CN114736710B - Inferior heavy oil processing method - Google Patents
Inferior heavy oil processing method Download PDFInfo
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- CN114736710B CN114736710B CN202110018995.4A CN202110018995A CN114736710B CN 114736710 B CN114736710 B CN 114736710B CN 202110018995 A CN202110018995 A CN 202110018995A CN 114736710 B CN114736710 B CN 114736710B
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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
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention discloses a poor-quality heavy oil hydrotreating method, which comprises the following steps: (1) The inferior heavy oil is separated into light distillate oil and heavy distillate oil by a fractionating tower; (2) Optionally, carrying out a hydrotreating reaction on the light distillate oil obtained in the step (1) to obtain hydrotreating generated oil; (3) Contacting the heavy distillate oil obtained in the step (1) with alkali metal to perform alkali metal desulfurization reaction; (4) And (4) optionally mixing the liquid-phase product obtained by separating the material reacted in the step (3) with the oil generated by hydrotreating in the step (2) or mixing the liquid-phase product with the light-fraction oil in the step (1), and separating by a fractionating tower to obtain naphtha, diesel oil and wax oil. The method can convert the low-quality and cheap heavy oil into the high-quality raw material, and has simple process, safety and reliability.
Description
Technical Field
The invention relates to the field of heavy oil processing and utilization, in particular to a processing and treating method for inferior heavy oil.
Background
The heavy and inferior crude oil in the world is increasingly serious, and the market demand for light oil products is continuously increased, so that the hydrogenation of residual oil as an effective means for modifying and lightening the residual oil has become one of the development key points of the oil refining industry. The most common residue hydrogenation technologies currently used in industry include fixed bed technology and ebullated bed technology, wherein ebullated bed hydrogenation processes have the following advantages: heavy and poor raw materials with high metal content and high carbon residue value can be processed; the temperature of the reactor is easy to control and uniform, and the pressure drop is low and constant; the catalyst can be added and taken out on line, so that the performance of the catalyst can be kept constant in the whole operation period; higher conversion and longer operating cycle times can be achieved. But the boiling bed hydrogenation process also has obvious defects which are reflected in harsh process operation conditions, low reaction efficiency and poor product quality.
CN201310498832.6 discloses a residual oil hydrogenation method. The method is carried out in a fluidized bed reactor, a three-phase separation zone, a fluidized zone and a circulating zone are sequentially arranged in the fluidized bed reactor from top to bottom, and the residual oil hydrogenation method comprises the following steps: and injecting a first boiling bed hydrogenation catalyst from the upper part of the circulating zone, and injecting a second boiling bed hydrogenation catalyst and a suspended bed hydrogenation catalyst from the upper part of the boiling zone, so that the residual oil and the hydrogen are subjected to hydrogenation reaction in the boiling bed reactor. The suspension bed hydrogenation catalyst is mainly used for converting asphaltene, and is matched with the fluidized bed reactor to achieve the expected effect. The hydrogenation effect is not obvious when processing high-metal, high-nitrogen and high-viscosity residual oil.
CN02109674.0 discloses a cascade boiling bed residual oil hydrogenation method and equipment, wherein a microspherical hydrogenation demetalization, desulfurization and denitrification catalyst combination is used for residual oil hydrogenation reaction in more than two stages of cascade boiling bed reactors, so that the residual oil conversion rate and the product quality can be effectively improved. The cascade boiling bed reactor has several reaction sections with independent catalyst adding and discharging ports, and each section has material feeding distributing plate with float valve structure and triphase separating part comprising flow guide member, flow blocking member, gas-liquid isolating plate and foam breaker. The method uses the combination of microspheric hydrodemetallization, desulfurization and denitrification catalysts to carry out the residual oil hydrogenation reaction, but the combination of a plurality of catalysts has low reaction efficiency.
CN200810228406.X discloses a heavy hydrocarbon multi-stage fluidized bed hydrogenation method. The process comprises the steps that viscous heavy hydrocarbon raw materials and gas-phase material flows discharged by a fluidized bed hydrodesulfurization and hydrodenitrogenation reactor are mixed and enter a hydrodemetallization reactor, the reacted gas-phase material flows can be used as circulating hydrogen after being cooled and purified, and the liquid-phase material flows after the demetalization reaction and hydrogen are mixed and enter the fluidized bed hydrodesulfurization reactor; mixing the liquid-phase material flow after the desulfurization reaction with hydrogen to enter a hydrodenitrogenation reactor; and (4) feeding the liquid phase material flow after denitrification reaction into a separation device. The process adopts a new reactor combination mode to process the high-viscosity inferior heavy oil raw material, can provide a new flexible, high-efficiency and energy-saving operation mode, organically combines the performance of the raw material with each hydrogenation reaction characteristic, fully utilizes the reaction heat release on the premise of ensuring the stable operation of the device, provides high-quality product quality, and can flexibly adjust the operation process according to the requirements of a refinery. But this process has limited ability to process high metal content feedstocks.
The alkali metal reacts with a part of the heteroatom and/or one or more heavy metals, i.e. the alkali metal desulfurization method, can improve the quality of the raw materials, but the reaction process of the method has low efficiency at present, particularly the utilization rate of the alkali metal is not high, the product contains unreacted alkali metal, and the unreacted alkali metal in the product needs to be further treated subsequently. How to realize the efficient application of the alkali metal desulfurization technology is a difficult problem to be overcome urgently in the field of oil refining.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the method for processing the inferior heavy oil, which can convert the inferior and cheap heavy oil into the high-quality raw material and has simple process, safety and reliability.
The invention relates to a processing method of inferior heavy oil, which comprises the following steps:
(1) The inferior heavy oil is separated into light distillate oil and heavy distillate oil by a fractionating tower;
(2) Optionally, carrying out a hydrotreating reaction on the light distillate oil obtained in the step (1) to obtain hydrotreating generated oil;
(3) Contacting the heavy distillate oil obtained in the step (1) with alkali metal to perform alkali metal desulfurization reaction;
(4) And (3) optionally mixing the liquid-phase product obtained by separating the material reacted in the step (3) with the oil generated by the hydrotreating in the step (2) or mixing the liquid-phase product with the light fraction oil in the step (1), and separating the mixture by a fractionating tower to obtain naphtha, diesel oil and wax oil.
In the method, the poor-quality heavy oil in the step (1) contains at least one carbon atom and heteroatom and/or one or more heavy metals.
In the method, the inferior heavy oil in the step (1) is one or more of straight-run wax oil, shale oil, jiao Huala oil and the like, the dry point of the inferior heavy oil is generally 500 to 600 ℃, the sulfur content is generally more than 1.0wt%, preferably 1.0 to 5.0wt%, and the metal content is generally more than 40mg g -1 Preferably 70 to 1200 mg/g -1 。
In the method, the cutting point for separating the light distillate oil and the heavy distillate oil in the step (1) is generally 320 to 400 ℃, and preferably 340 to 375 ℃.
In the method, the operation conditions of the hydrogenation treatment reaction in the step (2) are mild compared with those of a conventional hydrogenation treatment device, and the reaction temperature is generally 260-390 ℃, preferably 300-370 ℃; the reaction pressure is generally 3.0 to 14.0MPa, preferably 4.0 to 8.0MPa; the hydrogen-oil volume ratio is generally 200 to 3000, preferably 300 to 1500; the liquid hourly volume space velocity is generally 0.1-5.0 h -1 Preferably 0.6 to 3.0h -1 。
In the method of the present invention, the catalyst used in the hydrotreating reaction in step (2) is a hydrotreating catalyst conventional in the art, wherein the active metal component of the catalyst may be one or more of nickel, cobalt, molybdenum or tungsten. For example, the catalyst composition may include (in weight percent calculated as oxides): the content of nickel or cobalt is generally 0.1-18%, preferably 1-12%; molybdenum or tungsten is generally 2% to 28%, preferably 5% to 25%. The carrier can be one or more of alumina, silica, alumina-silica or titanium oxide. The catalyst can be in the form of common clover, cylindrical bar, sphere, tooth sphere, etc., and has bulk density of 0.3kg/m 3 ～1.1kg/m 3 Preferably 0.5kg/m 3 ～0.9kg/m 3 . The catalyst particles generally have a diameter of from 0.05mm to 3.0mm, preferably from 0.08mm to 1.5mm. The specific surface area of the catalyst is generally 80m 2 /g～250m 2 A ratio of/g, preferably 100m 2 /g～220m 2 /g。
In the method, part or all of the heavy distillate oil obtained in the step (2) in the hydrotreating generated oil synchronous step (1) is mixed and then contacted with alkali metal to carry out alkali metal desulfurization reaction, and the mixing mass ratio of the hydrotreating generated oil and the heavy distillate oil is preferably 1:9 to 3:7, more preferably 1: 9-2: 8.
in the method, the alkali metal desulfurization reaction is carried out in the presence of an auxiliary agent, wherein the auxiliary agent is condensed aluminum phosphate and a silicon phosphate curing agent; the condensed aluminum phosphate can be one or more of aluminum tripolyphosphate, modified aluminum tripolyphosphate and aluminum dihydrogen tripolyphosphate; the mass ratio of the condensed aluminum phosphate to the silicon phosphate curing agent is 1:9 to 9:1, preferably 4: 6-6: 4; the mass ratio of the auxiliary agent to the heavy distillate oil in the step (1) is 0.5:99.5 to 3.0:97.0, preferably 1.0:99.0 to 2.5:97.5.
in the method, the auxiliary agent can be added into the heavy distillate before or simultaneously with the addition of the alkali metal, the addition of the auxiliary agent before the addition of the alkali metal is not limited in the following mode, and the heavy distillate is mixed with the auxiliary agent and then contacted with the alkali metal to carry out alkali metal desulfurization reaction or the heavy distillate, the hydrotreating generated oil and the auxiliary agent are mixed and then contacted with the alkali metal to carry out alkali metal desulfurization reaction or the heavy distillate.
In the method, the auxiliary agent is firstly mixed with part of the light fraction oil in the step (1) or mixed with part of the oil generated by hydrotreating in the step (2), and then mixed with the heavy fraction oil in the step (1) and then contacted with alkali metal for alkali metal desulfurization reaction. The mixing conditions of the heavy distillate oil are as follows: the reaction pressure is generally 4.0MPa to 10.0MPa, and is preferably consistent with the pressure of the alkali metal desulfurization reactor; the reaction temperature is generally from 150 ℃ to 300 ℃ and preferably from 200 ℃ to 260 ℃.
In the method of the present invention, the alkali metal desulfurization reaction in step (3) is carried out under the action of a hydrogen donor, which is a substance containing at least one hydrogen atom, preferably hydrogen gas or a substance containing at least one carbon atom and at least one hydrogen atom.
In the method of the invention, the alkali metal desulfurization reaction in the step (3) is carried out under the action of a hydrogen donor, wherein the hydrogen donor is hydrogen or a lower hydrocarbon, and the lower hydrocarbon is methane, ethane, propane, butane, pentane, ethylene, propylene, butylene, pentene, diene, isomers of the foregoing substances and/or a mixture of the foregoing substances.
In the method, the alkali metal in the step (3) is one or more of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr).
In the method, the proportion of heavy fraction metals in the step (3) is determined according to the content of sulfur in the heavy fraction oil, the mass ratio of the addition amount of alkali metals to the content of sulfur in the heavy fraction oil is 0.5-2.0: 1, preferably 0.9 to 1.5:1.
in the method of the invention, the alkali metal desulfurization reaction in the step (3) is carried out under the action of a hydrogen donor, wherein the amount of the hydrogen donor is determined according to the sulfur content in the heavy fraction raw material, and is generally 1.0-3.0 mol of hydrogen per mol of sulfur, and preferably 1.5-2.5 mol of hydrogen per mol of sulfur.
In the method of the present invention, the operation pressure of the alkali metal desulfurization reaction in the step (3) is generally 4.0 to 10.0Mpa, preferably 5.0 to 8.0Mpa; the reaction temperature is generally from 220 ℃ to 430 ℃ and preferably from 310 ℃ to 380 ℃.
In the method of the present invention, the reaction material obtained in step (3) is preferably subjected to a stabilization treatment and then separated, the stabilization operation condition is consistent with that of the alkali metal desulfurization reaction, and the stabilization time is generally 1h to 6h, preferably 2h to 3h.
In the method of the present invention, the separation in step (4) may be one or more of cyclone separation, centrifugal separation, extraction separation, filtration separation, and sedimentation separation. In one or more embodiments of the invention, cyclonic separation is used, which is known as a cyclone separator with cyclonic and separation functions, and which is typically operated at a temperature of from 150 ℃ to 380 ℃, preferably from 200 ℃ to 330 ℃.
In the method, the fractionating tower in the step (1) or the fractionating tower in the step (4) is a conventional fractionating tower or a conventional fractionating system in the field, and can be flexibly adjusted according to the product requirement so as to meet the actual production requirement.
Compared with the prior art, the method has the advantages that:
(1) The method realizes the processing treatment of the inferior heavy oil under the particularly mild operating condition, improves the raw material adaptability of the whole technology, and effectively prolongs the operating period of the device;
(2) The method adds the auxiliary agent in the process of the alkali metal desulfurization reaction, properly promotes the polymerization reaction of macromolecular components, accelerates the separation effect of the macromolecule which is difficult to react and the lighter components, is favorable for the contact of sodium metal and the lighter components, and improves the sodium desulfurization effect.
Drawings
FIG. 1 is a flow chart of the present invention for processing inferior heavy oil.
Wherein, raw oil 1, fractionating tower 2, light fraction raw material 3, heavy fraction raw material 4, auxiliary agent 5, stirred tank 6, modified hydrotreating produced oil 7, stirred tank 8, heavy fraction raw material 9, alkali metal 10, hydrogen donor 11, stirred tank reactor 12, stirred tank reactor 13, hydrotreating reactor 14, hydrotreating produced oil 15, separating tower 16, solid mixture of alkali metal sulfide and metal 17, liquid phase product 18, fractionating tower 19, naphtha 20, diesel oil 21, wax oil 22 and hydrogen 23.
FIG. 2 is another flow chart of the present invention for processing inferior heavy oil.
Wherein, raw material oil 1, fractionating tower 2, light fraction raw material 3, heavy fraction raw material 4, auxiliary agent 5, stirring kettle 6, modified light fraction raw material 7, stirring kettle 8, heavy fraction raw material 9, alkali metal 10, hydrogen donor 11, stirring kettle reactor 12, stirring kettle reactor 13 to generate oil, separation tower 14, solid mixture of alkali metal sulfide and metal 15, liquid phase product 16, fractionating tower 17, naphtha 18, diesel oil 19 and wax oil 20.
Detailed Description
The method of the present invention will be described in detail below with reference to the accompanying drawings.
FIG. 1:
The method for processing inferior heavy oil according to the present invention will be further described by the following specific examples. The examples are merely illustrative of specific embodiments of the process of the present invention and do not limit the scope of the invention.
Examples 1 to 2
Raw oil is separated into light fraction raw material and heavy fraction raw material by a fractionating tower with 360 ℃ as a cutting point; the light fraction raw material and hydrogen gas enter a hydrotreater together, and hydrotreatment reactions such as hydrodesulfurization, hydrodenitrogenation and the like are carried out under mild operation conditions to obtain hydrotreatment generated oil; the heavy fraction raw material and metal sodium enter a stirring reactor together, reactions such as hydrodeoxygenation, hydrodemetallization, hydrodesulfurization and the like are carried out under the action of hydrogen, and the obtained material is separated by a cyclone separator to obtain a liquid-phase product, a solid mixture of sodium sulfide, metal and the like; the liquid phase product and the oil generated by the hydrotreatment enter a fractionating tower to be fractionated, and products such as naphtha, diesel oil, wax oil and the like are obtained.
Examples 3 to 4
Raw oil is separated into light fraction raw material and heavy fraction raw material by a fractionating tower with 375 ℃ as a cutting point; the light fraction raw material and hydrogen gas enter a hydrotreatment device together, and hydrotreatment reactions such as hydrodesulfurization, hydrodenitrogenation and the like are carried out under mild operation conditions to obtain hydrotreatment generated oil; stirring and mixing part of the hydrotreating produced oil, aluminum tripolyphosphate and a silicon phosphate curing agent (the ratio is 3: 9; the heavy fraction raw material and metal sodium enter a stirring reactor together, reactions such as hydrodeoxygenation, hydrodemetallization, hydrodesulfurization and the like are carried out under the action of methane, and the obtained material is separated by a cyclone separator to obtain a liquid-phase product, a solid mixture such as sodium sulfide, metal and the like; the liquid phase product and the oil generated by the hydrotreatment enter a fractionating tower to be fractionated, and products such as naphtha, diesel oil, wax oil and the like are obtained.
Comparative examples 1 to 2
The conventional wax oil hydrotreating process is used for carrying out the hydrodemetallization, hydrodesulfurization and hydrodenitrogenation reactions of inferior heavy oil. The raw materials and hydrogen are mixed and then enter a fixed bed wax oil hydrotreating reactor, and the reacted material flow is discharged from the bottom of the reactor and enters a separation and fractionation system to obtain naphtha, diesel oil, wax oil and heavy wax oil.
The properties of the feedstock oils used in examples 1 to 4 and comparative examples 1 to 2 are shown in Table 1, the properties of the catalysts used in examples 1 to 4 and comparative examples 1 to 2 are shown in Table 2, the operating conditions of examples 1 to 4 and comparative examples 1 to 2 are shown in Table 3, and the properties of the products of examples 1 to 4 and comparative examples 1 to 2 are shown in Table 4.
TABLE 1 Properties of the stock oils
TABLE 2 catalyst Properties
TABLE 3
TABLE 4 results of refined wax oils as main products of examples 1 to 4 and comparative examples 1 to 2
FIG. 2 is a drawing:
The method for simply hydrotreating inferior heavy oil of the present invention will be further described by the following specific examples. The examples are merely illustrative of specific embodiments of the process of the present invention and do not limit the scope of the invention.
Examples 5 to 6
Raw oil is separated into light fraction raw material and heavy fraction raw material by a fractionating tower with 360 ℃ as a cutting point; the heavy fraction raw material and metal sodium enter a stirring reactor together, reactions such as hydrodeoxygenation, hydrodemetallization, hydrodesulfurization and the like are carried out under the action of hydrogen, and the obtained material is separated by a cyclone separator to obtain a liquid-phase product, a solid mixture such as sodium sulfide, metal and the like; the liquid phase product and the light fraction raw material enter a fractionating tower together for fractionation to obtain naphtha, diesel oil, wax oil and other products.
Examples 7 to 8
Raw oil is separated into light fraction raw material and heavy fraction raw material by a fractionating tower with 375 ℃ as a cutting point; stirring and mixing part of the light fraction raw material, aluminum tripolyphosphate and a silicon phosphate curing agent (ratio 2: 9; the heavy fraction raw material and metal sodium enter a stirring reactor together, reactions such as hydrodeoxygenation, hydrodemetallization, hydrodesulfurization and the like are carried out under the action of methane, and the obtained material is separated by a cyclone separator to obtain a liquid-phase product, a solid mixture such as sodium sulfide, metal and the like; the liquid phase product and the light fraction raw material enter a fractionating tower together for fractionation to obtain products such as naphtha, diesel oil, wax oil and the like.
Comparative example 3
In comparative example 3, which is consistent with the flow of the invention in examples 3 and 4, raw oil is separated into light fraction raw material and heavy fraction raw material by a fractionating tower with 375 ℃ as a cutting point; the light fraction raw material and hydrogen gas enter a hydrotreatment device together, and hydrotreatment reactions such as hydrodesulfurization, hydrodenitrogenation and the like are carried out under mild operation conditions to obtain hydrotreatment generated oil; the heavy fraction raw material and metal sodium enter a stirring reactor together, reactions such as hydrodeoxygenation, hydrodemetallization, hydrodesulfurization and the like are carried out under the action of methane, and the obtained material is separated by a cyclone separator to obtain a liquid-phase product, a solid mixture such as sodium sulfide, metal and the like; the liquid phase product and the oil generated by the hydrotreatment enter a fractionating tower to be fractionated, and products such as naphtha, diesel oil, wax oil and the like are obtained.
The properties of the feedstock oils used in examples 5 to 8 and comparative example 3 are shown in Table 1, the properties of the catalysts used in examples 5 to 8 and comparative example 3 are shown in Table 2, the operating conditions of examples 5 to 8 and comparative example 3 are shown in Table 5, and the properties of the products of examples 5 to 8 and comparative example 3 are shown in Table 6.
TABLE 5 operating conditions for examples 5 to 8 and comparative example 3
TABLE 6 results of refined wax oils as main products of examples 5 to 8 and comparative example 3
Claims (13)
1. A method for processing inferior heavy oil comprises the following steps:
(1) The inferior heavy oil is separated into light distillate oil and heavy distillate oil by a fractionating tower;
(2) Optionally, carrying out a hydrotreating reaction on the light distillate oil obtained in the step (1) to obtain hydrotreating generated oil;
(3) Contacting the heavy fraction oil obtained in the step (1) with alkali metal to perform alkali metal desulfurization reaction;
(4) Optionally mixing the liquid-phase product obtained by separating the material reacted in the step (3) with the oil generated by the hydrotreating in the step (2) or the light fraction oil obtained in the step (1), and separating the mixture by a fractionating tower to obtain naphtha, diesel oil and wax oil;
the inferior heavy oil in the step (1) contains at least one carbon atom and heteroatom and/or one or more heavy metals, the inferior heavy oil is one or more of straight-run wax oil, shale oil and coking wax oil, the dry point of the inferior heavy oil is 500-600 ℃, the sulfur content is more than 1.0wt%, and the metal content is more than 40mg g -1 ；
In the step (3), the alkali metal desulfurization reaction is carried out in the presence of an auxiliary agent, the auxiliary agent is condensed aluminum phosphate and a silicon phosphate curing agent, the condensed aluminum phosphate is one or more of aluminum tripolyphosphate, modified aluminum tripolyphosphate and aluminum dihydrogen tripolyphosphate, and the mass ratio of the condensed aluminum phosphate to the silicon phosphate curing agent is 1:9 to 9:1, the mass ratio of the auxiliary agent to the heavy distillate oil in the step (1) is 0.5:99.5 to 3.0:97.0, the alkali metal desulfurization reaction is carried out under the action of a hydrogen donor, the hydrogen donor is a substance containing at least one hydrogen atom, and the mass ratio of the addition amount of the alkali metal to the sulfur content in the heavy distillate oil is 0.5-2.0: 1, the dosage of the hydrogen donor is determined according to the sulfur content in the heavy fraction raw material, calculated by hydrogen, the dosage is 1.0-3.0 mol of hydrogen per mol of sulfur, and the operating pressure of the alkali metal desulfurization reaction is 4.0-10.0 MPa; the reaction temperature is 220-430 ℃.
2. The method of claim 1, wherein: the cutting point of the separation of the light distillate oil and the heavy distillate oil in the step (1) is 320-400 ℃.
3. The method of claim 1, wherein: the hydrogenation reaction conditions in the step (2) are as follows: the reaction temperature is 260-390 ℃; the reaction pressure is 3.0-14.0 MPa; the volume ratio of hydrogen to oil is 200;the liquid hourly space velocity is 0.1-5.0 h -1 。
4. The method of claim 1, wherein: and (3) mixing part or all of the heavy fraction oil obtained in the hydrotreating generated oil obtained in the step (2) and then contacting with alkali metal to perform alkali metal desulfurization reaction, wherein the mixing mass ratio of the hydrotreating generated oil to the heavy fraction oil is 1:9 to 3:7.
5. the method of claim 1, wherein: the auxiliary agent is added to the heavy distillate before or simultaneously with the addition of the alkali metal.
6. The method of claim 5, wherein: the heavy distillate oil is mixed with an auxiliary agent and then contacted with alkali metal to carry out alkali metal desulfurization reaction, or the heavy distillate oil, the hydrotreating generated oil and the auxiliary agent are mixed and then contacted with the alkali metal to carry out alkali metal desulfurization reaction.
7. The method of claim 1, wherein: the auxiliary agent is firstly mixed with part of the light fraction oil in the step (1) or mixed with part of the oil generated by hydrotreating in the step (2), and then mixed with the heavy fraction oil in the step (1) and then contacted with alkali metal to carry out alkali metal desulfurization reaction.
8. The method of claim 7, wherein: the mixing conditions of the heavy distillate oil in the same step (1) are as follows: the reaction pressure is 4.0 MPa-10.0 MPa; the reaction temperature is 150-300 ℃.
9. The method of claim 1, wherein: and (3) carrying out alkali metal desulfurization reaction under the action of a hydrogen donor, wherein the hydrogen donor is hydrogen or low-carbon hydrocarbon, and the low-carbon hydrocarbon is methane, ethane, propane, butane, pentane, ethylene, propylene, butylene, pentene, diene or a mixture thereof.
10. The method of claim 1, wherein: in the step (3), the alkali metal is one or more of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr).
11. The method of claim 1, wherein: and (4) separating the reaction material obtained in the step (3) after stabilizing treatment, wherein the stabilizing treatment condition is consistent with the alkali metal desulfurization reaction operating condition, and the stabilizing time is 1-6 h.
12. The method of claim 1, wherein: the separation in the step (4) adopts one or more of cyclone separation, centrifugal separation, extraction separation, filtration separation and sedimentation separation.
13. The method of claim 1, wherein: the separation in the step (4) adopts cyclone separation, and the operating temperature of the cyclone separation is 150-380 ℃.
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| CN101117596A (en) * | 2006-07-31 | 2008-02-06 | 中国石油化工股份有限公司 | Hydrogenation method capable of producing diesel oil and chemical materials flexibly |
| CN101684417A (en) * | 2008-09-27 | 2010-03-31 | 中国石油化工股份有限公司 | Optimized hydrogenation-catalytic cracking combination process |
| CN111378491A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Inferior heavy oil hydrotreating process |
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| CN101117596A (en) * | 2006-07-31 | 2008-02-06 | 中国石油化工股份有限公司 | Hydrogenation method capable of producing diesel oil and chemical materials flexibly |
| CN101684417A (en) * | 2008-09-27 | 2010-03-31 | 中国石油化工股份有限公司 | Optimized hydrogenation-catalytic cracking combination process |
| CN111378491A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Inferior heavy oil hydrotreating process |
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