CN1062584C - Producing white oil by hydrogenation - Google Patents
Producing white oil by hydrogenation Download PDFInfo
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- CN1062584C CN1062584C CN96120125A CN96120125A CN1062584C CN 1062584 C CN1062584 C CN 1062584C CN 96120125 A CN96120125 A CN 96120125A CN 96120125 A CN96120125 A CN 96120125A CN 1062584 C CN1062584 C CN 1062584C
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Abstract
The present invention provides a method for producing white oil by direct hydrogenation with naphthenic straight run, which adopts a serial single-section technology, wherein a first reactor is operated under the conditions of hydrodesulfurization and denitrification; a second reactor is operated under the conditions of dehydrogenation and aromatic hydrocarbon. The method uses a non-noble metal catalyst. The method has the advantages of reasonable resource utilization, simple technological process, mild condition, low production cost, etc.
Description
The present invention relates to a kind of technological process of producing white oil by the direct hydrogenation of fraction oil of naphthenic base crude.
White oil has lubricated oil properties, and it is by the oil advanced treatment, removes desulfuration, nitrogen, oxygen compound, and active hydro carbons such as aromatic hydrocarbons, alkene and the industrial white oil that obtains.White oil divides three classes, the special-purpose white oil of instant food machinery, cosmetic white oil, industrial white oil.Can be used as the lubricant of cosmetic material, pharmaceutical composition, preparation medium and food processing machinery and prevent embroidering agent etc.Therefore, white oil must be colourless, tasteless, odorless and non-blooming transparent oil product, has unreactiveness, and must satisfy strict specification.For example, color is necessary for+30 Saybolt colors, must pass through the uv-absorbing test of mensuration polycyclic aromatic hydrocarbon content etc.
At present, the technology of manufacture white oil mainly contains sulfonation method and hydrogenation method.Sulfonation method is many to be raw material with the hydrocracking tail oil, is that sulphonating agent is produced white oil 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, and then has limited the development of its technology.
Characteristics such as that producing white oil by hydrogenation has is pollution-free, product yield is high and quality is good have become a kind of sophisticated method.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 technical process complexity, technical requirements is higher, causes its production cost higher relatively; In addition, because of the restriction of raw material, this process only can production low viscosity white oil again.
US 3,392, and 112 have announced the two-stage hydrogenation technological process of producing white oil, i.e. first section hydrogenating desulfurization, denitrogenation, second section saturated aromatic hydrocarbons of hydrogenation.The raw material that this patent is mentioned comprises the lubricating oil and the white oil raw material part of crude oil straight run.But this patent admits that its two-stage hydrogenation process must adopt two kinds of different catalyzer; And second section aromatic hydrogenation saturation history, under the condition of hydrogen to oil volume ratio about 200, the sulphur content of oil is limited in below the 10 μ g/g in its charging, could guarantee the saturated effect of nickel hydrogenation catalyst performance ideal aromatic hydrocarbons of this section.And this adopts the reason of two-stage hydrogenation technology just to the restriction of sulphur content.
The object of the present invention is to provide a kind of single hop tandem process to produce the method for white oil, rationally utilize petroleum resources, simplify production technique, reduce investment and production cost.
For a long time, because the strictness of white oil foreign matter content is limited, people adopt complicated technological process and harsh processing condition always, and noble metal catalyst is produced white oil.And in fact,,, just can satisfy the requirement of WHITE OIL PRODUCTION by simple technological process, proper technical conditions as long as select proper raw material, and particularly the catalyzer Manufacturing Technology Development is to today, and general non-precious metal catalyst can both reach requirement.Therefore, can develop more simple, economic method and produce white oil.
By the chemical constitution classification, crude oil is broadly divided into paraffinic base, intermediate base, cycloalkyl three classes.Specifically,, adopt 250-275 ℃ and 395-425 ℃ of cut that the true boiling point device steams respectively according to key fraction property sort method, as first key fraction and second key fraction, with their density as the foundation of dividing the crude oil type.For example, the relative density d of first key fraction of certain crude oil
20 4Greater than 0.8562, then this first key fraction belongs to the cycloalkyl type; If the relative density d of second key fraction of this crude oil
20 4Greater than 0.9305, then this second key fraction also belongs to the cycloalkyl type.According to the attribute of first key fraction and second key fraction, promptly claim this crude oil to belong to the cycloalkyl type.
The characteristics of naphthenic base crude fraction are to contain naphthenic hydrocarbon and aromatic hydrocarbons is more, and it is less to contain alkane, and density is bigger, and condensation point is low, and general sulfur-bearing is more.Therefore, the viscosity temperature characteristic of lubricating oil is poor, and producing needs the wax that removes less in the process of lubricating oil.
The raw material of technological process of the present invention is some fraction of naphthenic base crude, and its concrete feature comprises: boiling range is 270-500 ℃, and density (20 ℃) is 900.0-940.0kg/m
3, viscosity (40 ℃) is 9-70mm
2/ s.
The support of the catalyst of process using of the present invention is the wide aperture, the porous silicon aluminum oxide of high pore volume.The main component molybdenum of catalyzer, nickel.By element, molybdenum accounts for the 9-17% of catalysis weight, and nickel accounts for the 2-7% of catalyst weight.
Technological process of the present invention adopts two placed in-line reactors.Stock oil and hydrogen are mixed into first reactor, carry out the desulfurization removing nitric reaction.Its temperature of reaction is 320-390 ℃ (preferably 340-370 a ℃), air speed 0.2-1.0h
-1(0.2-0.6h preferably
-1), hydrogen-oil ratio 500-1500: 1 (500-800 preferably: 1), hydrogen dividing potential drop 13.0-16.0MPa (preferably 14.0-15.0MPa).Through first reactor, sulphur, nitrogen, the oxygen heteroatom compound of the overwhelming majority are removed in the stock oil, and the part aromatic hydrogenation is saturated.
The generation material of first reactor directly enters second reactor, and it is saturated to carry out further aromatic hydrocarbons.Its temperature of reaction is 250-300 ℃ (preferably 270-290 a ℃), air speed 0.2-1.0h
-1(0.2-0.6h preferably
-1), hydrogen-oil ratio 500-1500: 1 (500-800 preferably: 1), hydrogen dividing potential drop 13.0-16.0MPa (preferably 14.0-15.0MPa).Through second reactor, most aromatic hydrogenations are saturated in the stock oil.Behind resultant of reaction material process high pressure, low pressure separation, the stripping, obtain qualified white oil.
Compared with prior art, the advantage of technology of the present invention is, the desulfurization removing nitric process of technology of the present invention and aromatic hydrogenation saturation history can employing with a kind of Hydrobon catalyst with anti-sulphur ability; Another advantage of the present invention is, the simple relatively single hop serial hydrogenation technology of adopting process flow process.
Obviously, single hop serial hydrogenation technology is saved in the two-stage hydrogenation technology two intersegmental desulfurization deamination processes, simultaneously, also saves a cover recycle hydrogen system.Therefore, the single hop series process flow is simpler than two-stage process flow process.
Because the catalyzer that the present invention can adopt is the non-precious metal catalyst with certain anti-sulphur ability, the sulphur content of aromatic hydrogenation saturation history charging is had no particular limits, so can adopt single hop serial hydrogenation technology.On the other hand, contain non-white oil components such as sulphur, nitrogen, oxygen and aromatic hydrocarbons in the stock oil, wherein impurity such as sulphur, nitrogen, oxygen removes the temperature of reaction of having relatively high expectations, and the saturated lesser temps that requires of aromatic hydrogenation.For saturated two hydrogenation processes of desulfurization removing nitric and aromatic hydrocarbons are carried out under different temperature of reaction respectively, the present invention adopts the serial hydrogenation technological process.
Technology of the present invention also has characteristics, and promptly some fraction with naphthenic base crude is a raw material, does not therefore need dewaxing process, directly carries out the single hop serial hydrogenation, under different reaction conditionss, produces other white oil of different viscosity level.
Embodiment 1-5
The feasibility of technology of the present invention is described with concrete experimental run result now.Testing apparatus adopts two placed in-line reactors.Hydrogen once passes through testing apparatus.For making beds reach isothermal operation, adopt inert diluent, promptly suitably the quartz sand of granularity comes dilute catalyst.The loading amount of first reactor and second reactor catalyst and quartz sand is 200ml and 100ml.
The catalyzer that embodiment adopts is the 481-2B that Shenyang Catalyst Plant produces.
Test raw material oil is the normal two wires oil and the atmosphere 3rd side cut oil of Liaohe River naphthenic base crude, and stock oil character sees Table 1.The reaction conditions of each example experiment and the main character of purpose product are listed in table 2.
Experimental result shows, the ultraviolet absorptivity of white oil of explained hereafter of the present invention is low, pour point is low, flash-point is high, colourity is shallow, normal two line products and atmosphere 3rd side cut product are through concocting or not concocting, quality can reach the quality index of 7#, 10#, 15# salable product industrial white oil respectively, and the quality index of the special-purpose white oil of 10#, 15#, 22# food machinery.Thus, technological process flow process of the present invention is simple, is the good method of directly producing white oil with the cycloalkyl distillate.
Table 1 stock oil character
Table 2 test conditions, purpose product main character and white oil quality index
Claims (3)
1. a distillate hydrogenation is produced the method for white oil, adopt two placed in-line reactors, stock oil and hydrogen are mixed into first reactor, the generation material of first reactor directly enters second reactor, behind resultant of reaction material process high pressure, low pressure separation, the stripping, obtain qualified white oil;
Employed raw material is the distillate of naphthenic base crude, and character is: boiling range is 270-500 ℃, and 20 ℃ of density are 900.0-940.0kg/m
3, 40 ℃ of viscosity are 9-70mm
2/ s;
Employed catalyzer is a carrier with the porous silicon aluminum oxide of wide aperture, high pore volume, is active ingredient with molybdenum, nickel, accounts for the 9-17% of catalysis weight by the element molybdenum, and nickel accounts for the 2-7% of catalyst weight;
First reactor operating condition: temperature of reaction 320-390 ℃, liquid hourly space velocity 0.2-1.0h
-1, hydrogen/oil volume is than 500-1500: 1, hydrogen dividing potential drop 13-16Mpa; Second reactor operating condition: temperature of reaction 250-300 ℃, liquid hourly space velocity 0.2-1.0h
-1, hydrogen/oil volume is than 500-1500: 1, hydrogen dividing potential drop 13-16MPa.
2. method according to claim 1 is characterized in that first reactor operating condition: temperature of reaction 340-370 ℃, liquid hourly space velocity 0.2-0.6h
-1, hydrogen/oil volume is than 500-800: 1, hydrogen dividing potential drop 14-15MPa, second reactor operating condition: temperature of reaction 270-290 ℃, liquid hourly space velocity 0.2-1.0h
-1, hydrogen/oil volume is than 500-1500: 1, hydrogen dividing potential drop 13-16MPa.
3. method according to claim 1 is characterized in that described stock oil is 270-500 ℃ of virgin oil of naphthenic base crude.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120125A CN1062584C (en) | 1996-10-09 | 1996-10-09 | Producing white oil by hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120125A CN1062584C (en) | 1996-10-09 | 1996-10-09 | Producing white oil by hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1178824A CN1178824A (en) | 1998-04-15 |
| CN1062584C true CN1062584C (en) | 2001-02-28 |
Family
ID=5126153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96120125A Expired - Lifetime CN1062584C (en) | 1996-10-09 | 1996-10-09 | Producing white oil by hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1062584C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075547C (en) * | 1998-09-28 | 2001-11-28 | 中国石油化工集团公司 | One-stage hydrogenation process for preparing industrial white oil |
| JP2004269685A (en) * | 2003-03-07 | 2004-09-30 | Nippon Oil Corp | Gas oil composition and its manufacturing method |
| CN101144034B (en) * | 2006-09-14 | 2010-08-25 | 中国石油化工股份有限公司 | Method for producing lubricating oil base oil and white oil by hydrorefining |
| CN103965953B (en) | 2013-01-30 | 2015-07-22 | 中国石油天然气股份有限公司 | Distillate oil two-phase hydrogenation reactor and hydrogenation process method |
| 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 |
| CN104232159B (en) * | 2014-09-10 | 2016-05-11 | 北京优工科技有限公司 | A kind of production method of polyolefin white oil |
| CN106753550B (en) * | 2016-11-16 | 2018-07-20 | 中国海洋石油集团有限公司 | A kind of food-level white oil and preparation method thereof |
| CN106479565B (en) * | 2016-11-16 | 2018-01-26 | 中国海洋石油总公司 | A kind of special white oil of polystyrene and preparation method thereof |
| CN107629817B (en) * | 2017-10-20 | 2020-01-31 | 神华集团有限责任公司 | Preparation method of white oil |
| CN107987881B (en) * | 2017-11-30 | 2020-04-17 | 中海沥青股份有限公司 | Preparation method of crude white oil |
| CN108865256A (en) * | 2018-07-23 | 2018-11-23 | 榆林红石化工有限公司 | A kind of preparation method of easy emulsification content of wax 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 |
| CN112625743A (en) * | 2020-11-26 | 2021-04-09 | 罗智刚 | High-quality medicinal white oil and preparation process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4183801A (en) * | 1977-11-29 | 1980-01-15 | Shell Oil Company | Process for preparing hydrocarbons |
| US4786402A (en) * | 1986-08-30 | 1988-11-22 | Basf Aktiengesellschaft | Preparation of medicinal white oils and medicinal paraffins |
-
1996
- 1996-10-09 CN CN96120125A patent/CN1062584C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4183801A (en) * | 1977-11-29 | 1980-01-15 | Shell Oil Company | Process for preparing hydrocarbons |
| US4786402A (en) * | 1986-08-30 | 1988-11-22 | Basf Aktiengesellschaft | Preparation of medicinal white oils and medicinal paraffins |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1178824A (en) | 1998-04-15 |
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Free format text: CORRECT: PATENTEE; FROM: FUSHUN PETROCHEMICAL INSTITUTE., CHINA PETROCHEMICAL CORP. TO: CHINA PETROLEUM + CHEMICAL CORPORATION, FUSHUN PETROL-CHEMICAL INSTITUTE |
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Patentee after: Sinopec Group Fushun Research Institute of Petroleum and Petrochemicals Patentee before: Fushun Research Inst. of Petroleum Processing, China Petro-chem. Corp. |
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Owner name: CHINA PETROLEUM AND CHEMICAL CORPORATION FUSHUN P Free format text: FORMER OWNER: CHINA PETROLEUM + CHEMICAL CORPORATION, FUSHUN PETROL-CHEMICAL INSTITUTE Effective date: 20071019 |
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Effective date of registration: 20071019 Address after: The eastern section of Dandong road 113001 in Liaoning province Fushun City Wanghua District No. 31 Patentee after: Sinopec Fushun Research Institute of Petroleum and Petrochemicals Address before: The eastern section of Dandong road 113001 in Liaoning province Fushun City Wanghua District No. 31 Patentee before: Sinopec Group Fushun Research Institute of Petroleum and Petrochemicals |
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