CN104312614B - The complexometry denitrogenation tail oil treatment process of lubricant base - Google Patents

The complexometry denitrogenation tail oil treatment process of lubricant base Download PDF

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CN104312614B
CN104312614B CN201410594078.0A CN201410594078A CN104312614B CN 104312614 B CN104312614 B CN 104312614B CN 201410594078 A CN201410594078 A CN 201410594078A CN 104312614 B CN104312614 B CN 104312614B
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denitrogenation
oil
tail oil
treatment process
aqueous solution
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CN104312614A (en
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王虹
田同虎
宋以常
付成刚
王明锦
蔡卡莎
李翠清
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Beijing Institute of Petrochemical Technology
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Beijing Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/02—Non-metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1062—Lubricating oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The present invention relates to a kind of denitrogenation tail oil treatment process of lubricant base, comprise following steps: a) make the aqueous solution of alkali mix to obtain denitrogenation tail oil mixture with denitrogenation tail oil heat; B) water-oil phase separation is carried out to denitrogenation tail oil mixture; C) oil phase is reclaimed.Method of the present invention can process the denitrogenation tail oil that the denitrogenation of lubricant base complexometry produces, and achieves the Appropriate application to described denitrogenation tail oil, has both decreased the pollution to environment, also effectively can utilize waste resource, produce considerable economic benefit.

Description

The complexometry denitrogenation tail oil treatment process of lubricant base
Technical field
The present invention relates to the complexometry denitrogenation tail oil treatment process of lubricant base.
Background technology
Oxidation stability is one of main physical property of lubricant base, is the key affecting Working Life of Lubricating Oil, and the oxidation stability improving lubricant base receives publicity always.Result of study shows, the oxidation stability of lubricant base and its chemical constitution have close ties, and some sulfide is natural antioxidative components, has certain restraining effect, also can improve oil product resistance to emulsification and the susceptibility to additive simultaneously to oxidation; And nitride especially basic nitrogen compound (BNC) can cause or promote the formation of free radical, and accelerating the consumption of oil oxidation and oxidation inhibitor, is one of principal element affecting its oxidation stability.
Lubricant base is a lot of for the method removing nitrogenous compound in producing, and is mainly divided into hydrodenitrification and Non-hydrogenation technology.High for nitrogen content, low-sulfur content lubricant base, should adopt Non-hydrogenation technology method to remove nitrogenous compound in base oil.Basic nitrogen compound in lubricant base exists mainly with ring texture greatly, mainly contains aliphatic amide, pyridine, quinoline and aniline; When basic nitrogen compound is more stable during Individual existence in oil product, be difficult to react, but owing to there are a large amount of acidic components in oil product, as acid sulphide, non basic nitrogen compound etc., the existence of basic nitrogen compound can promote these substance reactions, thus plays katalysis.Owing to the nitrogen-atoms in basic nitrogen compound there being a pair unscreened lone-pair electron, it can with the denitrfying agent with proton feature, or there is outer unoccupied orbital, transition metal ion compound generation complex reaction that ionic radius is less, form complex compound, and some solvents can be dissolved in, the object removing basic nitrogen compound can be reached like this.Complexometry denitrogenation is the good method of current denitrification effect, and it adopts the basic nitrogen compound in the denitrfying agent and oil product being mainly phosphate compound to form complex compound, reaches the object removing nitrogenous compound.The method is high to basic nitrogen compound decreasing ratio, and product yield is high, but also produces a certain amount of reluctant waste residue, i.e. denitrogenation tail oil simultaneously, and these waste residues all do not dissolve in coil neutralization water, as dealt with improperly serious environment pollution.
Therefore, to the processing and utilizing of complexometry denitrogenation tail oil, be the problem needing at present to solve.
Summary of the invention
An object of the present invention is to provide a kind of complexometry denitrogenation tail oil treatment process of lubricant base, it comprises following steps:
A) aqueous solution of alkali is made to mix to obtain denitrogenation tail oil mixture with denitrogenation tail oil heat;
B) water-oil phase separation is carried out to denitrogenation tail oil mixture;
C) oil phase is reclaimed.
The phosphorus content of the oil content in described final denitrogenation tail oil lower than 0.15%, preferably lower than 0.1%, more preferably less than 0.06%, based on the quality meter of this oil content in often kind of situation.
Method of the present invention can process the denitrogenation tail oil that the denitrogenation of lubricant base complexometry produces, its by denitrogenation tail oil with carry out water-oil phase after the aqueous solution of alkali again and be separated, and reclaim the oil content in oil phase.The present invention by containing the aqueous phase of the denitrfying agent component being mainly phosphate compound with the alkali added, recycles after dewatering, as done the raw material of chemical fertilizer simultaneously.Thus, achieve the Appropriate application to described denitrogenation tail oil, both decreased the pollution to environment, also effectively can utilize waste resource, produce considerable economic benefit.
Embodiment
The denitrogenation tail oil treatment process of lubricant base of the present invention, it comprises following steps:
A) aqueous solution of alkali is made to mix to obtain denitrogenation tail oil mixture with denitrogenation tail oil heat;
B) water-oil phase separation is carried out to denitrogenation tail oil mixture;
C) oil phase is reclaimed.
Can directly use as the oil content in final denitrogenation tail oil according to the oil phase that the method for water-oil phase separation reclaims, or through using as the oil content in final denitrogenation tail oil after further aftertreatment.Therefore, preferably, the inventive method also comprises the step of the oil phase that aftertreatment is reclaimed.
Oil content in described denitrogenation tail oil can be used as the stock oil of catalytic cracking, shortening, delayed coking or the doping composition as the raw material with above-mentioned technique, particularly advantageously separately for above technique, in addition, also can be used as oil fuel.In a preferred embodiment of the inventive method, the oil phase that aftertreatment is reclaimed obtains the oil content in final denitrogenation tail oil.Described aftertreatment be dry step is carried out to the oil phase reclaimed or desolventize, dry step.Specifically, with regard to the water-oil phase separation of EDN, the drying to oil phase is referred to; And with regard to the water-oil phase of solvent extration is separated, refer to oil content in oil phase and solvent be separated and oil content dry.
In described final denitrogenation tail oil, the phosphorus content of oil content is lower than 0.15%, preferably lower than 0.1%, more preferably less than 0.06%, based on the quality meter of this oil content in often kind of situation.
The complexometry denitrogenation tail oil of the lubricant base of the inventive method is for adopting the denitrfying agent being mainly phosphate compound to the waste residue produced in lubricant base (such as from solvent deasphalting, furfural treatment, benzol-kentone dewaxing technique) denitrogenation processing.
The inventive method step a) in, described alkali can be mineral alkali or organic bases, or its mixture; Inorganic basis, as the oxyhydroxide for potassium metal, sodium, calcium, magnesium or ammonium, preferably uses the aqueous solution of described mineral alkali, more preferably KOH or NH 4the aqueous solution of OH, or both mixtures; Organic bases such as, as being alkylamine, the primary alkyl such as ethamine, Tri N-Propyl Amine amine, or alcohol amine compound, as thanomin, diethanolamine, trolamine etc.
In a preferred embodiment of the inventive method, the aqueous solution of alkali is KOH and/or NH 4the aqueous solution of OH, its mass concentration can be 2-25%, preferred 5-25%, more preferably 10-20%; KOH and NH when if both are used in combination 4oH is according to 5:1-30:1, and preferred 10:1-25:1, more preferably the mass ratio of 10:1-20:1 mixes.
The inventive method step a) in, the aqueous solution of described alkali and the hot mixing temperature of denitrogenation tail oil are 25-95 DEG C, preferred 45-85 DEG C, preferred 60-80 DEG C; Described mixing time is 5-90 minute, preferred 15-90 minute, more preferably 25-60 minute.
The inventive method step a) in, the add-on of the aqueous solution of described alkali according to the following formula (I) calculates:
m j＝m y/[(T-289) 0.446×(t/32.909) 0.284](I)
Wherein m jfor the quality that the aqueous solution of the alkali added calculates by the pure substance of alkali;
M yfor the quality of denitrogenation tail oil;
T is the hot mixing temperature of 298-368K;
T is the mixing time 300-5400 second of basic component and denitrogenation tail oil.
Above experimental formula is for adopting method of least squares, and return experimental data in following table 1 and obtain, the experimental formula obtained and experimental data are coincide good, and error is ± 2%.
Basic component under table 1 different condition and denitrogenation tail oil combined amount
Sequence number m j[Kg] m y[Kg] T[K] t[s]
1 0.166 2 318 900
2 0.117 2 318 3600
3 0.113 2 333 1800
4 0.0952 2 333 3600
5 0.102 2 350 1500
6 0.0851 2 350 3600
7 0.427 5 320 900
8 0.303 5 333 1500
9 0.215 5 350 3600
In one embodiment of the invention, step is a) 318-368K at the temperature T of formula (I), and churning time t carries out under the condition of more than 900 seconds.
In another embodiment of the invention, step is a) 333-358K at the temperature T of formula (I), and churning time t carries out under the condition of 1500-3600 second.
In a preferred embodiment of the inventive method, step a) is implemented as follows: denitrogenation tail oil is heated to 25-40 DEG C, then the aqueous solution of the alkali prepared in advance is added, stir and be heated to 60-95 DEG C simultaneously, stir more than 30 minutes, the complex decomposes formed with the nitrogenous compound made in Complex denitrogenation process in denitrfying agent and lubricant base; Wherein the aqueous solution of alkali is the amount first calculating soda ash according to formula (I), then is formulated as the aqueous solution of desired concn.
Step b in the inventive method) in, the water-oil phase of denitrogenation tail oil mixture is separated and can adopts EDN.Electrical dehydrator used is not particularly limited, and can be the commercially available electrical dehydrator that any applicable water-oil phase is separated.
Step b in the inventive method) in, water-oil phase is separated also can adopt solvent extration, and extraction solvent can be sherwood oil, heptane, pentane or its mixture of gasoline, diesel oil, boiling range 60-120 DEG C.
Step b in the inventive method) in, described solvent is that 1:1-1:5 adds according to the mass ratio of denitrogenation tail oil and solvent, and preferred 1:1.5-1:4, more preferably 1:2-1:4 adds.
Step c in the inventive method) in, aftertreatment can be carried out to the oil phase of described recovery, with regard to the water-oil phase separation of EDN, refer to the drying to oil phase; And with regard to the water-oil phase of solvent extration is separated, refer to oil content in oil phase and solvent be separated and oil content dry.
In the present invention, if illustrate without contrary, then operate in condition of normal pressure and carry out.
In the present invention, unless otherwise indicated, otherwise all numbers, percentage ratio all in mass.
In the present invention, material used is known substance, can buy or be synthesized by known method.
In the present invention, equipment therefor or equipment are the known conventional equipment in described field or equipment, all can buy.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment
Raw material information in embodiment 1-4 is as follows:
Potassium hydroxide, ammoniacal liquor and heptane are all purchased from Chemical Reagent Co., Ltd., Sinopharm Group; The sherwood oil of boiling range 60-120 DEG C, purchased from Shanghai Ya Bang Chemical Co., Ltd.; Gasoline, purchased from Hua Feng petrochemical complex company limited of Shenzhen.
Embodiment 1
Take certain factory to subtract three line denitrogenation tail oil 2000g and add in reactor, stir and be heated to 30 DEG C, add the KOH aqueous solution 1660g of 10% of preparation under then stirring, be warming up to 45 DEG C and stir 15 minutes, obtaining denitrogenation tail oil mixture.The denitrogenation tail oil mixture of gained is introduced electrical dehydrator (purchased from Beijing Ke Anbo Science and Technology Ltd.), and be separated into aqueous phase and oil phase wherein, the oil phase drying of gained is recycled oil content, and described recovery oil content character is in table 1.
Embodiment 2
Take certain factory to subtract three line denitrogenation tail oil 2000g and add in reactor, stir and be heated to 30 DEG C, add the KOH aqueous solution 585g of 20% of preparation under then stirring, be warming up to 45 DEG C and stir 60 minutes, obtaining denitrogenation tail oil mixture.In the denitrogenation tail oil mixture of gained, add extraction solvent sherwood oil 2000g, sedimentation forms aqueous phase and oil phase, isolates oil phase and decompression removes wherein sherwood oil, then dry, be recycled oil content, described recovery oil content character is in table 1.
Embodiment 3
Take certain factory to subtract three line denitrogenation tail oil 2000g and add in reactor, stir and be heated to 30 DEG C, add the KOH aqueous solution 1130g of 10% of preparation under then stirring, be warming up to 60 DEG C and stir 30 minutes, obtaining denitrogenation tail oil mixture.In the denitrogenation tail oil mixture of gained, add extraction solvent heptane 3000g, sedimentation forms aqueous phase and oil phase, isolates oil phase and decompression removes wherein heptane, then dry, be recycled oil content, described recovery oil content character is in table 1.
Embodiment 4
Take certain factory to subtract three line denitrogenation tail oil 2000g and add in reactor, stir and be heated to 30 DEG C, add the KOH aqueous solution 952g of 10% of preparation under then stirring, be warming up to 60 DEG C and stir 60 minutes, obtaining denitrogenation tail oil mixture.In the denitrogenation tail oil mixture of gained, add extraction solvent gasoline 2600g, sedimentation forms aqueous phase and oil phase, isolates oil phase and decompression removes wherein gasoline, then dry, be recycled oil content, described recovery oil content character is in table 1.
Embodiment 5
Taking certain factory second line of distillation denitrogenation tail oil 2000g adds in reactor, stirs and is heated to 30 DEG C, adds the NH of 15% under then stirring 4oH aqueous solution 680g, is warming up to 77 DEG C and stirs 25 minutes, obtains denitrogenation tail oil mixture.In the denitrogenation tail oil mixture of gained, add extraction solvent gasoline 2600g, sedimentation forms aqueous phase and oil phase, isolates oil phase and decompression removes wherein gasoline, then dry, be recycled oil content, described recovery oil content character is in table 1.
Embodiment 6
Taking certain factory second line of distillation denitrogenation tail oil 2000g adds in reactor, stirs and is heated to 30 DEG C, adds the NH of 10% under then stirring 4oH aqueous solution 851g, is warming up to 77 DEG C and stirs 60 minutes, obtains denitrogenation tail oil mixture.In the denitrogenation tail oil mixture of gained, add extraction solvent gasoline 3000g, sedimentation forms aqueous phase and oil phase, isolates oil phase and decompression removes wherein gasoline, then dry, be recycled oil content, described recovery oil content character is in table 1.
Embodiment 7
Taking certain factory second line of distillation denitrogenation tail oil 5000g adds in reactor, stirs and is heated to 35 DEG C, adds the KOH aqueous solution 4270g of 10%, be warming up to 45 DEG C and stir 15 minutes, obtaining denitrogenation tail oil mixture under then stirring.In the denitrogenation tail oil mixture of gained, add extraction solvent gasoline 5500g, sedimentation forms aqueous phase and oil phase, isolates oil phase and decompression removes wherein gasoline, then dry, be recycled oil content.
Embodiment 8
Taking certain factory second line of distillation denitrogenation tail oil 5000g adds in reactor, stirs and is heated to 35 DEG C, adds the KOH aqueous solution 3030g of 10%, be warming up to 60 DEG C and stir 25 minutes, obtaining denitrogenation tail oil mixture under then stirring.In the denitrogenation tail oil mixture of gained, add extraction solvent gasoline 6000g, sedimentation forms aqueous phase and oil phase, isolates oil phase and decompression removes wherein gasoline, then dry, be recycled oil content.
Embodiment 9
Taking certain factory second line of distillation denitrogenation tail oil 5000g adds in reactor, stirs and is heated to 35 DEG C, adds the KOH aqueous solution 2150g of 10%, be warming up to 77 DEG C and stir 60 minutes, obtaining denitrogenation tail oil mixture under then stirring.In the denitrogenation tail oil mixture of gained, add extraction solvent gasoline 6000g, sedimentation forms aqueous phase and oil phase, isolates oil phase and decompression removes wherein gasoline, then dry, be recycled oil content.
Reclaim the mensuration of the character of oil content
Divide the refiltered oil in embodiment 1-6 and carry out following performance test, relevant nature is in table 1:
(1) acid number reclaiming oil content measures according to GB/T264;
(2) carbon residue reclaiming oil content measures according to GB/T17144;
(3) metal content reclaiming oil content adopts aas determination;
(4) the P content reclaiming oil content adopts X-ray fluorescence spectra assay;
(5) S and the N content that reclaim oil content adopt sulphur blood urea/nitrogen analyzer (German Elementar company, sulphur nitrogen elemental analyser traceSNcube) to measure;
(6) rate of recovery reclaiming oil content obtains with the Mass Calculation reclaiming oil content by weighing denitrogenation tail oil.
Table 1 reclaims the character of oil content
From the character of the recovery oil content in table 1, the sulphur contained by oil content of final denitrogenation tail oil that the present invention reclaims, nitrogen, phosphorus and metal content are lower, its can separately as catalytic cracking, shortening, delayed coking stock oil or can be used as the doping composition with the raw material of above-mentioned technique, particularly advantageously can separately for above technique, in addition, also directly oil fuel can be used as.In addition, for the aqueous phase in above-described embodiment, separated by water wherein, residuum is the mixture of phosphorus, the mixture of nitrogen compound or phosphorus, potassium compound, can as the raw material producing chemical fertilizer.

Claims (21)

1. a complexometry denitrogenation tail oil treatment process for lubricant base, comprises following steps:
A) aqueous solution of alkali is made to mix to obtain denitrogenation tail oil mixture with denitrogenation tail oil heat;
B) water-oil phase separation is carried out to denitrogenation tail oil mixture;
C) oil phase is reclaimed;
The add-on of wherein said alkali calculates according to formula (I):
m j＝m y/[(T-289) 0.446×(t/32.909) 0.284](I)
Wherein m jfor the quality that the aqueous solution of the alkali added calculates by the pure substance of alkali;
M yfor the quality of denitrogenation tail oil;
T is the hot mixing temperature of 298-368K;
T is the aqueous solution of alkali and the mixing time of denitrogenation tail oil, and it is 300-5400 second.
2. treatment process according to claim 1, characterized by further comprising the step of the oil phase that aftertreatment is reclaimed; Described aftertreatment be dry step is carried out to the oil phase reclaimed or desolventize, dry step.
3. the treatment process described in claim 1 or 2, is characterized in that described alkali is mineral alkali or organic bases, or its mixture; Mineral alkali is the oxyhydroxide of potassium metal, sodium, calcium, magnesium or ammonium; Organic bases is alkylamine or alkanolamine compound.
4. treatment process according to claim 3, is characterized in that described alkali is the aqueous solution of mineral alkali.
5. treatment process according to claim 4, is characterized in that the aqueous solution of described mineral alkali is KOH or NH 4the aqueous solution of OH, or both mixtures.
6. treatment process according to claim 3, is characterized in that organic bases is thanomin, diethanolamine, ethamine, Tri N-Propyl Amine.
7. treatment process according to claim 5, is characterized in that KOH and/or NH 4the mass concentration of the aqueous solution of OH can be 2-25%; KOH and NH during both used in combination 4oH mixes according to 5:1-30:1.
8. treatment process according to claim 7, is characterized in that KOH and/or NH 4the mass concentration of the aqueous solution of OH can be 5-25%.
9. treatment process according to claim 8, is characterized in that KOH and/or NH 4the mass concentration of the aqueous solution of OH can be 10-20%.
10. treatment process according to claim 7, KOH and NH when it is characterized in that both used in combination 4oH mixes according to 10:1-25:1.
11. treatment processs according to claim 10, KOH and NH when it is characterized in that both used in combination 4oH mixes according to 10:1-20:1.
Treatment process described in 12. claims 1 or 2, is characterized in that the hot mixing temperature of described basic component and denitrogenation tail oil is 45-85 DEG C; Described mixing time 15-90 minute.
13. treatment processs according to claim 12, is characterized in that the hot mixing temperature of described basic component and denitrogenation tail oil is 60-80 DEG C.
14. treatment processs according to claim 12, is characterized in that the mixing time of described basic component and denitrogenation tail oil is 25-60 minute.
15. treatment processs according to claim 1, it is characterized in that, in formula (I), temperature T is 318-368K, and churning time t are more than 900 seconds.
16. treatment processs according to claim 15, is characterized in that temperature T is 333-358K, and churning time t is 1500-3600 second.
Treatment process described in 17. claims 1 or 2, is characterized in that water-oil phase is separated and adopts EDN.
Treatment process described in 18. claims 1 or 2, it is characterized in that water-oil phase is separated and adopt solvent extration, its extraction solvent is sherwood oil, heptane, pentane or its mixture of gasoline, diesel oil, boiling range 60-120 DEG C.
19. treatment processs according to claim 18, is characterized in that described solvent is that 1:1-1:5 adds according to the mass ratio of denitrogenation tail oil and solvent.
20. treatment processs according to claim 19, is characterized in that described solvent is that 1:1.5-1:4 adds according to the mass ratio of denitrogenation tail oil and solvent.
21. treatment processs according to claim 20, is characterized in that described solvent is that 1:2-1:4 adds according to the mass ratio of denitrogenation tail oil and solvent.
CN201410594078.0A 2014-10-29 2014-10-29 The complexometry denitrogenation tail oil treatment process of lubricant base Active CN104312614B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1103660A (en) * 1994-10-10 1995-06-14 中国石油化工总公司 After-treatment of sulfur-preserving and denitrifying additive for base oil of lubricating oil
CN102485842A (en) * 2010-12-03 2012-06-06 中国石油天然气股份有限公司 Processing method for supplementing refined coker gas oil by fixed bed

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1103660A (en) * 1994-10-10 1995-06-14 中国石油化工总公司 After-treatment of sulfur-preserving and denitrifying additive for base oil of lubricating oil
CN102485842A (en) * 2010-12-03 2012-06-06 中国石油天然气股份有限公司 Processing method for supplementing refined coker gas oil by fixed bed

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