CN1249326A - One-stage hydrogenation process for preparing industrial white oil - Google Patents
One-stage hydrogenation process for preparing industrial white oil Download PDFInfo
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- CN1249326A CN1249326A CN 98114344 CN98114344A CN1249326A CN 1249326 A CN1249326 A CN 1249326A CN 98114344 CN98114344 CN 98114344 CN 98114344 A CN98114344 A CN 98114344A CN 1249326 A CN1249326 A CN 1249326A
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Abstract
An one-stage hydrogenation process for preparing industrial white oil features that the base oil of lubricating oil, which has high contents of impurities (S and N)and arene, or poor-distillate oil is used as raw material, in the presence of sulfur-resistant catalyst the industrial white oil is prepared by one-stage hydrogenating in the conditions of 200-370 deg.C, 10-30 MPa, 0.1-2.0/hr of volume space velocity, and 200-2000 of hydrogen/oil volume ratio. Its advantages are high quality of industrial white oil, simple process, low cost and widely available raw materials.
Description
The present invention relates to a kind of hydrogenation process for preparing industrial white oil technology, particularly one-stage hydrogenation process for preparing industrial white oil technology.
For WHITE OIL PRODUCTION, acid--methods such as clay treatment and hydrogenation are arranged generally.Acid--clay treatment be with the white oil raw material under certain conditions with the vitriol oil (or sulphur trioxide) hybrid reaction, wherein heterocycle and many ring materials form acid sludge, reacted oil plant obtains the white oil product through alkali neutralization, extracting, carclazyte refining with adsorbents, the product yield of this method has only 60--75%, and produce a large amount of acid sludges, waste water, very big to environmental hazard.
Producing white oil by hydrogenation is that heterocycle in the raw material and aromatic hydrocarbons are converted into useful components, and removes impurity wherein, has overcome low, the heavy-polluted problem of yield, and product yield can reach more than 85%, with acid--and clay treatment is compared has remarkable advantages.The difficult point of producing white oil by hydrogenation is to remove the requirement that impurity such as most sulphur, nitrogen and saturated most of aromatic hydrocarbons reach industrial white oil from relatively poor raw material, then difficulty is smaller relatively for the further refining product that becomes high grade requirements more, therefore produce high-grade white oil from the lubricant base two-stage hydrogenation and be easier to, but one-stage hydrogenation can not get industrial white oil.Hydrogenation method mainly contains one-stage hydrogenation process and two-stage hydrogenation method, one-stage process will use the low high quality stock oil of foreign matter content just can produce industrial white oil, though and the two-stage hydrogenation method can the relatively poor stock oil of functional quality, its technical process is long, complicated operation, the investment cost height.
US4072603 has described an one-stage hydrogenation and has prepared the industrial white oil technology, hydroconversion condition is temperature 316-372 ℃, pressure 14-21MPa, employing is supported on the W content 13-18w% on silicon-alumina supporter, the catalyzer of Ni content 5-6w%, but raw material is the aromaticity content that has passed through hydrocracking only is the high quality raw material of 10.8w%, the difficulty of its hydrogenation production white oil is little, and this has just limited the source and the broad application of raw material.
US4055481 has described a two-stage hydrogenation system white oil technology, use the lubricant base raw material, first section is adopted sulfur resistant catalyst, temperature 300--400 ℃, pressure 5.6-28MPa, hydrogen to oil volume ratio 540--900 (3000～5000SCF/Barrel), during volume space velocity 0.1--2.0
-1Condition under hydrogenation, obtain a kind of sulphur content, intermediates that aromaticity content is low, enter second section hydrogenation after lighting end is extracted.Second section employing contains Ni60% and (accounts for Al
2O
3) Ni-Al
2O
3Catalyzer, hydroconversion condition be temperature 225--333 ℃, when pressure 14-28MPa, volume space velocity 0.1--2.0
-1, hydrogen to oil volume ratio 630-1500 (3500～8000SCF/Barrel).Its product can satisfy the food-level white oil standard.This technology one section outlet product does not meet the industrial white oil quality standard, must adopt two-stage hydrogenation, and this has just increased investment cost, and handiness is also relatively poor.
The method that the purpose of this invention is to provide a kind of one-stage hydrogenation manufacture white oil, its raw material can adopt lubricant base even the worse distillate of quality.
The present invention adopts one-stage hydrogenation process for preparing industrial white oil, and stock oil and hydrogen enter reactor after mixing, and contacts with catalyzer under suitable condition, takes off the reaction of impurity such as S, N and saturated aromatic hydrocarbons, and reaction product obtains industrial white oil through stripping or after distilling.Wherein hydrogenation conditions is: temperature 200-370 ℃, pressure 10-30MPa is during volume space velocity 0.1-2.0
-1, hydrogen to oil volume ratio 200-2000.
Catalyst system therefor pore volume of the present invention is 0.3-0.5ml/g, mean pore size 6.0-10.0nm, specific surface area 150-200m
2/ g.This catalyzer contains a kind of VIII family's metal such as Ni, take on the activity of such catalysts component with at least a group vib metal such as W, Mo and a kind of non-metal assistant such as P, these active ingredients are supported on by on a kind of macroporous aluminium oxide of siliceous and phosphorus and the carrier that little porous aluminum oxide is mixed and made into, the content that the group VIII metal is fit to is (in oxide compound) 1--15w%, preferred content is 2--10w%, group vib metal content (in oxide compound) is 10--40w%, and preferred content is 15--35w%.Active metal component can be to go back ortho states, oxidation state or sulphided state, and is wherein better with sulphided state.
The carrier of catalyst system therefor of the present invention is mixed and made into by siliceous and macroporous aluminium oxide and little porous aluminum oxide phosphorus.Wherein be with the catalyzer in the macroporous aluminium oxide of the siliceous and phosphorus of benchmark silicone content (with SiO
2Meter) be 1-20w%, more preferably silicone content is (with SiO
2Meter) be 1--10w%, phosphorus content is (with P
2O
5Meter) be 1-10w%,, preferred phosphorus content is (with P
2O
5Meter) be 1-6w%.Little porous aluminum oxide is a pseudo-boehmite, requires it to contain the gibbsite amount and is no more than 5w%.The weight ratio of macroporous aluminium oxide and little porous aluminum oxide is 1～6.
The preferred reaction conditions of hydrogenation reaction of the present invention is temperature 250--350 ℃, and pressure 12--20MPa is during volume space velocity 0.1--1.2
-1, hydrogen to oil volume ratio 300--1000.
Preparation of catalysts method used herein is as follows: macroporous aluminium oxide, the aperture aluminum oxide of siliceous and phosphorus are mixed back adding mineral acid, make the plasticity-mashed prod, be extruded into leafy careless type by orifice plate, become the carrier of this catalyzer after drying, the activation.Active ingredient Mo, Ni, P adopt a step to be total to steeping fluid and are dipped on the carrier by the spraying pickling process.Promptly get catalyzer of the present invention after catalyzer drying behind the dipping, the activation.The macroporous aluminium oxide of above-mentioned siliceous and phosphorus becomes the preparation of glue method by substep, can make silicon and phosphoric be well-dispersed in alumina surface like this, helps improving activity of such catalysts.
The raw material of technical solution of the present invention can be hydrogenation tail oil, lubricant base or distillate, requires viscosity 5--50mm
2/ s (40 ℃), sulphur content＜1000mg/kg, aromaticity content＜30w%.
Because of the hydrogenation of condensed-nuclei aromatics and heterogeneous ring compound is undertaken by ring stage by stage, removing of impurity such as ring filling and sulphur, nitrogen is relevant with the hydrogenation performance, and open loop is relevant with acid function, so it is difunctional to require catalyst system therefor to have.Catalyst metal content height of the present invention, and add silicon and auxiliary agent P and make this catalyzer have certain acid function, thereby have the higher activity and the hydrogenation degree of depth with acid function, impurity such as its sulphur, nitrogen remove and the aromatic hydrocarbons saturability stronger.Under processing condition of the present invention and catalyzer, use foreign matter content height such as sulphur, nitrogen, lubricant base inferior or the worse distillate of quality that aromaticity content is high to be raw material, also can under the one-stage hydrogenation condition, promptly obtain the industrial white oil of top grade product.Technology of the present invention is simple, and is easy to operate, and investment and process cost are low, and raw material sources are extensive, have obvious improvement.
Further specify the present invention below by embodiment.
The embodiment of the invention is all carried out on the small-sized trickle bed hydrogenation unit of continous way, and the catalyst system therefor carrier is identical.Embodiment 1
Lubricant base is a raw material, viscosity (40 ℃) 17.26mm
2/ s, sulphur content 206mg/kg, nitrogen content 70mg/kg, aromaticity content 13.3w%.Adopt MoO
3Content 21.6w%, NiO content 3.3w%, auxiliary agent P content (in oxide compound) is 2.8w%, specific surface area 176m
2/ g, pore volume 0.33ml/g, the catalyzer of tap density 0.90Kg/l.Hydroconversion condition: 290 ℃ of temperature; Pressure 15MPa is during volume space velocity 0.8
-1Hydrogen to oil volume ratio 700.Its hydrogenated products meet the standard of industrial white oil top grade product behind stripping.The results are shown in Table 1.Embodiment 2
Distillate feedstock, viscosity (40 ℃) 24.2mm
2/ s, sulphur content 534mg/kg, aromaticity content 19w%, catalyzer are MoO
3Content 25.6w%, NiO content 3.8w%, auxiliary agent P content (in oxide compound) is 3.8w%, specific surface area 186m
2/ g, pore volume 0.35ml/g, tap density 0.92Kg/l.When 320 ℃ of temperature, pressure 15MPa, volume space velocity 0.2
-1, hydrogen to oil volume ratio 500 condition under hydrogenation, its product can reach the industrial white oil standard-required through stripping.The result is referring to table 1.Embodiment 3
Distillate feedstock, viscosity (40 ℃) 10.3mm
2/ s, sulphur content 924mg/kg, aromaticity content 22.2w% adopts MoO
3Content 26w%, NiO content 4.6w%, P
2O
5Content 3.9w%, specific surface area 179m
2/ g, pore volume 0.33ml/g, the catalyzer of tap density 0.91Kg/l is when 330 ℃ of temperature, pressure 15MPa, volume space velocity 0.2
-1, hydrogen to oil volume ratio 500 condition under hydrogenation, product satisfies the industrial white oil requirement through stripping.The result is referring to table 1.Embodiment 4
The lubricant base raw material, viscosity (40 ℃) 40.08mm
2/ s, sulphur content 386mg/kg, aromaticity content 11.49w%, catalyzer consists of: MoO
3Content 27w%, NiO content 4.8w%, P
2O
5Content 3.8w%, specific surface area 180m
2/ g, pore volume 0.31ml/g, tap density 0.92Kg/l.Hydroconversion condition is: 335 ℃ of temperature, pressure 15MPa is during volume space velocity 0.3
-1, hydrogen to oil volume ratio 500.Product meets the industrial white oil standard through stripping.The result is referring to table 1.Reference example 1
Adopt example 1 raw material, adopt a kind of MoO that is supported on silicon-alumina supporter
3The sulfur resistant catalyst of content 19W%, NiO content 5W% is when 290 ℃ of temperature, pressure 15MPa, air speed 0.2
-1, hydrogen to oil volume ratio 700 condition under hydrogenation, product does not meet the industrial white oil requirement.The result is referring to table 1.Reference example 2
Other is identical except that temperature is 320 ℃ for raw material and the catalyzer identical with reference example 1, reaction conditions, and its hydrogenated products do not meet the industrial white oil requirement.The result is referring to table 1.Reference example 3
The raw material identical with reference example 1 adopts WO
3Content 18.7%, MoO
3Content 9w%, the sulfur resistant catalyst of NiO content 4w%, at 300 ℃, 15MPa is during air speed 0.2
-1, hydrogenation under the condition of hydrogen to oil volume ratio 500, product can not satisfy the industrial white oil standard-required.The result is referring to table 1.
Table 1 one-stage hydrogenation process for preparing industrial white oil quality product
| Project | Example 1 product | Example 2 products | Example 3 products | Example 4 products | Reference example 1 product | Reference example 2 products | Reference example 3 products |
| 40 ℃ of mm of viscosity 2/s | 16.5 | 21.2 | 9.8 | 34.8 | 16.7 | 15.5 | 16.3 |
| Flash-point ℃ | 177 | 180 | 160 | 182 | 178 | 164 | 177 |
| Condensation point ℃ | -11 | -12 | -18 | -10 | -11 | -12 | -11 |
| Sulfuric acid color test | By | By | By | By | Do not pass through | Do not pass through | Do not pass through |
| Color, Sai Shi number | +30 | +30 | +30 | +30 | +25 | +26 | +26 |
| Corrosion test (100 ℃ of 3h) level | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Outward appearance | No fluorescence | No fluorescence | No fluorescence | No fluorescence | Fluorescence is arranged | Fluorescence is arranged | Fluorescence is arranged |
Claims (5)
1. the production method of an industrial white oil in the presence of catalyzer, adopts one-stage hydrogenation technology, it is characterized in that using viscosity (40 ℃) 5--45mm
2/ s, the lubricant base of aromaticity content＜30w% or distillate are raw material, temperature 200--370 ℃, when pressure 10--30MPa, volume space velocity 0.1--2.0
-1, raw material contacts with catalyzer under the hydrogen to oil volume ratio 200--2000 condition.
2. according to the method for claim 1, it is characterized in that described catalyzer pore volume is 0.2--0.6ml/g, aperture 1.0--10.0nm, specific surface area 150～200m
2/ g, active ingredient is for containing a kind of VIII family's metal and at least a group vib metal and a kind of non-metal assistant, active ingredient is supported on silicon--on the alumina supporter, the group VIII metal content is for to count 1--15w% with oxide compound, the group vib metal content is counted 10--40w% with oxide compound, and amount of auxiliary is counted 1--10w% with oxide compound.
3. according to the method for claim 1 or 2, it is characterized in that the VIII family metal content in the described catalyzer is counted 2--10w% with oxide compound, the group vib metal content is counted 15--35w% with oxide compound.
4. according to the method for claim 2, it is characterized in that described non-metal assistant is P, its content is counted 1～6w% with oxide compound.
5. according to the method for claim 1, it is characterized in that described reaction conditions is temperature 250--350 ℃, pressure 12--20MPa is during volume space velocity 0.1--1.2
-1, hydrogen to oil volume ratio 300--1000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114344A CN1075547C (en) | 1998-09-28 | 1998-09-28 | One-stage hydrogenation process for preparing industrial white oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114344A CN1075547C (en) | 1998-09-28 | 1998-09-28 | One-stage hydrogenation process for preparing industrial white oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1249326A true CN1249326A (en) | 2000-04-05 |
| CN1075547C CN1075547C (en) | 2001-11-28 |
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ID=5224015
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98114344A Expired - Fee Related CN1075547C (en) | 1998-09-28 | 1998-09-28 | One-stage hydrogenation process for preparing industrial white oil |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318549C (en) * | 2005-10-26 | 2007-05-30 | 长春惠工催化剂有限责任公司 | Method for producing industrial grade white oil |
| CN100419048C (en) * | 2002-06-24 | 2008-09-17 | 国际壳牌研究有限公司 | Process to prepare medicinal and technical white oils |
| CN104232159A (en) * | 2014-09-10 | 2014-12-24 | 北京优工科技有限公司 | Production method of polyolefin white oil |
| CN109735365A (en) * | 2019-02-26 | 2019-05-10 | 宁波科元精化有限公司 | A kind of technique that heavy raw oil produces No. 7 white oils |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4072603A (en) * | 1976-10-29 | 1978-02-07 | Suntech, Inc. | Process to make technical white oils |
| CN1093737A (en) * | 1993-04-16 | 1994-10-19 | 王非 | With alkylbenzene byproduct hydrogenation of tar manufacture white oil technology |
| CN1062584C (en) * | 1996-10-09 | 2001-02-28 | 中国石油化工集团公司抚顺石油化工研究院 | Producing white oil by hydrogenation |
-
1998
- 1998-09-28 CN CN98114344A patent/CN1075547C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100419048C (en) * | 2002-06-24 | 2008-09-17 | 国际壳牌研究有限公司 | Process to prepare medicinal and technical white oils |
| CN1318549C (en) * | 2005-10-26 | 2007-05-30 | 长春惠工催化剂有限责任公司 | Method for producing industrial grade white oil |
| CN104232159A (en) * | 2014-09-10 | 2014-12-24 | 北京优工科技有限公司 | Production method of polyolefin white oil |
| CN109735365A (en) * | 2019-02-26 | 2019-05-10 | 宁波科元精化有限公司 | A kind of technique that heavy raw oil produces No. 7 white oils |
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| CN1075547C (en) | 2001-11-28 |
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Granted publication date: 20011128 Termination date: 20100928 |