CN114437813A - Heavy oil lightening method - Google Patents
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Images
Classifications
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- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
Abstract
The invention provides a method for lightening heavy oil, which comprises the following steps: dispersing hydrogen and heavy oil raw material mixed with a catalyst by a micro-element generating device to form a micro-element dispersion system in which the hydrogen is dispersed in the heavy oil raw material in the form of bubbles with the size of not more than 500 microns; allowing the infinitesimal dispersion system to enter a hydrogenation reactor for hydrogenation reaction to obtain a hydrogenation reaction product; after the hydrogenation reaction product is output from the hydrogenation reactor, one part of the hydrogenation reaction product returns to the hydrogenation reactor to form circulation, and the rest part of the hydrogenation reaction product is the light product. The method for lightening the silicon carbide can achieve higher conversion rate and has the advantages of simple process flow and the like.
Description
Technical Field
The invention belongs to the field of petroleum processing, and particularly relates to a heavy oil lightening method.
Background
With continuous heavy and inferior petroleum resources, heavy oil becomes an important raw material for refineries, and the efficient conversion processing of inferior heavy oil resources to produce more clean light oil products becomes an important way for dealing with the shortage of petroleum resources. According to the change of the mass ratio of carbon to hydrogen of oil products in the processing process, the heavy oil upgrading process can be divided into two types of hydrogenation and decarburization, wherein the decarburization process mainly comprises the processes of catalytic cracking, delayed coking and the like, is the main processing process for upgrading the heavy oil at the present stage, and accounts for about 83% of the processing amount of the whole heavy oil, however, the coke yield is high, and precious carbon atoms in the heavy oil are difficult to be fully utilized, which is a major problem in the process; the hydrogenation process accounts for about 17% of the total heavy oil processing amount, and compared with the decarburization process, the hydrogenation process can basically realize 100% utilization of carbon atoms in the heavy oil, so the hydrogenation process gradually becomes a main development trend of heavy oil lightening.
At present, a heavy oil hydrogenation process mainly comprises fixed bed hydrogenation, fluidized bed hydrogenation and suspension bed hydrogenation processes, and is taken as general knowledge in the industry, the fixed bed hydrogenation process generally requires that the total metal content in raw oil is not higher than 150ppm (mu g/g), the carbon residue value is not higher than 15%, the asphaltene content is not higher than 5%, and the raw material adaptability is limited; the fluidized bed hydrogenation process needs continuous replacement of partial catalyst in the reactor, and has the problems of complex engineering equipment, poor operation stability and the like; the suspension bed hydrogenation process can process inferior heavy oil with relatively poorer properties, and has the advantages of larger conversion depth, higher yield of light oil, higher carbon residue removal rate, higher metal removal rate and the like compared with other hydrogenation processes.
The suspension bed hydrogenation process is a hydrogenation process in which a catalyst with a certain particle size is driven to move by adjusting the flow velocity of a fluid to form a gas-liquid-solid three-phase bed layer, so that hydrogen, raw oil and the catalyst are contacted to complete a hydrocracking reaction.
U.S. patent document US2011303580a1 discloses a slurry hydrocracking process in which one or more hydrocarbon feedstocks and a slurry hydrocracking catalyst comprising a carrier are combined as a feed to a slurry hydrocracking reaction zone; fractionating the effluent (product) from the slurry hydrogenation reaction zone to obtain a light vacuum gas oil, a heavy vacuum gas oil, a mixture comprising bitumen and a slurry hydrocracking catalyst; separating the pitch from at least a portion of the slurry hydrocracking catalyst, the slurry hydrocracking catalyst obtained after separation being contained in a suspension; the suspension is recycled back to the slurry hydrocracking reaction zone. The process aims to improve the utilization rate of the asphalt, and therefore, the proposal of separating the asphalt from the slurry hydrogenation catalyst after vacuum distillation is provided, although the process can realize the lightening of heavy oil to a certain extent, the process has the defects of low single-pass conversion rate, large tail oil circulation amount, high energy consumption, high operation cost and the like.
Another U.S. patent document US2016122663a1 discloses an integrated slurry hydrocracking process in which a heavy residual hydrocarbon feedstock and a hydrogen stream are introduced into a slurry hydrocracking zone, the heavy residual hydrocarbon feedstock is hydrocracked under slurry hydrocracking conditions over a shiny hydrocracking catalyst to form a slurry hydrocracked effluent (product), at least a portion of said effluent is introduced into a first end of a distillate hydrotreater and hydrogen is supplied to said first end, said at least a portion of the effluent is hydrotreated under hydrotreating conditions, the resulting hydrotreated product exits the distillate hydrotreater from a second end opposite the first end, the hydrotreated product is then separated into a liquid stream and a gaseous stream, and at least a portion of the gaseous stream containing hydrogen is recycled to the slurry hydrocracking zone. The process also has the problems of complex process flow, limited conversion rate and the like.
Chinese patent document CN001239929A discloses a normal pressure heavy oil suspension bed hydrogenation process using a multi-metal liquid catalyst, wherein the slurry after being fully mixed and heated enters a suspension bed hydrocracking reactor from the bottom, the top effluent of the reactor enters a high temperature and high pressure separation system for separation, a vapor phase material flow enters an on-line fixed bed hydrofining reactor, a liquid phase material flow enters a low pressure separation system, the liquid phase material flow of the low pressure separation system also enters a previous fixed bed hydrofining reactor, and the material flow after being hydrofined by the fixed bed finally enters a conventional separation system for separation to obtain various products. The process combines a suspension bed hydrocracking reactor and a fixed bed hydrofining reactor and needs to be matched with at least three stages of separation systems (a high-temperature high-pressure separation system, a low-pressure separation system, a conventional separation system and the like) to realize the lightening of heavy oil, and the whole process system and flow are complex, the energy consumption is high and the cost is high.
Chinese patent document CN107892941B discloses a heavy oil suspension bed hydrocracking method, in the method, an inferior heavy oil suspension bed hydrogenation catalyst and inferior heavy oil are mixed uniformly and then enter a suspension bed hydrogenation reactor, then the reactor is heated to 320-500 ℃ for hydrogenation reaction, the reaction pressure is 5-20 MPa, the time is 0.5-4h, the hydrogen-oil volume ratio is 100-2000, and the space velocity is 0.2-4.0h-1(ii) a Wherein, the hydrogenation catalyst consists of zinc oxide powder (with the content of 10-56 wt%) and fluidized ore component powder, or the hydrogenation catalyst consists of zinc oxide powder (with the content of 10-56 wt%), vulcanized ore component powder and vulcanized micro-mesoporous lanthanum ferrite (with the content of 0.2-8 wt%). The method improves the effect of lightening the heavy oil raw material by improving the hydrogenation catalyst, but the special requirement on the catalyst also increases the cost and complexity of the whole process flow, and the practical industrial application has greater limitation.
The heavy oil is lightened through the hydrogenation process, and no matter which hydrogenation process is adopted, the common mechanism of the system material is that hydrogen is firstly dispersed and dissolved in the heavy oil, and then is activated by the hydrogenation catalyst dissolved or dispersed in the heavy oil, and further reacts with the component to be reacted in the heavy oil, so that the heavy oil is hydrogenated and lightened. In the process, the full contact of the heavy oil raw material, hydrogen and the catalyst is realized, which is very important for ensuring the high efficiency of the heavy oil hydrogenation and is the common essence of the difficult problems in the implementation process of various hydrogenation processes. Taking the suspension bed hydrogenation process as an example, after hydrogen enters a suspension bed hydrogenation reactor in a bubble form, the hydrogen needs to be transferred to liquid-phase heavy oil through a bubble-heavy oil phase interface and then is activated by a catalyst dissolved (oil-soluble or water-soluble homogeneous catalyst) or dispersed (solid granular heterogeneous catalyst) in the heavy oil, under a certain operating pressure (mass transfer driving force), the mass transfer rate of the hydrogen to the heavy oil is determined by the phase interface area between the hydrogen bubbles and the heavy oil, while the size of the hydrogen bubbles dispersed in the heavy oil in the existing suspension bed hydrogenation reactor is generally not less than 5mm, which cannot provide enough phase interface area for the transfer of the hydrogen to the heavy oil, and because the bubbles are large, the buoyancy in the heavy oil is also large, the rising speed is fast, the retention time is short, and the hydrogen has insufficient time to contact and react with the heavy oil, sufficient hydrogen radicals which can quickly capture macromolecular radicals generated by heating heavy oil are difficult to supplement in time, heavy oil macromolecular radicals are easy to collide with each other to cause superposition and even coking, so that the existing suspension bed hydrogenation process is usually implemented under a large operating pressure (most of which is greater than 18MPa) to increase the mass transfer driving force of hydrogen to the heavy oil and relieve the problems of poor contact reaction between the hydrogen and the heavy oil, easy coking and the like, and the large operating pressure has high requirements on equipment, an operating process and the like, so that the industrial application of the suspension bed hydrogenation process is very limited.
In fact, the hydrogenation processes such as the above-mentioned suspension bed generally face the common problem that it is difficult to achieve full contact of the heavy oil, hydrogen and the catalyst, which is also the essential reason that these processes have the defects of large operation pressure, harsh conditions, etc., although the above-mentioned suspension bed hydrogenation processes such as the above-mentioned reports can achieve effective conversion of heavy oil or reduce the operation pressure of the suspension bed reactor to a certain extent by jointly adopting a plurality of reactors and/or improving catalysts, etc., these processes generally face the problems of complicated process flow, etc., and are limited in industrial application.
Therefore, the development of a novel heavy oil lightening process can reduce the operation pressure, simplify the process flow and improve the industrial applicability while ensuring or even improving the heavy oil conversion rate, and has become a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a heavy oil lightening method which can realize high-efficiency conversion of heavy oil, and has simple process flow and strong industrial practicability.
The invention provides a method for lightening heavy oil, which comprises the following steps: dispersing hydrogen and heavy oil raw material mixed with a catalyst by a micro-element generating device to form a micro-element dispersion system in which the hydrogen is dispersed in the heavy oil raw material in the form of bubbles with the size of not more than 500 microns; allowing the infinitesimal dispersion system to enter a hydrogenation reactor for hydrogenation reaction to obtain a hydrogenation reaction product; after the hydrogenation reaction product is output from the hydrogenation reactor, one part of the hydrogenation reaction product returns to the hydrogenation reactor to form circulation, and the rest part of the hydrogenation reaction product is the light product.
The invention provides a heavy oil lightening method, which combines a infinitesimal generating device and a hydrogenation reactor, forms a dispersion system (also called dispersion flow form) taking heavy oil raw material (liquid phase) as a continuous phase, a catalyst and highly dispersed micron-scale (not more than 500 microns) hydrogen bubbles as a discrete phase in a reaction state in the hydrogenation reactor, and simultaneously, a part of hydrogenation reaction products are circularly returned to the hydrogenation reactor, so that the fluid disturbance in the hydrogenation reactor is intensified, the back mixing and dispersion of hydrogen in the hydrogenation reactor are intensified, the dispersion flow form in the hydrogenation reactor is intensified, the hydrogenation reaction is carried out in the dispersion system state, the heavy oil raw material, the catalyst and the hydrogen can be fully contacted, and the conversion rate of the heavy oil raw material is obviously improved, and can inhibit the condensation of heavy oil raw materials to produce coke; meanwhile, as the raw materials are fully contacted under the dispersion system, the hydrogenation reaction can be carried out under the conditions of lower operation pressure and the like, so that the reaction conditions are more moderate, and the energy consumption and the cost are saved.
Specifically, in an embodiment of the present invention, the part of the hydrogenation reaction product (i.e., the hydrogenation reaction product returned to the hydrogenation reactor for circulation) may be 10 to 90% of the total mass of the hydrogenation reaction product output from the hydrogenation reactor (i.e., after the hydrogenation reaction product is output from the hydrogenation reactor, 10 to 90% of the hydrogenation reaction product may be returned to the hydrogenation reactor for circulation, and the remaining part may be a light product), and may further be 20 to 80%, for example, 20 to 70%, 20 to 60%, 20 to 50%, or 20 to 40%, which is beneficial to the conversion rate of the heavy oil raw material and the stability of the operation of the whole light system.
Furthermore, the infinitesimal dispersion system can enter the hydrogenation reactor from the bottom of the hydrogenation reactor, after the hydrogenation reaction product is output from the hydrogenation reactor, a part of the hydrogenation reaction product returns to the hydrogenation reactor from the middle part of the hydrogenation reactor to form a cycle, the condition can ensure that the main body flow direction in the hydrogenation reactor is an upward flow (namely a reverse gravity field), a part of the hydrogenation reaction product is injected from the middle part, and upward and downward materials collide with each other, thereby further strengthening the dispersion flow form, increasing the retention time of hydrogen in the hydrogenation reactor, increasing the contact chance of the hydrogen and the heavy oil raw material, and being beneficial to the lightening effect of the heavy oil raw material; the part of the hydrogenation reaction product is preferably injected into the hydrogenation reactor from the middle part of the hydrogenation reactor downwards, for example, a material inlet at the middle part can be embedded into the hydrogenation reactor, and the feeding mode is to inject the material downwards, so that the part of the hydrogenation reaction product enters the hydrogenation reactor from the material inlet at the middle part.
The middle part of the hydrogenation reactor may be specifically a position accounting for 10-50% of the total height of the hydrogenation reactor from the bottom of the hydrogenation reactor, and may further be 20-50%, for example, 20-40% or 20-30%.
In the above process, the hydrogenation reaction product can be output from one or more of the bottom, middle part and top of the hydrogenation reactor. In one embodiment, the hydrogenation reaction product is output from the top of the hydrogenation reactor, wherein the hydrogenation reaction product contains unreacted hydrogen, and a part of the hydrogenation reaction product is returned to the hydrogenation reactor to form a cycle, so that the retention time of the hydrogen in the hydrogenation reactor can be further increased, the contact chance of the hydrogen and the heavy oil raw material is increased, and the hydrogenation reaction efficiency of the heavy oil raw material is further improved; in another embodiment, the hydrogenation reaction product is output from a plurality of positions such as the top, the middle and the bottom of the hydrogenation reactor, the product flowing out from each position has different fraction distribution (i.e. equivalent to the hydrogenation reactor performing a primary separation treatment on the hydrogenation reaction product), generally, the output product gradually becomes heavier from top to bottom, wherein the product output from the bottom is generally rich in tail oil, and in particular, the part can be returned to the hydrogenation reactor to form a circulation to further enhance the lightening degree of the heavy oil raw material.
It will be appreciated that the hydrogen bubbles dispersed in the heavy oil feedstock are similar to spheres, and that the above-mentioned dimensions generally refer to the diameter of the hydrogen bubbles, and that the methods of measurement and control are conventional. Specifically, the above-mentioned infinitesimal generating device may be a material microdispersion or bubble generating device that is conventional in the art, for example, may be selected from at least one of a microporous ceramic membrane infinitesimal generating device, a venturi-type infinitesimal generating device, and an ultrasonic cavitation device, and the size of the formed hydrogen bubbles may be generally adjusted by selecting a microporous ceramic membrane infinitesimal generating device with a certain aperture, or adjusting conditions (or parameters) such as gas velocity of the venturi-type infinitesimal generating device/ultrasonic cavitation device, for example, when bubbles are generated by using a microporous ceramic membrane infinitesimal generating device with a pore diameter of 100 μm (where the pore diameter of the microporous ceramic membrane is 100 μm), a gas phase (such as the above-mentioned hydrogen) enters a liquid phase (such as the above-mentioned heavy oil raw material) through a microporous ceramic membrane to form bubbles, and the size of the formed bubbles is generally considered to be also about 100 μm on average; when the Venturi type micro-element generating device (or the ultrasonic cavitation device) is used for generating bubbles, the larger the gas velocity of a gas phase is, the larger the size of the formed bubbles is, and vice versa, and the bubbles with specific sizes can be formed through gas velocity control. In practice, the gas phase and the liquid phase may be introduced into the micro-element generating device together to form a micro-element dispersion system in which the gas phase (e.g., hydrogen) is dispersed in the liquid phase (e.g., heavy oil feedstock) in the form of bubbles.
Considering the weight reduction effect, the system operation stability, the operation difficulty and other factors, in one embodiment of the present invention, the size of the hydrogen bubbles may be 10-500 μm, further 50-350 μm, such as 100-.
According to the research of the present invention, the conditions of the hydrogenation reactor (i.e. hydrogenation reaction conditions) may be: the operating pressure is 6-15 MPa, further 8-15 MPa or 8-13 MPa, the reaction temperature is 420-480 ℃, further 450-470 ℃ and the weight hourly space velocity is 0.1-1.5 h-1Further, the time can be 0.2 to 0.8h-1The hydrogen-oil ratio is 600-2500 Nm3/m3Further, it may be 800-2000Nm3/m3Further, the number of the first and second fibers may be 1000 to 2000Nm3/m3For example, it may be 1000-1500Nm3/m3The condition is favorable for hydrogenation reaction of heavy oil raw materials, improves the conversion rate and simultaneously is favorable for ensuring the running stability of the whole system.
Further, in the heavy oil feedstock mixed with the catalyst, the mass ratio of the catalyst to the heavy oil feedstock may be 0.5 to 3.0%, further 0.8 to 2.3%, and for example, 0.8 to 1.5% or 1 to 1.3%.
The catalyst may be a hydrogenation catalyst having hydrogenation activity and/or coking-inhibiting property, which is conventional in the art, and may be at least one selected from a homogeneous hydrogenation catalyst and a heterogeneous hydrogenation catalyst, for example, wherein the homogeneous hydrogenation catalyst may be at least one selected from an oil-soluble catalyst and a water-soluble catalyst, a raw material of the heterogeneous hydrogenation catalyst includes a carrier and a metal component (denoted as a first metal component) supported on the carrier, the carrier may be at least one selected from coal dust and activated carbon, and the first metal component may be at least one selected from Fe, Co, Mo, Zn, and the like.
In a preferred embodiment of the present invention, the catalyst used may include the above heterogeneous hydrogenation catalyst, and under the process conditions of the present invention, the catalyst can achieve excellent catalytic effect, and has the advantages of cheap and easily available raw materials, simple preparation, low cost, and the like, and has great practical significance in industry.
Furthermore, in the heterogeneous hydrogenation catalyst, the mass content (mass fraction) of the first metal component can be 1-10%, which is beneficial to further improving the lightening effect of the heavy oil raw material.
Of course, homogeneous hydrogenation catalysts, or a mixture of homogeneous and heterogeneous hydrogenation catalysts, may also be employed in the present invention. Specifically, the oil-soluble catalyst may be at least one of an organic acid salt and an organic metal compound, the organic acid salt may be one or more selected from naphthenate, fatty acid salt of C2 or more, citrate, aromatic acid salt, tartrate, fatty group-substituted formate, fatty group-substituted phosphate, and the like, and the organic metal compound may be one or more selected from organic compounds such as acetylacetone compound, carbonyl compound, (sulfonated) phthalocyanine compound, cyclopentadienyl compound, EDTA compound, porphyrin compound, nitrile compound, and the like, and organic metal compounds formed from metals; the water-soluble catalyst may include a complex which is at least one of a heteropoly acid such as one or more of phosphomolybdic acid, homomolybdic acid, phosphotungstic acid, phosphovanadic acid, silicomolybdic acid, silicotungstic acid, silicovanadic acid, thiomolybdic acid, and the like, a complex of a carbonyl compound and a metal component (referred to as a second metal component), a second metal component such as at least one selected from Mo, Fe, Ni, Co, and the like, and/or an inorganic salt such as at least one selected from a heteropoly acid salt (such as a salt formed from the heteropoly acid as described above) which is generally specifically an ammonium salt or an alkali metal salt of the heteropoly acid, and a sulfate, a hydrochloride, a carbonate, a basic carbonate, a nitrate, and the like containing a metal component (referred to as a third metal component) which is generally a heteropoly acid salt or an alkali metal salt, and/or a third metal component which is specifically selected from Mo, a carbonyl compound, a metal component (referred to as a second metal component), Fe. At least one of Ni and Co.
In the process, when the catalyst is a homogeneous hydrogenation catalyst, the dispersion system in the hydrogenation reactor is a gas-liquid two-phase system; when the catalyst used comprises a heterogeneous hydrogenation catalyst (either a heterogeneous hydrogenation catalyst or a mixture of a homogeneous hydrogenation catalyst and a heterogeneous hydrogenation catalyst), the dispersion is a three-phase gas-liquid-solid system (but may also be referred to as a two-phase gas-liquid system because the amount of catalyst used is generally small (i.e., the solid phase is small).
The present invention can mix the catalyst in the heavy oil feedstock by a method conventional in the art to form the above-mentioned heavy oil feedstock mixed with the catalyst, and is not particularly limited. In specific implementation, the catalyst is generally dispersed or dissolved in the heavy oil feedstock as uniformly as possible, for example, when a heterogeneous hydrogenation catalyst or other catalyst that is not soluble in the heavy oil feedstock is used, the catalyst can form a micro-element structure such as solid particles with micron scale (e.g., the size of hydrogen bubbles) and is uniformly dispersed in the heavy oil feedstock, which is beneficial to forming a uniformly distributed dispersion system in the hydrogenation reactor, wherein the heavy oil is used as a continuous phase, and the highly dispersed micron scale hydrogen bubbles and the catalyst particles are used as discrete phases, and is more beneficial to the reaction and the lightening effect.
Generally, the hydrogenation reaction product from the hydrogenation reactor mainly contains a mixture of distillate oil including light oil and tail oil, cracked gas, coke and unreacted hydrogen, and after the mixture is output from the hydrogenation reactor, a part of the mixture is returned to the hydrogenation reactor for hydrogenation reaction (i.e. forming a cycle), and a part of the mixture is used as a light product. In an embodiment of the present invention, the method may further include: separating the light products, circularly processing the separated tail oil (namely mixing the tail oil and the fresh heavy oil raw material to be used as the heavy oil raw material in the light process), and controlling the circulation ratio (the mass ratio of the tail oil to the fresh heavy oil raw material) to be 0.1-0.7, further 0.2-0.5, so as to be beneficial to the high conversion of the heavy oil raw material; in specific implementation, coke in the tail oil can be removed by a device such as a liquid-solid separator and then returned for circulation. Of course, the separated tail oil may be thrown off, for example, as fuel.
Specifically, the light product may be first introduced into a gas-liquid separator or other device for gas-liquid separation to obtain a gas phase component (mainly a mixed gas of cracked gas and hydrogen gas) and a liquid phase component (distillate oil and a small amount of coke entrained therein); then the liquid phase components enter devices such as a fractionating tower (a distillation tower) and the like for fractionation treatment to obtain products such as gasoline fractions (less than 200 ℃ fraction section), diesel oil fractions (200-350 ℃ fraction section), wax oil fractions (350-500 ℃ fraction section), tail oil (more than 500 ℃ fraction section) and the like; wherein, the hydrogen (recycle hydrogen) in the gas phase component can be further separated, and the hydrogen is mixed with fresh hydrogen for recycling.
The gas-liquid separator can be one or a combination of more of hot high fraction, hot low fraction, cold high fraction and cold low fraction, and can be assembled with a hydrogenation reactor, a fractionating tower and the like by adopting a conventional method in the field. The hydrogenation reactor of the present invention may be a conventional hydrogenation reactor in the art, such as a high pressure resistant hollow cylinder device without any internal components, or a high pressure resistant reaction device with one or more sections of circulating internal components or other internal components, etc.
The method of the invention can particularly aim at the lightening of heavy oil raw materials with the characteristics of high carbon residue value, high content of heavy metals (such as nickel (Ni), vanadium (V) and the like), high content of sulfur and nitrogen and the like, wherein in one embodiment, the Conradson carbon residue value (CCR) of the heavy oil raw materials is more than 10 wt%, and/or the total content of the heavy metals is more than 150 mu g/g. Specifically, the heavy oil raw material may be one or a mixture of several of low-quality heavy oils such as heavy oil, super heavy oil, oil sand bitumen, atmospheric pressure heavy oil, vacuum residue oil, FCC oil slurry, solvent deoiled bitumen and the like, and derived low-quality heavy oils such as heavy tar and residue oil generated in a coal pyrolysis or liquefaction process, heavy oil generated in oil shale dry distillation, biomass medium-low temperature pyrolysis liquid products and the like.
The implementation of the invention has at least the following beneficial effects:
compared with the existing hydrogenation processes of a suspension bed and the like, the heavy oil hydrogenation process has the advantages of high conversion rate of heavy oil raw materials (up to 80 percent or even more than 85 percent), mild and non-harsh conditions such as operating pressure and the like, simple process flow and the like, has the advantages of easiness in operation, low cost and the like, and is beneficial to industrial production and application.
Drawings
FIG. 1 is a flow chart of a heavy oil upgrading process according to an embodiment of the present invention;
description of reference numerals:
1: a infinitesimal generating device; 2: a hydrogenation reactor; 3: a gas-liquid separator; 4: a distillation column; a: hydrogen gas; b: a heavy oil feedstock mixed with a catalyst; c 1: a portion of the hydrogenation reaction product; c 2: the rest of the hydrogenation reaction products (i.e. lightening products); d: a mixed gas of cracked gas and hydrogen; e: a gasoline fraction; f: a diesel fraction; g: a wax oil fraction; h: tail oil.
Detailed Description
The present invention will be described in more detail with reference to examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
Example 1
This example provides a method for converting heavy oil into light oil, as shown in fig. 1, a hydrogen gas a and a heavy oil raw material b mixed with a catalyst are introduced into a micro-element generating apparatus 1 to be subjected to a dispersion treatment, thereby forming a micro-element dispersion system in which hydrogen gas is dispersed in the heavy oil raw material in the form of bubbles having a size of not more than 500 μm; the infinitesimal dispersion system enters a hydrogenation reactor 2 from the bottom of the hydrogenation reactor for hydrogenation reaction to obtain a hydrogenation reaction product; after the hydrogenation reaction product is output from the top of the hydrogenation reactor, returning a part of the hydrogenation reaction product c1 (accounting for 30% of the total mass of the hydrogenation reaction product) from the middle of the hydrogenation reactor to form a cycle, and obtaining the rest part of the hydrogenation reaction product c2 (accounting for 70% of the total mass of the hydrogenation reaction product) as a light product; the light product c2 enters a gas-liquid separator 3 for gas-liquid separation to respectively obtain a gas-phase component (a mixed gas d of cracked gas and hydrogen) and a liquid-phase component; the liquid phase component enters a distillation tower 4 for fractionation to respectively obtain a gasoline fraction e below 200 ℃, a diesel fraction f below 200-350 ℃, a wax oil fraction g below 350-500 ℃ and tail oil h above 500 ℃; wherein, the hydrogen in the mixed gas d is separated and mixed with fresh hydrogen for recycling.
Specifically, c1 is injected into the hydrogenation reactor from a material inlet in the middle of the hydrogenation reactor, the material inlet is embedded into the hydrogenation reactor, and the feeding mode is to spray the material downwards; the middle part is at a position accounting for about 25% of the total height of the hydrogenation reactor from the bottom of the hydrogenation reactor; the above-described infinitesimal generator 1 is a venturi-type infinitesimal generator.
Application examples
In the following test examples 1 and 2 and comparative examples 1 and 2, the heavy oil feedstock used was vacuum residue, and its properties are shown in table 1; the catalyst is a heterogeneous catalyst formed by loading iron element on activated carbon (carbon powder), and the mass fraction of the iron element in the catalyst is 5%.
Test example 1 and test example 2
Test examples 1 and 2 were conducted by the method for upgrading heavy oil of example 1, and conditions such as hydrogen bubble size (micro-scale), operating pressure, reaction temperature, space velocity, hydrogen-oil ratio, and mass ratio of the catalyst to the heavy oil feedstock (catalyst addition amount) of the dispersoid in the hydrogenation reactor are shown in table 2, and product distribution in the upgraded product is shown in table 3.
Comparative examples 1 and 2
The heavy oil raw material is subjected to lightening treatment by adopting a conventional suspension bed hydrogenation process, conditions such as the size of hydrogen bubbles (infinitesimal scale), the operating pressure, the reaction temperature, the space velocity, the hydrogen-oil ratio, the mass ratio of the catalyst to the heavy oil raw material (catalyst addition amount) and the like dispersed in the heavy oil raw material in the suspension bed reactor are shown in table 2, and the product distribution in the lightening product is shown in table 3.
TABLE 1 heavy oil feedstock Properties
TABLE 2 reaction conditions
| Item | Test example 1 | Test example 2 | Comparative example 1 | Comparative example 2 |
| Infinitesimal scale, mum | 210 | 500 | 5000 | 5000 |
| Operating pressure, MPa | 13 | 13 | 13 | 22 |
| Reaction temperature of | 457 | 457 | 457 | 459 |
| Weight hourly space velocity, h-1 | 0.4 | 0.4 | 0.4 | 0.4 |
| Hydrogen to oil ratio, Nm3/m3 | 1200 | 1200 | 1200 | 2278 |
| The addition amount of the catalyst is wt% | 1.2 | 1.2 | 1.2 | 1.2 |
TABLE 3 Main product distribution
| Product distribution, wt% | Test example 1 | Test example 2 | Comparative example 1 | Comparative example 2 |
| Cracked gas | 3.9 | 3.8 | 4.6 | 2.3 |
| Gasoline (gasoline) | 11.5 | 8.4 | 5.1 | 20.2 |
| Diesel oil | 27.1 | 22.1 | 16.8 | 42.0 |
| Wax oil | 47.1 | 44.7 | 34.7 | 22.7 |
| Tail oil | 10.2 | 18.9 | 34.9 | 12.1 |
| Coke | 0.2 | 2.1 | 3.9 | 0.7 |
| Is totaled | 100.0 | 100.0 | 100.0 | 100.0 |
| Conversion rate | 89.8％ | 81.1％ | 65.1％ | 87.9％ |
The results show that at lower hydrogen to oil ratios (1200 Nm)3/m3) Under the conditions of operating pressure (13MPa) and the like, the test example 1 and the test example 2 can achieve excellent lightening effect, the conversion rate of heavy oil raw materials is up to more than 81 percent and is far higher than that of the traditional suspension bed process (such as a comparative example 1); the traditional suspension bed hydrogenation process has very poor light-weight effect under the conditions of lower pressure, hydrogen-oil ratio and the like (such as comparative example 1), and the high pressure (22MPa) and high hydrogen-oil ratio (2278Nm & lt/EN & gt) of comparative example 2 are often needed to improve the light-weight effect3/m3) The conditions further show through test example 1 and comparative example 2 that the test example 1 can still achieve the heavy oil raw material conversion rate and the low coke yield which are equivalent to those of the comparative example 2 under the conditions of far lower hydrogen-oil ratio, operation pressure and the like than those of the comparative example 2, which shows that the heavy oil lightening method can greatly reduce the conditions of operation pressure, hydrogen-oil ratio and the like, and has very obvious advantages compared with the conventional hydrogenation processes such as a suspended bed and the like; in addition, in the lightening process of the test examples 1 and 2, the whole system runs stably, and the method also has the advantages of simple process flow, easiness in operation and the like, and further ensures that the heavy oil lightening method is beneficial to practical industrial application.
Claims (10)
1. A method for lightening heavy oil, comprising: dispersing hydrogen and a heavy oil raw material mixed with a catalyst by a micro element generating device to form a micro element dispersion system in which the hydrogen is dispersed in the heavy oil raw material in the form of bubbles with the size of not more than 500 micrometers; allowing the infinitesimal dispersion system to enter a hydrogenation reactor for hydrogenation reaction to obtain a hydrogenation reaction product; after the hydrogenation reaction product is output from the hydrogenation reactor, one part of the hydrogenation reaction product returns to the hydrogenation reactor to form circulation, and the rest part of the hydrogenation reaction product is the light product.
2. A weight reduction method according to claim 1, wherein the portion of the hydrogenation reaction product accounts for 10 to 90% of the total mass of the hydrogenation reaction product discharged from the hydrogenation reactor.
3. A lightening process according to claim 1 or 2, wherein said micro-disperse system enters the hydrogenation reactor from the bottom thereof, and said portion of the hydrogenation reaction product returns to the hydrogenation reactor from the middle portion thereof to form said cycle.
4. A method for weight reduction according to claim 1, wherein said infinitesimal generating device is at least one selected from the group consisting of a microporous ceramic membrane infinitesimal generating device, a Venturi infinitesimal generating device, and an ultrasonic cavitation device.
5. A lightening process according to claim 1 or 4, wherein said bubbles have a size of 10 to 500 μm.
6. A lightening process according to claim 1, wherein the conditions of said hydrogenation reactor are: the operating pressure is 6-15 MPa, the reaction temperature is 420-480 ℃, and the weight hourly space velocity is 0.1-1.5 h-1The hydrogen-oil ratio is 600-2500 Nm3/m3。
7. A lightening process according to claim 1 or 6, wherein the catalyst is present in an amount of 0.5 to 3.0% by mass based on the heavy oil feedstock.
8. A lightening process according to claim 1 or 7, wherein said catalyst is selected from at least one of a homogeneous hydrogenation catalyst and a heterogeneous hydrogenation catalyst; wherein the content of the first and second substances,
the homogeneous hydrogenation catalyst is selected from at least one of oil-soluble catalyst and water-soluble catalyst;
the heterogeneous hydrogenation catalyst comprises raw materials comprising a carrier and a metal component loaded on the carrier, wherein the carrier is selected from at least one of coal dust and activated carbon, and the metal component is selected from at least one of Fe, Co, Mo and Zn.
Preferably, in the heterogeneous catalyst, the mass content of the metal component is 1-10%.
9. A lightening method according to claim 1 or 6, further comprising: and (3) separating the light products, and circularly processing the separated tail oil, wherein the circulation ratio is controlled to be 0.1-0.7.
10. A lightening process according to any one of claims 1 to 9, wherein the heavy oil feedstock is one or a mixture of more of heavy oil, ultra-heavy oil, oil sand bitumen, atmospheric heavy oil, vacuum residue, FCC slurry oil, solvent de-oiled bitumen, heavy tar and residue from coal pyrolysis or liquefaction processes, heavy oil from dry distillation of oil shale, and low temperature pyrolysis liquid products from biomass.
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| US20090134064A1 (en) * | 2005-12-16 | 2009-05-28 | Bruce Reynolds | Reactor for use in upgrading heavy oil |
| CN102049220A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for enhancing gas-liquid mass transfer of ebullated bed hydrogenation reactor |
| CN111482144A (en) * | 2019-01-29 | 2020-08-04 | 南京延长反应技术研究院有限公司 | Bottom-mounted micro-interface enhanced reaction device and method for residual oil hydrogenation reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090134064A1 (en) * | 2005-12-16 | 2009-05-28 | Bruce Reynolds | Reactor for use in upgrading heavy oil |
| CN102049220A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for enhancing gas-liquid mass transfer of ebullated bed hydrogenation reactor |
| CN111482144A (en) * | 2019-01-29 | 2020-08-04 | 南京延长反应技术研究院有限公司 | Bottom-mounted micro-interface enhanced reaction device and method for residual oil hydrogenation reaction |
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