A kind of combined method of processing inferior heavy oil
Technical field
The present invention relates to hydrocarbon ils treating processes in gasification, a situation that has hydrogen of heavy oil in a kind of situation that does not have hydrogen contact cracking process, a contenting carbon material and the catalytic cracking process of a hydrocarbon ils, is by the effectively method of combination of above-mentioned several technological processs.
Background technology
In recent years, day by day become the demand of heavy and environmentally friendly fuel oil for petroleum resources, domestic and international each major oil companies and scientific research institution efficiently utilize problem around heavy oil, as how improved liquid product yield, how utilizing refinery coke inferior etc. to carry out a large amount of research work.
CN1165601C discloses a kind of method of residual hydrocracking and catalytically cracking heavy oil, the method is carried out hydrogenation reaction by residual oil at hydrotreater, the hydrogenated residue of gained enters catalytic cracking unit and carries out cracking reaction together with optional vacuum gas oil, the heavy cycle oil of catalytic cracking returns to hydrotreater, and the thing that steams that distillation slurry oil obtains returns to hydrotreater.The method is organically joined together two devices, residual oil, heavy cycle oil and slurry oil can be converted into light-end products.But this method can not be processed carbon residue and the very high inferior heavy oil of metal content.
US4263128 discloses a kind of Fluid thermal cracking and catalytic cracking combined technique, through the stock oil of preheating in riser tube bottom first with water vapour by resid feed atomization, then the inert heat carrier that is called " ARTCAT " with one mixes, (temperature is greater than 482 DEG C in pipe, to do contact between high temperature, short time, be less than 2s duration of contact, be preferably 0.5s) be injected in riser tube and contact with high temperature contact substance, enter catalytic cracking unit production benzoline through the demetallated heavy distillate of decarburization.Although this combination process can provide qualified raw material for catalytic cracking, because it is rich in aromatic hydrocarbons, in catalytic cracking, light oil yield is low, and green coke amount is large, and revivifier load is heavy, and product sulphur content is high.
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, and the method can be processed the inferior raw material of high carbon residue, high metal content, and can solve the problem how carbon in oil and hydrogen make full use of.
Method provided by the present invention comprises the following steps:
(1) heavy oil feedstock is in contact cracking unit, contact cracking reaction with contact substance, reaction effluent obtains gas I, gasoline fraction I, diesel oil distillate I, heavy oil fraction I and band charcoal contact substance after separating, wherein heavy oil fraction I enters hydrotreating unit, and band charcoal contact substance enters gasification unit;
(2) band charcoal contact substance and the vaporized chemical of step (1) gained carry out gasification reaction in gasification unit, the gas products of synthetic gas is rich in generation, this gas products is after water-gas shift, the high-purity hydrogen of gained enters hydrotreating unit, and the contact substance that gasification unit obtains regeneration returns to the contact cracking unit in step (1);
(3) the heavy oil fraction I of step (1) gained enters hydrotreating unit, under hydrogen and hydrotreating catalyst existence, carry out hydrotreatment reaction, the resultant of reaction of gained is isolated to gas II, gasoline fraction II, diesel oil distillate II and heavy oil fraction II;
(4) the heavy oil fraction II of step (3) gained enters catalytic cracking unit, and under catalytic cracking condition, reaction generates gas III, gasoline fraction III, diesel oil distillate III, heavy cycle oil and slurry oil;
(5) heavy cycle oil of step (4) gained returns to hydrotreating unit, and the slurry oil of gained returns to contact cracking unit, and the regenerated flue gas of catalytic cracking unit gained returns to gasification unit as vaporized chemical.
The carbon residue of described heavy oil feedstock is 10 % by weight-50 % by weight, and metal content is 25-1000 μ g/g; Be selected from one or more in oil at the bottom of 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, tank, coal liquefaction residue oil or other secondary processing distillate.
Inferior heavy oil raw material in contact cracking case with contact substance contact reacts, can realize the lighting of the larger degree of depth, and decarburization, demetalization.Contact cracking reaction condition in described step (1) is: 450~650 DEG C of temperature of reaction, weight hourly space velocity 1~100h
-1, the mass ratio of contact substance and heavy oil feedstock is 1~20: 1, the mass ratio of water vapour and heavy oil feedstock 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, rhombspar, one or more in Wingdale, magnesium oxide, particle size range is between 20-1000 μ m, median size is between 70-150 μ m, and particle shape is generally spherical, can be dried or method of agglomeration preparation by spraying.Described silica-alumina material is selected from one or more in molecular sieve, amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite, aluminum oxide, quartz sand, silicon sol.
The reactor types of contact cracking unit is selected from riser reactor, fluidized-bed reactor, moving-burden bed reactor or downer reactor, or is two or more reactor combining in them.Wherein riser reactor and downer reactor can be the isodiametric footpaths that also can straighten.
On described band charcoal contact substance, coke content is 0.8 % by weight-25.0 % by weight.Coke on contact substance reacts with vaporized chemical generating gasification, generates and is rich in CO+H
2gaseous product.In described step (2), gasification reaction conditions is: gasification temperature 500-1100 DEG C, preferably 650~850 DEG C, gas empty bed speed 0.03-6.0m/s, preferably 0.1~3.0m/s.Described vaporized chemical is the mixed gas that is selected from one or more formation in oxygen, air, nitrogen, water vapor, carbonic acid gas, and the oxygen level of vaporized chemical is 0-50 volume %.
The gasifier of gasification unit is selected from riser tube gasifier, fluidized-bed gasifier or moving-bed gasification device, or is the two or more gasifiers that combine in them.
The heavy oil fraction I of step (1) gained enters hydrotreating unit, contacts mainly carry out hydrogenating desulfurization, hydrodenitrification and the reaction of part aromatic saturation under the existence of hydrogen with hydrotreating catalyst.In the charging of hydrotreating unit, can also have other distillates, described distillate be selected from coker gas oil, ethylene bottom oil, deasphalted oil, vacuum gas oil or solvent treatment extract out in oil any or appoint several.Hydrotreatment reaction conditions is: hydrogen dividing potential drop 3.0~20.0MPa, 330~450 DEG C of temperature of reaction, hydrogen to oil volume ratio 200~2000Nm
3/ m
3, volume space velocity 0.3~3.0h
-1.The active metal component of described hydrotreating catalyst is selected from nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum, and carrier is selected from one or more in aluminum oxide, silicon-dioxide, amorphous aluminum silicide.
After hydrotreatment, the heavy oil fraction II of gained enters catalytic cracking unit, carries out catalytic cracking reaction under the effect of catalytic cracking catalyst.Catalytic cracking reaction condition described in step (4) is: 470~650 DEG C of temperature of reaction, 0.5~5.0 second reaction times, the weight ratio 3~20 of catalyzer and stock oil.Catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, and the weight percentage of each component is respectively: zeolite 5%~50%, inorganic oxide 5%~95%, clay 0~70%.
In the charging of catalytic cracking unit, can also have other distillates, described distillate be selected from long residuum, coker gas oil, ethylene bottom oil, deasphalted oil, vacuum gas oil or solvent treatment extract out in oil any or appoint several.
In another preferred scheme, the slurry oil of described step (4) gained distills, the slurry oil of gained steams thing and returns to hydrotreating unit, it is 400~500 DEG C that slurry oil steams thing boiling spread, by weight percentage, slurry oil steams thing and accounts for 15%~80% of the full cut of catalytically cracked oil.
Compared with prior art, beneficial effect of the present invention is mainly reflected in the following aspects:
First, the present invention is intended to process inferior heavy oil, integrated inferior heavy oil deep processing and residue carbon resistates rationally utilize two aspects, taking inferior heavy oil as raw material, maximize under the prerequisite of producing light oil, the coke of having more than needed gasifies and generates synthetic gas in vapourizing furnace, and after synthetic gas conversion, the high-purity hydrogen of gained can be for hydrotreating unit, realizes the hydrogen balance of heavy oil upgrading.Therefore the processing that, the method is inferior heavy oil provides a kind of economy, effective approach.
Secondly, the viscosity of raw material that enters hydrotreating unit is low, can improve diffusibility and the removing impurities qualitative response speed of reactant, reduces the sulphur, nickel, the content of vanadium that generate in oil, increases substantially raw material air speed; Because carbon residue, heavy metal and sulphur, the nitrogen content of the raw material of hydrotreating unit are low, can extend the hydrogenation unit operational cycle.Hydroconversion condition relaxes simultaneously, reduces plant investment cost.
The 3rd, improve catalytically cracked material, reduce coking and the metal deposition of catalytic cracking catalyst, reduce the magnitude of recruitment of catalytic cracking catalyst; The heavy cycle oil and the slurry oil that rationally utilize catalytic cracking unit to produce, reduce catalytic cracking catalyst carbon deposit, reduced revivifier load; Make full use of regenerated flue gas, set it as the vaporized chemical of gasification unit; Therefore treatment capacity and the economic benefit of heavy oil catalytically cracking equipment, have been improved.
Brief description of the drawings
Accompanying drawing is the schematic flow sheet of the combined method of processing inferior heavy oil provided by the present invention.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further described, but not thereby limiting the invention.
Processing inferior heavy oil combined method provided by the present invention comprises:
(1) inferior heavy oil raw material enters and contacts cracking unit 2 after pipeline 1 mixes with the atomized water from pipeline 11, contact cracking reaction with the regeneration contact substance from pipeline 10 with the fresh contact substance from pipeline 12, reaction product dry gas I, liquefied gas I, gasoline fraction I, the diesel oil distillate I of gained draw via pipeline 3,4,5,6 respectively, gained heavy oil fraction I enters hydrotreating unit 15 through pipeline 7, and band charcoal contact substance enters gasification unit 9 via pipeline 8;
(2) carry out gasification reaction with charcoal contact substance with from the vaporized chemical of pipeline 13 in gasification unit 9 from pipeline 8, the gas products of synthetic gas is rich in generation, this gas products is after water-gas shift, the high-purity hydrogen of gained enters hydrotreating unit 15 through pipeline 14, and the contact substance that gasification unit obtains regeneration returns to the contact cracking unit 2 in step (1) through pipeline 10;
(3) from the heavy oil fraction I of pipeline 7 with enter hydrotreating unit 15 from the hydrogen of pipeline 14 with from the hydrogen make-up of pipeline 32, under hydrogen and hydrotreating catalyst existence, carry out hydrotreatment reaction, the resultant of reaction of gained is isolated to gas II, gasoline fraction II, diesel oil distillate II and heavy oil fraction II and draws through pipeline 19,17,16 and 18 respectively; From the heavy catalytic cycle oil of pipeline 26, all can be used as hydrotreated feedstock from the optional distillate that steams thing and introduce from pipeline 28 of the catalytically cracked oil of pipeline 30 and enter hydrotreater 15.
(4) from the heavy oil fraction II of pipeline 18 separately or be mixed into catalytic cracking unit 24 with the distillate of introducing from pipeline 20, under catalytic cracking condition, reaction generates dry gas III, liquefied gas III, gasoline fraction III, diesel oil distillate III, heavy cycle oil and slurry oil and draws through pipeline 25,21,22,23,26 and 27 respectively.
(5) heavy cycle oil is circulated to hydrotreating unit 15 through pipeline 26, slurry oil can return to contact cracking unit 2 through pipeline 33, also can enter water distilling apparatus 29 after distillation through pipeline 27, steam thing and enter hydrotreating unit 15 through pipeline 30, distillation residue are discharged through pipeline 31, and the regenerated flue gas of catalytic cracking unit gained returns to gasification unit 9 as vaporized chemical through pipeline 34.
Describe the present invention in detail with embodiment below, but embodiment use range not thereby limiting the invention.
The contact substance adopting is the contact substance that the spraying dry roasting of the Y molecular sieve of salic, kaolin and 8 % by weight makes.The hydrotreating catalyst adopting is Mo-Ni/Al
2o
3catalyzer, wherein taking catalyzer entirety as basis, by weight, MoO
3be that 25.1%, NiO is that 3.4%, P is 2.5%.The catalytic cracking catalyst adopting is that trade names are CRC-1 catalytic cracking catalyst.
Embodiment 1
Enter contact cracking unit at fixed fluidized-bed reactor Raw oil A (its character is in table 1), contact cracking with contact substance, contact cracking processing condition are: 510 DEG C of temperature of reaction, and agent-oil ratio 15.0, weight hourly space velocity is 5.0h
-1.The heavy oil fraction I of reaction gained enters hydrotreating unit, and band charcoal contact substance enters gasification unit and reacts with vaporized chemical generating gasification, and the temperature of reaction of gasifying reactor is 750 DEG C, and gasification product makes the required purity hydrogen of hydrogenation after transformationreation.Contact cracking and gasification distribution of reaction products are in table 2.
The mixture of the heavy oil fraction I of contact cracking unit and the heavy cycle oil of catalytic cracking, at 385 DEG C of hydrogen dividing potential drop 10MPa, temperature of reaction, hydrogen-oil ratio 1000Nm
3/ m
3, air speed 1.0h
-1under condition, contact and react with hydrotreating catalyst, wherein hydrogen is from gasification unit.Hydrotreatment reaction product obtains gasoline fraction II, diesel oil distillate II and heavy oil fraction II after separating.Heavy oil fraction II mixes (ratio of mixing refining is 35%) and enters catalytic cracking unit with the normal slag of grand celebration, enter catalytic cracking unit feedstock property in table 3.The processing condition of catalytic cracking unit are: 500 DEG C of temperature of reaction, agent-oil ratio 8.0,0.8 second reaction times.The heavy cycle oil of catalytic cracking gained returns to hydrotreating unit, and slurry oil returns to contact cracking unit, and the regenerated flue gas of catalytic cracking unit gained returns to gasification unit as vaporized chemical.The products distribution of catalytic cracking unit gained is in table 4.
Embodiment 2
Enter contact cracking unit at fixed fluidized-bed reactor Raw oil B (its character is in table 1), contact cracking with contact substance, contact cracking processing condition are: 560 DEG C of temperature of reaction, and agent-oil ratio 10.0, weight hourly space velocity is 20.0h
-1.The heavy oil fraction I of reaction gained enters hydrotreating unit, and band charcoal contact substance enters gasification unit and reacts with vaporized chemical generating gasification, and the temperature of reaction of gasifying reactor is 850 DEG C, and gasification product makes the required purity hydrogen of hydrogenation after transformationreation.Contact cracking and gasification distribution of reaction products are in table 2.
The heavy oil fraction I of contact cracking unit, the heavy cycle oil of catalytic cracking, catalytically cracked oil steam the mixture of thing and solvent-refined oil, at 390 DEG C of hydrogen dividing potential drop 10MPa, temperature of reaction, hydrogen-oil ratio 1000Nm
3/ m
3, air speed 1.5h
-1under condition, contact and react with hydrotreating catalyst, wherein hydrogen is from gasification unit.Hydrotreatment reaction product obtains gasoline fraction II, diesel oil distillate II and heavy oil fraction II after separating.Heavy oil fraction II enters catalytic cracking unit, enters catalytic cracking unit feedstock property in table 3.The processing condition of catalytic cracking unit are: 500 DEG C of temperature of reaction, agent-oil ratio 5.0,2.0 seconds reaction times.The heavy cycle oil of catalytic cracking gained returns to hydrotreating unit, and slurry oil enters water distilling apparatus after distillation, and slurry oil steams thing and enters hydrotreating unit, and the regenerated flue gas of catalytic cracking unit gained returns to gasification unit as vaporized chemical.The products distribution of catalytic cracking unit gained is in table 4.
Embodiment 3
Enter contact cracking unit at fixed fluidized-bed reactor Raw oil B (its character is in table 1), contact cracking with contact substance, contact cracking processing condition are: 600 DEG C of temperature of reaction, and agent-oil ratio 5.0, weight hourly space velocity is 50.0h
-1.The heavy oil fraction I of reaction gained enters hydrotreating unit, and band charcoal contact substance enters gasification unit and reacts with vaporized chemical generating gasification, and the temperature of reaction of gasifying reactor is 900 DEG C, and gasification product makes the required purity hydrogen of hydrogenation after transformationreation.Contact cracking and gasification distribution of reaction products are in table 2.
The mixture of the heavy oil fraction I of contact cracking unit, the heavy cycle oil of catalytic cracking and vacuum gas oil, at 385 DEG C of hydrogen dividing potential drop 12MPa, temperature of reaction, hydrogen-oil ratio 1200Nm
3/ m
3, air speed 1.2h
-1under condition, contact and react with hydrotreating catalyst, wherein hydrogen is from gasification unit.Hydrotreatment reaction product obtains gasoline fraction II, diesel oil distillate II and heavy oil fraction II after separating.The normal slag of heavy oil fraction II and grand celebration (ratio of mixing refining is 30%) enters catalytic cracking unit, enters catalytic cracking unit feedstock property in table 3.The processing condition of catalytic cracking unit are: 510 DEG C of temperature of reaction, agent-oil ratio 10.0,3.0 seconds reaction times.The heavy cycle oil of catalytic cracking gained returns to hydrotreating unit, and slurry oil returns to contact cracking unit, and the regenerated flue gas of catalytic cracking unit gained returns to gasification unit as vaporized chemical.The products distribution of catalytic cracking unit gained is in table 4.
Comparative example
Residual oil A in fixed fluidized-bed reactor (its character is in table 1) enters catalyst cracker, react with catalytic cracking catalyst, catalytic cracking process condition is: 500 DEG C of temperature of reaction, agent-oil ratio 7.0, in 1.5 seconds reaction times, catalytic cracking production distributes in table 4.As can be seen from Table 4, the transformation efficiency of catalytic cracking is only 66.60 % by weight, and catalytic cracking total liquid yield is only 65.49 weight, all lower than method provided by the invention.
Table 1
Table 2
|
Embodiment 1 |
Embodiment 2 |
Embodiment 3 |
Contact crackate distributes, % by weight |
|
|
|
Dry gas |
1.24 |
2.56 |
3.48 |
Liquefied gas |
2.35 |
10.89 |
8.88 |
Gasoline fraction |
15.32 |
28.75 |
25.16 |
Diesel oil distillate |
24.68 |
22.14 |
24.33 |
Heavy oil fraction |
37.66 |
15.54 |
18.87 |
Coke |
18.75 |
20.12 |
19.28 |
Total liquid yield, % by weight |
80.01 |
77.32 |
77.24 |
Gasification product, volume % |
|
|
|
(CO+H
2)
|
52.34 |
71.83 |
69.28 |
CO |
30.15 |
46.26 |
38.45 |
H
2 |
22.19 |
25.57 |
30.83 |
Table 3
Catalytic cracking unit feedstock property |
Embodiment 1 |
Embodiment 2 |
Embodiment 3 |
Carbon residue, % by weight |
3.15 |
1.61 |
4.50 |
Metal content, μ g/g |
5.21 |
4.38 |
3.68 |
S, % by weight |
0.85 |
0.76 |
1.01 |
N, % by weight |
0.05 |
0.08 |
0.25 |
Catalytic cracking catalyst regeneration temperature, DEG C |
679 |
675 |
688 |
Table 4
|
Embodiment 1 |
Embodiment 2 |
Embodiment 3 |
Comparative example |
Products distribution, % by weight |
|
|
|
|
Dry gas |
1.99 |
2.34 |
2.97 |
3.16 |
Liquefied gas |
16.78 |
15.45 |
17.00 |
16.44 |
Gasoline fraction |
36.23 |
37.75 |
37.69 |
26.72 |
Diesel oil distillate |
18.35 |
18.02 |
16.77 |
22.33 |
Heavy cycle oil+slurry oil |
13.51 |
13.32 |
12.79 |
11.07 |
Coke |
13.14 |
13.12 |
12.78 |
20.28 |
Transformation efficiency, % |
68.14 |
68.66 |
70.44 |
66.60 |
Total liquid yield, % by weight |
71.36 |
71.22 |
71.46 |
65.49 |
Note: catalytic cracking transformation efficiency=dry gas+liquefied gas+gasoline+coke
Total liquid receipts=liquefied gas+gasoline+diesel oil