CN103789019B - Method for hydrogenation of medium-low temperature coal tar to produce transformer oil base oil - Google Patents
Method for hydrogenation of medium-low temperature coal tar to produce transformer oil base oil Download PDFInfo
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Abstract
The invention discloses a method for hydrogenation of medium-low temperature coal tar to produce transformer oil base oil. The method includes: fractionating the medium-low temperature coal tar to obtain light fraction and heavy fraction, mixing the light fraction with hydrogen and leading the mixture into a hydrotreating reaction area to contact a hydrogenation protective catalyst and a hydrofining catalyst in order to undergo hydrogenation reaction; separating the hydrofining effluent, making the obtained liquid phase product enter a fractionating tower; bringing the 280-320DEG C diesel fraction obtained by fractionation into a hydro-upgrading reaction area where a hydro-upgrading catalyst containing amorphous aluminium silicon and modified Y zeolite is adopted, and performing hydro-upgrading reaction in the presence of hydrogen; subjecting the hydro-upgrading effluent into a hydrofinishing reaction area to undergo hydrofinishing reaction, and separating the hydrofinishing product to obtain the transformer oil base oil. The method provided by the invention adopts the medium-low temperature coal tar as the raw material to maximumly produce the transformer oil base oil with the advantages of high density, volume, high volume calorific value, low aromatic hydrocarbon content, and good low temperature performance.
Description
Technical field
The present invention relates to a kind of production method of transformer oil base oil, specifically a kind ofly adopt in raw materials pretreatment, method that coalite tar adopts hydrotreatment-hydro-upgrading/hydrofinishing two-stage hydrogenation produces the method for transformer oil base oil.
Background technology
Transformer oil refers to in the oil-filled electric equipments such as transformer, reactor, mutual inductor, sleeve pipe, oil switch, plays insulation, cooling and a class transformer oil product of arc extinguishing effect.The use properties of transformer oil is had to the requirement of three aspects: 1. good physicals; 2. good electric property; 3. good oxidation stability.
Transformer oil base oil is the raw material producing transformer oil.The performance of transformer oil depends on the performance of transformer oil base oil to a great extent.Usually, paraffinic base transformer oil base oil pour point is high, the acidic cpd that oxidizable production is a large amount of, and aromaticity content is few, comes with some shortcomings in the life-span of transformer oil, anti-oxidant, anti-gassing etc.And cycloalkyl transformer oil base oil can meet the requirement such as insulation, cooling of transformer oil, again can long-term stable operation, therefore become the optimum feed stock of acknowledged production transformer oil base oil.
The production technique of transformer oil base oil is along with the development of oil refining process.Be using naphthenic base crude as raw material the earliest, adopt sulfuric acid-clay-filtered explained hereafter transformer oil base oil, but the method cost be high, yield is low, treatment capacity is little, the most important thing is to produce a large amount of acid sludge contaminate environment.
CN200810226047.4 discloses a kind of production method of transformer oil base oil.First normal for Suizhong 36-1 two wires distillate is carried out furfural treatment, obtains treated oil, then add denitrfying agent and carry out denitrogenation, except denitrification slag, then add carclazyte, carry out clay-filtered, finally obtain transformer oil base oil.But the method yield is low, poor continuity, also there is nitrogen slag and clay treated environmental problem.
CN201010222066.7 discloses a kind of method adopting perhydro method to produce transformer oil base oil.With cycloalkyl distillate for raw material, the one-stage serial hydrogenation technique of hydrotreatment-hydrodewaxing-hydrofinishing is adopted to produce transformer oil base oil and other specialty oil products.The method energy consumption is low, good product quality, but there is the problem of cycloalkyl distillate resource-constrained.
At present, the naphthenic base crude resource of China mainly concentrates on the large block in Karamay, Xinjiang, Liaohe Huanxiling and Bohai Sea Gulf three, and the raw material for the production of transformer oil base oil is Karamay, Xinjiang crude oil and Liaohe Huanxiling crude oil.Wherein, at home and abroad share of market is higher to utilize the cycloalkyl transformer oil base oil of Karamay, Xinjiang crude production, and effect is better.And Liaohe Huanxiling crude oil reduces and quality variation along with output, can not as the stable resources producing transformer oil.Along with China's power industry great development and the Domestic Transformers oil market requirement constantly increase, imbalance between supply and demand is more outstanding, therefore opens up the transformer oil raw materials for production that other is suitable, realizes transformer oil and significantly domesticize, be of great immediate significance.
China is the very abundant countries of coal resources, and a large amount of coal tar of Coal Chemical Industry process by-product, has certain natural crude oil characteristic, how to effectively utilize the important step that coal tar is the comprehensive utilization of coal.It is high that coal tar has aromaticity content, after hydrotreatment and hydro-upgrading, can be transformed into naphthenic hydrocarbon, can production low-temperature performance is good, electric property is outstanding, oxidation stability is good transformer oil base oil.
Summary of the invention
For the deficiencies in the prior art, the invention provides one with middle coalite tar for raw material, the method for employing hydrotreatment-hydro-upgrading-hydrofinishing Unionfining produces the method for transformer oil base oil.
Middle coalite tar hydrogenation of the present invention is produced transformer oil base oil method and is comprised following content:
(1) in, coalite tar obtains lighting end and last running through fractionation, and cut point is 480 ~ 510 DEG C;
(2) step (1) described lighting end enters hydrotreatment reaction zone after mixing with hydrogen, contacts successively carry out hydrogenation reaction with hydrogenation protecting catalyst with Hydrobon catalyst;
(3) step (2) gained hydrofining effluent carries out gas-liquid separation, and separating obtained liquid product enters separation column;
(4) step (3) fractionation gained 280 ~ 320 DEG C of diesel oil distillates enter hydro-upgrading reaction zone, and hydro-upgrading reaction zone uses the catalyst for hydro-upgrading containing amorphous aluminum silicide and modified Y zeolite, in presence of hydrogen, carries out hydro-upgrading reaction;
(5) step (4) gained hydro-upgrading effluent enters hydrofinishing reaction zone, and in presence of hydrogen, with hydrofinishing catalyst exposure, carry out hydrofinishing reaction, hydrofinishing product is isolated to transformer oil base oil.
In the inventive method, the described middle coalite tar of step (1) carries out fractionation after first carrying out dewatering and remove mechanical impurity again.
In the inventive method, after the described middle coalite tar fractionation of step (1), gained last running can be used as modifying asphalt, heavy fuel oil (HFO), or is used as coking raw material.
In the inventive method, hydrotreatment reaction zone loads hydrogenation protecting catalyst and Hydrobon catalyst from top to bottom, and the admission space of hydrogenation protecting catalyst and Hydrobon catalyst is than being 10:25 ~ 75:90.
In the inventive method; hydrotreatment reaction zone uses conventional hydrogenation protecting catalyst; the FZC series protective material of Fushun Petrochemical Research Institute (FRIPP) development and production can be adopted; also can conventionally prepare; these catalyzer generally with porous refractory inorganic oxide if aluminum oxide is for carrier; group vib and/or group VIII metal such as the oxide compound of W, Mo, Co, Ni etc. are active ingredient, optionally add other various auxiliary agent as the catalyzer of the elements such as P, Si, F, B.
In the inventive method, the Hydrobon catalyst that hydrotreatment reaction zone uses, can select this field general goods catalyzer, also can prepare by this area general knowledge.The commercial catalysts that can select as Fushun Petrochemical Research Institute (FRIPP) development and production 3936,3996, the Hydrobon catalyst such as FF-16, FF-26.
In the inventive method, in order to play the performance of catalyst for hydro-upgrading better, at the better Hydrobon catalyst of a certain proportion of Hydrogenation of top grading loading of catalyst for hydro-upgrading, carry out desulfurization, denitrogenation, saturated condensed-nuclei aromatics, play the open-loop performance of catalyst for hydro-upgrading better, increase the running period of whole device.Hydro-upgrading reaction zone uses Hydrobon catalyst in the catalyst for hydro-upgrading top filling containing amorphous aluminum silicide and modified Y zeolite, and the admission space of Hydrobon catalyst and the catalyst for hydro-upgrading containing amorphous aluminum silicide and modified Y zeolite is than being 25:75 ~ 60:40.
In the inventive method, the Hydrobon catalyst on top, hydro-upgrading district can select this field general goods catalyzer, also can prepare by this area general knowledge.The commercial catalysts that can select is as commodity Hydrobon catalysts such as the FTX of Fushun Petrochemical Research Institute (FRIPP) development and production.
In the inventive method, hydro-upgrading reaction zone uses the catalyst for hydro-upgrading containing amorphous aluminum silicide and modified Y zeolite.Contain in described catalyst for hydro-upgrading: the group VIII metal (with oxide basis) of the modified Y zeolite of 20wt% ~ 60wt% amorphous aluminum silicide, 5wt% ~ 25wt%, the group VIB metal (with oxide basis) of 10wt% ~ 30wt% and 4wt% ~ 10wt%.The character of amorphous aluminum silicide wherein used is as follows: silicon oxide-containing 10wt% ~ 60wt%, and specific surface is 400 ~ 650m
2/ g, pore volume is 1.0 ~ 1.8mL/g, and infrared acidity is 0.34 ~ 0.50mmol/g, and the pore volume that the pore volume of bore dia 4 ~ 10nm accounts for 85% ~ 95%, >15nm of total pore volume accounts for less than 5% of total pore volume; Preferred property is as follows: silicon oxide-containing 10wt% ~ 35wt%, and specific surface is 530 ~ 650m
2/ g, pore volume is 1.2 ~ 1.5mL/g.The character of modified Y zeolite wherein used is as follows: SiO
2/ Al
2o
3mol ratio is 40 ~ 60, and lattice constant is 2.425 ~ 2.440nm, and relative crystallinity is 80% ~ 100%, infrared acidity 0.1 ~ 0.5mmol/g, and wherein the middle strong acid distribution of 250 ~ 550 DEG C is concentrated, and account for 60 ~ 70% of total acid, specific surface area is 600 ~ 900m
2/ g, pore volume 0.3 ~ 0.6mL/g, wherein the pore volume of the secondary mesopore of 4 ~ 15nm accounts for 40% ~ 50% of total pore volume.The components such as aluminum oxide, zirconium white, titanium oxide can also be contained in catalyst for hydro-upgrading.The specific surface area of catalyst for hydro-upgrading is 220 ~ 300m
2/ g, pore volume is 0.3 ~ 0.6mL/g, and the pore volume of bore dia 3 ~ 10nm accounts for 75% ~ 95% of total pore volume, and be preferably 85% ~ 95%, infrared acidity is at 0.3 ~ 0.5mmol/g.
In the inventive method, hydrofinishing reaction zone uses conventional hydrofinishing catalyzer, its active metal component is group vib and group VIII metal, uses procatalyst to carry out prevulcanized, ensures that hydrogenation active metals is in sulphided state in reaction process.Described group vib metal is selected from Mo and/or W, its content with oxide basis for 10 ~ 25%; Group VIII metal is selected from Co and/or Ni, its content with oxide basis for 3 ~ 7%.
In the inventive method, in step (3), the reaction conditions of hydrotreatment reaction zone is: reaction pressure 5.0 ~ 20.0MPa, preferably 12.0 ~ 15.0MPa; Temperature of reaction 250 ~ 420 DEG C, preferably 300 ~ 400 DEG C; Hydrogen to oil volume ratio 500:1 ~ 1500:1, preferred 1000:1 ~ 1200:1; Volume space velocity 0.1 ~ 1.0h
-1, preferably 0.5 ~ 0.7h
-1.
In the inventive method, in step (4), the reaction conditions of hydro-upgrading reaction zone is: reaction pressure 5.0 ~ 20.0MPa, preferably 12.0 ~ 15.0MPa; Temperature of reaction 250 ~ 370 DEG C, preferably 300 ~ 350 DEG C; Hydrogen to oil volume ratio 500:1 ~ 1500:1, preferred 800:1 ~ 1000:1; Volume space velocity 0.1 ~ 1.5h
-1, preferably 0.8 ~ 1.0h
-1.
In the inventive method, in step (5), the reaction conditions of hydrofinishing reaction zone is: reaction pressure 5.0 ~ 20.0MPa, preferably 12.0 ~ 15.0MPa; Temperature of reaction 200 ~ 350 DEG C, preferably 290 ~ 320 DEG C; Hydrogen to oil volume ratio 500:1 ~ 1500:1, preferred 1000:1 ~ 1200:1; Volume space velocity 0.1 ~ 1.5h
-1, preferably 0.8 ~ 1.0h
-1.
Compared with prior art, tool of the present invention has the following advantages:
(1) first the present invention will carry out hydrotreatment through pretreated middle coalite tar, because coal tar is different from distillate molecular structure, desulfurization during hydrotreatment, denitrogenation and aromatic moiety are saturated causes structure collapses, and then coal tar is done and is greatly moved forward (maximum move forward about 100 DEG C), structure redistributes, distillate characteristic increases greatly, and aromaticity content is higher than cycloalkyl straight-run diesel oil simultaneously.The present invention adopts suitable catalyst for hydro-upgrading, saturated open loop is carried out to two rings and a small amount of thrcylic aromatic hydrocarbon, on rear side of maintenance open loop simultaneously, chain is complete, become monocycle or two Polycyclic aromatic hydrocarbons of belt length side chain, after hydro-upgrading and hydrofinishing, generate the naphthenic hydrocarbon of a large amount of many side chains of band, the transformer oil base oil that electric property, oxidation stability and anti-gassing property can be all good can be obtained.There is a small amount of straight-chain paraffin isomery of certain influence to become branched paraffin to condensation point simultaneously, ensure the low-temperature performance of product.
(2) the inventive method is that the middle coalite tar that added value is lower provides a kind of processing works improving its economy, and is a kind of new raw material of production development of transformer oil base oil.China is the country of a rich coal resources, there is a large amount of tar resources, utilize the inventive method can substitute rare naphthenic base crude resource, produce the high-quality transformer oil base oil that China's power industry is badly in need of, effectively can promote the Appropriate application of tar resource simultaneously.
(3) other cut after the inventive method hydrotreatment can as the blend component of gasoline and diesel oil, or the raw material of other specialty oil products.
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, through dehydration with remove coalite tar 1 in mechanical impurity and enter vacuum still 2 and carry out fractionation, obtain lighting end 3 and last running 4, gained last running 4 can be used as modifying asphalt, heavy fuel oil (HFO), or as coking raw material.Lighting end 3 mixes back end hydrogenation treatment reactor 6 with hydrogen 5, contact with Hydrobon catalyst with hydrogenation protecting catalyst successively, carry out hydrogenation reaction, gained hydrofining effluent 7 is after separation system 8 is separated, described separation system 8 generally comprises high-pressure separator and light pressure separator, separating obtained gas phase 9 returns hydrotreating reactor 6 as recycle hydrogen, isolated liquid phase 10 removes after hydrogen sulfide and gas products 12 through stripping tower 11, stripping tower bottom liquid phase 13 removes separation column 14, obtain respectively being less than 160 DEG C of cuts 15, 160 ~ 280 DEG C of cuts 16, 280 ~ 320 DEG C of cuts 17 and be greater than 320 DEG C of cuts 18.Wherein, be less than 160 DEG C of cuts 15 and can do gasoline blending component, 160 ~ 280 DEG C of cuts 16 can do diesel oil blending component, are greater than 320 DEG C of cuts 18 and can cut further as refrigerator oil base oil raw material, rubber filling oil raw material or environment-friendly type aromatic hydrocarbon oil raw material.280 ~ 320 DEG C of cuts 17 enter hydro-upgrading reaction zone 19, in presence of hydrogen, contact with catalyst for hydro-upgrading, carry out saturated open loop to two rings and a small amount of thrcylic aromatic hydrocarbon, and on rear side of maintenance open loop simultaneously, chain is complete, becomes the monocycle or two Polycyclic aromatic hydrocarbons of being with many side chains.Hydro-upgrading reaction product 20 enters hydrofinishing reaction zone 21, under hydrogen and Hydrobon catalyst exist, carries out aromatic hydrocarbons degree of depth saturated reaction, reduces aromaticity content, ensure the oxidation stability index of product.Then hydrofinishing product 22 is isolated after gas 24 through separator 23, and liquid product 25 enters after separation column 26 isolates a small amount of byproduct 27, obtains transformer oil base oil product 28.
Below in conjunction with embodiment, the present invention will be further described.
The various catalyzer related in embodiment can select commercial catalyst by character, also can prepare by this area knowledge.The commercial catalysts that the hydrogenation protecting agent of hydroprocessing processes can be selected is as hydrogenation protecting agent such as FZC-100, FZC-102A, FZC-103 of Fushun Petrochemical Research Institute's development and production; The commercial catalysts that can select of Hydrobon catalyst as Fushun Petrochemical Research Institute's development and production 3936,3996, the Hydrobon catalyst such as FF-16, FF-26; The commercial catalysts that the Hydrobon catalyst on top, hydro-upgrading district can be selected is as commodity Hydrobon catalysts such as the FTX of Fushun Petrochemical Research Institute's development and production; The commercial catalysts that catalyst for hydro-upgrading can be selected is as commodity hydrotreating catalysts such as FC-14, FC-26 of Fushun Petrochemical Research Institute's development and production; The commercial catalysts that hydrofinishing process can be selected is as commodity Hydrobon catalysts such as FV-10, FV-20 of Fushun Petrochemical Research Institute's development and production.
Embodiment 1
With Datang coalite tar for raw material, cut point is 500 DEG C, and specific nature is in table 1.Hydrotreatment reaction zone filling hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936, the admission space of hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936 is than being 1:4.Hydro-upgrading reaction zone filling FTX catalyzer and FC-28 catalyzer, admission space is than being 1:1, and hydrofinishing reaction zone filling Hydrobon catalyst FV-10, the processing condition of hydrogenation process and product property are in table 2.
Embodiment 2
With her eastern coal-tar middle oil for raw material, cut point is 500 DEG C, and specific nature is in table 1.Hydrotreatment reaction zone filling hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936, the admission space of hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936 is than being 1:4.Hydro-upgrading reaction zone filling FTX catalyzer and FC-28 catalyzer, admission space is than being 1:1, and hydrofinishing reaction zone filling Hydrobon catalyst FV-10, the processing condition of hydrogenation process and product property are in table 2.
Comparative example 1
Adopt the raw material identical with embodiment 1, difference is that hydrotreatment products cuts out diesel oil distillate without hydro-upgrading, directly enters hydrofinishing reactor.Hydrotreatment reaction zone filling hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936, the admission space of hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936 is than being 1:4.Hydrofinishing reaction zone filling Hydrobon catalyst FV-10, the processing condition of hydrogenation process and product property are in table 2.
Comparative example 2
With Datang coalite tar 280 ~ 320 DEG C of diesel oil distillates for raw material, specific nature is in table 1.Raw material Datang coalite tar 280 ~ 320 DEG C of diesel oil distillates carry out hydrofining reaction merely through hydrotreatment reaction zone; hydrotreatment reaction zone filling hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936, the admission space of hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936 is than being 1:4.The processing condition of hydrogenation process and product property are in table 2.
Table 1 test feedstock property
| Material name | Datang coalite tar | Her eastern coal-tar middle oil | Datang coalite tar 280 ~ 320 DEG C of cuts |
| Density (20 DEG C), g.cm -3 | 1.0284 | 1.010 | 0.9032 |
| Boiling range (simulation distil), DEG C | |||
| IBP | 77 | 39 | 291 |
| 10%/30%/50% | 161/205/253 | 216/276/328 | 295/300/304 |
| 70%/90%/95% | 311/390/425 | 374/428/444 | 309/313/316 |
| EBP | 495 | 513 | 319 |
| Sulphur, μ g.g -1 | 8800 | 2300 | 5760 |
| Nitrogen, μ g.g -1 | 9500 | 6283 | 7500 |
| Viscosity (100 DEG C), mm.s -2 | 3.004 | ||
| Carbon residue, % | 0.45 | 1.14 | 0.10 |
| Condensation point, DEG C | 8 | 5 | -21(freezing point) |
| Flash-point (opening), DEG C | 112 | 142 | 93(remains silent) |
| Acid number, mgKOH.g -1 | 0.81 | 0.45 | |
| Mechanical impurity, wt% | 0.023 | 0 | |
| Mass spectrum forms, wt% | |||
| Colloid | 33.5 | 22.0 | |
| Paraffinic hydrocarbons | 6.9 | 0 | 6.4 |
| Naphthenic hydrocarbon | 7.6 | 0 | 52.7 |
| Aromatic hydrocarbons | 52.0 | 78.0 | 40.9 |
| Monocycle/dicyclo/tri-ring | 13.1/24.4/8.5 | 21.3/31.7/13.5 | 31.7/5.9/3.3 |
| Fourth Ring/five rings/thiophene | 2.0/0.2/3.4 | 6.1/0.5/4.0 | |
| Do not identify aromatic hydrocarbons | 0.4 | 0.9 | |
| Heavy metal, μ g.g -1 | <5 | <5 |
The processing condition of table 2 embodiment and comparative example and result
| Test number | Embodiment 1 | Comparative example 1 | Embodiment 2 | Comparative example 2 |
| Hydroprocessing technique condition | ||||
| Temperature of reaction, DEG C | 380 | 380 | 380 | 320 |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Volume space velocity, h -1 | 0.5 | 0.5 | 0.5 | 1.0 |
| 280 ~ 320 DEG C of cut yields, wt% | 20.62 | 20.62 | 19.25 | 25.47 |
| Hydro-upgrading reaction process condition | ||||
| Temperature of reaction, DEG C | 330 | 325 | ||
| Reaction pressure, MPa | 15.0 | 15.0 | ||
| Hydrogen to oil volume ratio | 800:1 | 800:1 | ||
| Volume space velocity, h -1 | 1.0 | 1.0 | ||
| Hydrofinishing reaction process condition | ||||
| Temperature of reaction, DEG C | 280 | 285 | 280 | |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 | |
| Hydrogen to oil volume ratio | 800:1 | 800:1 | 800:1 | |
| Volume space velocity, h -1 | 1.0 | 1.0 | 1.0 | |
| Object product yield, wt% | 71.2 | 90.3 | 69.5 | |
| Product property | ||||
| Colourity (D1500) | <0.5 | <0.5 | <0.5 | <0.5 |
| Kinematic viscosity (40 DEG C), mm.s -2 | 7.33 | 7.57 | 7.25 | 8.32 |
| Kinematic viscosity (-30 DEG C), mm.s -2 | 545.2 | 609.3 | 553.7 | 690.4 |
| Rotary oxygen bomb (150min), min | 245 | 230 | 245 | 220 |
| Structural group forms, wt% | ||||
| C A | 4.1 | 5.0 | 3.6 | 5.5 |
| C P | 45.9 | 43.0 | 45.5 | 41.9 |
| Aromaticity content (fluorescence chromatogram), wt% | <5 | 12.4 | <5 | 28.6 |
| C N | 50.0 | 52.0 | 50.9 | 52.6 |
| Flash-point (remaining silent), DEG C | 145 | 142 | 143 | 144 |
| Condensation point, DEG C | <50 | -42 | <50 | -38 |
| Acid number, mgKOH.g -1 | 0.001 | 0.002 | 0.001 | 0.003 |
| Density (20 DEG C), g.cm -3 | 0.8776 | 0.8803 | 0.8756 | 0.8903 |
| Basic nitrogen, μ g.g -1 | <1 | <1 | <1 | <1 |
| Voltage breakdown, KV | 75.9 | 72.8 | 77.6 | 65.9 |
| Dielectric dissipation factor (20 DEG C) | 0.00092 | 0.00105 | 0.00105 | 0.00156 |
As can be seen from the product property of embodiment 1 and comparative example 1, the transformer oil base oil product only having hydrofining not have the middle coalite tar of hydro-upgrading process process to obtain, anti-gassing property can slightly well, but oxidation stability is poor, and electric property is bad, and (dielectric dissipation factor is high, breakdown potential is forced down), and poor performance at low temperatures (-42 DEG C), defective.And the product directly cutting 280 ~ 320 DEG C of cut fraction hydrogenation process in comparison example 2 is the poorest, except aromaticity content is high, beyond anti-gassing property can be got well, electric property, low temperature flowability are all defective.
As can be seen from the product property of embodiment 1,2, in employing, coalite tar is by hydrotreatment-hydro-upgrading/hydrogenation post-refining process, low-temperature fluidity can be given birth to, (dielectric loss index is low for electric property, voltage breakdown is high) and all good transformer oil base oil of oxidation stability, embodiment of the present invention gained transformer oil base oil character can meet the performance perameter index of No. 45 transformer oil base oils.Greatly can expand the raw material sources of transformer oil base oil, meet the needs of State Grid's industry great development, also enriched the deep exploitation of tar resource simultaneously, there is very large economic benefit and social benefit.
Claims (14)
1. in, coalite tar hydrogenation produces a transformer oil base oil method, comprises following content:
(1) in, coalite tar obtains lighting end and last running through fractionation, and cut point is 480 ~ 510 DEG C;
(2) step (1) described lighting end enters hydrotreatment reaction zone after mixing with hydrogen, contacts successively carry out hydrogenation reaction with hydrogenation protecting catalyst with Hydrobon catalyst;
(3) step (2) gained hydrofining effluent carries out gas-liquid separation, and separating obtained liquid product enters separation column;
(4) step (3) fractionation gained 280 ~ 320 DEG C of diesel oil distillates enter hydro-upgrading reaction zone, and hydro-upgrading reaction zone uses the catalyst for hydro-upgrading containing amorphous aluminum silicide and modified Y zeolite, in presence of hydrogen, carries out hydro-upgrading reaction;
(5) step (4) gained hydro-upgrading effluent enters hydrofinishing reaction zone, and in presence of hydrogen, with hydrofinishing catalyst exposure, carry out hydrofinishing reaction, hydrofinishing product is isolated to transformer oil base oil.
2. in accordance with the method for claim 1, it is characterized in that: the described middle coalite tar of step (1) carries out fractionation after first carrying out dewatering and remove mechanical impurity again.
3. in accordance with the method for claim 1, it is characterized in that: after the described middle coalite tar fractionation of step (1), gained last running is used as modifying asphalt, heavy fuel oil (HFO), or as coking raw material.
4. in accordance with the method for claim 1, it is characterized in that: hydrotreatment reaction zone loads hydrogenation protecting catalyst and Hydrobon catalyst from top to bottom, the admission space of hydrogenation protecting catalyst and Hydrobon catalyst is than being 10:25 ~ 75:90.
5. in accordance with the method for claim 1, it is characterized in that: hydro-upgrading reaction zone is at the catalyst for hydro-upgrading top filling Hydrobon catalyst containing amorphous aluminum silicide and modified Y zeolite, and the admission space of described Hydrobon catalyst and the catalyst for hydro-upgrading containing amorphous aluminum silicide and modified Y zeolite is than being 25:75 ~ 60:40.
6. in accordance with the method for claim 1, it is characterized in that: in step (2), the operational condition of hydrotreatment reaction zone is: reaction pressure 5.0 ~ 20.0MPa, temperature of reaction 250 ~ 420 DEG C, hydrogen to oil volume ratio 500:1 ~ 1500:1, volume space velocity 0.1 ~ 1.0h
-1.
7. in accordance with the method for claim 1, it is characterized in that: in step (4), the operational condition of hydro-upgrading reaction zone is: reaction pressure 5.0 ~ 20.0MPa, temperature of reaction 250 ~ 370 DEG C, hydrogen to oil volume ratio 500:1 ~ 1500:1, volume space velocity 0.1 ~ 1.5h
-1.
8. in accordance with the method for claim 1, it is characterized in that: in step (5), the operational condition of hydrofinishing reaction zone is: reaction pressure 5.0 ~ 20.0MPa, temperature of reaction 200 ~ 350 DEG C, hydrogen to oil volume ratio 500:1 ~ 1500:1, volume space velocity 0.1 ~ 1.5h
-1.
9. 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%.
10. according to the method described in claim 1 or 9, 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.
11. in accordance with the method for claim 10, 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%, and specific surface is 530 ~ 650m
2/ g, pore volume is 1.2 ~ 1.5mL/g.
12. 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.
13. 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.
14. in accordance with the method for claim 1, it is characterized in that: the hydrofinishing catalyzer that hydrofinishing reaction zone uses, its active metal component is group vib and group VIII metal, and described group vib metal is selected from Mo and/or W, its content with oxide basis for 10 ~ 25%; Group VIII metal is selected from Co and/or Ni, its content with oxide basis for 3 ~ 7%.
Priority Applications (1)
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| CN106350111B (en) * | 2016-10-18 | 2018-05-29 | 山东宝塔新能源有限公司 | A kind of coal tar deep processing method based on hydrofining reaction, modification reaction |
| CN111378502B (en) * | 2018-12-31 | 2021-12-07 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon solvent oil by hydrogenating C9 aromatic hydrocarbon fraction cracked by ethylene |
| CN113122324B (en) * | 2019-12-31 | 2022-11-11 | 中国石油化工股份有限公司 | Method for producing special oil product by catalyzing slurry oil hydrogenation |
| CN112280612A (en) * | 2020-11-08 | 2021-01-29 | 盘锦北方沥青股份有限公司 | High-performance transformer oil and preparation method thereof |
| CN115820298A (en) * | 2022-12-06 | 2023-03-21 | 中国石油化工股份有限公司 | Transformer oil production process |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2064002C1 (en) * | 1994-06-22 | 1996-07-20 | Всероссийский научно-исследовательский институт по переработке нефти | Method for production of base of electric insulating oil |
| CN1225662A (en) * | 1996-07-15 | 1999-08-11 | 切夫里昂美国公司 | Lubricating base oil mfg. process |
| CN1676585A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Method for preparing lubricating oil base oil |
| CN101307257A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Coal tar hydrogenating modified method by two-stage method |
| CN101343564A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Method for producing lubricating oil basic oil |
| CN101386792A (en) * | 2008-11-04 | 2009-03-18 | 中国海洋石油总公司 | Transformer oil base oil and preparation method and applications thereof |
| CN101688131A (en) * | 2007-07-13 | 2010-03-31 | Sk能源株式会社 | Process for manufacturing naphthenic base oils from effluences of fluidized catalytic cracking unit |
| CN102311785A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for hydrogenating naphthenic base distillate to produce lubricating oil basic oil |
| CN102485846A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Preparation method of transformer oil base oil |
-
2012
- 2012-11-05 CN CN201210433517.0A patent/CN103789019B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2064002C1 (en) * | 1994-06-22 | 1996-07-20 | Всероссийский научно-исследовательский институт по переработке нефти | Method for production of base of electric insulating oil |
| CN1225662A (en) * | 1996-07-15 | 1999-08-11 | 切夫里昂美国公司 | Lubricating base oil mfg. process |
| CN1676585A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Method for preparing lubricating oil base oil |
| CN101307257A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Coal tar hydrogenating modified method by two-stage method |
| CN101343564A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Method for producing lubricating oil basic oil |
| CN101688131A (en) * | 2007-07-13 | 2010-03-31 | Sk能源株式会社 | Process for manufacturing naphthenic base oils from effluences of fluidized catalytic cracking unit |
| CN101386792A (en) * | 2008-11-04 | 2009-03-18 | 中国海洋石油总公司 | Transformer oil base oil and preparation method and applications thereof |
| CN102311785A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for hydrogenating naphthenic base distillate to produce lubricating oil basic oil |
| CN102485846A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Preparation method of transformer oil base oil |
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