CN112625744B - System and method for comprehensively utilizing oil products - Google Patents

System and method for comprehensively utilizing oil products Download PDF

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Publication number
CN112625744B
CN112625744B CN201910947922.6A CN201910947922A CN112625744B CN 112625744 B CN112625744 B CN 112625744B CN 201910947922 A CN201910947922 A CN 201910947922A CN 112625744 B CN112625744 B CN 112625744B
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aromatic hydrocarbon
solvent
oil
eutectic solvent
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CN112625744A (en
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宋奇
郑均林
孔德金
姜向东
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • C10G67/0409—Extraction of unsaturated hydrocarbons
    • C10G67/0418—The hydrotreatment being a hydrorefining
    • 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
    • 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
    • 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
    • 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
    • C10G2300/44—Solvents
    • 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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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a system and a method for comprehensively utilizing oil products in the field of petrochemical industry. The system comprises a hydrofining unit, a non-aromatic hydrocarbon and aromatic hydrocarbon separation unit and an aromatic hydrocarbon conversion unit; wherein the non-aromatics and aromatics separation unit comprises a secondary unit: A. the unit B is an aromatic hydrocarbon separation unit A and an aromatic hydrocarbon removal unit B respectively; one outlet of the hydrofining unit is connected with one inlet of the unit A, one outlet of the unit A is connected with one inlet of the unit B, and one outlet of the unit B is connected with one inlet of the aromatic hydrocarbon conversion unit. By adopting the system, non-aromatic hydrocarbon of oil products after hydrofining can be separated, secondary conversion is avoided, the separated aromatic hydrocarbon can be further converted, light hydrocarbon and light aromatic hydrocarbon are obtained, and the conversion efficiency is high.

Description

System and method for comprehensively utilizing oil products
Technical Field
The invention relates to the field of petrochemical industry, in particular to a system and a method for comprehensively utilizing oil products.
Background
The quality of oil products such as coking gasoline diesel oil, catalytic diesel oil, heavy diesel oil and the like is poor, and the oil products can be used by further conversion. With the top of gasoline and diesel consumption, the conversion of the oil products into aromatic hydrocarbons is an important conversion route. And the oil product is directly converted, and the non-aromatic hydrocarbon is subjected to hydrocracking again, so that hydrogen is excessively consumed, and the catalyst occupies an active site, so that carbon deposition of the catalyst is possibly inactivated, and the service life of the catalyst is reduced. Thus, separation of the heavy oil prior to hydrocracking can greatly improve efficiency.
The separation of aromatic hydrocarbons from non-aromatic hydrocarbons is an important step in industrial production. The solvent extraction and extraction rectification technology developed in the existing industry has better separation effect and is widely applied, but has the problems of high energy consumption, easy deterioration of the extraction solvent, easy corrosion of the device and the like, and has still room for improvement in the technology. In addition, the effective separation of non-aromatic hydrocarbons in aromatic hydrocarbons has important significance for the upgrading of oil products and the improvement of enterprise benefits.
The Deep Eutectic Solvent (DES) is used as a novel green solvent, has the properties similar to those of ionic liquid, extremely low volatility and stable physical properties, and shows excellent dissolving and separating capacity for various organic mixture systems. The eutectic solvent used in the separation process is generally formed by hydrogen bond interaction between a hydrogen bond acceptor (such as organic salt choline chloride, quaternary ammonium salt, quaternary phosphonium salt and the like) and a hydrogen bond donor (such as urea, hexanediol, sorbitol, butanediol, malic acid, amino acid, glucose and the like), and therefore has strong polarity. Eutectic solvents can also achieve a certain specific functional property by designing different combinations of hydrogen bond acceptors and hydrogen bond donors. Compared with the traditional ionic liquid, the eutectic solvent generally has polarity, is simple to prepare, has weak corrosivity, and can be biodegraded. Due to the excellent characteristics, the eutectic solvent has the tendency of replacing the traditional organic solvent and ionic liquid for chemical separation, has good application prospect in the extraction and separation of aromatic hydrocarbon and alkane mixtures, and is greatly concerned. For example, tetraethylammonium chloride has been reported in the literature as a DES with levulinic acid and ethylene glycol and is used to separate toluene/heptane mixed systems (Wang Y, Hou Y C, Wu W Z, et al. circles of a hydrogen bond and a hydrogen bond acceptor in the extraction of a toluene from n-heptane using depleted electrolytic solutions. Green Chemistry,2016,18:3089 and 3097.) the authors found that shorter alkyl chains on quaternary ammonium salts are more advantageous for separating toluene. Chinese patent publication No. CN 107311833A describes the separation of toluene/cyclohexane systems using DES of tetrabutylammonium bromide with levulinic acid or ethylene glycol. But the eutectic solvent is used as an extracting agent to operate in a batch rectifying tower, and cannot continuously operate.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a system for comprehensively utilizing oil products. In particular to a system and a method for comprehensively utilizing oil products. According to the technical scheme, non-aromatic hydrocarbon is separated by using a eutectic solvent after hydrofining, and aromatic hydrocarbon is enriched. And taking out the non-aromatic hydrocarbon, and selling the non-aromatic hydrocarbon as solvent oil or blending the solvent oil into gasoline and diesel oil to blend oil products. The conversion of the enriched aromatic hydrocarbon is more targeted, and the economy can be improved.
One of the purposes of the invention is to provide a system for comprehensively utilizing oil products, which can comprise a hydrofining unit, a non-aromatic hydrocarbon and aromatic hydrocarbon separation unit and an aromatic hydrocarbon conversion unit; wherein the non-aromatics and aromatics separation unit comprises a secondary unit: A. the unit B is an aromatic hydrocarbon separation unit A and an aromatic hydrocarbon removal unit B respectively;
an outlet of the hydrofining unit is connected with an inlet of the unit A, an outlet of the unit A is connected with an inlet of the unit B, and an outlet of the unit B is connected with an inlet of the aromatic hydrocarbon conversion unit;
passing the oil product through a hydrofining unit to obtain a non-aromatic hydrocarbon and aromatic hydrocarbon material flow;
respectively introducing the eutectic solvent and the non-aromatic hydrocarbon and aromatic hydrocarbon material flows into a unit A, extracting the non-aromatic hydrocarbon obtained after liquid-liquid extraction, and simultaneously introducing the obtained eutectic solvent carrying aromatic hydrocarbon into a unit B;
and injecting a second solvent into the top of the aromatic hydrocarbon removal unit B, extracting the obtained aromatic hydrocarbon after the eutectic solvent carrying aromatic hydrocarbon enters the unit B and is mixed with the second solvent, and simultaneously enabling the obtained mixture flow of the eutectic solvent and the second solvent to flow out of the unit B.
And non-aromatic hydrocarbon components are extracted from the top of the separation tower A, and the extraction position can be adjusted randomly according to needs.
Preferably, the first and second electrodes are formed of a metal,
and the extracted aromatic hydrocarbon enters the aromatic hydrocarbon conversion unit to react to obtain light aromatic hydrocarbon and low-carbon alkane. The non-aromatic and aromatic separation unit may further comprise a secondary unit C unit, the C unit being a eutectic solvent regeneration unit; an outlet of the unit B is connected with an inlet of the unit C; one outlet of the unit C is connected with one inlet of the unit A, and the other outlet of the unit C is connected with one inlet of the unit B;
and the mixed material flow of the eutectic solvent and the second solvent flowing out of the unit B enters the unit C, the eutectic solvent obtained after the second solvent is removed is recycled and returned to the unit A for recycling, and the second solvent obtained after the removal can be recycled and returned to the unit B for recycling.
The oil product can be one or more of dead weight gasoline, light diesel oil, catalytic diesel oil, heavy diesel oil, coking gasoline and coking diesel oil; the non-aromatic hydrocarbon in the oil product can comprise at least one of straight-chain, branched-chain alkane and cyclane of C1-C20.
The eutectic solvent can comprise a hydrogen bond acceptor and a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor can be 1: 0.1-1: 20, and the eutectic solvent is optimized to be 1: 0.5-1: 8;
wherein the content of the first and second substances,
the hydrogen bond acceptor can be selected from at least one of tetraethyl ammonium halide, tetrabutyl ammonium halide, choline chloride, betaine, methyl triethyl ammonium halide, tetraphenyl phosphonium halide, methyl triphenyl phosphonium halide, ethyl triphenyl phosphonium halide and butyl triphenyl phosphonium halide; preferably at least one of tetraethyl ammonium halide, tetrabutyl ammonium halide, methyltriethyl ammonium halide, tetraphenyl phosphonium halide, methyltriphenyl phosphonium halide, ethyltriphenyl phosphonium halide and butyltriphenyl phosphonium halide. Wherein the halide is one of fluoride, chloride, bromide and iodide;
the hydrogen bond donor can be selected from at least one of tributyl phosphate, dimethylformamide, morpholine, urea, citric acid, succinic acid, propionic acid, acetic acid, ethylene glycol, propylene glycol, glycerol, xylitol, glucose, levulinic acid, oxalic acid and lactic acid, and preferably is at least one of ethylene glycol, propylene glycol, levulinic acid, tributyl phosphate, dimethylformamide, succinic acid, lactic acid and propionic acid.
The preparation method of the eutectic solvent may include the steps of:
and mixing and stirring the hydrogen bond acceptor and the hydrogen bond donor according to the using amount at 0-180 ℃, wherein the preferable temperature range is 20-120 ℃, and the more preferable temperature range is 20-90 ℃.
The second purpose of the invention is to utilize the system to carry out the oil product comprehensive utilization method, which comprises the following steps:
passing an oil product to be extracted through a hydrofining unit to obtain a non-aromatic hydrocarbon and aromatic hydrocarbon material flow;
respectively introducing the eutectic solvent and the non-aromatic hydrocarbon and aromatic hydrocarbon material flows into a unit A, extracting the non-aromatic hydrocarbon through liquid-liquid extraction, and simultaneously introducing the obtained eutectic solvent carrying aromatic hydrocarbon into a unit B;
injecting a second solvent into the top of the removing tower B of the eutectic solvent, enabling the eutectic solvent to carry aromatic hydrocarbon to enter a unit B and further mix with the second solvent, extracting the obtained aromatic hydrocarbon, and enabling the obtained mixture flow of the eutectic solvent and the second solvent to flow out of the unit B; and the obtained aromatic hydrocarbon enters the aromatic hydrocarbon conversion unit to react to obtain light aromatic hydrocarbon and low-carbon alkane. Wherein the injection volume of the second solvent is 0.2-10 times of the volume of the eutectic solvent entering the tower, and preferably 0.5-5 times.
Preferably, the second solvent may be selected from one or more of water, ethyl acetate, butyl acetate and methanol.
And the mixed material flow of the eutectic solvent and the second solvent flowing out of the unit B enters the unit C, the eutectic solvent obtained after the second solvent is removed can be recycled and returned to the unit A, and the second solvent obtained after the removal can be recycled and returned to the unit B for recycling.
More preferably, the method comprises the steps of:
1) the oil product is subjected to a hydrofining unit to obtain a mixed material flow of non-aromatic hydrocarbon and aromatic hydrocarbon;
2) introducing a eutectic solvent into a separation tower A through the upper side of the tower, introducing a mixture flow of non-aromatic hydrocarbon and aromatic hydrocarbon into the separation tower A through the lower side of the separation tower A, enriching the non-aromatic hydrocarbon at the top of the tower after liquid-liquid extraction, and then extracting the enriched non-aromatic hydrocarbon, wherein the eutectic solvent carries the aromatic hydrocarbon and enters an aromatic hydrocarbon separation unit B through the bottom of the tower;
3) after the material flow entering the aromatic hydrocarbon separation unit B is mixed with a second solvent, the aromatic hydrocarbon is extracted from the tower top 4 and enters an aromatic hydrocarbon conversion utilization unit R2 hydrocracking reactor; the eutectic solvent carries a second solvent to enter a regeneration unit separation tower C through the tower bottom;
4) the eutectic solvent at the bottom of the tower enters a regeneration unit, is subjected to second solvent removal and then is recycled and returned to the separation tower A of the non-aromatic hydrocarbon removal unit, so that the recycling of the eutectic solvent is realized;
5) the aromatic hydrocarbon reacts in a hydrocracking reactor R2 to obtain light aromatic hydrocarbon and light alkane.
Wherein the content of the first and second substances,
the overhead pressure of the unit A, the unit B and the unit C can be 20-1500 kPa, the preferable range of the pressure of the unit A and the unit B is 900-250 kPa, and the preferable range of the pressure of the unit C is 20-900 kPa.
The temperature of the unit A can be 10-120 ℃, preferably 10-100 ℃, and more preferably 10-60 ℃.
The temperature of the unit B can be 10-100 ℃, and preferably 10-50 ℃.
The temperature of the C unit can be 10-300 ℃, preferably 20-200 ℃, and more preferably 60-150 ℃.
The volume ratio of the eutectic solvent to the oil to be extracted can be 1/0.2-1/50, preferably 1/0.2-1/20, further preferably 1/0.2-1/10, and more preferably 1/0.2-1/5.
The catalyst used in the hydrofining unit is a conventional hydrofining catalyst, and the reaction conditions can include: the volume ratio of hydrogen to oil is 500-3000 Nm 3 /m 3 Preferably 800 to 2000Nm 3 /m 3 More preferably 1000 to 1500Nm 3 /m 3 (ii) a And/or:
the inlet temperature of the reactor is 280-420 ℃, preferably 300-410 ℃, and more preferably 310-390 ℃; and/or:
the hydrogen partial pressure is 5-10 MPa, preferably 5-8 MPa, and more preferably 6-7 MPa; and/or:
the airspeed is 0.5-2.0 hours -1 Preferably 0.6 to 1.5 hours -1 More preferably 0.8 to 1.2 hours -1 。
The aromatic hydrocarbon conversion catalyst used in the aromatic hydrocarbon conversion unit may comprise the following components in parts by weight:
a 2 ) 5-80 parts of solid acid zeolite;
b 2 )0.05 to 8 parts of a group VIII metal;
c 2 ) 3-25 parts of a group VIB metal oxide;
d 2 ) 0.1-2 parts of a group VIB metal sulfide;
e 2 ) 20-95 parts of a first binder;
wherein the content of the first and second substances,
the solid acid zeolite may be selected from at least one of mordenite, beta zeolite, ZSM zeolite, EU-1 zeolite, SAPO zeolite, and Y zeolite;
the group VIII metal may be selected from at least one of platinum, palladium, cobalt, nickel and iridium;
the group VIB metal oxide may be selected from at least one of molybdenum oxide and tungsten oxide;
the group VIB metal sulfide can be selected from at least one of molybdenum sulfide and tungsten sulfide;
the first binder may be selected from binders commonly used in the art, such as at least one of free alumina, silica-alumina composite, titania-alumina composite, and magnesia-alumina composite. Preferably, the free alumina can refer to a macroporous alumina carrier disclosed in chinese patent 106669850a (application No. 201510761554.8); the silica-alumina composite can be prepared by a preparation method in a reference document (c.l. gutzeit, n.j. woodbury, US patent 2,735,801, assembled to soony, mobile oil company, inc.1956), the titania-alumina composite can be prepared by a preparation method of a titania/alumina composite oxide in chinese patent CN 101204671a (application No. 200610165596.6), and the magnesia-alumina composite can be prepared by a preparation method of a magnesia-alumina composite catalyst in chinese patent No. 109420482A (application No. CN 201710792805.8).
Wherein the reaction conditions of the aromatic conversion unit may include:
the volume ratio of hydrogen to oil is 800-5000 Nm 3 /m 3 Preferably 1000 to 4000Nm 3 /m 3 More preferably 1500 to 3000Nm 3 /m 3 (ii) a And/or:
the inlet temperature of the reactor is 280-450 ℃, preferably 300-430 ℃, and more preferably 310-400 ℃; and/or:
the hydrogen partial pressure is 5-10 MPa, preferably 5-9 MPa, and more preferably 6-8 MPa; and/or:
airspeed of 0.5-2.0Hour(s) -1 Preferably 0.6 to 1.5 hours -1 More preferably 0.8 to 1.2 hours -1 。
After the oil product passes through the hydrofining unit, the non-aromatic hydrocarbon is separated by the non-aromatic hydrocarbon removing unit and non-aromatic hydrocarbon is obtained, the non-aromatic hydrocarbon can be directly blended with the oil product or directly sold, the invalid secondary conversion of the non-aromatic hydrocarbon entering the aromatic hydrocarbon converting unit is avoided, and the economical efficiency of the whole process can be improved. Aromatic hydrocarbon in the raw material is enriched, so that the later concentrated conversion of the aromatic hydrocarbon is facilitated, and meanwhile, an aromatic hydrocarbon catalyst with high pertinence can be used without considering the conversion of non-aromatic hydrocarbon, so that the pertinence of the whole aromatic hydrocarbon conversion process and the process comprehensive economy are improved.
The application extracts non-aromatic hydrocarbons and then converts the non-aromatic hydrocarbons, and has various advantages. First, the energy consumption is reduced. Under the condition of the same conversion depth, after non-aromatic hydrocarbon is separated, ineffective conversion of the non-aromatic hydrocarbon is reduced, and aromatic hydrocarbon conversion is more effective, so that the standard oil index for measuring energy consumption in the conversion process is reduced. Second, the conversion of aromatics is improved. Third, the tail oil is reduced after conversion in the R2 aromatics conversion reactor. After the whole system adopts the scheme of the invention, a plurality of indexes of the system are improved. The conversion of polycyclic aromatic hydrocarbons is used as an index to measure the effect of the invention. Since the active sites of the catalyst will be used to convert aromatics after non-aromatics are separated, the conversion of aromatics will be increased. In particular, the conversion rate of the polycyclic aromatic hydrocarbon is improved.
Polycyclic aromatic hydrocarbon conversion rate (total amount of polycyclic aromatic hydrocarbon in the raw oil before conversion-total amount of polycyclic aromatic hydrocarbon in the raw oil after conversion)/total amount of polycyclic aromatic hydrocarbon in the raw oil before conversion x 100%.
Drawings
FIG. 1 is a flow chart of a system for oil comprehensive utilization according to example 1 of the present invention; wherein R1 is a hydrofining unit, R2 is an aromatic hydrocarbon conversion unit; A. b, C units, which are an aromatic hydrocarbon separation unit A, an aromatic hydrocarbon removal unit B and a eutectic solvent regeneration unit C respectively; 1.2, 3, 4, 5, 6 and 7 are pipelines.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.
The composition analysis of the catalyst involved in the present invention adopts the analysis method existing in the field. For example, the composition of the catalyst can be analyzed by ICP (inductively coupled plasma) and XRF (X-ray fluorescence) methods for the selective conversion catalyst. The composition ratio of the group VIB metal oxide and the metal sulfide is determined by XPS (X-ray photoelectron spectroscopy). The ICP test conditions were: the Varian 700-ES series XPS instrument. XRF test conditions were: rigaku ZSX 100e model XRF instrument. XPS test conditions: perkin Elmer PHI 5000C ESCA type X-ray photoelectron spectrometer uses Mg K excitation light source, operating voltage l0kV, current 40mA, vacuum degree 4.0X 10-8 Pa.
[ COMPARATIVE EXAMPLES ]
Building a system: the system for comprehensively utilizing the oil comprises an R1 hydrofining unit and an R2 aromatic hydrocarbon conversion unit;
wherein, the reaction conditions of the R1 hydrofining unit are shown in the following table:
hydrorefining catalyst 3.0wt％NiO-10.5wt％MoO 3 -12.7wt％WO 3 /73.8wt％Al 2 O 3
Pressure of hydrorefining 8.5MPa
Reaction temperature of hydrorefining 315 ℃ entrance
Hydrofining LHSV space velocity 1.2h -1
Hydrogen to oil ratio of hydrofining 1500(v/v)
The preparation method of the hydrofining catalyst comprises the following steps: adding 2g of sesbania powder, 9ml of nitric acid and 60ml of water into 100g of pseudo-boehmite, kneading into a cluster, extruding into strips, curing at room temperature for 24h, drying at 100 ℃ for 12h, and roasting at 550 ℃ in air atmosphere for 3h to obtain the hydrofining catalyst carrier. 7.90g of nickel nitrate hexahydrate, 8.71g of ammonium molybdate, 9.18g of ammonium metatungstate and 10ml of ammonia were dissolved in water to give 50ml of a clear solution. 50g of hydrofining catalyst carrier is taken, 50ml of solution is added to soak for 3 hours in an isovolumetric soaking mode, the hydrofining catalyst A1 is obtained after drying for 12 hours at the temperature of 110 ℃ and roasting for 4 hours at the temperature of 500 ℃ in air atmosphere. The composition of the material is 3.0 wt% NiO-10.5 wt% MoO 3 -12.7wt％WO 3 /73.8wt％Al 2 O 3 It contains three metals of nickel, molybdenum and tungsten.
The reaction conditions of the R2 aromatic hydrocarbon conversion unit are as follows:
selective conversion catalyst 3.50 parts of Ni-5.00 parts of WO 3 0.27 parts of WS 2 50 parts of beta zeolite-41.23 parts of Al 2 O 3
Selection of transformation pressure 7.0MPa
Selection of the conversion reaction temperature Inlet 340 deg.C
Space velocity of selective conversion LHSV 1.0h -1
Selective hydrogen to oil ratio 1600(v/v)
Preparation of the selective conversion catalyst: 70 wt% of beta zeolite (the silicon-aluminum molecular ratio SAR is 25) and 30 wt% of alumina are kneaded, extruded and molded to obtain the catalyst carrier. And preparing a proper amount of nickel nitrate and ammonium tungstate into a clear solution, soaking in the same volume, drying at 100 ℃, and roasting in air at 500 ℃ for 2 hours to obtain the catalyst precursor. The catalyst precursor is reduced to 450 ℃ for 4 hours under the condition of hydrogen, and then the dimethyl disulfide is injected for 4 hours after the temperature is reduced to 330 ℃, so that the required hydrocracking catalyst can be obtained. The catalyst comprises 3.5 parts of Ni-5.0 parts of WO by weight based on 100 parts of the total weight of the catalyst 3 0.27 parts of WS 2 50 parts of beta zeolite-41.23 parts of Al 2 O 3 。
After the process, the aromatic hydrocarbon enters the R2 reactor for reaction after passing through R1, wherein the conversion rate of the polycyclic aromatic hydrocarbon is 71%.
[ example 1 ]
Building a system: the system for comprehensively utilizing the oil comprises an R1 hydrofining unit, a non-aromatic hydrocarbon and aromatic hydrocarbon separation unit and an R2 aromatic hydrocarbon conversion unit;
wherein, the reaction conditions of the R1 hydrofining unit are shown in the following table:
Figure GDA0003651448710000081
Figure GDA0003651448710000091
the reaction conditions of the aromatic hydrocarbon conversion unit R2 are as follows:
selective conversion catalyst 3.50 parts of Ni-5.00 parts of WO 3 0.27 parts of WS 2 50 parts of beta zeolite-41.23 parts of Al 2 O 3
Selection of transformation pressure 7.0MPa
Selection of the conversion reaction temperature Inlet 340 deg.C
Space velocity of selective conversion LHSV 1.0h -1
Selective hydrogen to oil ratio 1600(v/v)
The non-aromatics and aromatics separation unit includes a secondary unit: A. b, C units, which are an aromatic hydrocarbon separation unit A, an aromatic hydrocarbon removal unit B and a eutectic solvent regeneration unit C respectively;
an outlet of the R1 hydrofining unit is connected with an inlet of the A unit, an outlet of the A unit is connected with an inlet of the B unit, and an outlet of the B unit is connected with an inlet of the R2 aromatic hydrocarbon conversion unit; an outlet of the unit B is connected with an inlet of the unit C; and one outlet of the unit C is connected with one inlet of the unit A, and the other outlet of the unit C is connected with one inlet of the unit B.
The specific separation method comprises the following steps:
raw oil adopts catalytic diesel oil, firstly enters an R1 hydrofining reactor for processing, and the obtained hydrofined oil has the mass composition of 26% of non-aromatic hydrocarbon and 74% of aromatic hydrocarbon after analysis. The hydrofined oil is introduced into a tower A of a secondary aromatic hydrocarbon separation unit through a pipeline 1, and a fresh eutectic solvent is introduced into the tower A through a pipeline 6 and is obtained by mixing and stirring uniformly at 25 ℃ in advance before use. The eutectic solvent consists of ethyl triphenyl phosphonium chloride/levulinic acid in a molar ratio of 1/5. The volume ratio of the eutectic solvent to the hydrofined oil is 1/0.5, the eutectic solvent and the hydrofined oil are in countercurrent contact, non-aromatic hydrocarbon is extracted from a tower A of the secondary aromatic hydrocarbon separation unit through a pipeline 2, the pressure of the tower A is 200kPa, and the temperature is 30 ℃;
the eutectic solvent containing aromatic hydrocarbon at the bottom of the tower A enters the tower B of the secondary aromatic hydrocarbon removal unit through a pipeline 3, meanwhile, 1/1 volume of second solvent water of the eutectic solvent entering the tower B is injected into the tower B through a pipeline 7, the second solvent and the eutectic solvent containing aromatic hydrocarbon contact with each other in the tower B and then descend to the bottom of the tower, the aromatic hydrocarbon ascends to a lateral line 4 to be extracted, the extracted aromatic hydrocarbon stream accounts for 99.3 percent of the total aromatic hydrocarbon of the outlet material of the R1 hydrofining reactor, the pressure of the tower B is 100kPa, and the temperature is 30 ℃;
the mixture of the eutectic solvent and the second solvent obtained from the tower bottom B flows through a pipeline 5 to enter a tower C of the secondary eutectic solvent regeneration unit, the second solvent is removed from the tower C to obtain the regenerated eutectic solvent, the regenerated eutectic solvent returns to the tower A of the secondary aromatic hydrocarbon separation unit through a pipeline 6, and the second solvent returns to the tower B through a pipeline 7 for recycling. The column C pressure was 35kPa, the temperature 80 ℃.
After the process, the separated and concentrated aromatic hydrocarbon enters an R2 reactor for reaction, wherein the conversion rate of the polycyclic aromatic hydrocarbon is 99%.
[ example 2 ]
The system constructed in embodiment 1 is used in this embodiment.
Wherein, the reaction conditions of the R1 hydrofining unit are shown in the following table:
hydrorefining catalyst 3.0wt％NiO-10.5wt％MoO 3 -12.7wt％WO 3 /73.8wt％Al 2 O 3
Pressure of hydrorefining 8.5MPa
Reaction temperature of hydrorefining 315 ℃ entrance
Hydrofining LHSV space velocity 1.2h -1
Hydrogen to oil ratio of hydrofining 1500(v/v)
The reaction conditions of the aromatic hydrocarbon conversion unit R2 are as follows:
Figure GDA0003651448710000101
the specific separation method comprises the following steps:
raw oil adopts catalytic diesel oil, firstly enters an R1 hydrofining reactor for processing, and the obtained hydrofined oil has the mass composition of 26% of non-aromatic hydrocarbon and 74% of aromatic hydrocarbon after analysis. The hydrofined oil is introduced into a tower A of a secondary aromatic hydrocarbon separation unit through a pipeline 1, and a fresh eutectic solvent is introduced into the tower A through a pipeline 6 and is obtained by mixing and stirring uniformly at 45 ℃ before use. The eutectic solvent consists of tetrabutylammonium chloride/dimethylformamide in a molar ratio of 1/2. The volume ratio of the eutectic solvent to the hydrofined oil is 1/0.2, the eutectic solvent and the hydrofined oil are in countercurrent contact, non-aromatic hydrocarbon is extracted from a tower A of the secondary aromatic hydrocarbon separation unit through a pipeline 2, the pressure of the tower A is 100kPa, and the temperature is 30 ℃;
the eutectic solvent containing aromatic hydrocarbon at the bottom of the tower A enters the secondary aromatic hydrocarbon removing unit B through a pipeline 3, meanwhile, 1/1-volume second solvent butyl acetate of the eutectic solvent entering the tower B is injected into the tower B through a pipeline 7, the second solvent and the eutectic solvent containing aromatic hydrocarbon contact with each other in the tower B and then descend to the bottom of the tower, aromatic hydrocarbon ascends and is extracted at a lateral line 4, the extracted aromatic hydrocarbon material flow accounts for 98.8% of the total aromatic hydrocarbon of the material at the outlet of the R1 hydrofining reactor, the pressure of the tower B is 200kPa, and the temperature is 80 ℃;
the mixture of the eutectic solvent and the second solvent obtained from the tower bottom B enters the secondary eutectic solvent regeneration unit C tower through a pipeline 5, the regenerated eutectic solvent obtained after the second solvent is removed from the tower C is returned to the secondary aromatic hydrocarbon separation unit A tower through a pipeline 6, and the second solvent is returned to the tower B for recycling through a pipeline 7. The column C pressure was 40kPa, and the temperature was 150 ℃.
After the process, the separated and concentrated aromatic hydrocarbon enters an R2 reactor for reaction, wherein the conversion rate of the polycyclic aromatic hydrocarbon is 97%.
[ example 3 ]
The system constructed in embodiment 1 is used in this embodiment. The reaction conditions of hydrofinishing R1 and aromatics conversion R2 of example 1 were used.
The specific separation method comprises the following steps: raw oil adopts catalytic diesel oil, firstly enters an R1 hydrofining reactor for processing, and the obtained hydrofined oil has the mass composition of 26% of non-aromatic hydrocarbon and 74% of aromatic hydrocarbon after analysis. The hydrofined oil is introduced into a tower A of a secondary aromatic hydrocarbon separation unit through a pipeline 1, and a fresh eutectic solvent is introduced into the tower A through a pipeline 6 and is obtained by mixing and stirring uniformly at 60 ℃ before use. The eutectic solvent consists of methyltriethylammonium chloride/succinic acid in a molar ratio of 1/1. The volume ratio of the eutectic solvent to the hydrofined oil is 1/1.5, the eutectic solvent and the hydrofined oil are in countercurrent contact, non-aromatic hydrocarbon is extracted from a tower A of the secondary aromatic hydrocarbon separation unit through a pipeline 2, the pressure of the tower A is 100kPa, and the temperature is 40 ℃;
the eutectic solvent containing aromatic hydrocarbon at the bottom of the tower A enters the tower B of the secondary aromatic hydrocarbon removal unit through a pipeline 3, meanwhile, 1/5 volume of second solvent water of the eutectic solvent entering the tower B is injected into the tower B through a pipeline 7, the second solvent and the eutectic solvent containing aromatic hydrocarbon contact with each other in the tower B and then descend to the bottom of the tower, the aromatic hydrocarbon ascends to a lateral line 4 to be extracted, the extracted aromatic hydrocarbon stream accounts for 99.5 percent of the total aromatic hydrocarbon of the outlet material of the R1 hydrofining reactor, the pressure of the removal tower B is 100kPa, and the temperature is 30 ℃;
the mixture of the eutectic solvent and the second solvent obtained from the tower bottom B enters the secondary eutectic solvent regeneration unit C tower through a pipeline 5, the regenerated eutectic solvent obtained after the second solvent is removed from the tower C is returned to the secondary aromatic hydrocarbon separation unit A tower through a pipeline 6, and the second solvent is returned to the tower B for recycling through a pipeline 7. The column C pressure was 40kPa, and the temperature was 80 ℃.
After the process, the separated and concentrated aromatic hydrocarbon enters an R2 reactor for reaction, wherein the conversion rate of the polycyclic aromatic hydrocarbon is 97%.
[ example 4 ] A method for producing a polycarbonate
The system constructed in embodiment 1 is used in this embodiment. The reaction conditions of hydrofinishing R1 and aromatics conversion R2 of example 1 were used.
The specific separation method comprises the following steps: raw oil adopts heavy diesel oil, firstly enters an R1 hydrofining reactor for processing, and the obtained hydrofined oil has the mass composition of 29 percent of non-aromatic hydrocarbon and 71 percent of aromatic hydrocarbon after analysis. The hydrofined oil is introduced into a tower A of a secondary aromatic hydrocarbon separation unit through a pipeline 1, and a fresh eutectic solvent is introduced into the tower A through a pipeline 6 and is obtained by mixing and stirring uniformly at 85 ℃ before use. The eutectic solvent consists of tetraphenylphosphonium chloride/levulinic acid in a molar ratio of 1/0.5. The volume ratio of the eutectic solvent to the hydrofined oil is 1/0.5, the eutectic solvent and the hydrofined oil are in countercurrent contact, non-aromatic hydrocarbon is extracted from a tower A of the secondary aromatic hydrocarbon separation unit through a pipeline 2, the pressure of the tower A is 1000kPa, and the temperature is 20 ℃;
the eutectic solvent containing aromatic hydrocarbon at the bottom of the tower A enters the tower B of the secondary aromatic hydrocarbon removal unit through a pipeline 3, meanwhile, a second solvent butyl acetate with the volume of 1/2 of the eutectic solvent entering the tower B is injected into the tower B through a pipeline 7, the second solvent and the eutectic solvent containing aromatic hydrocarbon contact with each other in the tower B and then descend to the bottom of the tower, the aromatic hydrocarbon ascends to be extracted at a lateral line 4, the extracted aromatic hydrocarbon stream accounts for 99.5 percent of the total aromatic hydrocarbon of the outlet material of the R1 hydrofining reactor, the pressure of the removal tower B is 1500kPa, and the temperature is 10 ℃;
the mixture of the eutectic solvent and the second solvent at the bottom of the tower B enters the tower C of the secondary eutectic solvent regeneration unit through a pipeline 5, the regenerated eutectic solvent obtained after the second solvent is removed from the tower C returns to the tower A of the secondary aromatic hydrocarbon separation unit through a pipeline 6, and the second solvent returns to the tower B for recycling through a pipeline 7. The column C pressure was 20kPa and the temperature was 70 ℃.
After the process, the separated and concentrated aromatic hydrocarbon enters an R2 reactor for reaction, wherein the conversion rate of the polycyclic aromatic hydrocarbon is 97%.
[ example 5 ]
The system constructed in embodiment 1 is used in this embodiment. The reaction conditions of hydrofinishing R1 and aromatics conversion R2 of example 1 were used.
The specific separation method comprises the following steps: raw oil adopts coker gasoline, and firstly enters an R1 hydrofining reactor for processing, and the obtained hydrofined oil has the mass compositions of 26% of non-aromatic hydrocarbon and 74% of aromatic hydrocarbon through analysis. The hydrofined oil is introduced into a tower A of a secondary aromatic hydrocarbon separation unit through a pipeline 1, and a fresh eutectic solvent is introduced into the tower A through a pipeline 6 and is obtained by mixing and stirring uniformly at 50 ℃ before use. The eutectic solvent consists of methyl triphenyl phosphonium bromide/propionic acid in a molar ratio of 1/1. The volume ratio of the eutectic solvent to the hydrofined oil is 1/2, the eutectic solvent and the hydrofined oil are in countercurrent contact, non-aromatic hydrocarbon is extracted from a secondary aromatic hydrocarbon separation unit A tower through a pipeline 2, the pressure of the separation tower A is 500kPa, and the temperature is 10 ℃;
the eutectic solvent containing aromatic hydrocarbon at the tower bottom of the tower A enters the secondary aromatic hydrocarbon removal unit B tower through a pipeline 3, meanwhile, second solvent water with the volume of 1/0.5 of that of the eutectic solvent entering the tower B is injected into the tower B through a pipeline 7, the second solvent and the eutectic solvent containing aromatic hydrocarbon descend to the tower bottom after contacting with the tower B, the aromatic hydrocarbon ascends to a lateral line 4 to be extracted, the extracted aromatic hydrocarbon stream accounts for 98.7% of the total aromatic hydrocarbon of the material at the outlet of the R1 hydrofining reactor, the pressure of the tower B is 800kPa, and the temperature is 60 ℃;
the mixture of the eutectic solvent and the second solvent obtained from the tower bottom B enters the secondary eutectic solvent regeneration unit C tower through a pipeline 5, the regenerated eutectic solvent obtained after the second solvent is removed from the tower C is returned to the secondary aromatic hydrocarbon separation unit A tower through a pipeline 6, and the second solvent is returned to the tower B for recycling through a pipeline 7. The column C pressure was 20kPa and the temperature was 90 ℃.
After the process, the separated and concentrated aromatic hydrocarbon enters an R2 reactor for reaction, wherein the conversion rate of the polycyclic aromatic hydrocarbon is 99%.
[ example 6 ]
The system constructed in embodiment 1 is used in this embodiment. The reaction conditions of hydrofinishing R1 and aromatics conversion R2 of example 1 were used.
The specific separation method comprises the following steps: raw oil adopts heavy gasoline, firstly enters an R1 hydrofining reactor for processing, and the obtained hydrofined oil has the mass composition of 31 percent of non-aromatic hydrocarbon and 69 percent of aromatic hydrocarbon after analysis. The hydrofined oil is introduced into a tower A of a secondary aromatic hydrocarbon separation unit through a pipeline 1, and a fresh eutectic solvent is introduced into the tower A through a pipeline 6 and is obtained by mixing and stirring uniformly at 40 ℃ before use. The eutectic solvent consists of methyltriethylammonium chloride/tributyl phosphate in a molar ratio of 1/5. The volume ratio of the eutectic solvent to the hydrofined oil is 1/5, the eutectic solvent and the hydrofined oil are in countercurrent contact, non-aromatic hydrocarbon is extracted from a tower A of the secondary aromatic hydrocarbon separation unit through a pipeline 2, the pressure of the tower A is 1500kPa, and the temperature is 30 ℃;
the eutectic solvent containing aromatic hydrocarbon at the bottom of the tower A enters the tower B of the secondary aromatic hydrocarbon removal unit through a pipeline 3, meanwhile, a second solvent butyl acetate with the volume of 1/1 of the eutectic solvent entering the tower B is injected into the tower B through a pipeline 7, the second solvent and the eutectic solvent containing aromatic hydrocarbon contact with each other in the tower B and then descend to the bottom of the tower, the aromatic hydrocarbon ascends to be extracted at a lateral line 4, the extracted aromatic hydrocarbon stream accounts for 98.5% of the total aromatic hydrocarbon of the outlet material of the R1 hydrofining reactor, the pressure of the tower B is 100kPa, and the temperature is 20 ℃;
and the mixture of the eutectic solvent and the second solvent obtained from the tower bottom B enters the secondary eutectic solvent regeneration unit C tower through a pipeline 5, the regenerated eutectic solvent obtained after the second solvent is removed from the tower C is returned to the secondary aromatic hydrocarbon separation unit A tower through a pipeline 6, and the second solvent is returned to the tower B for recycling through a pipeline 7. The column C pressure was 40kPa, and the temperature was 60 ℃.
After the process, the separated and concentrated aromatic hydrocarbon enters an R2 reactor for reaction, wherein the conversion rate of the polycyclic aromatic hydrocarbon is 97%.
[ example 7 ]
The system constructed in embodiment 1 is used in this embodiment. The reaction conditions of hydrofinishing R1 and aromatics conversion R2 of example 1 were used.
The specific separation method comprises the following steps: raw oil adopts catalytic diesel oil, firstly enters an R1 hydrofining reactor for processing, and the obtained hydrofined oil has the mass composition of 26% of non-aromatic hydrocarbon and 74% of aromatic hydrocarbon after analysis. The hydrofined oil is introduced into a tower A of a secondary aromatic hydrocarbon separation unit through a pipeline 1, and a fresh eutectic solvent is introduced into the tower A through a pipeline 6, and the solvent is obtained by mixing and stirring uniformly at 30 ℃ before use. The eutectic solvent consists of tetrabutylammonium chloride/lactic acid in a molar ratio of 1/1. The volume ratio of the eutectic solvent to the hydrofined oil is 1/0.5, the eutectic solvent and the hydrofined oil are in countercurrent contact, non-aromatic hydrocarbon is extracted from a secondary aromatic hydrocarbon separation unit A tower through a pipeline 2, the pressure of the separation tower A is 100kPa, and the temperature is 50 ℃;
the eutectic solvent containing aromatic hydrocarbon at the bottom of the tower A enters the tower B of the secondary aromatic hydrocarbon removal unit through a pipeline 3, a second solvent ethyl acetate with the volume of 1/5 of the eutectic solvent entering the tower B is injected into the tower B through a pipeline 7, the second solvent and the eutectic solvent containing aromatic hydrocarbon contact with each other in the tower B and then descend to the bottom of the tower, the aromatic hydrocarbon ascends to be extracted at a lateral line 4, the extracted aromatic hydrocarbon stream accounts for 99.3 percent of the total aromatic hydrocarbon of the material at the outlet of the R1 hydrofining reactor, the pressure of the tower B is 90kPa, and the temperature is 25 ℃;
the mixture of the eutectic solvent and the second solvent obtained from the tower bottom B enters the secondary eutectic solvent regeneration unit C tower through a pipeline 5, the regenerated eutectic solvent obtained after the second solvent is removed from the tower C is returned to the secondary aromatic hydrocarbon separation unit A tower through a pipeline 6, and the second solvent is returned to the tower B for recycling through a pipeline 7. The column C pressure was 20kPa and the temperature was 160 ℃.
After the process, the separated and concentrated aromatic hydrocarbon enters an R2 reactor for reaction, wherein the conversion rate of the polycyclic aromatic hydrocarbon is 96%.
[ example 8 ]
The system constructed in embodiment 1 is used in this embodiment. The reaction conditions of hydrofinishing R1 and aromatics conversion R2 of example 1 were used.
The specific separation method comprises the following steps: raw oil is coked diesel oil, and firstly enters an R1 hydrofining reactor for processing, and the obtained hydrofining oil comprises 18% of non-aromatic hydrocarbon and 82% of aromatic hydrocarbon by mass through analysis. The hydrofined oil is introduced into a tower A of a secondary aromatic hydrocarbon separation unit through a pipeline 1, and a fresh eutectic solvent is introduced into the tower A through a pipeline 6 and is obtained by mixing and stirring uniformly at 50 ℃ before use. The eutectic solvent consists of ethyl triphenyl phosphonium chloride/dimethylformamide in a molar ratio of 1/3. The volume ratio of the eutectic solvent to the hydrofined oil is 1/0.8, the eutectic solvent and the hydrofined oil are in countercurrent contact, non-aromatic hydrocarbon is extracted from a secondary aromatic hydrocarbon separation unit A tower through a pipeline 2, the pressure of the separation tower A is 800kPa, and the temperature is 60 ℃;
the eutectic solvent containing aromatic hydrocarbon at the bottom of the tower A enters the tower B of the secondary aromatic hydrocarbon removal unit through a pipeline 3, meanwhile, a second solvent butyl acetate with the volume of 1/1 of the eutectic solvent entering the tower B is injected into the tower B through a pipeline 7, the second solvent and the eutectic solvent containing aromatic hydrocarbon contact with each other in the tower B and then descend to the bottom of the tower, the aromatic hydrocarbon ascends to be extracted at a lateral line 4, the extracted aromatic hydrocarbon stream accounts for 98.1% of the total aromatic hydrocarbon of the outlet material of the R1 hydrofining reactor, the pressure of the tower B is 600kPa, and the temperature is 30 ℃;
the mixture of the eutectic solvent and the second solvent obtained from the tower bottom B enters the secondary eutectic solvent regeneration unit C tower through a pipeline 5, the regenerated eutectic solvent obtained after the second solvent is removed from the tower C is returned to the secondary aromatic hydrocarbon separation unit A tower through a pipeline 6, and the second solvent is returned to the tower B for recycling through a pipeline 7. The column C pressure was 90kPa, and the temperature was 80 ℃.
After the process, the separated and concentrated aromatic hydrocarbon enters an R2 reactor for reaction, wherein the conversion rate of the polycyclic aromatic hydrocarbon is 97%.
[ example 9 ]
The system constructed in embodiment 1 is used in this embodiment. The reaction conditions of hydrofinishing R1 and aromatics conversion R2 of example 1 were used.
The specific separation method comprises the following steps: raw oil adopts catalytic diesel oil, firstly enters an R1 hydrofining reactor for processing, and the obtained hydrofined oil has the mass composition of 26% of non-aromatic hydrocarbon and 74% of aromatic hydrocarbon after analysis. The hydrofined oil is introduced into a tower A of a secondary aromatic hydrocarbon separation unit through a pipeline 1, and a fresh eutectic solvent is introduced into the tower A through a pipeline 6 and is obtained by mixing and stirring uniformly at 60 ℃ before use. The eutectic solvent consists of ethyl triphenyl phosphonium chloride/levulinic acid in a molar ratio of 1/3. The volume ratio of the eutectic solvent to the hydrofined oil is 1/0.2, the eutectic solvent and the hydrofined oil are in countercurrent contact, non-aromatic hydrocarbon is extracted from a tower A of the secondary aromatic hydrocarbon separation unit through a pipeline 2, the pressure of the tower A is 80kPa, and the temperature is 30 ℃;
the eutectic solvent containing aromatic hydrocarbon at the bottom of the tower A enters the secondary aromatic hydrocarbon removal unit B tower through a pipeline 3, meanwhile, a second solvent methanol with the volume of 1/1 of the eutectic solvent entering the tower B is injected into the tower B through a pipeline 7, the second solvent and the eutectic solvent containing aromatic hydrocarbon contact with each other in the tower B and then descend to the bottom of the tower, the aromatic hydrocarbon ascends to a lateral line 4 to be extracted, the extracted aromatic hydrocarbon stream accounts for 98.1% of the total aromatic hydrocarbon of the outlet material of the R1 hydrofining reactor, the pressure of the removal tower B is 20kPa, and the temperature is 10 ℃;
the mixture of the eutectic solvent and the second solvent obtained from the tower bottom B enters the secondary eutectic solvent regeneration unit C tower through a pipeline 5, the regenerated eutectic solvent obtained after the second solvent is removed from the tower C is returned to the secondary aromatic hydrocarbon separation unit A tower through a pipeline 6, and the second solvent is returned to the tower B for recycling through a pipeline 7. The column C pressure was 70kPa and the temperature was 80 ℃.
After the process, the separated and concentrated aromatic hydrocarbon enters an R2 reactor for reaction, wherein the conversion rate of the polycyclic aromatic hydrocarbon is 96%.
[ example 10 ]
The system constructed in embodiment 1 is used in this embodiment. The reaction conditions of hydrofinishing R1 and aromatics conversion R2 of example 1 were used.
The specific separation method comprises the following steps: raw oil adopts catalytic diesel oil, firstly enters an R1 hydrofining reactor for processing, and the obtained hydrofined oil is analyzed to be 7% of non-aromatic hydrocarbon, 39% of monocyclic aromatic hydrocarbon and 54% of polycyclic aromatic hydrocarbon. The hydrofined oil is introduced into a tower A of a secondary aromatic hydrocarbon separation unit through a pipeline 1, and a fresh eutectic solvent is introduced into the tower A through a pipeline 6 and is obtained by mixing and stirring uniformly at 70 ℃ before use. The eutectic solvent consists of tetrabutylammonium chloride/levulinic acid in a molar ratio of 1/3. The volume ratio of the eutectic solvent to the oil to be extracted is 1/1, the eutectic solvent and the hydrofined oil are in countercurrent contact, non-aromatic hydrocarbon is extracted in a secondary aromatic hydrocarbon separation unit A tower through a pipeline 2, the pressure of the tower A is 100kPa, and the temperature is 30 ℃;
the eutectic solvent containing aromatic hydrocarbon at the bottom of the tower A enters the secondary aromatic hydrocarbon removal unit B tower through a pipeline 3, meanwhile, 1/1 volume of second solvent water with the eutectic solvent entering the tower B is injected into the tower B through a pipeline 7, the second solvent and the eutectic solvent containing aromatic hydrocarbon contact with each other in the tower B and then descend to the bottom of the tower, the aromatic hydrocarbon ascends to a lateral line 4 to be extracted, the extracted aromatic hydrocarbon stream accounts for 99.5 percent of the total aromatic hydrocarbon of the material at the outlet of the R1 hydrofining reactor, the pressure of the removal tower B is 100kPa, and the temperature is 30 ℃;
the mixture of the eutectic solvent and the second solvent obtained from the tower bottom B enters the secondary eutectic solvent regeneration unit C tower through a pipeline 5, the regenerated eutectic solvent obtained after the second solvent is removed from the tower C is returned to the secondary aromatic hydrocarbon separation unit A tower through a pipeline 6, and the second solvent is returned to the tower B for recycling through a pipeline 7. The column C pressure was 35kPa, the temperature 80 ℃.
After the process, the separated and concentrated aromatic hydrocarbon enters an R2 reactor for reaction, wherein the conversion rate of the polycyclic aromatic hydrocarbon is 96%.

Claims (30)

1. A system for comprehensively utilizing oil products is characterized by comprising a hydrofining unit, a non-aromatic hydrocarbon and aromatic hydrocarbon separation unit and an aromatic hydrocarbon conversion unit; wherein the non-aromatics and aromatics separation unit comprises a secondary unit: A. the unit B is an aromatic hydrocarbon separation unit A and an aromatic hydrocarbon removal unit B respectively;
an outlet of the hydrofining unit is connected with an inlet of the unit A, an outlet of the unit A is connected with an inlet of the unit B, and an outlet of the unit B is connected with an inlet of the aromatic hydrocarbon conversion unit;
passing the oil product through a hydrofining unit to obtain a non-aromatic hydrocarbon and aromatic hydrocarbon material flow;
respectively feeding the eutectic solvent and the non-aromatic hydrocarbon and aromatic hydrocarbon material flows into a unit A, extracting the non-aromatic hydrocarbon obtained after liquid-liquid extraction, and feeding the aromatic hydrocarbon carried by the obtained eutectic solvent into a unit B;
after the eutectic solvent carrying aromatic hydrocarbon enters the unit B and is mixed with the second solvent, the obtained aromatic hydrocarbon is extracted, and simultaneously the obtained mixture flow of the eutectic solvent and the second solvent flows out of the unit B;
the non-aromatics and aromatics separation unit comprises a secondary unit C; the unit C is a eutectic solvent regeneration unit C; an outlet of the unit B is connected with an inlet of the unit C; one outlet of the unit C is connected with one inlet of the unit A, and the other outlet of the unit C is connected with one inlet of the unit B;
the mixed material flow of the eutectic solvent and the second solvent flowing out of the unit B enters the unit C, the eutectic solvent obtained after the second solvent is removed is recycled and returned to the unit A for recycling, and the removed second solvent is returned to the unit B for recycling;
the eutectic solvent comprises a hydrogen bond acceptor and a hydrogen bond donor, and the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1: 0.1-1: 20;
the hydrogen bond acceptor is selected from at least one of tetraethyl ammonium halide, tetrabutyl ammonium halide, choline chloride, betaine, methyl triethyl ammonium halide, tetraphenyl phosphonium halide, methyl triphenyl phosphonium halide, ethyl triphenyl phosphonium halide and butyl triphenyl phosphonium halide;
the hydrogen bond donor is selected from at least one of tributyl phosphate, dimethylformamide, morpholine, urea, citric acid, succinic acid, propionic acid, acetic acid, ethylene glycol, propylene glycol, glycerol, xylitol, glucose, levulinic acid, oxalic acid and lactic acid.
2. The system for the integrated utilization of oil products according to claim 1, characterized in that:
injecting a second solvent into the top of the aromatic hydrocarbon removal unit B; the second solvent is selected from one or more of water, ethyl acetate, butyl acetate and methanol.
3. The system for the integrated utilization of oil products according to claim 1, characterized in that:
and the extracted aromatic hydrocarbon enters the aromatic hydrocarbon conversion unit to react to obtain light aromatic hydrocarbon and low-carbon alkane.
4. The system for the integrated utilization of oil products according to claim 1, characterized in that:
the oil product is selected from one or more of heavy gasoline, light diesel oil, catalytic diesel oil, heavy diesel oil, coker gasoline and coker diesel oil; the non-aromatic hydrocarbon in the oil product comprises at least one of straight-chain alkane, branched-chain alkane and cycloalkane of C1-C20.
5. The system for comprehensively utilizing oil products according to any one of claims 1 to 4, characterized in that:
the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1: 0.5-1: 8.
6. The system for comprehensively utilizing oil products according to any one of claims 1 to 4, characterized in that:
the hydrogen bond acceptor is selected from at least one of tetraethyl ammonium halide, tetrabutyl ammonium halide, methyltriethyl ammonium halide, tetraphenyl phosphonium halide, methyltriphenyl phosphonium halide, ethyltriphenylphosphonium halide and butyltriphenylphosphonium halide.
7. The system for comprehensively utilizing oil products according to any one of claims 1 to 4, characterized in that:
the hydrogen bond donor is at least one selected from ethylene glycol, propylene glycol, levulinic acid, tributyl phosphate, dimethylformamide, succinic acid, lactic acid and propionic acid.
8. The system for the integrated utilization of oil products according to claim 1, characterized in that:
the preparation method of the eutectic solvent comprises the following steps:
and mixing the hydrogen bond acceptor and the hydrogen bond donor according to the using amount at 0-180 ℃.
9. The system for the integrated utilization of oil products according to claim 8, characterized in that:
the preparation method of the eutectic solvent comprises the following steps:
and mixing the hydrogen bond acceptor and the hydrogen bond donor according to the using amount at 20-120 ℃.
10. A method for oil product comprehensive utilization by using the system of any one of claims 1 to 9, characterized by comprising the steps of:
passing an oil product to be extracted through a hydrofining unit to obtain a non-aromatic hydrocarbon and aromatic hydrocarbon material flow;
respectively introducing the eutectic solvent and the non-aromatic hydrocarbon and aromatic hydrocarbon material flows into a unit A, extracting the non-aromatic hydrocarbon through liquid-liquid extraction, and simultaneously introducing the obtained eutectic solvent carrying aromatic hydrocarbon into a unit B;
the eutectic solvent carrying aromatic hydrocarbon enters a unit B and is further mixed with a second solvent, the obtained aromatic hydrocarbon is extracted, and simultaneously the obtained mixture flow of the eutectic solvent and the second solvent flows out of the unit B; and the obtained aromatic hydrocarbon enters the aromatic hydrocarbon conversion unit to react to obtain light aromatic hydrocarbon and low-carbon alkane.
11. The method for oil product comprehensive utilization according to claim 10, characterized in that:
and the mixed material flow of the eutectic solvent and the second solvent flowing out of the unit B enters the unit C, the eutectic solvent obtained after the second solvent is removed is recycled and returned to the unit A for recycling, and the removed second solvent is returned to the unit B for recycling.
12. The method for oil product comprehensive utilization according to claim 10, characterized in that:
and injecting a second solvent into the top of the removing tower B of the eutectic solvent, wherein the injection volume of the second solvent is 0.2-10 times of the volume of the eutectic solvent entering the tower.
13. The method for oil product comprehensive utilization according to claim 12, characterized in that:
the injection volume of the second solvent is 0.5-5 times of the volume of the eutectic solvent entering the tower.
14. The method for oil product comprehensive utilization according to claim 10, characterized in that:
the tower top pressure of the unit A, the unit B and the unit C is 20-1500 kPa.
15. The method for oil product comprehensive utilization according to claim 14, characterized in that:
the pressure ranges of the unit A and the unit B are 900-250 kPa, and the pressure range of the unit C is 20-900 kPa.
16. The method for oil product comprehensive utilization according to claim 10, characterized in that:
the temperature of the unit A is 10-120 ℃.
17. The method for oil product comprehensive utilization according to claim 16, characterized in that:
the temperature of the unit A is 10-60 ℃.
18. The method for oil product comprehensive utilization according to claim 10, characterized in that:
the temperature of the unit B is 10-100 ℃.
19. The method for oil product comprehensive utilization according to claim 18, characterized in that:
the temperature of the unit B is 10-50 ℃.
20. The method for oil product comprehensive utilization according to claim 10, characterized in that:
the temperature of the C unit is 10-300 ℃.
21. The method for oil product comprehensive utilization according to claim 20, characterized in that:
the temperature of the C unit is 60-150 ℃.
22. The method for oil product comprehensive utilization according to claim 10, characterized in that:
the volume ratio of the eutectic solvent to the oil to be extracted is 1/0.2-1/50.
23. The method for oil product comprehensive utilization according to claim 22, characterized in that:
the volume ratio of the eutectic solvent to the oil to be extracted is 1/0.2-1/5.
24. The method for oil product comprehensive utilization according to claim 10, characterized in that:
the conversion catalyst used in the aromatics conversion unit comprises the following components in parts by weight:
a 2 ) 5-80 parts of solid acid zeolite;
b 2 )0.05 to 8 parts of a group VIII metal;
c 2 ) 3-25 parts of a group VIB metal oxide;
d 2 ) 0.1-2 parts of a group VIB metal sulfide;
e 2 ) 20-95 parts of a first binder;
wherein the content of the first and second substances,
the solid acid zeolite is at least one of mordenite, beta zeolite, ZSM zeolite, EU-1 zeolite, SAPO zeolite and Y zeolite;
the VIII group metal is at least one selected from platinum, palladium, cobalt, nickel and iridium;
the group VIB metal oxide is at least one selected from molybdenum oxide and tungsten oxide;
the VIB group metal sulfide is selected from at least one of molybdenum sulfide and tungsten sulfide;
the first binder is at least one selected from the group consisting of alumina, a silica-alumina composite, a titania-alumina composite, and a magnesia-alumina composite.
25. The method for oil product comprehensive utilization according to claim 10, characterized in that:
the reaction conditions of the hydrofining unit include:
the volume ratio of hydrogen to oil is 500-3000 Nm 3 /m 3 (ii) a And/or:
the inlet temperature of the reactor is 280-420 ℃; and/or:
the partial pressure of hydrogen is 5-10 MPa; and/or:
the airspeed is 0.5-2.0 hours -1 。
26. The method for oil product comprehensive utilization according to claim 25, characterized in that:
the reaction conditions of the hydrofining unit include:
the volume ratio of hydrogen to oil is 800-2000 Nm 3 /m 3 (ii) a And/or:
the inlet temperature of the reactor is 300-410 ℃; and/or:
the partial pressure of hydrogen is 5-8 MPa; and/or:
the airspeed is 0.6-1.5 h -1 。
27. The method for oil product comprehensive utilization according to claim 26, characterized in that:
the reaction conditions of the hydrofining unit include:
the volume ratio of hydrogen to oil is 1000-1500 Nm 3 /m 3 (ii) a And/or:
the inlet temperature of the reactor is 310-390 ℃; and/or:
the partial pressure of hydrogen is 6-7 MPa; and/or:
the airspeed is 0.8-1.2 hours -1 。
28. The method for oil product comprehensive utilization according to claim 10, characterized in that:
the reaction conditions of the aromatic conversion unit include:
the volume ratio of hydrogen to oil is 800-5000 Nm 3 /m 3 (ii) a And/or:
the inlet temperature of the reactor is 280-450 ℃; and/or:
the partial pressure of hydrogen is 5-10 MPa; and/or:
the airspeed is 0.5-2.0 hours -1 。
29. The method for oil product comprehensive utilization according to claim 28, characterized in that:
the reaction conditions of the aromatic conversion unit include:
the volume ratio of hydrogen to oil is 1000-4000 Nm 3 /m 3 (ii) a And/or:
the inlet temperature of the reactor is 300-430 ℃; and/or:
the partial pressure of hydrogen is 5-9 MPa; and/or:
the airspeed is 0.6-1.5 hours -1 。
30. The method for oil product comprehensive utilization according to claim 29, characterized in that:
the reaction conditions of the aromatic conversion unit include:
the volume ratio of hydrogen to oil is 1500-3000 Nm 3 /m 3 (ii) a And/or:
the inlet temperature of the reactor is 310-400 ℃; and/or:
the partial pressure of hydrogen is 6-8 MPa; and/or:
the airspeed is 0.8-1.2 hours -1 。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106753514A (en) * 2016-12-27 2017-05-31 江苏大学 A kind of method of choline eutectic solvent abstraction desulfurization
CN107974287A (en) * 2016-10-25 2018-05-01 中国石油化工股份有限公司 A kind of method for producing the hydrocarbon raw material rich in mononuclear aromatics
CN108690655A (en) * 2017-04-06 2018-10-23 中国石油化工股份有限公司 A kind of method of polycyclic aromatic hydrocarbon in removing diesel oil distillate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107974287A (en) * 2016-10-25 2018-05-01 中国石油化工股份有限公司 A kind of method for producing the hydrocarbon raw material rich in mononuclear aromatics
CN106753514A (en) * 2016-12-27 2017-05-31 江苏大学 A kind of method of choline eutectic solvent abstraction desulfurization
CN108690655A (en) * 2017-04-06 2018-10-23 中国石油化工股份有限公司 A kind of method of polycyclic aromatic hydrocarbon in removing diesel oil distillate

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