CN109082302B - Method for producing distillate oil by mild hydrogenation of inferior/heavy oil slurry bed - Google Patents
Method for producing distillate oil by mild hydrogenation of inferior/heavy oil slurry bed Download PDFInfo
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- CN109082302B CN109082302B CN201810889774.2A CN201810889774A CN109082302B CN 109082302 B CN109082302 B CN 109082302B CN 201810889774 A CN201810889774 A CN 201810889774A CN 109082302 B CN109082302 B CN 109082302B
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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
Abstract
The invention relates to a method for producing distillate oil by mild hydrogenation of a slurry bed of inferior/heavy oil, which relates to the coupling of slurry bed temperature and hydrotreating with fixed bed hydrofining and specifically comprises the following steps: mixing raw oil and a catalyst with optional circulating slurry oil and circulating wax oil, and introducing the mixture into a slurry bed reactor; separating and fractionating the obtained product to obtain intermediate oil and heavy oil slurry; introducing the intermediate oil into a fixed bed reactor; separating and fractionating the obtained product to obtain naphtha, aviation kerosene, diesel oil and wax oil; in addition, diesel oil and wax oil can be preferably treated by a catalytic cracking unit to obtain catalytic cracked gasoline. The invention realizes the effective matching of the thermal cracking and the hydrogenation of the materials in the slurry bed reactor through the regulation and control of the process conditions. The invention can be directly used for treating inferior/heavy oil and has the advantages of simple process, mild operating conditions of a slurry bed, high oil yield, adjustable product distribution, low sulfur content of the product, low investment and operating cost and the like.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a method for producing distillate oil by mild hydrogenation of inferior/heavy oil slurry bed.
Background
Low grade/heavy oils include virgin geological storage heavy oils (e.g., heavy oil, highly viscous crude oil, natural bitumen), heavy oils that are by-products of petroleum refining and processing processes (e.g., atmospheric residue, vacuum residue, coker wax oil), and heavy oils and bitumens extracted from oil sands and oil shale. Because the inferior/heavy oil has the characteristics of high viscosity, high carbon/hydrogen atomic ratio, high heteroatom content, high metal content, high colloid/asphaltene content and the like, the problems of low oil yield, short device operation period, easy inactivation of a catalyst and the like exist when the inferior/heavy oil is treated by adopting the conventional petroleum refining technology.
The slurry bed (suspension bed) hydrogenation process route is a heavy oil hydrogenation technology researched and developed for over ten years, has the advantages of wide raw material application, high heavy oil conversion depth, flexible product distribution and the like, and can treat various inferior/heavy oils with high sulfur, high carbon residue, high viscosity, high metal, high asphaltene and the like.
The slurry bed hydrogenation catalyst is one of the key factors influencing the slurry bed hydrogenation efficiency. Slurry bed hydrogenation catalysts can be classified into inexpensive Fe-based catalysts and noble metal (e.g., Ni, Mo) catalysts. Because the catalyst is not easy to be recovered in the slurry bed process and the price of noble metal is high, the Fe-based catalyst is mostly used in the industry at present. The Fe-based catalyst mainly comprises: oxides of Fe (e.g. Fe)2O3FeOOH), sulfides of Fe (e.g.: FeS, FeS2、Fe2S3) And Fe-based organic compounds (e.g.: ferrous acetylacetonate, iron epoxy). Wherein, the Fe-based organic compound is artificially synthesized, the price is expensive, and the use cost is high; FeS2The catalyst is cheap and easy to obtain, but has high hardness, and is difficult to be crushed into nano-scale particles with high catalytic efficiency on a large scale; the hardness of Fe oxide is not very high, so that the Fe oxide is easy to crush, but the Fe oxide is easy to agglomerate after being crushed and is difficult to disperse in heavy oil with high density and high viscosity. Chinese patent CN105363450B discloses a creamy Fe-based catalyst for hydrogenation of carbon-containing raw materials. The active component of the catalyst is Fe, and the precipitate formed by Fe and the auxiliary agent is highly dispersed by solvent oil to form the missible oil catalyst, so that the catalyst has high viscosity, is not layered in the storage process, can be continuously stored for more than one year without deterioration, and is suitable for large-scale industrial use. Meanwhile, due to the high dispersibility and high catalytic activity of the missible oil catalyst, the hydrogenation reaction pressure can be reduced to 1 MPa. The slurry bed hydrogenation process of the invention uses the patent catalyst disclosed in CN105363450B toEnsures high dispersion and high activity of the catalyst in a slurry bed, and has the advantage of low price.
The slurry bed process and conditions are also key factors influencing the hydrogenation efficiency of the slurry bed. The heavy oil hydrocracking method disclosed in the Chinese patent application CN1459490A comprises the following process flows: mixing residual oil and a catalyst, and then feeding the mixture into a circulating type full back-mixing suspension bed reactor; the product at the top of the reactor is subjected to thermal high-temperature separation, and the gas phase is mixed with the gas phase at the top of the normal-pressure flash tower and enters a hydrofining reactor; separating the product at the bottom of the reactor by a cyclone separator, mixing the liquid phase with the liquid phase of the hot high-pressure separator, and feeding the mixture into the hot low-pressure separator; after separation, the liquid phase enters a normal pressure flash tower; and (4) introducing the flash oil into a fixed bed for hydrofining, and returning a product at the bottom of the flash tower as circulating oil to the suspension bed reactor. The reaction conditions of the suspension bed hydrocracking reactor are as follows: the reaction pressure is 8-15MPa, the reaction temperature is 420-.
The method for producing high-quality fuel oil by hydrocracking heavy oil disclosed in Chinese patent CN104388117B comprises the following steps: mixing heavy oil, a catalyst and hydrogen and feeding the mixture into a plug flow suspension bed hydrocracking reactor; separating the obtained gas-liquid mixture by a hot high-pressure separator and a cold high-pressure separator, feeding the gas-phase product into two sections of fixed bed reactors, and feeding the liquid-phase product into a reduced pressure distillation tower; decompressing tower bottom residue discharge device, gas phase entering fixed bed reactor; after hydrogen and light hydrocarbon are separated from the reaction product of the fixed bed, the reaction product enters a fractionating tower to be separated to obtain high-quality gasoline and diesel components, and the tower bottom oil returns to the fixed bed reactor to be recycled. The reaction conditions of the suspension bed hydrocracking reactor are as follows: the reaction pressure is 12-20MPa, the reaction temperature is 400-500 ℃, and the catalyst can be solid powder, oil-soluble or water-soluble catalyst.
The combined process and system for hydrogenation of heavy oil in suspension bed disclosed in chinese patent application CN107641525A includes high-temperature cracking of heavy oil and hydrogenation catalyst in a suspension bed cracking reactor, and hydrorefining of high-temperature cracked products and hydrogenation stable catalyst in a suspension bed stable reactor. The pressure of the suspension bed hydrocracking reactor and the pressure of the suspension bed hydrogenation stabilizing reactor are both 18-35MPa, the reaction temperature is 420-.
The prior slurry bed heavy oil hydrogenation technology has the problems of high operation pressure, high equipment investment and operation cost, poor safety and the like. In a slurry bed reactor, heavy oil macromolecules are thermally cracked to generate free radical fragments. The free radicals are unstable and have high reactivity, and if the free radicals cannot be extinguished or inerted in time, the free radicals return to the original macromolecules and are also polycondensed into larger molecules to form coke. Hydrogenation is an effective method for stabilizing thermal cracking free radicals, so that the prior art adopts high hydrogen pressure operation to improve the hydrogenation efficiency of the reaction and reduce the coke rate.
Poor/heavy slurry bed hydrogenation involves both cracking and hydrogenation processes that are important. Theoretically, the hydrogenation efficiency of the system can be improved by using the high-efficiency catalyst, and the generation rate of pyrolysis free radicals can be adjusted and the balance of pyrolysis-hydrogenation reaction can be maintained by optimizing process conditions. Therefore, the invention realizes the effective matching of the thermal cracking and hydrogenation of the raw oil in the slurry bed reactor by using the high-efficiency patent catalyst (Chinese patent CN105363450B) and regulating and controlling the process conditions.
The invention can be directly used for treating inferior/heavy oil, and has the advantages of mild operating conditions of a slurry bed, high yield of distillate oil, adjustable product distribution, low sulfur content of products, low investment and operating cost and the like.
Disclosure of Invention
The invention aims to provide a method for producing distillate oil by mild hydrogenation of a poor/heavy oil slurry bed, wherein the method comprises the following steps:
(1) mixing the raw oil, the catalyst and optional circulating slurry oil and optional circulating wax oil to prepare raw slurry oil;
(2) preheating the raw material slurry oil and fresh hydrogen and/or circulating hydrogen in the step (1), and introducing into a slurry bed hydrogenation reactor to obtain a slurry bed hydrogenation gas-phase product and a slurry bed hydrogenation liquid-phase product;
(3) introducing the slurry bed hydrogenation gas-phase product obtained in the step (2) into a thermal high-pressure separator, and separating to obtain thermal high-pressure gas and thermal high-pressure oil;
(4) introducing the hot high-pressure gas obtained in the step (3) into a cold high-pressure separator, and separating to obtain cold high-pressure gas and cold high-pressure oil;
(5) introducing the slurry bed liquid phase product obtained in the step (2) into a gas-liquid separator, and separating to obtain a gas-liquid separator gas phase product and a gas-liquid separator liquid phase product;
(6) introducing the gas-liquid separator gas-phase product obtained in the step (5) into a condensate collecting tank, and separating to obtain gas-liquid separator tail gas and gas-liquid separator tail oil;
(7) introducing the hot high-fraction oil obtained in the step (3) and the liquid-phase product obtained in the gas-liquid separator obtained in the step (5) into a fractionation system I, and separating to obtain distillate oil with the distillation range of less than 520 ℃, heavy oil slurry and a fractionation system I tail gas, wherein part of the heavy oil slurry is optionally returned to the step (1) as circulating oil slurry for recycling;
(8) mixing the cold high-fraction oil in the step (4), the tail oil of the gas-liquid separator in the step (6) and the distillate oil with the distillation range of less than 520 ℃ in the step (7) into intermediate oil;
(9) preheating the intermediate oil in the step (8) and fresh hydrogen and/or circulating hydrogen, introducing the preheated intermediate oil into a fixed bed hydrogenation reactor, and reacting to obtain a fixed bed hydrogenation product;
(10) introducing the fixed bed hydrogenation product obtained in the step (9) into a gas-liquid separation system, and separating to obtain a liquid-phase product of the gas-liquid separation system and a tail gas of the gas-liquid separation system;
(11) introducing the liquid-phase product of the gas-liquid separation system in the step (10) into a fractionation system II to obtain naphtha, aviation kerosene, diesel oil, wax oil and fractionation system II tail gas, wherein part of the wax oil is optionally returned to the step (1) as circulating wax oil for recycling;
(12) introducing the cold high-pressure separation gas in the step (4), the tail gas of the gas-liquid separator in the step (6), the tail gas of the fractionation system I in the step (7), the tail gas of the gas-liquid separation system in the step (10) and the tail gas of the fractionation system II in the step (11) into a gas treatment unit, and performing separation, enrichment and purification treatment to obtain recycle hydrogen and liquidFossil oil gas (LPG), dry gas, C5 +Hydrocarbons or/and sulphur; wherein the recycle hydrogen is optionally returned to steps (2) and (9) for recycling.
The method of the invention has the advantages that: can directly treat inferior/heavy oil, and has the advantages of simple process, mild operating conditions of a slurry bed, high oil yield, adjustable distillation range distribution of oil products, low sulfur content of products, and low investment and operating cost.
Drawings
FIG. 1 is an exemplary process flow diagram of a process for producing distillate oil by mild hydrogenation of a slurry bed of low/heavy oil, wherein the reference numerals in the drawing respectively represent the following:
1 a slurry bed hydrogenation reactor, 2 a hot high-pressure separator, 3 a cold high-pressure separator, 4 a gas-liquid separator, 5a condensate collecting tank, 6 a fractionating system I, 7 a fixed bed hydrogenation reactor, 8 a gas-liquid separating system, 9 a fractionating system II, 10 a gas treatment unit and 11 a catalytic cracking unit
Detailed Description
In the present invention, the terms "slurry bed hydrogenation reactor", "slurry bed" and "slurry bed reactor" are used interchangeably unless otherwise indicated; the terms "fixed bed hydrogenation reactor", "fixed bed" and "fixed bed reactor" are used interchangeably.
In the present invention, the terms "slurry bed" and "suspended bed" are used interchangeably unless otherwise indicated.
In the present invention, the terms "raw oil" and "low grade/heavy oil" are used interchangeably unless otherwise indicated.
In an exemplary embodiment of the invention, fig. 1 of the present invention relates to the following process flow:
raw oil, circulating slurry oil, circulating wax oil and a catalyst are mixed to prepare raw slurry oil, and the prepared raw slurry oil is mixed with fresh hydrogen and circulating hydrogen (also called hydrogen-rich gas) and preheated, and then introduced into a slurry bed hydrogenation reactor 1 for reaction.
Introducing a slurry bed hydrogenation gas-phase product generated by the slurry bed hydrogenation reactor 1 into a thermal high-pressure separator 2 to obtain thermal high-pressure gas and thermal high-pressure oil.
And guiding the obtained hot high-pressure gas into a cold high-pressure separator 3 to obtain cold high-pressure gas and cold high-pressure oil.
And (3) introducing the slurry bed hydrogenation liquid phase product generated by the slurry bed hydrogenation reactor 1 into a gas-liquid separator 4 to obtain a gas-liquid separator gas phase product and a gas-liquid separator liquid phase product.
And introducing the obtained gas-phase product of the gas-liquid separator into a condensate collecting tank 5 to obtain tail gas of the gas-liquid separator and tail oil of the gas-liquid separator.
And introducing the obtained liquid phase product of the thermal high-separation oil and gas-liquid separator into a fractionation system I6 to obtain distillate oil with the distillation range of less than 520 ℃ and heavy oil slurry.
A part (0% to 100%) of the heavy slurry oil obtained is taken as a circulating slurry oil (namely, the circulating slurry oil shown in figure 1) and sent to the step of preparing the raw slurry oil for recycling; the other part is led out of the system (i.e. the outer throw slurry shown in fig. 1).
And mixing the obtained cold high-pressure separation oil, tail oil of the gas-liquid separator and distillate oil to obtain intermediate oil.
Preheating the obtained intermediate oil, catalytic cracking diesel oil which is a byproduct of the catalytic cracking unit, and fresh hydrogen and/or circulating hydrogen, and introducing into a fixed bed hydrogenation reactor 7 to obtain a fixed bed hydrogenation product.
And introducing the obtained fixed bed hydrogenation product into a gas-liquid separation system 8 to obtain tail gas of the gas-liquid separation system and liquid phase products of the gas-liquid separation system.
And introducing the obtained liquid-phase product of the gas-liquid separation system 8 into a fractionation system II 9 to obtain naphtha, aviation kerosene, diesel oil, wax oil and fractionation system II tail gas.
A portion (0% to 100%) of the obtained wax oil was recycled as a recycle wax oil (i.e., the recycle wax oil shown in fig. 1) back to the step of preparing the raw slurry oil. And guiding a part (0-100%) of the obtained wax oil and/or a part of the obtained diesel oil into a catalytic cracking unit 11 to obtain catalytic cracked gasoline, catalytic cracked diesel oil and catalytic cracking unit tail gas. The remaining part of wax oil and diesel oil was collected as product.
Will obtainIntroducing the tail gas of the cold high-pressure gas-liquid separator, the tail gas of the fractionation system I, the tail gas of the gas-liquid separation system 8, the tail gas of the fractionation system II and the tail gas of the catalytic cracking unit into a gas treatment unit 10 to obtain circulating hydrogen, Liquefied Petroleum Gas (LPG), dry gas and C5 +Hydrocarbon and/or sulphur, wherein the recycled hydrogen is recycled, optionally after mixing with fresh hydrogen, to the slurry bed hydrogenation reactor 1 and the fixed bed hydrogenation reactor 7.
In one embodiment of the invention, the invention relates to a method for producing oil products by mild hydrogenation of poor/heavy oil slurry in a bed, wherein the method comprises the following steps:
(1) mixing the raw oil, the catalyst and optional circulating slurry oil and optional circulating wax oil to prepare raw slurry oil;
(2) preheating the raw material slurry oil and fresh hydrogen and/or circulating hydrogen in the step (1), and introducing into a slurry bed hydrogenation reactor to obtain a slurry bed hydrogenation gas-phase product and a slurry bed hydrogenation liquid-phase product;
(3) introducing the slurry bed hydrogenation gas-phase product obtained in the step (2) into a thermal high-pressure separator, and separating to obtain thermal high-pressure gas and thermal high-pressure oil;
(4) introducing the hot high-pressure gas obtained in the step (3) into a cold high-pressure separator, and separating to obtain cold high-pressure gas and cold high-pressure oil;
(5) introducing the slurry bed liquid phase product obtained in the step (2) into a gas-liquid separator, and separating to obtain a gas-liquid separator gas phase product and a gas-liquid separator liquid phase product;
(6) introducing the gas-liquid separator gas-phase product obtained in the step (5) into a condensate collecting tank, and separating to obtain gas-liquid separator tail gas and gas-liquid separator tail oil;
(7) introducing the hot high-fraction oil obtained in the step (3) and the liquid-phase product obtained in the gas-liquid separator obtained in the step (5) into a fractionation system I, and separating to obtain distillate oil with the distillation range of less than 520 ℃, heavy oil slurry and a fractionation system I tail gas, wherein part of the heavy oil slurry is optionally returned to the step (1) as circulating oil slurry for recycling;
(8) mixing the cold high-fraction oil in the step (4), the tail oil of the gas-liquid separator in the step (6) and the distillate oil with the distillation range of less than 520 ℃ in the step (7) into intermediate oil;
(9) preheating the intermediate oil in the step (8) and fresh hydrogen and/or circulating hydrogen, introducing the preheated intermediate oil into a fixed bed hydrogenation reactor, and reacting to obtain a fixed bed hydrogenation product;
(10) introducing the fixed bed hydrogenation product obtained in the step (9) into a gas-liquid separation system, and separating to obtain a liquid-phase product of the gas-liquid separation system and a tail gas of the gas-liquid separation system;
(11) introducing the liquid-phase product of the gas-liquid separation system in the step (10) into a fractionation system II to obtain naphtha, aviation kerosene, diesel oil, wax oil and fractionation system II tail gas, wherein part of the wax oil is optionally returned to the step (1) as circulating wax oil for recycling;
(12) introducing the cold high-pressure separation gas in the step (4), the tail gas of the gas-liquid separator in the step (6), the tail gas of the fractionation system I in the step (7), the tail gas of the gas-liquid separation system in the step (10) and the tail gas of the fractionation system II in the step (11) into a gas treatment unit, and performing separation, enrichment and purification treatment to obtain circulating hydrogen, Liquefied Petroleum Gas (LPG), dry gas and C5 +Hydrocarbons or/and sulphur; wherein the recycle hydrogen is optionally returned to steps (2) and (9) for recycling.
In a preferred embodiment, the feedstock oil may be selected from, but is not limited to, one or more of the following: crude geological storage heavy oil (e.g., heavy oil, highly viscous crude oil, natural bitumen), heavy oil by-produced from petroleum refining and processing processes (e.g., atmospheric residue, vacuum residue, coker wax oil), and heavy oil and bitumen extracted from oil sands and oil shale.
In a preferred embodiment, in the step (1), the catalyst is a catalyst suitable for slurry bed hydrogenation, such as the catalyst disclosed in chinese patent CN 105363450B. In a preferred embodiment, in the step (1), the raw oil, the circulating slurry oil + the circulating wax oil and the catalyst are mixed in a mass ratio of 100 (0-100) to (0.1-20), wherein the amount of the catalyst is calculated by active metals.
In a preferred embodiment, in the step (2), the operating conditions of the slurry bed hydrogenation reactor are as follows: the reaction temperature is 300-;
in a preferred embodiment, in the step (3), the operating conditions of the hot high-pressure separator are as follows: the temperature is 200-;
in a preferred embodiment, in the step (4), the operating conditions of the cold high-pressure separator are as follows: the temperature is 0-50 ℃, and the pressure is 2-10 MPa;
in a preferred embodiment, in the step (5), the operating pressure of the gas-liquid separator is 1/3-1 of the pressure of the slurry bed hydrogenation reactor;
in a preferred embodiment, in the step (7), the fractionation system I is a vacuum distillation column or an atmospheric + vacuum distillation column.
In a preferred embodiment, apart from returning a part of the heavy slurry oil obtained in step (7) to step (1) as a circulating slurry oil for recycling, the other part of the heavy slurry oil is taken as an external throwing slurry oil export system.
In a preferred embodiment, in the step (9), the operating conditions of the fixed bed hydrogenation reactor are as follows: the reaction temperature is 280-410 ℃, the reaction pressure is 5-25MPa, the hydrogen/oil volume ratio is 500-2000, and the volume space velocity is 0.2-2h-1(ii) a Preferably, the catalyst used in the fixed bed hydrogenation reactor is a conventional fixed bed catalyst for oil hydrogenation known in the art, such as: catalyst containing molybdenum, tungsten, cobalt and/or nickel active metal components with alumina as carrier.
In a preferred embodiment, in step (10), the gas-liquid separation system is a conventional gas-liquid separation device used alone or in series, such as: high-pressure gas-liquid separator and low-pressure gas-liquid separator connected in series, or suspension liquid separator.
In a preferred embodiment, in step (11), the fractionation system II is an atmospheric distillation column or an atmospheric + vacuum distillation column.
In a preferred embodiment, the wax oil is a distillate fraction with a distillation range >360 ℃. In a preferred embodiment, a portion of the diesel oil and/or wax oil is introduced into a catalytic cracking unit to obtain catalytically cracked gasoline, catalytically cracked diesel oil, and a catalytic cracking unit tail gas. Preferably, the remaining part of the wax oil obtained in step (11) is collected as product wax oil. In a preferred embodiment, the remainder of the diesel obtained in step (11) is collected as product diesel. Preferably, the catalytic cracking unit tail gas is directed to a gas treatment unit.
In a preferred embodiment, catalytically cracked diesel oil as a by-product of the catalytic cracking unit is introduced into the fixed bed hydrogenation reactor in step (9) together with the intermediate oil described in step (8).
In a preferred embodiment, the separation and enrichment of the gas in step (12) is performed by conventional methods known in the art, such as pressure swing adsorption, membrane separation or cryogenic separation; preferably, the purification is performed by a conventional method known in the art, such as an alcohol amine absorption method, a liquid-phase redox method, a copper washing method, a crystallized sulfur method, or a claus sulfur recovery method.
The invention can directly treat inferior/heavy oil and has the advantages of simple process, mild operating pressure of slurry bed, high oil yield, low investment and operating cost, and the like.
Examples
Next, the technical solution of the present invention will be described in further detail with reference to the following examples. It should be understood, however, that the scope of the present invention is not limited to these examples.
In the following examples, the following representative feed oils were used: a (heavy oil), B (vacuum residuum), and C (coker gas oil), the compositions and properties of which are shown in table 1:
TABLE 1 Properties of feedstocks A, B and C
In the following examples, unless otherwise specified, each of the reagents, raw materials, apparatuses and the like used are commercial reagents, raw materials and apparatuses.
Example 1
Mixing raw oil A (thickened oil) and a catalyst according to a mass ratio of 100:5 (the amount of the catalyst is calculated by active metal) to prepare raw oil slurry, mixing the raw oil slurry with fresh hydrogen and part of circulating hydrogen, preheating to about 390 ℃, and then feeding the mixture into a slurry bed hydrogenation reactor; and fresh hydrogen is preheated to about 430 ℃ and then is fed into the bottom of the slurry bed hydrogenation reactor. Wherein, the operating conditions of the slurry bed are as follows: the temperature is 430 ℃, the pressure is 2MPa, and the average residence time is 15min, wherein the catalyst is disclosed in Chinese patent CN 105363450B.
Introducing the gas-phase product of the slurry bed hydrogenation reactor into a hot high-pressure separator, wherein the operation conditions are as follows: obtaining hot high-pressure gas and hot high-pressure oil at the temperature of 400 ℃ and the pressure of 2 MPa; introducing hot high-pressure gas into a cold high-pressure separator under the following operating conditions: obtaining cold high-pressure gas and cold high-pressure oil at the temperature of 30 ℃ and the pressure of 2 MPa; the cold high partial gas is introduced into a gas treatment unit.
Introducing a liquid-phase product of a slurry bed hydrogenation reactor into a gas-liquid separator, wherein the operating pressure is 1 MPa; and introducing the gas-phase product separated by the gas-liquid separator into a condensate collecting tank to obtain tail gas of the gas-liquid separator and tail oil of the gas-liquid separator, and sending the tail gas of the gas-liquid separator into a gas treatment unit.
Introducing a gas-liquid separator liquid phase product at the bottom of a gas-liquid separator and hot high-fraction oil into a fractionation system I (an atmospheric distillation tower and a reduced pressure distillation tower) for separation to obtain fraction oil with the distillation range of less than 520 ℃, heavy oil slurry and fractionation system I tail gas; sending tail gas of the fractionation system I into a gas treatment unit; and (4) leading all the obtained heavy oil slurry out of the system to be used as external throwing oil slurry.
Mixing the obtained cold high-fraction oil, tail oil of a gas-liquid separator and distillate oil to obtain intermediate oil, preheating the intermediate oil, catalytic cracking diesel oil obtained by a catalytic cracking unit, fresh hydrogen and circulating hydrogen, and introducing into a fixed bed hydrogenation reactor. Wherein, the catalyst adopted by the fixed bed is a medium petrochemical hydrorefining catalyst; the fixed bed operating conditions were: the temperature is 280 ℃, the pressure is 5MPa, the hydrogen/oil volume ratio is 500, and the volume space velocity is 0.2h-1。
Introducing the fixed bed hydrogenation product into a gas-liquid separation system to obtain tail gas of the gas-liquid separation system and liquid phase products of the gas-liquid separation system; and sending tail gas of the gas-liquid separation system into a gas treatment unit.
And (3) introducing the liquid-phase product of the gas-liquid separation system into a fractionation system II (an atmospheric distillation tower and a reduced pressure distillation tower) to obtain the tail gas of the fractionation system II, naphtha, aviation kerosene, diesel oil and wax oil with the distillation range of more than 360 ℃. Wherein, the tail gas of the fractionation system II is sent to a gas treatment unit; collecting a part of wax oil and a part of diesel oil as product wax oil and product diesel oil; and guiding the residual wax oil and the residual diesel oil into a catalytic cracking unit to obtain catalytic cracking gasoline, catalytic cracking diesel oil and catalytic cracking unit tail gas. Wherein, the tail gas of the catalytic cracking unit is sent to a gas treatment unit.
In the gas treatment unit (membrane separation + alcohol amine absorption), the introduced gases are treated to obtain circulating hydrogen, Liquefied Petroleum Gas (LPG), dry gas and C5 +And (c) hydrocarbons, wherein the recycle hydrogen is mixed with fresh hydrogen and recycled to the slurry bed hydrogenation reactor and the fixed bed hydrogenation reactor.
Example 2
Mixing raw oil B (vacuum residuum), circulating oil slurry, circulating wax oil and a catalyst according to a mass ratio of 100:50:20 to prepare raw oil slurry, mixing the raw oil slurry with fresh hydrogen and part of circulating hydrogen, preheating to about 440 ℃, and then feeding the mixture into a slurry bed hydrogenation reactor; fresh hydrogen is preheated to about 480 ℃ and then is fed into the bottom of a slurry bed hydrogenation reactor. Wherein, the operating conditions of the slurry bed are as follows: the temperature is 480 ℃, the pressure is 4MPa, the average residence time is 30min, and the catalyst is the same as that of example 1.
Introducing the gas-phase product of the slurry bed hydrogenation reactor into a hot high-pressure separator, wherein the operation conditions are as follows: obtaining hot high-pressure gas and hot high-pressure oil at the temperature of 300 ℃ and the pressure of 4 MPa; introducing hot high-pressure gas into a cold high-pressure separator under the following operating conditions: obtaining cold high-pressure gas and cold high-pressure oil at the temperature of 45 ℃ and the pressure of 4 MPa; the cold high partial gas is introduced into a gas treatment unit.
Introducing a liquid-phase product generated by a slurry bed hydrogenation reactor into a gas-liquid separator, wherein the operating pressure is 2 MPa; and introducing the gas-phase product separated by the gas-liquid separator into a condensate collecting tank to obtain tail gas of the gas-liquid separator and tail oil of the gas-liquid separator, and sending the tail gas of the gas-liquid separator into a gas treatment unit.
Introducing the gas-liquid separator liquid phase product at the bottom of the gas-liquid separator and the hot high-fraction oil into a fractionation system I (reduced pressure distillation tower) for separation to obtain distillate oil with the distillation range of less than 520 ℃, heavy oil slurry and fractionation system I tail gas; and sending tail gas of the fractionation system I into a gas treatment unit. Wherein, one part of the obtained heavy oil slurry is used as circulating oil slurry and returned to the step of preparing raw material oil slurry for cyclic utilization, and the other part is led out of the system to be used as external throwing oil slurry.
Mixing the obtained cold high-fraction oil, tail oil of a gas-liquid separator and distillate oil to obtain intermediate oil, preheating the intermediate oil, catalytic cracking diesel oil obtained by a catalytic cracking unit, fresh hydrogen and circulating hydrogen, and introducing into a fixed bed hydrogenation reactor. Wherein the catalyst used in the fixed bed was the same as in example 1; the operating conditions were: the temperature is 410 ℃, the pressure is 25MPa, the hydrogen/oil volume ratio is 2000, and the volume space velocity is 1.0h-1。
Introducing the fixed bed hydrogenation product into a gas-liquid separation system to obtain tail gas of the gas-liquid separation system and liquid phase products of the gas-liquid separation system, and sending the tail gas of the gas-liquid separation system into a gas treatment unit; and (3) introducing the liquid-phase product of the gas-liquid separation system into a fractionation system II (an atmospheric distillation tower and a reduced pressure distillation tower) to obtain the tail gas of the fractionation system II, naphtha, aviation kerosene, diesel oil and wax oil with the distillation range of more than 360 ℃. Wherein, the tail gas of the fractionation system II is sent to a gas treatment unit; one part of the wax oil is used as circulating wax oil and sent to the step of preparing raw material oil slurry for recycling, and the other part of the wax oil is collected as a wax oil product; collecting a portion of the diesel as a diesel product; and guiding the residual wax oil and the residual diesel oil into a catalytic cracking unit to obtain catalytic cracking gasoline, catalytic cracking diesel oil and catalytic cracking unit tail gas. Wherein the catalytic cracking unit tail gas is sent to a gas treatment unit.
In a gas treatment unit (pressure swing adsorption + Claus sulfur recovery method), the introduced gases are treated to obtain circulating hydrogen, Liquefied Petroleum Gas (LPG), dry gas and C5 +Hydrocarbon, sulfur. Wherein, the circulating hydrogen and the fresh hydrogen are mixed and sent into a slurry bed hydrogenation reactor and a fixed bed hydrogenation reactor.
Example 3
Mixing raw oil C (coking wax oil), circulating slurry oil, circulating wax oil and a catalyst according to a mass ratio of 100:30:0.1 to prepare raw slurry oil, mixing the raw slurry oil with fresh hydrogen and part of circulating hydrogen, preheating to about 280 ℃, and then feeding the mixture into a slurry bed hydrogenation reactor; fresh hydrogen is preheated to about 300 ℃ and then fed into the bottom of a slurry bed hydrogenation reactor. Wherein, the operating conditions of the slurry bed hydrogenation reactor are as follows: the temperature is 300 ℃, the pressure is 10MPa, the average residence time is 120min, and the catalyst is the same as that of example 1.
Introducing the gas-phase product of the slurry bed hydrogenation reactor into a hot high-pressure separator, wherein the operation conditions are as follows: obtaining hot high-pressure gas and hot high-pressure oil at the temperature of 200 ℃ and the pressure of 10 MPa; introducing hot high-pressure gas into a cold high-pressure separator under the following operating conditions: obtaining cold high-pressure gas and cold high-pressure oil at the temperature of 2 ℃ and the pressure of 10 MPa; the cold high partial gas is introduced into a gas treatment unit.
Introducing a liquid-phase product generated by a slurry bed hydrogenation reactor into a gas-liquid separator, wherein the operating pressure is 5 MPa; and introducing the gas-phase product separated by the gas-liquid separator into a condensate collecting tank to obtain tail gas of the gas-liquid separator and tail oil of the gas-liquid separator, and sending the tail gas of the gas-liquid separator into a gas treatment unit.
Introducing the gas-liquid separator liquid phase product at the bottom of the gas-liquid separator and the hot high-fraction oil into a fractionating system I (a reduced pressure distillation tower) for separation to obtain distillate oil with the distillation range of less than 520 ℃, heavy oil slurry and tail gas of the fractionating system I. Wherein, the tail gas of the fractionation system I is sent to a gas treatment unit; taking one part of the obtained heavy oil slurry as circulating oil slurry, sending the part of the obtained heavy oil slurry to the step of preparing raw material oil slurry for recycling, and leading the other part out of the system to be used as external throwing oil slurry; mixing the obtained cold high-pressure separation oil, tail oil of a gas-liquid separator and distillate oil to obtain intermediate oil.
Preheating intermediate oil, catalytic cracking diesel oil obtained by a catalytic cracking unit, fresh hydrogen and circulating hydrogen, and introducing the preheated intermediate oil, the catalytic cracking diesel oil, the fresh hydrogen and the circulating hydrogen into a fixed bed hydrogenation reactor, wherein the adopted catalyst is the same as that in example 1; the operating conditions were: the temperature is 350 ℃, the pressure is 15MPa, the hydrogen/oil volume ratio is 1200, and the volume space velocity is 0.5h-1。
Introducing the fixed bed hydrogenation product into a gas-liquid separation system to obtain tail gas of the gas-liquid separation system and liquid phase products of the gas-liquid separation system, and sending the tail gas of the gas-liquid separation system into a gas treatment unit; and (3) introducing the liquid-phase product of the gas-liquid separation system into a fractionation system II (an atmospheric distillation tower) to obtain fractionation system II tail gas, naphtha, aviation kerosene, diesel oil and wax oil with the distillation range of more than 360 ℃. Wherein, the tail gas of the fractionation system II is sent to a gas treatment unit; collecting a part of diesel oil as a product; taking a part of wax oil as circulating wax oil, and sending the circulating wax oil to the step of preparing raw material slurry oil for recycling; and guiding the residual wax oil and the residual diesel oil into a catalytic cracking unit to obtain catalytic cracking gasoline, catalytic cracking diesel oil and catalytic cracking unit tail gas. Wherein, the tail gas of the catalytic cracking unit is sent to a gas treatment unit.
In a gas treatment unit (pressure swing adsorption + alcohol amine absorption), the introduced gases are treated to obtain circulating hydrogen, Liquefied Petroleum Gas (LPG), dry gas and C5 +And (c) hydrocarbons, wherein the circulating hydrogen is mixed with fresh hydrogen and circulated back to the slurry bed hydrogenation reactor and the fixed bed hydrogenation reactor.
Example 4
Mixing raw oil A + C (the mass ratio is 1:1), circulating oil slurry and a catalyst according to the mass ratio of 100:100:10 to prepare raw oil slurry, mixing the raw oil slurry with fresh hydrogen and part of circulating hydrogen, preheating to about 320 ℃, and then feeding the mixture into a slurry bed hydrogenation reactor; fresh hydrogen is preheated to about 350 ℃ and then fed into the bottom of the slurry bed hydrogenation reactor. Wherein, the operating conditions of the slurry bed hydrogenation reactor are as follows: the temperature is 350 ℃, the pressure is 4.8MPa, the average residence time is 60min, and the catalyst is the same as that in example 1.
Introducing the gas-phase product of the slurry bed hydrogenation reactor into a hot high-pressure separator, wherein the operation conditions are as follows: obtaining hot high-pressure gas and hot high-pressure oil at the temperature of 230 ℃ and the pressure of 4.8 MPa; introducing hot high-pressure gas into a cold high-pressure separator under the following operating conditions: obtaining cold high-pressure gas and cold high-pressure oil at the temperature of 35 ℃ and the pressure of 4.8 MPa; the cold high partial gas is introduced into a gas treatment unit.
Introducing a liquid-phase product generated by a slurry bed hydrogenation reactor into a gas-liquid separator, wherein the operating pressure is 3 MPa; introducing the gas-phase product separated by the gas-liquid separator into a condensate collecting tank to obtain tail gas of the gas-liquid separator and tail oil of the gas-liquid separator; and sending the tail gas of the gas-liquid separator into a gas treatment unit.
Introducing a gas-liquid separator liquid phase product at the bottom of a gas-liquid separator and hot high-fraction oil into a fractionation system I (an atmospheric distillation tower and a reduced pressure distillation tower) for separation to obtain fraction oil with the distillation range of less than 520 ℃, heavy oil slurry and fractionation system I tail gas; sending tail gas of the fractionation system I into a gas treatment unit; and (4) taking all the obtained heavy oil slurry as circulating oil slurry, and sending the circulating oil slurry to the step of preparing the raw oil slurry for recycling.
Mixing the obtained cold high-pressure separation oil, tail oil of a gas-liquid separator and distillate oil to obtain intermediate oil; preheating the intermediate oil, fresh hydrogen and circulating hydrogen, and introducing into a fixed bed hydrogenation reactor. Wherein the catalyst used was the same as in example 1; the operating conditions of the fixed bed hydrogenation reactor are as follows: the temperature is 380 ℃, the pressure is 12MPa, the hydrogen/oil volume ratio is 1000, and the volume space velocity is 2.0h-1。
Introducing the fixed bed hydrogenation product into a gas-liquid separation system to obtain tail gas of the gas-liquid separation system and liquid phase products of the gas-liquid separation system, and sending the tail gas of the gas-liquid separation system into a gas treatment unit; and (3) introducing the liquid-phase product of the gas-liquid separation system into a fractionation system II (an atmospheric distillation tower and a reduced pressure distillation tower) to obtain the tail gas of the fractionation system II, naphtha, aviation kerosene, diesel oil and wax oil with the distillation range of more than 360 ℃. Wherein, the tail gas of the fractionation system II is sent to a gas treatment unit; all diesel and all wax oils are collected as diesel and wax oil products.
In a gas treatment unit (pressure swing adsorption + membrane separation), the introduced gases are treated to obtain circulating hydrogen, Liquefied Petroleum Gas (LPG), dry gas, and C5 +And (3) hydrocarbon, wherein the circulating hydrogen is mixed with fresh hydrogen and sent to the slurry bed hydrogenation reactor and the fixed bed hydrogenation reactor.
Table 2 below shows the yields of the major products of the slurry mild hydrogenation in examples 1-4, and tables 3 and 4 show the product yields and the sulfur content in the major products of the poor/heavy oil slurry mild hydrogenation processes in examples 1-4, respectively.
Table 2 yield (% of main product of slurry bed mild hydrogenation) in examples 1 to 4
TABLE 3 yield (%)
TABLE 4 Sulfur content (. mu.g/g) in the base products of examples 1-4
Claims (24)
1. A method for producing distillate oil by mild hydrogenation of a poor/heavy oil slurry bed, wherein the method comprises the following steps:
(1) mixing the raw oil, the catalyst and optional circulating slurry oil and optional circulating wax oil to prepare raw slurry oil;
(2) preheating the raw material slurry oil and fresh hydrogen and/or circulating hydrogen in the step (1), and introducing into a slurry bed hydrogenation reactor to obtain a slurry bed hydrogenation gas-phase product and a slurry bed hydrogenation liquid-phase product;
(3) introducing the slurry bed hydrogenation gas-phase product obtained in the step (2) into a thermal high-pressure separator, and separating to obtain thermal high-pressure gas and thermal high-pressure oil;
(4) introducing the hot high-pressure gas obtained in the step (3) into a cold high-pressure separator, and separating to obtain cold high-pressure gas and cold high-pressure oil;
(5) introducing the slurry bed hydrogenation liquid phase product in the step (2) into a gas-liquid separator, and separating to obtain a gas-liquid separator gas phase product and a gas-liquid separator liquid phase product;
(6) introducing the gas-liquid separator gas-phase product obtained in the step (5) into a condensate collecting tank, and separating to obtain gas-liquid separator tail gas and gas-liquid separator tail oil;
(7) introducing the hot high-fraction oil obtained in the step (3) and the liquid-phase product obtained in the gas-liquid separator obtained in the step (5) into a fractionation system I, and separating to obtain distillate oil with the distillation range of less than 520 ℃, heavy oil slurry and a fractionation system I tail gas, wherein part of the heavy oil slurry is optionally returned to the step (1) as circulating oil slurry for recycling;
(8) mixing the cold high-fraction oil in the step (4), the tail oil of the gas-liquid separator in the step (6) and the distillate oil with the distillation range of less than 520 ℃ in the step (7) into intermediate oil;
(9) preheating the intermediate oil in the step (8) and fresh hydrogen and/or circulating hydrogen, introducing the preheated intermediate oil into a fixed bed hydrogenation reactor, and reacting to obtain a fixed bed hydrogenation product;
(10) introducing the fixed bed hydrogenation product obtained in the step (9) into a gas-liquid separation system, and separating to obtain a liquid-phase product of the gas-liquid separation system and a tail gas of the gas-liquid separation system;
(11) introducing the liquid-phase product of the gas-liquid separation system in the step (10) into a fractionation system II to obtain naphtha, aviation kerosene, diesel oil, wax oil and fractionation system II tail gas, wherein part of the wax oil is optionally returned to the step (1) as circulating wax oil for recycling;
(12) introducing the cold high-pressure separation gas in the step (4), the tail gas of the gas-liquid separator in the step (6), the tail gas of the fractionation system I in the step (7), the tail gas of the gas-liquid separation system in the step (10) and the tail gas of the fractionation system II in the step (11) into a gas treatment unit, and performing separation, enrichment and purification treatment to obtain circulating hydrogen, Liquefied Petroleum Gas (LPG), dry gas and C5 +Hydrocarbons or/and sulphur; wherein the recycle hydrogen is optionally returned to steps (2) and (9) for recycling.
2. The method of claim 1, wherein the feedstock oil is selected from one or more of: virgin geological storage of heavy oil, heavy oil by-product of petroleum refining and processing, and heavy oil and bitumen extracted from oil sands and oil shale.
3. The method of claim 2, wherein the virgin reservoir oil is heavy oil, highly viscous crude oil, or natural bitumen.
4. The method of claim 2 wherein the heavy oil by-product of the petroleum refining and processing process is atmospheric resid, vacuum resid, or coker gas oil.
5. The method according to any one of claims 1 to 4, wherein in the step (1), the raw oil, the recycled slurry oil + the recycled wax oil and the catalyst are mixed in a mass ratio of 100 (0-100) to (0.1-20), wherein the amount of the catalyst is calculated on the active metal basis.
6. The process of any one of claims 1 to 4, wherein in step (2), the operating conditions of the slurry bed hydrogenation reactor are as follows: the reaction temperature is 300-.
7. The process according to any one of claims 1 to 4, wherein in step (3) the operating conditions of the hot high pressure separator are as follows: the temperature is 200 ℃ and 480 ℃, and the pressure is 2-10 MPa.
8. The process according to any one of claims 1 to 4, wherein in step (4) the operating conditions of the cold high-pressure separator are as follows: the temperature is 0-50 ℃, and the pressure is 2-10 MPa.
9. The process of any one of claims 1 to 4, wherein in step (5), the operating pressure of the gas-liquid separator is 1/3-1 of the pressure of the slurry bed hydrogenation reactor.
10. The process according to any one of claims 1 to 4, wherein in the step (7), the fractionation system I is a vacuum distillation column or an atmospheric + vacuum distillation column.
11. The method according to any one of claims 1-4, wherein, in addition to returning a part of the heavy slurry oil obtained in step (7) as recycled slurry oil to step (1) for recycling, another part of the heavy slurry oil is used as an external throwing slurry oil export system.
12. As claimed inThe process according to any one of claims 1 to 4, wherein in the step (9), the operating conditions of the fixed bed hydrogenation reactor are as follows: the reaction temperature is 280-410 ℃, the reaction pressure is 5-25MPa, the hydrogen/oil volume ratio is 500-2000, and the volume space velocity is 0.2-2h-1。
13. The process of claim 12 wherein the catalyst used in the fixed bed hydrogenation reactor is a catalyst comprising molybdenum, tungsten, cobalt and/or nickel active metal components on alumina support.
14. The method according to any one of claims 1 to 4, wherein in step (10), the gas-liquid separation system is a gas-liquid separation device used alone or in series.
15. The method of claim 14, wherein the gas-liquid separation system is a high pressure gas-liquid separator and a low pressure gas-liquid separator in series, or a suspension separator.
16. The method according to any one of claims 1 to 4, wherein in the step (11), the fractionation system II is an atmospheric distillation column or an atmospheric + vacuum distillation column.
17. The process according to any one of claims 1 to 4, wherein in step (11) the wax oil is a distillate with a boiling range >360 ℃.
18. The process according to any one of claims 1 to 4, wherein a portion of the diesel and/or wax oil is introduced into a catalytic cracking unit to obtain catalytically cracked gasoline, catalytically cracked diesel and catalytic cracking unit tail gas.
19. The method of claim 18, wherein the remaining portion of the wax oil is collected as a product wax oil.
20. The method of claim 18, wherein the remaining portion of the diesel is collected as product diesel.
21. The method of claim 18, wherein the catalytically cracked diesel fuel is introduced into a fixed bed hydrogenation reactor in step (9) together with the intermediate oil of step (8).
22. The method of claim 18, wherein the catalytic cracking unit tail gas is directed to the gas treatment unit.
23. The method according to any one of claims 1 to 4, wherein, in step (12), the separation and enrichment is performed by pressure swing adsorption, membrane separation or cryogenic separation.
24. The method according to any one of claims 1 to 4, wherein in step (12), the purification is performed using an alcohol amine absorption method, a liquid phase redox method, a copper washing method, a crystalline sulfur method, or a Claus sulfur recovery method.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295112A (en) * | 2000-11-02 | 2001-05-16 | 中国石油天然气股份有限公司 | Normal pressure suspension bed hydrogenation process adopting liquid multiple-metal catalyst |
| CN1594507A (en) * | 2004-07-02 | 2005-03-16 | 中国科学院山西煤炭化学研究所 | Process for hydrocracking of Fischer-Tropsch synthesized heavy hydrocarbon and/or kettle bottom wax |
| CN107557064A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | Coal tar combination cot method of hydrotreating and the system for coal tar combination bed hydroprocessing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1295112A (en) * | 2000-11-02 | 2001-05-16 | 中国石油天然气股份有限公司 | Normal pressure suspension bed hydrogenation process adopting liquid multiple-metal catalyst |
| CN1594507A (en) * | 2004-07-02 | 2005-03-16 | 中国科学院山西煤炭化学研究所 | Process for hydrocracking of Fischer-Tropsch synthesized heavy hydrocarbon and/or kettle bottom wax |
| CN107557064A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | Coal tar combination cot method of hydrotreating and the system for coal tar combination bed hydroprocessing |
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