 percent.
TABLE 1.13 comparison of the combined Process and yield of light aromatic hydrocarbons/wt% of light olefins in an Integrated refinery at present
Example 2
The process flow profile is identical to that of example 1.
The feedstock used in this example was crude oil with a characteristic factor K of 11.5, the properties of which are shown in table 2.1.
The catalyst for the cleavage reaction of this example (catalyst grade: LPS-67C, purchased from Petroleum Rana catalyst division, china) was: FAU type molecular sieve with 3wt% lanthanum, MFI type molecular sieve with 2wt% phosphorus, 1wt% magnesium, 4wt% iron and 1wt% nickel, and MTT type molecular sieve with 2wt% phosphorus and 0.5wt% zinc; the mass ratio of the FAU type molecular sieve to the MFI type molecular sieve to the MTT type molecular sieve in the composite catalyst is 2:10:1, the silicon-aluminum molar ratio of the MFI type molecular sieve is 100, and the silicon-aluminum molar ratio of the MTT type molecular sieve is 70.
TABLE 2.1 raw oil Properties
The 84.87wt% of heavy distillate oil obtained by flash evaporation based on the unit mass of crude oil enters a cracking reactor of a heavy oil catalytic cracking unit for cracking reaction, the process operation conditions of the cracking reactor of the heavy oil catalytic cracking unit are shown in table 2.2, and the product distribution of the heavy oil catalytic cracking unit is shown in table 2.3. The 15.13wt% light naphtha obtained after flash evaporation enters the bottom of a cracking reactor of a light oil catalytic cracking unit to carry out cracking reaction (the process operation conditions and the main product distribution are shown in tables 2.7 and 2.8).
TABLE 2.2 Process operating conditions for heavy oil catalytic cracking unit cracking reactor
TABLE 2.3 product distribution/wt% of heavy oil catalytic cracking units (based on unit weight heavy distillate)
The yield of the catalytic cracking dry gas from the oil gas fractionation device of the heavy oil catalytic cracking unit is 6.75 weight percent based on the unit weight of heavy distillate oil, wherein the yield of ethylene is 3.41 weight percent (see table 2.3); wherein the yield of the catalytic cracking liquefied gas is 39.05wt%, the yield of propylene is 16.49wt%, the yield of butylene is 12.61wt%, and the yield of butane is 7.26wt% (see table 2.3); the composition of the dry gas entering the dry gas separation unit is shown in table 2.4, and the separated dry gas is used as hydrogen, methane, ethane and ethylene products respectively.
TABLE 2.4 composition of dry gas entering the dry gas separation unit/wt%
The composition of the liquefied gas entering the liquefied gas separation unit is shown in table 2.5, main products of propylene, butylene and byproducts of propane and butane are obtained after separation, the separated butane enters the bottom of a light oil catalytic cracking unit cracking reactor to react to produce low-carbon olefin, and a small part of byproduct dry gas (the process operation conditions and the main product distribution are shown in table 2.7 and table 2.8) enters the lower part of the light oil catalytic cracking unit cracking reactor to react to produce ethylene and propylene (the process operation conditions and the main product distribution are shown in table 2.7 and table 2.8).
TABLE 2.5 composition of liquefied gas entering the liquefied gas separation unit/wt%
The yield of the catalytic pyrolysis gasoline from the oil-gas fractionation device of the catalytic pyrolysis unit is 22.36wt% (calculated in tables 2.1, 2.3 and 2.8) based on the unit mass of crude oil, the composition of the gasoline entering the gasoline separation unit and the composition of the separated alkane-rich gasoline and the composition of the separated alkene-rich gasoline are shown in table 2.6, the separated alkane-rich gasoline enters the bottom of the cracking reactor of the light oil catalytic pyrolysis unit to react (the process operation conditions and the main product distribution are shown in tables 2.7 and 2.8), and the separated alkene-rich gasoline is returned to the lower part of the cracking reactor of the light oil catalytic pyrolysis unit to react (the process operation conditions and the main product distribution are shown in tables 2.7 and 2.8).
TABLE 2.6 composition of gasoline entering separation unit and composition of separated alkane-rich, olefin-rich gasoline and light aromatic hydrocarbon/wt%
Table 2.7 shows the process conditions of the pyrolysis reactor of the light oil catalytic pyrolysis unit, and Table 2.8 shows the main product distribution of the light oil catalytic pyrolysis unit.
TABLE 2.7 Process operating conditions for light oil catalytic cracking Unit cracking reactor
TABLE 2.8 distribution of light oil catalytic cracking Unit products/wt% (based on unit mass of light oil catalytic cracking Unit feed)
The yield of the catalytic cracking dry gas from the oil gas fractionation device of the light oil catalytic cracking unit is 33.67wt percent based on the unit mass of the light oil catalytic cracking unit feed, wherein the yield of ethylene is 25.72wt percent (see table 2.8); wherein the yield of the catalytic cracking liquefied gas is 41.25wt%, the yield of propylene is 25.76wt%, the yield of butylene is 8.51wt%, and the yield of butane is 6.50wt% (see Table 2.8); the composition of the dry gas entering the dry gas separation unit is shown in table 2.4, the composition of the liquefied gas entering the liquefied gas separation unit is shown in table 2.5, and the composition of the gasoline entering the gasoline separation unit and the composition of the separated alkane-rich gasoline and olefin-rich gasoline are shown in table 2.6.
The recovery rate of the catalytic cracking cycle oil from the oil and gas fractionation device of the catalytic cracking unit was 9.64wt% (calculated in tables 2.1, 2.3 and 2.8) based on the unit mass of crude oil, and the composition of the cycle oil entering the cycle oil separation unit and the composition of the separated saturated hydrocarbon-rich fraction oil and aromatic hydrocarbon-rich fraction oil were shown in table 2.9. The separated saturated hydrocarbon-rich distillate oil is further sent back to the heavy oil catalytic cracking unit and mixed with the heavy distillate oil to enter a cracking reactor for reaction to produce light olefins and light aromatics (the process operating conditions and the main product distribution are shown in tables 2.2 and 2.3), the aromatic hydrocarbon-rich distillate oil enters a hydrocracking unit for hydrocracking and conversion to produce light aromatics, and a small part of byproduct dry gas and liquefied gas are produced.
TABLE 2.9 composition of cycle oil and composition of saturated hydrocarbon-rich fraction and aromatic hydrocarbon-rich fraction after separation/wt%
Table 2.10 shows the process conditions for the reaction of the aromatic-rich distillate into the hydrocracking unit, and Table 2.11 shows the main product distribution of the hydrocracking unit.
TABLE 2.10 Process operating conditions for hydrocracking Unit reactions of aromatic-rich distillate
TABLE 2.11 Main product distribution/wt% of hydrocracking Unit
The yields of the low-carbon olefin (ethylene+propylene+butylene, ethylene+propylene) and the light aromatic hydrocarbon (benzene+toluene+xylene) in the cracking and cracking processes are shown in table 2.12, by taking crude oil as a unit mass basis, the heavy oil is catalytically cracked to obtain 43.02wt% of the low-carbon olefin (ethylene+propylene+butylene) and 12.99wt% of the light aromatic hydrocarbon, the light oil is catalytically cracked to obtain 26.53wt% of the low-carbon olefin (ethylene+propylene+butylene) and 6.66wt% of the light aromatic hydrocarbon, and the hydrocracking is performed to obtain 4.81wt% of the light aromatic hydrocarbon.
TABLE 2.12 yields of light olefins and aromatics for cracking and cracking processes (based on crude oil unit mass)
The yield of the low-carbon olefin (ethylene+propylene+butylene, ethylene+propylene) and the yield of the light aromatic hydrocarbon (benzene+toluene+xylene) obtained by adopting the combined process are shown in Table 2.13, compared with the yield of the low-carbon olefin and the yield of the light aromatic hydrocarbon in the existing refining integrated refinery (constant force petrochemical 20Mt/a refining integrated project is comprehensively put into production, china petrochemical organic raw material science and technology center station, petrochemical technology and economy, 2019, 35 (04): 37. Anti-epidemic situation acts as constant force petrochemical 150 ten thousand t/a ethylene project to produce qualified products, petrochemical design 2020, 37 (01): 14.), the yield of the low-carbon olefin (ethylene+propylene+butylene) is improved by 32.79 percent, the yield of the ethylene+propylene is improved by 30.14 percent, and the yield of the low-carbon olefin and the light aromatic hydrocarbon is improved by 34.54 percent.
Table 2.13 comparison of the combined Process and yield of light aromatic hydrocarbons/wt% of light olefins in an Integrated refinery at present
Example 3
The process flow profile is identical to that of example 1.
The feedstock used in this example was crude oil with a characteristic factor K of 12.3, the properties of which are shown in table 3.1.
The catalyst for the cleavage reaction of this example (catalyst grade: LPS-67C, purchased from Petroleum Rana catalyst division, china) was: an FAU type molecular sieve with 2wt% of lanthanum, an MFI type molecular sieve with 3wt% of phosphorus, 0.8wt% of magnesium, 5wt% of iron and 0.5wt% of nickel, and an MTT type molecular sieve with 2wt% of phosphorus and 0.7wt% of zinc; the mass ratio of the FAU type molecular sieve to the MFI type molecular sieve to the MTT type molecular sieve in the composite catalyst is 2:10:2, the silicon-aluminum molar ratio of the MFI type molecular sieve is 80, and the silicon-aluminum molar ratio of the MTT type molecular sieve is 65.
TABLE 3.1 raw oil Properties
The unit mass of crude oil is taken as a reference, 78.05wt% of heavy distillate oil obtained after flash evaporation enters a cracking reactor of a heavy oil catalytic cracking unit for cracking reaction, the process operation conditions of the cracking reactor of the heavy oil catalytic cracking unit are shown in table 3.2, and the product distribution of the heavy oil catalytic cracking unit is shown in table 3.3. The 21.95wt% light naphtha obtained after flash evaporation enters the bottom of a cracking reactor of a light oil catalytic cracking unit to carry out cracking reaction (the process operation conditions and the main product distribution are shown in tables 3.7 and 3.8).
TABLE 3.2 Process operating conditions for cracking reactors of heavy oil catalytic cracking units
TABLE 3.3 product distribution/wt% of heavy oil catalytic cracking units (based on unit weight heavy distillate)
The yield of the catalytic cracking dry gas from the oil gas fractionation device of the heavy oil catalytic cracking unit is 8.86 weight percent based on the unit weight of heavy distillate oil, wherein the yield of ethylene is 5.12 weight percent (see table 3.3); wherein the catalytic cracking liquefied gas yield is 44.05wt%, the propylene yield is 20.22wt%, the butene yield is 12.69wt%, and the butane yield is 7.80wt% (see table 3.3); the composition of the dry gas entering the dry gas separation unit is shown in table 3.4, and the separated dry gas is used as hydrogen, methane, ethane and ethylene products respectively.
TABLE 3.4 composition of dry gas entering the dry gas separation unit/wt%
The composition of the liquefied gas entering the liquefied gas separation unit is shown in table 3.5, main products of propylene, butylene and byproducts of propane and butane are obtained after separation, the separated butane enters the bottom of a light oil catalytic cracking unit cracking reactor to react to produce low-carbon olefin, and a small part of byproduct dry gas (the process operation conditions and the main product distribution are shown in table 3.7 and table 3.8) enters the lower part of the light oil catalytic cracking unit cracking reactor to react to produce ethylene and propylene (the process operation conditions and the main product distribution are shown in table 3.7 and table 3.8).
TABLE 3.5 composition of liquefied gas entering the liquefied gas separation unit/wt%
The yield of the catalytic pyrolysis gasoline from the oil-gas fractionation device of the catalytic pyrolysis unit is 20.94wt% (calculated in tables 3.1, 3.3 and 3.8) based on the unit mass of crude oil, the composition of the gasoline entering the gasoline separation unit and the composition of the separated alkane-rich gasoline and the composition of the separated alkene-rich gasoline are shown in table 3.6, the separated alkane-rich gasoline enters the bottom of the cracking reactor of the light oil catalytic pyrolysis unit to react (the process operation conditions and the main product distribution are shown in tables 3.7 and 3.8), and the separated alkene-rich gasoline is returned to the lower part of the cracking reactor of the light oil catalytic pyrolysis unit to react (the process operation conditions and the main product distribution are shown in tables 3.7 and 3.8).
TABLE 3.6 composition of gasoline entering separation unit and composition of separated alkane-rich, olefin-rich gasoline and light aromatic hydrocarbon/wt%
Table 3.7 shows the process conditions of the pyrolysis reactor of the light oil catalytic pyrolysis unit, and Table 3.8 shows the main product distribution of the light oil catalytic pyrolysis unit.
TABLE 3.7 Process operating conditions for light oil catalytic cracking Unit cracking reactor
TABLE 3.8 distribution of light oil catalytic cracking Unit products/wt% (based on unit mass of light oil catalytic cracking Unit feed)
The yield of the catalytic cracking dry gas from the oil gas fractionation device of the light oil catalytic cracking unit is 36.12 weight percent based on the unit mass of the light oil catalytic cracking unit feed, wherein the yield of ethylene is 30.21 weight percent (see table 3.8); wherein the yield of the catalytic cracking liquefied gas is 45.25wt%, the yield of propylene is 29.92wt%, the yield of butylene is 7.76wt%, and the yield of butane is 6.74wt% (see Table 3.8); the composition of the dry gas entering the dry gas separation unit is shown in table 3.4, the composition of the liquefied gas entering the liquefied gas separation unit is shown in table 3.5, and the composition of the gasoline entering the gasoline separation unit and the composition of the separated alkane-rich gasoline and olefin-rich gasoline are shown in table 3.6.
The yield of the catalytic cracking cycle oil from the oil and gas fractionation device of the catalytic cracking unit was 5.70wt% (calculated in tables 3.1, 3.3 and 3.8) based on the unit mass of crude oil, and the composition of the cycle oil entering the cycle oil separation unit and the composition of the separated saturated hydrocarbon-rich fraction oil and aromatic hydrocarbon-rich fraction oil are shown in table 3.9. The separated saturated hydrocarbon-rich distillate oil is further sent back to the heavy oil catalytic cracking unit and mixed with the heavy distillate oil to enter a cracking reactor for reaction to produce light olefins and light aromatics (the process operation conditions and the main product distribution are shown in tables 3.2 and 3.3), the aromatic hydrocarbon-rich distillate oil enters a hydrocracking unit for hydrocracking and conversion to produce light aromatics, and a small part of byproduct dry gas and liquefied gas are produced.
TABLE 3.9 composition of cycle oil and composition of saturated hydrocarbon-rich fraction and aromatic hydrocarbon-rich fraction after separation/wt%
Table 3.10 shows the process conditions for the reaction of the aromatic-rich distillate into the hydrocracking unit, and Table 3.11 shows the main product distribution of the hydrocracking unit.
TABLE 3.10 Process operating conditions for hydrocracking Unit reactions of aromatic-rich distillate
TABLE 3.11 Main product distribution/wt% of hydrocracking Unit
The yields of the low-carbon olefin (ethylene+propylene+butylene, ethylene+propylene) and the light aromatic hydrocarbon (benzene+toluene+xylene) in the cracking and cracking processes are shown in table 3.12, and based on the unit mass of crude oil, the heavy oil is catalytically cracked to obtain 41.65wt% of the low-carbon olefin (ethylene+propylene+butylene) and 13.26wt% of the light aromatic hydrocarbon, the light oil is catalytically cracked to obtain 31.20wt% of the low-carbon olefin (ethylene+propylene+butylene) and 6.80wt% of the light aromatic hydrocarbon, and the hydrocracking is performed to obtain 3.27wt% of the light aromatic hydrocarbon.
TABLE 3.12 yields of light olefins and aromatics for cracking and cracking processes (based on crude oil unit mass)
The yield of the low-carbon olefin (ethylene+propylene+butylene, ethylene+propylene) and the yield of the light aromatic hydrocarbon (benzene+toluene+xylene) obtained by adopting the combined process are shown in Table 3.13 on the basis of crude oil of unit mass, compared with the yield of the low-carbon olefin and the yield of the light aromatic hydrocarbon in the existing refining integrated refinery (constant force petrochemical 20Mt/a refining integrated project is comprehensively put into production, china petrochemical organic raw material science and technology center station, petrochemical technology and economy, 2019, 35 (04): 37. Anti-epidemic situation acts as a qualified product produced by all chemical devices of the constant force petrochemical (large connection) 150 ten thousand t/a ethylene project, petrochemical design, 2020, 37 (01): 14.) the yield of the low-carbon olefin (ethylene+propylene+butylene) is improved by 40.34 percent, the yield of the ethylene+propylene is improved by 37.89 percent, and the yield of the low-carbon olefin and the light aromatic hydrocarbon is improved by 40.98 percent.
TABLE 3.13 comparison of the combined Process and yield of light aromatic hydrocarbons/wt% of light olefins in an Integrated refinery at present
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. The combined processing method for producing the basic organic chemical raw material from the crude oil is characterized by comprising the following steps of:
Step one: crude oil enters a desalting and dewatering pretreatment unit and exchanges heat with a high-temperature heat exchange medium after being desalted and dewatered;
step two: the crude oil enters a flash evaporation unit to be separated into light naphtha and heavy distillate after heat exchange and temperature rise;
step three: sending the light naphtha obtained after flash evaporation in the second step into a light oil catalytic cracking unit, sending the light naphtha into a light oil cracking reactor for cracking reaction, and sending the reacted oil gas into a first oil gas fractionation device of the light oil catalytic cracking unit for separation into dry gas, liquefied gas, cracked gasoline, recycle oil and slurry oil;
Step four: sending the heavy fraction oil obtained after flash evaporation in the second step into a heavy oil catalytic cracking unit, sending the heavy fraction oil into a heavy oil cracking reactor for cracking reaction, and sending the reacted oil gas into a second oil gas fractionation device of the heavy oil catalytic cracking unit for separation into dry gas, liquefied gas, pyrolysis gasoline, recycle oil and slurry oil;
step five: separating main product ethylene and byproduct hydrogen, methane and ethane from the dry gas obtained in the third step and the fourth step through a dry gas separation unit;
Step six: separating the liquefied gas obtained in the third step and the fourth step into main products of propylene, butylene and byproducts of propane and butane through a liquefied gas separation unit, and further sending the butylene and the butane back to a light oil cracking reactor of a light oil catalytic cracking unit for reaction to produce low-carbon olefin;
Step seven: separating the main product light aromatic hydrocarbon, the alkane-rich gasoline and the olefin-rich gasoline from the pyrolysis gasoline obtained in the third step and the fourth step through a gasoline separation unit, and further returning the alkane-rich gasoline and the olefin-rich gasoline to a light oil catalytic pyrolysis unit light oil pyrolysis reactor for reaction to produce light olefins and light aromatic hydrocarbon;
Step eight: separating saturated hydrocarbon-rich distillate and aromatic hydrocarbon-rich distillate from the cycle oil obtained in the third and fourth steps through a cycle oil separation unit; the saturated hydrocarbon-rich distillate oil is further sent back to the heavy oil catalytic cracking unit to enter a heavy oil cracking reactor for reaction to produce low-carbon olefin and light aromatic hydrocarbon, and the aromatic hydrocarbon-rich distillate oil enters a hydrocracking unit to be subjected to hydrocracking conversion to produce light aromatic hydrocarbon, and a small part of byproduct dry gas and liquefied gas are produced;
the characteristic factor of the crude oil is 11.5-13.0, and the mass of the fraction of the crude oil at the temperature of less than 200 ℃ is more than 15wt%;
The light naphtha obtained after flash evaporation has a distillation range of between an initial distillation point and 240 ℃, and the heavy distillate oil obtained has a distillation range of more than 240 ℃;
The light naphtha obtained after flash evaporation enters the bottom of a light oil cracking reactor of a light oil catalytic cracking unit to carry out cracking reaction in the presence of a cracking catalyst to obtain cracked oil gas; the heavy fraction oil obtained after flash evaporation enters a heavy oil cracking reactor of a heavy oil catalytic cracking unit to carry out cracking reaction in the presence of a cracking catalyst to obtain cracked oil gas; the cracking catalyst is a composite catalyst formed by mixing a metal modified FAU type molecular sieve, an MFI molecular sieve and an MTT molecular sieve; the silicon-aluminum molar ratio of the FAU type molecular sieve is 6-12; the silicon-aluminum molar ratio of the MFI molecular sieve is 30-200; the silicon-aluminum mole ratio of the MTT molecular sieve is 30-100; the mass ratio of the FAU molecular sieve to the MFI molecular sieve to the MTT molecular sieve in the composite catalyst is (1-2): 10: (0-3);
the light oil catalytic cracking unit and the heavy oil catalytic cracking unit are continuous reaction-regeneration catalytic cracking devices, and the light oil catalytic cracking unit comprises a light oil cracking reactor, a first catalyst regenerator and a first oil gas fractionation device; the heavy oil catalytic cracking unit comprises a heavy oil cracking reactor, a second catalyst regenerator and a second oil gas fractionation device; the light oil cracking reactor and the heavy oil cracking reactor are both gas-solid fluidization type reactors with a combination of a conveying bed and a rapid bed or a turbulent bed;
The reaction conditions of the light oil cracking reactor include: the reaction temperature is 550-720 ℃, the catalyst-oil ratio is 10-40, the water-oil ratio is 0.2-0.5, the reaction time is 1.0-6.0 s, and the reaction pressure is 0.1-0.25 MPa;
The reaction conditions of the heavy oil cracking reactor include: the reaction temperature is 530-650 ℃, the agent-oil ratio is 10-40, the water-oil ratio is 0.2-0.4, the reaction time is 2-8 s, and the reaction pressure is 0.1-0.25 MPa;
The reaction conditions of the hydrocracking unit include: the reaction temperature is 300-450 ℃, the hydrogen-oil volume ratio is 700-1500, the weight hourly space velocity is 0.6-2.0 h -1, and the reaction pressure is 3.0-10.0 MPa.
2. The method of combined processing of a basic organic chemical feedstock from crude oil according to claim 1, wherein the crude oil has a characteristic factor of 12.0 to 12.7.
3. The method for combined processing of a basic organic chemical raw material from crude oil according to claim 1, wherein the water content of the crude oil after the crude oil is subjected to a desalting and dewatering unit is less than 0.5wt% and the salt content is less than 0.3mg/L.
4. The method for combined processing of organic chemical raw materials based on crude oil production according to claim 1, wherein the crude oil after desalting and dewatering is subjected to heat exchange by a heat exchange medium to reach 220-300 ℃.
5. The method for combined processing of basic organic chemical raw materials from crude oil according to claim 1, wherein the heat exchange medium is pyrolysis oil gas of a catalytic pyrolysis unit.
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| CN105349179A (en) * | 2015-10-28 | 2016-02-24 | 中国石油大学(华东) | Combined process of heavy petroleum hydrocarbon catalytic cracking and light petroleum hydrocarbon steam cracking |
| CN111825514A (en) * | 2020-08-12 | 2020-10-27 | 浙江科茂环境科技有限公司 | Method for maximizing production of ethylene or propylene |
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| CN101362669A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ethylene, propylene and aromatic hydrocarbon preparation |
| CN105349179A (en) * | 2015-10-28 | 2016-02-24 | 中国石油大学(华东) | Combined process of heavy petroleum hydrocarbon catalytic cracking and light petroleum hydrocarbon steam cracking |
| CN111825514A (en) * | 2020-08-12 | 2020-10-27 | 浙江科茂环境科技有限公司 | Method for maximizing production of ethylene or propylene |
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