CN111909723A - Supercritical extraction system and extraction method for heavy oil raw material - Google Patents
Supercritical extraction system and extraction method for heavy oil raw material Download PDFInfo
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- CN111909723A CN111909723A CN202010564493.7A CN202010564493A CN111909723A CN 111909723 A CN111909723 A CN 111909723A CN 202010564493 A CN202010564493 A CN 202010564493A CN 111909723 A CN111909723 A CN 111909723A
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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
- C10G67/04—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 solvent extraction as the refining step in the absence of hydrogen
Abstract
The invention relates to a supercritical extraction system of a heavy oil raw material, which comprises a supercritical extraction unit and a suspension bed hydrogenation unit, wherein the supercritical extraction unit comprises an asphalt separation tower, an asphalt stripping tower, a deasphalted oil separation tower, a deasphalted oil stripping tower, a first air cooler and a separation tank, the asphalt separation tower is connected with a solvent feeding pipeline and a heavy oil feeding pipeline, a bottom discharge port of the asphalt separation tower is connected to the asphalt stripping tower, a top gas outlet of the asphalt separation tower is connected to the deasphalted oil separation tower, a bottom outlet of the deasphalted oil separation tower is connected to the deasphalted oil stripping tower, a discharge port of the asphalt stripping tower is connected to the suspension bed hydrogenation unit, and a top gas outlet of the asphalt stripping tower is connected to the separation tank through the first air cooler. According to the supercritical extraction system and the supercritical extraction method for the heavy oil raw material, granulation dissolution is adopted to replace a decompression tower, so that the operation stability and the operation elasticity of the device can be greatly improved, and the operation cost and the investment cost are reduced.
Description
Technical Field
The invention belongs to the technical field of heavy oil treatment, and particularly relates to a supercritical extraction system and an extraction method for a heavy oil raw material.
Background
In the next 10-15 years, the national economy of China is expected to continue to develop rapidly at a speed of about 6-7%, the consumption of petroleum products is still in a growth period, the consumption of crude oil is increased by 6.4% every year, and the annual growth rate of the domestic crude oil yield is only 1.9%. With the increasing quantity of imported crude oil, the selectivity of high-quality crude oil in the international market is reduced, the proportion of light crude oil in the imported crude oil is reduced day by day, and the proportion of various high-density heavy oil and inferior high-sulfur and high-acid heavy oil is increased continuously. The relative density of these heavy oil and extra heavy oil is above 0.96, and the processing difficulty is large, and how to convert the large amount of residual oil generated from these heavy oil and extra heavy oil has become an important issue in the oil refining industry today.
At present, the methods of delayed coking, deasphalting by an extracting agent and the like are adopted in the processing process of residual oil in China, but the treatment depth is not enough, the processing method and the process are laggard, the separation and purification difficulty is higher, a large amount of sewage, waste residue and environmental pollution are generated, and the hydrogenation process can be used for effectively removing sulfur, nitrogen, metal and other impurities in the residual oil, reducing the density and realizing the lightening. However, the prior hydrogenation process has insufficient treatment depth and cannot efficiently convert colloid, asphaltene and heavy components above 525 ℃. If a conventional fixed bed hydrogenation method is adopted, a reaction system is easy to coke and deposit, so that the service life of the catalyst is greatly shortened.
Meanwhile, FCC slurry oil and coal tar belong to similar inferior heavy oil and are characterized by high density, more heterocycles and high metal impurity content. How to effectively process such heavy oil will directly determine and influence the product structure and economic benefits of the refinery.
The extractant separating process is an important process in oil refining and chemical industry and is widely applied in the oil refining industry. For example, deasphalting with an extractant to obtain residual lube oil feedstock and catalytic cracking feedstock from residual oil, refining with an extractant and dewaxing with an extractant used in producing lube oil, and aromatic extraction to extract aromatic hydrocarbons from reformate or catalytic cracking cycle oil are all extraction separation processes.
In the oil refining industry, the extraction agent deasphalting process is mainly used for preparing high-viscosity lubricating oil base oil and catalytic cracking raw oil from vacuum residue, and the deasphalted asphalt can be used for producing road asphalt under the condition of proper raw materials. Wherein the main function of the extractant deasphalting process is to remove the asphalt from the residual oil to obtain deasphalted oil with lower carbon residue value and improve color. The vacuum residue is added into catalytic cracking raw material gas oil to be an important way for improving the yield of light oil, but many vacuum residues contain more metals and substances which are easy to generate coke, and are not easy to be directly added into the catalytic cracking raw material, and most of the metals and the substances which are easy to generate coke can be removed through deasphalting of an extracting agent, so that the quality of the heavy oil catalytic cracking feed is obviously improved.
The traditional extractant deasphalting process is operated under the temperature and pressure conditions below the critical point of the extractant. The process uses a large amount of extractant, the adopted extractant ratio is generally 3-5 (mass ratio), and the extractant must be recovered and recycled. The investment and operating costs of the extractant recovery section have a significant impact on the overall plant economics. Of the amount of extractant recovered, about 90% comes from the extract (deasphalted oil phase) and the remainder from the raffinate (deasphalted oil phase). Therefore, the important point of extractant recovery is to recover the extractant from the extract. In recent years, research and technical development have been greatly advanced on extraction of a supercritical extraction agent and recovery of the supercritical extraction agent, which are operated under conditions of temperature and pressure at or above the critical point of the extraction agent. Compared with the traditional extractant deasphalting technology, the supercritical extraction technology has qualitative leap in the aspects of energy consumption, operation reliability and the like.
In addition, some researches on the heavy oil suspension bed hydrogenation technology have been made by domestic and foreign research institutions, but the technology is not completely mature at present. Chinese patent CN1766058A discloses a method for producing gasoline and diesel oil by mixing coal tar whole fraction with homogeneous catalyst water-soluble nickel phosphomolybdate, hydrogenating in a suspension bed reactor, subjecting the fraction below 370 ℃ to fixed bed hydrogenation refining treatment, and simultaneously recycling part of tail oil above 370 ℃ to the suspension bed reactor to further convert light oil, and partially throwing. The disadvantage of this patent is that the coal tar feedstock is not fully utilized and the tail oil is hydrogenated cyclically increasing the coking tendency.
The conventional hydrotreating method usually needs to add a catalyst to ensure the conversion rate, but the catalyst is easy to coke and deactivate due to more heavy components in the raw material. In order to slow down the coking and deactivation of the catalyst, a large amount of aromatic hydrocarbon extractant oil is usually added as a raw material diluent, so that the production cost is increased, and the processing capacity of the device is reduced.
The suspension bed hydrogenation system is a solid-containing system, a vacuum tower system is generally adopted to recover light distillate oil, and the bottom material of the vacuum tower is used for residue granulation, is convenient to transport and is used as a gasification furnace raw material or fuel. However, the vacuum tower system has a large proportion of solid content in the feed, high temperature and serious abrasion to pipelines, valves and equipment. And is sensitive to the conversion rate operation of the front-end suspension bed reaction system, and if the front-end reaction system is unstable in operation, continuous and stable feeding cannot be guaranteed. For example, if the conversion rate of the reaction system is too high, the solid content of the feed of the vacuum tower system can be greatly increased, and the feed is easy to block or even break. If the conversion rate of the reaction system is too low, the feeding of the vacuum tower system is greatly increased, and the load of the vacuum tower is exceeded, enough light distillate oil cannot be extracted from the lateral line, so that the tower bottom material is light, the softening point is low, and granulation cannot be performed.
Content providing method and apparatus
The supercritical extraction system and the supercritical extraction method for the heavy oil raw material overcome the defects of the prior art, adopt granulation dissolution and desorption to replace a decompression tower, can greatly improve the operation stability and the operation elasticity of the device, and simultaneously reduce the operation cost and the investment cost.
The technical problem to be solved is realized by the following technical scheme:
a supercritical extraction system for heavy oil raw materials comprises a supercritical extraction unit and a suspension bed hydrogenation unit, wherein the supercritical extraction unit comprises an asphalt separation tower, an asphalt stripping tower, a deasphalted oil separation tower, a deasphalted oil stripping tower, a first air cooler and a separation tank, the asphalt separation tower is connected with an extractant feeding pipeline and a heavy oil feeding pipeline, a bottom discharge port of the asphalt separation tower is connected to the asphalt stripping tower, a top gas outlet of the asphalt separation tower is connected to the deasphalted oil separation tower, a bottom outlet of the deasphalted oil separation tower is connected to the deasphalted oil stripping tower, a discharge port of the asphalt stripping tower is connected to the suspension bed hydrogenation unit, and a top gas outlet of the asphalt stripping tower is connected to the separation tank through the first air cooler;
the suspension bed hydrogenation unit comprises an additive mixing tank, a feeding buffer tank, a new hydrogen machine, a heating furnace, a suspension bed hydrogenation reactor, a hot high-temperature separator, a hot medium-temperature separator, an air cooler, a cold high-temperature separator, a cold low-temperature separator, a hydrogen circulating machine, a flow dividing tower and PSA (pressure swing adsorption), wherein a bottom discharge port of the asphalt stripping tower is connected to the feeding buffer tank through a first pipeline and is connected to the additive mixing tank through a second pipeline, the additive mixing tank is connected to the feeding buffer tank, the feeding buffer tank and the new hydrogen machine are connected to an inlet of the heating furnace, an outlet of the heating furnace is connected to the suspension bed hydrogenation reactor, and a top outlet of the suspension bed hydrogenation reactor is connected with the granulation dissolution unit; the hot high branch top export is connected cold high branch, cold low branch through the air cooler, and cold low branch export is connected to the fractionating tower, and cold high branch top exit linkage is to PSA, and the top hydrogen export of cold high branch is connected to new hydrogen machine outlet pipe through the hydrogen circulation machine, and fractionating tower upper portion is the naphtha export, and the middle part is the diesel oil export, and the bottom is the VGO export.
The granulation dissolving and removing unit comprises a granulation asphalt separation tower and a granulation asphalt stripping tower; the hot high-branch outlet of the suspension bed hydrogenation unit is connected with the hot medium branch, the hot medium-branch outlet is connected to a granulated asphalt separating tower, the top outlet of the granulated asphalt separating tower is connected to the top outlet of the asphalt separating tower, the bottom outlet of the granulated asphalt separating tower is connected to a granulated asphalt stripping tower, the top outlet of the granulated asphalt stripping tower is connected to the top outlet of the asphalt stripping tower, the bottom of the granulated asphalt stripping tower is a residue outlet, and the extracting agent feeding pipeline is connected to the granulated asphalt separating tower.
And an extractant outlet of the separation tank is connected to an extractant feeding pipeline and is respectively connected with an extractant inlet of the asphalt separation tower and an extractant inlet of the granulated asphalt separation tower.
A supercritical extraction method of heavy oil raw material comprises the following steps:
1) heavy oil supercritical extraction: the extraction agent and the residual oil enter an asphalt separation tower of a supercritical extraction unit according to the volume ratio of 6-10:1, the operation condition of the asphalt separation tower is 4-5Mpag and 50-80 ℃, the deasphalted oil and the extraction agent which are products at the top of the asphalt separation tower enter the deasphalted oil separation tower to separate the deasphalted oil and the extraction agent, the operation condition of the deasphalted oil separation tower is 4-5Mpag and 90-120 ℃, the products at the bottom of the asphalt separation tower are dissolved and deasphalted, and the dissolved and deasphalted asphalt is subjected to suspension bed hydrogenation reaction after the extraction agent is recovered by an asphalt stripping tower;
2) suspension bed hydrogenation reaction: the dissolved and removed asphalt, the additive and hydrogen enter a suspension bed hydrogenation reactor of a suspension bed hydrogenation unit for hydrogenation reaction, the hydrogenation reaction product enters a thermal high-temperature separator for separation, the top product of the thermal high-temperature separator is distillate oil and light component gas, and the bottom product of the thermal high-temperature separator is unconverted asphalt, the additive and wax oil;
3) granulation and dissolution: and the unconverted asphalt, the additive and the wax oil enter a granulating asphalt separation tower of a granulating dissolution and separation unit, extraction is carried out by using an extracting agent of a supercritical extraction unit under the operation conditions of 4-5Mpag and 50-80 ℃, the volume ratio of the extracting agent entering the granulating asphalt separation tower to the unconverted asphalt is 6-10:1, and the residual extracting agent is recovered by a granulating asphalt stripping tower to obtain the granulating asphalt.
And the granulated asphalt is granulated after being cooled at normal temperature, so as to reach the transportation condition.
And the weight part ratio of the asphalt product, the additive and the hydrogen is 100: 0.5-3: 1-4; the reaction conditions of the suspension bed hydrogenation reactor are as follows: the space velocity is 0.3-0.8h-1Inlet pressure of 160-250bar g, average temperature of 440-480 deg.C, hydrogen-oil ratio of 600-1000Nm3And (4) reacting to generate naphtha, diesel oil, wax oil, unconverted hydrogenation residual oil and other light component products.
And the extraction extractant is one or the mixture of two or more of propane, isobutane, n-butane and isopentane.
This advantage and beneficial effect do:
1. the supercritical extraction system and the extraction method of the heavy oil raw material adopt the production combining the supercritical extraction and the suspension bed hydrogenation, a granulation dissolution is adopted in a supercritical extraction unit to replace a decompression tower, the supercritical extraction step is used for extracting and separating the heavy oil raw material to separate out an asphaltene product which is used as a feed of the suspension bed hydrogenation unit, and the suspension bed hydrogenation step is used for converting asphalt into light distillate oil, so that the operation stability and the operation elasticity of the device are greatly improved, and the operation cost and the investment cost are reduced.
2. According to the supercritical extraction system and the extraction method of the heavy oil raw material, a dissolution extraction method is adopted to treat the thermal high-fraction bottom material, a granulated asphalt separation tower and a granulated asphalt stripping tower are added in a supercritical extraction unit, an original pressure reduction tower system is cancelled, the operation stability is enhanced, and the dissolution maintains a larger extraction agent/feeding ratio (mass ratio of 4: 1), so that the feeding operation elasticity of the granulation dissolution is large, and the residue granulation is hardly influenced even if the feeding fluctuation is greatly fluctuated; if a pressure reducing tower system is adopted, a high-pressure system of a suspension bed hydrogenation unit needs two-stage pressure reduction, and the pressure reduction comprises that a hot high-pressure separating tank is reduced to 1.2MPag from 21MPag to a hot low-pressure separating tank, and the pressure reduction of the hot low-pressure separating tank is reduced to-0.1 MPag from 1.2MPag, because the pressure difference of a pressure reducing valve and a pipeline of the pressure reducing tower is large, the temperature is high, the solid content is large, a valve pipeline is easy to wear, special material selection is needed, and a two-stage pressure reducing valve bank is expensive; the heat medium distribution and granulation stripping unit can adopt first-stage pressure reduction, the heat medium distribution is reduced from 21MPag to 4.0MPag, a second-stage pressure reduction valve bank is omitted, the pressure difference of the first-stage pressure reduction is reduced by about 20%, the abrasion is greatly reduced, a heating furnace of a pressure reduction tower system is saved, and the investment and the occupied area are saved.
3. According to the supercritical extraction system and the supercritical extraction method for the heavy oil raw material, the extractant outlet of the separation tank is connected to the extractant feeding pipeline and is respectively connected with the extractant inlet of the asphalt separation tower and the extractant inlet of the granulation asphalt separation tower, the supercritical extraction unit and the granulation dissolution-separation unit share the extractant system, the investment of the extractant system can be greatly saved, and the operation cost is low.
4. According to the supercritical extraction system and the supercritical extraction method for the heavy oil raw material, the treatment capacity of the thermal high-fraction bottom material is about 14 wt% of the feeding capacity of a suspension bed hydrogenation unit, taking the total device vacuum residue oil feeding as an example, 46 wt% of DAO is extracted by a supercritical extraction unit, the remaining 54 wt% of asphalt enters a suspension bed hydrogenation reaction unit, and the thermal high-fraction bottom material is 7.56 wt% of the total feeding capacity, so that the thermal high-fraction bottom material comprises three parts: small amount of light components, H2O, NH3、H2S、C1-C4(ii) a Light distillate, a naphtha component, a diesel component, a VGO component; and solid particles which are an additive of the suspension bed hydrogenation unit and a coke substance attached to the additive; light components are flashed out through thermal medium separation at the operating pressure of 4.0MPag, the liquid phase at the bottom of the tank enters a granulation dissolution and separation unit, the material at the bottom of the thermal medium separation tank enters a granulated asphalt separation tower, the operating pressure is the same as that of a supercritical extraction unit, and the granulated deasphalted oil and the deasphalted oil in the asphalt separation tower are merged and then enter a downstream deasphalted oil separation tower; and (3) the granulated asphalt enters a granulation stripping tower, residue granulation is carried out after the residual extracting agent is recovered, the solid-liquid phase ratio (wt%) of the granulated asphalt is 41:59, the ring-ball softening point 120C can be reached, and the granulation requirement is met.
5. The supercritical extraction system of the heavy oil raw material adopts a production system combining the supercritical extraction unit and the suspension bed hydrogenation unit, and adopts the granulation elution unit to replace a vacuum tower system, so that the operation stability and the operation elasticity of the device can be greatly improved, and the operation cost and the investment cost are reduced.
Drawings
FIG. 1 is a flow chart of the system of the present invention.
The method comprises the following steps of 1-an asphalt separation tower, 2-an asphalt stripping tower, 3-a deasphalted oil separation tower, 4-a deasphalted oil stripping tower, 5-a granular asphalt separation tower, 6-a granulated asphalt stripping tower, 7-a separation tank, 8-a first air cooler, 9-a second separation tank, 10-a new hydrogen machine, 11-a feeding buffer tank, 12-an additive mixing tank, 13-a hydrogen circulating machine, 14-a heating furnace, 15-a suspension bed hydrogenation reactor, 16-hot high fraction, 17-cold high fraction, 18-cold low fraction, 19-an air cooler, 20-PSA, 21-a splitting tower and 22-hot medium fraction.
Detailed Description
The present invention is further described in the following detailed description with reference to specific examples, which are intended to be illustrative, not limiting, and thus not limiting.
The supercritical extraction system adopted by the supercritical extraction method of the heavy oil raw material comprises the following steps:
the system comprises a supercritical extraction unit and a suspension bed hydrogenation unit, wherein the supercritical extraction unit comprises an asphalt separation tower 1, an asphalt stripping tower 2, a deasphalted oil separation tower 3 (same as a DAO separation tower in the figure), a deasphalted oil stripping tower 4 (same as a DAO stripping tower in the figure), a first air cooler 8 and a separation tank 7, the asphalt separation tower is connected with an extractant feeding pipeline and a heavy oil feeding pipeline, a bottom discharge port of the asphalt separation tower is connected to the asphalt stripping tower, a top gas outlet of the asphalt separation tower is connected to the deasphalted oil separation tower, a bottom outlet of the deasphalted oil separation tower is connected to the deasphalted oil stripping tower, and a bottom discharge port of the deasphalted oil stripping tower is connected to a VGO outlet; the discharge port of the asphalt stripping tower is connected to the suspension bed hydrogenation unit, dissolved and deasphalted asphalt is conveyed to the suspension bed hydrogenation unit, and the top gas outlet of the asphalt stripping tower is connected to the separation tank through the first air cooler.
The suspension bed hydrogenation unit comprises an additive mixing tank 12, a feeding buffer tank 11, a new hydrogen machine 10, a heating furnace 14, a suspension bed hydrogenation reactor 15, a hot high-temperature separator 16, a hot medium-temperature separator 22, an air cooler 19, a cold high-temperature separator 17, a cold low-temperature separator 18, a hydrogen circulation machine 13, a diversion tower 21 and PSA20, wherein a discharge port at the bottom of the asphalt stripping tower is connected to the feeding buffer tank through a first pipeline and is connected to the additive mixing tank through a second pipeline, the additive mixing tank is connected to the feeding buffer tank, the feeding buffer tank and the new hydrogen machine are connected to an inlet of the heating furnace, an outlet of the heating furnace is connected to the suspension bed hydrogenation reactor, and a top outlet of the suspension bed hydrogenation reactor is connected with a granulation dissolution unit through; the hot high branch top export is connected cold high branch, cold low branch through the air cooler, and cold low branch export is connected to the fractionating tower, and cold high branch top exit linkage is to PSA, and the top hydrogen export of cold high branch is connected to new hydrogen machine outlet pipe through the hydrogen circulation machine, and fractionating tower upper portion is the naphtha export, and the middle part is the diesel oil export, and the bottom is the VGO export.
The granulation stripping unit comprises a granulation asphalt separation tower 5 and a granulation asphalt stripping tower 6; suspension bed hydrogenation unit's hot high branch outlet is connected hot well and is divided, divides the outlet in the heat and is connected to the granulation pitch knockout tower, and the top exit linkage of granulation pitch knockout tower is to pitch knockout tower top export, and the bottom exit linkage of granulation pitch knockout tower is to granulation pitch strip tower, and the top exit linkage of granulation pitch strip tower is to the top export of pitch strip tower, and granulation pitch strip tower bottom is the residue export, extractant feed line is connected to granulation pitch knockout tower.
An extractant outlet of the separation tank is connected to an extractant feeding pipeline and is respectively connected with an extractant inlet of the asphalt separation tower and an extractant inlet of the granulated asphalt separation tower.
The top outlet of the deasphalted oil separation column is connected to the extractant feed line via a second air cooler 9.
The supercritical extraction method of the heavy oil raw material comprises the following steps:
1) heavy oil supercritical extraction: the total extraction extractant and the residual oil enter an asphalt separation tower of a supercritical extraction unit according to the volume ratio of 6:1, the operation condition of the asphalt separation tower is 4-5Mpag, the operation condition of the asphalt separation tower is 50-80 ℃, the bottom product of the asphalt separation tower enters an asphalt stripping tower, the operation condition of the asphalt stripping tower is 4-5Mpag, the operation condition of the asphalt stripping tower is 90-120 ℃, and 54 wt% of asphalt product and 46% of deasphalted oil product are obtained; the extraction extractant is mixed butane (iC 450%, nC 450%). The deasphalted oil product is used as the feed of downstream lubricating oil equipment to produce high-viscosity lubricating oil, and the asphalt is used as the feed of the suspension bed hydrogenation unit.
2) Suspension bed hydrogenation reaction: the asphalt product, the additive and hydrogen obtained in the step 1) enter a suspension bed hydrogenation reactor of a suspension bed hydrogenation unit for hydrogenation reaction, and the weight part ratio of the asphalt product, the additive and the hydrogen is 100: 1: 2.77; the number of the suspension bed hydrogenation reactors can be 2-4, and the reaction conditions of the suspension bed hydrogenation reactors are as follows: space velocity of 0.5h-1An inlet pressure of 213bar g, an average temperature of 470 ℃ and a hydrogen-oil ratio of 750Nm3And per ton, the asphalt product reacts to generate 13.57 of low boiling point products or gas phase products, 10.59 of naphtha, 47.61 of diesel oil, 25.97 of VGO, 3.67 of unconverted hydrogenation residual oil and 2.36 of solid residue.
About 90-95% of the bitumen feed is converted to low boiling or gas phase products, the remainder being unconverted material. The unconverted material comprises two parts, wherein one part of unconverted material is hydrogenated residual oil, contains solid substances and is toluene insoluble substances; the other part is hydrogenated residual oil without solid, and is toluene soluble matter and asphalt phase. Because the adsorbent is a porous carbonaceous material, the hydrogenation of residual oil and the adsorbent generates a product containing high contents of Conradson carbon residue, metals and sulfur. The material has a ring and ball softening point of 80-120 deg.C, and can be easily cured in conventional residue curing process.
Therefore, the method for treating vacuum residue by using the suspension bed hydrogenation process can convert the components in the asphalt at the temperature of more than 525 ℃, the conversion rate is 95 percent, and the yield of liquid products is 84.79 percent. The existing processing technology can be adopted to carry out quality improvement processing to produce fuel oil and chemical raw materials. Wherein the naphtha fraction and the diesel fraction can adopt hydrotreating to produce qualified fuel oil products, and the VGO fraction can be used as FCC feed for continuous processing.
3) Granulation and dissolution: and the hydrogenated residual oil enters a granulation asphalt separation tower and a granulation asphalt stripping tower of a granulation dissolution and desorption unit, an extracting agent of a supercritical extraction unit is used for extraction, the operation condition is 4-5Mpag, the temperature is 50-80 ℃, the volume ratio of the total extraction extracting agent entering the granulation asphalt separation tower to the unconverted hydrogenated residual oil is 6:1, the residual extracting agent is recovered, and the obtained granulation asphalt is subjected to subsequent residue granulation.
The operation stability is enhanced, and the dissolution maintains a larger extraction agent/feeding ratio (mass ratio of 4: 1), so that the feeding elasticity of the granulation dissolution is large, and even if the feeding fluctuation is greatly fluctuated, the influence on the residue granulation is hardly caused. The operation cost is low, and the extractant system is shared with the previous stripping unit, so that the investment of the extractant system can be greatly saved. The pressure reducing valve and pipeline wear is greatly reduced.
If a pressure reducing tower system is adopted, a suspension bed high-pressure system needs two-stage pressure reduction: the pressure difference is large, the temperature is high, the solid content is large, so that valve pipelines and valve groups are easy to wear, special materials are needed, and the price of the two-stage pressure reducing valve group is high. If the device is changed into a hot middle-dividing tank and a granulating and dissolving-removing unit, primary pressure reduction can be adopted: the hot high-pressure separating tank is connected with the hot middle tank, the pressure of 21MPag is reduced to 4.0MPag, a secondary pressure reducing valve bank is omitted, the pressure difference of primary pressure reduction is reduced by about 20%, and the abrasion is greatly reduced. The heating furnace of the decompression tower system is saved, and the investment and the occupied area are saved.
The bottom material treatment capacity of the thermal head is about the same14 wt% of the feed amount of the floating bed reaction unit, taking the total device vacuum residue feed as an example, after 46 wt% of DAO is extracted through the stripping unit, the remaining 54 wt% of asphalt enters the floating bed reaction unit, and the bottom material of the hot high part is 7.56 wt% of the total feed amount. The material comprises three parts: 1) small amount of light component H2O、NH3、H2S、C1-C4(ii) a 2) Light distillate, a naphtha component, a diesel component, a VGO component; 3) solid particles, additives that are suspended bed units, and char matter attached to the additives. Light components are flashed off by a hot middle separating tank with the operation pressure of 4.0MPag, and the liquid phase at the bottom of the tank enters a granulation dissolving and removing unit. The granulation deasphalted oil and the deasphalted oil in the asphalt separating tower are combined and then enter a downstream deasphalted oil separating tower. And (4) the granulated asphalt enters a granulation stripping tower, and residue granulation is carried out after the residual extracting agent is recovered.
Although the embodiments and drawings of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various substitutions, alterations, and modifications are possible without departing from the spirit and scope of the present invention and appended claims, and thus the scope of the present invention is not limited to those disclosed in the embodiments and drawings.
Claims (7)
1. A supercritical extraction system for heavy oil raw materials is characterized in that: the device comprises a supercritical extraction unit and a suspension bed hydrogenation unit, wherein the supercritical extraction unit comprises an asphalt separation tower, an asphalt stripping tower, a deasphalted oil separation tower, a deasphalted oil stripping tower, a first air cooler and a separation tank, the asphalt separation tower is connected with an extractant feeding pipeline and a heavy oil feeding pipeline, a bottom discharge port of the asphalt separation tower is connected to the asphalt stripping tower, a top gas outlet of the asphalt separation tower is connected to the deasphalted oil separation tower, a bottom outlet of the deasphalted oil separation tower is connected to the deasphalted oil stripping tower, a discharge port of the asphalt stripping tower is connected to the suspension bed hydrogenation unit, and a top gas outlet of the asphalt stripping tower is connected to the separation tank through the first air cooler;
the suspension bed hydrogenation unit comprises an additive mixing tank, a feeding buffer tank, a new hydrogen machine, a heating furnace, a suspension bed hydrogenation reactor, a hot high-temperature separator, a hot medium-temperature separator, an air cooler, a cold high-temperature separator, a cold low-temperature separator, a hydrogen circulating machine, a flow dividing tower and PSA (pressure swing adsorption), wherein a bottom discharge port of the asphalt stripping tower is connected to the feeding buffer tank through a first pipeline and is connected to the additive mixing tank through a second pipeline, the additive mixing tank is connected to the feeding buffer tank, the feeding buffer tank and the new hydrogen machine are connected to an inlet of the heating furnace, an outlet of the heating furnace is connected to the suspension bed hydrogenation reactor, and a top outlet of the suspension bed hydrogenation reactor is connected with the granulation dissolution unit; the hot high branch top export is connected cold high branch, cold low branch through the air cooler, and cold low branch export is connected to the fractionating tower, and cold high branch top exit linkage is to PSA, and the top hydrogen export of cold high branch is connected to new hydrogen machine outlet pipe through the hydrogen circulation machine, and fractionating tower upper portion is the naphtha export, and the middle part is the diesel oil export, and the bottom is the VGO export.
2. The supercritical extraction system for heavy oil feedstock of claim 1 wherein: the granulation stripping unit comprises a granulation asphalt separation tower and a granulation asphalt stripping tower; the hot high-branch outlet of the suspension bed hydrogenation unit is connected with the hot medium branch, the hot medium-branch outlet is connected to a granulated asphalt separating tower, the top outlet of the granulated asphalt separating tower is connected to the top outlet of the asphalt separating tower, the bottom outlet of the granulated asphalt separating tower is connected to a granulated asphalt stripping tower, the top outlet of the granulated asphalt stripping tower is connected to the top outlet of the asphalt stripping tower, the bottom of the granulated asphalt stripping tower is a residue outlet, and the extracting agent feeding pipeline is connected to the granulated asphalt separating tower.
3. The supercritical extraction system for heavy oil feedstock of claim 1 wherein: and an extractant outlet of the separation tank is connected to an extractant feeding pipeline and is respectively connected with an extractant inlet of the asphalt separation tower and an extractant inlet of the granulated asphalt separation tower.
4. A supercritical extraction method of heavy oil raw materials is characterized in that: the method comprises the following steps:
1) heavy oil supercritical extraction: the extraction agent and the residual oil enter an asphalt separation tower of a supercritical extraction unit according to the volume ratio of 6-10:1, the operation condition of the asphalt separation tower is 4-5Mpag and 50-80 ℃, the deasphalted oil and the extraction agent which are products at the top of the asphalt separation tower enter the deasphalted oil separation tower to separate the deasphalted oil and the extraction agent, the operation condition of the deasphalted oil separation tower is 4-5Mpag and 90-120 ℃, the products at the bottom of the asphalt separation tower are dissolved and deasphalted, and the dissolved and deasphalted asphalt is subjected to suspension bed hydrogenation reaction after the extraction agent is recovered by an asphalt stripping tower;
2) suspension bed hydrogenation reaction: the dissolved and removed asphalt, the additive and hydrogen enter a suspension bed hydrogenation reactor of a suspension bed hydrogenation unit for hydrogenation reaction, the hydrogenation reaction product enters a thermal high-temperature separator for separation, the top product of the thermal high-temperature separator is distillate oil and light component gas, and the bottom product of the thermal high-temperature separator is unconverted asphalt, the additive and wax oil;
3) granulation and dissolution: and the unconverted asphalt, the additive and the wax oil enter a granulating asphalt separation tower of a granulating dissolution and separation unit, extraction is carried out by using an extracting agent of a supercritical extraction unit under the operation conditions of 4-5Mpag and 50-80 ℃, the volume ratio of the extracting agent entering the granulating asphalt separation tower to the unconverted asphalt is 6-10:1, and the residual extracting agent is recovered by a granulating asphalt stripping tower to obtain the granulating asphalt.
5. The supercritical extraction process of a heavy oil feedstock as recited in claim 1, further comprising: and granulating the granulated asphalt after cooling at normal temperature to achieve transportation conditions.
6. The supercritical extraction process of a heavy oil feedstock as recited in claim 1, further comprising: the asphalt product, the additive and the hydrogen are mixed according to the following weight part ratio of 100: 0.5-3: 1-4; the reaction conditions of the suspension bed hydrogenation reactor are as follows: the space velocity is 0.3-0.8h-1Inlet pressure of 160-250bar g, average temperature of 440-480 deg.C, hydrogen-oil ratio of 600-1000Nm3And (4) reacting to generate naphtha, diesel oil, wax oil, unconverted hydrogenation residual oil and other light component products.
7. The supercritical extraction process of a heavy oil feedstock as recited in claim 1, further comprising: the extractant is one or the mixture of two or more of propane, isobutane, n-butane and isopentane.
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