CN1803997A - Method for preparing base oil of heat transfer oil - Google Patents
Method for preparing base oil of heat transfer oil Download PDFInfo
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- CN1803997A CN1803997A CN 200510107261 CN200510107261A CN1803997A CN 1803997 A CN1803997 A CN 1803997A CN 200510107261 CN200510107261 CN 200510107261 CN 200510107261 A CN200510107261 A CN 200510107261A CN 1803997 A CN1803997 A CN 1803997A
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Abstract
The disclosed production method for heat-transfer base oil comprises: contacting the raw oil and H2 with hydrogenation prerefining catalyst firstly to strip impurity of sulfur and nitrogen and then contact with hydrogenation modifying catalyst; fractionating the hydrogenated oil to obtain the 45~285Degdistillate oil, 285~305Deg distillate oil, 305~325Deg distillate oil, and 325~360Deg distillate oil as the heat-transfer base oil of L-QB and L-QC series. The product has large density, low viscosity and solidifying point, little toxicity, and no pollution to environment.
Description
Technical field
The invention belongs to petrochemical industry, the production method that relates to a kind of base oil of heat transfer oil relates in particular to a kind of extraction oil of coal tar fraction and/or catalytic cracking heavy oil (comprising recycle stock and slurry oil) and method that preparing ethylene by steam cracking tar passes through hydro-upgrading heat production in next life conductive liquid base oil utilized.
Background technology
Heat transfer oil (or thermal oil) is a kind of heat-transfer medium, and this medium absorbs heat at high temperature heat source, makes its temperature improve back and cryogen heat exchange, thereby plays the effect of transmitting heat.
Heat transfer oil is widely used in fields such as refining of petroleum, chemical industry, foodstuffs industry, textile industry, medicine industry, coatings industry, timber industry, fast development along with domestic economy, demand to heat transfer oil grows with each passing day, and its quality has been proposed requirements at the higher level:
(1) thermostability and chemical stability are good, can in the temperature index allowed band, use for a long time, and renewable;
(2) density is big, viscosity is low, and pump-conveying property is good;
(3) steam force down, flash-point height, boiling range height, use loss little, safe;
(4) zero pour is low, good fluidity;
Energy power saving, fuel saving when (5) using are to the equipment non-corrosiveness;
(6) perviousness is low;
(7) hot coefficient height, good heat conductivity;
(8) nontoxic, tasteless, non-environmental-pollution.
At present, heat transfer oil has synthetic oil and mineral oil two classes.Synthetic oil (as hydrogenated terphenyl) has following advantage: Heat stability is good, and use temperature is higher, in the temperature index allowed band, can use for a long time, and renewable; Toxicity is little, tasteless, non-environmental-pollution, and perviousness is little under the high temperature; Normal temperature viscosity is lower, and viscosity temperature characteristic is good, good heat conductivity; Equipment there is not corrosion.But the production cost height of synthetic oil, price per ton are restricted its application more than 10,000 yuan.
The mineral oil origin heat transfer oil is made up of base oil and additive, and because of its production cost is lower, price per ton is about 5500 yuan, and its application quantity is bigger when use temperature is relatively low.But present mineral oil origin base oil of heat transfer oil exists density little, makes its specific heat low; The pour point height makes its flowability relatively poor; The sulphur content height is corrosive to equipment when at high temperature using; Peculiar smell is arranged, and in the temperature index allowed band during long-time the use, thermostability is relatively poor relatively, the deterioration rate height, regeneration is comparatively frequent wait not enough.Therefore, the production method of seeking new mineral oil origin base oil of heat transfer oil is of great practical significance.
China is a country that coal resource is very abundant, the coal tar of Coal Chemical Industry process by-product has the characteristic of natural crude oil, how effectively utilizing coal tar is the important step of the comprehensive utilization of coal, usual method is to produce Chemicals such as benzene, phenol, naphthalene, pyridine with the chemical industry method, but this method is separated or the purification difficulty is bigger, is difficult for the formation scale; Have after overpickling, alkali cleaning yet and make oil fuel, but acid sludge, alkaline residue that this method produces are difficult to processing, seriously polluted, oil fuel does not meet environmental protection standard yet.Therefore, it is most important sufficiently and reasonably to utilize abundant coal tar fraction to produce high-value product.
Higher by the value-added contents of product such as light oil, dephenolize oil, washing oil, crude phenols and NAPTHALENE FLAKES. (INDUSTRIAL GRADE that coal tar is produced, and carbolineum has unpleasant stink especially because of its condensation point height, sulphur content and nitrogen content height, makes its added value lower, its range of application is restricted.
In the process of refining of petroleum, problem such as the tar of the heavy oil of being produced by catalytic cracking unit (recycle stock and slurry oil) by-product in extraction oil that solvent treatment obtains and preparing ethylene by steam cracking process exists added value lower too, and range of application is narrower.
It is exactly all to be rich in heavy aromatics that the extraction oil of above-mentioned coal tar fraction, catalysis heavy oil and preparing ethylene by steam cracking tar etc. have a common characteristic, and utilize the hydro-upgrading technology that heavy aromatics is made with extra care and upgrading, can make the base oil of heat transfer oil of its production high added value, up to now, the report of the relevant this respect of Shang Weijian.
Summary of the invention
The present invention be directed to the second-rate problem of present base oil of heat transfer oil, and provide a kind of extraction oil that utilizes dead oil, catalytic cracking heavy oil and/or preparing ethylene by steam cracking tar method through hydro-upgrading heat production in next life conductive liquid base oil, the base oil of heat transfer oil density of using this method to produce is big, viscosity is low, zero pour is low, good fluidity, and toxicity is lower, free from extraneous odour, environmentally safe, and very little to the corrodibility of equipment.
The production method of base oil of heat transfer oil of the present invention is:
(1) stock oil contacts with hydrogenation pre-refining catalyzer earlier in hydro-upgrading unit with hydrogen, remove sulphur, impurity such as nitrogen, the reaction product of hydrogenation pre-refining contacts with catalyst for hydro-upgrading again reacts, and remove sulphur, impurity such as nitrogen, obtain hydrogenated oil, described stock oil is dead oil, one or more mixing oil in the extraction oil of catalytic cracking heavy oil and the preparing ethylene by steam cracking tar, the weight ratio of described hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading is 1～6: 4～9, the operational condition of hydrogenation pre-refining and hydro-upgrading is, the hydrogen dividing potential drop is 8.0Mpa～20.0Mpa, preferred 10.0Mpa～15.0Mpa; Volume space velocity is 0.1h during liquid
-1～1.5h
-1, preferred 0.3h
-1～1.0h
-1Temperature of reaction is 300 ℃～450 ℃, preferred 350 ℃～400 ℃; Hydrogen and stock oil volume ratio are 500～3000, preferred 1000～2000.Described hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading comprise carrier and active ingredient, carrier is the resistant to elevated temperatures inorganic oxide of porous (as silicon-dioxide, aluminum oxide and a silicon-aluminum mixture etc.), active ingredient is the oxide compound (as the oxide compound of W, Mo, Ni or Co) of group vib and/or VIII family metal, also contains some other auxiliary element (as F, B and P etc.) in the catalyzer.
(2) the above-mentioned hydrogenated oil that obtains is carried out fractionation, obtain different narrow fractions, 245 ℃～285 ℃ distillates that wherein obtain, 285 ℃～305 ℃ distillates, 305 ℃～325 ℃ distillates and 325 ℃～360 ℃ distillates are L-QB and L-QC heat transfer oil series base oil.
Above-mentioned fractionation process can carry out in a plurality of separation columns or one have the separation column of a plurality of side lines, the resulting narrow fraction less than 245 ℃ of the present invention also can be used as aromatic solvent naphtha and uses, and the residue last running that the generation oil of high boiling range is promptly produced base oil of heat transfer oil can be used as the Rubber Softener use.
Hydrogenation technique of the present invention can adopt single hop series connection, one way to pass through or partial hydrogenation heavy oil round-robin operating method, so the hydrogenation technique condition can require to select appropriate volume air speed and hydrogen dividing potential drop according to the transformation efficiency of the oil properties that processes raw material, requirement and to giving birth to olefiant refining depth.The hydro-upgrading technology adopts hydrogenation pre-refining well known to those skilled in the art of the present technique or hydro-upgrading technology, comprises fixed bed hydrogenation treatment technology, floating bed hydrogenation treatment technology, boiling bed hydrogenation treatment technology and expanded bed hydrotreatment technology etc.Using comparatively sophisticated on full scale plant at present is the fixed bed hydrogenation treatment technology.When adopting the fixed bed hydrogenation treatment technology, can adopt one-stage process or two-stage method hydrotreatment technology.
Coal tar fraction of the present invention is before the tar-bitumen or less than 500 ℃ full cut or part cut.Wherein full cut comprises the mixing oil of light oil, dephenolize oil, carbolic oil (crude phenols), naphtalene oil (NAPTHALENE FLAKES. (INDUSTRIAL GRADE), washing oil, a carbolineum and anthracene oil that coal tar obtains through distillation; The part cut comprises the mixing oil of light oil, dephenolize oil, washing oil, a carbolineum and anthracene oil that coal tar obtains through distillation; Preferred boiling range is 240 ℃～460 ℃ coal tar fraction, the i.e. mixing oil of washing oil, a carbolineum and anthracene oil.The extraction oil of described catalytic cracking heavy oil and system ethylene bottom oil are the distillate before 500 ℃, and wherein the boiling range of the extraction oil of catalytic cracking heavy oil is preferred 300 ℃～460 ℃; Preferred 240 ℃～460 ℃ of the boiling range of system ethylene bottom oil.
Raw material sources of the present invention are wide, especially by the carbolineum of coal tar processing because of its peculiar smell is big, the oil that acts as a fuel is difficult to sell, price is lower, after the technology of the present invention processing, can significantly improve value-added content of product.Hydro-upgrading generation oil can be according to the demand flexible production decision in market among the present invention, Industrial products such as by-product aromatic solvent naphtha and Rubber Softener when producing base oil of heat transfer oil.Adopting the base oil of the heat transfer oil of the present invention's production is the aromatic hydrocarbons mixture of hydrogen-rich component, this mixture can produce active hydrogen under the condition of use temperature, this active hydrogen can effectively be blocked free radical reaction under this condition, make the thermostability and the chemical stability of base oil of heat transfer oil good, can in the temperature index allowed band, use for a long time, and it is renewable, its sulphur content＜300 μ g/g, nitrogen content＜500 μ g/g, the ring-type hydro carbons is not less than 90m%, good security, and toxicity is lower, free from extraneous odour, and environment is had no adverse effects.The density of the base oil of heat transfer oil of producing is big, hot coefficient height, good heat conductivity; Viscosity is low, and pump-conveying property is good; Zero pour is low, good fluidity; And toxicity is lower, free from extraneous odour, environmentally safe; Corrodibility to equipment is very little.
Embodiment
The present invention will be described in detail with specific embodiment below, but do not limit the scope of the invention.
Embodiment 1
On medium-sized fixed bed hydrogenation testing apparatus, with Mo-Ni/Al
2O
3The type catalyzer is hydrogenation pre-refining (R1) catalyzer (MoO wherein
3Account for 15.62% of total catalyst weight, NiO account for total catalyst weight 2.91%), with W-Mo-Ni/Al
2O
3The type catalyzer is hydro-upgrading (R2) catalyzer (WO wherein
3Account for 21.27% of total catalyst weight, MoO
3Account for 5.91% of total catalyst weight, NiO account for total catalyst weight 2.84%), the filling ratio of hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading is 2: 3 (weight), two reactors in series, and adopt operating method that one way passes through that the mixing oil (stock oil 1) of washing oil, a carbolineum and the anthracene oil of coal tar fraction has been carried out hydro-upgrading.Catalyzer adopts conventional pre-vulcanization process to carry out prevulcanized before use, treat that catalyst activity is stable after, carry out processing condition again and investigate test.
Stock oil 1 and hydrogen enter hydrogenator, elder generation and Mo-Ni/Al after mixing
2O
3The contact of hydrogenation pre-refining catalyzer removes impurity such as sulphur, nitrogen, the direct and W-Mo-Ni/Al of reaction intermediate
2O
3The catalyst for hydro-upgrading contact is carried out the saturated reaction of part aromatic ring, and is removed impurity such as sulphur, nitrogen.Reaction product is isolated gaseous fraction through separator, stabilizer, obtains the liquid ingredient behind the upgrading; The hydrogen-rich gas that removes behind the impurity such as hydrogen sulfide, ammonia recycles.
On the true boiling point distillation device, the product liquid behind the above-mentioned hydro-upgrading is carried out fractionation, cut out different narrow fractions.Wherein 245 ℃～285 ℃ distillates, 285 ℃～305 ℃ distillates, 305 ℃～325 ℃ distillates and 325 ℃～360 ℃ distillates are respectively as the base oil of L-QB and L-QC heat transfer oil series.
The stock oil 1 of hydro-upgrading is that the main character of mixing oil of washing oil, a carbolineum and the anthracene oil of coal tar fraction sees Table 1, has also listed the processing condition of hydro-upgrading in the table 1 and has given birth to olefiant main character.Generate oil by hydro-upgrading and see Table 2 through the narrow fraction character that the fractionation cutting obtains.For ease of relatively, in table 3, listed the technological standard of heat transfer oil series.
Synopsis 2 and table 3 are found out, can satisfy technical requirements by dead oil through the main character of the base oil of the heat transfer oil of hydro-upgrading production, because of it is rich in hydrogen donor, and its Heat stability is good.
Table 1 stock oil 1 once passes through the character of flow process and hydrogenated oil thereof
| Project | Stock oil 1 | Hydrogenated oil 1 |
| Processing condition | ||
| The hydrogen dividing potential drop, MPa | 15.0 | |
| Temperature of reaction (R 1/R 2)，℃ | 375/375 | |
| Volume space velocity (R 1/R 2)，h -1 | 2.50/1.67 | |
| Hydrogen to oil volume ratio | 1200 | |
| Main character | ||
| Density, 20 ℃, kg/m 3 | 1140.1 | 986.3 |
| Carbon residue, m% | 1.05 | 0.05 |
| Viscosity (80 ℃), mm 2/s | 4.126 | 2.281 |
| Sulphur content, μ g/g | 7082 | 92 |
| Nitrogen content, μ g/g | 8955 | 256 |
| Smell | Pungent odour | Free from extraneous odour |
Table 2 stock oil 1 once passes through the property analysis of the hydrogenated oil part narrow fraction of flow process
| Initial boiling point, ℃ greater than | 240 | 280 | 300 | 320 |
| The boiling range scope, ℃ | 245～285 | 285～305 | 305～325 | 325～360 |
| Density, 20 ℃, kg/m 3 | 1013.1 | 1019.6 | 1032.5 | 1051.0 |
| Open flash point, ℃ | 165 | 192 | 204 | 213 |
| Close flash point, ℃ | 146 | 169 | 183 | 196 |
| Pour point ℃ is not higher than | -25 | -20 | -15 | -5 |
| Viscosity, 40 ℃, mm 2/s | 21.22 | 25.97 | 117.6 | 302.0 |
| Acid number, mgKOH/g | 0.017 | 0.018 | 0.020 | 0.021 |
| Copper corrosion; (100 ℃, 3h) | 1a | 1a | 1a | 1a |
| Carbon residue; M% less than | 0.01 | 0.01 | 0.01 | 0.01 |
| Ash content; M% less than | 0.01 | 0.01 | 0.01 | 0.01 |
| Sulphur content, μ g/g | 115 | 146 | 191 | 259 |
| Nitrogen content, μ g/g | 238 | 385 | 509 | 740 |
| Aromaticity content, m% | 93.1 | 92.5 | 93.8 | ≮85.0 |
| Deterioration rate, m% | 3.2 | 3.7 | 4.1 | 6.2 |
| Moisture, v% | Trace | Trace | Trace | Trace |
| Smell | Free from extraneous odour | Free from extraneous odour | Free from extraneous odour | Free from extraneous odour |
| Outward appearance | Pale yellow transparent | Pale yellow transparent | Pale yellow transparent | Pale yellow transparent |
The technical requirements of table 3 heat transfer oil
| Project name | Quality index | |||
| L-QB | L-QC | |||
| 240 | 280 | 300 | 320 | |
| Initial boiling point ℃ is not less than | 240 | 280 | 300 | 320 |
| Moisture, mg/kg | 200 | 500 | 500 | 500 |
| Open flash point, ℃ | 160 | 180 | 190 | 200 |
| Close flash point, ℃ | 100 | |||
| Pour point ℃ is not higher than | -9 | |||
| Acid number, mgKOH/g is not more than | 0.02 | |||
| Sulphur content, m% is not more than | 0.2 | |||
| Copper corrosion; (100 ℃ 3h) are not more than | 1 | |||
| Density, 20 ℃, kg/m 3 | Report | |||
| Viscosity, 40 ℃, mm 2/s | Report | |||
| Carbon residue; M% | Report | |||
| Ash content; M% | Report | |||
| Thermostability (heating under the maximum operation (service) temperature) | 720h | 720 | 720 | 1000h |
| Outward appearance | Transparent, no suspended substance and precipitation | |||
| Deterioration rate is not more than | 10 | |||
Embodiment 2
On medium-sized fixed bed hydrogenation testing apparatus, with Mo-Ni/Al
2O
3The type catalyzer is hydrogenation pre-refining (R1) catalyzer (MoO wherein
3Account for 15.62% of total catalyst weight, NiO account for total catalyst weight 2.91%), with W-Mo-Ni/Al
2O
3The type catalyzer is hydro-upgrading (R2) catalyzer (WO wherein
3Account for 21.27% of total catalyst weight, MoO
3Account for 5.91% of total catalyst weight, NiO account for total catalyst weight 2.84%), the filling ratio of hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading is 3: 7 (weight), two reactors in series, and the operating method that the employing one way is passed through is based on coal tar fraction (mixing oil of washing oil, a carbolineum and anthracene oil), mix the extraction oil (boiling range is 300 ℃～460 ℃ cuts) and the system ethylene bottom oil (boiling range is 240 ℃～460 ℃) of part catalytic cracking heavy oil, its ratio is 8: 1: 1.Above-mentioned mixing oil (stock oil 2) has been carried out hydro-upgrading.Catalyzer had adopted conventional pre-vulcanization process that catalyzer is carried out prevulcanized before using, treat that catalyst activity is stable after, carry out the investigation test of processing condition again.
Stock oil 2 and hydrogen enter hydrogenator, elder generation and Mo-Ni/Al after mixing
2O
3The contact of hydrogenation pre-refining catalyzer removes impurity such as sulphur, nitrogen, the direct and W-Mo-Ni/Al of reaction intermediate
2O
3The catalyst for hydro-upgrading contact is carried out the saturated reaction of part aromatic ring, and is removed impurity such as sulphur, nitrogen.Reaction product is isolated gaseous fraction through separator, stabilizer, obtains the liquid ingredient behind the upgrading; The hydrogen-rich gas that removes behind the impurity such as hydrogen sulfide, ammonia recycles.
On the true boiling point distillation device, the product liquid behind the above-mentioned hydro-upgrading is carried out fractionation, cut out different narrow fractions.Wherein 245 ℃～285 ℃ distillates, 285 ℃～305 ℃ distillates, 305 ℃～325 ℃ distillates and 325 ℃～360 ℃ distillates are respectively as the base oil of L-QB and L-QC heat transfer oil series.
The main character of the stock oil 2 of hydro-upgrading sees Table 4, has listed file names with the processing condition of hydro-upgrading and give birth to olefiant main character in table 4.Generate oil by hydro-upgrading and see Table 5 through the narrow fraction character that the fractionation cutting obtains.
Synopsis 5 and table 3 are found out, can satisfy technical requirements by stock oil 2 through the main character of the base oil of the heat transfer oil of hydro-upgrading production, because of it is rich in hydrogen donor, and its Heat stability is good.
Table 4 stock oil 2 once passes through the character of flow process and hydrogenated oil thereof
| Project | Stock oil 2 | Hydrogenated oil 2 |
| Processing condition | ||
| The hydrogen dividing potential drop, MPa | 15.0 | |
| Temperature of reaction (R 1/R 2)，℃ | 375/375 | |
| Volume space velocity (R 1/R 2)，h -1 | 3.33/1.43 | |
| Hydrogen to oil volume ratio | 1200 | |
| Main character | ||
| Density, 20 ℃, kg/m 3 | 1121.5 | 979.8 |
| Carbon residue, m% | 1.97 | 0.09 |
| Viscosity (80 ℃), mm 2/s | 6.921 | 2.729 |
| Sulphur content, μ g/g | 6246 | 83 |
| Nitrogen content, μ g/g | 7718 | 237 |
| Smell | Pungent odour | Free from extraneous odour |
Table 5 stock oil 2 once passes through the property analysis of the hydrogenated oil part narrow fraction of flow process
| Initial boiling point, ℃ greater than | 240 | 280 | 300 | 320 |
| The boiling range scope, ℃ | 245～285 | 285～305 | 305～325 | 325～360 |
| Density, 20 ℃, kg/m 3 | 1010.3 | 1015.2 | 1026.8 | 1043.6 |
| Open flash point, ℃ | 163 | 191 | 205 | 210 |
| Close flash point, ℃ | 145 | 167 | 186 | 195 |
| Pour point ℃ is not higher than | -25 | -15 | -10 | -5 |
| Viscosity, 40 ℃, mm 2/s | 22.51 | 27.23 | 113.2 | 306.7 |
| Acid number, mgKOH/g less than | 0.02 | 0.02 | 0.02 | 0.02 |
| Copper corrosion; (100 ℃, 3h) | 1a | 1a | 1a | 1a |
| Carbon residue; M% less than | 0.01 | 0.01 | 0.01 | 0.02 |
| Ash content; M% less than | 0.01 | 0.01 | 0.01 | 0.01 |
| Sulphur content, μ g/g | 106 | 147 | 187 | 265 |
| Nitrogen content, μ g/g | 213 | 356 | 472 | 651 |
| Aromaticity content, m% | 92.2 | 93.7 | 93.1 | ≮85.0 |
| Deterioration rate, m% | 3.5 | 3.9 | 4.2 | 6.7 |
| Moisture, v% | Trace | Trace | Trace | Trace |
| Smell | Free from extraneous odour | Free from extraneous odour | Free from extraneous odour | Free from extraneous odour |
| Outward appearance | Pale yellow transparent | Pale yellow transparent | Pale yellow transparent | Pale yellow transparent |
Embodiment 3
On medium-sized fixed bed hydrogenation testing apparatus, with W-Ni/Al
2O
3The type catalyzer is hydrogenation pre-refining (R1) catalyzer (WO wherein
3Account for 24.79% of total catalyst weight, NiO account for total catalyst weight 3.05%), with W-Mo-Ni/Al
2O
3The type catalyzer is hydro-upgrading (R2) catalyzer (WO wherein
3Account for 21.27% of total catalyst weight, MoO
3Account for 5.91% of total catalyst weight, NiO account for total catalyst weight 2.84%), the filling ratio of hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading is 1: 4 (weight), two reactors in series operations are adopted and greater than 420 ℃ last running round-robin operating method stock oil 1 have been carried out hydro-upgrading.Catalyzer adopts conventional pre-vulcanization process to carry out prevulcanized before use, treat that catalyst activity is stable after, carry out processing condition again and investigate test.
Stock oil 1 and hydrogen enter hydrogenator, elder generation and W-Ni/Al after mixing
2O
3The contact of hydrogenation pre-refining catalyzer removes impurity such as sulphur, nitrogen, the direct and W-Mo-Ni/Al of reaction product
2O
3The catalyst for hydro-upgrading contact is carried out the saturated reaction of part aromatic ring, and is removed impurity such as sulphur, nitrogen.Reaction product is isolated gaseous fraction through separator, stabilizer, obtains the liquid ingredient behind the upgrading; The hydrogen-rich gas that removes behind the impurity such as hydrogen sulfide, ammonia recycles.
On the true boiling point distillation device, the product liquid behind the above-mentioned hydro-upgrading is carried out fractionation, cut out different narrow fractions.Wherein 245 ℃～285 ℃ distillates, 285 ℃～305 ℃ distillates, 305 ℃～325 ℃ distillates and 325 ℃～360 ℃ distillates are respectively as the base oil of L-QB and L-QC heat transfer oil series.
The main character of the stock oil 1 of hydro-upgrading sees Table 6, has listed file names with the processing condition of hydro-upgrading and give birth to olefiant main character in table 6.Generate oil by hydro-upgrading and see Table 7 through the narrow fraction character that the fractionation cutting obtains.
Synopsis 7 and table 3 are found out, can satisfy technical requirements by the circulation of stock oil 1 hydrogenation heavy oil through the main character of the base oil of the heat transfer oil of hydro-upgrading production, because of it is rich in hydrogen donor, and its Heat stability is good.
The character of table 6 stock oil 1 hydrogenation heavy oil circulation process and hydrogenated oil thereof
| Project | Stock oil 1 | Hydrogenated oil 1 |
| Processing condition | ||
| The hydrogen dividing potential drop, MPa | 15.0 | |
| Temperature of reaction (R 1/R 2)，℃ | 375/375 | |
| Volume space velocity (R 1/R 2)，h -1 | 5.00/1.25 | |
| Hydrogen to oil volume ratio | 1200 | |
| Main character | ||
| Density, 20 ℃, kg/m 3 | 1140.1 | 974.2 |
| Carbon residue, m% | 1.05 | 0.03 |
| Viscosity (80 ℃), mm 2/s | 4.126 | 2.016 |
| Sulphur content, μ g/g | 7082 | 71 |
| Nitrogen content, μ g/g | 8955 | 203 |
| Smell | Pungent odour | Free from extraneous odour |
The property analysis of the hydrogenated oil part narrow fraction of table 7 stock oil 1 hydrogenation heavy oil circulation process
| Initial boiling point, ℃ greater than | 240 | 280 | 300 | 320 |
| The boiling range scope, ℃ | 245～285 | 285～305 | 305～325 | 325～360 |
| Density, 20 ℃, kg/m 3 | 1014.2 | 1020.3 | 1034.1 | 1053.8 |
| Open flash point, ℃ | 166 | 195 | 205 | 215 |
| Close flash point, ℃ | 148 | 171 | 183 | 197 |
| Pour point ℃ is not higher than | -25 | -20 | -15 | -5 |
| Viscosity, 40 ℃, mm 2/s | 21.34 | 26.02 | 118.5 | 304.1 |
| Acid number, mgKOH/g | 0.016 | 0.018 | 0.021 | 0.022 |
| Copper corrosion; (100 ℃, 3h) | 1a | 1a | 1a | 1a |
| Carbon residue; M% less than | 0.01 | 0.01 | 0.01 | 0.01 |
| Ash content; M% less than | 0.01 | 0.01 | 0.01 | 0.01 |
| Sulphur content, μ g/g | 112 | 143 | 193 | 262 |
| Nitrogen content, μ g/g | 235 | 380 | 515 | 752 |
| Aromaticity content, m% | 93.5 | 92.8 | 94.1 | ≮85.0 |
| Deterioration rate, m% | 3.3 | 3.9 | 4.0 | 6.5 |
| Moisture, v% | Trace | Trace | Trace | Trace |
| Smell | Free from extraneous odour | Free from extraneous odour | Free from extraneous odour | Free from extraneous odour |
| Outward appearance | Pale yellow transparent | Pale yellow transparent | Pale yellow transparent | Pale yellow transparent |
Embodiment 4
On medium-sized fixed bed hydrogenation testing apparatus, with W-Ni/Al
2O
3The type catalyzer is hydrogenation pre-refining (R1) catalyzer (WO wherein
3Account for 24.79% of total catalyst weight, NiO account for total catalyst weight 3.05%), with W-Mo-Ni/Al
2O
3The type catalyzer is hydro-upgrading (R2) catalyzer (WO wherein
3Account for 21.27% of total catalyst weight, MoO
3Account for 5.91% of total catalyst weight, NiO account for total catalyst weight 2.84%), the filling ratio of hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading is 1: 4 (weight), two reactors in series operations adopt the hydrogenated oil round-robin operating method of 20m% that stock oil 1 has been carried out hydro-upgrading.Catalyzer adopts conventional pre-vulcanization process to carry out prevulcanized before use, treat that catalyst activity is stable after, carry out processing condition again and investigate test.
Stock oil 1 and hydrogen enter hydrogenator, elder generation and W-Ni/Al after mixing
2O
3The contact of hydrogenation pre-refining catalyzer removes impurity such as sulphur, nitrogen, the direct and W-Mo-Ni/Al of reaction product
2O
3The catalyst for hydro-upgrading contact is carried out the saturated reaction of part aromatic ring, and is removed impurity such as sulphur, nitrogen.Reaction product is isolated gaseous fraction through separator, stabilizer, obtains the liquid ingredient behind the upgrading; The hydrogen-rich gas that removes behind the impurity such as hydrogen sulfide, ammonia recycles.
On the true boiling point distillation device, the product liquid behind the above-mentioned hydro-upgrading is carried out fractionation, cut out different narrow fractions.Wherein 245 ℃～285 ℃ distillates, 285 ℃～305 ℃ distillates, 305 ℃～325 ℃ distillates and 325 ℃～360 ℃ distillates are respectively as the base oil of L-QB and L-QC heat transfer oil series.
The main character of the stock oil 1 of hydro-upgrading sees Table 8, has listed file names with the processing condition of hydro-upgrading and give birth to olefiant main character in table 8.Generate oil by hydro-upgrading and see Table 9 through the narrow fraction character that the fractionation cutting obtains.
Synopsis 9 and table 3 are found out, can satisfy technical requirements by the circulation of stock oil 1 hydrogenation heavy oil through the main character of the base oil of the heat transfer oil of hydro-upgrading production, because of it is rich in hydrogen donor, and its Heat stability is good.
The hydrogenated oil character of table 8 stock oil 1 under the hydrogenated oil circulation of 20m%
| Project | Stock oil 1 | Hydrogenated oil 1 |
| Processing condition | 986.3 | |
| The hydrogen dividing potential drop, MPa | 0.05 | 13.5 |
| Temperature of reaction (R 1/R 2)，℃ | 2.281 | 370/370 |
| Volume space velocity (R 1/R 2)，h -1 | 92 | 5.00/1.25 |
| Hydrogen to oil volume ratio | 256 | 1200 |
| Main character | ||
| Density, 20 ℃, kg/m 3 | 1140.1 | 967.2 |
| Carbon residue, m% | 1.05 | 0.02 |
| Viscosity (80 ℃), mm 2/s | 4.126 | 1.905 |
| Sulphur content, μ g/g | 7082 | 63 |
| Nitrogen content, μ g/g | 8955 | 176 |
| Smell | Pungent odour | Free from extraneous odour |
The character of the hydrogenated oil part narrow fraction of table 9 stock oil 1 under the 20m% generation is oil circulation
| Initial boiling point, ℃ greater than | 240 | 280 | 300 | 320 |
| The boiling range scope, ℃ | 245～285 | 285～305 | 305～325 | 325～360 |
| Density, 20 ℃, kg/m 3 | 1010.5 | 1016.3 | 1028.1 | 1047.9 |
| Open flash point, ℃ | 163 | 190 | 201 | 210 |
| Close flash point, ℃ | 143 | 167 | 182 | 193 |
| Pour point ℃ is not higher than | -25 | -20 | -15 | -5 |
| Viscosity, 40 ℃, mm 2/s | 21.01 | 25.56 | 115.2 | 298.3 |
| Acid number, mgKOH/g | 0.015 | 0.016 | 0.019 | 0.020 |
| Copper corrosion; (100 ℃, 3h) | 1a | 1a | 1a | 1a |
| Carbon residue; M% less than | 0.01 | 0.01 | 0.01 | 0.01 |
| Ash content; M% less than | 0.01 | 0.01 | 0.01 | 0.01 |
| Sulphur content, μ g/g | 109 | 132 | 169 | 218 |
| Nitrogen content, μ g/g | 225 | 356 | 475 | 692 |
| Aromaticity content, m% | 92.2 | 91.8 | 93.1 | ≮85.0 |
| Deterioration rate, m% | 3.0 | 3.5 | 4.0 | 6.1 |
| Moisture, v% | Trace | Trace | Trace | Trace |
| Smell | Free from extraneous odour | Free from extraneous odour | Free from extraneous odour | Free from extraneous odour |
| Outward appearance | Pale yellow transparent | Pale yellow transparent | Pale yellow transparent | Pale yellow transparent |
Claims (2)
1. the production method of a base oil of heat transfer oil, it is characterized in that: stock oil contacts with hydrogenation pre-refining catalyzer earlier in hydro-upgrading unit with hydrogen, remove sulphur, impurity such as nitrogen, the reaction product of hydrogenation pre-refining contacts with catalyst for hydro-upgrading again reacts, and remove sulphur, impurity such as nitrogen, obtain hydrogenated oil, described stock oil is dead oil, one or more mixing oil in the extraction oil of catalytic cracking heavy oil and the preparing ethylene by steam cracking tar, the weight ratio of described hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading is 1～6: 4～9, the operational condition of hydrogenation pre-refining and hydro-upgrading is, the hydrogen dividing potential drop is 8.0～20.0Mpa, and volume space velocity is 0.1～1.5h during liquid
-1Temperature of reaction is 300～450 ℃, the volume ratio of hydrogen and stock oil is 500～3000, described hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading comprise carrier and active ingredient, wherein carrier is the resistant to elevated temperatures inorganic oxide of porous, and active ingredient is the oxide compound of group vib and/or VIII family metal;
The above-mentioned hydrogenated oil that obtains is carried out fractionation, obtain different narrow fractions, 245 ℃～285 ℃ distillates that wherein obtain, 285 ℃～305 ℃ distillates, 305 ℃～325 ℃ distillates and 325 ℃～360 ℃ distillates are L-QB and L-QC heat transfer oil series base oil.
2. method according to claim 1 is characterized in that: the operational condition of described hydrogenation pre-refining and hydro-upgrading is: the hydrogen dividing potential drop is 10.0～15.0Mpa; Volume space velocity is 0.3～1.0h during liquid
-1Temperature of reaction is 350～400 ℃; The volume ratio of hydrogen and stock oil is 1000～2000.
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