CN101942334B - Production method of molecular sieve dewaxing raw material - Google Patents
Production method of molecular sieve dewaxing raw material Download PDFInfo
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- CN101942334B CN101942334B CN 200910012477 CN200910012477A CN101942334B CN 101942334 B CN101942334 B CN 101942334B CN 200910012477 CN200910012477 CN 200910012477 CN 200910012477 A CN200910012477 A CN 200910012477A CN 101942334 B CN101942334 B CN 101942334B
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Abstract
The invention discloses a production method of a molecular sieve dewaxing raw material. In the method, a coking light distillate raw material and hydrogen are contacted with a Mo-Ni hydrogenation catalyst under a hydrorefining condition to obtain naphtha fraction, kerosene fraction and diesel fraction through fractionation, wherein the kerosene fraction can be directly taken as the raw material of a molecular sieve dewaxing device, the naphtha fraction is taken as an ethylene cracking raw material, a reforming raw material or a synthetic ammonia raw material and can be also directly taken as a raw material for producing hydrogen, the diesel fraction is taken as a clean diesel blending component, and hydrogen-rich gas can be recycled. By adopting the method of the invention, poor-quality coking light distillate can be processed into the high value-added raw material for the molecular sieve dewaxing device for producing fluid wax by a simple process as well as good-quality naphtha and the clean diesel blending component as byproducts. The production method has the advantages of wide raw material adaptability, high product additional value, flexible operation, stable running and the like, and the method can effectively improve economic benefit of enterprises.
Description
Technical field
The present invention relates to a kind of production method of dewaxing by molecular sieve raw material, be applicable to that the oil refining enterprise of molecular sieve dewaxing unit is selected for use.
Background technology
Whiteruss (liquid wax) is important chemical material, has purposes widely, its production method mainly comprises methods such as Virahol-urea dewaxing and dewaxing by molecular sieve, wherein the dewaxing by molecular sieve arts demand is selected strict raw material, generally be virgin kerosene, simultaneously also need be through preprocessing process such as hydrogenation.
Virgin kerosene is mainly for the production of rocket engine fuel and partial solvent oil, because the virgin kerosene yield is lower, it is higher to obtain value-added content of product by it, and therefore, the virgin kerosene supply of raw material is very nervous.At present, though adopt the high-pressure hydrocracking technology can production part rocket engine fuel, along with the fast development of aviation industry, the supply of kerosene(oil)fraction be eased yet.Simultaneously, the high-pressure hydrocracking Technology Need is operated under High Temperature High Pressure, and investment and tooling cost are all higher, its competitive edge deficiency economically.
The delayed coking technology of residual oil is the important process process of heavy oil lighting in the refinery, because there is delayed coking unit the low therefore most of refineries of investment, coking distillate can fractionate out coker gasoline, coker gas oil and wax tailings, but all have characteristics of poor quality, that foreign matter content is high, must could use through behind the hydrogenation.General hydrogenated gasoline is as reformer feed or cracking of ethylene raw material, and hydrogenated diesel oil is as the derv fuel oil blend component.Though prior art also can make coking light distillate be fully used, added value of product is lower, and the coker gasoline hydrogenation unit is also through regular meeting's too fast ordinary production that influences device that rises owing to pressure falls; The coker gas oil hydrogenated oil is as vehicle fuel, because national regulation and control to market, profit margin is very little.
Though comprise kerosene(oil)fraction in the coking distillate, produce rocket engine fuel and still need special treatment process.CN1478867A discloses a kind of method of producing rocket engine fuel from coking distillate.This method adopts an acidic catalyst that contains zeolite at coker gas oil or coking gasoline and diesel raw material, under appropriate processing condition, coking stock oil is carried out hydrotreatment, and product can obtain the rocket engine fuel product after fractionation.Adopt this method can only produce the rocket engine fuel product, still can not produce the raw material of liquid wax apparatus as dewaxing by molecular sieve, and relatively poor to the adaptability of coking gasoline and diesel raw material, and it is bigger to handle cycloalkyl coking distillate difficulty inferior.
CN1458233A discloses a kind of method of coking full fraction oil hydrogenation refining.This method adopts the coking full fraction oil hydrogenation refining flow process, for the production of the cleaning cart diesel oil fuel.This method is not separated kerosene(oil)fraction, and kerosene(oil)fraction if isolate kerosene(oil)fraction, does not meet the specification of quality of rocket engine fuel as the part in the wide cut diesel fuel product yet, produces the liquid wax apparatus with dewaxing by molecular sieve and requires quality at a distance of farther.
So, except virgin kerosene, still do not have suitable dewaxing by molecular sieve to produce the raw material of liquid wax at present in this area.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of method that dewaxing by molecular sieve is produced liquid wax apparatus raw material that from coking light distillate, obtains, expand the raw material sources that the liquid wax apparatus is produced in the molecule dewaxing, alleviate virgin kerosene situation in short supply, improve the added value of product of coking light distillate, increase refinery's economic benefit.
The production method of dewaxing by molecular sieve raw material of the present invention comprises following content: coking light distillate raw material and hydrogen pass through Mo-Ni series hydrocatalyst bed in the hydrofining condition, the hydrofining reaction effluent is through gas-liquid separation, liquid phase after the gas-liquid separation fractionates out kerosene(oil)fraction, and this kerosene(oil)fraction is produced the raw material of liquid wax apparatus as dewaxing by molecular sieve.Wherein the initial boiling point of coking light distillate raw material is generally 30 ℃～70 ℃, and final boiling point is generally 245 ℃～370 ℃.It is Hydrobon catalyst that Hydrobon catalyst is selected Mo-Ni, and support of the catalyst is aluminum oxide or siliceous aluminum oxide, also contains nanometer grade silica in the support of the catalyst, and nano silicon accounts for 1%～10% of support of the catalyst weight.Catalyzer is formed and comprised: molybdenum oxide 10wt%～25wt%, nickel oxide 1.5wt%～5wt%, total metal contents in soil are at 11.5wt%～30wt%, and support of the catalyst is aluminum oxide or siliceous aluminum oxide.
Coking light distillate raw material hydrofining reaction condition is: hydrogen dividing potential drop 4.8MPa～10.0MPa is preferably 4.8MPa～8.0MPa; Temperature of reaction is 260 ℃～360 ℃, is preferably 280 ℃～350 ℃; Volume space velocity is 0.5h
-1～3.0h
-1, be preferably 1.0h
-1～2.0h
-1Hydrogen to oil volume ratio is 300～800, is preferably 300～600.
In the production method of dewaxing by molecular sieve raw material of the present invention, Hydrobon catalyst can use has the suitable commodity Hydrobon catalyst that requires, also can adopt existing method preparation by composition requirement, alumina raw material or siliceous alumina raw material and nano silicon are mixed and made into support of the catalyst, adopt pickling process supported active hydrogenation metal component to get final product then, can add suitable auxiliary agent in the catalyzer, as P, B, Ti, Zr etc.Nano silicon can use the commercially available prod, is 6～100nm nano silicon as particle diameter.
In the inventive method, the kerosene(oil)fraction sulphur content that obtains less than 1 μ/g, the bromine index quality index less than 150mgBr/100g oil, can directly be produced the raw material of liquid wax apparatus less than 1 μ g/g, nitrogen content as dewaxing by molecular sieve.By-product high-quality petroleum naphtha heats up in a steamer and the clean diesel cut simultaneously, and naphtha fraction can be used as cracking of ethylene raw material, reformer feed or synthetic ammonia feedstock, also can be directly as hydrogen feedstock, and diesel oil distillate can be used as the clean diesel blend component.
The invention has the advantages that: by adopting suitable raw material, technical process, processing condition and catalyzer, the dewaxing by molecular sieve that is worth lower coking light distillate direct production high added value can be produced the raw material of liquid wax apparatus, simultaneously by-product high-quality hydrotreated naphtha and cleaning cart diesel oil blending component.Technical process is simple, the operating severity of system is lower, easy coking when having overcome the independent hydrogenation of coker gasoline, short problem of operational cycle.Stock oil adaptability of the present invention is strong, can process various coking light distillates of different nature, and quality product can meet the demands fully.The device flexibility of operation is big, according to the difference of feedstock property, only needs suitable adjusting process condition to produce and satisfies the raw material that dewaxing by molecular sieve is produced the liquid wax apparatus.
Embodiment
Process of the present invention adopts the single hop single reactor, coking light distillate raw material and hydrogen directly enter reactor, reaction mass contacts with the catalyzer of high hydrogenation activity under the temperature and pressure condition that relaxes, remove the alkene of impurity such as sulphur in the liquid wax slop, nitrogen and saturated trace, product enters high-pressure separator, carries out gas-liquid separation in high-pressure separator.The isolated hydrogen-rich gas of hydrofining reaction effluent recycles, isolated liquid product enters the air lift fractionating system, the kerosene(oil)fraction that fractionates out is as the raw material of molecular sieve dewaxing unit, naphtha fraction is as cracking of ethylene raw material, reformer feed or synthetic ammonia feedstock, also can be directly as hydrogen feedstock, diesel oil distillate is as the clean diesel blend component.
The following examples will the invention will be further described.
Coking light distillate raw material Hydrobon catalyst is the Hydrobon catalyst that contains nano silicon in the carrier, method for preparing catalyst adopts pickling process, contain the nanometer titanium dioxide silicon components in the support of the catalyst, reactive metal and auxiliary agent content are the per-cent that accounts for catalyst weight.The Hydrobon catalyst FF-36 catalyzer of Fushun Petrochemical Research Institute's development and production has similarity, and its physico-chemical property sees Table 1.
Embodiment 1
Coking light distillate raw material 1 with enter reactor after hydrogen contacts, at reaction conditions be: hydrogen pressure component 6.8MPa, volume space velocity 1.6h
-1, 340 ℃ of temperature of reaction, hydrogen to oil volume ratio 450: 1, catalyzer uses the FF-36 Hydrobon catalyst.Stock oil character and test-results are listed in table 2.
By table 2 as seen, kerosene(oil)fraction can satisfy the requirement of molecular sieve dewaxing unit raw material fully; Hydrotreated naphtha can be used as the requirement of reformer feed, also can be used as cracking of ethylene raw material or hydrogen feedstock; Hydrogenated diesel oil is the cleaning cart diesel oil blending component.
Embodiment 2
Coking light distillate raw material 2 with enter reactor after hydrogen contacts, at reaction conditions be: hydrogen pressure component 7.5MPa, volume space velocity 1.5h
-1, 350 ℃ of temperature of reaction, hydrogen to oil volume ratio 500: 1, catalyzer uses A in the table 1.Stock oil character and test-results are listed in table 3.
By table 3 as seen, kerosene(oil)fraction can satisfy the requirement of molecular sieve dewaxing unit raw material fully; Hydrotreated naphtha can be used as the requirement of reformer feed, also can be used as cracking of ethylene raw material or hydrogen feedstock; Hydrogenated diesel oil is the cleaning cart diesel oil blending component.
Embodiment 3
Coking light distillate raw material 3 with enter reactor after hydrogen contacts, at reaction conditions be: hydrogen pressure component 6.0MPa, volume space velocity 1.5h
-1, 330 ℃ of temperature of reaction, hydrogen to oil volume ratio 550: 1, catalyzer uses B in the table 1.Stock oil character and test-results are listed in table 4.
By table 4 as seen, kerosene(oil)fraction can satisfy the requirement of molecular sieve dewaxing unit raw material fully; Hydrotreated naphtha can be used as the requirement of reformer feed, also can be used as cracking of ethylene raw material or hydrogen feedstock; Hydrogenated diesel oil is the cleaning cart diesel oil blending component.
Comparative example
Press CN1458233A embodiment 1 described method, document embodiment 1 does not fractionate out kerosene(oil)fraction, kerosene(oil)fraction partly enters gasoline fraction, part enters diesel oil distillate, the sulphur content that obtains gasoline fraction is 18 μ g/g, and nitrogen content is 20 μ g/g, and the sulphur content that obtains diesel oil distillate is 384 μ g/g, nitrogen content is 370 μ g/g, therefore the wherein sulphur content of kerosene(oil)fraction and the requirement that nitrogen content can not satisfy the molecular sieve dewaxing unit raw material certainly.
The character index request of table 1 catalyzer
| The catalyzer numbering | FF-36 | A | B |
| Reactive metal | MoO 3-NiO | MoO 3-NiO | MoO 3-NiO |
| Carrier | Al 2O 3-SiO 2 | Al 2O 3 | Al 2O 3 |
| The weight content of nano silicon in carrier, wt% | 2 | 5 | 8 |
| Active metallic content, wt% | 11.5～20.0 | MoO 3/18 NiO/3 | MoO 3/22 NiO/4 |
| Auxiliary agent, wt% | Zr/2 | P/3 | |
| Physical properties | |||
| Pore volume, ml/g | ≮0.32 | 0.38 | 0.35 |
| Specific surface area, m 2/g | ≮160 | 185 | 178 |
Table 2 embodiment 1 stock oil character and test-results
| Oil property | Raw material 1 | Hydrotreated naphtha | Kerosene(oil)fraction | Hydrogenated diesel oil |
| Density, g/cm 3 | 0.7640 | 0.7116 | 0.7953 | 0.8649 |
| Boiling range (IBP～EBP), ℃ | 60～331 | 58～178 | 180～242 | 243～330 |
| S，μg/g | 7583 | ＜0.5 | ＜1.0 | 5.6 |
| N，μg/g | 484 | ＜0.5 | ＜1.0 | 2.8 |
| Composition/v% | ||||
| Alkene | 38.2 | ＜1.0 | ||
| Aromatic hydrocarbons | 2.6 | |||
| Bromine index, mgBr/100g | 87.8 | |||
| Cetane value | 64 |
Table 3 embodiment 2 stock oil character and test-results
| Oil property | Raw material 2 | Hydrotreated naphtha | Kerosene(oil)fraction | Hydrogenated diesel oil |
| Density, g/cm 3 | 0.7835 | 0.7048 | 0.7812 | 0.8604 |
| Boiling range (IBP～EBP), ℃ | 34～346 | 36～176 | 178～240 | 243～347 |
| S，μg/g | 9300 | ＜0.5 | ＜1.0 | 8.7 |
| N，μg/g | 688 | ＜0.5 | ＜1.0 | 1.6 |
| Composition/v% | ||||
| Alkene | 27.3 | ＜1.0 | ||
| Aromatic hydrocarbons | 1.7 | |||
| Bromine index, mgBr/100g | 52.9 | |||
| Cetane value | 58 |
Table 4 embodiment 3 stock oil character and test-results
| Oil property | Raw material 3 | Hydrotreated naphtha | Kerosene(oil)fraction | Hydrogenated diesel oil |
| Density, g/cm 3 | 0.7611 | 0.7028 | 0.7809 | 0.8569 |
| Boiling range (IBP～EBP), ℃ | 54～368 | 58～180 | 178～239 | 242～367 |
| S，μg/g | 6541 | ＜0.5 | ＜1.0 | 5.6 |
| N，μg/g | 342 | ＜0.5 | ＜1.0 | 2.8 |
| Composition/v% | ||||
| Alkene | 33.8 | ＜1.0 | ||
| Aromatic hydrocarbons | 3.8 | |||
| Bromine index, mgBr/100g | 126.8 | |||
| Cetane value | 55 |
Claims (4)
1. the production method of a dewaxing by molecular sieve raw material, coking light distillate raw material and hydrogen pass through Mo-Ni series hydrocatalyst bed in the hydrofining condition, the hydrofining reaction effluent is through gas-liquid separation, liquid phase after the gas-liquid separation fractionates out kerosene(oil)fraction, it is characterized in that: this kerosene(oil)fraction is produced the raw material of liquid wax apparatus as dewaxing by molecular sieve, the initial boiling point of coking light distillate raw material is 30 ℃～70 ℃, final boiling point is 245 ℃～370 ℃, it is Hydrobon catalyst that Hydrobon catalyst is selected Mo-Ni, contain nanometer grade silica in the support of the catalyst, nano silicon accounts for 1%～10% of support of the catalyst weight; Coking light distillate raw material hydrofining reaction condition is: hydrogen dividing potential drop 4.8MPa～10.0MPa, and temperature of reaction is 260 ℃～360 ℃, volume space velocity is 0.5h
-1～3.0h
-1, hydrogen to oil volume ratio is 300～800.
2. in accordance with the method for claim 1, it is characterized in that: the composition of hydrogenation catalyst comprises: molybdenum oxide 10wt%～25wt%, nickel oxide 1.5wt%～5wt%, total metal contents in soil are at 11.5wt%～30wt%, and support of the catalyst is aluminum oxide or siliceous aluminum oxide.
3. in accordance with the method for claim 1, it is characterized in that: coking light distillate raw material hydrofining reaction condition is: hydrogen dividing potential drop 4.8MPa～8.0MPa, and temperature of reaction is 280 ℃～350 ℃, volume space velocity is 1.0h
-1～2.0h
-1, hydrogen to oil volume ratio is 300～600.
4. it is characterized in that in accordance with the method for claim 1: the particle diameter of nano silicon is 6～100nm in the hydrofining catalyst carrier.
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| CN1048037C (en) * | 1994-04-13 | 2000-01-05 | 中国石油化工总公司 | Heavy oil hydrotreatment catalyst |
| CN1488718A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Hydroprocessing catalyst for heavy oil and preparing method thereof |
| CN101085933A (en) * | 2006-06-07 | 2007-12-12 | 神华煤制油研究中心有限公司 | Coal liquefied oil boiling bed hydrogenation technique |
| CN101376832A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Preparation of bubbling bed hydrotreating catalyst |
| CN101376826A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Hydrogenation technological process for long distillate coking kerosene |
| CN101434864A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Coking light distillate hydrogenation modification method |
| CN101434851A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Mixed hydrogenation process for coker gasoline and coking kerosene |
-
2009
- 2009-07-09 CN CN 200910012477 patent/CN101942334B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048037C (en) * | 1994-04-13 | 2000-01-05 | 中国石油化工总公司 | Heavy oil hydrotreatment catalyst |
| CN1488718A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Hydroprocessing catalyst for heavy oil and preparing method thereof |
| CN101085933A (en) * | 2006-06-07 | 2007-12-12 | 神华煤制油研究中心有限公司 | Coal liquefied oil boiling bed hydrogenation technique |
| CN101376832A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Preparation of bubbling bed hydrotreating catalyst |
| CN101376826A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Hydrogenation technological process for long distillate coking kerosene |
| CN101434864A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Coking light distillate hydrogenation modification method |
| CN101434851A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Mixed hydrogenation process for coker gasoline and coking kerosene |
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