CN102311804B - Paraffin wax hydrogenation refining method - Google Patents
Paraffin wax hydrogenation refining method Download PDFInfo
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- CN102311804B CN102311804B CN201010222054.4A CN201010222054A CN102311804B CN 102311804 B CN102311804 B CN 102311804B CN 201010222054 A CN201010222054 A CN 201010222054A CN 102311804 B CN102311804 B CN 102311804B
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- reduction catalyst
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Abstract
The invention discloses a paraffin wax one-step hydrogenation method. In the method, coarse paraffin wax is used as a raw material, a reduction catalyst is used, the reactions for removing sulfur, nitrogen, oxygen and saturation of aromatic hydrocarbons are accomplished by using one reduction catalyst, and the hydrogenation reaction conditions include: the reaction pressure is 4 to 10MPa, the temperature is 200 to 300 DEG C, the volume space velocity is 0.2 to 3.5h<-1>, and the hydrogen to oil volume ratio ranges from 100:1 to 800:1. The reduction catalyst is a reduction nickel catalyst. The method disclosed by the invention has the advantages of short flow, simple and flexible operation, low cost, environment friendliness and the like.
Description
Technical field
The present invention has narrated a kind of method of hydrorefining paraffin wax, particularly uses reduction catalyst one-stage hydrogenation to produce the method for food paraffin wax.
Background technology
Paraffin is the solid petroleum products being obtained after solvent dewaxing and de-oiling by vacuum distillate, and take normal paraffin as main, carbon number is conventionally between C20～C40.Be widely used with its intrinsic special physical and chemical performance.But unpurified paraffin contains a small amount of impurity and condensed-nuclei aromatics, unfavorable to people's health.Therefore, paraffin needs suitable treating process.
The refining method that adopts bleaching earth adsorption of early stage paraffin, but replaced by hydrofining gradually because of shortcomings such as its technique backwardness, poor product quality, contaminate environment.
Hydrorefining paraffin wax is the heteroatoms such as sulphur, nitrogen the saturated condensed-nuclei aromatics removing when the character such as oleaginousness, penetration degree, fusing point do not change wherein.Therefore, technical process, catalyzer and operational condition all have a great impact quality product.
CN02109666.X discloses a kind of method of hydrorefining paraffin wax, adopts the mode of single hop, two kinds of catalyzer series connection grading loadings.Under proper condition, paraffin raw material first contacts with Mo-Ni catalyzer, then mixes and contacts with W-Ni catalyzer with cold hydrogen, and products therefrom, through separating, taking off after taste, obtains paraffin wax product.But the method adopts sulphided state catalyzer, and between two beds, utilize cold hydrogen to reduce stream temperature, sulfide type catalyst arene saturating activity under normal circumstances can not meet the demands, if make aromatic hydrocarbons saturated better, will improve operating severity, such as improving reaction pressure, reduce air speed; And utilize cold hydrogen to reduce also more difficult control of stream temperature.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of one-stage hydrogenation production food paraffin wax.
The method of paraffin one-stage hydrogenation of the present invention is take scale wax as raw material, uses reduction catalyst, adopts single hop medium-pressure hydrocracking technology to produce high-grade paraffin, adopts a kind of reduction catalyst to complete desulfurization, nitrogen, oxygen and aromatic saturation reaction.
Catalyzer is reduced form nickel catalyzator.Preferably Ni/Al
2o
3catalyzer, active component nickel is supported on alumina supporter, and catalyzer nickeliferous (in nickel oxide) is generally 20wt%～70wt%, and surplus is carrier.Described Ni/Al
2o
3the character of catalyzer is as follows: specific surface area 120～200m
2/ g, pore volume 0.2～0.4ml/g.This Ni/Al
2o
3before catalyzer uses, catalyzer reduce to processing, reduction process be at 2～8MPa preferably under 3～5MPa, within the scope of 120 to 300 ℃, use hydrogen treat 18 to 30 hours.
Reaction conditions is generally: control bed layer pressure 4MPa～10MPa, preferably 5MPa～9MPa; 200～300 ℃ of temperature, are preferably 230～290 ℃, volume space velocity 0.2～3.5h
-1, be preferably 0.5～1.5h
-1hydrogen to oil volume ratio 100: 1～800: 1, preferably 200: 1～500: 1; After reaction product separation, de-taste, obtain food paraffin wax product.
The paraffin that uses the inventive method to produce, meets People's Republic of China's food paraffin wax standard-required.
In hydrorefining paraffin wax process, the reaction that removes of the impurity such as sulphur, nitrogen, oxygen is mainly subject to kinetic control, and temperature is the key factor that determines desulfurization, denitrogenation, deoxygenation speed, and temperature is more high more favourable; And aromatic saturation reaction is thermopositive reaction, be subject to thermodynamics and kinetics co-controlling, temperature of reaction is high, aromatic saturation molecular balance low conversion rate.Prior art is difficult to meet refining requirement.Sulphur in raw material is generally the poisonous substance of reduced form nickel catalyzator, the reduced form nickel catalyzator that the inventive method obtains in the lower reduction of suitable condition (low-pressure low-temperature) has certain resistance to sulphur effect, can realize one stage hydrofining and produce high quality paraffin.
Compared with prior art, the inventive method is all carried out impurity removal and aromatic saturation reaction under top condition, has short, simple to operate flexible, low, the eco-friendly advantage of cost of flow process.
Embodiment
Further set forth content of the present invention below in conjunction with embodiment.The paraffin raw material that the embodiment of the present invention and comparative example adopt is No. 58 waxes of Daqing crude oil, No. 60 waxes and No. 66 waxes.Paraffin character is in table 1.
The condensed-nuclei aromatics content of the embodiment of the present invention and comparative example characterizes with simplified method ultraviolet absorptivity.
In the embodiment of the present invention, composition and the character of catalyzer are as follows: the content of Ni is 47.76wt%, and surplus is carrier A l
2o
3, specific surface area 172m
2/ g, pore volume 0.246ml/g.
Embodiment 1
No. 58 waxes of Daqing crude oil that adopt one-stage hydrogenation art breading oil-containing 0.43wt%, catalyst reduction process is under pressure 3MPa,, processes 12 hours at 300 ℃ by hydrogen treat 12 hours at 200 ℃.
After catalyst reduction is processed, adjusting process condition is carried out the hydrogenation of paraffin, and the processing condition that adopt and product property are in table 2, and products obtained therefrom meets the requirement of food paraffin wax national standard.
Embodiment 2
The handled paraffin of the present embodiment is No. 60 scale waxs of oil-containing 0.47wt%, and processing condition used are in table 2, catalyst reduction process be under pressure 4MPa and 220 ℃ of temperature at carry out 20 hours, remaining is with embodiment 1, products obtained therefrom character is in table 2.
Embodiment 3
The handled paraffin of the present embodiment is No. 66 scale waxs of oil-containing 0.40wt%, and processing condition used are in table 2, and catalyst reduction process is to carry out 24 hours at 180 ℃ of pressure 5MPa and temperature, and remaining is with embodiment 1, and products obtained therefrom character is in table 2.
Comparative example 1
With one-stage serial technique and the catalyzer of CN02109666.X embodiment 2, the first beds adopts Mo-Ni catalyzer, and the second beds adopts W-Ni catalyzer, processes the raw material in the embodiment of the present invention 1, and processing condition and product property are in table 3.
Comparative example 2
With one-stage serial technique and the catalyzer of CN02109666.X embodiment 2, the first beds adopts Mo-Ni catalyzer, and the second beds adopts W-Ni catalyzer, processes the raw material in the embodiment of the present invention 2, and processing condition and product property are in table 3.
Comparative example 3
With one-stage serial technique and the catalyzer of CN02109666.X embodiment 2, the first beds adopts Mo-Ni catalyzer, and the second beds adopts W-Ni catalyzer, processes the raw material in the embodiment of the present invention 3, and processing condition and product property are in table 3.
Table 1 paraffin raw material character
Table 2 embodiment product property
Table 3 comparative example product property
Can find out from embodiment and comparative example, while processing identical raw material, all, under suitable condition, the ultraviolet absorptivity of the hydrogenation products that the inventive method obtains (representing to go back the aromatic hydrogenation degree of depth) is starkly lower than comparative example (general low more than 10%) more.
Claims (4)
1. the method for a paraffin one-stage hydrogenation, take scale wax as raw material, it is characterized in that: use reduction catalyst, adopt a kind of reduction catalyst to complete desulfurization, nitrogen, oxygen and aromatic saturation reaction, hydrogenation conditions is: reaction pressure 4MPa～10MPa, 200～300 ℃ of temperature, volume space velocity 0.2～3.5h
-1, hydrogen to oil volume ratio 100: 1～800: 1; Reduction catalyst is reduced form nickel catalyzator; Reduced form nickel catalyzator is Ni/Al
2o
3catalyzer, active component nickel is supported on alumina supporter, nickeliferous as 20wt%～70wt% take nickel oxide catalyzer, and surplus is carrier; Ni/Al
2o
3before catalyzer uses, catalyzer reduce to processing, reduction process under 2～5MPa, within the scope of 120 to 300 ℃, use hydrogen treat 18 to 30 hours.
2. it is characterized in that in accordance with the method for claim 1: Ni/Al
2o
3the character of catalyzer is as follows: specific surface area 120～200m
2/ g, pore volume 0.2～0.4ml/g.
3. it is characterized in that in accordance with the method for claim 1: reduction process is carried out under 3～5MPa.
4. in accordance with the method for claim 1, it is characterized in that hydrogenation conditions is: reaction pressure is 5MPa～9MPa, temperature is 230～290 ℃, volume space velocity 0.5～1.5h
-1, hydrogen to oil volume ratio 200～500: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010222054.4A CN102311804B (en) | 2010-07-07 | 2010-07-07 | Paraffin wax hydrogenation refining method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010222054.4A CN102311804B (en) | 2010-07-07 | 2010-07-07 | Paraffin wax hydrogenation refining method |
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| CN102311804A CN102311804A (en) | 2012-01-11 |
| CN102311804B true CN102311804B (en) | 2014-05-21 |
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| CN201010222054.4A Active CN102311804B (en) | 2010-07-07 | 2010-07-07 | Paraffin wax hydrogenation refining method |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111978989B (en) * | 2019-05-23 | 2021-12-07 | 中国石油化工股份有限公司 | Method for stably producing fully refined paraffin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1339984A (en) * | 1999-02-12 | 2002-03-13 | 帝国化学工业公司 | Nickel calalyst on transition alumina |
| CN1769395A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Method for producing white microcrystalline wax by one-step hydrogenation |
| CN101147866A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Paraffin hydrogenation refined catalyst and its preparing process and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1015902B (en) * | 1988-08-20 | 1992-03-18 | 北京大学 | Catalyst for hydrodesulfurization of hydrocarbons |
| CN101249440B (en) * | 2007-12-21 | 2010-12-15 | 中国科学院山西煤炭化学研究所 | Aromatic hydrocarbons or hydrogenation adsorption desulfurize catalyst containing aromatic hydrocarbons raw material and preparing method and applications |
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2010
- 2010-07-07 CN CN201010222054.4A patent/CN102311804B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1339984A (en) * | 1999-02-12 | 2002-03-13 | 帝国化学工业公司 | Nickel calalyst on transition alumina |
| CN1769395A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Method for producing white microcrystalline wax by one-step hydrogenation |
| CN101147866A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Paraffin hydrogenation refined catalyst and its preparing process and application |
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