CN103773493A - Production method of environmentally friendly aromatic hydrocarbon oil - Google Patents
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Abstract
The invention discloses a production method of environmentally friendly aromatic hydrocarbon oil. Vacuum distillate oil, light deasphalted oil and other furfural extract oil are used as a raw material for production of the environmentally friendly aromatic hydrocarbon oil meeting EU (European Union) standards for tires by means of a solvent extraction-hydrotreating combination process. The method is as follows: raw material oil is simply extracted by a solvent to partly remove condensed-nuclei aromatics, colloid, asphaltene and heavy metals in the raw material, a solvent in raffinate oil is extracted, then the condensed-nuclei aromatics which are not extracted out can be further saturated by mild hydrogenation, the condensed-nuclei aromatic content is less than 3.0%, the aromatic hydrocarbon content is greater than 20%, and the excellent environmentally friendly aromatic hydrocarbon oil can be obtained.
Description
Technical field
The present invention relates to a kind of production method of environment-friendly aromatic oil, specifically a kind of method that adopts 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 sizing material plasticity, reduce compound viscosity and the temperature when mixing, can promote dispersion and the mixing of other Synergist S-421 95, to the lubricate of extruding of calendering, and can reduce the hardness of vulcanized rubber, 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.
As a kind of consumption maximum, the rubber filling oil that purposes is wider, the consistency that aromatic hydrocarbon oil (DAE) and rubber are good and can give the high-performances such as anti-slippery that tire is good and cheap price and preferably adaptability extensively use 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 of its filling, NBR and BR have good processing characteristics, and tensile strength and tear strength are high.At rubber item, particularly in the manufacturing processed of tire, traditional aromatic hydrocarbon oil (DAE) of use contains a large amount of condensed-nuclei aromaticss (PCA), due to bringing into of aromatic hydrocarbon oil, more or less contains PCA in tire and rubber item.Along with developed countries is to the going deep into of its toxic research, in aromatic hydrocarbon oil, contain Carcinogenic Polycyclic Aromatic Hydrocarbons, the problem that can work the mischief to human body and environment has obtained the public's approval.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 be followed similar compatibility principle as rubber oil simultaneously, need to keep good intermiscibility with rubber, performance to rubber product has no adverse effects, therefore environment-friendly aromatic oil, in guaranteeing PCA content < 3%, also should guarantee 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 environment-friendly aromatic oil mainly contains solvent extraction and the hydrogenation two schemes of aromatic hydrocarbon oil at present.
EP-A-417980 discloses a kind of method of solvent extraction processing aromatic hydrocarbon oil.Take the solvent-extracted oil of Process of Lube Solvent Refining as raw material, select furfural, phenol and NMP isopolarity 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 simpler, but need to be on the basis of existing solvent refining unit, a more newly-built liquid-liquid extraction tower, to avoid environment-friendly aromatic oil production to be subject to the pollution of condensed-nuclei aromatics.
WO9844075 discloses a kind of selective solvent method of extracting processing aromatic hydrocarbon oil again.Take the solvent-extracted oil of Process of Lube Solvent Refining as raw material, adopting methyl-sulphoxide (DMSO) be solvent, extracting production environment-friendly aromatic oil.
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 of hydrotreatment production aromatic hydrocarbon oil.The solvent-extracted oil of vacuum distillate and Process of Lube Solvent Refining is mixed as raw material, adopt nickel-molybdenum or nickel-cobalt type Hydrobon catalyst, at reaction pressure 6.0～8.0MPa, 265～320 ℃ of temperature of reaction, 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 hydrofining condition, meet environment-friendly quality index for condensed-nuclei aromatics is reduced to, the loss of aromatic hydrocarbons value is more, and both indexs can not be taken into account, and hydrogen consumption is larger 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 to solvent treatment, then extraction oil is carried out to hydrotreatment.Shortcoming is that condensed-nuclei aromatics, bituminous matter, the gum level by extracting out after solvent extraction in oil increases substantially, and has increased the difficulty of hydrotreatment, also affects the work-ing life of catalyzer simultaneously.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of solvent extraction-hydrotreatment combination process production environment-friendly aromatic oil of processing condition mitigation.
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 contacts and carries out mass transfer with stock oil countercurrent flow with solvent, raffinates oil and extract oil content out not flow out from top and the bottom of extraction tower;
(2) in step (1), extraction tower top gained is raffinated oil after separator is isolated solvent, be mixed into hydro-upgrading reactor with 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 that contains amorphous aluminum silicide and modified Y zeolite.
Described in the inventive method, stock oil can be one or more in vacuum distillate, frivolous pitch wet goods furfural extract oil.Extracting solvent used can be wherein one or more of furfural, tetramethylene sulfone, dimethyl sulfone, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP).
In step (1), the extraction process condition of extraction tower is: agent (solvent) oil (stock oil) volume ratio 0.5:3～3:0.5, preferably 1:1～2:1; 10～50 ℃ of column bottom temperatures, tower top temperature is higher 10 ~ 50 ℃ than column bottom temperature, preferably 15～40 ℃ of column bottom temperatures, tower top temperature is higher 20～40 ℃ than column bottom temperature; Extracting 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; 230～420 ℃ of temperature of reaction, preferably 350～400 ℃; Hydrogen to oil volume ratio 200:1～1500:1, preferably 600:1～1000:1; Volume space velocity 0.5～6.0h
-1, preferably 0.8～1.5h
-1.
In the catalyst for hydro-upgrading using in the inventive method step (2), generally contain: the group VIII metal (in oxide compound) of the modified Y zeolite of 20wt%～60wt% amorphous aluminum silicide, 5wt%～25wt%, the group VIB metal (in oxide compound) of 10wt%～30wt% and 4wt%～10wt%.Wherein amorphous aluminum silicide used preferably has 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 of bore dia 4～10nm accounts for 85%～95% of total pore volume, and the pore volume of >15nm accounts for below 5% of total pore volume; Most preferably there is 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 of 250～550 ℃ distributes and concentrates, and accounts for 60～70% of total acid, and 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.In catalyst for hydro-upgrading, can also contain the components such as aluminum oxide, zirconium white, titanium oxide.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, is preferably 85%～95%, and 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 aromaticss out, reach European Union's standard, product yield is very low.Moreover according to this area general knowledge and prior art, use Hydrobon catalyst, the hydrogenation that solvent treatment extraction oil is carried out to the degree of depth is saturated to meet the requirement of PCA < 3%, not only need to be compared with carrying out under exacting terms, and extraction oil belongs to heavy distillate, contain higher metal, colloid, the materials such as bituminous matter, whole hydrogenation process hydrogen consumption is increased, catalyst activity is impaired, the more important thing is in the saturated condensed-nuclei aromatics of hydrogenation, be subject to the restriction of chemical equilibrium, a large amount of monocycles and double ring arene are also saturated by hydrogenation, cause the lower (C of aromaticity content of aromatic hydrocarbon oil product
a<10%), solvability reduces larger, is unwell in tire production and uses.
The present invention is first through the shallow degree extracting of suitable solvent by stock oil, remove condensed-nuclei aromatics, colloid, bituminous matter and the heavy metal in raw material with part, then adopt suitable catalyst for hydro-upgrading, under the hydroconversion condition relatively relaxing, condensed-nuclei aromatics part aromatic ring is opened, generate monocycle or double ring arene, rather than simple hydrogenation is saturated, therefore in reducing 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 improve the yield of 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 relatively relax operational condition under through the shallow degree extracting of solvent, part has removed the condensed-nuclei aromatics in raw material, colloid, bituminous matter and heavy metal, so in ensuing hydro-upgrading process, hydroconversion condition can relax more, aromatic hydrocarbons loss is reduced, viscosity influence to product is very little, and reduce hydrogen consumption, extend catalyst life, effectively save process cost, and compared with solvent extraction process of the present invention is produced aromatic hydrocarbon oil technique with simple extracting, agent-oil ratio and extraction temperature are reduced, 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, carry out extracting in the interior counter current contact of extraction tower 3, in this process, by condensed-nuclei aromaticss more than three rings, the components such as pitch are partly dissolved in solvent 2, and be deposited in extraction tower bottom and obtain extracting out oil 4, raffinate oil 5 the tops from extraction tower 3 discharge, after separator 6 separates, can obtain refining solvent 7 and take out remaining product 8, refining solvent 7 can return to solvent extraction apparatus and recycle, after more than taking out, product 8 mixes with hydrogen 9, enter hydro-upgrading reactor 10, desulfurization with the 10 interior fillings of hydro-upgrading reactor, denitrogenation, hydro-upgrading reaction is carried out in the catalyst for hydro-upgrading contact that aromatic saturation and open-loop performance are strong, make the above condensed-nuclei aromatics generation ring-opening reaction of the ring of three in raw material generate monocycle or double ring arene, hydrogenation reaction resultant 11 enters separator 12, obtain hydrogen-rich gas 13, after purifying, can return to hydrogenation unit recycles, separator bottom obtains PCA content <3% and C
athe environment-friendly type aromatic hydrocarbon oil 14 of content >20%.
The catalyst for hydro-upgrading using in the present invention can be selected commercial catalysts of the prior art, or can be prepared according to the state of the art.As the inventive method 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 preparation, and preparation method as concrete in one comprises the steps:
A, preparation sodium aluminate solution, sodium silicate solution;
B, sodium aluminate solution and sodium silicate solution stream are joined in plastic cans, ventilate simultaneously and pass into CO
2gas, adjusts 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 ℃, and the neutralization reaction time is 0.5～1.5 hour;
C, at 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 is filtered and washed;
E, steps d drying and crushing is obtained to amorphous aluminum silicide.
In step a, the concentration of described sodium aluminate solution is 25～60 gAl
2o
3/ L, is preferably 30～45gAl
2o
3/ L, the concentration of sodium silicate solution is 100～250 gSiO
2/ L, is preferably 100～150 g SiO
2/ L.
The slurries of steps d gained filtered and use 50～90 ℃ of deionized waters to be washed till neutrality, being then dried 6～8 hours at 110～130 ℃.
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 containing CO
2gas.
Amorphous aluminum silicide is prepared take sodium aluminate, water glass and carbonic acid gas as raw material.The method is particularly suitable for adopting the producer of 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 producing
2cO
3mother liquor can be circulated to sintering process so that part Na to be provided
2cO
3, form closed cycle, and do not produce contaminated wastewater.
Modified Y zeolite by NaY zeolite by pH value the NH 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 NH for the second time between 1～3 in pH value
4 +exchange, then under 0.080～0.098MPa and 500～550 ℃ of conditions, carry out hydrothermal treatment consists for the first time, after hydrothermal treatment consists, carry out again for the first time NH
4nO
3exchange, carries out hydrothermal treatment consists for the second time, and hydrothermal treatment consists condition is 0.1～0.2MPa and 500～700 ℃ for the second time.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 preparation of the routine techniques such as kneading method, pickling process, preferably adopts 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 appropriate by SB aluminum oxide and nitric acid peptization and the tackiness agent of preparing, kneading or be rolled into paste, extruded moulding, is generally the cylindrical bars of diameter 3～8mm.Carrier through 100～130 ℃ dry 4～14 hours, 500～600 ℃ of roastings 3～10 hours.After activation, adopt the steeping fluid of saturated or excessive steeping fluid dipping containing hydrogenation metal, then carry out 100～130 ℃ dry 4～14 hours, roasting 3～10 hours at 450～550 ℃ and make catalyzer.
Below by particular content and the effect of specific embodiment explanation the inventive method.
Implementation column below will be further described method provided by the invention, but scope not thereby limiting the invention.The feedstock property of processing of the present invention is in table 1.
Table 1 test feedstock property
| Project | Data |
| Density (20 ℃), kg/m 3 | 997.2 |
| Boiling range, ℃ | ? |
| 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, |
10 |
| Refractive index (20 ℃) | 1.5668 |
| PCA，% | 21.70 |
| Carbon type analysis, % | ? |
| C A | 39 |
| Mass spectrum composition, 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 |
It is 200gAl that 700g solid sodium aluminate is mixed with to concentration
2o
3the dense sodium aluminate solution of/L, it is 35gAl that redilution becomes concentration
2o
3/ L sodium aluminate working solution (a), gets containing SiO
2the sodium silicate solution of 28wt%, it is 150gSiO that redilution becomes concentration
2/ L water glass working solution 2L(b).Get the steel plastic cans of a 30L, open simultaneously and have respectively working solution (a) and container valve (b), ventilate simultaneously and pass into the CO that concentration is 45v%
2gas, sets (a) and flow (b) and makes the reaction times at 1 hour, and adjust rapidly CO
2flow, make the pH value of system remain on 10.0 left and right, 30 ℃ of temperature of reaction, after until (a) and (b) having reacted, stop passing into CO
2, then ventilating and stablize 40 minutes, slurries filter and use 85 ℃ of deionized waters to be washed till neutrality.120 ℃ dry 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 the pore volume of bore dia 4～10nm accounts for 90% of total pore volume, and >15nm pore volume accounts for 3% of total pore volume.
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, strong acid accounts for 65% of total acid in 250-550 ℃, 4-15nm secondary pore account for total pore volume 46%) tackiness agent made by nitric acid and SB aluminum oxide peptization with 310g, kneading, roll, make can extrusion paste, extruded moulding.110 ℃ dry 6 hours, 550 ℃ of roastings 4 hours, make carrier A.By the excessive dipping of the Mo-Mi co-impregnated solution 80g carrier A of 200mL 2 hours, 110 ℃ were dried 6 hours again, and 500 ℃ of roastings 4 hours, make 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 numbering | 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 |
91.4 |
| Infrared total acidity, mmol/g | 0.361 |
The present embodiment has been introduced employing solvent extraction-hydrotreatment combination process, listed raw material in processing list 1, and extracting solvent is furfural.What wherein hydrotreatment process 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 has been introduced listed raw material in independent employing solvent extraction processing list 1, 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 has been introduced the catalyst for hydro-upgrading described in independent employing embodiment 2, listed raw material 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 relaxes 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 | |
| Extraction process condition | ? | ? | ? |
| Tower top temperature, ℃ | 80 | ? | 50 |
| Column bottom temperature, ℃ | 40 | ? | 30 |
| Agent-oil ratio | 3:1 | ? | 2:1 |
| Extracting pressure, MPa | 0.3 | ? | 0.2 |
| Hydrogenation modifying process condition | ? | ? | ? |
| Temperature of reaction, ℃ | ? | 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, % | ? | ? | ? |
| |
6 | 21 | 25 |
| Mass spectrum composition, 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 (10)
1. a production method for environment-friendly aromatic oil, comprises the steps:
(1) first stock oil enter extraction tower and carry out extracting, and extraction solvent contacts and carries out mass transfer with stock oil countercurrent flow, raffinates oil and extract oil content out not flow out from top and the bottom of extraction tower;
(2) in step (1), extraction tower top gained is raffinated oil after separator is isolated solvent, be mixed into hydro-upgrading reactor with 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 that contains amorphous aluminum silicide and modified Y zeolite.
2. in accordance with the method for claim 1, it is characterized in that: described extraction tower operational condition is: solvent/stock oil volume ratio 0.5:3～3:0.5,10～50 ℃ of column bottom temperatures, tower top temperature is higher 10 ~ 50 ℃ than column bottom temperature, extracting pressure 0.1～0.4MPa.
3. the right method described in 1 as requested, is characterized in that: described extraction tower operational condition is: solvent/stock oil volume ratio 1:1～2:1, and 15～40 ℃ of column bottom temperatures, tower top temperature is higher 20～40 ℃ than column bottom temperature, and extracting pressure is 0.1～0.3MPa.
4. it is characterized in that in accordance with the method for claim 1: described extraction solvent is one or more in furfural, tetramethylene sulfone, dimethyl sulfone, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone.
5. 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, 230～420 ℃ of temperature of reaction, hydrogen to oil volume ratio 200:1～1500:1, volume space velocity 0.5～6.0h
-1.
6. it is characterized in that in accordance with the method for claim 1: in described catalyst for hydro-upgrading, contain the modified Y zeolite of amorphous aluminum silicide, the 5wt%～25wt% of 20wt%～60wt%, in the group VIB metal of oxide compound 10wt%～30wt% with in the group VIII metal of oxide compound 4wt%～10wt%.
7. according to the method described in claim 1 or 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%～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 of bore dia 4～10nm accounts for 85%～95% of total pore volume, and the pore volume of >15nm accounts for below 5% of total pore volume.
8. in accordance with the method for claim 7, 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.
9. it is characterized in that in accordance with the method for claim 1: 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 of 250～550 ℃ distributes and concentrates, and accounts for 60～70% of total acid, and 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.
10. it is characterized in that in accordance with the method for claim 1: 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.
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| CN111378499A (en) * | 2018-12-31 | 2020-07-07 | 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 |
| CN111378498A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Production method of environment-friendly aromatic oil for tires |
| CN111378500A (en) * | 2018-12-31 | 2020-07-07 | 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 |
| 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 |
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| 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 |
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| 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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN111378499A (en) * | 2018-12-31 | 2020-07-07 | 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 |
| CN111378498A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Production method of environment-friendly aromatic oil for tires |
| CN111378500A (en) * | 2018-12-31 | 2020-07-07 | 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 |
| 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 |
| 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 |
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| CN103773493B (en) | 2016-01-20 |
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