CN100457862C - One-step hydrogenation method for producing super white oil - Google Patents
One-step hydrogenation method for producing super white oil Download PDFInfo
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- CN100457862C CN100457862C CNB2004100507351A CN200410050735A CN100457862C CN 100457862 C CN100457862 C CN 100457862C CN B2004100507351 A CNB2004100507351 A CN B2004100507351A CN 200410050735 A CN200410050735 A CN 200410050735A CN 100457862 C CN100457862 C CN 100457862C
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Abstract
The invention provides the method of producing white oil with paraffinic bas crude oil distillate oil or fluid oil base oil. The method adopts the series technology, comprising the following: different catalysts graded and stuffed, hydrogenation refining, hydro-pour point depression, hydrofinishing. The first reactor is operatored at the condition of hydrogenation refining. The second reactor is operatored at the condition of hydro-pour point depression and hydrofinishing. The method adopts non-metal catalyst to produce the high quality industrial white oil. The method posseses the characteristics of simple technology, easy operation and moderate condition. The catalyst possesses the high capacity of sulfur resistant and nitrogen resistant. So the contents of sulfur and nitrogen in raw oil are not limited. The raw material needn`t desulfurize and denitrify before producing the white oil. The source of raw material is extensive. The technology possesses the pour point depression function, so the white oil pour point is not rised again.
Description
Technical field
The present invention relates to a kind ofly comprise that by the paraffinic crude distillate lubricant base is the technology of raw material one-stage hydrogenation process production high-quality industrial white oil.
Background technology
White oil is colourless, the tasteless transparent oily liquid of deep refining, has excellent chemical stability and light stability.Be widely used in industries such as cosmetic, food, medicine, plastics, chemical fibre, machinery and light industry.Therefore, white oil must satisfy strict specification requirement, and the high-quality white oil must be by standard-requireds such as sulfuric acid chromogenic assay and ultra-violet absorption spectrum detections.
WHITE OIL PRODUCTION technology mainly contains traditional oleum method of sulfonation and modern hydrogenation technique.It is raw material with the hydrocracking tail oil that sulfonation method is produced white oil many, is sulphonating agent with oleum or sulphur trioxide.The white oil yield of this explained hereafter is lower, and acid sludge and useless carclazyte are difficult to handle, and environment is produced severe contamination.Therefore, limited the development of this technology.
Producing white oil by hydrogenation technology has advantages such as pollution-free, that yield is high, raw material sources are extensive, and range of product is complete, is developed rapidly and widespread usage.
Producing white oil by hydrogenation generally is to be raw material with the hydrocracking tail oil, through solvent dewaxing or catalytic dewaxing, again through the saturated production white oil of high-nickel catalyst high-pressure hydrogenation.This high pressure flow process complexity, technical requirements is higher.Cause its production cost higher relatively, again because of the restriction of raw material, only can production low viscosity white oil.
US3392112 has announced the two-stage hydrogenation technological process of producing white oil.I.e. first section hydrogenating desulfurization, denitrogenation, second section hydrogenation saturation history, under about 200: 1 condition of hydrogen to oil volume ratio, the sulphur content in its feed oil must be limited in below the 10ug/g, could guarantee the nickel hydrogenation catalyst performance ideal aromatic hydrocarbons saturation effect of this section.The restriction of sulphur content is adopted just the reason of two-stage hydrogenation technology.US4055481 has described a two-stage hydrogenation system white oil technology, uses the lubricant base raw material, and first section is adopted sulfur resistant catalyst to carry out hydrogenation, obtains a kind of sulphur content, intermediates that aromaticity content is low, enters second section hydrogenation after lighting end is extracted.Second section employing contains Ni60% and (accounts for Al
2O
3) Ni-Al
2O
3Catalyzer.Product can satisfy the food-level white oil standard.Because second section is adopted the reduced nickel catalyzer, therefore, must adopt complicated two-stage method technology.
Petroleum crude oil roughly can be divided into three types: paraffinic crude, intermediate base crude oil, naphthenic base crude.Paraffinic crude wax content height wherein, the condensation point height, sulfur-bearing is lower, because the wax content height, distillate must be after solvent dewaxing, the saturated refining production white oil product of ability hydrogenation, after but hydrogenation was saturated, there was rise in various degree in its pour point, and the finished product are difficult to reach desired index.Chinese patent CN 1062584C has announced a kind of method of producing white oil by hydrogenation.Adopt two placed in-line reactors of one-stage hydrogenation, contact the method for production white oil under stock oil and the hydrogen mixing condition with catalyzer.Its stock oil is confined to the distillate of naphthenic base crude, because the distillate content of wax of naphthenic base crude is few, pour point is low.There is not the problem of pour point reversion in product.And be that the distillate of raw material comprises oil lubrication oil base oil because the wax content height with the paraffinic crude, pour point is higher.Especially the paraffin base oil component is after hydrogenation is saturated, and pour point all has rise in various degree, have in addition go up more than 10 ℃, will cause product defective and increase the working depth of other operations like this, the oil product yield is descended, and power consumption of polymer processing increases, and increases production cost.Therefore, CN 1062584C disclosed method is unsuitable for processing the distillate of paraffinic crude.
Summary of the invention
At the deficiencies in the prior art, it is raw material that the present invention proposes a kind of distillate or lubricant base with paraffinic crude, adopts the method for one-stage hydrogenation process production high-quality white oil.The inventive method has been expanded the raw material sources scope of producing white oil, good product quality, and technical process is simple.
The technology detailed process of one-stage hydrogenation process production high-quality white oil of the present invention comprises: stock oil and hydrogen are under suitable processing condition, successively by comprising the reaction zone of three kinds of catalyzer, the catalyzer that the filling of first reaction zone has the hydrofining function, the catalyzer that the filling of second reaction zone has the pour point depression function, the catalyzer that the 3rd reaction filling has the saturated function of hydrogenation.Three reaction zone catalyst loading volume ratios are generally 1: 0.1～1.0: 0.1～1.0, be preferably 1: 0.2～0.6: 0.2～and 0.6.The temperature of reaction in differential responses district can be identical, also can be different.
Stock oil is some distillate or the lubricant base of paraffinic crude, as: boiling range is in 250～550 ℃, and density (20 ℃) is 820.0～920.0kg/m
3, viscosity (40 ℃) is 10～90mm
2/ s.
Reaction conditions is: 200～370 ℃ of temperature of reaction;
Hydrogen dividing potential drop 1.0～16.0MPa;
Liquid volume air speed 0.1～3.0h
-1
Hydrogen to oil volume ratio 80～1200.
Optimized process conditions is: 220～360 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0～16.0MPa, liquid volume air speed 0.2～3.0h
-1, hydrogen to oil volume ratio 120～1000.Actual conditions can require to adjust by this area general knowledge according to feedstock property and quality product.
Compared with prior art, technological advantage of the present invention is, can use paraffinic crude distillate or lubricant base to be raw material, and raw material sources are extensive.There is not the problem of pour point reversion in product, and the pour point of product also have to descend, and has further advanced product property high.Sulphur content to stock oil does not have strict restriction, integrates hydrogenation pre-refining, hydrodewaxing, hydrofinishing, and technical process is simple, and production cost is low.
Embodiment
Technical process of the present invention can be seated in different catalyzer layerings in the reactor, also can adopt two reactors in series.Preferred Hydrobon catalyst is seated in first reactor, and pour point depression catalyzer and hydrocatalyst for saturating are seated in second reactor successively.Adopt different catalyst combination loadings, integrate hydrofining, hydrodewaxing, hydrogenation saturated hydrogenation post-refining.
Corresponding catalyzer can be selected by this area general knowledge: Hydrobon catalyst is the catalyzer (catalyst I) with hydrogenating desulfurization, hydrodenitrification isoreactivity; The pour point depression catalyzer is to have the active higher non-noble metal hydrogenation catalyst (catalyst I I) of hydrodewaxing; Hydrocatalyst for saturating is to have the active higher non-noble metal hydrogenation catalyst (catalyst I II) of hydrogenation saturated hydrogenation post-refining.
Catalyst I can be selected a kind of hydrogenation pre-refining catalyzer, and support of the catalyst is the wide aperture, the aluminum oxide of high pore volume.Wherein also add other refractory oxides.The main component of catalyzer, group VIII metal oxide content are 1～10wt%, preferred 2～6wt%; The group vib metal oxide content is 10～50wt%, preferred 15～40wt%.Wherein group VIII metal oxide cobalt oxide or nickel oxide, the group vib metal oxide is Tungsten oxide 99.999 or molybdenum oxide preferably.This catalyzer adopts base metal as hydrogenation pre-refining catalyzer, and this catalyzer contamination resistance is strong, and stock oil need not through pre-treatment.
Catalyst I I can select a kind of highly active Hydrodewaxing catalyst.Catalyzer is a support of the catalyst with ZSM-8 or ZSM-5 or beta-zeolite, wherein also adds the mixture of refractory oxides.Refractory oxides is oxide compound and its mixture of elements such as silicon, aluminium, zirconium, thorium, boron and titanium.Preferably select porous alumina.Carrier is preferably selected ZSM-8 or ZSM-5 or beta-zeolite, and content 3%～90%, preferred content are 20%～80%.Active ingredient comprises VIII family metallic element and group vib metallic element, described catalyzer pour point depression hydrogenation component is tungsten-nickel-molybdenum-tin-zinc preferably, in this catalyzer trioxygen-containing of catalyst weight tungsten 3～25%, molybdic oxide 2～10%, nickel oxide 1～10%, zinc oxide 1～8%, stannic oxide 1～10%.
Catalyst I II can select a kind of highly active hydrofinishing catalyzer, and this catalyzer contains a kind of VIII family's metal such as Ni or Co and at least a group vib metal such as W or Mo, and a kind of non-metal assistant such as P take on the activity of such catalysts component.These active ingredients are dispersed on a kind of alumina supporter, and carrier can siliceously wait auxiliary agent, and the content of group VIII metal is (in oxide compound) 1～15wt%, and preferred content is 2～10wt%; The content of group vib metal is (in oxide compound) 10～40wt%, and preferred content is 15～40wt%.
Above-mentioned catalyzer is preferably through sulfuration and change into sulphided state.Above-mentioned catalyzer is a non-precious metal catalyst, and very strong anti-sulphur, nitrogen ability are arranged, and sulphur, the nitrogen content of stock oil is not had the restriction of strictness.Stock oil need not pass through desulfurization, and denitrification process gets final product charging, directly carries out the one-stage serial hydrogenation, under different reaction conditionss, produces other white oil of different viscosity level.
Further specify feasibility of the present invention below by embodiment.
The catalyzer that embodiment selects is a commercial catalysts, and trade names are 3996 (productions of Fushun Petrochemical Company catalyst plant), 3792 (productions of Fushun Petrochemical Company catalyst plant) and FV-1 (Qilu Petrochemical company catalyst plant is produced).Embodiment is contained in first kind of catalyzer in the reactor, and back two kinds of catalyzer are seated in another reactor successively.The catalyzer that comparative example is selected is 3996 and two kinds of different catalysts of FV-1.The composition of catalyzer is listed in table 1.
The stock oil of embodiment is paraffin base lubricating oil base oil and distillate, and raw material properties is listed in table 2, and hydrogenation technique condition and hydrogenated products are listed in table 3.Hydrogenated products are cut into No. 10 white oils and No. 32 white oils behind stripping.
Table 1 catalyzer is formed
Table 2 stock oil main character
| Raw material | 150SN | 200SN | Distillate |
| Density (20 ℃), Kg/m 3 | 874.1 | 875.0 | 865.6 |
| Boiling range (D1160), ℃ | |||
| IBP/10％ | 335/383 | 327/410 | 332/378 |
| 30％/50％ | 407/427 | 426/438 | 398/410 |
| 70％/90％ | 440/457 | 452/469 | 432/472 |
| 95％/EBP | 466/475 | 478/480 | 493/521 |
| Sulphur, μ g/g | 462.5 | 495.6 | 694.5 |
| Nitrogen, μ g/g | 17.9 | 25 | 34.8 |
| Viscosity, mm 2/s(40℃) | 30.95 | 38.61 | 11.4 |
| Flash-point (opening), ℃ | 212 | 222 | 221 |
| Colourity (D1500), number | ＜1.0 | 1.0 | 2.5 |
| Pour point, ℃ | -3 | -3 | 5 |
| Compositional analysis, wt% | |||
| Total paraffinic hydrocarbons | 24.8 | 28.4 | 67.3 |
| Total naphthenic hydrocarbon | 59.2 | 53.7 | 30.4 |
| Total aromatic hydrocarbons | 16.0 | 17.9 | 2.3 |
Table 3 one-stage process hydrogenation manufacture white oil quality product
Experimental result shows that the white oil of explained hereafter of the present invention is cut apart through stripping, and product reaches top grade white oil standard respectively.
Claims (10)
1, a kind of one-stage hydrogenation method of producing top grade product white oil, process comprises: stock oil and hydrogen are under suitable reaction condition, successively by comprising the reaction zone of three kinds of catalyzer, the catalyzer that the filling of first reaction zone has the hydrofining function, the catalyzer that the filling of second reaction zone has the pour point depression function, the catalyzer that the filling of the 3rd reaction zone has the saturated function of hydrogenation; Three reaction zone catalyst loading volume ratios are 1: 0.1～1.0: 0.1～1.0.
2, in accordance with the method for claim 1, it is characterized in that described three reaction zone catalyst loading volume ratios are 1: 0.2～0.6: 0.2～0.6.
3,, it is characterized in that described stock oil is the distillate or the lubricant base of paraffinic crude according to claim 1 or 2 described methods.
4, in accordance with the method for claim 3, it is characterized in that described stock oil boiling range in 250～550 ℃, 20 ℃ of density are 820.0～920.0kg/m
3, 40 ℃ of viscosity are 10～90mm
2/ s.
5, in accordance with the method for claim 1, it is characterized in that described reaction conditions is: 200～370 ℃ of temperature of reaction, hydrogen dividing potential drop 1.0～16.0MPa, liquid volume air speed 0.1～3.0h
-1, hydrogen to oil volume ratio 80～1200.
6, in accordance with the method for claim 1, it is characterized in that described reaction conditions is: 220～360 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0～16.0MPa, liquid volume air speed 0.2～3.0h
-1, hydrogen to oil volume ratio 120～1000.
7, in accordance with the method for claim 1, it is characterized in that the temperature of reaction of described three reaction zones is identical or different.
8, in accordance with the method for claim 1, it is characterized in that described three reaction zone catalyst loadings in an anti-device, or be seated in successively in two reactors.
9, in accordance with the method for claim 1, it is characterized in that described Hydrobon catalyst has hydrogenating desulfurization, hydrodenitrogenationactivity activity, carrier is the aluminum oxide of wide aperture, high pore volume, the main component of catalyzer, the group VIII metal oxide content is 1～10wt%, and the group vib metal oxide content is 10～50wt%; Described pour point depression catalyzer is to have the active higher non-noble metal hydrogenation catalyst of hydrodewaxing, with the aluminum oxide is carrier, hydrogenation component is tungsten-nickel-molybdenum-tin-zinc, in this catalyzer trioxygen-containing of catalyst weight tungsten 3～25%, molybdic oxide 2～10%, nickel oxide 1～10%, zinc oxide 1～8%, stannic oxide 1～10%, auxiliary agent fluorine content 2～7% contains molecular sieve 3～90% simultaneously; Hydrocatalyst for saturating is to have the active higher non-noble metal hydrogenation catalyst of hydrogenation saturated hydrogenation post-refining, contain a kind of VIII family's metal and at least a group vib metal, and a kind of non-metal assistant P takes on the activity of such catalysts component, active ingredient is dispersed on the alumina supporter, the content of group VIII metal is counted 1～15wt% with oxide compound, and the content of group vib metal is counted 10～40wt% with oxide compound.
10, in accordance with the method for claim 9, it is characterized in that described group VIII metal is nickel or cobalt, the group vib metal is tungsten or molybdenum.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265419B (en) * | 2007-03-16 | 2011-05-25 | 中国石油天然气股份有限公司 | Method for producing food-grade white oil by one-stage medium-pressure hydrogenation |
| CN102311788B (en) * | 2010-07-07 | 2014-05-21 | 中国石油化工股份有限公司 | Shale oil one-stage in series hydrofining technological method |
| CN103820146B (en) * | 2012-11-16 | 2016-03-09 | 中国石油天然气股份有限公司 | Optical fiber ointment filling oil and preparation method thereof |
| CN104560179B (en) * | 2013-10-22 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of hydrogenation combination technique producing high quality white oil plant |
| CN104611023B (en) * | 2013-11-05 | 2017-02-08 | 中国石油化工股份有限公司 | Method for producing special lubricating oil base oil |
| CN109266381A (en) * | 2018-11-30 | 2019-01-25 | 山东齐胜工贸股份有限公司 | A kind of high-sulfur light distillate and organic heat carrier feedstock oil hybrid process technique |
| CN111334330B (en) * | 2018-12-19 | 2021-09-28 | 中国石油天然气股份有限公司 | White oil for poultry vaccine injection and preparation method thereof |
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|---|---|---|---|---|
| CN1218094A (en) * | 1998-09-14 | 1999-06-02 | 薛世峰 | Preparation of fundamental oil of lubricant oil |
| US5935416A (en) * | 1996-06-28 | 1999-08-10 | Exxon Research And Engineering Co. | Raffinate hydroconversion process |
| US5976353A (en) * | 1996-06-28 | 1999-11-02 | Exxon Research And Engineering Co | Raffinate hydroconversion process (JHT-9601) |
| US6245221B1 (en) * | 1997-08-22 | 2001-06-12 | Exxon Research And Engineering Company | Desulfurization process for refractory organosulfur heterocycles |
| CN1352233A (en) * | 2000-11-08 | 2002-06-05 | 中国石油化工股份有限公司 | Process for producing white oil from solvent refining oil |
-
2004
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5935416A (en) * | 1996-06-28 | 1999-08-10 | Exxon Research And Engineering Co. | Raffinate hydroconversion process |
| US5976353A (en) * | 1996-06-28 | 1999-11-02 | Exxon Research And Engineering Co | Raffinate hydroconversion process (JHT-9601) |
| US6245221B1 (en) * | 1997-08-22 | 2001-06-12 | Exxon Research And Engineering Company | Desulfurization process for refractory organosulfur heterocycles |
| CN1218094A (en) * | 1998-09-14 | 1999-06-02 | 薛世峰 | Preparation of fundamental oil of lubricant oil |
| CN1352233A (en) * | 2000-11-08 | 2002-06-05 | 中国石油化工股份有限公司 | Process for producing white oil from solvent refining oil |
Non-Patent Citations (2)
| Title |
|---|
| 白油加氢装置技术改造. 金熙俊.当代化工，第31卷第4期. 2002 |
| 白油加氢装置技术改造. 金熙俊.当代化工，第31卷第4期. 2002 * |
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