CN116004272A - Steam cracking process and system - Google Patents
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Abstract
The invention relates to the field of low-carbon olefin preparation, and discloses a steam cracking method and a steam cracking system. The method is implemented in a pyrolysis furnace comprising a convection section, a gas-liquid separator, and a radiant section, the method comprising: contacting the pyrolysis raw material with water vapor in a convection section, heating to a crossing temperature, and then conveying to a gas-liquid separator for gas-liquid separation to obtain a gas-phase material and a liquid-phase material; conveying the gas-phase material to a radiation section for cracking to obtain low-carbon olefin; wherein the cross temperature is 350-500 ℃. By adopting the method, the coking phenomenon in the convection section furnace tube of the cracking furnace can be reduced, the burning period of the radiant section is prolonged, the device online rate is improved, and the cracking efficiency of the cracking raw material is improved.
Description
Technical Field
The invention relates to the field of preparation of low-carbon olefins, and discloses a steam cracking method and a steam cracking system.
Background
In order to fully utilize crude oil resources and improve the yield of low-carbon olefins, various hydrocarbon raw materials are usually cracked into olefins by steam cracking in a cracking furnace. A common pyrolysis furnace includes a convection section and a radiant 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 with boiling point exceeding 590 ℃, 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 easily caused, even the radiation section is blocked, the online rate of a cracking device is influenced, and the product yield is influenced.
CN101583697a discloses a process for cracking a feedstock comprising synthetic oil, the process comprising: 1. hydroprocessing includes a broad boiling range aliquot of: a normally liquid hydrocarbon portion boiling in the range of 50°f to 800°f that is substantially free of resid, and b a thermally cracked hydrocarbon liquid boiling in the range of 600°f to 1050°f to provide a synthetic crude oil boiling in the range of 73°f to 1070°f that comprises greater than 25wt% aromatics, greater than 25wt% naphthenes, less than 0.3wt% S, less than 0.02wt% asphaltenes, and substantially free of resids other than asphaltenes; 2. adding to the synthetic crude a normally liquid hydrocarbon component boiling in the range of 100 DEG F to 1050 DEG F; and 3, cracking the mixture produced by 2 in a cracking furnace to provide a cracked effluent, wherein the cracking furnace includes a radiant coil outlet, wherein the cracking is conducted under conditions sufficient to obtain a temperature greater than an optimal radiant coil outlet temperature for cracking the synthetic crude oil alone.
The method mixes the crude oil with the existing ethylene production raw material, dilutes the crude oil, improves the cracking performance of the crude oil, and improves the conversion rate of olefins. However, the method is limited by the source of the existing ethylene production raw materials, and can not effectively utilize a large amount of crude oil to produce low-carbon olefin.
In addition to improvements in the process to reduce the impact of raw materials such as crude oil on the cracking furnace tubes, improvements in the design of the cracking furnace tubes are contemplated. As known by those skilled in the art, the radiant section furnace tube of the cracking furnace has the characteristics of high temperature, short residence time, low hydrocarbon partial pressure and the like, and is beneficial to high selectivity, high capacity and long-period operation of ethylene production. The cracking furnace has the technical patent that two-pass branch reducing furnace tubes or two-pass reducing furnace tubes with high selectivity are adopted, the first pass adopts a small-diameter furnace tube, the aim of rapid temperature rise is achieved by utilizing the characteristic of large specific surface area, and the second pass adopts a large-diameter furnace tube, so that coking sensitivity in the later stage of hydrocarbon cracking reaction is reduced. At present, two-pass high-selectivity radiation furnace tubes for industrial application mainly comprise a type 2-1 type, a type 4-1 type, a type 5-1 type, a type 6-1 type, a type 8-1 type and a type U (1-1), and the high-selectivity furnace tube has large specific surface area and high heating speed, thereby being very beneficial to hydrocarbon cracking reaction.
CN101333147a proposes an ethylene cracking furnace, in which furnace tubes are located in a radiant section, each furnace tube is composed of an inlet tube and an outlet tube, the furnace tubes are arranged in two rows in the radiant section, each row forms a plane of a tube row, the inlet tube and the outlet tube of the furnace tube are located in two different planes of the tube row respectively in an alternate interval form, and are connected together at the bottom by a symmetrical U-shaped connector. The cracking furnace is considered to be large in size, the radiant heat transfer efficiency is improved by the arrangement mode of the furnace tubes, the operation period is prolonged, and the energy consumption of products is reduced.
CN103992812a describes a cracking furnace, in which four rows of burners and two groups of radiant tubes are arranged at the bottom of the radiant section, and each group of radiant tubes is arranged in two rows, so that four rows of radiant tubes are provided in total in the radiant section, which is considered to realize the large-scale of the cracking furnace and reduce the occupation and investment.
CN103992813a describes an ethylene cracking furnace comprising a radiant section, a convection section, a quench heat exchanger, and an induced draft fan and chimney, wherein two rows of radiant tubes are provided in the radiant section, including an inlet tube row formed by a row of inlet tubes and an outlet tube row formed by a row of outlet tubes, a plurality of burners are arranged on both sides of the two rows of radiant tubes, the burners being arranged to be able to asymmetrically supply heat to the radiant tubes such that the heat release of the burners near the inlet tube row is greater than the heat release of the burners near the outlet tube row. It is considered that the cracking furnace has long operation period, high product yield and large production capacity.
CN104232146a discloses an ethylene cracking furnace, which comprises a radiant section coil pipe assembly, the assembly is composed of X-type radiant coil pipe modules which are arranged in the radiant section along the length direction of the furnace body and perpendicular to the bottom surface, each X-type radiant coil pipe module is composed of four groups of radiant coil pipes, and each group of radiant coil pipes is composed of furnace pipes. The four groups of radiant coils are connected with four-in-one stereoscopic polymeric pipes at the center of the X-type radiant coil module to serve as material outlets, the farthest gate of the four groups of radiant coils, which is far away from the center of the X-type radiant coil module, serves as a material inlet and is connected with an inlet collecting pipe together, and the bottom burner is arranged at a gap between every two adjacent radiant coils. It is considered that each furnace tube on each independent radiant coil is heated uniformly, so that the service life of the furnace tube is prolonged and the ethylene production capacity is improved.
The focus of the above patent is focused on how the furnace tubes in the radiant section of the cracking furnace are arranged to ensure more arrangement of the furnace tubes in the furnace chamber and better radiant heat transfer, so that the materials in the furnace tubes can be quickly heated in a very short residence time, but are not suitable for cracking crude oil. Because crude oil is often insufficiently gasified and has the characteristic of coking when used directly as a cracking feedstock, it results in low yields of low olefins, which is also an important reason why it has not been used as a cracking feedstock before. Moreover, coking occurs in a convection section of the cracking furnace, namely a relatively low-temperature area, once the convection section is coked, the coking cannot be removed by an on-line coking means, and the furnace is usually stopped for manual coke cleaning, so that the on-line time of the cracking furnace is greatly influenced.
Disclosure of Invention
The invention aims to solve the problems of insufficient gasification, convection Duan Yi coking, low yield of low-carbon olefin and the like in the prior art when crude oil is used for cracking and producing low-carbon olefin, and provides a steam cracking method and a steam cracking system.
In order to achieve the above object, a first aspect of the present invention provides a steam cracking method implemented in a cracking furnace including a convection section, a gas-liquid separator, and a radiation section, the method comprising:
(1) Contacting the pyrolysis raw material with water vapor in a convection section, heating to a crossing temperature, and then conveying to a gas-liquid separator for gas-liquid separation to obtain a gas-phase material and a liquid-phase material;
(2) Conveying the gas-phase material to a radiation section for cracking to obtain low-carbon olefin;
wherein the cross temperature is 350-500 ℃.
In a second aspect, the present invention provides a steam cracking system, the system comprising:
the cracking furnace comprises a convection section, a gas-liquid separator and a radiation section which are connected in series, wherein a material outlet of the convection section is connected with a material inlet of the gas-liquid separator, and a gas phase outlet of the gas-liquid separator is connected with a material inlet of the radiation section; and
wherein the convection section is used for contacting the pyrolysis raw material with steam and heating to a crossing temperature, and the number of the convection section furnace tubes can enable the crossing temperature to be 350-500 ℃.
By adopting the method, the pyrolysis raw materials are gasified, gas-liquid separated and cracked in sequence, and the cross temperature is controlled within the range of 350-500 ℃, so that coking phenomena in the pyrolysis furnace tube, particularly the convection section furnace tube, can be reduced, the shutdown treatment steps required by the decoking of the convection section are avoided, and the burning period of the radiation section is prolonged; meanwhile, the cracking raw material is subjected to light and heavy component separation hydrogenation and then enters the cracking furnace for cracking, so that the operation period of the cracking furnace is further prolonged, and the online rate of the device is improved.
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 a first aspect the present invention provides a steam cracking process carried out in a cracking furnace comprising a convection section, a gas-liquid separator and a radiant section, the process comprising:
(1) Contacting the pyrolysis raw material with water vapor in a convection section, heating to a crossing temperature, and then conveying to a gas-liquid separator for gas-liquid separation to obtain a gas-phase material and a liquid-phase material;
(2) Conveying the gas-phase material to a radiation section for cracking to obtain low-carbon olefin;
wherein the cross temperature is 350-500 ℃.
In the present invention, the cross-over temperature may be, for example, 350, 360, 380, 400, 420, 430, 435, 440, 445, 450, 455, 460, 465, 470, 475, 480, 490, 500 ℃ and any range between any two values; preferably, the cross-over temperature is 430-480 ℃.
This can be achieved by reducing the number of rows of hybrid heating section tubes in the convection section and adjusting the set temperature.
In the present invention, the pyrolysis feedstock is a pyrolysis feedstock in the conventional sense in the art, and specifically, the pyrolysis feedstock may include light naphtha, diesel, hydrogenated tail oil, light crude oil, crude oil having a final boiling point of above 600 ℃ and below 700 ℃ and dehydrated and desalted crude oil.
Preferably, the cracking raw material is at least one selected from diesel oil, hydrogenated tail oil, light crude oil, dehydrated and desalted crude oil and crude oil with a final boiling point higher than 600 ℃ and lower than 700 ℃.
Preferably, the cracking feedstock has an API greater than 18, more preferably greater than 22, such as may be 24, 26, 28, 30, 32, 34, 36, 38, 40 or more and any range between any two values.
API gravity is a measure developed by the American Petroleum Institute (API) to represent the density of petroleum and petroleum products. The API gravity can be obtained by measuring the density of the raw material and then converting the raw material.
In the present invention, the low-carbon olefin means an olefin having a relatively small number of carbon atoms, for example, an olefin having 4 or less carbon atoms.
In order to make full use of the heat of the high temperature flue gas from the radiant section, the convection section of the pyrolysis furnace is typically provided with a plurality of sections for recovering heat. Typically, the convection section may be provided with a feed preheating section, a boiler feedwater preheating section, a dilution steam superheating section, an ultra-high pressure steam superheating section, and a hybrid heating section. The feedstock preheating stage is typically used to preheat the pyrolysis feedstock. The boiler feed water preheating section is typically used to preheat the boiler feed water supplied to the drum. The dilution steam superheating section is typically used to preheat the dilution steam (i.e., water vapor). The super-high pressure steam superheating section is typically used to heat high pressure steam from a drum to obtain super-high pressure steam. The hybrid heating stage is typically used to heat the pyrolysis feedstock to a cross-over temperature.
Preferably, the method further comprises: before mixing steam with the pyrolysis raw material, preheating the pyrolysis raw material in a convection section to obtain a preheated raw material.
Preferably, the temperature of the preheated feedstock is 120-300 ℃, more preferably 150-250 ℃.
Preferably, the temperature of the water vapour is 480-560 ℃, preferably 500-540 ℃.
Preferably, the weight ratio of the cracking raw material to the water vapor is 1-4:1, more preferably 1.5-2.5:1.
the material from the convection section is separated into gas and liquid through a gas-liquid separator, the gas phase part is removed from the radiation section for pyrolysis, and the liquid phase part is directly discharged out of the system. The gas-liquid separator utilizes heat in the hearth to reach the required temperature.
The gas-liquid separator can be a flash evaporator, a cyclone separator or other devices with gas-liquid separation function, wherein the cyclone separator can be selected from a volute cyclone separator, an axial flow guide vane type cyclone separator, a straight cylinder type cyclone separator, a cone cylinder combined cyclone separator or a direct current cyclone separator. The cyclone separator is provided with an inner member comprising a skimming barrel positioned at the top of the cyclone separator and/or a separation plate and a vortex breaker positioned at the lower part of the cyclone separator.
Preferably, the liquid phase volume content at the inlet of the gas-liquid separator is 0.01 to 5% by volume, more preferably 0.02 to 2% by volume.
Preferably, the liquid phase content in the gas phase outlet of the gas-liquid separator is less than 10g/m 3 More preferably less than 200mg/m 3 。
The cleavage of the material to a cross-over temperature is carried out in the radiant section, preferably the cleavage reaction conditions include: the outlet temperature of the radiation section is 780-850 ℃, preferably 790-840 ℃.
In the present invention, the radiant section comprises a multi-pass furnace, preferably a 2-6 pass furnace, more preferably a two pass furnace.
The two-pass furnace tube, for example, the first pass is two parallel vertical inlet tubes, the second pass is a vertical outlet tube, and a 2-1 type radiation furnace tube is formed; or the first pass is four parallel vertical inlet pipes, and the second pass is a vertical outlet pipe, so that a 4-1 type radiation furnace tube is formed.
Preferably, the ratio of the inner diameter of the outlet tube to the inner diameter of the inlet tube of the multi-pass furnace tube is in the range of: more than 1 and less than or equal to 2.5.
In a preferred embodiment of the present invention, the inlet tube inner diameter of the multi-pass furnace tube ranges from 25mm to 70mm, more preferably from 40mm to 65mm.
In a preferred embodiment of the present invention, the inner diameter of the outlet tube of the multi-pass furnace tube ranges from 45mm to 120mm, more preferably from 60mm to 95mm.
The radiation section furnace tube can also adopt an enhanced heat transfer element, and the enhanced heat transfer element can be various known or unknown elements, such as a spiral sheet insert, a twisted belt insert, a crossed zigzag insert, a coil core insert, a filament winding porous body, a spherical substrate insert and the like, so as to facilitate heat transfer. Different reinforced heat transfer elements can also be respectively added in different parts of the furnace tube.
In the invention, the material obtained after the pyrolysis of the radiation section can enter a quenching device for cooling and is separated to obtain the low-carbon olefin.
The quench device may be a quench device conventional in the art, such as a quench boiler. The quench device may be external to the pyrolysis furnace.
In the present invention, unless otherwise specified, the methods and apparatus involved are conventional in the art.
In a second aspect, the present invention provides a steam cracking system, the system comprising:
the cracking furnace comprises a convection section, a gas-liquid separator and a radiation section which are connected in series, wherein a material outlet of the convection section is connected with a material inlet of the gas-liquid separator, and a gas phase outlet of the gas-liquid separator is connected with a material inlet of the radiation section; and
wherein the convection section is used to contact and heat the pyrolysis feedstock with steam to a cross-over temperature, and the number of convection section furnace tubes (particularly the rows of mixed heating section tubes) is such that the cross-over temperature is in the range of 350-500 ℃.
The specific structure of each device is described in the first aspect, and will not be described herein. The equipment used is of a construction conventional in the art, unless otherwise specified.
It will be appreciated that other ancillary facilities may be provided in the system, such as a quench device, for cooling the cracked material from the radiant section and separating the lower olefins. Preferably, the material inlet of the quenching device is connected with the material outlet of the radiation section.
The present invention will be described in detail by examples.
In the examples below, the cleavage feed usedFor dewatering desalted crude oil, the density at 20 ℃ is 862.4kg/m 3 The API level is about 33.
The cracking furnace used in the following examples was modified based on a CBL-III cracking furnace purchased from chinese petrochemical company, in which a spiral case type cyclone was added, the material inlet was connected to the convection section, the gas phase material outlet was connected to the material inlet of the radiant section, the liquid phase material outlet was connected to the material inlet of the hydrogenation catalytic reactor, and two sets of mixed heating section tube banks were reduced as the cracking furnace used in example 1.
Example 1
This example is presented to illustrate a steam cracking system and method.
The system for steam cracking comprises a cracking furnace and a quenching boiler, wherein the cracking furnace comprises a convection section, a gas-liquid separator (volute cyclone separator) and a radiation section which are connected in series, wherein a material outlet of the convection section is connected with a material inlet of the gas-liquid separator, and a gas phase outlet of the gas-liquid separator is connected with a material inlet of the radiation section. The convection section of the cracking furnace comprises a raw material preheating section, a boiler feed water preheating section, a dilution steam superheating section, an ultrahigh pressure steam superheating section and a mixed heating section. The raw material preheating section is used for preheating crude oil; the boiler feed water preheating section is used for preheating boiler feed water supplied into the steam drum; the dilution steam superheating section is used for preheating dilution steam; the ultrahigh pressure steam superheating section is used for heating high pressure steam from the steam drum to obtain ultrahigh pressure steam; the hybrid heating section is used to heat the crude oil to a cross-over temperature. The radiation section is connected with the quenching boiler through a pipeline and is used for conveying the cracking product to the quenching boiler and cooling and separating the cracking product to obtain the low-carbon olefin.
The steam cracking method comprises the following steps: the crude oil at 60 ℃ is gasified and preheated in the convection section, and then enters a gas-liquid separator for gas-liquid separation. Wherein the crude oil is 47000kg/h and the dilution steam is 37600kg/h. Wherein the inlet liquid phase content of the gas-liquid separator is 0.08% by volume; the density of the liquid phase is 1200kg/m 3 The gas phase density was 0.87kg/m 3 . The separation efficiency of the gas-liquid separator is 98, the density of the liquid phase in the gas phase outlet of the gas-liquid separator is 500mg/m 3 。
The separated gas phase enters the radiant section furnace tube through a gas phase outlet of the gas-liquid separator for cracking reaction, and the liquid phase is directly discharged out of the system through a liquid phase outlet. And conveying the cracked product to a quenching boiler for cooling and separating to obtain the low-carbon olefin. The radiant section furnace tube adopts a two-pass furnace tube, the inlet tube diameter of the furnace tube is 51mm, the outlet tube diameter of the furnace tube is 73mm, and the tube length of the furnace tube is 26.6m. Wherein the feedstock is heated in the convection section to a cross temperature (XOT) of 450 ℃; the radiant section inlet pressure XOP was 0.127MPaG, the outlet temperature (COT) was 790 ℃, and the radiant section outlet pressure COP was 0.083MPaG.
In the embodiment 1, the heat exchange tube rows of the mixed heating section are reduced in the convection section, and the cross temperature of the materials is reduced by reducing the heat exchange between the raw materials and the water vapor mixture in the mixed heating section and the smoke, so that the cracking reaction in the convection section is effectively reduced, and the coking condition is reduced.
The running period of the cracking furnace is 68 days, the on-line burning is carried out for 5 times in one year, and the burning time is 2 days each time; the main composition of the cleavage product is shown in Table 1.
Comparative example 1
This comparative example is used to illustrate the steam cracking process of the reference.
The cracking was carried out in a steam cracking system consisting of a CBL-III type cracking furnace and a quenching boiler connected in series therewith, i.e., unlike example 1, in which the cracking furnace did not contain a gas-liquid separator, and two more groups of tube rows were arranged in the mixed heating section in the convection section.
The procedure of example 1 was followed, except that the crossover temperature was 520 ℃. The results are shown in Table 1.
The running period of the cracking furnace is 65 days, the convection section is decoked once (7 days, and the furnace is additionally stopped and opened once) within one year, the on-line coke is burnt for 5 times, and the time for each coke burning is 2 days; the main composition of the cleavage product is shown in Table 1.
TABLE 1
| The yield of the main product is wt% | Example 1 | Comparative example 1 |
| Ethylene | 23.95 | 23.01 |
| Propylene | 12.78 | 13.02 |
| Butadiene | 5.45 | 5.05 |
It can be seen that the on-line time of the cracking furnace is increased by 10 days in one year in example 1, and the yield of the products is also improved, and the yield of the products of only triene (ethylene, propylene and butadiene) is increased by 7429 tons. For example, according to the unit price of 7000 yuan Renzhen/ton (since the price of the product is changed, a conventional fixed value is taken here for convenient calculation), the income of the triene product is up to 5201 ten thousand yuan Renzhen. In addition, the example saves a lot of costs for starting and stopping and maintaining compared with comparative example 1. That is, the technical scheme of the invention achieves better effect.
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 (10)
1. A steam cracking process carried out in a cracking furnace comprising a convection section, a gas-liquid separator and a radiant section connected in series, the process comprising:
(1) Contacting the pyrolysis raw material with water vapor in a convection section, heating to a crossing temperature, and then conveying to a gas-liquid separator for gas-liquid separation to obtain a gas-phase material and a liquid-phase material;
(2) Conveying the gas-phase material to a radiation section for cracking to obtain low-carbon olefin;
wherein the cross temperature is 350-500 ℃.
2. The method of claim 1, wherein the cross-over temperature is 430-480 ℃.
3. The process according to claim 1, wherein the cracking feedstock has an API gravity of 18 or more, preferably 22 or more;
preferably, the cracking feedstock is selected from at least one of light naphtha, diesel, hydrogenated tail oil, light crude oil, crude oil with a final distillation point higher than 600 ℃ and lower than 700 ℃ and dehydrated desalted crude oil, more preferably diesel, hydrogenated tail oil, light crude oil, dehydrated desalted crude oil and crude oil with a final distillation point higher than 600 ℃ and lower than 700 ℃.
4. The method of claim 1, wherein the method further comprises: preheating the pyrolysis raw material in a convection section before mixing steam with the pyrolysis raw material to obtain a preheated raw material;
preferably, the temperature of the preheated feedstock is 120-300 ℃, more preferably 150-250 ℃.
5. A process according to claim 1, wherein the temperature of the water vapour is 480-560 ℃, preferably 500-540 ℃.
6. The process according to any one of claims 1 to 5, wherein the weight ratio of the amount of cracking feedstock to water vapor is 1 to 4:1, preferably 1.5-2.5:1.
7. the process according to any one of claims 1 to 6, wherein the volume content of the liquid phase at the inlet of the gas-liquid separator is 0.01 to 5% by volume, preferably 0.02 to 2% by volume; and/or
The liquid phase content in the gas phase outlet of the gas-liquid separator is lower than 10g/m 3 Preferably less than 200mg/m 3 。
8. The method of any one of claims 1-7, wherein the cleavage reaction conditions comprise: the outlet temperature of the radiation section is 780-850 ℃, preferably 790-840 ℃.
9. A steam cracking system, the system comprising:
the cracking furnace comprises a convection section, a gas-liquid separator and a radiation section which are connected in series, wherein a material outlet of the convection section is connected with a material inlet of the gas-liquid separator, and a gas phase outlet of the gas-liquid separator is connected with a material inlet of the radiation section;
wherein the convection section is used for contacting the pyrolysis raw material with steam and heating to a crossing temperature, and the number of the convection section furnace tubes can enable the crossing temperature to be 350-500 ℃.
10. The system of claim 9, further comprising a quench device coupled to the radiant section material outlet for cooling and separating the radiant section material to provide the light olefins.
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