CN104593059A - Hydrogenation process for FCC recycle oil - Google Patents
Hydrogenation process for FCC recycle oil Download PDFInfo
- Publication number
- CN104593059A CN104593059A CN201310532400.2A CN201310532400A CN104593059A CN 104593059 A CN104593059 A CN 104593059A CN 201310532400 A CN201310532400 A CN 201310532400A CN 104593059 A CN104593059 A CN 104593059A
- Authority
- CN
- China
- Prior art keywords
- hydro
- catalyst
- upgrading
- reaction
- reaction zone
- 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.)
- Granted
Links
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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
Landscapes
- 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)
- Catalysts (AREA)
Abstract
The invention discloses a hydrogenation process for FCC recycle oil. The method comprises the following steps that: after mixing of FCC recycle oil with hydrogen, the obtained mixture enters a hydro-treating reaction zone and sequentially contacts with a hydro-protecting catalyst, a hydrofining catalyst and a hydro-upgrading catalyst A for hydrogenation reaction; the effluent obtained after hydro-treatment enters a hydro-upgrading reaction zone where a hydro-upgrading catalyst B containing amorphous silicon aluminum and modified Y zeolite is used, and undergoes hydro-upgrading reaction in the presence of hydrogen; and the effluent obtained after hydro-upgrading enters a hydro-finishing reaction zone and undergoes hydro-finishing reaction, and hydro-finishing products are separated so as to obtain transformer oil. The hydrogenation processing method for FCC recycle oil provided by the invention uses FCC recycle oil as a raw material to produce transformer oil, so raw material sources of transformer oil products can be broadened and special oil products meeting higher quality requirements can be produced.
Description
Technical field
The present invention relates to a kind of production method of specialty oil products, specifically a kind of FCC recycle oil adopts hydrotreatment-hydro-upgrading-hydrofinishing combined hydrogenation processing method.
Background technology
Catalytic cracking (FCC) process is one of important means of light materialization of heavy oil, and catalytic cracking heavy oil refers to catalytic cracking recycle oil, reprocessed oil slurry or externally extracting oil, and its main component is the stable hydrocarbon of aromatic hydrocarbons and easy cracking.A large amount of commercial practice and research work show, existing catalytic cracking unit adopts full freshening to operate, and occur that green coke amount increases in recycle stock containing higher heavy arene, and the treatment capacity of device declines.
As secondary processing product, compound containing a large amount of alkene, aromatic hydrocarbons and sulphur, nitrogen, oxygen in recycle stock, sulphur, the compound of nitrogen oxygen and metal is concentrated again in the heavy arene obtained after furfural extraction, these are all the active ingredients of oxidation, condensation reaction, thus, the heavy arene stability of extracting out in FCC recycle stock is poor, heat, light, air all can affect its stability, the very fast blackening caking of color in put procedure, when using as industrial chemicals, color crosses the dark and unstable obstacle becoming processing further, affects use value.
CN200810226047.4 discloses a kind of production method of transformer oil base oil.First normal for Suizhong 36-1 two wires distillate is carried out furfural treatment, obtains treated oil, then add denitrfying agent and carry out denitrogenation, except denitrification slag, then add carclazyte, carry out clay-filtered, finally obtain transformer oil base oil.But the method yield is low, poor continuity, also there is nitrogen slag and clay treated environmental problem.
CN201010222066.7 discloses a kind of method adopting perhydro method to produce transformer oil base oil.With cycloalkyl distillate for raw material, the one-stage serial hydrogenation technique of hydrotreatment-hydrodewaxing-hydrofinishing is adopted to produce transformer oil base oil and other specialty oil products.The method energy consumption is low, good product quality, but there is the problem of cycloalkyl distillate resource-constrained.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of with the method for FCC recycle oil hydrotreatment-hydro-upgrading-hydrofinishing combined hydrogenation technique.
FCC recycle oil method of hydrotreating of the present invention, comprises following content:,
(1) FCC recycle oil enters hydrotreatment reaction zone after mixing with hydrogen, contacts successively carry out hydrogenation reaction with hydrogenation protecting catalyst, Hydrobon catalyst with catalyst for hydro-upgrading A;
(2) step (1) gained hydrotreatment effluent enters hydro-upgrading reaction zone, and hydro-upgrading reaction zone uses the catalyst for hydro-upgrading B containing amorphous aluminum silicide and modified Y zeolite, in presence of hydrogen, carries out hydro-upgrading reaction;
(3) step (2) gained hydro-upgrading effluent enters hydrofinishing reaction zone, in presence of hydrogen, with hydrofinishing catalyst exposure, carry out hydrofinishing reaction, hydrofinishing product is isolated to low fragrant spirit fraction, transformer oil cut and refrigerator oil cut.
In the inventive method; hydrotreatment reaction zone loads hydrogenation protecting catalyst, Hydrobon catalyst and catalyst for hydro-upgrading A from top to bottom; the admission space ratio of hydrogenation protecting catalyst, Hydrobon catalyst and catalyst for hydro-upgrading A is 10 ~ 60:20 ~ 70:20 ~ 70, is preferably 10 ~ 30:45 ~ 60:30 ~ 45.
In the inventive method; hydrotreatment reaction zone uses conventional hydrogenation protecting catalyst; the FZC series protective material of Fushun Petrochemical Research Institute (FRIPP) development and production can be adopted; also can conventionally prepare; these catalyzer generally with porous refractory inorganic oxide if aluminum oxide is for carrier; group vib and/or group VIII metal such as the oxide compound of W, Mo, Co, Ni etc. are active ingredient, optionally add other various auxiliary agent as the catalyzer of the elements such as P, Si, F, B.
In the inventive method, the Hydrobon catalyst that hydrotreatment reaction zone uses, can select this field general goods catalyzer, also can prepare by this area general knowledge.The commercial catalysts that can select as Fushun Petrochemical Research Institute (FRIPP) development and production 3936,3996, the Hydrobon catalyst such as FF-16, FF-26.
In the inventive method, hydrotreatment reaction zone uses the catalyst for hydro-upgrading A containing amorphous aluminum silicide and modified Y zeolite.Contain in described catalyst for hydro-upgrading A: the group VIII metal (with oxide basis) of the modified Y zeolite of 10wt% ~ 35wt% amorphous aluminum silicide, 2wt% ~ 15wt%, the group VIB metal (with oxide basis) of 20wt% ~ 50wt% and 8wt% ~ 15wt%.The character of amorphous aluminum silicide wherein used is as follows: silicon oxide-containing 20wt% ~ 70wt%, and specific surface is 350 ~ 600m
2/ g, pore volume is 1.0 ~ 2.0mL/g, and infrared acidity is 0.20 ~ 0.40mmol/g, and the pore volume that the pore volume of bore dia 4 ~ 10nm accounts for 85% ~ 95%, >15nm of total pore volume accounts for less than 5% of total pore volume; Preferred property is as follows: silicon oxide-containing 25wt% ~ 40wt%, and specific surface is 500 ~ 630m
2/ g, pore volume is 1.2 ~ 1.6mL/g.The character of modified Y zeolite wherein used is as follows: SiO
2/ Al
2o
3mol ratio is 40 ~ 60, and lattice constant is 2.420 ~ 2.450nm, and relative crystallinity is 85% ~ 95%, infrared acidity 0.2 ~ 0.4mmol/g, and wherein the middle strong acid distribution of 300 ~ 500 DEG C is concentrated, and account for 60 ~ 70% of total acid, specific surface area is 500 ~ 1000m
2/ g, pore volume 0.35 ~ 0.55mL/g, wherein the pore volume of the secondary mesopore of 4 ~ 15nm accounts for 35% ~ 55% of total pore volume.The specific surface area of catalyst for hydro-upgrading is 220 ~ 300m
2/ g, pore volume is 0.3 ~ 0.5mL/g, and the pore volume of bore dia 3 ~ 10nm accounts for 80% ~ 95% of total pore volume, and be preferably 85% ~ 95%, infrared acidity is at 0.2 ~ 0.4mmol/g.
In the inventive method, hydro-upgrading reaction zone uses the high-activity hydrogenation modifying catalyst B containing amorphous aluminum silicide and modified Y zeolite.Contain in described catalyst for hydro-upgrading B: the group VIII metal (with oxide basis) of the modified Y zeolite of 20wt% ~ 60wt% amorphous aluminum silicide, 5wt% ~ 25wt%, the group VIB metal (with oxide basis) of 10wt% ~ 30wt% and 4wt% ~ 10wt%.The character of amorphous aluminum silicide wherein used is as follows: silicon oxide-containing 10wt% ~ 60wt%, and specific surface is 400 ~ 650m
2/ g, pore volume is 1.0 ~ 1.8mL/g, and infrared acidity is 0.34 ~ 0.50mmol/g, and the pore volume that the pore volume of bore dia 4 ~ 10nm accounts for 85% ~ 95%, >15nm of total pore volume accounts for less than 5% of total pore volume; Preferred property is as follows: silicon oxide-containing 10wt% ~ 35wt%, and specific surface is 530 ~ 650m
2/ g, pore volume is 1.2 ~ 1.5mL/g.The character of modified Y zeolite wherein used is as follows: SiO
2/ Al
2o
3mol ratio is 40 ~ 60, and lattice constant is 2.425 ~ 2.440nm, and relative crystallinity is 80% ~ 100%, infrared acidity 0.1 ~ 0.5mmol/g, and wherein the middle strong acid distribution of 250 ~ 550 DEG C is concentrated, and account for 60 ~ 70% of total acid, specific surface area is 600 ~ 900m
2/ g, pore volume 0.3 ~ 0.6mL/g, wherein the pore volume of the secondary mesopore of 4 ~ 15nm accounts for 40% ~ 50% of total pore volume.The components such as aluminum oxide, zirconium white, titanium oxide can also be contained in catalyst for hydro-upgrading.The specific surface area of catalyst for hydro-upgrading is 220 ~ 300m
2/ g, pore volume is 0.3 ~ 0.6mL/g, and the pore volume of bore dia 3 ~ 10nm accounts for 75% ~ 95% of total pore volume, and be preferably 85% ~ 95%, infrared acidity is at 0.3 ~ 0.5mmol/g.
In the inventive method, catalyst for hydro-upgrading A is compared with the composition of catalyst for hydro-upgrading B, group VIB metal in catalyst for hydro-upgrading B and group VIB total metal content 10 ~ 25 percentage ratios higher than the total content of the two in catalyst for hydro-upgrading A, the amorphous aluminum silicide in catalyst for hydro-upgrading B and the total content of modified Y zeolite 10 ~ 25 percentage ratios lower than the total content of the two in catalyst for hydro-upgrading A.
In the inventive method, hydrofinishing reaction zone uses conventional hydrofinishing catalyzer, its active metal component is group vib and group VIII metal, uses procatalyst to carry out prevulcanized, ensures that hydrogenation active metals is in sulphided state in reaction process.Described group vib metal is selected from Mo and/or W, its content with oxide basis for 10 ~ 25%; Group VIII metal is selected from Co and/or Ni, its content with oxide basis for 3 ~ 7%.
In the inventive method, the reaction conditions of hydrotreatment reaction zone is: reaction pressure 10.0 ~ 20.0MPa, preferably 12.0 ~ 15.0MPa; Temperature of reaction 320 ~ 400 DEG C, is preferably 350 ~ 385 DEG C; Hydrogen to oil volume ratio 500:1 ~ 5000:1; Preferred 800:1 ~ 1000:1; Volume space velocity 0.1 ~ 10.0h
-1, preferably 0.4 ~ 1.0h
-1.
In the inventive method, the reaction conditions of hydro-upgrading reaction zone is: reaction pressure 5.0 ~ 20.0MPa, preferably 12.0 ~ 15.0MPa; Temperature of reaction 250 ~ 410 DEG C, preferably 330 ~ 390 DEG C; Hydrogen to oil volume ratio 500:1 ~ 1500:1, preferred 800:1 ~ 1000:1; Volume space velocity 0.1 ~ 1.5h
-1, preferably 0.5 ~ 1.2h
-1.
In the inventive method, in step (3), the reaction conditions of hydrofinishing reaction zone is: reaction pressure 10.0 ~ 20.0MPa, preferably 12.0 ~ 15.0MPa; Temperature of reaction 250 ~ 350 DEG C, preferably 280 ~ 320 DEG C; Hydrogen to oil volume ratio 500:1 ~ 1500:1, preferred 800:1 ~ 1000:1; Volume space velocity 0.1 ~ 10.0h
-1, preferably 0.5 ~ 1.2h
-1.
Compared with prior art, tool of the present invention has the following advantages:
(1) in the inventive method, FCC recycle oil first removes a large amount of sulphur nitrogen by hydrofining reaction on top, hydrotreatment reaction zone, fractional saturation condensed-nuclei aromatics simultaneously, due to hydrofining reaction heat release, make hydrotreatment reaction zone temperature of lower relatively high, due to hydrotreated lube base oil reaction be one not only by thermodynamic effects but also by the reversible reaction of kinetic effect, in the inventive method, by low at bottom, hydrotreatment reaction zone filling vector contg, hydrogenation component content height and hydrogenation activity high, the catalyst for hydro-upgrading A that upgrading activity is low, under the matching effect of catalyst for hydro-upgrading A Hydrogenation and open-loop performance, ensure that condensed-nuclei aromatics hydrotreated lube base oil reaction forward carries out ring-opening reaction while carrying out, the generation of the reversed reaction at utmost avoiding condensed-nuclei aromatics hydrotreated lube base oil to react, and catalyst for hydro-upgrading A open loop activity is low, side chain cleavage reaction can not be there is, make the aromatic hydrocarbons that the number of rings of condensed-nuclei aromatics hydrotreated lube base oil generation belt length side chain is lower, and sulphur nitrogen can be removed further, ensure that liquid is received and object product yield, object product viscosity declines little, to break simultaneously and hindered condensed-nuclei aromatics saturated sterically hindered further, can react under the condition more relaxed for hydro-upgrading reaction zone and create condition.
(2) the inventive method adopts suitable high and low Active hydrogenation modifying catalyst combination, after the open loop of hydro-upgrading reaction zone and hydrofinishing, in raw material, most of thrcylic aromatic hydrocarbon and double ring arene change into dicyclo and mononuclear aromatics, can obtain low-temperature performance, with rubber mutual solubility and all good transformer oil of oxidation stability.For the FCC recycle oil that added value is lower provides a kind of processing works improving its economy, and develop a kind of new raw material for transformer oil.Adopt one-stage serial combination process, make each section process raw material with processing condition and catalyzer reasonably combined, give full play to the activity of catalyzer, ensure quality product, expand transformer oil raw material sources.Adopt the catalytic cracking recycle oil processing scheme production lightweight transformer oil progressively removing various impurity relaxed, aromatic hydrocarbons condensation carbon deposit in catalytic cracking recycle oil can be avoided under single hop high temperature, thus has a strong impact on the work-ing life of catalyzer.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
Below in conjunction with accompanying drawing, the inventive method is described in detail.
As shown in Figure 1; FCC recycle oil 1 mixes back end hydrogenation treatment reactor 3 with hydrogen 2; contact with catalyst for hydro-upgrading A with hydrogenation protecting catalyst, Hydrobon catalyst successively; carry out hydrogenation reaction, gained hydrofining effluent 4 enters hydro-upgrading reaction zone 5, in presence of hydrogen; contact with catalyst for hydro-upgrading B; carry out saturated open loop to two rings and a small amount of thrcylic aromatic hydrocarbon, on rear side of maintenance open loop simultaneously, chain is complete, becomes the monocycle or two Polycyclic aromatic hydrocarbons of being with many side chains.Hydro-upgrading reaction product 6 enters hydrofinishing reaction zone 7, react under hydrogen and Hydrobon catalyst exist, hydrofinishing product 8 enters separation system 9, described separation system 9 generally comprises high-pressure separator and light pressure separator, separating obtained gas phase 10 returns hydrotreating reactor 3 as recycle hydrogen, liquid product 11 obtains low fragrant solvent oil 13, transformer oil 14 and refrigerator oil 15 after entering separation column 12 separation.
Below in conjunction with embodiment, the present invention will be further described.
The various catalyzer related in embodiment can select commercial catalyst by character, also can prepare by this area knowledge.The commercial catalysts that the hydrogenation protecting agent of hydroprocessing processes can be selected is as hydrogenation protecting agent such as FZC-100, FZC-102A, FZC-103 of Fushun Petrochemical Research Institute's development and production; The commercial catalysts that can select of Hydrobon catalyst as Fushun Petrochemical Research Institute's development and production 3936,3996, the Hydrobon catalyst such as FF-16, FF-26; The commercial catalysts that hydrofinishing process can be selected is as commodity Hydrobon catalysts such as FV-10, FV-20 of Fushun Petrochemical Research Institute's development and production.
The preparation process of catalyst for hydro-upgrading of the present invention comprises: after amorphous aluminum silicide and modified Y zeolite being mixed, add tackiness agent kneading, roll agglomerating after, extruded moulding on banded extruder and obtain carrier, then load hydrogenation active metals.
The preparation method of amorphous aluminum silicide used, comprises the steps:
A, preparation sodium aluminate solution, sodium silicate solution;
B, by sodium aluminate solution and sodium silicate solution and stream joins in plastic cans, ventilate simultaneously and pass into CO
2gas, adjustment sodium aluminate solution, sodium silicate solution and CO
2flow, controlling material pH value in plastic cans is 9 ~ 11, and controlling neutralization reaction temperature is 20 ~ 50 DEG C, and the neutralization reaction time is 0.5 ~ 1.5 hour;
C, under the control temperature and pH value of step b, said mixture ventilate stablize 0.5 ~ 3.0 hour, be preferably 0.5 ~ 1.0 hour;
D, the solidliquid mixture of step c gained filtered and washs;
E, steps d drying and crushing is obtained amorphous aluminum silicide.
In step a, the concentration of sodium aluminate solution is 25 ~ 60 gAl
2o
3/ L, is preferably 30 ~ 45gAl
2o
3/ L, the concentration of sodium silicate solution is 100 ~ 250gSiO
2/ L, is preferably 100 ~ 150 g SiO
2/ L.
The slurries of steps d gained are filtered and uses 50 ~ 90 DEG C of deionized waters to be washed till neutrality, then 110 ~ 130 DEG C of dryings 6 ~ 8 hours.
PH value in step b is generally constant is 9 ~ 11, is preferably 9.5 ~ 10.5; The neutralization reaction time is generally 0.5 ~ 1.5 hour, is preferably 45 ~ 60 minutes.
In step b, CO
2concentration is 20v% ~ 50v%.Ventilation refers to pass into gas from reaction plastic pot bottom, makes reaction system even, can pass into air or other is not containing CO
2gas.
Amorphous aluminum silicide with sodium aluminate, water glass and carbonic acid gas for prepared by raw material.The method is particularly suitable for the producer adopting sintering process explained hereafter aluminum oxide, with its intermediates sodium aluminate solution and by-product CO
2gas is raw material production amorphous aluminum silicide, the Na produced
2cO
3mother liquor can be circulated to sintering process to provide part Na
2cO
3, form closed cycle, and do not produce contaminated wastewater.
Modified Y zeolite by NaY by the NH of pH value between 1 ~ 3
4 +exchange, hydrothermal treatment consists and acid treatment are prepared from.Concrete preparation process is as follows:
NaY zeolite is by a NH
4nO
3after exchange, and then with oxalic acid and NH
4nO
3mixed solution, carries out second time NH in pH value between 1 ~ 3
4 +exchange, then under 0.080 ~ 0.098 MPa and 500 ~ 550 DEG C condition, carry out first time hydrothermal treatment consists, carry out NH again after hydrothermal treatment consists for the first time
4nO
3exchange, carry out second time hydrothermal treatment consists, second time hydrothermal conditions is 0.1 ~ 0.2MPa and 500 ~ 700 DEG C.Finally use HNO
3carry out acid treatment, obtain modified Y zeolite.
The carrying method of catalyst for hydro-upgrading active metal, can adopt the routine techniques such as kneading method, pickling process to prepare, preferably adopt first extruded moulding, then the mode of impregnating metal component.After the preparation of catalyzer of the present invention adopts modified Y zeolite to mix with contained amorphous silica-alumina dry glue powder, add the appropriate tackiness agent prepared by SB aluminum oxide and nitric acid peptization, kneading or be rolled into paste, extruded moulding, is generally the cylindrical bars of diameter 3 ~ 8 millimeters.Carrier through 100 ~ 130 DEG C of dryings 4 ~ 14 hours, 500 ~ 600 DEG C of roastings 3 ~ 10 hours.After activation, adopt saturated or excessive impregnation fluid containing the steeping fluid of hydrogenation metal, then carry out 100 ~ 130 DEG C of dryings 4 ~ 14 hours, roasting 3 ~ 10 hours at 450 ~ 550 DEG C and make catalyzer.
Particular content and the effect of the inventive method are described below by specific embodiment.
Implementation column below will be further described method provided by the invention, but scope not thereby limiting the invention.The catalytic cracking recycle oil feedstock property of process of the present invention is: density (20 DEG C): 0.988 g/cm
3, boiling range 160 ~ 450 DEG C, carbon residue: 0.01%; Sulphur: 9000 μ g/g, nitrogen: 1500 μ g/g, paraffinic hydrocarbons is: 10%; Naphthenic hydrocarbon is: 7%; Aromatic hydrocarbons is 83%, condensation point-20 DEG C, and bituminous matter is 3%; Wherein metal impurities 0.85 μ g/g.
Embodiment 1 amorphous aluminum silicide preparation process involved by catalyzer of the present invention below, example 2 is hydro-upgrading catalyst for hydro-upgrading A preparation process, and example 3 is hydro-upgrading catalyst for hydro-upgrading B preparation process.
Embodiment 1
700 solid sodium aluminates being mixed with concentration is 200gAl
2o
3the dense sodium aluminate solution of/L, redilution becomes concentration to be 35gAl
2o
3/ L sodium aluminate working solution (a), gets containing SiO
2the sodium silicate solution of 28wt%, redilution becomes concentration to be 150gSiO
2/ L water glass working solution 2L(b).Get the steel plastic cans of a 30L, open the container valve having (a) and (b) respectively simultaneously, ventilate simultaneously and pass into the CO that concentration is 45v%
2gas, the flow of setting (a) and (b) makes the reaction times at 1 hour, and adjusts CO rapidly
2flow, make the pH of system remain on about 10.0, temperature of reaction 30 DEG C, after (a) and (b) have reacted, stop passing into CO
2, then ventilate and stablize 40 minutes, slurries filter and use 85 DEG C of deionized waters to be washed till neutrality.120 DEG C of dryings 8 hours, pulverize and sieve to obtain amorphous aluminum silicide GL.This amorphous aluminum silicide silicon oxide-containing 30wt%, after activation, specific surface is 560m
2/ g, pore volume is 1.41ml/g, and infrared acidity is 0.42mmol/g, and 90%, the >15nm pore volume that the pore volume of bore dia 4 ~ 10nm accounts for total pore volume accounts for 3% of total pore volume.
Embodiment 2
Get 80g sial GL, 30g modified Y zeolite (SiO
2/ Al
2o
3be 40, lattice constant is 2.432nm, infrared acidity 0.19mmol/g specific surface 866m
2/ g, pore volume 0.52ml/g) tackiness agent be made up of nitric acid and SB alumina peptization with 250g, kneading, rolls, and making can the paste of extrusion, extruded moulding.110 DEG C of dryings 6 hours, 550 DEG C of roastings 4 hours, obtained carrier A.Again with 200ml Mo-Mi co-impregnated solution excessive dipping 80gA2 hour, 110 DEG C of dryings 6 hours, 500 DEG C of roastings 4 hours, obtain catalyst for hydro-upgrading A.Catalyst for hydro-upgrading physical property is in table 2.
Embodiment 3
Get 100g sial GL, 45g modified Y zeolite (SiO
2/ Al
2o
3be 40, lattice constant is 2.432nm, infrared acidity 0.19mmol/g specific surface 866m
2/ g, pore volume 0.52ml/g) tackiness agent be made up of nitric acid and SB alumina peptization with 310g, kneading, rolls, and making can the paste of extrusion, extruded moulding.110 DEG C of dryings 6 hours, 550 DEG C of roastings 4 hours, obtained carrier B.Again with 200ml Mo-Mi co-impregnated solution excessive dipping 80gA2 hour, 110 DEG C of dryings 6 hours, 500 DEG C of roastings 4 hours, obtain catalyst for hydro-upgrading B.Catalyst for hydro-upgrading physical property is in table 1.
Table 1 catalyst for hydro-upgrading physico-chemical property
| Catalyzer is numbered | Catalyst for hydro-upgrading A | Catalyst for hydro-upgrading B |
| MoO 3，wt% | 28.5 | 19.0 |
| NiO，wt% | 10.0 | 6.0 |
| Specific surface area, m 2/g | 241 | 256 |
| Pore volume, ml/g | 0.42 | 0.46 |
| The pore volume of bore dia 3 ~ 10nm accounts for total pore volume, % | 91.0 | 91.4 |
| Infrared total acidity, mmol/g | 0.285 | 0.361 |
Embodiment 4
The admission space of hydrotreatment reaction zone filling hydrogenation protecting catalyst FZC-103, Hydrobon catalyst 3936 and catalyst for hydro-upgrading A, hydrogenation protecting catalyst FZC-103, Hydrobon catalyst 3936 and catalyst for hydro-upgrading A is than being 1:3:2; Hydro-upgrading reaction zone filling catalyst for hydro-upgrading B; Hydrofinishing reaction zone filling Hydrobon catalyst FV-10, the processing condition of hydrogenation process and product property are in table 2.
Comparative example 1
Adopt the raw material identical with embodiment 1, difference be hydrotreatment products without hydro-upgrading, directly enter hydrofinishing reactor.The admission space of hydrotreatment reaction zone filling hydrogenation protecting catalyst FZC-103, Hydrobon catalyst 3936 and catalyst for hydro-upgrading A, hydrogenation protecting catalyst FZC-103, Hydrobon catalyst 3936 and catalyst for hydro-upgrading A is than being 1:3:2.Hydrofinishing reaction zone filling Hydrobon catalyst FV-10, the processing condition of hydrogenation process and product property are in table 2.
Comparative example 2
Adopt the raw material identical with embodiment 1; difference is that bottom, hydrotreatment reaction zone does not fill catalyst for hydro-upgrading A; hydrotreatment reaction zone filling hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936; the admission space of hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936 is than being 1:5; hydro-upgrading reaction zone filling catalyst for hydro-upgrading B; hydrofinishing reaction zone filling Hydrobon catalyst FV-10, the processing condition of hydrogenation process and product property are in table 2.
The processing condition of table 2 embodiment and comparative example and result
| Test number | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Hydroprocessing technique condition | |||
| Temperature of reaction, DEG C | 370 | 370 | 385 |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 |
| Volume space velocity, h -1 | 0.4 | 0.4 | 0.4 |
| Process oily nitrogen content/μ gg -1 | 10 | 10 | 10 |
| Hydro-upgrading reaction process condition | |||
| Temperature of reaction, DEG C | 375 | 375 | |
| Reaction pressure, MPa | 15.0 | 15.0 | |
| Hydrogen to oil volume ratio | 800:1 | 800:1 | |
| Volume space velocity, h -1 | 0.6 | 0.6 | |
| Post-refining reaction process condition | |||
| Temperature of reaction, DEG C | 300 | 310 | 305 |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 800:1 | 800:1 | 800:1 |
| Volume space velocity, h -1 | 0.6 | 0.6 | 0.6 |
| Product property | |||
| Low fragrant solvent oil | |||
| Yield, % | 12.85 | 2.86 | 11.40 |
| S，μg/g | 3.5 | 3.9 | 4.8 |
| Color (Sai Shi), number | +30 | +30 | +30 |
| Aromaticity content, % | 0.15 | 0.85 | 0.29 |
| Bromine index, mgBr/100g | 95 | 75 | 116 |
| Transformer oil | |||
| Yield, % | 58.4 | 65.1 | 58.9 |
| Density (20 DEG C), g/cm 3 | 890.1 | 896.5 | 885.6 |
| S，μg/g | 10.5 | 10.3 | 9.2 |
| N，μg/g | 5.6 | 6.0 | 6.3 |
| Flash-point (closing), DEG C | 146 | 144 | 143 |
| Acid number, mgKOH/g | 0 | 0 | 0 |
| Color (Sai Shi), number | +30 | +30 | +30 |
| Viscosity (40 DEG C), mm 2/s | 7.512 | 8.522 | 7.223 |
| Condensation point, DEG C | -33 | -21 | -27 |
| Refrigerator oil | |||
| Yield, % | 28.75 | 31.04 | 39.7 |
| Condensation point, DEG C | -24 | -15 | -21 |
| Acid number, mgKOH/g | 0 | 0 | 0 |
| Color (Sai Shi), number | +30 | +30 | +30 |
| S，μg/g | 12.6 | 10.9 | 11.6 |
| Viscosity (40 DEG C), mm 2/s | 21.33 | 25.75 | 23.40 |
Claims (13)
1. a FCC recycle oil method of hydrotreating, comprises following content:
(1) FCC recycle oil enters hydrotreatment reaction zone after mixing with hydrogen, contacts successively carry out hydrogenation reaction with hydrogenation protecting catalyst, Hydrobon catalyst with catalyst for hydro-upgrading A;
Step (1) gained hydrotreatment effluent enters hydro-upgrading reaction zone, and hydro-upgrading reaction zone uses
(2) the catalyst for hydro-upgrading B containing amorphous aluminum silicide and modified Y zeolite, in presence of hydrogen, carries out hydro-upgrading reaction;
(3) step (2) gained hydro-upgrading effluent enters hydrofinishing reaction zone, in presence of hydrogen, with hydrofinishing catalyst exposure, carry out hydrofinishing reaction, hydrofinishing product is isolated to low fragrant spirit fraction, transformer oil cut and refrigerator oil cut.
2. in accordance with the method for claim 1; it is characterized in that: hydrotreatment reaction zone loads hydrogenation protecting catalyst, Hydrobon catalyst and catalyst for hydro-upgrading A from top to bottom, the admission space ratio of hydrogenation protecting catalyst, Hydrobon catalyst and catalyst for hydro-upgrading A is 10 ~ 60:20 ~ 70:20 ~ 70.
3. according to the method described in claim 1 or 4; it is characterized in that: hydrotreatment reaction zone loads hydrogenation protecting catalyst, Hydrobon catalyst and catalyst for hydro-upgrading A from top to bottom, the admission space ratio of hydrogenation protecting catalyst, Hydrobon catalyst and catalyst for hydro-upgrading A is 10 ~ 30:45 ~ 60:30 ~ 45.
4. in accordance with the method for claim 1, it is characterized in that: the operational condition of hydrotreatment reaction zone is: reaction pressure 10.0 ~ 20.0MPa, temperature of reaction 320 ~ 400 DEG C, hydrogen to oil volume ratio 500:1 ~ 5000:1, long-pending air speed 0.1 ~ 10.0h
-1.
5. according to the method described in claim 1 or 4, it is characterized in that: the operational condition of hydrotreatment reaction zone is: reaction pressure 12.0 ~ 15.0MPa, temperature of reaction 350 ~ 385 DEG C, hydrogen to oil volume ratio 800:1 ~ 1000:1, volume space velocity 0.4 ~ 1.0h
-1.
6. the method for right as requested described in 1, is characterized in that: the operational condition of hydro-upgrading reaction zone is: reaction pressure 5.0 ~ 20.0MPa; Temperature of reaction 250 ~ 410 DEG C; Hydrogen to oil volume ratio 500:1 ~ 1500:1; Volume space velocity 0.1 ~ 1.5h
-1.
7. the method for right as requested described in 1 or 6, is characterized in that: the operational condition of hydro-upgrading reaction zone is: reaction pressure 12.0 ~ 15.0MPa; Temperature of reaction 330 ~ 390 DEG C; Hydrogen to oil volume ratio 800:1 ~ 1000:1; Volume space velocity 0.5 ~ 1.2h
-1.
8. the method for right as requested described in 1, is characterized in that: the operational condition of hydrofinishing reaction zone is: reaction pressure 10.0 ~ 20.0MPa; Temperature of reaction 250 ~ 350 DEG C; Hydrogen to oil volume ratio 500:1 ~ 1500:1; Volume space velocity 0.1 ~ 10.0h
-1.
9. the method for right as requested described in 1 or 8, is characterized in that: the operational condition of hydrofinishing reaction zone is: reaction pressure 12.0 ~ 15.0MPa; Temperature of reaction 280 ~ 320 DEG C; Hydrogen to oil volume ratio 800:1 ~ 1000:1; Volume space velocity 0.5 ~ 1.2h
-1.
10. in accordance with the method for claim 1, it is characterized in that: contain in described catalyst for hydro-upgrading A: the modified Y zeolite of 10wt% ~ 35wt% amorphous aluminum silicide, 2wt% ~ 15wt%, with the group VIII metal of the group VIB metal of oxide basis 20wt% ~ 50wt% and 8wt% ~ 15wt%; Modified Y zeolite containing the amorphous aluminum silicide of 20wt% ~ 60wt%, 5wt% ~ 25wt% in described catalyst for hydro-upgrading B, with the group VIB metal of oxide basis 10wt% ~ 30wt% with the group VIII metal of oxide basis 4wt% ~ 10wt%.
11. in accordance with the method for claim 10, it is characterized in that: catalyst for hydro-upgrading A is compared with the composition of catalyst for hydro-upgrading B, group VIB metal in catalyst for hydro-upgrading B and group VIB total metal content 10 ~ 25 percentage ratios, amorphous aluminum silicide in catalyst for hydro-upgrading B and the total content of modified Y zeolite than in catalyst for hydro-upgrading A the two total content low 10 ~ 25 percentage ratios higher than the two total content in catalyst for hydro-upgrading A.
12. in accordance with the method for claim 10, it is characterized in that: in described catalyst for hydro-upgrading A and catalyst for hydro-upgrading B, the character of amorphous aluminum silicide is as follows: silicon oxide-containing 10wt% ~ 60wt%, and specific surface is 400 ~ 650m
2/ g, pore volume is 1.0 ~ 1.8mL/g, and infrared acidity is 0.34 ~ 0.50mmol/g, and the pore volume that the pore volume of bore dia 4 ~ 10nm accounts for 85% ~ 95%, >15nm of total pore volume accounts for less than 5% of total pore volume.
13. in accordance with the method for claim 10, it is characterized in that: the modified Y zeolite in described catalyst for hydro-upgrading A and catalyst for hydro-upgrading B has following character: SiO
2/ Al
2o
3mol ratio is 40 ~ 60, and lattice constant is 2.425 ~ 2.440nm, and relative crystallinity is 80% ~ 100%, infrared acidity 0.1 ~ 0.5mmol/g, and wherein the middle strong acid distribution of 250 ~ 550 DEG C is concentrated, and account for 60 ~ 70% of total acid, specific surface area is 600 ~ 900m
2/ g, pore volume 0.3 ~ 0.6mL/g, wherein the pore volume of the secondary mesopore of 4 ~ 15nm accounts for 40% ~ 50% of total pore volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310532400.2A CN104593059B (en) | 2013-11-04 | 2013-11-04 | A kind of FCC recycle oil hydrogenation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310532400.2A CN104593059B (en) | 2013-11-04 | 2013-11-04 | A kind of FCC recycle oil hydrogenation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104593059A true CN104593059A (en) | 2015-05-06 |
| CN104593059B CN104593059B (en) | 2016-05-18 |
Family
ID=53119130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310532400.2A Active CN104593059B (en) | 2013-11-04 | 2013-11-04 | A kind of FCC recycle oil hydrogenation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104593059B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117886A (en) * | 2016-11-30 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of production method of specialty oil |
| CN108977224A (en) * | 2018-08-01 | 2018-12-11 | 国家能源投资集团有限责任公司 | Transformer oil base oil and preparation method thereof |
| CN109722301A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | Produce the method for hydrotreating of transformer oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4169040A (en) * | 1978-04-26 | 1979-09-25 | Chevron Research Company | Staged process for the production of middle distillate from a heavy distillate |
| CN1990833A (en) * | 2005-12-27 | 2007-07-04 | 中国石油化工股份有限公司 | Production method for extra high voltage transformer oil |
| CN101250432A (en) * | 2008-03-28 | 2008-08-27 | 湖南长岭石化科技开发有限公司 | Method for producing fuel oil by hydrogenation modification of coal tar |
| CN102465033A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Processing method of medium-low temperature coal tar |
-
2013
- 2013-11-04 CN CN201310532400.2A patent/CN104593059B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4169040A (en) * | 1978-04-26 | 1979-09-25 | Chevron Research Company | Staged process for the production of middle distillate from a heavy distillate |
| CN1990833A (en) * | 2005-12-27 | 2007-07-04 | 中国石油化工股份有限公司 | Production method for extra high voltage transformer oil |
| CN101250432A (en) * | 2008-03-28 | 2008-08-27 | 湖南长岭石化科技开发有限公司 | Method for producing fuel oil by hydrogenation modification of coal tar |
| CN102465033A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Processing method of medium-low temperature coal tar |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117886A (en) * | 2016-11-30 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of production method of specialty oil |
| CN108117886B (en) * | 2016-11-30 | 2021-05-04 | 中国石油化工股份有限公司 | Production method of special oil product |
| CN109722301A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | Produce the method for hydrotreating of transformer oil |
| CN109722301B (en) * | 2017-10-27 | 2020-12-04 | 中国石油化工股份有限公司 | Hydrogenation method for producing transformer oil |
| CN108977224A (en) * | 2018-08-01 | 2018-12-11 | 国家能源投资集团有限责任公司 | Transformer oil base oil and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104593059B (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102311784B (en) | Method for producing environment-friendly aromatic oil | |
| CN105733793A (en) | Hydrogenation method for regenerating waste lubricating oil, | |
| CN100422295C (en) | Method for producing food grade white oil by hydrogenating tail oil | |
| CN103773493B (en) | A kind of production method of environment-friendly aromatic oil | |
| CN102021021A (en) | Method of producing pre-refining synthetic oil by using a switchable reactor fixed bed hydrogenation conversion topping or other crude oil | |
| CN102453538B (en) | Production method of environmentally friendly tyre aromatic oil | |
| CN104593063B (en) | A kind of middle coalite tar produces the method for rubber filling oil base oil | |
| CN100413944C (en) | Method for producing lubricating oil base oil by hydrogenating tail oil | |
| CN104593065B (en) | A kind of production method of environment-friendly rubber extending oil | |
| CN104593059A (en) | Hydrogenation process for FCC recycle oil | |
| CN102443426A (en) | Start-up activation method for hydrogenation cracking process | |
| CN101184552A (en) | Method for the selective hydrodesulfurization of an olefin containing hydrocarbon feedstock | |
| CN102010751A (en) | Efficient combined production method for gasoline with ultralow sulfur and high octane value | |
| CN104593066B (en) | Middle coalite tar produces the method for environment-friendly rubber extending oil | |
| CN1952076A (en) | Paraffin-hydrogenating refining process | |
| CN104593067A (en) | Method for producing white rubber filling oil base oil from catalytic slurry oil | |
| CN102626635B (en) | Coal tar denitrification catalyst and its preparation method and use | |
| CN100558862C (en) | The method of white oil is produced in a kind of hydrofining | |
| CN101148606B (en) | One-stage hydrogenation method for producing food-level white oil | |
| CN111378498B (en) | Production method of environment-friendly aromatic oil for tires | |
| CN102847549B (en) | Coal tar hydrocracking catalyst and preparation method thereof | |
| CN102311792A (en) | Hydrocracking process start-up vulcanization method | |
| CN104593074B (en) | A kind of high melting-point wax hydrogenation method | |
| CN111378500B (en) | Combination method for producing high-quality lubricating oil base oil and environment-friendly aromatic oil | |
| CN101148610B (en) | Method for producing food-level white oil by hydrogenation technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |