CN106929101B - A kind of processing method by shale oil production diesel oil - Google Patents
A kind of processing method by shale oil production diesel oil Download PDFInfo
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- CN106929101B CN106929101B CN201511032283.9A CN201511032283A CN106929101B CN 106929101 B CN106929101 B CN 106929101B CN 201511032283 A CN201511032283 A CN 201511032283A CN 106929101 B CN106929101 B CN 106929101B
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- oil
- fraction
- diesel oil
- hydrocracked
- diesel
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Classifications
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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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 present invention relates to a kind of processing methods by shale oil production diesel oil, comprising the following steps: the full fraction of shale oil enters distilling apparatus and carries out fraction cutting, and the 500 DEG C of parts < are light fraction, and >=500 DEG C of parts are heavy distillat；Heavy distillat carries out delayed coking, and separation reaction product obtains gas, gasoline fraction, diesel oil distillate, wax oil fraction and petroleum coke；Wax oil fraction mixes progress hydrofinishing with light fraction and obtains gas, gasoline fraction, diesel oil distillate and tail oil, and wherein tail oil boiling range is greater than 350 DEG C；Hydrofinishing tail oil is hydrocracked, and is obtained gas, gasoline fraction, diesel oil distillate and recycle oil, recycle oil and tail oil mixing, is continued to be hydrocracked；Whole diesel oil distillates mix to obtain diesel product.The present invention by delayed coking and the group technology that is hydrocracked, can obtain higher yields, meet the diesel oil of state's V standard.
Description
Technical field
The present invention relates to a kind of using delayed coking and the method for being hydrocracked Combined machining shale oil, belongs to shale oil and adds
Work technical field.
Background technique
With the continuous consumption of petroleum resources, oil shale is only second to coal as unconventional petroleum resources reserves, as one
The important supplement of the kind energy, effective supplement by its extracted shale oil as petroleum resources have attracted increasing attention.
Shale oil is compared with natural oil, and unsaturated hydrocarbon content is high, non-hydrocarbon compound (O, S, N, heterocyclic arene etc.) content is high, shale
Oil quality is very poor, can not be used as gasoline, diesel oil or industrial chemicals application, at present mainly as fuel oil utilize, use value compared with
It is low.If deep processing can be carried out shale oil, the value of shale oil can be increased substantially.
United States Patent (USP) US4342641 is by the full fraction of shale oil at relatively low 650 °F and relatively high 800 °F of temperature
Two-stage hydrogenation is carried out at a temperature of above, hydrogenated oil can be used as jet fuel by being fractionated lighter component；Wherein compared with
The component of weight can continue to be hydrocracked, and increase jet fuel production.The patent diesel yield is low.
United States Patent (USP) US4344840 by the full fraction of shale oil be heated to it is slightly lower do not occur the temperature of sediment also, then
It is carried out in the replaceable boiling bed hydrogenation reactor of catalyst plus hydrogen, boiling bed hydrogenation product continues to react in fixed bed hydrogenation
Add hydrogen in device under higher reaction temperature, produces jet fuel and diesel oil.The patent needs to include that ebullated bed and fixed bed exist
Interior two-stage hydrogenation, investment are big.
Shale oil is carried out demetalization first by United States Patent (USP) US4950383, takes off the shale oil of metal successively by containing Ni-
The refining agent of Mo-P and cracking agent containing Co-Cr-Mo and molecular sieve carry out hydrocracking reaction, produce jet fuel.The party
Method is hydrocracking process, and target product is jet fuel rather than diesel oil.
Chinese patent 200610136416 describes the method for processing shale oil: shale oil carries out hydrofinishing first, adds
Hydrogen generates oil and distills out 350 DEG C of pervious light fractions, and the heavy distillat greater than 350 DEG C carries out catalytic cracking and produces dry gas, gasoline, bavin
Oil and catalytic heavy.But the diesel product low output and of poor quality that this method obtains.
Summary of the invention
The purpose of the present invention is to provide a kind of processing methods by shale oil production diesel oil, using delayed coking and plus hydrogen
Cracking Combined machining shale oil, production meet the high-quality diesel of state's V standard.
Above-mentioned purpose of the invention is achieved in that a kind of processing method by shale oil production diesel oil, including following
Step:
(1) the full fraction of shale oil enters distilling apparatus progress fraction cutting, and the 500 DEG C of parts < are light fraction, >=500 DEG C of portions
It is divided into heavy distillat；
(2) heavy distillat obtained by step (1) is subjected to delayed coking, separation reaction product obtains gas, gasoline fraction, diesel oil
Fraction, wax oil fraction and petroleum coke；
(3) wax oil fraction obtained by step (2) is mixed with light fraction obtained by step (1) progress hydrofinishing obtain gas,
Gasoline fraction, diesel oil distillate and tail oil, wherein tail oil boiling range is greater than 350 DEG C；
(4) hydrofinishing tail oil obtained by step (3) is hydrocracked, obtain gas, gasoline fraction, diesel oil distillate and
Recycle oil, recycle oil and tail oil mixing, continue to be hydrocracked；
(5) whole diesel oil distillates are mixed into obtain diesel product.
Processing method of the present invention by shale oil production diesel oil, in step (3), it is preferred that described plus hydrogen essence
It makes and is hydrocracked and constitute hydroconversion reaction zone, the hydroconversion reaction zone is connected by hydrofining reactor and hydrocracking reactor
It forms.
Processing method of the present invention by shale oil production diesel oil, in step (3), it is preferred that described plus hydrogen essence
Temperature processed is 280~300 DEG C, pressure is 5.0~6.0MPa, hydrogen to oil volume ratio is 800~1000, air speed is 0.5~1.5s-1；
Be hydrocracked described in step (4) temperature be 340~380 DEG C, pressure is 6.0~8.0MPa, hydrogen to oil volume ratio be 800~
1000, air speed is 1.0~2.0s-1。
Processing method of the present invention by shale oil production diesel oil, in step (3), it is preferred that described plus hydrogen essence
It makes and is hydrocracked and constitute hydroconversion reaction zone, the hydroconversion reaction zone is top filling Hydrobon catalyst, a lower part dress
Fill out the hydrogenator of the hydrocracking catalyst of anti-N low activity.
Processing method of the present invention by shale oil production diesel oil, in step (3), it is preferred that described plus hydrogen essence
Temperature processed is 280~300 DEG C, pressure is 5.0~6.0MPa, hydrogen to oil volume ratio is 800~1000, air speed is 0.5~1.5s-1；
Be hydrocracked described in step (4) temperature be 340~380 DEG C, pressure is 6.0~8.0MPa, hydrogen to oil volume ratio be 800~
1000, air speed is 1.0~2.0s-1。
Processing method of the present invention by shale oil production diesel oil, in step (1), the distilling apparatus is preferably normal
Vacuum distillation tower.
Advantages of the present invention: by the way that delayed coking and hydrocracking process to be combined, heavy constituent carries out delayed coking
Nitrogen is enriched in petroleum coke, wax oil and lighter component are mixed, carry out hydrofinishing and is hydrocracked, product is effectively reduced
The content of middle nitrogen produces the high-quality diesel for meeting state's V standard.
Detailed description of the invention
Fig. 1 is the process flow chart of the processing method of existing shale oil production diesel oil；
Fig. 2 is the process flow chart of the processing method of shale oil production diesel oil of the present invention.
Specific embodiment
The present invention will be further described in detail below with reference to specific embodiments.
Hydrobon catalyst is and hydrocracking catalyst is the independent research of middle petroleum and petrochemical industry institute:
Hydrobon catalyst is using aluminium oxide as carrier, with catalyst weight, active component include 3.5% nickel oxide,
18.0% tungsten oxide and 8.7% molybdenum oxide, surplus are alumina support；
Hydrocracking catalyst is using aluminium oxide as carrier, with catalyst weight, active component include 4.7% nickel oxide,
28.9% tungsten oxide and 6.3% fluorine, surplus are alumina support.
Comparative example 1
Shown in Figure 1, using the full fraction of Fushun shale as raw material, property is shown in Table 1.Raw material hydrofinishing first obtains
Naphtha (200 DEG C of <), diesel oil distillate (200 DEG C~350 DEG C) and tail oil (350 DEG C of >), the reaction condition of hydrofinishing are as follows: temperature
Spend 285 DEG C, pressure 5.0MPa, light oil volume ratio 850, air speed 1.0s-1；
The tail oil of hydrofinishing passes through by being hydrocracked to obtain naphtha (220 DEG C of <), diesel oil distillate (220 DEG C~350
DEG C) and tail oil (350 DEG C of >), the reaction condition being hydrocracked are as follows: 380 DEG C of reactor bed mean temperature, pressure 8.0MPa, hydrogen
Oil volume is than 800, volume space velocity 1.0h-1；The tail oil being hydrocracked is recycled back to unifining process.All diesel oil distillates mix
Diesel product, gained diesel yield 60wt%, sulfur content 30-86 μ g/g, nitrogen content 3-55 μ g/g, Cetane number 65-69.
1 shale oil properties of table
Embodiment 1
Shown in Figure 2, using the full fraction of Fushun shale as raw material, property is shown in Table 1.Feedstock oil enters atmospheric and vacuum distillation
Tower, cutting obtain light fraction (500 DEG C of <) and heavy distillat (>=500 DEG C)；Delayed coking unit is added in heavy distillat, and separation reaction produces
Object obtains gas, gasoline fraction (30~220 DEG C), diesel oil distillate (220~350 DEG C), wax oil fraction (350~500 DEG C) and stone
Oil coke (>=500 DEG C).Wax oil fraction mixed with light fraction carry out hydrofinishing obtain: gas, gasoline fraction (30~220 DEG C),
Diesel oil distillate (220~350 DEG C) and tail oil (>=350 DEG C).The tail oil of hydrofinishing, which is hydrocracked, obtains gas, gasoline evaporates
Divide (30~220 DEG C), diesel oil distillate (220~350 DEG C) and recycle oil (>=350 DEG C)；All diesel oil distillates mix to obtain diesel oil production
Product, gained diesel yield 75wt%, sulfur content < 10 μ g/g, nitrogen content 3-15 μ g/g, Cetane number 65-69.
The reaction condition of above-mentioned delayed coking are as follows: 510 DEG C of temperature, pressure 0.17MPa, recycle ratio 0.20.
The reaction condition of above-mentioned hydrofinishing are as follows: 285 DEG C of temperature, pressure 5.5MPa, hydrogen to oil volume ratio 850, air speed 1.0s-1.Hydrobon catalyst: using aluminium oxide as carrier, on the basis of catalyst entirety, each component content by weight are as follows: 3.5%
Nickel oxide, 18.0% tungsten oxide and 8.7% molybdenum oxide, surplus are alumina support.
The above-mentioned reaction condition being hydrocracked are as follows: 385 DEG C of temperature, pressure 8.0MPa, hydrogen to oil volume ratio 900, air speed 1.0s-1.Hydrocracking catalyst: using aluminium oxide as carrier, on the basis of catalyst entirety, each component content by weight are as follows: 4.7%
Nickel oxide, 28.9% tungsten oxide and 6.3% fluorine, surplus are alumina support.
The hydrofinishing and be hydrocracked and constitute hydroconversion reaction zone, the hydroconversion reaction zone by hydrofining reactor and
Hydrocracking reactor is connected in series.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (6)
1. a kind of processing method by shale oil production diesel oil, which comprises the following steps:
(1) the full fraction of shale oil enters distilling apparatus progress fraction cutting, and the 500 DEG C of parts < are light fraction, and >=500 DEG C of parts are
Heavy distillat；
(2) heavy distillat obtained by step (1) is subjected to delayed coking, separation reaction product obtains gas, gasoline fraction, diesel oil and evaporates
Point, wax oil fraction and petroleum coke；
(3) wax oil fraction obtained by step (2) is mixed into progress hydrofinishing with light fraction obtained by step (1) and obtains gas, gasoline
Fraction, diesel oil distillate and tail oil, wherein tail oil boiling range is greater than 350 DEG C；
(4) hydrofinishing tail oil obtained by step (3) is hydrocracked, obtains gas, gasoline fraction, diesel oil distillate and circulation
Oil, recycle oil and tail oil mixing, continue to be hydrocracked；
(5) whole diesel oil distillates are mixed into obtain diesel product；
In step (3), the hydrofinishing temperature is 280~300 DEG C, pressure is 5.0~6.0MPa, hydrogen to oil volume ratio 800
~1000, air speed is 0.5~1.5s-1；Be hydrocracked described in step (4) temperature be 340~385 DEG C, pressure be 6.0~
8.0MPa, hydrogen to oil volume ratio are 800~1000, air speed is 1.0~2.0s-1。
2. the processing method according to claim 1 by shale oil production diesel oil, which is characterized in that described in step (3)
Hydrofinishing and be hydrocracked constitute hydroconversion reaction zone, the hydroconversion reaction zone is by hydrofining reactor and hydrocracking reaction
Device is connected in series.
3. the processing method according to claim 1 by shale oil production diesel oil, which is characterized in that described in step (3)
Hydrofinishing and be hydrocracked and constitute hydroconversion reaction zone, the hydroconversion reaction zone be top filling Hydrobon catalyst,
Load the hydrogenator of the hydrocracking catalyst of anti-N low activity in lower part；The catalyst being hydrocracked: it is with aluminium oxide
Carrier, on the basis of catalyst entirety, each component content by weight are as follows: 4.7% nickel oxide, 28.9% tungsten oxide and 6.3%
Fluorine, surplus are alumina support.
4. the processing method according to claim 1 by shale oil production diesel oil, which is characterized in that described in step (1)
Distilling apparatus is atmospheric and vacuum tower.
5. the processing method according to claim 1 by shale oil production diesel oil, which is characterized in that described in step (3)
The catalyst of hydrofinishing: using aluminium oxide as carrier, on the basis of catalyst entirety, each component content by weight are as follows: 3.5%
Nickel oxide, 18.0% tungsten oxide and 8.7% molybdenum oxide, surplus are alumina support.
6. the processing method according to claim 1 by shale oil production diesel oil, which is characterized in that described in step (2)
The reaction condition of delayed coking are as follows: 510 DEG C of temperature, pressure 0.17MPa, recycle ratio 0.20.
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| CN109722302B (en) * | 2017-10-31 | 2021-06-11 | 中国石油化工股份有限公司 | Cracking and desulfurization combined method and device and combined process of catalytic cracking and adsorption desulfurization |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9644157B2 (en) * | 2012-07-30 | 2017-05-09 | Headwaters Heavy Oil, Llc | Methods and systems for upgrading heavy oil using catalytic hydrocracking and thermal coking |
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- 2015-12-31 CN CN201511032283.9A patent/CN106929101B/en active Active
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|---|---|---|---|---|
| CN103102975A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Method for producing clean fuel oil from ethylene tar |
| CN103102977A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Method for producing light fuel oil from ethylene tar |
| CN103102983A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Delayed coking-hydrorefining process for shale oil |
| CN103540357B (en) * | 2012-07-09 | 2015-04-08 | 中国石油化工集团公司 | Heavy oil treatment process |
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