Pyrolysis of crude oil and crude oil fractions containing pitch

 

The invention relates to a method of pyrolysis of raw materials, consisting of crude oil and/or crude oil fractions containing pitch. The raw material is fed into the heater first stage, located in the convection section of the pyrolysis furnace, while the heated raw material in the heater first stage to the output temperature at least equal 375With receiving the heated gas-liquid mixture, remove gas-liquid mixture from the heater first step in the separator separating vapor and liquid, separating and removing the gas from the liquid in the separator for the separation of vapor and liquid. Remote gas is fed into the second stage heater located in the convection zone, thus increase the gas temperature to a temperature higher than the temperature of gas leaving separator separation of vapor and liquid. Heated gas is introduced into the radiation zone of the pyrolysis furnace and carry out its pyrolysis to olefins and related by-products. The invention allows to process any kind of heavy raw materials to obtain high yield of the desired olefin products. 8 C.p. f-crystals, 6 ill., table 2.

The invention relates to a method of pyrolysis of raw materials, consisting of crude oil and its fractions, crude, not what kingom petroleum hydrocarbons using liquefied natural gas, such as ethane, or by using fractions of naphtha or gas oil obtained from the rectification column of crude oil, working under pressure above atmospheric. Recently in some regions there is a tendency to establish the cracking installation, which made use of heavier feedstocks such as gas oil vacuum distillation. But it is more difficult raw material contaminates sediments coke tube heaters convection section and the subsequent equipment. Usually the process temperature at the output of the first stage heaters convection section are within 200-400With, and therefore completely evaporated feedstock in the convection section; or in the case of a heavy feedstock such as gas oil and gas oil vacuum distillation, finally and completely evaporated raw materials externally, when it comes to the heaters of the second stage through the mixing nozzle, superheated steam, according to US-A-4498629.

In US-A-5580443 disclosed method of cracking of low-quality raw materials, such as heavy liquefied part of natural gas, which is associated with oil, found in small quantities in the production of gas in gas fields. In this way the vapor and liquid, which is external with respect to the convection zone, after mixing with the superheated steam in the heater of the second stage in the convection zone and, finally, in the area of radiation heating. Feedstock is subjected to cracking by separation and removal of the separator separation of vapor and liquid of some part of the heavy fractions of the sections of the heater first stage, and by the subsequent return of the evaporated part of the raw materials in the heater of the second stage to the pyrolysis of the raw material. The temperature and pressure in the tubes of the heater first stage is kept in this range, in which the fraction of raw materials, which otherwise would create problems in the tubes remain in the liquid state, and the evaporated fraction, which probably will not create problems of coking. Usually the temperature at the exit of the first section of the heater are in the range of 150-350To avoid evaporation of the coke forming fractions in tubes.

The mixture of gas and liquid leaving the first section of the heater according to US-A-5580443, has a ratio of from 60/40 to 98/2. This ratio can be adjusted by the introduction of superheated dilution water vapor between the outlet of the first heating section and prior to the receipt of all the shares were removed and released from the system, and the gas fraction is served by the gas supply lines, again mixed with superheated dilution steam and then fed to the second heater. In the second heater, the gas is heated to a temperature which is slightly does not reach the temperature of the implementation of the cracking, and then the gas is sent to the section for radiation of heat, where it is subjected to cracking.

It is preferable to recycle raw materials that are not heavy liquefied part of the natural gas in the pyrolysis furnace to produce ethylene. The necessary raw materials include crude oil or long remnant of madoona the rectification column of crude oil, operating under atmospheric pressure. Raw materials - crude oil obtained from the oil field development, and 60% or more of the extraction liquid is crude oil. The heavy flow of natural gas liquids in the earth is in a gaseous or supercritical state, and condenses to a liquid, when it comes to the temperature and pressure of the earth's surface. Processing of raw materials - crude oil or long residue working under atmospheric pressure of the rectification column of crude oil in the pyrolysis furnace in the temperature conditions according to US-A-5580443, and, in particular, at a temperature of from 150 to 350With, share the evaporated crude oil or long residue extracted insufficient, resulting from this feedstock receive a reduced yield of the desired olefin products.

Heavy end fraction of crude oil and long residue cannot evaporate under normal conditions the convection section of the pyrolysis furnace of olefins. Heavy end fraction of crude oil and long rest is usually removed by distillation, and the resulting distillation lighter evaporated fractions, most often fractions of naphtha or gas oil, is used as raw material for pyrolysis of olefins. For this stage of the distillation of crude oil and long residue requires additional capital and operating costs in this way.

Currently established method of pyrolysis of crude oil and/or crude oil fractions containing pitch feedstock in a pyrolysis furnace olefins, according to which: in the heater first stage in the convection zone of the furnace serves crude oil and/or fractions of the shining at least 375In order to obtain a heated mixture of gas and liquid; select the heated mixture of gas and liquid from the heater first step in the separator separating vapor and liquid; separating and removing the gas from the liquid in the separator for the separation of vapor and liquid; and serves remote gas in the heater of the second stage in the convection zone; further heat the gas to a temperature above the temperature of gas leaving separator separation of vapor and liquid; introducing the heated gas into the radiation zone of the pyrolysis furnace; and subjecting the gas to pyrolysis with obtaining olefins and related by-products.

This method can be used for processing long residue and crude oil fractions containing pitch.

The method according to the invention makes it possible to bring raw materials - crude oil or fractions of crude oil containing baked in the convection zone of the pyrolysis furnace, without the need to remove the coke in the tubes of the convection zone more often than in the radiation tube furnace. This method enhances the ability olefin furnace to carry out a single equilibrium evaporation of raw materials (crude oil or oil fraction containing pitch) at a higher temperature (for example, 480(C) that it is usually impossible to carry out hr/176.gif">C), resulting in provide extract a larger share of crude oil or crude oil fractions containing pitch, as a pair, are provided for cracking in the area of radiation heat transfer in the furnace of pyrolysis, recovery using operating under atmospheric pressure column or vacuum distillation columns. The method according to this invention also has the advantage of refining crude oil or crude oil fractions containing pitch, without the need for pre-fractionation of the raw crude oil or crude oil fractions containing pitch, resulting allow processing of cheaper raw materials in the pyrolysis furnace. Finally, a significant number of fractions with higher boiling point of the crude oil or crude oil fractions containing pitch, in contrast to the heavy liquefied parts of oil, natural gas, wets the inner surface of the tubes in the convection zone at a suitable linear velocities at these temperatures, resulting in a crude oil or fraction of crude oil that contains peck, become suitable raw materials, and reduces the formation of coke in the tubes of the convection zone.

Si is sparyatsya at 350With; and 90 wt.%, or less, raw materials - crude oil evaporates at 400With ASTM D-2887.

Used in this invention, the raw materials - crude oil has the following characteristics. Each of the following characteristics of the raw crude oil is measured according to ASTM D-2887:

85 wt.%, or less, raw materials - crude oil evaporates at 350With, and

90 wt.%, or less, raw materials - crude oil evaporates at 400C.

Raw materials with the above characteristics to minimize coking in the tubes of the convection section of the pyrolysis furnace under the described operating conditions. Weight fraction of lighter materials, such as most heavy liquefied part of the oil, natural gas, evaporating at 300, 350 or 400With so significant that the evaporation of coking fractions quickly sakakawea tube in the heater first stage at temperatures used according to this invention.

In a preferred embodiment of the present invention crude oil as a raw material has the following characteristics:

65 wt.%, or less evaporated at 300With,

80 wt.%, or less, raw - raw �://img.russianpatents.com/chr/176.gif">C.

According to a more preferred variant implementation of:

60 wt.%, or less of crude oil and long residue evaporated at 300With,

70 wt.%, or less, raw materials - crude oil evaporate at 350With, and

80 wt.%, or less, raw materials - crude oil evaporate at 400C.

According to a preferred variant implementation of the raw materials - crude oil has the following features:

55 wt.%, or less of crude oil evaporate at 300With,

65 wt.%, or less of crude oil evaporate at 350With, and

75 wt.%, or less of crude oil evaporate at 400C.

Typical raw materials - crude oil has a density of petroleum products in degrees American petroleum Institute not above 45.

Raw materials - long the rest is nedogona operating at atmospheric pressure distillation column and is used for processing and fractionation desalted crude oil, and is also known under the name of nedogona operating at atmospheric pressure columns. This working under atmospheric pressure distillation column separates diesel fuel, kerosene, naphtha, gasoline Stuudio raw materials, used according to this invention, and will also meet the following conditions:

35 wt.%, or less, or more preferably 15 wt.%, or less, or even 10 wt.%, or less evaporate at 350With, and

55 wt.%, or less, or more preferably 40 wt.%, or less, and even 30 wt.%, or less evaporated at 400C.

The pressure and temperature at which the raw material is crude oil and/or long residue serves the inlet heater first stage in the convection zone are not critical, if the raw material is a fluid. The pressure is typically in the range of 8-28 bar, more preferably 11-18 bar; and the temperature of the crude oil is typically set in the value from the ambient temperature to a value below the temperature of the flue gas in the convection zone, where its first increase, usually from 140-300C. Consumption of raw materials has no significant importance, although it is desirable to carry out this method with a flow rate in 22000-50000 kg of crude oil and/or long residue per hour.

Fig.1 is a process diagram of the pyrolysis furnace.

Fig.2 is a vertical projection of the separator for the separation of vapor and liquid.

Fig.3 is a horizontal projection of the separator shown in the th in Fig.2.

Fig.5 is a process diagram of the pyrolysis furnace.

Fig.6 is a process diagram of the pyrolysis furnace.

The invention is hereinafter described with reference to Fig.1. It is implied that the scope of the present invention may also include any number and any type of process stages between each of the described process step, or between the described source and destination points in this process step. For example, between the separator for the separation of vapor and liquid and the heater of the second stage can be any number of additional equipment or any number of process stages; and any number of additional equipment or processing steps can occur between the submission of a remote gas from the separator separation of vapor and liquid as a starting point) and the heater of the second stage (the destination).

In furnace 10 olefins pyrolysis serves crude oil or fractions of crude oil containing baked or raw 11 - long the rest is introduced into the heater 12 of the first stage of the convection zone A. In this description raw materials - crude oil everywhere referred to as raw materials according to the invention, but it is understood that when referring to raw materials - crude oil raw materials - long the rest is predpochtitelney, each reference crude oil includes crude oil or fractions of crude oil containing peck. Accordingly, the scope of the present invention includes a long rest and fractions of crude oil containing peck at each mention of raw materials.

The heater 12 of the first stage in the convection zone is usually the beam tubes, the contents of the tubes are heated mainly by convection heat transfer from the flue gas emerging from the radiation section of the pyrolysis furnace. Preferably serves feedstocks, 85 wt.%, or less, which evaporates at 350With; and 90 wt.%, or less, raw materials - crude oil evaporates at 400Since, according to the standard ASTM D-2887. According to one implementation with the passage of the raw material - crude oil and/or long residue through the heater 12 of the first stage is heated to a temperature of performing the evaporation of non-coking fractions in the vapor state, and the evaporation of some portion of the coking fractions in the vapor state, and the remaining coking fractions remains in the liquid state. It was found that the use of raw materials - crude oil and/or long residue, it is desirable to completely vaporize faction shiroikuma this, it is desirable to keep the temperature high enough to vaporize some of the raw materials - crude oil and/or long residue containing fractions contributing to zakochani tubes in the heater first stage and/or the heater of the second stage. The coke formation in the heater first stage is essentially reduced by providing a wet surface on the walls of the heating tubes. If the heating surface is wetted with a sufficient linear velocity of the liquid, inhibited the coking of these surfaces.

The optimum temperature at which the raw material - crude oil and/or long residue is heated in the heater first stage of the convection zone will depend on the specific composition of the raw material - crude oil and/or long residue from the pressure of the raw material in the heater first stage and from the performance and actions of the separator for the separation of vapor and liquid. In one implementation of the invention, the raw materials - crude oil and/or long residue is heated in the heater first stage to the output temperature of at least 375With; and more preferably at least 400°C. In one embodiment, the implementation of the output temperature of the raw material and the temperature of the raw material crude oil and/or long residue in the tubes 12 of the heater first stage is limited by the limit at which the stability of raw materials crude oil and/or long residue is broken. At a certain temperature the tendency of materials to coxworthy increased because asphaltenes in the pitch start to fall out of solution or phase separate from solubilizing resin in the raw material. This temperature limit is applicable to tubes of the heater first stage, and to the tubes connecting to the separator separation of vapor and liquid, and in it. The output temperature of the raw material - crude oil and/or long residue in the heater first stage is preferably not more than 520S and most preferably not more than 500C.

All heater temperature of the first stage are measured as the temperature at which the mixture of gas and liquid reaches at any point in the heater first stage, including the outlet of the heater first stage. Knowing that the temperature of the raw material of crude oil and/or long residue inside the heater tubes of the first stage changes in the continuum, essentially elevating, with the passage of crude oil and/or long residue on the pipes, dusken hole heater first stage of the convection zone. During this weekend the temperatures and coke forming a faction, and not forming coke fraction of the raw material - crude oil and/or long residue will evaporate into the gas phase, while the remaining coke forming fraction in the liquid phase is maintained in the liquid phase, in order to properly moisten the walls of all of the heating surfaces. The ratio of gas/liquid is preferably within the range of from 60/40 to 98/2 by weight; more preferably 90/10-95/5 by weight, in order to provide sufficiently wetted wall of the tube, to minimize the coke formation and to increase the output.

Temperature conditions in the heater first stage properly create such to apply raw materials - crude oil and/or long residue; and they are not recommended for heavy raw materials, representing sizenew part of natural gas. Submission of the heavy liquefied natural gas with coke forming factions, through the heater first stage in the process conditions according to this invention could vaporize the raw materials to its end of the boil, and within a few days of the week could zakoksovanie tube furnace convection section to such an extent that it took ocalenie in the first heater first stage essentially is in the range of values 4-21 bar and more preferably 5-13 bar.

In an optional but preferred embodiment of the present invention diluting the fluid, preferably diluting gas 13 can be inserted in the raw material - crude oil and/or long residue in the heater first stage at any point to exit the mixture of gas and liquid from the heater first stage. In a more preferred embodiment, the dilution gas 13 is introduced into the raw material - crude oil and/or long residue heater first stage at a point which is external to the pyrolysis furnace, for ease of maintenance and replacement of equipment.

Dilution gas is a stream representing pairs, at the point of introduction into the heater first stage. You can use any gas which provides the evaporation of non-coking fractions and parts of coking fractions in raw materials - crude oil and/or long residue. The introduction of the diluted gas also provides for the maintenance of such a mode of flow of raw material through tubes in which the tubes remain soaked, and there is no stratified flow regime. Examples of dilution gases are water vapor, preferably dilution water vapor (saturated water vapor at the point of condensation), methane, ethane, nitrogen, bodoro aetsa dilution water vapor, waste refinery gases, vaporized naphtha or mixtures thereof.

The temperature of the dilution gas is at least sufficient to ensure flow in the gaseous state. In the case of dilution water vapor it is preferably introduced at a temperature below the temperature of the raw crude oil, measured at the point of injection to ensure that no condensation dilution gas, more preferably, 25 toC below the temperature of the raw crude oil at the point of injection. Normal temperature dilution water vapor in the transition dilution gas/raw materials are in the range of values 140-260S, more preferably 150-200C.

The pressure of the dilution gas has no particular limitation, but is preferably sufficient to ensure the possibility of its introduction. The normal pressure of the dilution gas introduced into crude oil typically is in the range of values 6-15 bar.

Dilution gas, it is desirable to introduce into the heater first stage in the amount of from 0.5:1 kg of gas per kg of crude oil, preferably up to 0.3:1 kg of gas per kg of raw material - crude oil and/or long residue.

Alternatively, the dilution tekucu is avatele first stage at any point to exit gazogidrat mixture of the heater first stage. Examples of the diluting fluid are liquids that evaporate easily together with crude oil, such as liquid water or naphtha in combination with other diluting liquids or gases. Typically, the dilution fluid is preferred in the case when the point of introduction is the place where crude oil is still in the liquid phase; and dilution gases are preferred, when the point of introduction is in place, in which crude oil or partially or completely evaporated. Preferred is a method, whereby the amount of water introduced into the raw material is 1 mol.%, or less, from the moles of raw materials.

In yet another embodiment, the superheated steam can be introduced into the heater first stage in line 13 to facilitate further evaporation of raw materials - crude oil in the tubes of the heater first stage.

After raw materials - crude oil is heated to obtain a gas-liquid mixture, it is removed from the heater first stage through line 14, directly or indirectly, in the separator for separation of vapor and liquid in the form of heated gas-liquid mixture. The separator for the separation of vapor and liquid not evaporated removes some of the raw materials - crude oil and/or balance. The separator for the separation of vapor and liquid can be any separator, including a cyclone separator, a centrifuge or a fractionation device, typically used for processing heavy fuel oil. The separator for the separation of vapor and liquid can be made with side injection, when the steam leaves the top of the separator, and the liquid come out from the bottom of the separator; or with the ability of the upper administration, when we receive the gases flow from the side of the separator.

The operating temperature of the separator for the separation of vapor and liquid sufficient to maintain the temperature of the gas-liquid mixture in the range of values from 375 to 520With, preferably, from 400 to 500C. the temperature of the vapor-liquid can be adjusted in any way, including an increase in the flow of superheated dilution steam in the gas-liquid mixture designed separator for separation of vapor and liquid according to the below description with reference to Fig.5, and/or by increasing the temperature of the raw materials fed into the furnace from an external heat exchangers.

In a preferred embodiment, the separator for the separation of vapor and liquid are described in co-pending application, VT 1497 "Separ zobrazen vertically, in partial cross-section according to Fig.2 and in horizontal section according to Fig.3. The state of the gas-liquid mixture in line 14 at the inlet to the separator 20 of the separation of vapor and liquid depends on the properties of the raw material 11. It is preferable to have sufficient not evaporated liquid 15 (between 2-40% vol. raw materials, preferably 2-5% vol. raw materials) to wet the surface of the separator 20 of the separation of vapor and liquid. This requirement wetting of the walls is essential to reduce speed, if not prevent, coke formation and coke deposits on the surface of the separator 20. Evaporation rate (or% vol. neizprotamas fluid 15) can be controlled by regulating the relationship dilution water steam/feedstock and temperature of a single equilibrium evaporation gas-liquid mixture 14.

The separator 20 of the separation of vapor and liquid enables a separation of liquid phases 15 and a pair of 16 mixture of single equilibrium evaporation so that solid particles of coke are unable to form and then to contaminate either the separator 20 or downstream equipment (not shown). Due to this relatively compact design of the separator 20 of the separation of vapor and liquid from the wetted walls can provide more high is by removing a greater proportion of the evaporated fraction 16 raw material 11 for further processing. As a result of this increased share of raw material 11, which can be used for more valuable products 23, and reduced the proportion of heavy hydrocarbon liquid fraction 15 having a smaller value.

In Fig.2 shows the separator 20 of the separation of vapor and liquid, which contains a container with walls 20A, the inlet opening 14a for receiving the incoming gas-liquid mixture 14, the discharge opening 16A pair for directing the vapor phase 16 and the exhaust port 15A fluid for directing the liquid phase 15. Close to the intake opening 14a is a sleeve 25, having a set of blades 25A located at intervals around the circumference of the sleeve 25, preferably near the end nearest to the inlet opening 14a. The site of the blades is more clearly shown in perspective in Fig.4. The incoming gas-liquid mixture 14 is dispersed by spraying on the middle end of the sleeve 25 and, in particular, the blades 25A, the guide portion of the liquid phase 15 mixture 14 in the outer direction 5 to the walls 20A of the separator 20 of the separation of vapor and liquid, resulting in a complete wetting of the walls 20A fluid and a decrease in the rate of coke formation on the inner surface of the walls 20A, if not its exception. Similarly, the outer surface Na surface of the bushing 25 due to lack of effort, required for transportation of the liquid 15 in contact with the surface of the sleeve 25 to the inside walls 20A. Skirt 25b around the far end of the sleeve 25 and contributes to the forced displacement of fluid transported down the outer surface of the bushing 25, the inside walls 20A by introducing liquid in the vortex pairs. The upper part of the separator 20 of the separation of vapor and liquid is filled in the location 20b between the inlet 14a and the sleeve 25, to facilitate wetting of the inner surface of the walls 20A when entering the gas-liquid mixture 14 to the separator 20 of the separation of vapor and liquid. During transportation of the liquid 15 down she constantly washes walls 20A and the sleeve 25 and prevent, if not eliminate, the formation of coke on their surfaces. The liquid 15 continues to fall in and out of the separator 20 of the separation of vapor and liquid through the outlet 15A of the liquid. A pair of inlet nozzles 26 mounted below the tube 16A of the inlet steam to supply cooling water for cooling the accumulation of fluid 15 and reduce coke formation in the downstream equipment. Vapor phase 16 enters into the exhaust channel 16A pair at its highest point 16C, comes out of the outlet openings 16A and goes into the evaporator 17 at last the channel 16 and contributes to the deviation of the liquid 15 in the outer direction to the walls of the separator 20A.

The length of the sleeve 25 under the blades 25A was selected on the basis of estimates of the size of the liquid droplets, which will be captured before it will move more than half way after the sleeve 25. A significant amount of fluid 15 will drain down the sleeve 25 (according to the observations on air-to-water model), and the presence of a "skirt" 25b on the sleeve 25 will cause the introduction of liquid droplets in the vapor phase is much lower blades 25A, and the accumulation will continue below the skirt 25b of the sleeve 25 due to the ongoing turbulence pair 16 when it is moved to the outlet of the tube 16A.

Size skirts 25b of the sleeve was selected to allow movement of the fluid from the sleeve 25 as close as possible to the outer wall 20A, without reducing the space for the passage of steam 16 is smaller than the area on the blades 25A. In practice, for the stream was provided with an area of about 20% more than available on the blades 25A.

The distance between the bottom of the sleeve 25 and the highest point of the tube 16C 16A steam release was chosen four times larger than the diameter of the tube 16A steam release. This corresponded to air-to-water model. The objective is to provide space for movement of the steam in the outlet 16A without the necessity of ensuring a very high p the Asti tube 16A steam release picked up about three times as large, than the diameter of the tube. The objective is to provide such a distance, which will be provided by the vertical turbulence above the tube 16A of issue without the need of a breach by the proximity of the trajectory of the horizontal steam flow 16 emerging from the discharge tube 16A. The position and size of the fixing ring 16b of the tube 16A steam release determined arbitrarily. It is installed close to, but not below the rim and is relatively small in order to provide space for coke, drop down between the outer wall 20A and ring 16b.

Details of the separator 20 below the discharge tube 16A is caused by problems outside the scope of this separator. Because any reason to liquid jet directed above the inlet 16C in the discharge tube 16A, there is, therefore, the separation efficiency will not decrease.

The main areas that are important from the point of view of coke formation, include sections where the recirculation of steam, or where the metal is not well washed with liquid. Section 20b inside the upper part may have such a form, or may be filled with such material, in order to get closer to the expected zone of recirculation. The inner space of the sleeve 25 is EA steam release, then the stream would be created a significant obstacle (as a closed stop valve). For this reason, you can use the cage or screen 25s made either from a rod, or in the form of a stub tube. This decision does not preclude the buildup of coke, but mostly will be his to keep, to avoid the loss of large pieces. The areas under the skirts of the blades and skirts 16b of the tube 16A steam release is also not "washed out", and the buildup of coke in these areas possible.

Gaseous evaporated part 16 raw materials - crude oil and/or long residue entering the separator 20 of the separation of vapor and liquid in the form of a gas-liquid mixture from the heater 12 of the first stage, and then supplied to the mixer 17 of the evaporator, where steam is mixed with the superheated steam is 18, which heats the steam to a higher temperature. The steam is preferably mixed with superheated steam, in order to guarantee that the thread will remain in the gaseous state by reducing the partial pressure of hydrocarbons in the pair. Because the vapor leaving the separator for the separation of vapor and liquid is saturated, then the introduction of superheated water vapor will minimize the possibility coke forming factions in pairs to condense on the inside is the motor of the second stage. Source of superheated water vapor is water vapor 18, served in the convection section of the pyrolysis furnace between the heaters of the first and second stages. The exhaust gas from the radiation section preferably act as a heating source to raise the temperature of the water vapor to a superheated state.

The appropriate temperature superheated water vapor specific upper limit is not limited, but should be sufficient to ensure overheating above the condensation point of steam. As a rule, superheated steam is introduced into the mixer 17 of the evaporator at an approximate temperature of from 450 to 600C.

The mixer 17 of the evaporator is preferably outside the pyrolysis furnace, for ease of maintenance. Can be used any conventional mixing paddle, but it is preferable mixing nozzle according to US-A-4498629 to minimize the possibility of coke formation around the inner surfaces of the mixing nozzle. The preferred mixing nozzle, as described in US-A-4498629, contains the first tubular member and the second tubular element surrounding the first tubular element, with the formation of the annular space. ProTool pairs preferably combined with a removable gas before it enters the heater of the second stage. Therefore, the first inlet means to provide for the introduction of the evaporated raw material crude oil and/or long residue, or a long rest in the first tubular element, and a second inlet means provide for the introduction of superheated steam in the annular space. And the first tubular member and second tubular elements have open end for supplying superheated water vapor, in the form of an annular space around the feeder pair; the open ends of the end holes made in a plane essentially perpendicular to the longitudinal axis. The device also contains an element in the form of a truncated cone, one end of which is connected with the open end of the second tubular element having a longitudinal axis essentially coincides with the longitudinal axes of the tubular elements and is inclined in the direction from the second tubular element, and the angle of the top element in the form of a truncated cone is equal to the maximum 20. Due to the fact that having the shape of a truncated cone element has some deviation behind where superheated steam occurs with supplied material, avoid contact of liquid droplets with the wall element, thereby reducing to a minimum the of soaring glider on line 19, served in the heater 21 of the second stage through the tubes and is heated in the heater of the second stage exhaust gases from the radiation section of the furnace. The heater 21 of the second stage mixed mixture of superheated steam and gas is fully pre-heated almost to, or slightly less than the temperature at which substantial cracking of the raw materials and the corresponding deposition of coke in the heater. Then the feed mixture is in the radiation section on line 22 of the furnace of pyrolysis olefins, where gaseous hydrocarbons are subjected to thermal cracking to olefins and related product leaving the kiln through line 23. Usually the temperature at the entrance of the radiation zone In amount to more than 480C, more preferably at least 510C, most preferably at least 537With, and at least 732With output, more preferably at least 760S, and most preferably at least 760With up to 815With to facilitate cracking of the molecules of long and short chain to olefins. The products of pyrolysis furnace ol the corresponding olefin, paraffin and aromatic product. Generally, the predominant product is ethylene, which typically ranges from 15 to 30 wt.% the evaporated raw material.

According to an optimal implementation of the superheated steam can be introduced into the heater 12 of the first stage in the convection section on line 13 instead of diluting water vapor, according to Fig.1; or it can be inserted between the outlet of the heater first stage and a separator for separation of vapor and liquid, according to Fig.5, for further enhancement of the desired temperature gas-liquid mixture, thereby increasing the proportion or percentage of steam extracted from the raw crude oil and/or long residue.

The percentage of evaporated components in a gas-liquid mixture in the heater first stage can be controlled by regulating the temperature of a single equilibrium evaporation, the amount of additional input superheated water vapor and the amount and temperature of the superheated water vapor introduced into the raw material crude oil and/or long residue in the heater 12 of the first stage. The amount of steam extracted from the raw crude oil and/or long residue must not exceed the ratio of gas and structure can prevent coke formation in the separator 20 of the separation of vapor and liquid, the mixer 17 of the evaporator and the heater 21 of the second stage due to constant wetting of the heating surfaces in the heater first stage separator and separation of vapor and liquid. The method according to this invention provides a high degree of extraction of crude oil and/or long residue, which is otherwise impossible with the temperature of the heater first stage in the value 350With or less simultaneously inhibiting consobrina.

Microwave pyrolysis may be conventional microwave pyrolysis of olefins to obtain olefins of low molecular weight, in particular, tube furnace containing a vapor-phase cracking. Tubes in the convection zone of the pyrolysis furnace can be in the form of a bundle of parallel tubes, or tubes can be arranged for a single passage of the feedstock through the convection zone. Intake of raw materials can be divided into several single-pass tubes, or it can be served in a single-pass tube, on which all the raw material passes from the inlet to the outlet of the heater of the first degree, and more preferably over the entire convection zone. Pre-heater first stage preferably comprises odnoperogo convection zone contains forward-tube having two or more beam, which passes raw materials - crude oil and/or long residue. Each beam tube can be made in the form of a coil in one row, and each beam can have multiple rows of tubes.

To further minimize coke formation in the tubes of the heater first stage and tubes of equipment after it and in the separator separation of vapor and liquid linear velocity of flow of raw materials - crude oil and/or long residue is preferably chosen in such a way as to reduce the time spent evaporated gases coke forming fractions in tubes. The required linear speed will also contribute to the formation of thin uniform spacenot on the surface of the tubes. Although a higher linear velocity of the raw material - crude oil and/or long residue in the tubes of the heater first stage to reduce the rate of coke formation, there is an optimum range of linear speed for a given raw material, beyond which the preferred pace of reduction in coke formation begins to deteriorate for the reason that additional energy is needed for pumping raw materials, and in connection with the requirements to the size of the tubes to account for the range of speeds above optimalisatie in the range from 1.1 to 2.2 m/s, more preferably 1.7 to 2.1 m/s and most preferably from 1.9 to 2.1 m/s ensures optimum results in reduction of the balance of coke formation when compared with the cost of the tubes in the furnace and in terms of required energy.

One means for feeding raw material - crude oil and/or long residue at a linear speed in the range from 1.1 to 2.2 m/s is the usual pumping mechanism. In a preferred embodiment of the present invention, the linear speed of the raw crude oil and/or long residue is increased by introducing a small amount of liquid water in raw materials - crude oil before it enters the heater first stage, or at any desired point in the heater first stage. During the evaporation of liquid water in raw materials - crude oil and/or long residue speed of the feed material in the tubes increases. To achieve this effect, you need only a small amount of water, for example, 1 mol.% water, or less, from the moles of the raw material passing through the heater tubes of the first stage.

In many manufactured pyrolysis furnaces olefins in the tubes of the radiation section accumulates a sufficient amount of coke every 3-5 weeks, requiring its removal. The method according to olefin furnace without the need to shut down the furnace for removal of coke no more than for the furnace, which would otherwise have to stop to clean from coke in the tubes of the radiation section. According to the method of this invention, the term convection section of at least the same duration as the term of the radiation section.

According to another variant implementation of the invention tube convection section clear of coke on a regular schedule with the desired frequency and no more than cleaning up the radiation section. The convection section is preferably clear of coke at least 5 times less, and more preferably at least 6 to 9 times less than the radiation section. Cleaning of tubes from the coke can be done using a stream of water vapor and air.

In yet another preferred embodiment of the invention the flow of superheated water vapor is introduced into the tube heater first stage and/or between the exit point of the convection section of the heater of the first stage and a separator for separation of vapor and liquid through the mixing nozzle. That is, ensure the exercise, according to which the flow of superheated water vapor is included in the convection zone, preferably between heaters of the first and second stages, thus the source of superheated water vapor can be divided by the divisor for the flow of superheated water vapor in the separator 6 separation of vapor and liquid and the flow of superheated water vapor in the mixing nozzle 5, located between the output of the heater first stage, containing bundles of 2, 3 and 4 pipes, and a separator 6 separation of vapor and liquid.

According to another preferred variant of the invention, the raw material can also be divided by the divisor 1A according to Fig.6 between the heat exchangers 2 and 3 or between any other heat exchangers in the section of the heater first stage of convection section of the furnace. This divider may be desirable in the case where the raw material contains a large percentage of the pitch, and it is heated to a high temperature in the heat exchanger 1 to regulate its fluidity, thereby eliminating the need to process all the raw material through the first heat exchanger in the heater first stage of the convection zone.

The following example illustrates one of the embodiments of the invention and is not intended to limit the scope of the invention. This example is derived from the simulator Simulated Sciences Provision Version 5.1. To illustrate the implementation of this option, reference is made to Fig.5. In each case, the mixture of vapor and liquid emerging from the convection zone is at a temperature above 375C. Under conditions of pressure and trakcie cracking, resulting in the convection section will zakoksovanie much faster than in the oven, processing raw materials according to the conditions described below.

Example 1

Crude oil with the following properties is used as a raw material:

This raw material is crude oil with a density of 37,08 in degrees American petroleum Institute and with an average molecular weight of 211.5 served at a temperature of 27With and consumption 38500 kg/h into the external heat exchanger 1 for heating the crude oil to a temperature of 83With under a pressure of 15 bar before entering the first beam tubes 2 heater convection section. The heated raw material - crude oil, still remaining at this point the liquid is directed through one pass of the first beam tubes 2 having eight rows of tubes; each number is made in the form of a coil and is heated there to a temperature of 324With, and is published under a pressure of 11 bar. At this stage, the weight fraction of liquid is 0,845, and the liquid flows with a flow rate of 32,500 kg/h Density fluid is 612 kg/cubic m, and its average molecular weight is 247,4. The vapor phase flows with a flow rate 5950 kg/h and has an average molecular weight 117,9 and density 31 thereof with the first beam, where the liquid-vapor mixture is further heated to a temperature of 370With and comes under the pressure of 9 bar. Weight fraction of liquid coming out of this second beam tubes is 0,608. The liquid now has a density 619 kg/cubic meter and the average molecular weight of 312,7 and flows with flow 23400 kg/h steam phase goes with the flow 15100 kg/h and has an average molecular weight 141,0 and density 27,4 kg/cubic m

Vapor-liquid mixture is fed to the third beam tubes 4, identical with the first and second beams of the tube, where the liquid-vapor mixture is then heated to a temperature of 388With, and it comes out of the third beam and the convection zone at this temperature and under a pressure of about 7 bar. In the third beam tubes 4 dilution water vapor in the number 1359 kg/h, with a flow of 3.5, served in the third beam tubes 4 under a pressure of 10 bar and at a temperature of 182C. Weight fraction of liquid coming out of the third beam tubes 4, now reduced to 0,362. The average molecular weight of the liquid phase at the outlet of the third beam tubes upgraded to 419,4, she has a density of 667 kg/cubic meter and proceeds with the flow of 14400 kg/h steam phase goes with the flow 25400 kg/h, has an average molecular weight of about 114,0 and density of 14.5 to pass into the mixing nozzle 5. Stream 5A in an amount of about 17600 kg/h of water vapor, superheated to 594With under a pressure of 9 bar, is introduced into vapor-liquid mixture emerging from the convection zone through the mixing nozzle 5. Thus obtained liquid-vapor mixture passes into the separator 6 separation of vapor and liquid flow 57500 kg/h at a temperature of 427C and under a pressure of 6 bar. The average molecular weight of the liquid phase has now increased to 696,0. Weight fraction of liquid is now 0,070 due to input superheated water vapor.

The mixture of vapor and liquid are separated in a separator 6 separation of vapor and liquid. Separated liquid leaves the bottom of the separator. Separated couples 7 exits separator separation of vapor and liquid from the top or through the side outlet with flow 53500 kg/h, at a temperature of about 427C and under a pressure of 6 bar. The average molecular weight of the steam flow is 43.5, and he has a density of 4.9 kg/cubic meters Liquid bottom stream leaving the separator separation of vapor and liquid, is considered peck and subjected to appropriate processing. Consumption pitch is about 4025 kg/h, and it comes at a temperature of about 427C and under a pressure of 6 bar. This fluid has the heated beam tubes 8. Water vapor along the line 8A passes with a flow rate of about 1360 kg/h and is superheated to a temperature of 593With under a pressure of 9 bar. It takes place in the mixing nozzle 9, which is combined with stream 7 pair with the formation of the thread 9a couple passing by consumption 54800 kg/h at a temperature of 430C and under a pressure of about 6 bar heater 9b of the second stage of the convection zone, where it is further heated and enters the radiation zone (not shown). The average molecular weight of the thread 9a pair is 42,0, and its density is equal to 4.6 kg/cubic m

The steam flow then passes back into the convection zone and the radiative zone ethylene furnace for cracking pair.

Example 2

The flow of long residue obtained from crude oil and representing the flow of nedogona working under atmospheric pressure of the rectification column and a crude oil having the following properties, are used as raw materials:

This raw material - long residue, which has a density 25,85 in degrees American petroleum Institute and the average molecular weight of 422,2, served at a temperature of 38And with the consumption of 43000 kg/h into the external heat exchanger(s) 1 for heating long the 2 heater convection section. The heated raw material - long residue still remaining at this point the liquid is directed through one pass of the first beam tubes 2 having eight rows of tubes; each number is made in the form of a coil and is heated there to a temperature of 347With, and comes in liquid form under pressure 13 bar.

Long residue has a density of 710 kg/cubic meter when the output from the first beam tubes 2 and is fed to the second beam tubes 3, identical with the first beam, where it is further heated to a temperature of 394With and comes under a pressure of 10 bar. Evaporation does not occur, and the entire flow out in the form of a fluid current to flow 43000 kg/h, with a density of 670 kg/cubic m

Long remainder is then applied to the third beam tubes 4, identical with the first and second beam tubes, where it is further heated to a temperature of 410With, and he comes out of the third beam and the convection zone at this temperature and under a pressure of about 7 bar. In the third beam tubes 4 dilution water vapor in the number of 1360 kg/h, with a flow of 3.5, served in the third beam tubes 4 under a pressure of 10 bar and at a temperature of 182C. It comes from the third beam tubes 4 in the form of a vapor-liquid mixture with the weight fractions of the liquid the density of 665 kg/cubic meter and proceeds with the flow 36850 kg/H. Vapor phase passes with consumption 7540 kg/h, has an average molecular weight of about 80,5 and density of 9.6 kg/cubic m

Vapor-liquid mixture exits the third beam tubes 4 in the convection section of the ethylene furnace and passes into the mixing nozzle 5. Stream 5A in an amount of about 17935 kg/h of water vapor, superheated to 589With under a pressure of 9 bar, is introduced into vapor-liquid mixture emerging from the convection zone through the mixing nozzle 5. Thus obtained liquid-vapor mixture passes into the separator 6 separation of vapor and liquid flow 62330 kg/h at a temperature of 427C and under a pressure of 6 bar. The average molecular weight of the liquid phase has now increased to 599,0. Weight fraction of liquid is now 0,208 due to input superheated water vapor.

The mixture of vapor and liquid are separated in a separator 6 separation of vapor and liquid. Separated liquid leaves the bottom of the separator. Separated couples 7 exits separator separation of vapor and liquid from the top or through the side outlet with flow 49400 kg/h, at a temperature of about 427C and under a pressure of 6 bar. The average molecular weight of the steam flow is about 42,9, and the flux density is 4,84 kg/cubic meters Liquid nor is it processed. The flow rate of the pitch is about 13,000 kg/h, and it comes at a temperature of about 427C and under a pressure of 6 bar. This fluid has a density of 722 kg/cubic meter and the average molecular weight of 599.

Thread 7 of the water vapor is combined with steam 8A, heated in the beam tubes 8. Water vapor along the line 8A passes with a flow rate of about 1360 kg/h and is superheated to a temperature 589With under a pressure of 9 bar. It passes through the mixing nozzle 9, which is combined with stream 7 pair with the formation of the thread 9a couple passing by consumption 50730 kg/h at a temperature of about 430C and under a pressure of about 6 bar heater 9b of the second stage of the convection zone, where it is further heated and enters the radiation zone (not shown). The average molecular weight of the thread 9a pair is 41.3, and its density is equal to 4.5 kg/cubic m

The steam flow then passes back into the convection zone and the radiative zone ethylene furnace for cracking pair.

Claims

1. The method of pyrolysis of the raw material - crude oil and/or crude oil fractions containing pitch, in the pyrolysis furnace to olefins, including supply of raw materials in the heater first stage, in rc="https://img.russianpatents.com/chr/176.gif">With receiving the heated gas-liquid mixture, the output of a gas-liquid mixture from the heater first step in the separator separating vapor and liquid, separating and removing gas from the liquid in the separator for the separation of vapor and liquid and the supply of remote gas in the heater of the second stage, located in the convection zone, with increasing the temperature of the gas to a temperature above the temperature of gas leaving separator separation of vapor and liquid, the input of heated gas in the radiation zone of the pyrolysis furnace and the implementation of the pyrolysis gas to olefins and related by-products.

2. The method according to p. 1, in which 85 wt.% or less raw material is evaporated at 350And 90 wt.% or less of raw material - crude oil is evaporated at 400Since, in both cases, as measured by ASTM D-2887.

3. The method according to p. 1 or 2, in which the raw material is fed into the heater first stage pressure 11 - 18 bar and at a temperature of 140 - 300C.

4. The method according to any of paragraphs.1-3, in which the raw material in the heater first stage is heated to the exit temperature at least equal to 400C.

5. The method according to any of paragraphs.1-4, in which the ratio of gas and liquid NaF heater first stage.

7. The method according to any of paragraphs.1-6, in which superheated steam is combined with a remote gas before it enters the heater of the second stage.

8. The method according to any of paragraphs.1-7, in which the olefins include ethylene in amounts of 15 to 30 wt.% the weight of the evaporated raw material.

9. The method according to any of paragraphs.1-8, in which diluting the fluid, which is liquid or mixed liquid-gas phase is injected into the heater first stage.

 

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