CN106190288B - A kind of method for producing aromatic hydrocarbon rubber filling oil - Google Patents
A kind of method for producing aromatic hydrocarbon rubber filling oil Download PDFInfo
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Abstract
The invention discloses a kind of method for producing aromatic hydrocarbon rubber filling oil, this method includes：(1) wax tailings that boiling range is 350 560 DEG C are subjected to condensation-crystallization, obtain the dewaxing hydrocarbon ils that solidification point is less than 25 DEG C；(2) in presence of hydrogen, the dewaxing hydrocarbon ils is contacted with Hydrobon catalyst.The present invention can utilize the chemical industry aromatic hydrocarbon rubber filling oil of wax tailings production high added value inferior and high arene content by using the above method.Moreover, the above method of the present invention has the advantages that method is simple.
Description
Technical field
The present invention relates to a kind of methods for producing aromatic hydrocarbon rubber filling oil.
Background technology
Wax tailings are in petroleum refining process, and heavy charge is processed using method for thermal cracking in delay coking process unit
A kind of liquid distillate as obtained from vacuum bottoms oil or de-oiled asphalt.Wax tailings include normal pressure wax oil and decompressed wax oil, two
Person is the product obtained by inferior raw material by heat cracking reaction, wherein containing a large amount of nitride, sulfide and polycyclic virtue
Hydrocarbon.In existing common process such as catalytic cracking, being hydrocracked, be easy to cause carbon deposit on catalyst increases these components
And make catalyst inactivation, the service cycle for influencing hydrocracking unit or the product distribution for deteriorating catalytic cracking unit.At present
The processing of wax tailings is processed mostly by the way of being mixed with convenient source being hydrocracked in catalytic cracking process,
Target product is light-weight fuel oil, such as oil and gasoline.
CN101760233A discloses a kind of method for hydrogen cracking of wax tailings, and this method is used wax tailings or contained
There is the mixture of wax tailings under the conditions of hydrogenation protecting, above-mentioned raw materials are contacted in presence of hydrogen with hydrogenation protecting catalyst
Reaction；By the product of hydrogenation protecting reaction and the product and Hydrobon catalyst of hydrocracking reaction under Hydrofinishing conditions
Haptoreaction；The weight that light fraction, midbarrel and initial boiling point are 350-360 DEG C is isolated from the product of hydrofining reaction
Matter fraction；By the initial boiling point it is 350-360 DEG C of heavy end and hydrocracking catalyst under the conditions of hydrocracking reaction
Haptoreaction obtains the product of the hydrocracking reaction.
CN1546611A discloses a kind of coking petrolatum oil processing method.This method includes：(1) static mixing, (2) sedimentation point
4 units such as slag, (3) refined dehydration, (4) catalytic cracking.The alkali in wax tailings is removed by using wax tailings refining agent
Property nitride and part metals, the removal efficiency of basic nitrogen compound reach 40-70%；Decalcification rate reaches 70%, and deferrization rate reaches
75%, oil yield reaches more than 97%.Yield of light oil is compared with refined preceding raising during refined rear wax tailings catalytic cracking
More than 10%, yield of light oil is compared with raising 3% before refining when refined rear wax tailings mix refining straight-run gas oil progress catalytic cracking
More than.
As it can be seen that the above method includes the method for hydrogen cracking and catalyst cracking method of processing coked waxy oil, purpose is all
It is to improve the prior art, the operation cycle for extending device and/or the yield of the operation for improving catalytic cracking process or raising product,
Its target product is limited as the light oil of gasoline component or the midbarrel as diesel component.
The utilization of wax tailings is further opened up, the technology needs of chemical industry oil of the production with high added value are further big
Power is developed, however, wax tailings are that the inferior raw materials such as depressed heavy oil, pitch, coal tar or its mixture are passed through delayed coking
The heavy thermal cracking component that process obtains, arene content is higher, but stability is poor, is inferior to general wax oil component, and
And containing impurity elements such as a large amount of sulphur, nitrogen, its performance is influenced, if expanding the utilization ways of wax tailings, production is high
The chemical industry oil of added value, such as rubber filling oil, need to study new processing method, influence performance to solve it
Shortcoming reaches requirement.
Invention content
The purpose of the present invention is that further expands wax tailings utilizes field, it is different from and existing be hydrocracked and be catalyzed
Cracking method, and the process of gasoline or diesel oil small molecule fuel product is produced by wax tailings, one kind is provided and is given birth to by wax tailings
The method for producing aromatic hydrocarbon rubber filling oil.
To achieve these goals, the present invention provides a kind of method for producing aromatic hydrocarbon rubber filling oil, and this method includes：
(1) wax tailings that boiling range is 350-560 DEG C are subjected to condensation-crystallization, obtain the dewaxing hydrocarbon that solidification point is less than 25 DEG C
Oil, wherein, arene content is more than or equal to 60 weight % in the wax tailings；
(2) in presence of hydrogen, the dewaxing hydrocarbon ils is contacted with Hydrobon catalyst.
The present invention can utilize the chemical industry aromatic hydrocarbons of wax tailings production high added value inferior by using the above method
Type rubber filling oil.Method using the present invention can be seen that by coke inferior by the result of the subsequent embodiment of the present invention
When changing wax oil production aromatic hydrocarbon rubber filling oil, have the advantages that method is simple, method using the present invention produces aromatic hydrocarbons type rubber
The mass fraction of aromatic hydrocarbons in glue filling oil is above 80%, by adjusting operating parameter, it might even be possible to so that production obtained
The mass fraction of aromatic hydrocarbons in aromatic hydrocarbon rubber filling oil is up to 86%.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of method for producing aromatic hydrocarbon rubber filling oil, this method includes：
(1) wax tailings that boiling range is 350-560 DEG C are subjected to condensation-crystallization, obtain the dewaxing hydrocarbon that solidification point is less than 25 DEG C
Oil, wherein, arene content is more than or equal to 60 weight % in the wax tailings；
(2) in presence of hydrogen, the dewaxing hydrocarbon ils is contacted with Hydrobon catalyst.
The above-mentioned method by wax tailings production aromatic hydrocarbon rubber filling oil of the present invention has the simple aromatics quality of method
The advantages of score is high.
In the present invention, the aromatic hydrocarbon rubber filling oil refers to the higher a kind of rubber filling oil of aromatic hydrocarbon content,
According to according to ASTM D2226 rubber synthesis oil class standards, rubber oil described in the invention belongs to 101 in the standard
Type, asphalt content are not more than 0.75 weight %, and polar material is not more than 25 weight %, and saturated hydrocarbon content is not more than 20 weight %
And aromatic hydrocarbon content is not less than a kind of rubber filling oil of 80 weight %.
Environment-friendly aromatic type rubber filling oil of the present invention can be used for black rubber such as butadiene rubber, butadiene-styrene rubber
The processing such as Tire production industry of synthesis, butadiene rubber, butadiene-styrene rubber, natural rubber etc..The arene content of rubber filling oil is got over
Height, the compatibility of higher rubber such as butadiene rubber, butadiene-styrene rubber, natural rubber etc. is better with unsaturated constituent content, so as to
The physical mechanical property for making oil-extended rubber is more excellent.The present invention further calculates petroleum base insulating oil carbons according to ASTM D2140
The standard convention of type composition carries out the distribution of carbon type and calculates, and aromatic carbon contains in the environment-friendly aromatic type rubber filling oil of the invention
Amount is not less than 190 DEG C, under normal pressure not less than 30 weight %, flash-point, and the volatilization loss of the heating 3 hours at 163 DEG C is not more than 1.0 weights
Measure %.
Method according to the present invention, the wax tailings can be in petroleum refining process depressed heavy oil, drip
Blueness, it is one or more as raw material in the coal tar, heavy oil in coal conversion process, it is processed by delay coking process
The vacuum distillation side line component obtained afterwards, usually obtains from the vacuum distillation unit of the delayed coking unit of petroleum refining process,
Its flow range can be adjusted by adjusting the operation of vacuum distillation unit, specifically, the boiling range of this wax tailings component
It it is 350-560 DEG C, arene content therein is not less than 60 weight %.
Method according to the present invention, the temperature of the condensation-crystallization can be minus 30 DEG C to 25 DEG C above freezing.
Method according to the present invention, the temperature of preferably described condensation-crystallization is subzero 10 DEG C to 20 DEG C above freezing.
Method according to the present invention, the temperature of the further preferred condensation-crystallization is 0 DEG C to 15 DEG C above freezing.
In the present invention, the solvent used when carrying out the condensation-crystallization be preferably in pentane, toluene and butanone at least
It is a kind of.
Method according to the present invention, the solvent used when preferably carrying out the condensation-crystallization are toluene and butanone.
In method of the present invention, the dosage volume ratio of preferably described toluene and butanone can be 1：0.6-2, it is more excellent
It is selected as 1：0.8-2.
A kind of preferred embodiment according to the present invention, the step (1) are specifically as follows：It is 350- by boiling range
560 DEG C of wax tailings introduce cryogenic system, under solvent existence condition, make the component that condensation point is higher in the wax tailings cold
Condensation is brilliant to be formed solid and is simultaneously separated off solid, and the separation of crystalline solid can be by standing, settling, centrifuging and/or filters
It realizes, obtains the dewaxing hydrocarbon ils that solidification point is less than 25 DEG C.
Aromatic hydrocarbon rubber filling oil of the present invention meets rubber except through reaching the aromatic hydrocarbon content of certain level
And its outside the requirement of formulation compatibility, also meet and using process to indexs such as the volatility of rubber filling oil, pour point and flash-points
Requirement, the present invention by limiting the boiling range of raw material controls the flash-point of product rubber filling oil and volatility, and pass through by
The solidifying component of height carries out Crystallization Separation at a certain temperature, controls the pour point of the rubber filling oil.
In the present invention, dewaxing hydrocarbon ils of the solidification point less than 25 DEG C is as in the hydrocarbon ils group of liquid condition at normal temperatures
Point.
In the present invention, to the cryogenic system, there is no particular limitation, and those skilled in the art may be used various normal
The technological means of rule is selected, and details are not described herein by the present invention.
In the present invention, to it is described be separated off solid used by method there is no particular limitation, people in the art
Member the means such as may be used conventional use of standing separation, sedimentation separation, centrifuge, be separated by filtration and being detached.
A kind of preferred embodiment according to the present invention, the step (2) can be：In presence of hydrogen, will
The dewaxing hydrocarbon ils obtained by step (2) is contacted with Hydrobon catalyst.
In method of the present invention, the Hydrobon catalyst, which can include load, Ni elements and/or W elements
Hydrogenation protecting catalyst.
In method of the present invention, the Hydrobon catalyst can also include Hydrobon catalyst and/or
Hydrodenitrogenation catalyst.
Under preferable case, in method of the present invention, the Hydrobon catalyst includes at least two, and at least
There is the hydrogenation protecting catalyst of Ni elements and/or W elements including load.The hydrogenation protecting catalyst adds hydrogen to protect including RG series
Catalyst is protected, such as including at least one of RG-20, RG-20A, RG-20B, RG-20E and RG-1.In wax tailings usually
It is less than 25 μm of coke powder containing some diameters, this fine particulate matter is dispersed stably in oil, and do not allow in filtering
Easily remove.But it is easily deposited on the catalyst bed of hydrogenation process, catalyst in reactor bed pressure drop is caused to increase,
Influence unit normal run.The present invention is set by particularly selecting type and its type of feed of filling hydrogenation protecting catalyst
Meter intercepts coke powder.
A kind of preferred embodiment according to the present invention, the Hydrobon catalyst, which includes load, Ni elements
And/or the hydrogenation protecting catalyst and Hydrobon catalyst and/or hydrodenitrogenation catalyst of W elements.
A kind of preferred embodiment according to the present invention, along logistics direction, it is described load have Ni elements and/or
The hydrogenation protecting catalyst of W elements is set to the upstream of hydrofinishing district.In the present invention, the hydrofinishing district is wherein
The region of Hydrobon catalyst is filled with, the Hydrobon catalyst and/or hydrodenitrogeneration catalysis that hydrofinishing district is loaded
Agent includes at least one of RL-2, RJW-3 and RLF-2.
Method according to the present invention, under preferable case, filling side of the hydrogenation protecting catalyst in reactor
For formula to be tapered into along logistics direction granularity, granularity variation range is calculated as 20mm to 1.6mm, preferably 18mm extremely with equivalent diameter
1.8mm。
Method according to the present invention, under preferable case, filling side of the Hydrobon catalyst in reactor
Formula is gradually increases along logistics direction metal element content, and with the total weight of Hydrobon catalyst, metallic element is to aoxidize
The changes of contents range of object meter is in 0.5 weight % between 30 weight %；It is preferred that changes of contents of the metallic element in terms of oxide
Range is in 1.5 weight % between 28 weight %.
Method according to the present invention, under preferable case, filling side of the hydrogenation protecting catalyst in reactor
Formula is gradually increases along logistics direction metal element content, and with the total weight of hydrogenation protecting catalyst, metallic element is to aoxidize
The changes of contents range of object meter is in 1.5 weight % between 8.5 weight %；It is preferred that the change of content of the metallic element in terms of oxide
Change range in 1.5 weight % between 7.5 weight %.
Delayed coking belongs to hot procedure, and the heat cracking reaction occurred in the hot procedure of hydrocarbon ils makes coking
Containing a large amount of undersaturated olefin compounds in wax oil, the stability of these substances is poor, influences produced rubber filling oil
Color and stability.The present invention is by adding the method for hydrogen to improve its quality, but alkene easily generates in hydrogenation process
Carbon deposit, catalyst bed is caused, which to block, influences device operating, and the present invention is golden along reactor stream flow direction by catalyst
Belong to the mode that constituent content is gradually increased, adjust the activity and the extent of reaction of catalyst, improve carbon deposit distribution, stable hydrogenation process
Operation.
In method of the present invention, preferably described load has Ni elements and/or the hydrogenation protecting catalyst of W elements to account for
The 15-30% of the total volume of the Hydrobon catalyst.
Method according to the present invention, the condition that the dewaxing hydrocarbon ils is contacted with Hydrobon catalyst include：Pressure
For 3.5-10MPa, preferably 4.5-8MPa.
Method according to the present invention, the condition that the dewaxing hydrocarbon ils is contacted with Hydrobon catalyst include：Temperature
It is 280-400 DEG C, preferably 320-360 DEG C.
Method according to the present invention, the condition that the dewaxing hydrocarbon ils is contacted with Hydrobon catalyst include：During liquid
Volume space velocity is 0.5-2.5h-1, preferably 1.0-2.0h-1。
Method according to the present invention, the condition that the dewaxing hydrocarbon ils is contacted with Hydrobon catalyst include：Hydrogen oil
Volume ratio is 200-1000：1, preferably 260-800：1, further preferably 260-480：1.
In the present invention, can also the product that obtained after contact in step (2) be subjected to air lift, obtains the production of flash-point qualification
Product.
In method of the present invention, the condition of the air lift can include：Vacuum degree is 5-30mmHg, preferably
15-25mmHg。
In method of the present invention, the condition of the air lift can include：Stripping medium includes nitrogen and/or water steams
Gas, more preferably vapor.
Method according to the present invention, arene content is not less than 80 weight % in the aromatic hydrocarbon rubber filling oil.
In method of the present invention, when the arene content in the aromatic hydrocarbon rubber filling oil of acquisition is higher, aromatic hydrocarbons
The quality of type rubber filling oil is higher, and method of the invention avoids the supersaturation of aromatic hydrocarbons by preferably controlling hydrogenation depth,
Simultaneously so that the mass fraction of aromatic hydrocarbons significantly improves in product.
The present invention will be described in detail by way of examples below.In following embodiment, in the feelings being not particularly illustrated
Under condition, the substances such as used various raw materials are commercially available product.
The property of wax tailings used in following embodiment is identical, as shown in table 1.In table, the color uses
ASTM D1500 petroleum products color measuring methods are evaluated.
Table 1
| 100 DEG C of kinematic viscosity/(mm2/s) | 7.9 |
| Solidification point/(DEG C) | 32 |
| Nitrogen content/(μ g/g) | 5600 |
| Sulfur content/(μ g/g) | 3200 |
| Color/(number) | 8.0 |
| Aromatics quality score (%) | 62 |
| Initial boiling point/(DEG C) | 353 |
| The end point of distillation/(DEG C) | 546 |
Embodiment 1
The present embodiment is carried out using following steps：
(1) wax tailings are introduced into cryogenic system and carry out condensation-crystallization, used crystallization temperature is -5 DEG C, institute
The solvent used is toluene and the mixed solution of butanone, and the wherein volume ratio of toluene and butanone is 45：55.It is used after crystallization
It is separated by filtration, obtains filtrate, dewaxing hydrocarbon ils of the solidification point less than 25 DEG C will be obtained after filtrate recycling design.
(2) in presence of hydrogen, the dewaxing hydrocarbon ils is introduced into hydrofinishing district and carries out hydrofinishing processing, wherein, it should
The catalyst that hydrofinishing district is loaded is followed successively by RG-20 hydrogenation protecting catalysts, and (volume of filling accounts for the two total volume
20%) with RJW-3 catalyst, the pressure of the hydrofinishing district is 6.0MPa, and reaction temperature is 345 DEG C, volume space velocity 1.2h-1, hydrogen to oil volume ratio 450：1, obtain the hydrocarbon ils component by adding hydrogen.
(3) under vacuum, the hydrocarbon ils component for the process in step (2) being added hydrogen carries out air lift, wherein, vacuum degree is
15mmHg, stripping medium are overheated steam, and the property of obtained product is as shown in table 2.
Table 2
| 100 DEG C of kinematic viscosity/(mm2/s) | 8.52 |
| Pour point/(DEG C) | 8 |
| Nitrogen content/(μ g/g) | 5400 |
| Sulfur content/(μ g/g) | 1400 |
| Color/(number) | 2.5 |
| Aromatics quality score (%) | 86 |
| Flash-point/(DEG C) | 228 |
Embodiment 2
The present embodiment is carried out using following steps：
(1) wax tailings are introduced into cryogenic system and carry out condensation-crystallization, used crystallization temperature is 5 DEG C, institute
The solvent used is toluene and the mixed solution of butanone, and the wherein volume ratio of toluene and butanone is 50：50.It is used after crystallization
It is separated by filtration, obtains filtrate, dewaxing hydrocarbon ils of the solidification point less than 25 DEG C will be obtained after filtrate recycling design.
(2) in presence of hydrogen, the dewaxing hydrocarbon ils is introduced into hydrofinishing district and carries out hydrofinishing processing, wherein, it should
The catalyst that hydrofinishing district is loaded is followed successively by RG-20A hydrogenation protecting catalysts, and (volume of filling accounts for the two total volume
15%) with RJW-3 catalyst, the pressure of the hydrofinishing district is 8.0MPa, and reaction temperature is 360 DEG C, volume space velocity 2.0h-1, hydrogen to oil volume ratio 420：1, obtain the hydrocarbon ils component by adding hydrogen.
(3) under vacuum, the hydrocarbon ils component for the process in step (2) being added hydrogen carries out air lift, wherein, vacuum degree is
20mmHg, stripping medium are overheated steam, and the property of obtained product is as shown in table 3.
Table 3
| 100 DEG C of kinematic viscosity/(mm2/s) | 8.50 |
| Pour point/(DEG C) | 8 |
| Nitrogen content/(μ g/g) | 5415 |
| Sulfur content/(μ g/g) | 1415 |
| Color/(number) | 2.5 |
| Aromatics quality score (%) | 85.7 |
| Flash-point/(DEG C) | 230 |
Embodiment 3
The present embodiment is carried out using following steps：
(1) wax tailings are introduced into cryogenic system and carry out condensation-crystallization, used crystallization temperature is 10 DEG C, institute
The solvent used is toluene and the mixed solution of butanone, and the wherein volume ratio of toluene and butanone is 40：60.It is used after crystallization
It is separated by filtration, obtains filtrate, dewaxing hydrocarbon ils of the solidification point less than 25 DEG C will be obtained after filtrate recycling design.
(2) in presence of hydrogen, the dewaxing hydrocarbon ils is introduced into hydrofinishing district and carries out hydrofinishing processing, wherein, it should
The catalyst that hydrofinishing district is loaded is followed successively by RG-20B hydrogenation protecting catalysts, and (volume of filling accounts for the two total volume
30%) with RL-2 catalyst, the pressure of the hydrofinishing district is 4.5MPa, and reaction temperature is 290 DEG C, volume space velocity 1.0h-1,
Hydrogen to oil volume ratio is 300：1, obtain the hydrocarbon ils component by adding hydrogen.
(3) under vacuum, the hydrocarbon ils component for the process in step (2) being added hydrogen carries out air lift, wherein, vacuum degree is
10mmHg, stripping medium are overheated steam, and the property of obtained product is as shown in table 4.
Table 4
| 100 DEG C of kinematic viscosity/(mm2/s) | 8.51 |
| Pour point/(DEG C) | 8 |
| Nitrogen content/(μ g/g) | 5425 |
| Sulfur content/(μ g/g) | 1420 |
| Color/(number) | 2.5 |
| Aromatics quality score (%) | 85.5 |
| Flash-point/(DEG C) | 231 |
Embodiment 4
The present embodiment is carried out using method similar to Example 1, except that：
In step (1), volume ratio of the used solvent for toluene and the mixed solution, wherein toluene and butanone of butanone
It is 60：40.
Remaining method and condition is same as Example 1.
The property of obtained product is as shown in table 5.
Table 5
| 100 DEG C of kinematic viscosity/(mm2/s) | 8.48 |
| Pour point/(DEG C) | 8 |
| Nitrogen content/(μ g/g) | 5455 |
| Sulfur content/(μ g/g) | 1435 |
| Color/(number) | 2.5 |
| Aromatics quality score (%) | 82.8 |
| Flash-point/(DEG C) | 230 |
Embodiment 5
The present embodiment is carried out using method similar to Example 2, except that：
In step (2), catalyst that hydrofinishing district is loaded be followed successively by RG-20A hydrogenation protecting catalysts (filling
Volume both accounts for the 10% of total volume) and RJW-3 catalyst, remaining method and condition it is same as Example 2.
The property of obtained product is as shown in table 6.
Table 6
| 100 DEG C of kinematic viscosity/(mm2/s) | 8.48 |
| Pour point/(DEG C) | 8 |
| Nitrogen content/(μ g/g) | 5420 |
| Sulfur content/(μ g/g) | 1420 |
| Color/(number) | 2.5 |
| Aromatics quality score (%) | 81.8 |
| Flash-point/(DEG C) | 228 |
Embodiment 6
The present embodiment is carried out using method similar to Example 2, except that：
In step (2), catalyst that hydrofinishing district is loaded be followed successively by RG-20A hydrogenation protecting catalysts (filling
Volume both accounts for the 35% of total volume) and RJW-3 catalyst, remaining method and condition it is same as Example 2.
The property of obtained product is as shown in table 7.
Table 7
| 100 DEG C of kinematic viscosity/(mm2/s) | 8.48 |
| Pour point/(DEG C) | 8 |
| Nitrogen content/(μ g/g) | 5422 |
| Sulfur content/(μ g/g) | 1410 |
| Color/(number) | 2.5 |
| Aromatics quality score (%) | 81.9 |
| Flash-point/(DEG C) | 229 |
Embodiment 7
The present embodiment is carried out using method similar to Example 3, except that：
In step (2), the pressure of hydrofinishing district is 10MPa, and reaction temperature is 400 DEG C, volume space velocity 0.2h-1,
Hydrogen to oil volume ratio is 300：1, remaining method and condition is same as Example 3.
The property of obtained product is as shown in table 8.
Table 8
| 100 DEG C of kinematic viscosity/(mm2/s) | 8.50 |
| Pour point/(DEG C) | 8 |
| Nitrogen content/(μ g/g) | 5420 |
| Sulfur content/(μ g/g) | 1415 |
| Color/(number) | 2.5 |
| Aromatics quality score (%) | 83.5 |
| Flash-point/(DEG C) | 230 |
Embodiment 8
The present embodiment is carried out using method similar to Example 1, except that：
In step (3), vacuum degree 30mmHg, remaining method and condition is same as Example 1.
The property of obtained product is as shown in table 9.
Table 9
| 100 DEG C of kinematic viscosity/(mm2/s) | 8.50 |
| Pour point/(DEG C) | 8 |
| Nitrogen content/(μ g/g) | 5405 |
| Sulfur content/(μ g/g) | 1415 |
| Color/(number) | 2.5 |
| Aromatics quality score (%) | 83.5 |
| Flash-point/(DEG C) | 222 |
Method using the present invention can be seen that by the result of above example and produce aromatic hydrocarbons by wax tailings inferior
During type rubber filling oil, have the advantages that method is simple, the virtue in method production aromatic hydrocarbon rubber filling oil using the present invention
The mass fraction of hydrocarbon is above 80%, by adjusting operating parameter, it might even be possible to so that the aromatic hydrocarbon rubber filling that production obtains
The mass fraction of aromatic hydrocarbons in oil is up to 86%.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (19)
1. a kind of method for producing aromatic hydrocarbon rubber filling oil, this method include：
(1) wax tailings that boiling range is 350-560 DEG C are subjected to condensation-crystallization, obtain the dewaxing hydrocarbon ils that solidification point is less than 25 DEG C,
Wherein, arene content is more than or equal to 60 weight % in the wax tailings；
(2) in presence of hydrogen, the dewaxing hydrocarbon ils is contacted with Hydrobon catalyst, the Hydrobon catalyst includes
Load the hydrogenation protecting catalyst for having Ni elements and/or W elements and Hydrobon catalyst and/or hydrodenitrogenation catalyst；
The condition that the dewaxing hydrocarbon ils is contacted with Hydrobon catalyst includes：Pressure is 3.5-10MPa, temperature 280-400
DEG C, volume space velocity is 0.2-2.5h during liquid-1, hydrogen to oil volume ratio 200-1000：1.
2. according to the method described in claim 1, wherein, the temperature of the condensation-crystallization is minus 30 DEG C to 20 DEG C above freezing.
3. according to the method described in claim 1, wherein, the solvent of the condensation-crystallization is carried out as in pentane, toluene and butanone
At least one.
4. according to the method described in claim 3, wherein, the solvent for carrying out the condensation-crystallization is toluene and butanone.
5. according to the method described in claim 4, wherein, the dosage volume ratio of the toluene and butanone is 1：0.6-2.
6. according to the method described in claim 1, wherein, along logistics direction, the load has Ni elements and/or W elements
Hydrogenation protecting catalyst is set to the upstream of hydrofinishing district.
7. according to the method described in claim 1, wherein, type of feed of the hydrogenation protecting catalyst in reactor is edge
Logistics direction granularity tapers into, and granularity variation range is calculated as 20mm to 1.6mm with equivalent diameter.
8. according to the method described in claim 7, wherein, type of feed of the hydrogenation protecting catalyst in reactor is edge
Logistics direction granularity tapers into, and granularity variation range is calculated as 18mm to 1.8mm with equivalent diameter.
9. according to the method described in claim 1, wherein, type of feed of the Hydrobon catalyst in reactor is edge
Logistics direction metal element content gradually increases, and with the total weight of Hydrobon catalyst, metallic element is in terms of oxide
The variation range of content is in 0.5 weight % between 30 weight %.
10. according to the method described in claim 9, wherein, with the total weight of Hydrobon catalyst, metallic element is to aoxidize
The variation range of the content of object meter is in 1.5 weight % between 28 weight %.
11. according to the method described in claim 1, wherein, type of feed of the hydrogenation protecting catalyst in reactor is
It is gradually increased along logistics direction metal element content, with the total weight of hydrogenation protecting catalyst, metallic element is in terms of oxide
Changes of contents range in 1.5 weight % between 8.5 weight %.
12. according to the method for claim 11, wherein, with the total weight of hydrogenation protecting catalyst, metallic element is with oxygen
The variation range of the content of compound meter is in 1.5 weight % between 7.5 weight %.
13. according to the method described in claim 1, wherein, the load has the catalysis of the hydrogenation protecting of Ni elements and/or W elements
Agent accounts for the 15-30% of the total volume of the Hydrobon catalyst.
14. according to the method described in claim 1, wherein, condition packet that the dewaxing hydrocarbon ils is contacted with Hydrobon catalyst
It includes：Pressure is 4.5-8MPa, and temperature is 320-360 DEG C, and volume space velocity is 1.0-2.0h during liquid-1, hydrogen to oil volume ratio 260-
800：1.
15. according to the method described in claim 1, wherein, this method further includes：The product that will be obtained after contact in step (2)
Carry out air lift.
16. according to the method for claim 15, wherein, the condition of the air lift includes：Vacuum degree is 5-30mmHg；Air lift
Medium is nitrogen and/or vapor.
17. according to the method for claim 16, wherein, the condition of the air lift includes：Vacuum degree is 15-25mmHg.
18. according to the method for claim 16, wherein, stripping medium is vapor.
19. according to the method described in claim 1, wherein, arene content is not less than 80 weights in the aromatic hydrocarbon rubber filling oil
Measure %.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1042730A (en) * | 1989-09-11 | 1990-06-06 | 齐鲁石油化工公司研究院 | Utilize wax oil to produce the new technology of high-value product |
| EP1106673A2 (en) * | 1999-12-06 | 2001-06-13 | Shell Internationale Researchmaatschappij B.V. | Removal of polycyclic aromatic compounds from extracts |
| CN102660325A (en) * | 2012-05-19 | 2012-09-12 | 淄博汇佳橡胶新型材料有限公司 | Preparation method of environment-friendly rubber tire filling oil |
| CN102732291A (en) * | 2012-06-29 | 2012-10-17 | 新疆现代石油化工股份有限公司 | Method for preparing base oil of lubricating oil by dewaxing |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042730A (en) * | 1989-09-11 | 1990-06-06 | 齐鲁石油化工公司研究院 | Utilize wax oil to produce the new technology of high-value product |
| EP1106673A2 (en) * | 1999-12-06 | 2001-06-13 | Shell Internationale Researchmaatschappij B.V. | Removal of polycyclic aromatic compounds from extracts |
| CN102660325A (en) * | 2012-05-19 | 2012-09-12 | 淄博汇佳橡胶新型材料有限公司 | Preparation method of environment-friendly rubber tire filling oil |
| CN102732291A (en) * | 2012-06-29 | 2012-10-17 | 新疆现代石油化工股份有限公司 | Method for preparing base oil of lubricating oil by dewaxing |
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