CN103789019A - 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 of adopt through in raw materials pretreatment, coalite tar adopts the method for hydrotreatment-hydro-upgrading/hydrofinishing two-stage hydrogenation to produce the method for transformer oil base oil.
Background technology
Transformer oil refers to for oil-filled electric equipments such as transformer, reactor, mutual inductor, sleeve pipe, oil switchs, plays a class transformer oil product of insulation, cooling and 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 of producing transformer oil.The performance of transformer oil depends on the performance of transformer oil base oil to a great extent.Conventionally, paraffinic base transformer oil base oil pour point is high, and the acidic cpd that oxidizable production is a large amount of, and aromaticity content is few comes with some shortcomings at aspects such as life-span of transformer oil, anti-oxidant, anti-gassings.And cycloalkyl transformer oil base oil can meet the insulation of transformer oil, the requirement such as cooling, 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 Suizhong 36-1 two wires distillate is carried out to furfural treatment, obtain treated oil, then add denitrfying agent to carry out denitrogenation, except denitrification slag, then add carclazyte, carry out clay-filteredly, 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 that adopts perhydro method to produce transformer oil base oil.Take cycloalkyl distillate as raw material, adopt the one-stage serial hydrogenation technique of hydrotreatment-hydrodewaxing-hydrofinishing 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 Karamay, Xinjiang, the large block of Liaohe Huanxiling and Bohai Sea Gulf three, is Karamay, Xinjiang crude oil and Liaohe Huanxiling crude oil for the production of the raw material of transformer oil base 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 is along with yield reducation and quality variation, can not serve as the stable resources of 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 other suitable transformer oil raw materials for production, realizes transformer oil and significantly domesticizes, and is of great immediate significance.
China is a country that coal resources are very abundant, and a large amount of coal tar of Coal Chemical Industry process by-product has certain natural crude oil characteristic, and how effectively utilizing coal tar is the important step of 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, transformer oil base oil that can production low-temperature performance is good, electric property is outstanding, oxidation stability is good.
Summary of the invention
For the deficiencies in the prior art, the invention provides one take middle coalite tar as raw material, adopt the method for hydrotreatment-hydro-upgrading-hydrofinishing Unionfining to produce 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 ℃;
(2) the described lighting end of step (1) enters hydrotreatment reaction zone after mixing with hydrogen, contacts and carries out hydrogenation reaction successively 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) 280～320 ℃ of diesel oil distillates of step (3) fractionation gained enter hydro-upgrading reaction zone, and hydro-upgrading reaction zone is used the catalyst for hydro-upgrading that contains amorphous aluminum silicide and modified Y zeolite, under hydrogen exists, carry out hydro-upgrading reaction;
(5) step (4) gained hydro-upgrading effluent enters hydrofinishing reaction zone, under hydrogen exists, contacts with hydrofinishing catalyzer, carries out hydrofinishing reaction, and hydrofinishing product is isolated to transformer oil base oil.
In the inventive method, the described middle coalite tar of step (1) first dewater and remove mechanical impurity after carry out again fractionation.
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 as coking raw material.
In the inventive method, hydrotreatment reaction zone is loaded 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 is used conventional hydrogenation protecting catalyst; can adopt the FZC series protective material of Fushun Petrochemical Research Institute (FRIPP) development and production; also can prepare according to prior art; these catalyzer generally take porous refractory inorganic oxides if aluminum oxide is as carrier; group vib and/or VIII family metal, if the oxide compound of W, Mo, Co, Ni etc. is active ingredient, optionally add other various auxiliary agents as the catalyzer of the elements such as P, Si, F, B.
In the inventive method, the Hydrobon catalyst that hydrotreatment reaction zone is used, can select this field general goods catalyzer, also can prepare by this area general knowledge.The commercial catalysts that can select as 3936,3996 of Fushun Petrochemical Research Institute (FRIPP) development and production, the Hydrobon catalyst such as FF-16, FF-26.
In the inventive method, in order to bring into play better the performance of catalyst for hydro-upgrading, at the better Hydrobon catalyst of a certain proportion of Hydrogenation of the top of catalyst for hydro-upgrading grading loading, carry out desulfurization, denitrogenation, saturated condensed-nuclei aromatics, bring into play better the open-loop performance of catalyst for hydro-upgrading, increase the running period of whole device.Hydro-upgrading reaction zone is used Hydrobon catalyst in the catalyst for hydro-upgrading top filling that contains amorphous aluminum silicide and modified Y zeolite, and the admission space of Hydrobon catalyst and the catalyst for hydro-upgrading that contains 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 be selected 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 is used the catalyst for hydro-upgrading that contains amorphous aluminum silicide and modified Y zeolite.In described catalyst for hydro-upgrading, 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 the character of amorphous aluminum silicide used 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; Preferred property is as follows: silicon oxide-containing 10wt%～35wt%, specific surface is 530～650m
2/ g, pore volume is 1.2～1.5mL/g.Wherein the character of modified Y zeolite 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 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.
In the inventive method, hydrofinishing reaction zone is used conventional hydrofinishing catalyzer, its active metal component is group vib and group VIII metal, use procatalyst should carry out prevulcanized, guarantee hydrogenation active metals in reaction process in sulphided state.Described group vib metal is selected from Mo and/or W, and its content counts 10～25% with oxide compound; Group VIII metal is selected from Co and/or Ni, and its content counts 3～7% with oxide compound.
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; 250～420 ℃ of temperature of reaction, preferably 300～400 ℃; Hydrogen to oil volume ratio 500:1～1500:1, preferably 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; 250～370 ℃ of temperature of reaction, preferably 300～350 ℃; Hydrogen to oil volume ratio 500:1～1500:1, preferably 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; 200～350 ℃ of temperature of reaction, preferably 290～320 ℃; Hydrogen to oil volume ratio 500:1～1500:1, preferably 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 when hydrotreatment, denitrogenation and aromatic hydrocarbons fractional saturation cause structure to cave in, and then coal tar is done greatly reach (maximum can move forward 100 ℃ of left and right), structure redistribution, 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, two rings and a small amount of thrcylic aromatic hydrocarbon are carried out to saturated open loop, keep the complete of side chain after open loop simultaneously, become monocycle or two Polycyclic aromatic hydrocarbons of belt length side chain, after hydro-upgrading and hydrofinishing, generate a large amount of naphthenic hydrocarbon with many side chains, can obtain all good transformer oil base oils of electric property, oxidation stability and anti-gassing performance.There is a small amount of straight-chain paraffin isomery of certain influence to become branched paraffin to condensation point simultaneously, guarantee the low-temperature performance of product.
(2) the inventive method provides a kind of processing works that improve its economy for the lower middle coalite tar of added value, and be transformer oil base oil production development a kind of new raw material.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, can effectively promote the reasonable utilization of tar resource simultaneously.
(3) other cut after the inventive method hydrotreatment can be 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, enter vacuum still 2 carry out fractionation through dehydration and the middle coalite tar 1 that removes mechanical impurity, obtain lighting end 3 and last running 4, gained last running 4 can be used as modifying asphalt, heavy fuel oil (HFO), or is used 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 separates, described separation system 8 generally comprises high-pressure separator and light pressure separator, separating obtained gas phase 9 is returned to hydrotreating reactor 6 as recycle hydrogen, isolated liquid phase 10 is after stripping tower 11 removes hydrogen sulfide and gas products 12, stripping tower bottom liquid phase 13 is removed separation column 14, obtain being respectively less than 160 ℃ of cuts 15, 160～280 ℃ of cuts 16, 280～320 ℃ of cuts 17 and be greater than 320 ℃ of cuts 18.Wherein, be less than 160 ℃ of cuts 15 and can do gasoline blend component, 160～280 ℃ of cuts 16 can be done diesel oil blending component, are greater than 320 ℃ of cuts 18 and can further cut as refrigerator oil base oil raw material, rubber filling oil raw material or environment-friendly type aromatic hydrocarbon oil raw material.280～320 ℃ of cuts 17 enter hydro-upgrading reaction zone 19, under hydrogen exists, contact with catalyst for hydro-upgrading, to two rings and on a small quantity thrcylic aromatic hydrocarbon carry out saturated open loop, keep the complete of side chain after open loop simultaneously, become monocycle or two Polycyclic aromatic hydrocarbons with many side chains.Hydro-upgrading reaction product 20 enters hydrofinishing reaction zone 21, under hydrogen and Hydrobon catalyst existence, carries out aromatic hydrocarbons degree of depth saturated reaction, reduces aromaticity content, guarantees the oxidation stability index of product.Then hydrofinishing product 22 is after separator 23 is isolated gas 24, and liquid product 25 enters separation column 26 and isolates after 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 that relate in embodiment can be selected commercial catalyst by character, also can prepare by this area knowledge.The commercial catalysts that the hydrogenation protecting agent of hydrotreatment process can be selected is as hydrogenation protecting agent such as the FZC-100 of Fushun Petrochemical Research Institute's development and production, FZC-102A, FZC-103; The commercial catalysts that Hydrobon catalyst can be selected as 3936 of Fushun Petrochemical Research Institute's development and production, 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 the commodity such as FC-14, the FC-26 hydrotreating catalyst of Fushun Petrochemical Research Institute's development and production; The commercial catalysts that hydrofinishing process can be selected is as the commodity such as FV-10, the FV-20 Hydrobon catalyst of Fushun Petrochemical Research Institute's development and production.
Embodiment 1
Take Datang coalite tar as raw material, cut point is 500 ℃, 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 Hydrobon catalyst FV-10 is loaded in hydrofinishing reaction zone, and the processing condition of hydrogenation process and product property are in table 2.
Embodiment 2
Take her eastern coal-tar middle oil as raw material, cut point is 500 ℃, 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 Hydrobon catalyst FV-10 is loaded in hydrofinishing reaction zone, and 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
Take 280～320 ℃ of diesel oil distillates of Datang coalite tar as raw material, specific nature is in table 1.280～320 ℃ of diesel oil distillates of raw material Datang coalite tar only carry out hydrofining reaction 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 | 280～320 ℃ of cuts of Datang coalite tar |
| Density (20 ℃), g.cm -3 | 1.0284 | 1.010 | 0.9032 |
| Boiling range (simulation distil), ℃ | |||
| 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 ℃), mm.s -2 | 3.004 | ||
| Carbon residue, % | 0.45 | 1.14 | 0.10 |
| Condensation point, ℃ | 8 | 5 | -21(freezing point) |
| Flash-point (opening), ℃ | 112 | 142 | 93(remains silent) |
| Acid number, mgKOH.g -1 | 0.81 | 0.45 | |
| Mechanical impurity, wt% | 0.023 | 0 | |
| Mass spectrum composition, 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, ℃ | 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 ℃ of cut yields, wt% | 20.62 | 20.62 | 19.25 | 25.47 |
| Hydro-upgrading reaction process condition | ||||
| Temperature of reaction, ℃ | 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, ℃ | 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 ℃), mm.s -2 | 7.33 | 7.57 | 7.25 | 8.32 |
| Kinematic viscosity (30 ℃), mm.s -2 | 545.2 | 609.3 | 553.7 | 690.4 |
| Rotary oxygen bomb (150min), min | 245 | 230 | 245 | 220 |
| Structural group composition, 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), ℃ | 145 | 142 | 143 | 144 |
| Condensation point, ℃ | <50 | -42 | <50 | -38 |
| Acid number, mgKOH.g -1 | 0.001 | 0.002 | 0.001 | 0.003 |
| Density (20 ℃), 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 ℃) | 0.00092 | 0.00105 | 0.00105 | 0.00156 |
Product property by embodiment 1 and comparative example 1 can be found out, the transformer oil base oil product that only has hydrofining not have the middle coalite tar of hydro-upgrading process processing to obtain, anti-gassing performance 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 ℃), defective.And that comparison directly cuts the product of 280～320 ℃ of cut fraction hydrogenation processing in example 2 is the poorest, except aromaticity content high, anti-gassing performance well beyond, electric property, low temperature flowability are all defective.
Product property by embodiment 1,2 can be found out, in employing, coalite tar is by hydrotreatment-hydro-upgrading/hydrogenation post-refining process, can give birth to low-temperature fluidity, (dielectric loss index is low for electric property, voltage breakdown is high) and all good transformer oil base oils 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.Can greatly expand the raw material sources of transformer oil base oil, meet the needs of State Grid's industry great development, also enrich the deep exploitation of tar resource simultaneously, there is very large economic benefit and social benefit.
Claims (14)
1. in, coalite tar hydrogenation is produced 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 ℃;
(2) the described lighting end of step (1) enters hydrotreatment reaction zone after mixing with hydrogen, contacts and carries out hydrogenation reaction successively 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) 280～320 ℃ of diesel oil distillates of step (3) fractionation gained enter hydro-upgrading reaction zone, and hydro-upgrading reaction zone is used the catalyst for hydro-upgrading that contains amorphous aluminum silicide and modified Y zeolite, under hydrogen exists, carry out hydro-upgrading reaction;
(5) step (4) gained hydro-upgrading effluent enters hydrofinishing reaction zone, under hydrogen exists, contacts with hydrofinishing catalyzer, carries out hydrofinishing reaction, and hydrofinishing product is isolated to transformer oil base oil.
2. it is characterized in that in accordance with the method for claim 1: the described middle coalite tar of step (1) first dewater and remove mechanical impurity after carry out again fractionation.
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 is loaded 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 that contains amorphous aluminum silicide and modified Y zeolite, and the admission space of described Hydrobon catalyst and the catalyst for hydro-upgrading that contains amorphous aluminum silicide and modified Y zeolite is than being 25:75～60:40.
6. it is characterized in that in accordance with the method for claim 1: in step (3), the operational condition of hydrotreating reactor is: reaction pressure 5.0～20.0MPa, 250～420 ℃ of temperature of reaction, hydrogen to oil volume ratio 500:1～1500:1, volume space velocity 0.1～1.0h
-1.
7. the right method described in 1 as requested, is characterized in that: in step (4), the operational condition of hydro-upgrading reactor is:: reaction pressure 5.0～20.0MPa, 250～370 ℃ of temperature of reaction, hydrogen to oil volume ratio 500:1～1500:1, volume space velocity 0.1～1.5h
-1.
8. the right method described in 1 as requested, is characterized in that: in step (5), the operational condition of hydrofinishing reactor is: reaction pressure 5.0～20.0MPa, 200～350 ℃ of temperature of reaction, hydrogen to oil volume ratio 500:1～1500:1, volume space velocity 0.1～1.5h
-1.
9. 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%.
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 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.
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%, specific surface is 530～650m
2/ g, pore volume is 1.2～1.5mL/g.
12. 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.
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 is used, its active metal component is group vib and group VIII metal, and described group vib metal is selected from Mo and/or W, and its content counts 10～25% with oxide compound; Group VIII metal is selected from Co and/or Ni, and its content counts 3～7% with oxide compound.
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| CN111378502A (en) * | 2018-12-31 | 2020-07-07 | 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 |
| 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 |
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