CN103773493B - A kind of production method of environment-friendly aromatic oil - Google Patents
A kind of production method of environment-friendly aromatic oil Download PDFInfo
- Publication number
- CN103773493B CN103773493B CN201210408478.9A CN201210408478A CN103773493B CN 103773493 B CN103773493 B CN 103773493B CN 201210408478 A CN201210408478 A CN 201210408478A CN 103773493 B CN103773493 B CN 103773493B
- Authority
- CN
- China
- Prior art keywords
- oil
- pore volume
- hydro
- upgrading
- solvent
- 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.)
- Active
Links
Abstract
The invention discloses a kind of production method of environment-friendly aromatic oil.With vacuum distillate, frivolous pitch wet goods furfural extract oil for raw material, adopt solvent extraction-hydrotreatment combination process, produce the environment-friendly type tyre aromatic oil meeting EU criteria.The inventive method be first by stock oil through the extracting of solvent either shallow; with the condensed-nuclei aromatics in partial removal raw material, colloid, bituminous matter and heavy metal; then raffinate oil through mild hydrogenation, unpumped condensed-nuclei aromatics is saturated further after desolventizing process, make condensed-nuclei aromatics content & lt; 3.0%, aromaticity content & gt; 20%, obtain excellent environment-friendly aromatic oil.
Description
Technical field
The present invention relates to a kind of production method of environment-friendly aromatic oil, specifically a kind of method adopting solvent extraction-hydrogenation combination technique to produce environment-friendly aromatic oil.
Background technology
Rubber filling oil plays a part very important in rubber industry as a kind of auxiliary agent, can improve the plasticity of sizing material, reduce compound viscosity and mixing time temperature, dispersion and the mixing of other Synergist S-421 95 can be promoted, lubricate is extruded to what roll, and the hardness of vulcanized rubber can be reduced, and improve its performance.Rubber filling oil can also increase Rubber Yield, reduces costs, and improves processing characteristics and the use properties of rubber, in Rubber processing industry, has consequence.
Maximum as a kind of consumption, the rubber filling oil that purposes is wider, the consistency that aromatic hydrocarbon oil (DAE) and rubber the are good and high-performances such as the good anti-slippery of tire and cheap price and good adaptability thereof can be given be widely used in the rubber such as styrene-butadiene rubber(SBR) (SBR), cis-1,4-polybutadiene rubber (BR), paracril (NBR/IR, CR) and goods thereof, with the SBR that it is filled, NBR and BR has good processing characteristics, tensile strength and tear strength high.In the manufacturing processed of rubber item particularly tire, traditional aromatic hydrocarbon oil (DAE) of use containing a large amount of condensed-nuclei aromatics (PCA), due to bringing into of aromatic hydrocarbon oil, more or less containing PCA in tire and rubber item.That studies its toxic along with developed countries gos deep into, and containing Carcinogenic Polycyclic Aromatic Hydrocarbons in aromatic hydrocarbon oil, the problem that can work the mischief to human body and environment has obtained the accreditation of the public.European Union will put into effect the end of the year 2005 about the instruction of forbidding poisonous aromatic hydrocarbons wet goods rubber filling oil in tire production, must use the environment-friendly aromatic oil of PCA content (dimethyl sulfoxide (DMSO) extraction process IP346) <3% in 1 day January in 2010 in tire production.Aromatic hydrocarbon oil should follow similar dissolve mutually theory as rubber oil simultaneously, need to keep good intermiscibility with rubber, the performance of rubber product is had no adverse effects, therefore environment-friendly aromatic oil is while guarantee PCA content <3%, also should ensure that (aromaticity content accounts for the percentage ratio C of whole molecular carbon total atom number to higher aromaticity content with carbon atom on aromatic nucleus in carbon type analysis as far as possible
avalue is expressed, general requirement C
a>20%).
The production technology of current environment-friendly aromatic oil mainly contains solvent extraction and the hydrogenation two schemes of aromatic hydrocarbon oil.
EP-A-417980 discloses a kind of method of solvent extraction process aromatic hydrocarbon oil.With the solvent-extracted oil of Process of Lube Solvent Refining for raw material, select furfural, phenol and NMP polar solvent, carry out counter-current extraction with raw material and produce PCA<3%, C
athe environment-friendly aromatic oil of >50%.This technological process is comparatively simple, but needs on the basis of existing solvent refining unit, a more newly-built liquid-liquid extraction column, with the pollution avoiding environment-friendly aromatic oil production to be subject to condensed-nuclei aromatics.
WO9844075 discloses the method for a kind of selective solvent extracting process aromatic hydrocarbon oil again.With the solvent-extracted oil of Process of Lube Solvent Refining for raw material, adopt methyl-sulphoxide (DMSO) to be solvent, environment-friendly aromatic oil is produced in extracting.
CN101591453A discloses a kind of production method of environment-friendly rubber extending oil.Adopt furfural, dimethyl sulfoxide (DMSO), NMP equal solvent, environment-friendly rubber extending oil is produced in extracting.
EP1260569-A2 discloses a kind of method that aromatic hydrocarbon oil is produced in hydrotreatment.The solvent-extracted oil of vacuum distillate and Process of Lube Solvent Refining is mixed as raw material, adopts nickel-molybdenum or nickel-cobalt type Hydrobon catalyst, at reaction pressure 6.0 ~ 8.0MPa, temperature of reaction 265 ~ 320 DEG C, air speed 0.5h
-1condition under, produce environment-friendly aromatic oil.Adopt nickel-molybdenum or nickel-cobalt type Hydrobon catalyst, and solvent-extracted oil content is no more than 50%.In addition, under Hydrofinishing conditions, be reduced to meet environment-friendly quality index to make condensed-nuclei aromatics, then the loss of aromatic hydrocarbons value is more, and both indexs can not be taken into account, and hydrogen consumption is comparatively large simultaneously, and process cost increases.
CN1351114A discloses a kind of processing and treating method of heavy aromatic oil.Its scheme two adopts solvent treatment-hydrotreatment combination process, first heavy aromatic oil is carried out solvent treatment, then extraction oil is carried out hydrotreatment.Shortcoming be by extracting condensed-nuclei aromatics in oil after solvent extraction out, bituminous matter, gum level increase substantially, add the difficulty of hydrotreatment, also affect the work-ing life of catalyzer simultaneously.
Summary of the invention
For the deficiencies in the prior art, the invention provides the method for solvent extraction-hydrotreatment combination process production environment-friendly aromatic oil that a kind of processing condition relax.
The production method of environment-friendly aromatic oil of the present invention comprises the steps:
(1) first stock oil enter extraction tower and carry out extracting, and extracting solvent contacts with stock oil countercurrent flow and carries out mass transfer, raffinates oil and extract oil content out not flow out from the top of extraction tower and bottom;
(2) step (1) middle extraction tower top gained is raffinated oil and is isolated after solvent through separator, hydro-upgrading reactor is mixed into hydrogen, reaction under catalyst for hydro-upgrading exists, obtain the environment-friendly type aromatic hydrocarbon oil of condensed-nuclei aromatics mass content <3%, aromaticity content >20%, wherein hydro-upgrading reactor uses the catalyst for hydro-upgrading containing amorphous aluminum silicide and modified Y zeolite.
Stock oil described in the inventive method can be one or more in vacuum distillate, frivolous pitch wet goods furfural extract oil.Extracting solvent used can be furfural, tetramethylene sulfone, dimethyl sulfone, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP) wherein one or more.
In step (1), the extraction process condition of extraction tower is: agent (solvent) oil (stock oil) volume ratio 0.5:3 ~ 3:0.5, preferred 1:1 ~ 2:1; Column bottom temperature 10 ~ 50 DEG C, tower top temperature is higher than column bottom temperature 10 ~ 50 DEG C, preferred column bottom temperature 15 ~ 40 DEG C, and tower top temperature is higher than column bottom temperature 20 ~ 40 DEG C; Extraction pressure 0.1 ~ 0.4MPa, preferably 0.1 ~ 0.3MPa.
In step (2), the operational condition of hydro-upgrading reactor is: reaction pressure 4.0 ~ 15.0MPa, preferably 6.0 ~ 10.0MPa; Temperature of reaction 230 ~ 420 DEG C, preferably 350 ~ 400 DEG C; Hydrogen to oil volume ratio 200:1 ~ 1500:1, preferred 600:1 ~ 1000:1; Volume space velocity 0.5 ~ 6.0h
-1, preferably 0.8 ~ 1.5h
-1.
Generally contain in the catalyst for hydro-upgrading used in the inventive method step (2): 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%.Amorphous aluminum silicide wherein used preferably there is following character: silicon oxide-containing 10wt% ~ 60wt%, 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; Most preferably have following character: silicon oxide-containing 10wt% ~ 35wt%, specific surface is 530 ~ 650m
2/ g, pore volume is 1.2 ~ 1.5mL/g.Wherein modified Y zeolite used preferably 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.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.
Adopt traditional single solvent extraction technique to produce environment-friendly aromatic oil, although can extract a large amount of condensed-nuclei aromatics out, reach EU criteria, product yield is very low.Moreover according to this area general knowledge and prior art, use Hydrobon catalyst, extract solvent treatment out oil and carry out the hydrotreated lube base oil of the degree of depth to meet the requirement of PCA<3%, not only need to carry out under comparatively exacting terms, and extraction oil belongs to heavy distillate, containing higher metal, colloid, the materials such as bituminous matter, whole hydrogenation process hydrogen is consumed increase, catalyst activity is impaired, the more important thing is while hydrotreated lube base oil condensed-nuclei aromatics, by the restriction of chemical equilibrium, a large amount of monocycles and double ring arene are also by hydrotreated lube base oil, cause the lower (C of the aromaticity content of aromatic hydrocarbon oil product
a<10%), solvability reduces comparatively large, has been unwell to and has used in tire production.
The present invention is first through suitable solvent either shallow extracting by stock oil, with the condensed-nuclei aromatics in partial removal raw material, colloid, bituminous matter and heavy metal, then suitable catalyst for hydro-upgrading is adopted, under the hydroconversion condition relatively relaxed, condensed-nuclei aromatics part aromatic ring is opened, generate monocycle or double ring arene, instead of simple hydrotreated lube base oil, therefore while minimizing condensed-nuclei aromatics, the higher aromaticity content of favourable maintenance product, produces PCA<3% and C
athe environment-friendly aromatic oil of >20%, is conducive to the yield improving aromatic hydrocarbon oil.
The inventive method has the advantages such as adaptability to raw material is strong, processing condition relax, the catalyst for hydro-upgrading life-span is long.In the inventive method, stock oil first under the operational condition comparing mitigation through the extracting of solvent either shallow, condensed-nuclei aromatics in partial removal raw material, colloid, bituminous matter and heavy metal, so in ensuing hydro-upgrading process, hydroconversion condition can relax more, aromatic hydrocarbons loss is reduced, very little to the viscosity influence of product, and reduce hydrogen consumption, extend catalyst life, effectively save process cost, and compared with solvent extraction process of the present invention produces aromatic hydrocarbon oil technique with simple extracting, reduce agent-oil ratio and extraction temperature, and improve product yield.
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, stock oil 1 enters from the bottom of solvent tower 3, and extraction solvent 2 enters from the top of solvent tower 3.Utilize the difference in specific gravity of stock oil 1 and solvent 2, in extraction tower 3, counter current contact carries out extracting, in the process, by condensed-nuclei aromaticss more than three rings, the component Parts such as pitch are dissolved in solvent 2, and be deposited in and obtain bottom extraction tower extracting oil 4 out, raffinate oil and 5 to discharge from the top of extraction tower 3, refining solvent 7 can be obtained and take out remaining product 8 after separator 6 is separated, refining solvent 7 can return solvent extraction apparatus and recycle, take out after remaining product 8 mixes with hydrogen 9, enter hydro-upgrading reactor 10, with the desulfurization of loading in hydro-upgrading reactor 10, denitrogenation, aromatic saturation and open-loop performance strong catalyst for hydro-upgrading contact carry out hydro-upgrading reaction, the condensed-nuclei aromatics generation ring-opening reaction of more than three rings in raw material is made to generate monocycle or double ring arene, hydrogenation reaction resultant 11 enters separator 12, obtain hydrogen-rich gas 13, hydrogenation unit can be returned to recycle after purifying, separator bottom obtains PCA content <3% and C
athe environment-friendly type aromatic hydrocarbon oil 14 of content >20%.
The catalyst for hydro-upgrading used in the present invention can select commercial catalysts of the prior art, or can be prepared according to the state of the art.As present approach provides a kind of preparation method of catalyst for hydro-upgrading, comprise: after amorphous aluminum silicide and modified Y zeolite are mixed, add tackiness agent kneading, roll agglomerating after, extruded moulding on banded extruder and obtain carrier, then load hydrogenation active metals.
Amorphous aluminum silicide used can adopt existing method to prepare, and preparation method as concrete in one 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 described sodium aluminate solution is 25 ~ 60gAl
2o
3/ L, is preferably 30 ~ 45gAl
2o
3/ L, the concentration of sodium silicate solution is 100 ~ 250gSiO
2/ L, is preferably 100 ~ 150gSiO
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 zeolite 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 ~ 0.098MPa 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 described 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.The preparation method of catalyzer of the present invention is: after adopting 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 ~ 8mm.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 feedstock property of process of the present invention is in table 1.
Table 1 test feedstock property
| Project | Data |
| Density (20 DEG C), kg/m 3 | 997.2 |
| Boiling range, DEG C | |
| IBP/10%/30%/50% | 386/437/460/474 |
| 70%/90%/95%/EBP | 492/522/539/558 |
| Carbon/hydrogen | 86.58/10.59 |
| Sulphur/nitrogen, μ g.g -1 | 11700/4582 |
| Viscosity, mm 2/s（100℃） | 39.46 |
| Viscosity gravity constant (VGC) | 0.9273 |
| Condensation point, DEG C | 10 |
| Refractive index (20 DEG C) | 1.5668 |
| PCA，% | 21.70 |
| Carbon type analysis, % | |
| C A | 39 |
| Mass spectrum forms, wt% | |
| Colloid | 5.4 |
| Paraffinic hydrocarbons | 2.2 |
| Naphthenic hydrocarbon | 24.3 |
| Aromatic hydrocarbons | 68.1 |
| Monocycle/dicyclo/tri-ring/Fourth Ring/five rings | 13.4/17.1/13.0/7.1/2.3 |
| Thiophene/do not identify | 3.5/11.7 |
Embodiment 1 amorphous aluminum silicide preparation process involved by catalyzer of the present invention below, embodiment 2 is catalyst preparation process.
Embodiment 1
700g solid sodium aluminate 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 working solution (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 value 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 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
265%, the 4-15nm secondary pore that in/g, pore volume 0.52mL/g, 250-550 DEG C, strong acid accounts for total acid accounts for 46% of total pore volume) tackiness agent be made up of nitric acid and SB alumina peptization with 310g, kneading, roll, 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 by the Mo-Mi co-impregnated solution excessive dipping 80g carrier A 2 hours of 200mL, 110 DEG C of dryings 6 hours, 500 DEG C of roastings 4 hours, obtain catalyst for hydro-upgrading catA.Catalyst for hydro-upgrading physical property is in table 2.
Table 2 catalyst for hydro-upgrading physico-chemical property
| Catalyzer is numbered | catA |
| MoO 3，wt% | 22.0 |
| WO 3，wt% | － |
| NiO，wt% | 7.0 |
| Specific surface area, m 2/g | 256 |
| Pore volume, mL/g | 0.46 |
| The pore volume of bore dia 3 ~ 10nm accounts for total pore volume, % | 91.4 |
| Infrared total acidity, mmol/g | 0.361 |
Embodiment 3
This embodiment describes employing solvent extraction-hydrotreatment combination process, raw material listed in processing list 1, extracting solvent is furfural.What wherein hydroprocessing processes adopted is the catalyst for hydro-upgrading that table 2 is listed, and obtains result specifically in table 4.
Comparative example 1
This comparative example describes and adopts raw material listed in solvent extraction processing list 1 separately, and solvent for use is in the same manner as in Example 3.Extraction process condition and product property are specifically in table 3.
Comparative example 2
This comparative example describes and adopts the catalyst for hydro-upgrading described in embodiment 2 separately, raw material listed in processing list 1.Hydrogenation modifying process condition and product property are specifically in table 3.
From table 3, the data analysis of embodiment and comparative example is known, and compared with prior art, the inventive method can meet produces PCA<3%, C
athe environment-friendly aromatic oil requirement of >20%, and the solvent extraction operational condition of the inventive method and hydro-upgrading reaction conditions relax more, hydrogen consumption is low and quality product is high.
The processing condition of table 3 comparative example and embodiment and result
| Test number | Comparative example 1 | Comparative example 2 | Embodiment 3 |
| Extraction process condition | |||
| Tower top temperature, DEG C | 80 | 50 | |
| Column bottom temperature, DEG C | 40 | 30 | |
| Agent-oil ratio | 3:1 | 2:1 | |
| Extraction pressure, MPa | 0.3 | 0.2 | |
| Hydrogenation modifying process condition | |||
| Temperature of reaction, DEG C | 380 | 350 | |
| Reaction pressure, MPa | 8.0 | 8.0 | |
| Hydrogen to oil volume ratio | 1000 | 600 | |
| Volume space velocity, h -1 | 0.8 | 1.0 | |
| Chemical hydrogen consumption, % accounts for stock oil quality | 1.4 | 1.0 | |
| Condensed-nuclei aromatics (PCA), % | 2.5 | 4.8 | 2.67 |
| Carbon type analysis, % | |||
| C A | 6 | 21 | 25 |
| Mass spectrum forms, wt% | |||
| Paraffinic hydrocarbons | 15.5 | 12.2 | 7.4 |
| Naphthenic hydrocarbon | 44.0 | 39.3 | 41.1 |
| Aromatic hydrocarbons | 40.5 | 48.5 | 51.5 |
| Final environment-friendly type aromatic hydrocarbon oil yield, wt% | 33.5 | 74.8 | 83.5 |
Claims (9)
1. a production method for environment-friendly aromatic oil, comprises the steps:
(1) first stock oil enter extraction tower and carry out extracting, extraction solvent contacts with stock oil countercurrent flow and carries out mass transfer, raffinate oil and extract oil content out and do not flow out from the top of extraction tower and bottom, described extraction tower operational condition is: solvent/stock oil volume ratio 0.5:3 ~ 3:0.5, column bottom temperature 10 ~ 50 DEG C, tower top temperature is higher than column bottom temperature 10 ~ 50 DEG C, extraction pressure 0.1 ~ 0.4MPa;
(2) step (1) middle extraction tower top gained is raffinated oil and is isolated after solvent through separator, hydro-upgrading reactor is mixed into hydrogen, reaction under catalyst for hydro-upgrading exists, obtain the environment-friendly type aromatic hydrocarbon oil of condensed-nuclei aromatics mass content <3%, aromaticity content >20%, wherein hydro-upgrading reactor uses the catalyst for hydro-upgrading containing amorphous aluminum silicide and modified Y zeolite.
2. the method for right as requested described in 1, is characterized in that: described extraction tower operational condition is: solvent/stock oil volume ratio 1:1 ~ 2:1, column bottom temperature 15 ~ 40 DEG C, and tower top temperature is higher than column bottom temperature 20 ~ 40 DEG C, and extraction pressure is 0.1 ~ 0.3MPa.
3. in accordance with the method for claim 1, it is characterized in that: described extraction solvent is one or more in furfural, tetramethylene sulfone, dimethyl sulfone, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone.
4. in accordance with the method for claim 1, it is characterized in that: the operational condition of described hydro-upgrading reactor is: reaction pressure 4.0 ~ 15.0MPa, temperature of reaction 230 ~ 420 DEG C, hydrogen to oil volume ratio 200:1 ~ 1500:1, volume space velocity 0.5 ~ 6.0h
-1.
5. in accordance with the method for claim 1, it is characterized in that: the modified Y zeolite containing the amorphous aluminum silicide of 20wt% ~ 60wt%, 5wt% ~ 25wt% in described catalyst for hydro-upgrading, with the group VIB metal of oxide basis 10wt% ~ 30wt% with the group VIII metal of oxide basis 4wt% ~ 10wt%.
6. according to the method described in claim 1 or 5, it is characterized in that: in described catalyst for hydro-upgrading, the character of amorphous aluminum silicide is as follows: silicon oxide-containing 10wt% ~ 60wt%, 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.
7. in accordance with the method for claim 6, it is characterized in that: in described catalyst for hydro-upgrading, the character of amorphous aluminum silicide is as follows: silicon oxide-containing 10wt% ~ 35wt%, specific surface is 530 ~ 650m
2/ g, pore volume is 1.2 ~ 1.5mL/g.
8. in accordance with the method for claim 1, it is characterized in that: the modified Y zeolite in described catalyst for hydro-upgrading 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.
9. in accordance with the method for claim 1, it is characterized in that: the specific surface area of described 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 infrared acidity is at 0.3 ~ 0.5mmol/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210408478.9A CN103773493B (en) | 2012-10-24 | 2012-10-24 | A kind of production method of environment-friendly aromatic oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210408478.9A CN103773493B (en) | 2012-10-24 | 2012-10-24 | A kind of production method of environment-friendly aromatic oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103773493A CN103773493A (en) | 2014-05-07 |
| CN103773493B true CN103773493B (en) | 2016-01-20 |
Family
ID=50566261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210408478.9A Active CN103773493B (en) | 2012-10-24 | 2012-10-24 | A kind of production method of environment-friendly aromatic oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103773493B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298985A (en) * | 2016-04-14 | 2017-10-27 | 中国海洋石油总公司 | A kind of high viscosity environment-friendly rubber oil and preparation method thereof |
| CN111087016A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Method for removing vanadium from crude titanium tetrachloride |
| CN111378500B (en) * | 2018-12-31 | 2021-12-07 | 中国石油化工股份有限公司 | Combination method for producing high-quality lubricating oil base oil and environment-friendly aromatic oil |
| CN111378499B (en) * | 2018-12-31 | 2021-10-08 | 中国石油化工股份有限公司 | Combined method for producing high-quality lubricating oil base oil and environment-friendly aromatic oil |
| CN111378498B (en) * | 2018-12-31 | 2021-12-07 | 中国石油化工股份有限公司 | Production method of environment-friendly aromatic oil for tires |
| CN111410992A (en) * | 2020-03-09 | 2020-07-14 | 安徽海德化工科技有限公司 | Production process of environment-friendly aromatic oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1351114A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Process for treating heavy arylhydrocarbon oil |
| CN102453538A (en) * | 2010-10-14 | 2012-05-16 | 中国石油化工股份有限公司 | Production method of environmentally friendly tyre aromatic oil |
-
2012
- 2012-10-24 CN CN201210408478.9A patent/CN103773493B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1351114A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Process for treating heavy arylhydrocarbon oil |
| CN102453538A (en) * | 2010-10-14 | 2012-05-16 | 中国石油化工股份有限公司 | Production method of environmentally friendly tyre aromatic oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103773493A (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103773493B (en) | A kind of production method of environment-friendly aromatic oil | |
| CN102311784B (en) | Method for producing environment-friendly aromatic oil | |
| CN102453538B (en) | Production method of environmentally friendly tyre aromatic oil | |
| JPS601056B2 (en) | Hydrotreatment of heavy hydrocarbon oils containing asphaltenes | |
| CN1151238C (en) | Catalyst for hydrocracking medium oil and its preparing process | |
| CN101239314B (en) | Hydrocracking catalyst containing amorphous aluminum silicide and preparation thereof | |
| CN105733793A (en) | Hydrogenation method for regenerating waste lubricating oil, | |
| CN103769179B (en) | A kind of preparation method of catalyst for hydrotreatment of residual oil | |
| CN105709789B (en) | A kind of hydrocracking heavy oil catalyst and its preparation method and application | |
| CN105579135A (en) | Hydroprocessing catalyst for heavy hydrocarbon oil, method for manufacturing hydroprocessing catalyst for heavy hydrocarbon oil, and hydroprocessing method for heavy hydrocarbon oil | |
| CN106732636A (en) | A kind of sulphided state poor oil suspension bed hydrogenation catalyst and its preparation method and application | |
| CN104593065B (en) | A kind of production method of environment-friendly rubber extending oil | |
| CN103447074B (en) | A kind of preparation method controlling the hydrocracking catalyst of acidic site distribution | |
| CN104593063B (en) | A kind of middle coalite tar produces the method for rubber filling oil base oil | |
| CN104593066B (en) | Middle coalite tar produces the method for environment-friendly rubber extending oil | |
| CN103801346A (en) | Preparation method for hydrotreatment catalyst | |
| CN103801344B (en) | A kind of preparation method of hydrogenating catalyst composition | |
| CN102626635B (en) | Coal tar denitrification catalyst and its preparation method and use | |
| CN104593059A (en) | Hydrogenation process for FCC recycle oil | |
| CN111378498B (en) | Production method of environment-friendly aromatic oil for tires | |
| CN106179384B (en) | A kind of preparation method of Hydrobon catalyst | |
| CN104593067B (en) | A kind of catalytic slurry produces white rubber and fills oil base oil method | |
| CN107151564B (en) | A kind of production method of super-low sulfur clean gasoline | |
| CN102847549B (en) | Coal tar hydrocracking catalyst and preparation method thereof | |
| CN111378500B (en) | Combination method for producing high-quality lubricating oil base oil and environment-friendly aromatic oil |
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 |