CN117866661A - Heavy oil modification and viscosity reduction process - Google Patents
Heavy oil modification and viscosity reduction process Download PDFInfo
- Publication number
- CN117866661A CN117866661A CN202211243597.3A CN202211243597A CN117866661A CN 117866661 A CN117866661 A CN 117866661A CN 202211243597 A CN202211243597 A CN 202211243597A CN 117866661 A CN117866661 A CN 117866661A
- Authority
- CN
- China
- Prior art keywords
- reaction
- solvent
- heavy oil
- oil fraction
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000295 fuel oil Substances 0.000 title claims abstract description 148
- 238000012986 modification Methods 0.000 title abstract description 8
- 230000004048 modification Effects 0.000 title abstract description 8
- 238000011946 reduction process Methods 0.000 title abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 99
- 239000003921 oil Substances 0.000 claims abstract description 88
- 239000000047 product Substances 0.000 claims abstract description 54
- 238000005336 cracking Methods 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 239000000852 hydrogen donor Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000005580 one pot reaction Methods 0.000 claims abstract description 33
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 31
- 238000005520 cutting process Methods 0.000 claims abstract description 26
- 239000013067 intermediate product Substances 0.000 claims abstract description 19
- 238000007039 two-step reaction Methods 0.000 claims abstract description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 46
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- 230000000153 supplemental effect Effects 0.000 claims description 14
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 monocyclic cycloalkanes Chemical class 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000010779 crude oil Substances 0.000 claims description 12
- 150000001993 dienes Chemical class 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- 230000001603 reducing effect Effects 0.000 claims description 7
- 150000004947 monocyclic arenes Chemical class 0.000 claims description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims 1
- 238000009835 boiling Methods 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- 238000013112 stability test Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000004227 thermal cracking Methods 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 239000003027 oil sand Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/24—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen-generating compounds
- C10G45/28—Organic compounds; Autofining
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
Abstract
The invention relates to the technical field of viscosity reduction and viscosity reduction, and discloses a heavy oil modification, viscosity reduction and viscosity reduction process which comprises the following steps: (1) Cutting the heavy oil to obtain a light oil fraction and a heavy oil fraction; (2) Reacting the heavy oil fraction, the solvent and the hydrogen donor to obtain a reaction product; the reaction is selected from one-step reaction or two-step reaction; the one-step reaction comprises contacting the heavy oil fraction, a solvent and a hydrogen donor, and performing the reaction under a supercritical environment at least reaching the solvent; the two-step reaction comprises the steps of firstly carrying out a first-step reaction on heavy oil fraction and solvent under a supercritical environment at least reaching the solvent to obtain an intermediate product; then the intermediate product is contacted with a hydrogen donor and an optional supplementary solvent to carry out a second reaction; (3) Separating the reaction product to obtain a recovered solvent and a cracked product; (4) And mixing the light oil fraction with the cracked product to obtain the modified oil. The modifying and viscosity-reducing process can improve the viscosity-reducing cracking depth and ensure the stability of modified oil, and is suitable for popularization.
Description
Technical Field
The invention relates to the technical field of heavy oil modification and viscosity reduction, in particular to a heavy oil modification and viscosity reduction process.
Background
The visbreaking is a mature thermal processing technology without coke generation, is generally used for processing heavy oil with larger viscosity, and mainly aims to improve the fluidity of the heavy oil and improve the pour point and the viscosity, and the visbreaking-processed oil can provide raw materials for catalytic cracking or coking and other processes and can also be used for producing fuel oil meeting certain specification requirements.
The prior visbreaking process generally has the problem that the visbreaking depth and the stability of modified oil are difficult to be compatible. In addition, the cracked products obtained after high-temperature cracking of heavy oil often need further hydrotreatment, and are affected by high hydrogen sources and high cost of hydrogenation process, and the industrial application is limited.
Therefore, it is needed to provide a heavy oil modifying and viscosity reducing process which can improve the viscosity reducing cracking depth and ensure the stability of the oil product after viscosity reducing cracking.
Disclosure of Invention
The invention aims to solve the problem that the viscosity reduction depth and the oil stability are difficult to be compatible in the prior art, and provides a heavy oil modification and viscosity reduction process.
In order to achieve the above object, the present invention provides a heavy oil upgrading and viscosity reducing process, wherein the process comprises the following steps:
(1) Cutting the heavy oil to obtain a light oil fraction and a heavy oil fraction; wherein the cutting temperature of the light oil fraction and the heavy oil fraction is 200-540 ℃;
(2) Reacting the heavy oil fraction, the solvent and the hydrogen donor to obtain a reaction product; wherein the reaction is selected from one-step reaction or two-step reaction;
wherein the one-step reaction comprises contacting the heavy oil fraction, a solvent and a hydrogen donor, and reacting in a supercritical environment at least reaching the solvent to obtain a reaction product;
the two-step reaction comprises the steps of firstly mixing the heavy oil fraction with a solvent, and carrying out a first-step reaction under a supercritical environment at least reaching the solvent to obtain an intermediate product; then the intermediate product is contacted with a hydrogen donor and an optional supplementary solvent to carry out a second step of reaction to obtain a reaction product;
(3) Separating the reaction product to obtain a recovered solvent and a cracked product;
(4) And mixing the light oil fraction with the cracked product to obtain modified oil.
The heavy oil modification and viscosity reduction process provided by the invention can ensure the stability of modified oil while improving the viscosity reduction cracking depth, has simple process flow and low production cost, and is suitable for industrial popularization.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is a graph showing the results of stability test of the modified oil prepared in example 1 of the present invention;
FIG. 2 is a graph showing the stability test results of the modified oil prepared in example 2 of the present invention;
FIG. 3 is a graph showing the results of stability test of the modified oil prepared in example 3 of the present invention;
FIG. 4 is a graph showing the results of stability test of the modified oil prepared in example 4 of the present invention;
FIG. 5 is a graph showing the results of stability test of the modified oil prepared in example 5 of the present invention;
FIG. 6 is a graph showing the results of stability test of the modified oil prepared in comparative example 1 of the present invention;
FIG. 7 is a graph showing the results of stability test of the modified oil prepared in comparative example 2 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a heavy oil upgrading and viscosity reducing process, wherein the process comprises the following steps of:
(1) Cutting the heavy oil to obtain a light oil fraction and a heavy oil fraction; wherein the cutting temperature of the light oil fraction and the heavy oil fraction is 200-540 ℃;
(2) Reacting the heavy oil fraction, the solvent and the hydrogen donor to obtain a reaction product; wherein the reaction is selected from one-step reaction or two-step reaction;
wherein the one-step reaction comprises contacting the heavy oil fraction, a solvent and a hydrogen donor, and reacting in a supercritical environment at least reaching the solvent to obtain a reaction product;
the two-step reaction comprises the steps of firstly mixing the heavy oil fraction with a solvent, and carrying out a first-step reaction under a supercritical environment at least reaching the solvent to obtain an intermediate product; then the intermediate product is contacted with a hydrogen donor and an optional supplementary solvent to carry out a second step of reaction to obtain a reaction product;
(3) Separating the reaction product to obtain a recovered solvent and a cracked product;
(4) And mixing the light oil fraction with the cracked product to obtain modified oil.
In step (1):
in a preferred embodiment, the heavy oil is selected from one or more of paraffinic, intermediate and naphthenic crudes having a congealing point above 30 ℃.
In the present invention, the cutting temperature of the heavy oil may be adjusted according to the specific type of the heavy oil. For example, when the heavy oil is a paraffinic crude oil having a congealing point of 30 ℃ or higher, the cutting temperature of the light oil fraction and the heavy oil fraction is 350 to 540 ℃, preferably 420 to 520 ℃. When the heavy oil is an intermediate crude oil, the cutting temperature of the light oil fraction and the heavy oil fraction is 280 to 540 ℃, preferably 300 to 500 ℃. When the heavy oil is naphthenic crude oil, the cutting temperature of the light oil fraction and the heavy oil fraction is 200 to 500 ℃, preferably 200 to 450 ℃.
In a preferred embodiment, the cutting of the heavy oil is performed in a distillation column. The operation of the distillation column is not particularly limited, and may be carried out according to a conventional operation in the art.
In step (2):
in a preferred embodiment, the solvent is selected from monocyclic cycloalkanes and/or monocyclic arenes; wherein the monocyclic cycloalkane is selected from cyclopentane and/or cyclohexane, and the monocyclic arene is selected from one or more of benzene, toluene and xylene.
In a preferred embodiment, the hydrogen donor is selected from cycloalkyl aromatic hydrocarbons; wherein the naphthenic aromatic hydrocarbon is selected from one or more of tetrahydronaphthalene, decalin and dihydroanthracene.
In a one-step reaction:
in a preferred embodiment, the mass ratio of heavy oil fraction to solvent is 1:0.5 to 5, preferably 1:1-3; the hydrogen donor accounts for 0.1-10%, preferably 0.3-2% of the mass of the heavy oil fraction.
In a preferred embodiment, the heavy oil fraction, solvent and hydrogen donor are fed separately; wherein the feed temperature of the heavy oil fraction is from 40 to 150 ℃, preferably from 60 to 120 ℃; the solvent is fed at room temperature, preferably 10-40 ℃; the feeding temperature of the hydrogen donor is room temperature, preferably 10-40 ℃.
In a preferred embodiment, the solvent is divided into at least a portion a solvent and a portion B solvent, the portion a solvent comprising 5% to 50%, preferably 10% to 30% of the mass of the heavy oil fraction;
wherein the part A solvent, the heavy oil fraction and the hydrogen donor are mixed and then preheated to a temperature of less than or equal to 350 ℃, and the preheating is preferably 300-330 ℃; the solvent of the part B is independently preheated, and the preheating temperature of the solvent of the part B is 5-40 ℃ higher than the temperature of the cracking reaction.
In the invention, the solvent A part is mixed with the heavy oil fraction, so that the heavy oil fraction can be diluted, the conveying difficulty of the heavy oil fraction is reduced, the linear speed of the heavy oil fraction in a preheating furnace is improved, and the coking risk is reduced. The temperature of the preheated solvent of the part A and the heavy oil fraction is lower than 350 ℃, the temperature of the preheated solvent of the part B is higher than the temperature of the one-step reaction under the one-step reaction pressure, the two streams are mixed and enter the reactor of the one-step reaction, and the temperature difference between the two streams can reduce the coking risk of the heavy oil fraction preheating furnace wall, the pipeline and the reactor wall, and prolong the running period of the device.
In a preferred embodiment, the reaction conditions of the one-step reaction include: the one-step reaction temperature is 320-430 ℃, preferably 380-420 ℃; the reaction pressure of one step is 6-15MPa, preferably 8-12MPa; the one-step reaction time is 1-60min, preferably 1-30min.
In a two-step reaction:
in a preferred embodiment, in the first reaction step, the mass ratio of the heavy oil fraction to the solvent is 1:0.5 to 5, preferably 1:1-3.
In a preferred embodiment, in the first step of the reaction, the heavy oil fraction and the solvent are fed separately; preferably, the feed temperature of the heavy oil fraction is from 40 to 150 ℃, preferably from 60 to 120 ℃; the solvent is fed at room temperature, preferably 10-40 ℃.
In a preferred embodiment, in the first step of the reaction, the solvent is divided into at least a part C solvent and a part D solvent; wherein the C part solvent accounts for 5-50% of the mass of the heavy oil fraction, preferably 10-30%; wherein, the C part solvent is preheated to the temperature of less than or equal to 350 ℃ after being mixed with the heavy oil fraction, and is preferably preheated to 300-330 ℃; the solvent of the part D is independently preheated, and the preheating temperature of the solvent of the part D is 5-40 ℃ higher than the temperature of the cracking reaction.
In a preferred embodiment, the reaction conditions of the first reaction step include: the reaction temperature of the first step is 320-430 ℃, preferably 380-420 ℃; the reaction pressure of the first step is 6-15MPa, preferably 8-12MPa; the reaction time of the first step is 1-45min, preferably 1-20min.
In a preferred embodiment, in the second reaction step, the hydrogen donor is present in an amount of 0.1 to 10%, preferably 0.3 to 2% by mass of the heavy oil fraction based on the heavy oil fraction in the first reaction step.
In a preferred embodiment, in the second step, the intermediate product is contacted with a hydrogen donor to effect a second step reaction to yield a reaction product.
In a preferred embodiment, in the second step, the intermediate product is contacted with a hydrogen donor and a supplemental solvent to effect a second step reaction to yield a reaction product.
In the invention, the supplementary solvent is added in the second step reaction, so that the mass transfer strengthening effect can be realized, the reaction efficiency is improved and the reaction time of the second step reaction is shortened on the premise of ensuring equivalent viscosity reducing effect and product stability.
In a preferred embodiment, the solvent in the first step and the supplemental solvent in the second step are each independently selected from monocyclic cycloalkanes and/or monocyclic arenes, preferably each independently selected from one or more of cyclopentane, cyclohexane, benzene, toluene, xylene.
In the present invention, the solvent in the first reaction and the supplemental solvent in the second reaction may be the same or different, and preferably the same for convenience of operation.
In a preferred embodiment, the supplemental solvent in the second reaction step is mixed with the hydrogen donor and fed at a temperature of 320-430 c, preferably 400-420 c.
Wherein, in the present invention, the feeding temperature after the supplemental solvent and the hydrogen donor in the second-step reaction are mixed is preferably equal to the reaction temperature of the second-step reaction.
In a preferred embodiment, the supplemental solvent in the second reaction step comprises from 5% to 25%, preferably from 10% to 20% of the mass of the heavy oil fraction in the first reaction step.
In a preferred embodiment, the reaction conditions of the second reaction step include: the reaction temperature of the second step is 320-430 ℃, preferably 380-420 ℃; the reaction pressure of the second step is 6-15MPa, preferably 8-12MPa; the second reaction time is 1-30min, preferably 1-15min.
In a preferred embodiment, the first and second reactions are carried out in a shell-and-tube reactor.
In the present invention, the first reaction and the second reaction may be carried out in one reactor or in two reactors. When the first-stage reaction and the second-stage reaction are carried out in one reactor, a tubular fixed bed reactor may be divided into two reaction zones by controlling the feeding position of the hydrogen donor and/or the supplemental solvent in the second-stage reaction.
The hydrogen donor can saturate condensed ring aromatic carbon free radical by providing active hydrogen energy, so that the condensation reaction in the heavy oil thermal cracking process is partially inhibited. It should be noted that the presence of the hydrogen donor in the cracking system not only saturates the aromatic carbon radicals, but also saturates the alkyl carbon radicals that initiate the thermal cracking reaction network, resulting in a decrease in the concentration of radicals. This greatly prolongs the initiation time of thermal cracking and reduces the thermal cracking reaction efficiency. Therefore, the traditional way of directly adding hydrogen-supplying components into the viscosity-reducing raw materials to synchronously carry out thermal cracking generally causes delay in initiation and chain propagation efficiency of a heavy oil thermal cracking network. And the hydrogen donor is added in the later stage of the reaction, so that on one hand, the concentration of free radicals generated by hydrocarbon in the earlier stage of cracking reaction is not influenced, and on the other hand, the added hydrogen donor can be fully used for saturating the condensed ring aromatic carbon free radicals with the tendency of condensation coking, and unnecessary waste is not caused.
In step (3):
in a preferred embodiment, the separation is a flash; wherein the flashing is performed in a flash vessel. The operation of the flash evaporator is not particularly limited in the present invention, and may be carried out according to a conventional operation in the art.
In a preferred embodiment, the recovered solvent is returned to step (2) for recycling. In the two-step reaction, when the solvent in the first-step reaction is different from the supplemental solvent in the second-step reaction, the recovered solvent may be separated and then returned to the first-step reaction and the second-step reaction, respectively, for recycling.
In step (4):
in a preferred embodiment, the cracked product is pretreated to produce a pretreated product prior to combining the light oil fraction with the cracked product; and mixing the light oil fraction with the pretreatment product to obtain the modified oil.
In a preferred embodiment, the pretreatment comprises: rectifying the cracking product to obtain light oil and heavy oil; wherein the cutting temperature of the light oil and the heavy oil is 200-280 ℃; settling the light oil to remove diolefins; and mixing the settled light oil with heavy oil to obtain a pretreatment product.
In the invention, the diolefin can be removed through sedimentation treatment, so that the self-polymerization precipitation of the diolefin in the placing process is avoided, and the storage stability of the modified oil is prevented from being influenced.
In a preferred embodiment, the sedimentation treatment comprises a standing and a filtration, wherein the standing is performed at room temperature for a period of 4 to 10 days, preferably 5 to 7 days; the filtration is performed at room temperature, and the filtration mode is not particularly limited in the present invention.
In a preferred embodiment, the modificationThe stability of the modified oil is 1-2 grade, and the kinematic viscosity at 50 ℃ is less than or equal to 300mm 2 Preferably 50-200mm 2 /s。
In the invention, the light oil fraction and the cracked product or the pretreated product are mixed, so that the viscosity of the modified oil can be further reduced, and the stability of the modified oil can be improved.
The present invention will be described in detail by examples.
Example 1
(1) Introducing Canadian oil sand asphalt (naphthenic oil) into a distillation tower, and cutting at 420 ℃ to obtain light oil fraction with the boiling point less than 420 ℃ and heavy oil fraction with the boiling point more than or equal to 420 ℃;
(2) Mixing the heavy oil fraction and C part of cyclohexane, preheating to 330 ℃ under 10MPa, then mixing with D part of cyclohexane preheated to 422 ℃ under 10MPa, and introducing the mixture into a tubular cracking reactor from the bottom of the tubular cracking reactor; the heavy oil fraction, the C part cyclohexane and the D part cyclohexane react in a tubular cracking reactor for the first step to obtain an intermediate product;
wherein the mass ratio of the heavy oil fraction to cyclohexane (sum of the mass of part C cyclohexane and part D cyclohexane) is 1:2, the cyclohexane in the C part accounts for 20% of the mass of the heavy oil fraction, the temperature of the first step is 410 ℃, the reaction pressure of the first step is 10MPa, and the reaction time of the first step is 10min;
(3) The method comprises the steps of mixing supplementary cyclohexane and tetrahydronaphthalene, heating to 410 ℃ under 10MPa, introducing the mixture into a tubular cracking reactor from the middle upper part of the tubular cracking reactor, contacting with an intermediate product, and carrying out a second-step reaction to obtain a reaction product;
wherein tetrahydronaphthalene accounts for 0.5% of the heavy oil fraction, and the supplemental cyclohexane accounts for 15% of the heavy oil fraction, the second-step reaction temperature is 410 ℃, the second-step reaction pressure is 10MPa, and the second-step reaction time is 5min;
(4) Introducing the reaction product into a flash evaporator for flash evaporation to obtain a recovered solvent and a cracked product; introducing the obtained cracked product into a rectifying tower for rectification, extracting light oil with the boiling point less than or equal to 280 ℃ from the top of the rectifying tower, and extracting heavy oil with the boiling point more than 280 ℃ from the bottom of the rectifying tower; recycling the recovered cyclohexane to the step (2) and the step (3); introducing the light oil into a settler, performing sedimentation treatment, standing for 7 days at room temperature, filtering, removing diolefin, and mixing with heavy oil to obtain a pretreatment product.
(5) And mixing the light oil fraction with the pretreated product to obtain the modified oil.
Example 2
(1) Introducing Canadian oil sand asphalt (naphthenic oil) into a distillation tower, and cutting at 420 ℃ to obtain light oil fraction with the boiling point less than 420 ℃ and heavy oil fraction with the boiling point more than or equal to 420 ℃;
(2) Heating the heavy oil fraction to 330 ℃, heating tetrahydronaphthalene to 330 ℃, and heating cyclohexane to 415 ℃ under 10 MPa; introducing heated heavy oil fraction, cyclohexane and tetrahydronaphthalene into a tubular cracking reactor from the bottom of the tubular cracking reactor, and carrying out one-step reaction to obtain a reaction product;
wherein the mass ratio of the heavy oil fraction to cyclohexane is 1:2.2, tetrahydronaphthalene accounts for 0.5% of the mass of the heavy oil fraction, the temperature of one-step reaction is 410 ℃, the pressure of one-step reaction is 10MPa, and the time of one-step reaction is 15min;
(3) Introducing the reaction product into a flash evaporator for flash evaporation to obtain a recovered solvent and a cracked product; introducing the obtained cracked product into a rectifying tower for rectification, extracting light oil with the boiling point less than or equal to 280 ℃ from the top of the rectifying tower, and extracting heavy oil with the boiling point more than 280 ℃ from the bottom of the rectifying tower; recycling the recovered cyclohexane to the step (2) and the step (3); introducing the light oil into a settler, performing sedimentation treatment, standing for 7 days at room temperature, filtering, removing diolefin, and mixing with heavy oil to obtain a pretreatment product;
(4) And mixing the light oil fraction with the pretreated product to obtain the modified oil.
Example 3
(1) Introducing crude oil (paraffin-based crude oil with a condensation point higher than 30 ℃) into a distillation tower for cutting, wherein the cutting temperature is 500 ℃, and a light oil fraction with a boiling point less than 500 ℃ and a heavy oil fraction with a boiling point more than or equal to 500 ℃ are obtained;
(2) Mixing the heavy oil fraction and part C benzene, preheating to 330 ℃, then mixing with part D benzene preheated to 433 ℃ under 10MPa, and introducing the mixture into a tubular cracking reactor from the bottom of the tubular cracking reactor; the heavy oil fraction, part C benzene and part D benzene react in a first step in a tubular cracking reactor to obtain an intermediate product;
wherein the mass ratio of heavy oil fraction to benzene (sum of the mass of benzene part C and benzene part D) is 1:3, the benzene content of the C part accounts for 10% of the heavy oil fraction, the temperature of the first step reaction is 425 ℃, the pressure of the first step reaction is 10MPa, and the time of the first step reaction is 5min;
(3) Mixing the supplemental benzene and tetrahydronaphthalene, heating to 425 ℃ under 10MPa, introducing the mixture into a tubular cracking reactor from the middle upper part of the tubular cracking reactor, contacting with an intermediate product, and carrying out a second-step reaction to obtain a reaction product;
wherein tetrahydronaphthalene accounts for 1.0% of the heavy oil fraction, and the supplemental benzene accounts for 10% of the heavy oil fraction, the second-step reaction temperature is 425 ℃, the second-step reaction pressure is 10MPa, and the second-step reaction time is 5min;
(4) Introducing the reaction product into a flash evaporator for flash evaporation to obtain a recovered solvent and a cracked product; returning the recovered solvent to the step (2) and the step (3) for recycling;
(5) Mixing the cracked product with light distillate to obtain modified oil.
Example 4
(1) Introducing Russian crude oil (intermediate crude oil) into a distillation tower, and cutting at 450 ℃ to obtain a light oil fraction with the boiling point less than 450 ℃ and a heavy oil fraction with the boiling point more than or equal to 450 ℃;
(2) Mixing the heavy oil fraction and C part of cyclohexane, preheating to 330 ℃, then mixing with D part of cyclohexane preheated to 428 ℃ under 10MPa, and introducing the mixture into a tubular cracking reactor from the bottom of the tubular cracking reactor; the heavy oil fraction, the C part cyclohexane and the D part cyclohexane react in a tubular cracking reactor for the first step to obtain an intermediate product;
wherein the mass ratio of the heavy oil fraction to cyclohexane (sum of the mass of part C cyclohexane and part D cyclohexane) is 1:3, the cyclohexane in the C part accounts for 20% of the mass of the heavy oil fraction, the temperature of the first reaction is 415 ℃, the pressure of the first reaction is 10MPa, and the time of the first reaction is 8min;
(3) The method comprises the steps of mixing supplementary cyclohexane and decalin, heating to 415 ℃ under 10MPa, introducing the mixture into a tubular cracking reactor from the middle upper part of the tubular cracking reactor, contacting with an intermediate product, and carrying out a second-step reaction to obtain a reaction product;
wherein decalin accounts for 0.5% of the heavy oil fraction, and cyclohexane is added to account for 15% of the heavy oil fraction, the reaction temperature in the second step is 415 ℃, the reaction pressure in the second step is 10MPa, and the reaction time in the second step is 4min;
(4) Introducing the reaction product into a flash evaporator for flash evaporation to obtain a recovered solvent and a cracked product; introducing the obtained cracked product into a rectifying tower for rectification, extracting light oil with the boiling point less than or equal to 200 ℃ from the top of the rectifying tower, and extracting heavy oil with the boiling point more than 200 ℃ from the bottom of the rectifying tower; recycling the recovered cyclohexane to the step (2) and the step (3); introducing the light oil into a settler, performing sedimentation treatment, standing for 7 days at room temperature, filtering, removing diolefin, and mixing with heavy oil to obtain a pretreatment product.
(5) And mixing the light oil fraction with the pretreated product to obtain the modified oil.
Example 5
(1) Introducing crude oil (paraffin-based crude oil with a condensation point higher than 30 ℃) into a distillation tower for cutting, wherein the cutting temperature is 500 ℃, and a light oil fraction with a boiling point less than 500 ℃ and a heavy oil fraction with a boiling point more than or equal to 500 ℃ are obtained;
(2) Mixing the heavy oil fraction and C part of cyclohexane, preheating to 330 ℃, then mixing with D part of cyclohexane preheated to 433 ℃ under 10MPa, and introducing the mixture into a tubular cracking reactor from the bottom of the tubular cracking reactor; the heavy oil fraction, the C part cyclohexane and the D part cyclohexane react in a tubular cracking reactor for the first step to obtain an intermediate product;
wherein the mass ratio of the heavy oil fraction to cyclohexane (sum of the mass of part C cyclohexane and part D cyclohexane) is 1:2, the cyclohexane in the C part accounts for 20% of the mass of the heavy oil fraction, the temperature of the first step is 425 ℃, the reaction pressure of the first step is 10MPa, and the reaction time of the first step is 5min;
(3) The tetrahydronaphthalene is heated to 425 ℃ under 10MPa, is introduced into the tubular cracking reactor from the middle upper part of the tubular cracking reactor, contacts with the intermediate product and reacts in the second step to obtain a reaction product;
wherein tetrahydronaphthalene accounts for 1.0% of the mass of the heavy oil fraction, the reaction temperature of the second step is 425 ℃, the reaction pressure of the second step is 10MPa, and the reaction time of the second step is 5min;
(4) Introducing the reaction product into a flash evaporator for flash evaporation to obtain a recovered solvent and a cracked product; returning the recovered solvent to the step (2) and the step (3) for recycling;
(5) And mixing the cracked product and light distillate to obtain modified oil.
Comparative example 1
(1) Introducing Canadian oil sand asphalt into a distillation tower, and cutting at 420 ℃ to obtain light oil fraction with the boiling point less than 420 ℃ and heavy oil fraction with the boiling point more than or equal to 420 ℃;
(2) Heating the heavy oil fraction to 330 ℃, heating cyclohexane to 415 ℃ under 10MPa, introducing the heated heavy oil fraction and cyclohexane into a tubular cracking reactor from the bottom of the tubular cracking reactor, and carrying out one-step reaction to obtain a reaction product;
wherein the mass ratio of the heavy oil fraction to cyclohexane is 1:2.2, the temperature of the one-step reaction is 410 ℃, the pressure of the one-step reaction is 10MPa, and the time of the one-step reaction is 15min;
(3) Introducing the reaction product into a flash evaporator for flash evaporation to obtain a recovered solvent and a cracked product; introducing the obtained cracked product into a rectifying tower for rectification, extracting light oil with the boiling point less than or equal to 280 ℃ from the top of the rectifying tower, and extracting heavy oil with the boiling point more than 280 ℃ from the bottom of the rectifying tower; recycling the recovered cyclohexane to the step (2) and the step (3); introducing the light oil into a settler, performing sedimentation treatment, standing for 7 days at room temperature, filtering, removing diolefin, and mixing with heavy oil to obtain a pretreatment product;
(4) And mixing the light oil fraction with the pretreated product to obtain the modified oil.
Comparative example 2
(1) Introducing Canadian oil sand asphalt into a distillation tower, and cutting at 420 ℃ to obtain light oil fraction with the boiling point less than 420 ℃ and heavy oil fraction with the boiling point more than or equal to 420 ℃;
(2) Heating the heavy oil fraction to 330 ℃, heating tetrahydronaphthalene to 330 ℃, and heating cyclohexane to 415 ℃ under 0.6 MPa; introducing heated heavy oil fraction, cyclohexane and tetrahydronaphthalene into a tubular cracking reactor from the bottom of the tubular cracking reactor, and carrying out one-step reaction to obtain a reaction product;
wherein the mass ratio of the heavy oil fraction to cyclohexane is 1:2.2, tetrahydronaphthalene accounts for 1.5% of the mass of the heavy oil fraction, the temperature of one-step reaction is 410 ℃, the pressure of one-step reaction is 0.6MPa, and the time of one-step reaction is 15min;
(3) Introducing the reaction product into a flash evaporator for flash evaporation to obtain a recovered solvent and a cracked product; introducing the obtained cracked product into a rectifying tower for rectification, extracting light oil with the boiling point less than or equal to 280 ℃ from the top of the rectifying tower, and extracting heavy oil with the boiling point more than 280 ℃ from the bottom of the rectifying tower; recycling the recovered cyclohexane to the step (2) and the step (3); introducing the light oil into a settler, performing sedimentation treatment, standing for 7 days at room temperature, filtering, removing diolefin, and mixing with heavy oil to obtain a pretreatment product;
(4) And mixing the light oil fraction with the pretreated product to obtain the modified oil.
Test example 1
The heavy oil fractions, cracked products and upgraded oils obtained in examples 1-5 and comparative examples 1-2 were subjected to kinematic viscosity tests according to GB/T269, and the test results are shown in tables 1 and 2:
TABLE 1
Note that: in Table 1-it is shown that at the test temperature, the measurement cannot be performed due to too high viscosity of the sample to be measured.
TABLE 2
As shown in Table 1, the method provided by the invention can reduce the viscosity of the cracked product at 50 ℃ to below 200mPa.s, and can meet the requirement of heavy oil transportation. As can be seen from table 2, the viscosity of the oil product can be further reduced by mixing the cracked product with the light oil fraction.
Test example 2
The modified oils obtained in examples 1-5 and comparative examples 1-2 were subjected to stability testing in accordance with the spot test experiments specified in ASTM D4740-04 (2014), and the stability rating criteria are as follows.
Stage 1: the spots are uniform, and no ring is arranged in the spot;
2 stages: the inside of the spot is provided with a fine and fuzzy ring;
3 stages: the inside of the spot has a significantly thin ring, slightly darker than the natural color;
4 stages: having rings that are more concentrated than the tertiary grade, and also darker than the natural color;
5 stages: the ring inside the spot is almost solid or nearly solid, with the ring center being much darker than the background color.
Wherein, fig. 1-7 show the stability test results of the modified oils prepared in examples 1-5 and comparative examples 1-2, respectively, and it is known from analysis of fig. 1-7 that the spots in examples 1, 3, and 4 are uniform, the inside has no ring, the stability is 1 grade, the spots in examples 2 and 5 are uniform, the inside has a slight and blurred color difference, and the stability is between 1 grade and 2 grade. In comparative example 1, there was a fine and blurred ring, the center was darker, and the stability was grade 2. The comparative example 2 had a tertiary, more concentrated ring, also slightly darker than the true color, with a stability of 3.
The results of the viscosity test and the stability test are combined, and the hydrogen donor is introduced into the cracking reaction of the heavy oil fraction under the condition of being higher than the supercritical solvent, so that the requirements of the viscosity reduction of the heavy oil fraction and the stability of the modified oil can be simultaneously met, and the method is a modification technology which takes the cracking depth and the product stability into consideration.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (19)
1. A heavy oil upgrading and viscosity reducing process, which is characterized by comprising the following steps of:
(1) Cutting the heavy oil to obtain a light oil fraction and a heavy oil fraction; wherein the cutting temperature of the light oil fraction and the heavy oil fraction is 200-540 ℃;
(2) Reacting the heavy oil fraction, the solvent and the hydrogen donor to obtain a reaction product; wherein the reaction is selected from one-step reaction or two-step reaction;
wherein the one-step reaction comprises contacting the heavy oil fraction, a solvent and a hydrogen donor, and reacting in a supercritical environment at least reaching the solvent to obtain a reaction product;
the two-step reaction comprises the steps of firstly mixing the heavy oil fraction with a solvent, and carrying out a first-step reaction under a supercritical environment at least reaching the solvent to obtain an intermediate product; then the intermediate product is contacted with a hydrogen donor and an optional supplementary solvent to carry out a second step of reaction to obtain a reaction product;
(3) Separating the reaction product to obtain a recovered solvent and a cracked product;
(4) And mixing the light oil fraction with the cracked product to obtain modified oil.
2. The process of claim 1, wherein the heavy oil is selected from one or more of paraffinic, intermediate, and naphthenic crudes having a congealing point above 30 ℃;
preferably, the heavy oil is paraffin-based crude oil with a congealing point above 30 ℃, and the cutting temperature is 350-540 ℃, preferably 420-520 ℃;
preferably, the heavy oil is an intermediate crude oil, and the cutting temperature is 280-540 ℃, preferably 300-500 ℃;
preferably, the heavy oil is naphthenic crude oil and the cutting temperature is 200-500 ℃, preferably 200-450 ℃.
3. The process according to claim 1 or 2, wherein the solvent is selected from monocyclic cycloalkanes and/or monocyclic arenes;
preferably, the monocyclic cycloalkane is selected from cyclopentane and/or cyclohexane, and the monocyclic arene is selected from one or more of benzene, toluene and xylene.
4. A process according to any one of claims 1 to 3, wherein the hydrogen donor is selected from cycloalkyl aromatic hydrocarbons;
preferably, the cycloalkyl aromatic hydrocarbon is one or more of tetrahydronaphthalene, decalin and dihydroanthracene.
5. The process according to any one of claims 1-4, wherein in the one-step reaction, the mass ratio of heavy oil fraction to solvent is 1:0.5 to 5, preferably 1:1-3; the hydrogen donor accounts for 0.1-10%, preferably 0.3-2% of the mass of the heavy oil fraction.
6. The process according to any one of claims 1-5, wherein in the one-step reaction, the heavy oil fraction, solvent and hydrogen donor are fed separately; wherein the feed temperature of the heavy oil fraction is from 40 to 150 ℃, preferably from 60 to 120 ℃; the solvent is fed at room temperature, preferably 10-40 ℃; the feeding temperature of the hydrogen donor is room temperature, preferably 10-40 ℃.
7. The process according to any one of claims 1-6, wherein in the one-step reaction, the solvent is divided into at least a part a solvent and a part B solvent; wherein the solvent of the A part accounts for 5-50% of the mass of the heavy oil fraction, preferably 10-30%;
wherein the part A solvent, the heavy oil fraction and the hydrogen donor are mixed and then preheated to a temperature of less than or equal to 350 ℃, and the preheating is preferably 300-330 ℃; the solvent of the part B is independently preheated, and the preheating temperature of the solvent of the part B is 5-40 ℃ higher than the temperature of the cracking reaction.
8. The process of any one of claims 1-7, wherein the reaction conditions of the one-step reaction comprise: the one-step reaction temperature is 320-430 ℃, preferably 380-420 ℃; the reaction pressure of one step is 6-15MPa, preferably 8-12MPa; the one-step reaction time is 1-60min, preferably 1-30min.
9. The process according to any one of claims 1 to 8, wherein in the first step of reaction, the mass ratio of heavy oil fraction to solvent is 1:0.5 to 5, preferably 1:1-3.
10. The process according to any one of claims 1-9, wherein in the first step of reaction, the heavy oil fraction and the solvent are fed separately;
preferably, the feed temperature of the heavy oil fraction is from 40 to 150 ℃, preferably from 60 to 120 ℃; the solvent is fed at room temperature, preferably 10-40 ℃.
11. The process according to any one of claims 1 to 10, wherein in the first step of the reaction, the solvent is divided into at least a part C solvent and a part D solvent; wherein the C part solvent accounts for 5-50% of the mass of the heavy oil fraction, preferably 10-30%;
wherein, the C part solvent is preheated to the temperature of less than or equal to 350 ℃ after being mixed with the heavy oil fraction, and is preferably preheated to 300-330 ℃; the solvent of the part D is independently preheated, and the preheating temperature of the solvent of the part D is 5-40 ℃ higher than the temperature of the cracking reaction.
12. The process of any one of claims 1-11, wherein the reaction conditions of the first step reaction comprise: the reaction temperature of the first step is 320-430 ℃, preferably 380-420 ℃; the reaction pressure of the first step is 6-15MPa, preferably 8-12MPa; the reaction time of the first step is 1-45min, preferably 1-20min.
13. The process according to any one of claims 1 to 12, wherein in the second reaction step the hydrogen donor comprises 0.1 to 10%, preferably 0.3 to 2% by mass of the heavy oil fraction of the first reaction step.
14. The process according to any one of claims 1 to 13, wherein in the second step of reacting, the intermediate product is contacted with a hydrogen donor and a supplemental solvent to produce a second step of reaction product;
wherein the solvent in the first step reaction and the supplemental solvent in the second step reaction are each independently selected from monocyclic cycloalkanes and/or monocyclic arenes, preferably each independently selected from one or more of cyclopentane, cyclohexane, benzene, toluene, xylene;
preferably, the supplemental solvent in the second reaction step comprises from 5% to 25%, preferably from 10% to 20% of the mass of the heavy oil fraction in the first reaction step.
15. The process of any one of claims 1-14, wherein the reaction conditions of the second step reaction comprise: the reaction temperature of the second step is 320-430 ℃, preferably 380-420 ℃; the reaction pressure of the second step is 6-15MPa, preferably 8-12MPa; the second reaction time is 1-30min, preferably 1-15min.
16. The process of any one of claims 1-15, wherein the separation is flash evaporation.
17. The process of any one of claims 1-16, wherein the cracked product is pretreated to obtain a pretreated product prior to mixing the light oil fraction with the cracked product; mixing the light oil fraction with the pretreatment product to obtain modified oil;
wherein the preprocessing comprises: rectifying the cracking product to obtain light oil and heavy oil; wherein the cutting temperature of the light oil and the heavy oil is 200-280 ℃; settling the light oil to remove diolefins; and mixing the settled light oil with heavy oil to obtain a pretreatment product.
18. The process according to claim 17, wherein the sedimentation treatment comprises a standing and a filtration, wherein the standing is performed at room temperature for a time of 4-10 days, preferably 5-7 days.
19. The process of any one of claims 1-18, wherein the upgraded oil has a stability of 1-2 grade and an kinematic viscosity at 50 ℃ of 300mm or less 2 Preferably 50-200mm 2 /s。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211243597.3A CN117866661A (en) | 2022-10-11 | 2022-10-11 | Heavy oil modification and viscosity reduction process |
| PCT/CN2023/123583 WO2024078451A1 (en) | 2022-10-11 | 2023-10-09 | Heavy oil modification and viscosity reduction process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211243597.3A CN117866661A (en) | 2022-10-11 | 2022-10-11 | Heavy oil modification and viscosity reduction process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117866661A true CN117866661A (en) | 2024-04-12 |
Family
ID=90585180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211243597.3A Pending CN117866661A (en) | 2022-10-11 | 2022-10-11 | Heavy oil modification and viscosity reduction process |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN117866661A (en) |
| WO (1) | WO2024078451A1 (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294686A (en) * | 1980-03-11 | 1981-10-13 | Gulf Canada Limited | Process for upgrading heavy hydrocarbonaceous oils |
| JP2005307103A (en) * | 2004-04-26 | 2005-11-04 | Idemitsu Kosan Co Ltd | Method for carrying out hydrogenation refining of heavy oil |
| US9243193B2 (en) * | 2013-03-14 | 2016-01-26 | Exxonmobil Research And Engineering Company | Fixed bed hydrovisbreaking of heavy hydrocarbon oils |
| CN110551525B (en) * | 2018-05-31 | 2021-10-08 | 中国石油化工股份有限公司 | Method for producing BTX fraction by catalytically cracking diesel oil |
| KR102395826B1 (en) * | 2020-06-11 | 2022-05-06 | 단국대학교 산학협력단 | Method for upgrading heavy oil using heavy metal, contained in heavy oil, is used as catalyst |
| CN113214864A (en) * | 2020-07-10 | 2021-08-06 | 中国石油大学(北京) | Distillate oil supercritical/subcritical fluid enhanced hydrogenation combination method |
| CN114479929B (en) * | 2020-10-27 | 2023-09-26 | 中国石油天然气股份有限公司 | Crude oil continuous modification and viscosity reduction process |
-
2022
- 2022-10-11 CN CN202211243597.3A patent/CN117866661A/en active Pending
-
2023
- 2023-10-09 WO PCT/CN2023/123583 patent/WO2024078451A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024078451A1 (en) | 2024-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2005117790A (en) | METHOD FOR PROCESSING HEAVY RAW MATERIALS, SUCH AS HEAVY RAW OIL AND CUBE RESIDUES | |
| CN101724420B (en) | Production method of needle coke raw material | |
| RU2006115300A (en) | INTEGRATED METHOD FOR CONVERSION OF COAL-CONTAINING RAW MATERIALS IN LIQUID PRODUCTS | |
| RU2640419C2 (en) | Hydraulic processing of thermal craking products | |
| CN104395437A (en) | Integration of solvent deasphalting with resin hydroprocessing and with delayed coking | |
| RU2695381C2 (en) | Hydrocracking method combined with vacuum distillation and solvent deasphalting to reduce accumulation of heavy polycyclic aromatic compounds | |
| CN111676063A (en) | Processing technology for improving 5# and 7# white oil | |
| CN109988650B (en) | Hydrogenation modification and hydrofining combined method for poor diesel oil | |
| CN103666560A (en) | Method for increasing yields of low-carbon olefins and aromatics by coker gasoline steam cracking | |
| CN101619238A (en) | Delayed coking and reduced pressure distillation combined processing method | |
| CN109486518B (en) | Method and system for modifying low-quality oil | |
| CN117866661A (en) | Heavy oil modification and viscosity reduction process | |
| CN109988643B (en) | Hydrogenation modification and hydrofining combined process for poor diesel oil | |
| CN109486519B (en) | Upgrading method and system for producing high-octane gasoline from low-quality oil | |
| CN112391197B (en) | Suspension bed residual oil hydrocracking system and method | |
| CN100419046C (en) | Process for treating crude oil | |
| WO2013126364A2 (en) | Two-zone, close-coupled, dual-catalytic heavy oil hydroconversion process utilizing improved hydrotreating | |
| CN113817496A (en) | Crude oil or heavy oil pretreatment method | |
| CN114479929A (en) | Continuous modification and viscosity reduction process for crude oil | |
| US3669876A (en) | Hf extraction and asphaltene cracking process | |
| CN113817503B (en) | Combined process for preparing chemical products from crude oil | |
| CN114058405B (en) | Hydroconversion reaction method and system for inferior oil | |
| CN111378491A (en) | Inferior heavy oil hydrotreating process | |
| CN109486515B (en) | Method and system for efficiently modifying inferior oil | |
| CN112980504B (en) | Process and device for preparing oil product by mixing oil slurry, recycle oil and coking wax oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |