CN1133724C - Hydrogenation process of producing food-level white oil - Google Patents
Hydrogenation process of producing food-level white oil Download PDFInfo
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- CN1133724C CN1133724C CNB011060085A CN01106008A CN1133724C CN 1133724 C CN1133724 C CN 1133724C CN B011060085 A CNB011060085 A CN B011060085A CN 01106008 A CN01106008 A CN 01106008A CN 1133724 C CN1133724 C CN 1133724C
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Abstract
The present invention provides a method for producing food-grade white oil by hydrogenation, which mainly comprises the following processes: a layer-packed catalyst system is adopted in the traditional technological process of the production of white oil by hydrogenation, and catalysts used in the layer-packed catalyst system comprise a desulfurizing agent and a nickel hydrogenation saturation catalyst. Due to the adoption of the layer-packed catalyst, the method has the advantages of sulphur resisting capability improvement of the catalyst system, activity improvement of the catalyst system, and obvious prolongation of catalyst service life.
Description
The present invention relates to a kind of lubricant base or industrial white oil with deep refining is raw material, adopts the method for one-stage hydrogenation explained hereafter food-level white oil.
White oil is that deep refining is removed impurity such as aromatic hydrocarbons and sulfide in the lubricating oil distillate and obtain colourless, tasteless and a class petroleum products that chemical property is stable.White oil is divided into technical grade again, make up level and food grade.Because the white oil product is extremely strict to the restriction of aromaticity content, and the hydrogenation of aromatic hydrocarbons is subjected to thermodynamics equilibrium limit to be difficult at high temperature carry out, so in producing white oil by hydrogenation technology, adopt high-pressure hydrogenation without exception.According to the different of raw material and different to product requirement, adopt one-stage hydrogenation or multistage hydrogenation.With quality raw material preferably, as the hydrocracking unconverted oil, or through the lubricant base of peracid pre-refining, general aromaticity content can obtain industrial grade white oil even food-level white oil less than 5m% through one-stage hydrogenation.With fair raw material, as lubricant base or solvent treatment dewaxing wet goods, aromaticity content can reach 10～20m%, generally will pass through secondary hydrogenation, and one-stage hydrogenation can obtain industrial grade white oil, and secondary hydrogenation can obtain food-level white oil.If raw materials quality is poorer, as vacuum distillate, then generally will be through hydrogenation more than three sections.
Present method correlation technique is that one-stage hydrogenation is produced the food-level white oil processing method.Typical technology such as US5,736,484 is described, is raw material with the industrial grade white oil, adopts the reduced state nickel catalyzer, adopts a segment process to produce food-level white oil.This method deficiency is for making nickel catalyzator higher hydrogenation activity and long work-ing life are arranged, and the sulphur content in raw material and the hydrogen is proposed strict restriction, and general requirement is less than 5ppm, even requirement is less than 3ppm.Reason is that the sulfide in the raw material can be converted into H under the condition of hydrogen and hydrogenation catalyst existence
2S.Sulfide in the hydrogen also is with H
2S exists.H
2S is adsorbed on the metallic nickel of reduced state nickel catalyzer, and strong interaction generation nickelous sulfide takes place with it, and its hydrogenation activity is obviously reduced.In addition, at H
2Under the effect of S, also can cause the gathering of metallic nickel, the quantity of hydrogenation sites is reduced, thus the hydrogenation activity and the work-ing life of having reduced catalyzer.
The objective of the invention is to produce in the food-level white oil process in order to overcome above-mentioned one-stage hydrogenation process, nickel catalyzator needs sulphur content in raw material and the hydrogen is carried out the defective of strict restriction, widen requirement to sulphur content in raw material and the hydrogen, and the raising activity of such catalysts, the work-ing life of prolongation catalyzer.
Main process of the present invention comprises:
Adopt layer dress catalyst system in the technological process of traditional producing white oil by hydrogenation: the catalyzer that this layer dress catalyst system uses is sweetening agent and reduced state nickel catalyzer.
Layer dress catalyst body of the present invention is: dividing 4 beds at a hydrogenator, is the A bed from top to bottom: sweetening agent, B bed: reduced state nickel catalyzer, C bed: sweetening agent, D bed: reduced state nickel catalyzer.
The ratio of A, B, C and D bed is in the layer dress catalyst system of the present invention: the A bed: sweetening agent is 1～10v%, preferably 2～5v%.The B bed: the reduced state nickel catalyzer is 1～20v%, preferably 5～15v%.The C bed: sweetening agent is 1～20v%, preferably 5～15v%.The D bed: the reduced state nickel catalyzer is 50～97v%, preferably 65～88v%.
The sweetening agent that the present invention uses can be a kind of in the oxide compound of potassium, barium, calcium, zinc and copper, or any two or more the mixture in them; Also can be on aluminum oxide, spinel or zeolitic material, to sneak into or immerse a kind of of above-mentioned metal oxide or any two or more the mixture in them.Zinc oxide desulfurizer preferably.Zinc oxide is a kind of sweetening agent that is applied to industrial raw material gas such as synthetic ammonia, hydrogen manufacturing, synthesizing methanol, Coal Chemical Industry, petroleum refinement and petrochemical complex or oil purification.As: NCT305 and NCT310 Zinc oxide desulfurizer that Nanjing chemical industry company limited catalyst plant produces, T305 that Shenyang Catalyst Plant produces and T310 Zinc oxide desulfurizer etc.The main component of sweetening agent is a metal oxide, and the reaction of metal oxide and sulfide generates very stable metallic sulfide, and the chemical equation of it and various sulfide is:
M in the following formula represents metal, promptly is a kind of in potassium, barium, calcium, zinc and the copper.
The aromatic hydrocarbon saturation catalyst that the present invention uses can be any saturated reduced state nickel catalyzer of benzene, white oil, paraffin and other petrochemicals hydrogenation that is used for, and the nickel oxide content of this catalyzer is greater than 40m% (to catalyzer).NCG type benzene hydrogenating catalyst as the production of Nanjing chemical industry company limited.
The raw material that the present invention uses is the lubricant base of deep refining, thisly refiningly comprises that sulphur trioxide is refining, acid treating and hydrofining etc.Raw material also comprises industrial white oil.Aromaticity content is less than 10m% in the raw material, preferably 5m%; Sulphur content is preferably less than 30ppm less than 50ppm; Nitrogen content is preferably less than 5ppm less than 10ppm.
The hydrogen that the present invention uses is plant hydrogen, as lighter hydrocarbons hydrogen manufacturing, and the hydrogen that device such as catalytic reforming, steam cracking, cracking of ethylene, vinylbenzene is produced, hydrogen purity is greater than 85v%, preferably greater than 90v%.Hydrogen sulfide content is preferably less than 30ppm less than 50ppm in the hydrogen.
The hydrogenation technique condition that the present invention adopts: pressure 8.0～20.0MPa, best 12.0～18.0MPa; 150～300 ℃ of temperature of reaction, best 180～260 ℃; Volume space velocity 0.1～1.5h
-1, best 0.2～0.8h
-1Hydrogen to oil volume ratio 100～1500: 1, best 300～800: 1.
Raw material that the present invention uses and hydrogen are under above-mentioned hydrogenation technique condition, through above-mentioned catalyst system, at the A bed: hydrogen sulfide in the hydrogen and reactive desulfurizing agent generation metallic sulfide; At the B bed: in the raw material sulfide generated hydrogen sulfide by the nickel catalyzator hydrogenation and aromatic hydrocarbons saturated; At the C bed: hydrogen sulfide that the B bed generates and reactive desulfurizing agent generation metallic sulfide; At the D bed: contain the raw material of trace sulfide and hydrogen (＜1ppm) by the nickel catalyzator of D bed, produce food-level white oil.
By grating scheme of the present invention, make the sulfide that contains minute quantity in raw material by the D bed and the hydrogen (＜1ppm), the just few poisoning (hydrogen sulfide causes that the metallic nickel on the catalyzer generates nickelous sulfide and metallic nickel is assembled) that takes place because of hydrogen sulfide causes of the nickel catalyzator of D bed like this, thereby not only improved the anti-sulphur ability of whole catalyst system, and making the activity of catalyst system greatly improve, obviously prolong work-ing life.
The method that the present invention adopts layer dress catalyst system to produce food-level white oil is compared with the method that adopts single nickel catalyzator, and sulphur content in raw material and the hydrogen is required obviously to reduce, and activity of such catalysts greatly improves, and obviously prolong work-ing life.
The present invention will be further described for the following examples, rather than the restriction the spirit and scope of the present invention.
Embodiment 1
Get the T305 Zinc oxide desulfurizer 20ml that Shenyang Catalyst Plant produces, get the NCG benzene hydrogenating catalyst 180ml that Nanjing chemical industry company limited produces again.Adopt layer dress catalyst system I, from top to bottom, A bed: T305 Zinc oxide catalytic 6ml; B bed: NCG nickel catalyzator 20ml; C bed: T305 Zinc oxide desulfurizer 14ml; D bed: NCG nickel catalyzator 160ml.
Get Nanjing chemical industry company limited and produce NCT310 Zinc oxide desulfurizer 14ml, get NCG benzene hydrogenating catalyst 186ml again.Adopt layer dress catalyst system II, from top to bottom, A bed: NCT310 Zinc oxide catalytic 4ml; B bed: NCG nickel catalyzator 10ml; C bed: NCT310 Zinc oxide desulfurizer 10ml; D bed: NCG nickel catalyzator 176ml.
Get Nanjing chemical industry company limited and produce NCT305 Zinc oxide desulfurizer 40ml, get NCG benzene hydrogenating catalyst 190ml again.Adopt layer dress catalyst system III, from top to bottom, A bed: NCT305 Zinc oxide catalytic 10ml; B bed: NCG nickel catalyzator 30ml; C bed: NCT310 Zinc oxide desulfurizer 30ml; D bed: NCG nickel catalyzator 160ml.
Get the NCG benzene hydrogenating catalyst 180ml that Nanjing chemical industry company limited produces.Adopt single catalyst system IV:NCG nickel catalyzator 180ml.
Embodiment 2
Present embodiment is used for illustrating that the sulfide that contains in raw material and the hydrogen is to catalyst activity and stable influence.
Stock oil is the deep refining lubricant base, and character sees Table 1.Hydrogen is the 95v% plant hydrogen, and hydrogen sulfide content is 20ppm.Adopt layer dress catalyst system I, with embodiment 1, hydrogenation technique condition: pressure 15.0MPa, 210 ℃ of bed temperature of reaction, volume space velocity (to the NCG catalyzer) 0.3h
-1, hydrogen to oil volume ratio 500: 1.Can produce food-level white oil.Product property sees Table 2.With identical stock oil, hydrogen and technology volume, through the 1500h longevity test, product should reach the food-level white oil requirement, and product property sees Table 2, and the bed temperature of reaction does not have temperature rise, is 210 ℃.
Embodiment 3
Present embodiment is used for illustrating that the sulfide that contains in raw material and the hydrogen is to catalyst activity and stable influence.
Stock oil is the deep refining lubricant base, and character sees Table 1.Hydrogen is the 95v% plant hydrogen, and hydrogen sulfide content is 20ppm.Adopt layer dress catalyst system II, with embodiment 1, hydrogenation technique condition: pressure 18.0MPa, 260 ℃ of bed temperature of reaction, volume space velocity (to the NCG catalyzer) 0.8h
-1, hydrogen to oil volume ratio 800: 1.Can produce food-level white oil.Product property sees Table 2.With identical stock oil, hydrogen and technology volume, through the 1500h longevity test, product should reach the food-level white oil requirement, and product property sees Table 2, and the bed temperature of reaction does not have temperature rise, is 260 ℃.
Embodiment 4
Present embodiment is used for illustrating that the sulfide that contains in raw material and the hydrogen is to catalyst activity and stable influence.
The stock oil industrial white oil, character sees Table 1.Hydrogen is the 95v% plant hydrogen, and hydrogen sulfide content is 20ppm.Adopt layer dress catalyst system III, with embodiment 1, hydrogenation technique condition: pressure 12.0MPa, 180 ℃ of bed temperature of reaction, volume space velocity (to the NCG catalyzer) 0.2h
-1, hydrogen to oil volume ratio 300: 1.Can produce food-level white oil.Product property sees Table 2.With identical stock oil, hydrogen and technology volume, through the 1500h longevity test, product should reach the food-level white oil requirement, and product property sees Table 2, and the bed temperature of reaction does not have temperature rise, is 180 ℃.
Comparative example 1
This comparative example is used for illustrating that the sulfide that contains in raw material and the hydrogen is to catalyst activity and stable influence.
Stock oil and hydrogen are with embodiment 2.Adopt single NCG catalyst system IV, with embodiment 1, the hydrogenation technique condition: pressure, volume space velocity and hydrogen to oil volume ratio are with embodiment 2, the bed temperature of reaction is higher 6 ℃ than layer dress catalyst system, be 216 ℃, can produce food-level white oil, product property sees Table 2.With identical stock oil, hydrogen and hydrogenation technique condition, through the 1500h longevity test, product reaches the food-level white oil requirement, and 6 ℃ of catalyst bed reaction temperature temperature rises are 222 ℃, and product property sees Table 2.
The result shows that under the condition of sulphur content 20ppm, layer dress catalyst system of the present invention is compared with single catalyst, has the characteristics of active height and good stability in feed sulphur content 28ppm and hydrogen.
Table 1
| Project | The stock oil main character | |
| Material name | Deep refining lubricating oil | Industrial white oil |
| Density (20 ℃), kg/m 3 | 862.0 | 850.0 |
| Viscosity (40 ℃), mm 2/s | 71.40 | 34.50 |
| Sulphur, ppm | 28 | 5 |
| Aromatic hydrocarbons, m% | 3.9 | 0.1 |
| Color (Sai Shi), number | +23 | +27 |
| Pour point, ℃ | -15 | -10 |
Table 2
| Project | Product property | Test method | |||
| Embodiment 2 | Embodiment 3 | Comparative example 1 | Embodiment 4 | ||
| Density (20 ℃), kg/m 3 | 860.1 | 860.3 | 860.5 | 845.2 | |
| Viscosity (40 ℃), mm 2/s | 70.2 | 70.5 | 70.8 | 33.5 | GB/T265 |
| Color, Sai Shi number | ＞+30 | ＞+30 | ＞+30 | ＞+30 | GB/T3555 |
| Pour point, ℃ | -13 | -13 | -13 | -9 | |
| Water soluble acid or alkali | Do not have | Do not have | Do not have | Do not have | GB/T259 |
| Mechanical impurity, m% | Do not have | Do not have | Do not have | Do not have | GB/T511 |
| Moisture, m% | Do not have | Do not have | Do not have | Do not have | GB/T260 |
| Arsenic, mg/kg | ＜1 | ＜1 | ＜1 | ＜1 | GB/8450 |
| Lead, mg/kg | ＜1 | ＜1 | ＜1 | ＜1 | GB/8449 |
| Heavy metal, mg/kg | ＜10 | ＜10 | ＜10 | ＜10 | GB/8451 |
| Readily carbonizable substance | By | By | By | By | GB/T11079 |
| Solid paraffin | By | By | By | By | SH/T0134 |
| Condensed-nuclei aromatics, ultraviolet absorptivity/cm (260～420nm) | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | GB/T11081 |
Claims (12)
1. a hydrogenation method is produced the method for food-level white oil, it is characterized in that adopting a layer dress catalyst system in the technological process of traditional producing white oil by hydrogenation: the catalyzer that this layer dress catalyst system uses is sweetening agent and reduced state nickel catalyzer; The hydrogenation technique condition is: pressure 8.0～20.0MPa, 150～300 ℃ of temperature of reaction, volume space velocity 0.1～1.5h
-1, hydrogen to oil volume ratio 100～1500: 1.
2. in accordance with the method for claim 1, it is characterized in that described layer dress catalyst body is: dividing 4 beds at a hydrogenator, is the A bed from top to bottom: sweetening agent, B bed: nickel catalyzator, C bed: sweetening agent, D bed: nickel catalyzator.
3. in accordance with the method for claim 2, it is characterized in that the ratio that said layer is adorned A, B, C and D bed in the catalyst system is: A bed: 1～10v%, B bed: 1～20v%, C bed: 1～20v%, D bed: 50～97v%.
4. in accordance with the method for claim 2, it is characterized in that the ratio that said layer is adorned A, B, C and D bed in the catalyst system is: A bed: 2～5v%, B bed: 5～15v%, C bed: 5～15v%, D bed: 65～88v%.
5. in accordance with the method for claim 1, it is characterized in that said sweetening agent is a kind of in the oxide compound of potassium, barium, calcium, zinc and copper, or any two or more the mixture in them; Or on aluminum oxide, spinel or zeolitic material, sneak into or immerse a kind of of above-mentioned metal oxide or any two or more the mixture in them.
6. in accordance with the method for claim 5, it is characterized in that said sweetening agent is a Zinc oxide desulfurizer.
7. in accordance with the method for claim 1, it is characterized in that the handled raw material of this method is refined lubricant base and industrial white oil, saidly refining comprise that sulphur trioxide is refining, acid treating and hydrofining.
8. in accordance with the method for claim 1, it is characterized in that aromaticity content is less than 10m% in the handled raw material of this method; Sulphur content is less than 50ppm; Nitrogen content is less than 10ppm.
9. in accordance with the method for claim 8, it is characterized in that in this method that aromaticity content is less than 5m% in the handled raw material; The little 30ppm of sulphur content; Nitrogen content is less than 5ppm.
10. in accordance with the method for claim 1, it is characterized in that hydrogen purity used in this method greater than 85v%, hydrogen sulfide content is less than 50ppm in the hydrogen.
11. in accordance with the method for claim 10, it is characterized in that hydrogen purity used in this method greater than 90v%, hydrogen sulfide content is less than 30ppm in the hydrogen.
12. it is characterized in that in accordance with the method for claim 1, the hydrogenation technique condition of this method be: pressure 12.0～18.0MPa; 180～260 ℃ of temperature of reaction; Volume space velocity 0.2～0.8h
-1Hydrogen to oil volume ratio 300～800: 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011060085A CN1133724C (en) | 2001-01-05 | 2001-01-05 | Hydrogenation process of producing food-level white oil |
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| CNB011060085A CN1133724C (en) | 2001-01-05 | 2001-01-05 | Hydrogenation process of producing food-level white oil |
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| CN1133724C true CN1133724C (en) | 2004-01-07 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148606B (en) * | 2006-09-20 | 2010-08-18 | 中国石油化工股份有限公司 | One-stage hydrogenation method for producing food-level white oil |
| 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 |
| CN101429457B (en) * | 2007-11-08 | 2012-05-09 | 中国石油化工股份有限公司 | Method for distillate hydrogenation for feracity of white oil |
| CN107961777A (en) * | 2017-12-05 | 2018-04-27 | 广州高八二塑料有限公司 | It is used to prepare the composite catalyst of food-level white oil and the preparation method of food-level 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 |
| CN113349329A (en) * | 2021-06-21 | 2021-09-07 | 千禾味业食品股份有限公司 | Method for reducing sulfur dioxide content in ammonium sulfite process caramel color |
| CN113583706B (en) * | 2021-08-13 | 2023-02-10 | 广东省科学院动物研究所 | Mineral oil base oil for pesticide adjuvant and preparation method thereof |
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