CN102260528A - Heavy oil processing composition method for improving liquid yield - Google Patents
Heavy oil processing composition method for improving liquid yield Download PDFInfo
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- CN102260528A CN102260528A CN2010101843406A CN201010184340A CN102260528A CN 102260528 A CN102260528 A CN 102260528A CN 2010101843406 A CN2010101843406 A CN 2010101843406A CN 201010184340 A CN201010184340 A CN 201010184340A CN 102260528 A CN102260528 A CN 102260528A
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Abstract
The invention relates to a heavy oil processing composition method for improving liquid yield, which comprises the following steps of: reacting distill oil, catalytic cracking heavy cycle oil, an optional catalytic cracking oil slurry evaporated substance and an optional contact cracking wax oil mixture in a hydrogenation processing unit; after mixing the liquid material flow obtained by the hydrogenation processing unit with a heavy oil raw material, entering a contact cracking unit; and carrying out contact cracking reaction under the action of a contact agent to obtain gas, gasoline fraction, diesel oil fraction and wax oil fraction. The invention can process inferior heavy oil with high residue carbon content, improve the bed layer fluidization stability of the contact cracking process and the liquid yield, reduce the coke yield and efficiently utilize petroleum resources.
Description
Technical field
The present invention relates to a hydrocarbon ils treating processes under the situation that has hydrogen contacts cracking process with the heavy oil under a kind of situation that does not have hydrogen combined method, is a kind of processing heavy oil combined method that improves liquid yield.
Background technology
In recent years, become the demand of heavy and environmentally friendly fuel oil day by day at petroleum resources, both at home and abroad each major oil companies and scientific research institution efficiently utilize problem around heavy oil, as how improving liquid product yield, how utilizing refinery coke inferior etc. to carry out number of research projects.
The fluid coking and the flexicoking technology of Exxon Neftegas Limited's exploitation are the process that fluidisation is taken off charcoal, this process liquids product yield is than the obvious height of delayed coking process, coke yield is 1.1～1.3 times of carbon residue, but still has suitable carbon well not utilized in the oil.US4750985 has announced that a kind of heavy oil modification improves the method for liquid yield, this method is the combination process that coking and hydrocracking combine, under coking condition, handle carbon residue greater than 5.0% charging, the boiling point that obtains mixes mutually greater than 565 ℃ heavy distillate and a part of pitch and hydrogenation conversion catalyst or its presoma, starches the attitude bed hydroprocessing under the hydrogen condition and transforms having.Hydroconversion condition is: 343～538 ℃ of temperature, hydrogen dividing potential drop 0.69～55.15MPa.
In addition, the raw material carbon residue that various contact cracking processs are handled when reducing operating severity in order to increase the liquid receipts, contact substance particle bonding occurs through regular meeting all than higher in the contact cracking case, influence the problem of bed fluidizing stability.The method of taking at this problem among the US5094737 is to add Calucium Silicate powder in the fluid coking charging.But this method, the technological process of gasification installation is arranged is feasible at follow-up, but for the fluid coking process, then influences the use properties of coke.
Heavy catalytic cycle oil normally is circulated to and further adds man-hour in the catalytic cracking unit in the prior art, because heavy cycle oil contains polycyclic aromatic hydrocarbons, thereby light oil yield is low, the green coke amount is big, increase the revivifier load, reduced the treatment capacity and the economic benefit of heavy oil catalytically cracking equipment.The sulphur content of heavy cycle oil is higher in addition, and the heavy cycle oil circulation also makes the product sulphur content rise.
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of combined method of processing inferior heavy oil, the low problem of liquid yield when technical problem to be solved is the very high inferior heavy oil of processing carbon residue.
Method provided by the present invention may further comprise the steps:
(1) in the hydrotreatment unit, distillate, heavy catalytic cycle oil, optional catalytically cracked oil steam thing and the optional cracking wax-oil mixture that contacts, carry out the hydrotreatment reaction in the presence of hydrogen and hydrotreating catalyst, resultant of reaction obtains being rich in the gas stream and the liquid stream of hydrogen after separating;
(2) liquid stream of hydrotreatment unit gained, contact the cracking unit with entering after heavy oil feedstock mixes, contact cracking reaction under the effect of contact substance, resultant of reaction separates, obtain gas, gasoline fraction, diesel oil distillate and wax oil cut, and band charcoal contact substance.
In the unitary raw material of described hydrotreatment, distillate and heavy catalytic cycle oil are essential components, and it is selectable components with contacting the cracking wax oil that catalytically cracked oil steams thing.Distillate in the described step (1) is selected from one or more in coker gas oil, ethylene bottom oil, deasphalted oil, vacuum gas oil or the solvent treatment extraction oil.The thing boiling spread that steams of described catalytically cracked oil is 400～500 ℃, and by weight percentage, the thing that steams of catalytically cracked oil accounts for 15%～80% of the full cut of catalytically cracked oil.
The hydrotreatment reaction conditions is: hydrogen dividing potential drop 4.0～20.0MPa, 300～430 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000Nm
3/ m
3, volume space velocity 0.3～3.0h
-1
Hydrotreating catalyst is a loaded catalyst, and carrier is aluminum oxide and/or silica-alumina, and active metal component is selected from group VIB metal and/or VIII family base metal.
The hydrotreatment resultant of reaction obtains being rich in the gas stream and the liquid stream of hydrogen after separating, the gas stream that is rich in hydrogen can be recycled, and liquid stream then directly enters or contacts the cracking unit with entering after heavy oil feedstock mixes.To enter contact cracking unit feed integral body, by weight, the charge proportion of the liquid stream of hydrotreatment unit gained is 1.0%～20.0%.
The carbon residue of described heavy oil feedstock is 5 weight %-50 weight %, and metal content is 25-1000 μ g/g.Described heavy oil feedstock is one or more the mixture in conventional crude, acid-containing raw oil, super viscous crude, long residuum, vacuum residuum, vacuum gas oil, coker gas oil, deasphalted oil, oil sands bitumen, hydrocracking tail oil, coal tar, shale oil, jar end oil, coal liquefaction residue oil or other secondary processing distillate.
The unitary reaction conditions of described contact cracking is: 460～650 ℃ of temperature of reaction, weight hourly space velocity 1～100h
-1, the mass ratio of contact substance and hydrocarbon oil crude material is 1～20: 1, the mass ratio of water vapour and hydrocarbon oil crude material is 0.05～0.40: 1, reaction pressure 0.1MPa～1.0MPa.
Described contact substance is selected from coke, catalytic cracking spent catalyst, silica-alumina material, calcium oxide, calcium hydroxide, and rhombspar, one or more in Wingdale, the magnesium oxide, particle size range is between 20-1000 μ m, and median size is between 70-150 μ m.Particle shape is generally sphere, can be by spraying drying or method of agglomeration preparation.
Described silica-alumina material is selected from molecular sieve, amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite, aluminum oxide, quartz sand, the silicon sol one or more.
Contact cracked reaction product obtains gas, gasoline fraction, diesel oil distillate and wax oil cut after separating, and band charcoal contact substance.Described wax oil cut can loop back the hydrotreatment unit of step (1), and the raw material that also can be used as catalytic cracking enters catalytic cracking unit.Band charcoal contact substance can be recycled after regeneration.
Compared with prior art, beneficial effect of the present invention is mainly reflected in the following aspects:
At first, the present invention can process the high inferior heavy oil of carbon residue content, improves liquid yield, reduces coke yield, can efficiently utilize petroleum resources.
Secondly, the heavy cycle oil and the fluid catalytic cracking decant oil that rationally utilize catalytic cracking unit to produce reduce the catalytic cracking catalyst carbon deposit, have reduced the revivifier load, have increased the treatment capacity and the economic benefit of heavy oil catalytically cracking equipment.
The 3rd, because the charging of contact cracked is the product liquid of hydrotreatment and the mixture of inferior heavy oil raw material, so increase contact cracking process bed fluidizing stability.
Description of drawings
Accompanying drawing is the schematic flow sheet of the processing heavy oil combined method of raising liquid yield provided by the present invention.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is given further instruction, but not thereby limiting the invention.
Method provided by the present invention comprises: catalytically cracked material enters catalytic cracking unit via pipeline 1, in the presence of catalytic cracking catalyst, react, the reaction product of separating catalytic cracking, obtain dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil, heavy catalytic cycle oil and catalytically cracked oil, wherein through pipeline 3,4,5,6 caterpillars, heavy catalytic cycle oil enters hydrotreater 14 after filtering through pipeline 7 respectively for dry gas, liquefied gas, catalytically cracked gasoline and catalytic cracking diesel oil; Catalytically cracked oil enters water distilling apparatus 9 through pipeline 8, in water distilling apparatus 9, isolate resistates through pipeline 11 withdrawing devices, the thing that steams of catalytically cracked oil enters in the hydrotreater 14 through the logistics of pipeline 10 in pipeline 7, coker gas oil, ethylene bottom oil, deasphalted oil, vacuum gas oil or solvent treatment are extracted oil out and can be entered in the hydrotreater 14 via the logistics of pipeline 12 in pipeline 7, hydrogen enters hydrotreater through pipeline 13, carries out partial hydrogenation reaction under the hydrotreating catalyst existence condition having.The liquid stream that from hydrotreater 14, comes out through pipeline 15 with enter contact cracking unit the inferior heavy oil raw material after mixing by pipeline 17 enter the contact cracking unit 18, or the hydrogenation logistics of from hydrotreater 14, coming out through pipeline 15 by pipeline 16 with enter the inferior heavy oil raw material that contacts cracking unit and enter respectively in the contact cracking reaction device 18 through pipeline 17, in the presence of contact substance, contact cracking, the gas that produces, liquid mixture separates after pipeline 19 is drawn, obtain dry gas, liquefied gas, gasoline fraction, diesel oil distillate and wax oil cut, wax oil cut or advance catalytic cracking unit or advance hydrotreater, band charcoal contact substance are drawn through pipeline 20 and are entered regenerating unit or gasification installation carries out catalyst regeneration.
Describe the present invention in detail with embodiment below, but embodiment use range not thereby limiting the invention.
The hydrotreating catalyst that is adopted among the embodiment is Mo-Ni/Al
2O
3Catalyzer, wherein based on catalyzer integral body, by weight, MoO
3Be 25.1%, NiO is 3.4%, and P is 2.5%.
Contacting the contact substance that cracking process uses in embodiment and the Comparative Examples is spray-dried and kaolin high-temperature roasting.
Steam thing, the catalytic cracking of catalytically cracked oil heavily follow carburetion, the oily mixture of solvent treatment extraction, three's mass ratio was followed successively by 3: 5: 2, wherein the thing boiling spread that steams of catalytically cracked oil is 400～500 ℃, steams the 50 heavy % that thing accounts for the full cut of slurry oil.This mixture is at 385 ℃ of hydrogen dividing potential drop 12MPa, temperature of reaction, hydrogen-oil ratio 1000Nm
3/ m
3, volume space velocity 1.0h
-1Carry out the hydrotreatment reaction under the condition, the liquid stream that resultant of reaction obtains after separating is without separation, enter the contact cracking case with vacuum residuum A (its character sees Table 1) at 1: 9 by mass ratio, contact cracking with contact substance, contact cracking processing condition are: 510 ℃ of temperature of reaction, agent-oil ratio 18.0, weight hourly space velocity are 3.0h
-1The contact cracked reaction product distributes and sees Table 2.
Comparative Examples 1
Vacuum residuum A enters the contact cracking case, contacts cracking with contact substance, and contact cracking processing condition are: 510 ℃ of temperature of reaction, and agent-oil ratio 18.0, weight hourly space velocity is 3.0h
-1The contact cracked reaction product distributes and sees Table 2.
As can be seen from Table 2, liquid yield is up to 84.48% among the embodiment 1, and coke yield is 14.28%, and liquid yield only is 79.31% in the Comparative Examples 1, and coke yield is 19.53%.So, adopt method provided by the invention that contact cracking liquid product yield is increased, coke yield reduces.
Catalytic cracking heavily follows carburetion and oily mixture is extracted in solvent treatment out, and the mass ratio of the two is 6: 4, and this mixture is at 390 ℃ of hydrogen dividing potential drop 12MPa, temperature of reaction, hydrogen-oil ratio 1000Nm
3/ m
3, air speed 1.5h
-1Condition under carry out hydrotreatment reaction, the liquid stream that resultant of reaction obtains after separating is without separation, enter the contact cracking case with vacuum residuum A at 1: 19 by mass ratio, contact cracking with contact substance, contact cracking processing condition are: 580 ℃ of temperature of reaction, agent-oil ratio 10.0, weight hourly space velocity are 25.0h
-1The contact cracked reaction product distributes and sees Table 2.
Comparative Examples 2
Vacuum residuum A enters the contact cracking case, contacts cracking with contact substance, and contact cracking processing condition are: 580 ℃ of temperature of reaction, and agent-oil ratio 10.0, weight hourly space velocity is 25.0h
-1The contact cracked reaction product distributes and sees Table 2.
As can be seen from Table 2, liquid yield is up to 79.62% among the embodiment 2, and coke yield is 18.36%, and liquid yield only is 77.34% in the Comparative Examples 2, and coke yield is 20.16%.So, adopt method provided by the invention that contact cracking liquid product yield is increased, coke yield reduces.
Contact cracking wax oil, catalytic cracking heavily follow carburetion, oily mixture is extracted in solvent treatment out, and three's mass ratio was followed successively by 5: 3: 2.This mixture is at 390 ℃ of hydrogen dividing potential drop 13MPa, temperature of reaction, hydrogen-oil ratio 1000Nm
3/ m
3, air speed 1.0h
-1Condition under carry out hydrotreatment reaction, the liquid stream that resultant of reaction obtains after separating is without separation, enter the contact cracking case with vacuum residuum B (its character sees Table 1) at 1: 4 by mass ratio, contact cracking with contact substance, contact cracking processing condition are: 630 ℃ of temperature of reaction, agent-oil ratio 5.0, weight hourly space velocity are 80.0h
-1The contact cracked reaction product distributes and sees Table 2.
Comparative Examples 3
Vacuum residuum B enters the contact cracking case, contacts cracking with contact substance, and contact cracking processing condition are: 630 ℃ of temperature of reaction, and agent-oil ratio 5.0, weight hourly space velocity is 80.0h
-1The contact cracked reaction product distributes and sees Table 2.
As can be seen from Table 2, liquid yield is up to 80.39% among the embodiment 3, and coke yield is 17.11%, and liquid yield only is 73.90% in the Comparative Examples 3, and coke yield is 21.43%.So, adopt method provided by the invention that contact cracking liquid product yield is increased, coke yield reduces.
Table 1
Table 2
| |
Comparative Examples 1 | |
Comparative Examples 2 | |
Comparative Examples 3 | |
| Products distribution, weight % | ||||||
| Dry gas | 1.24 | 1.16 | 2.02 | 2.62 | 2.50 | 4.67 |
| Liquefied gas | 2.35 | 2.43 | 4.30 | 5.13 | 5.56 | 8.89 |
| Gasoline | 15.32 | 15.68 | 16.59 | 15.98 | 15.08 | 14.86 |
| Diesel oil | 25.68 | 24.16 | 26.22 | 25.13 | 26.01 | 24.55 |
| Wax oil | 41.13 | 37.04 | 32.51 | 30.98 | 33.74 | 25.60 |
| Coke | 14.28 | 19.53 | 18.36 | 20.16 | 17.11 | 21.43 |
| Liquid yield, weight % | 84.48 | 79.31 | 79.62 | 77.34 | 80.39 | 73.90 |
Annotate: liquid yield=liquefied gas+gasoline+diesel oil+wax oil
Claims (11)
1. processing heavy oil combined method that improves liquid yield comprises:
(1) in the hydrotreatment unit, distillate, heavy catalytic cycle oil, optional catalytically cracked oil steam thing and the optional cracking wax-oil mixture that contacts, carry out the hydrotreatment reaction in the presence of hydrogen and hydrotreating catalyst, resultant of reaction obtains being rich in the gas stream and the liquid stream of hydrogen after separating;
(2) liquid stream of hydrotreatment unit gained, contact the cracking unit with entering after heavy oil feedstock mixes, contact cracking reaction under the effect of contact substance, resultant of reaction separates, obtain gas, gasoline fraction, diesel oil distillate and wax oil cut, and band charcoal contact substance.
2. according to the method for claim 1, it is characterized in that distillate in the described step (1) is selected from coker gas oil, ethylene bottom oil, deasphalted oil, vacuum gas oil or solvent treatment and extracts in the oil one or more out.
3. according to the method for claim 1, it is characterized in that the thing boiling spread that steams of the catalytically cracked oil in the described step (1) is 400～500 ℃, by weight percentage, the thing that steams of catalytically cracked oil accounts for 15%～80% of the full cut of catalytically cracked oil.
4. according to the method for claim 1, it is characterized in that described step (1) hydrotreatment reaction conditions is: hydrogen dividing potential drop 4.0～20.0MPa, 300～430 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000Nm
3/ m
3, volume space velocity 0.3～3.0h
-1
5. according to the method for claim 1, it is characterized in that described step (1) hydrotreating catalyst is a loaded catalyst, carrier is aluminum oxide and/or silica-alumina, and active metal component is selected from group vib metal and/or group VIII base metal.
6. according to the method for claim 1, the carbon residue that it is characterized in that described heavy oil feedstock is 5 weight %-50 weight %, and metal content is 25-1000 μ g/g.
7. according to the method for claim 6, it is characterized in that described heavy oil feedstock is one or more the mixture in conventional crude, acid-containing raw oil, super viscous crude, long residuum, vacuum residuum, vacuum gas oil, coker gas oil, deasphalted oil, oil sands bitumen, hydrocracking tail oil, coal tar, shale oil, jar end oil, coal liquefaction residue oil or other secondary processing distillate.
8. according to the method for claim 1, it is characterized in that the unitary reaction conditions of described contact cracking is: 460～650 ℃ of temperature of reaction, weight hourly space velocity 1～100h-1, the mass ratio of contact substance and hydrocarbon oil crude material is 1～20: 1, the mass ratio of water vapour and hydrocarbon oil crude material is 0.05～0.40: 1, reaction pressure 0.1MPa～1.0MPa.
9. in accordance with the method for claim 1, it is characterized in that described contact substance is selected from coke, catalytic cracking spent catalyst, silica-alumina material, calcium oxide, calcium hydroxide, rhombspar, in Wingdale, the magnesium oxide one or more, particle size range is between 20-1000 μ m, and median size is between 70-150 μ m.
10. according to the method for claim 1, it is characterized in that described silica-alumina material is selected from molecular sieve, amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite, aluminum oxide, quartz sand, the silicon sol one or more.
11. the method according to claim 1 is characterized in that, to enter contact cracking unit feed integral body, by weight, the charge proportion of the liquid stream of hydrotreatment unit gained is 1.0%～20.0%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250567A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Hydrocracking-catalytic cracking combined treatment method for coal tar and residual oil |
| CN105586068A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Contact agent and processing method of heavy petroleum hydrocarbon |
| CN114341318A (en) * | 2019-08-12 | 2022-04-12 | 雪佛龙美国公司 | Process for increasing base oil yield |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661241A (en) * | 1985-04-01 | 1987-04-28 | Mobil Oil Corporation | Delayed coking process |
| CN1382776A (en) * | 2001-04-28 | 2002-12-04 | 中国石油化工股份有限公司 | Process for hydrogenating residual oil and catalytically cracking heavy oil |
| CN101638588A (en) * | 2008-07-31 | 2010-02-03 | 中国石油化工股份有限公司 | Combined process for delayed coking and hydrotreating |
-
2010
- 2010-05-27 CN CN201010184340.6A patent/CN102260528B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661241A (en) * | 1985-04-01 | 1987-04-28 | Mobil Oil Corporation | Delayed coking process |
| CN1382776A (en) * | 2001-04-28 | 2002-12-04 | 中国石油化工股份有限公司 | Process for hydrogenating residual oil and catalytically cracking heavy oil |
| CN101638588A (en) * | 2008-07-31 | 2010-02-03 | 中国石油化工股份有限公司 | Combined process for delayed coking and hydrotreating |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250567A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Hydrocracking-catalytic cracking combined treatment method for coal tar and residual oil |
| CN104250567B (en) * | 2013-06-25 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of coal tar and residual hydrocracking-catalytic cracking combination treatment method |
| CN105586068A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Contact agent and processing method of heavy petroleum hydrocarbon |
| CN105586068B (en) * | 2014-10-20 | 2018-08-28 | 中国石油化工股份有限公司 | A kind of processing method of contact agent and heavy petroleum hydrocarbon |
| CN114341318A (en) * | 2019-08-12 | 2022-04-12 | 雪佛龙美国公司 | Process for increasing base oil yield |
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| CN102260528B (en) | 2014-10-01 |
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