CN114478159B - Method and system for preparing low-carbon olefin - Google Patents
Method and system for preparing low-carbon olefin Download PDFInfo
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- CN114478159B CN114478159B CN202011157915.5A CN202011157915A CN114478159B CN 114478159 B CN114478159 B CN 114478159B CN 202011157915 A CN202011157915 A CN 202011157915A CN 114478159 B CN114478159 B CN 114478159B
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000005336 cracking Methods 0.000 claims abstract description 96
- 238000000926 separation method Methods 0.000 claims abstract description 77
- 239000010779 crude oil Substances 0.000 claims abstract description 45
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims description 26
- 238000000197 pyrolysis Methods 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 5
- 238000003776 cleavage reaction Methods 0.000 claims description 4
- 239000001282 iso-butane Substances 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 230000007017 scission Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004939 coking Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 31
- 239000002994 raw material Substances 0.000 description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000004230 steam cracking Methods 0.000 description 4
- -1 ethylene, propylene, butadiene Chemical class 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002352 steam pyrolysis Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- 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
- C07C4/04—Thermal processes
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/20—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert heated gases or vapours
-
- 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
- C10G7/00—Distillation of hydrocarbon oils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of preparation of low-carbon olefins, and discloses a method and a system for preparing low-carbon olefins. The method comprises the following steps: (1) mixing crude oil with light hydrocarbons of C1-C6 to form a mixture; under the high pressure condition of more than 0.9MPa, carrying out first separation on the mixture to obtain a light component and a heavy component; (2) Mixing the heavy component with water, and performing a lightening reaction to obtain a lightening component; (3) Cracking the light component and the light component to obtain a cracking product; (4) And (3) separating the cracking product to obtain the low-carbon olefin. The method for preparing the low-carbon olefin can improve the utilization rate of crude oil, reduce coking phenomenon during cracking, prolong the operation period and have the advantage of simple process.
Description
Technical Field
The invention relates to the field of preparation of low-carbon olefins, in particular to a method and a system for preparing low-carbon olefins.
Background
The low-carbon olefin generally refers to the general term of unsaturated hydrocarbon with four or less carbon atoms, and mainly comprises organic chemical raw materials with high economic value such as ethylene, propylene, butadiene and the like. With the development of the economy in China, the demand of the organic chemical raw materials is increased year by year, and the increasing demand cannot be met even though the production scale of the low-carbon olefin is also increased year by year.
For a long time, naphtha is used as a main raw material for crude oil pyrolysis in China. But in recent years, with the mass exploitation of oil field associated gas in the middle east and shale gas in the united states, these inexpensive oil and gas resources are used in large quantities as ethylene raw materials, resulting in the reduction of the price of ethylene-related products. In order to cope with the impact of market competition, the raw material source of the ethylene cracking device is expanded, the raw material cost is reduced, the ethylene cracking device becomes an effective means for reducing the cost and enhancing the efficiency of the traditional ethylene enterprises, and special heavy hydrocarbons, particularly crude oil which is not processed, are used as raw materials of a cracking furnace to produce low-carbon olefins, thereby being beneficial to reducing the raw material cost and energy consumption of the olefin production device and rapidly adapting to the supply and demand change of the cracking raw materials in the market.
In order to fully utilize crude oil resources and improve the yield of low-carbon olefins, various hydrocarbon raw materials are generally cracked into olefins by steam cracking through a cracking furnace, and the common cracking furnace comprises a convection section and a radiation section. Crude oil is generally divided into four components, saturated, aromatic, colloidal and asphaltene, where saturated and asphaltene represent the most stable and least stable components of crude oil, respectively. The crude oil contains high molecular weight non-volatile components, and when the non-volatile components are preheated in the convection section of a conventional cracking furnace, a small part of the non-volatile components are not gasified, and the non-volatile components which are not gasified are clamped to the radiation section along with the mixed airflow, so that coking deposition of the radiation section is easy to cause, even the radiation section is blocked, and the yield of cracked products is influenced.
CN1957068a discloses the steam cracking of a hydrocarbon feedstock containing salt and/or particulate matter, which process comprises: a adding a non-desalted feedstock comprising salt and optionally particulate matter to the convection section of a pyrolysis furnace; b heating the hydrocarbon feedstock; c feeding the hydrocarbon feedstock to a flash/separation vessel located upstream of the dry point; d separating the hydrocarbon feedstock into a vapor phase substantially depleted of non-volatile components and salts and a liquid phase enriched in non-volatile components and salts, said liquid phase containing 5% liquid phase at all points in the convection section upstream of the flash/separation vessel to maintain the salts and any particulate matter in suspension; e removing from 50 to 95% of the hydrocarbon feedstock of step a in the vapor phase from the flash/separation vessel and cracking the vapor phase to produce an effluent comprising olefins; and f removing at least 5% of the hydrocarbon feedstock in the liquid phase from the flash/separation vessel together with the salt and any particulate matter in suspension. US3617493 also discloses a process similar to the above process using steam cracking crude oil.
CN1041967a discloses a method for decomposing a low-grade raw material, which comprises extracting the low-grade raw material from a preheater of a decomposing furnace during the thermal decomposition treatment of the low-grade raw material containing heavy fraction in the decomposing furnace, separating and removing the heavy fraction from the low-grade raw material by a gas-liquid separation method, and returning the low-grade raw material to the preheater for thermal decomposition reaction.
The crude oil is subjected to flash separation by adopting the method, and part of crude oil components obtained by separation are subjected to cracking reaction, so that crude oil resources are not fully utilized.
Therefore, a method for preparing low-carbon olefin by effectively utilizing crude oil, which has simple process and is not easy to coke in the cracking process, is needed.
Disclosure of Invention
The invention aims to solve the technical problems that the process is complex, coking is easy to occur during cracking, crude oil resources cannot be effectively utilized and the like in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a process for producing a light olefin, comprising:
(1) Mixing crude oil with light hydrocarbon of C1-C6 to form a mixture; under the high pressure condition of more than 0.9MPa, carrying out first separation on the mixture to obtain a light component and a heavy component;
(2) Mixing the heavy component with water, and performing a lightening reaction to obtain a lightening component;
(3) Cracking the light component and the light component to obtain a cracking product;
(4) And (3) separating the cracking product to obtain the low-carbon olefin.
In a second aspect, the present invention provides a system for producing light olefins, the system comprising a first separation unit, a light-weight reactor, a cracking device, and a second separation unit;
the first separation unit is used for mixing crude oil with light hydrocarbons of C1-C6 and performing first separation to obtain light components and heavy components;
The lightening reactor is used for lightening the heavy component from the first separation unit to obtain a lightening component;
The cracking device is used for cracking the light components from the first separation unit and the light components from the light-weight reactor to obtain a cracking product;
And the second separation unit is used for carrying out second separation on the pyrolysis product from the pyrolysis device to obtain the low-carbon olefin.
Compared with the prior art, the method for cracking crude oil provided by the invention has the advantages that the crude oil and the light hydrocarbon are mixed and separated to obtain the light component and the heavy component, the heavy component is mixed with water to carry out the lightening reaction, and then the cracking product obtained by cracking the heavy component and the light component is separated to obtain the low-carbon olefin. The method can improve the utilization rate of crude oil, reduce coking phenomenon during cracking, prolong the operation period, and simultaneously has the advantage of simple process.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Fig. 1 is a schematic diagram of a method and a system for preparing a low-carbon olefin according to an embodiment of the present invention.
Description of the reference numerals
1. A first separation unit; 2. a pressurizing device; 3. a light reactor; 4. a pyrolysis device; 5. and a second separation unit.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In one embodiment of the present invention as shown in fig. 1, a first aspect of the present invention provides a method for preparing a light olefin, the method comprising:
(1) Mixing crude oil with light hydrocarbon of C1-C6 to form a mixture; under the high pressure condition of more than 0.9MPa, carrying out first separation on the mixture to obtain a light component and a heavy component;
(2) Mixing the heavy component with water, and performing a lightening reaction to obtain a lightening component;
(3) Cracking the light component and the light component to obtain a cracking product;
(4) And (3) separating the cracking product to obtain the low-carbon olefin.
In the present invention, generally, the light components include light hydrocarbons and non-asphaltic components in crude oil, and the heavy components include asphaltenes in crude oil; the light component comprises a hydrocarbon mixture of gas phase and liquid phase.
According to some embodiments of the present invention, preferably, in step (1), the weight ratio of the light hydrocarbon to the crude oil may be (0.1 to 10): 1, more preferably (2-6): 1.
According to some embodiments of the invention, preferably, the light hydrocarbon is selected from at least one of the alkanes of C3-C5, more preferably from at least one of propane, isobutane, n-butane and n-pentane.
In the present invention, in general, when the light hydrocarbon is selected from two or more components, the weight ratio between the components is not particularly limited as long as the first separation requirement of the present invention can be satisfied.
According to some embodiments of the invention, preferably, in step (1), the operating conditions of the first separation comprise: the pressure may be 1-8MPa, more preferably 2-6MPa; the temperature may be 80-220 ℃, more preferably 90-160 ℃.
In the invention, in order to fully utilize crude oil resources, the components separated in the step (1) can be subjected to a lightening reaction.
In the present invention, the light-weight reaction is preferably a supercritical water degradation reaction.
According to some embodiments of the invention, preferably, in step (2), the weight ratio of water to heavy component may be (0.1-10): 1, more preferably (2-6): 1.
According to some embodiments of the invention, preferably, in step (2), the operating conditions of the lightening reaction comprise: the pressure may be 15-50MPa, preferably 22-35MPa; the temperature may be 300-600 ℃, preferably 374-500 ℃; the time may be 0.01 to 10 hours, more preferably 0.1 to 1 hour.
In the present invention, the light-weight reaction operation condition is preferably close to the supercritical region or near-critical region of water.
According to some embodiments of the invention, preferably, the method may further comprise: the heavy component is subjected to a pressure treatment before the lightening reaction is performed so that the heavy component satisfies the pressure required for the lightening reaction.
According to some embodiments of the invention, preferably, the means of pyrolysis may be steam pyrolysis.
According to some embodiments of the invention, in the step (3), the cracking temperature may be 610-900 ℃, the pressure may be 0.01-1MPa, and the time may be 0.05-1s; more preferably, the cracking temperature is 780-850 ℃, the pressure is 0.1-0.3MPa, and the time is 0.1-0.3s.
According to some embodiments of the present invention, in order to achieve a better cracking effect, the weight ratio of water to oil for cracking may be (0.1-2): 1, preferably (0.4-1.5): 1.
According to some embodiments of the invention, the temperature difference between the cleavage and the lightening reaction is preferably 200-500 ℃, more preferably 300-400 ℃. Wherein the cracking temperature is higher than the light weight reaction temperature.
According to some embodiments of the invention, preferably, in step (3), the second separation may further comprise quenching and heat exchange.
In the quenching process, the cracking product is subjected to multistage cooling. Wherein the quenching is not particularly limited (as may be understood with reference to conventional means in the art) so long as the subsequent second separation of the present invention is satisfied.
In the present invention, preferably, the pyrolysis product is subjected to a second separation to obtain products such as hydrogen, methane, ethylene, propylene, butadiene, gasoline, fuel oil, diesel oil, etc., and then the products can be separated by referring to separation means (e.g., sequential separation, pre-deethanization, pre-depropanization, etc.) conventional in the art to obtain the low-carbon olefin. The second separation is preferably carried out in a rectification column.
In the invention, the heat exchange can reduce the temperature of the cracking product and also reduce the risk of coking of the cracking product during cooling separation.
The heat exchange is not particularly limited in the present invention (as may be understood by referring to the conventional manner in the art), as long as the subsequent second separation of the present invention can be satisfied, and for example, the cleavage product may be subjected to multi-step heat exchange with water and quench oil to generate ultra-high pressure steam, dilution steam, and the like.
In the present invention, it is preferable that heat of the convection section of the pyrolysis furnace be used to exchange heat between crude oil, light hydrocarbons, light components, heavy components and water in order to improve energy utilization efficiency.
According to a particularly preferred embodiment, the method comprises:
(1) Mixing crude oil with light hydrocarbons of C3-C5 to form a mixture; under the high pressure condition of 5-6MPa, carrying out first separation on the mixture to obtain a light component and a heavy component; wherein the operation pressure of the first separation is 5-6MPa, and the temperature is 90-160 ℃;
(2) Mixing the heavy component with water, and performing a lightening reaction to obtain a lightening component; wherein the operating temperature of the light-weight reactor is 400-500 ℃ and the pressure is 25-30MPa;
(3) Cracking the light component and the light component to obtain a cracking product; wherein, the weight ratio of water to oil is (0.6-0.8): 1, the outlet temperature (cracking temperature) of the cracking device is 800-850 ℃, and the cracking pressure is 0.1-0.2MPa;
(4) And (3) separating the cracking product to obtain the low-carbon olefin.
In a second aspect, the present invention provides a system for producing light olefins, the system comprising a first separation unit 1, a lightening reactor 3, a cracking device 4 and a second separation unit 5;
The first separation unit 1 is used for mixing crude oil with light hydrocarbons of C1-C6 and performing first separation to obtain light components and heavy components;
The lightening reactor 3 is used for lightening the heavy component from the first separation unit 1 to obtain a lightening component;
the cracking device 4 is used for cracking the light components from the first separation unit 1 and the light components from the light-weight reactor 3 to obtain cracking products;
and the second separation unit 5 is used for carrying out second separation on the pyrolysis product from the pyrolysis device to obtain the low-carbon olefin.
According to a preferred embodiment of the invention, a pressurizing device 2 is arranged between the first separation unit 1 and the lightening reactor 3.
In the present invention, the low-carbon olefin generally means ethylene, propylene and 1, 3-butadiene.
In the present invention, unless otherwise specified, the pressures are all referred to as "absolute pressures".
According to a preferred embodiment, in combination with fig. 1, the use of the method for preparing light olefins according to the present invention in the system for preparing light olefins according to the present invention may specifically include the following procedures:
(1) Mixing crude oil and light hydrocarbon (propane), then sending the mixture into a first separation unit 1 for first separation, controlling the weight ratio of the light hydrocarbon to the crude oil, controlling the operation pressure and the temperature of the first separation, and obtaining a light component at the top of the first separation unit and a heavy component at the bottom of the first separation unit;
(2) Mixing water and heavy components, and sending the mixture into a lightening reactor 3 for lightening reaction, and controlling the weight ratio of the water to the heavy components, the operating temperature, the operating pressure and the operating time of the lightening reactor to obtain lightening components;
(3) And mixing the light components and the light components, sending the mixture into a cracking device 4 for cracking, and controlling the weight ratio of water to oil, the outlet temperature of the cracking device (cracking temperature), the cracking pressure and the cracking time to obtain a cracking product.
(4) The obtained pyrolysis product is sent to a second separation unit 5, and the low-carbon olefin is obtained through separation.
The present invention will be described in detail by examples.
The compositions of crude oils used in the following examples and comparative examples, which were measured according to the ASTM D5307 method, are shown in table 1.
TABLE 1
| Analysis item | ASTM D5307 |
| IP，℃ | 69 |
| 10％，℃ | 192 |
| 20％，℃ | 272 |
| 30％，℃ | 337 |
| 40％，℃ | 393 |
| 50％，℃ | 446 |
| 60％，℃ | 508 |
| 70％，℃ | 595 |
| 75％，℃ | 653 |
| 80％，℃ | - |
| 90％，℃ | - |
| EP，℃ | - |
Example 1
(1) Mixing crude oil and light hydrocarbon (propane), and then sending the mixture into a first separation unit for first separation, wherein the weight ratio of the light hydrocarbon to the crude oil is 6:1, the operation pressure of the first separation is 6MPa, the temperature is 90 ℃, the top of the first separation unit is used for obtaining a light component, and the bottom of the first separation unit is used for obtaining a heavy component;
(2) Mixing water and heavy components (weight ratio is 6:1), and sending the mixture into a lightening reactor for lightening reaction to obtain lightening components; the operating temperature of the light-weight reactor is 500 ℃, the pressure is 25MPa, and the time is 0.5h;
(3) Mixing the light components and the light components, and sending the mixture into a cracking device for cracking, wherein the weight ratio of water to oil is 0.6:1, obtaining a cracking product, wherein the outlet temperature of a cracking device is 820 ℃, the cracking pressure is 0.17MPa, and the cracking time is 0.3 s;
(4) And sending the obtained cracking product into a second separation unit, and sequentially separating to obtain low-carbon olefin, wherein the ethylene yield is 30.45wt%, the propylene yield is 14.03wt%, the 1, 3-butadiene yield is 4.32wt%, and the operation period of the cracking device is 51 days.
Example 2
(1) Mixing crude oil and light hydrocarbon (calculated by weight ratio, 55% of isobutane and 45% of normal butane), and then sending the mixture into a first separation unit for first separation, wherein the weight ratio of the light hydrocarbon to the crude oil is 4:1, the operation pressure of the first separation is 5MPa, the temperature is 145 ℃, the top of the first separation unit is used for obtaining a light component, and the bottom of the first separation unit is used for obtaining a heavy component;
(2) Mixing water and heavy components (weight ratio is 5:1), and then sending the mixture into a lightening reactor for lightening reaction to obtain lightening components; the operating temperature of the light-weight reactor is 400 ℃, the pressure is 30MPa, and the time is 1h;
(3) Mixing the light components and the light components, and sending the mixture into a cracking device for cracking, wherein the weight ratio of water to oil is 0.8:1, the outlet temperature of a cracking device is 810 ℃, the cracking pressure is 0.16MPa, and the cracking time is 0.22s, so as to obtain a cracking product;
(4) And sending the obtained cracking product into a second separation unit, and sequentially separating to obtain low-carbon olefin, wherein the yield of ethylene is 29.55wt%, the yield of propylene is 14.23wt%, the yield of 1, 3-butadiene is 4.82wt%, and the operation period of the cracking device is 46 days.
Example 3
(1) Mixing crude oil and light hydrocarbon (calculated by mass ratio, 35% of isobutane, 55% of normal butane and 10% of normal pentane), and then sending the mixture into a first separation unit for first separation, wherein the weight ratio of the light hydrocarbon to the crude oil is 2:1, the operation pressure of the first separation is 3MPa, the temperature is 160 ℃, the top of the first separation unit is used for obtaining a light component, and the bottom of the first separation unit is used for obtaining a heavy component;
(2) Mixing water and heavy components (weight ratio is 2:1), and then sending the mixture into a lightening reactor for lightening reaction to obtain lightening components, wherein the operating temperature of the lightening reactor is 300 ℃, the pressure is 35MPa, and the time is 1h, so as to obtain a cracking product;
(3) Mixing the light components and the light components, and sending the mixture into a cracking device for cracking, wherein the weight ratio of water to oil is 1.5:1, the outlet temperature of the cracking device is 800 ℃, the cracking pressure is 0.18MPa, and the cracking time is 0.17s;
(4) And sending the obtained cracking product into a second separation unit, and sequentially separating to obtain low-carbon olefin, wherein the yield of ethylene is 29.11wt%, the yield of propylene is 14.45wt%, the yield of 1, 3-butadiene is 5.06wt%, and the operation period of the cracking device is 40 days.
Example 4
(1) Mixing crude oil and light hydrocarbon (n-butane), and then sending the mixture into a first separation unit for first separation, wherein the weight ratio of the light hydrocarbon to the crude oil is 6:1, the operation pressure of the first separation is 4MPa, the temperature is 160 ℃, the top of the first separation unit is used for obtaining a light component, and the bottom of the first separation unit is used for obtaining a heavy component;
(2) Mixing water and heavy components (weight ratio is 4:1), and then feeding the mixture into a lightening reactor for lightening reaction to obtain lightening components, wherein the operating temperature of the lightening reactor is 500 ℃, the pressure is 22MPa, and the time is 0.5h;
(3) Mixing the light components and the light components, and sending the mixture into a cracking device for cracking, wherein the weight ratio of water to oil is 0.5:1, the outlet temperature of a cracking device is 810 ℃, the cracking pressure is 0.17MPa, and the cracking time is 0.24s, so as to obtain a cracking product;
(4) And sending the obtained cracking product into a second separation unit, and sequentially separating to obtain low-carbon olefin, wherein the ethylene yield is 28.91wt%, the propylene yield is 14.56wt%, the 1, 3-butadiene yield is 5.35wt%, and the operation period of the cracking device is 42 days.
Example 5
The procedure of example 1 was followed, except that the cracker outlet temperature was 770 ℃.
And sending the obtained cracking product into a second separation unit, and sequentially separating to obtain the low-carbon olefin, wherein the yield of ethylene is 28.21wt%, the yield of propylene is 15.02wt%, the yield of 1, 3-butadiene is 5.21wt%, and the operation period of the cracking device is 42 days.
Comparative example
This comparative example was subjected to pyrolysis using a conventional pyrolysis furnace.
The dehydrated and desalted crude oil is directly sent into a cracking furnace, and is cracked after being mixed with steam. The pyrolysis gas adopts LUMMUS sequential separation flow. Analysis of the steam cracking reaction product revealed that the yield of ethylene was 21.49wt%, the yield of propylene was 13.29wt%, and the yield of 1, 3-butadiene was 4.03wt%. The run period was 5 days.
From the results of the above examples and comparative examples, it can be seen that the crude oil is taken in only 5 days of operation period by using the conventional cracking device, while the invention can ensure normal crude oil taking in the cracking device, effectively reduce coking, and the operation period is more than 40 days; and the crude oil is treated and then enters the cracking device for cracking reaction, so that the utilization rate of the crude oil is high.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (4)
1. A process for preparing a lower olefin comprising:
(1) Mixing crude oil with light hydrocarbons of C3-C5 to form a mixture; under the high pressure condition of 5-6MPa, carrying out first separation on the mixture to obtain a light component and a heavy component; the weight ratio of the light hydrocarbon to the crude oil is (2-6): 1, a step of;
(2) Mixing the heavy component with water, and performing a lightening reaction to obtain a lightening component; the weight ratio of the water to the heavy components is (2-6): 1, a step of; the operating conditions of the lightening reaction include: the pressure is 22-35MPa; the temperature is 374-500 ℃; the time is 0.1-1h;
(3) Cracking the light component and the light component to obtain a cracking product; the weight ratio of the water to the oil of the pyrolysis is (0.4-1.5): 1, a step of; the cracking temperature is 800-850 ℃, the pressure is 0.1-0.3MPa, and the time is 0.1-0.3s;
(4) The pyrolysis product is subjected to second separation to obtain low-carbon olefin;
the operating conditions of the first separation include: the operating pressure is 5-6MPa and the temperature is 90-160 ℃.
2. The method of claim 1, wherein in step (1), the light hydrocarbon is selected from at least one of propane, isobutane, n-butane, and n-pentane.
3. The process according to claim 1 or 2, wherein the temperature difference between the cleavage and the lightening reaction is 200-500 ℃.
4. The process according to claim 1 or 2, wherein the temperature difference between the cleavage and the lightening reaction is 300-400 ℃.
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