CN108203599A - Method for removing aromatic hydrocarbon from synthetic oil - Google Patents
Method for removing aromatic hydrocarbon from synthetic oil Download PDFInfo
- Publication number
- CN108203599A CN108203599A CN201611169547.XA CN201611169547A CN108203599A CN 108203599 A CN108203599 A CN 108203599A CN 201611169547 A CN201611169547 A CN 201611169547A CN 108203599 A CN108203599 A CN 108203599A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- air inlet
- inlet pipe
- hydrogenation
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 53
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 119
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 119
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 118
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 95
- 239000003921 oil Substances 0.000 claims abstract description 84
- 239000000047 product Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000002199 base oil Substances 0.000 claims abstract description 25
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- 238000005520 cutting process Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000007791 liquid phase Substances 0.000 claims description 23
- 210000000988 bone and bone Anatomy 0.000 claims description 17
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000010687 lubricating oil Substances 0.000 abstract description 4
- 230000001502 supplementing effect Effects 0.000 abstract 2
- 238000004821 distillation Methods 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 230000000153 supplemental effect Effects 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 65
- 239000002994 raw material Substances 0.000 description 26
- 229930195733 hydrocarbon Natural products 0.000 description 21
- 239000004215 Carbon black (E152) Substances 0.000 description 19
- 150000002430 hydrocarbons Chemical class 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 13
- 229920013639 polyalphaolefin Polymers 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 101150092791 PAO4 gene Proteins 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- -1 then Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000000819 phase cycle Methods 0.000 description 1
- 238000000079 presaturation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/04—Well-defined hydrocarbons aliphatic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/02—Well-defined aliphatic compounds
- C10M2203/024—Well-defined aliphatic compounds unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method for removing aromatics from synthetic oil comprises the following steps: mixing an oil product with hydrogen to form a hydrogen-oil mixture, and feeding the hydrogen-oil mixture into a hydrogenation reactor; carrying out hydrogenation reaction on the hydrogen-oil mixture in a hydrogenation reactor to obtain a hydrogenation reaction product, wherein a hydrogen supplementing inner member is arranged in the hydrogenation reactor, and the hydrogen supplementing inner member enables dissolved hydrogen with constant content to exist in a hydrogenation reaction area of the hydrogenation reactor all the time; feeding the hydrogenation reaction product into a distillation system, and cutting and separating to obtain lubricating oil base oil with different viscosity indexes; wherein the hydrogen supplemental internals comprise: the hollow ring is provided with an air inlet; and the plurality of air inlet pipes are communicated with the hollow circle, point to the circle center, the top ends of the plurality of air inlet pipes are sealed, and openings are formed in the two sides of the plurality of air inlet pipes. The invention has simple process flow, and the product does not need additional decoloration, stabilizer addition and the like.
Description
Technical field
The present invention relates to hydro carbons processing technologys, poly- more particularly to one kind for improving hydrocarbon-containing feedstock Oxidation Stability
Alpha-olefin (PAO) synthetic oil Porous deproteinized bone produces lube base oil.
Background technology
Base oil is the main body of lubricating oil, and the quality of base oil largely determines the inherent matter of lube product
Amount.Poly alpha olefin (PAO) synthetic oil is the best synthetic lubricant base oil of current performance, has high viscosity index, low volatilization
Property, lazy flow, preferable cutting performance and excellent high temperature oxidation resistance；With traditional mineral lubricant oil base oil (I, II,
III class base oil) compare, PAO evaporation losses are small, stability is good, use temperature range is wide, with common material compatibility is good and nothing
It is the features such as malicious, not only extensive in the civilian sector application such as automobile, industry, high-grade profit even more used in the industries such as Aeronautics and Astronautics, military project
The main source of lubricant base oil.
PAO is usually the oligomer that branch saturation is carried by one kind that C6-C20 alhpa olefin catalytic oligomerizations synthesize, wherein the 1- last of the ten Heavenly stems
Alkene is preferred material, and China begins to production synthetic hydrocarbon oil, but mostly using wax olefin cracking early in the seventies, and product viscosity refers to
Number is low, thermostability is poor.At the beginning of the nineties, Mobil Oil Corporation is improves lubricating oil performance, with C6-C20 linear alpha-alkenes
For raw material, HVI-PAO techniques are developed, generate high-viscosity index lubricating oil under polymerization conditions.
When olefinic polymerization prepares PAO, main reaction polymerize for branched alpha-olefins, and simultaneous isomerization reaction, cyclisation are de-
A series of side reactions such as hydrogen reaction, alkylated reaction, generate in short-side chain/heavy aromatics, and the viscosity index (VI) of base oil is caused to drop
Low, oxidation stability is deteriorated, causes that oil product yellowish, quality are unstable after oxidation.
In order to produce the base oil of high quality, conventional mineral oil other than using " old three sets " technique productions base oil,
Base oil is produced using hydrogenation technique more and more both at home and abroad, makes the quality level of base oil have comprehensive raising.It should add
Hydrogen technique is equally applicable to synthetic oil base oil hydrogenation dearomatization and takes off alkene.Method of hydrotreating is exactly under the effect of the catalyst, to make oil product
In alkene, aromatic hydrogenation saturation.This method has many advantages, such as liquid yield height, good product quality, does not pollute.
Currently, base oil adds hydrogen generally use phase reaction (gas liquid solid body catalyst), such as traditional drip bed technique.
In these systems, the continuous phase in reactor is gas phase, it usually needs a large amount of hydrogen is gas always in reactor to maintain
It is consecutive.This is because, on the one hand, hydrogenation reaction is a micro- exothermic reaction, in order to maintain reaction temperature, is needed excessive
Hydrogen takes away reaction heat by catalyst bed；On the other hand, in the reaction of airwater mist cooling, higher hydrogen partial pressure is maintained
Be conducive to hydrogenation reaction, inhibit coke generation, extend catalyst life.Hydrogen more than needed is usually after circulating hydrogen compressor is pressurized
Continue to feed as the hydrogen reacted with the mixing of new hydrogen.This technical process can also be defined as gas phase cycle drip bed hydroprocessing work
Skill.However, under this process conditions, bed Wen Sheng great, radial temperature difference are big, high energy consumption, increase investment and operating cost.
For example, to provide and maintaining gas phase continuously required amount of hydrogen, hydrogenation reactor final effluent is generally separated
Into the gaseous component and a liquid composition of a hydrogen.Gaseous component normally enters compressor, is then circulated back to reaction
To help to provide a large amount of hydrogen, continuous gas phase is maintained with this for device entrance.Also there are other situations, such as some refineries, hydrogen comes
Source is sufficient, and the directly outer row of hydrogen more than needed uses without circulating hydrogen compressor pressurization cycle, causes the serious waste of the energy.
Key equipment of the circulating hydrogen compressor as hydrogenation process, the ratio that investment accounts for entire hydrogenation plant cost is higher,
Hydrogen heat-exchange system energy consumption is larger, if it is possible to reduce the hydrogen flowing quantity in hydrogenation process and save hydrogen gas circulating system and follow
Ring hydrogen compressor, can reduce investment outlay cost for enterprise.
Two-phase hydrogenation technique (for example, a liquid material and solid catalyst) is also to propose in some cases, will
Certain hydrocarbon-bearing materials are converted to other more valuable hydro carbons.For example, by hydrogen presaturation, two-phase reactor reduction may be used
Sulphur, nitrogen, aromatic hydrocarbons and alkene rather than the traditional three-phase system of use in certain hydrocarbon streams.
To Liquid-phase reactor other using being to be hydrocracked and the hydrotreating of hydrocarbon-bearing material.However, hydrotreating and
Being hydrocracked needs a large amount of hydrogen that corresponding chemical conversion occurs.Therefore, even if these are reacted all in liquid phase systems, still
Need a large amount of hydrogen.Therefore, it in order to maintain such a liquid-phase hydrogenatin processing or hydrocracking reaction, provides needed for reaction
Hydrogen needs to introduce additional diluent or solvent in the raw material of existing liquid phase systems, comes relative to the amounts of hydrogen of dissolving
It says, reactive component and reduction reactor Wen Sheng in main dilution charging.Then, for raw material, diluent and molten
Agent provides the molten hydrogen concentration of a bigger, it is ensured that enough conversion ratios can occur in the liquid phase.Needed in these systems bigger,
More complicated, more expensive Liquid-phase reactor, to realize required conversion.
Two-phase technique mainly has an IsoTherming technologies of DuPont at present, the said firm patent US6881326B2 and
ZL200680018017.3 reports the molten hydrogen concentration that bigger is provided using diluent or solvent, using product as diluent or
Solvent, due to being hydrocracked or hydrotreating reaction, hydrogen gas consumption is larger, causes product internal circulating load larger, therefore needs
Increase the investment of liquid circulation pump.
And synthetic oil base oil, due to not sulfur-bearing, nitrogen, and aromatic hydrocarbons and olefin(e) centent are less, chemical hydrogen consumption is relatively low, especially
Suitable liquid-phase hydrogenatin refines.Inviolent due to reacting, heat release is less, and the hydrogen dissolved disclosure satisfy that chemical reaction demand, therefore
This base oil hydrogenated products does not need to recycle.
United States Patent (USP) US7803269B2 reports synthetic oil liquid-phase hydrogenatin isomerization processes, for by the straight chain alkane of C8~C30
The Fischer-Tropsch synthesis oil or vegetable oil hydroisomerizing of hydrocarbon composition, reduce cloud point, pour point, condensation point.The hydroisomerizing technique is consumed with hydrogen
Low, product is not required to recycle, and hydroisomerizing reaction zone, also without additional the features such as mending hydrogen, more than feature causes the technique not
Suitable for doing higher or/and higher arene content mineral oil fractions or synthetic oil hydroisomerizing.But have no that the technique has
Close the report in terms of synthetic oil hydrogenation dearomatization deolefination.
Invention content
The purpose of the present invention is to provide a kind of methods of synthetic oil Porous deproteinized bone, include the following steps：
Oil product and hydrogen are carried out being mixed to form hydrogen oil mixture by step 1, which is sent into hydrogenation reaction
Device；
Step 2 carries out hydrogenation reaction to hydrogen oil mixture in hydrogenation reactor, obtains hydrogenation reaction product, add hydrogen anti-
It answers and hydrogen make-up inner member is equipped in device, hydrogen make-up inner member makes the hydrogenation reaction region of hydrogenation reactor, and there are contents always
Constant dissolved hydrogen；And
Hydrogenation reaction product is sent into Distallation systm by step 3, isolates the lubrication oil base of different viscosities index after cutting
Plinth oil；
Wherein, the hydrogen make-up inner member includes：
One empty circles, the empty circles are equipped with an air inlet；And
Multiple air inlet pipe, the multiple air inlet pipe are connected with the empty circles, and the multiple air inlet pipe is directed to justify
The heart, the top of the multiple air inlet pipe are closed, and the both sides of the multiple air inlet pipe are equipped with trepanning.
Further, the distance at the top of the trepanning distance of center circle air inlet pipe of the air inlet pipe side is three points of air inlet pipe pipe range
Two, the distance at the top of the trepanning distance of center circle air inlet pipe of the air inlet pipe opposite side is 1/3rd of air inlet pipe pipe range.
Further, the multiple air inlet pipe is uniformly arranged and length is identical.
Further, the open pore size of the air inlet pipe both sides is identical, is 2-10mm.
Further, the air inlet pipe top is apart from half of the center of circle for reactor radius.
Further, hydrogen reaches dissolving saturation state in the hydrogen oil mixture in step 1.
Further, it is from hydrogenation reactor by the feeding manner of hydrogen oil mixture feeding hydrogenation reactor in step 1
Bottom is fed.
Further, hydrogenation reaction is Continuous Liquid Phase hydrogenation reaction in step 2.
Further, hydrogenation conditions are in step 2：Reaction pressure 2.0MPa~6.0MPa, reaction temperature 220
DEG C~300 DEG C, volume space velocity 0.1h-1~2.0h-1。
Wherein, in step 1, the process that oil product and hydrogen are mixed is the gas before hydrogenation reactor
It is carried out in liquid mixer.The main function of air and liquid mixer is to make to reach dissolving saturation into the hydrogen in the distillate of reactor
State.The hydrogen that experiment shows to make part reaction required in advance is dissolved in feedstock oil, can accelerate the rate of reaction,
Improve reaction effect.
Wherein, in step 2, hydrogenation catalyst is placed in catalyst bed, hydrogen oil mixture is made to pass through from below to up
It can react when catalyst bed；In addition, further including hydrogen make-up inner member in catalyst bed, pass through benefit
Being flushed with hydrogen gas inner member, (hydrogen is still in the oil fully dissolved state after supplement, and what is supplemented herein is anti-to hydrogen oil mixture hydrogen make-up
The hydrogen that should fall).The hydrogenation reactor of the present invention can set one or more catalyst beds according to the scale requirements of device
Layer, hydrogen make-up inner member is installed on catalyst support plate.There are two aspect, (1) supplements molten hydrogen for the effect of inner member, and maintenance is anti-
Answer device hydrogen partial pressure；(2) supplement is by the consumed hydrogen of previous bed reaction；(3) the partial reaction heat of a upper bed is absorbed,
Reduce bed Wen Sheng.
The method of the present invention is the oxidation stability for improving hydrocarbon raw material.This method is in a Continuous Liquid Phase reaction zone profit
The Porous deproteinized bone of hydrocarbon raw material is carried out with hydrogenation reaction and deolefination reacts rather than one needs a large amount of high pressure hydrogens to maintain gas phase
Continuous three-phase reaction system.Referring herein to liquid-phase reaction system in a certain amount of hydrogen is mixed into hydrocarbon raw material, with
The reaction rate of the condition of one Continuous Liquid Phase of holding and continuous equilibrium in hydrogenation reaction region.
The method of the present invention is the aromatic hydrocarbons reduced by Continuous Liquid Phase hydrogenation process in hydrocarbon raw material, experiments have shown that merely
Reduction alkene can not ensure oxidation stability.Can be that hydrogen and hydrocarbon raw material respectively enter hydrogenation reaction before hydrogenation reaction
Area, hydrogen are mixed into hydrocarbon raw material, full of in Continuous Liquid Phase hydroconversion reaction zone, while keep continuing liquid-phase condition；It can also
It is that hydrogen is first mixed into the hydrogen come in hydrocarbon raw material in saturated hydrocarbons raw material, then, hydrocarbon raw material is directly entered Continuous Liquid Phase and adds
Hydroformylation reaction zone.In the region, hydrocarbon raw material (or part) at least one hydrogenation catalyst and under Hydrofinishing conditions into
Row reaction is so as to generate the product compared with low arene content.
In addition, state of the art form may be used in the hydrocarbon raw material hydrogenation technique of the present invention, such as single hop plus hydrogen work
Skill carries out hydrofinishing (hydrogenation reactor), one-stage serial hydrogenation technique carries out hydrofinishing --- post-refining (two
Hydrogenation reactor).
The present invention has no hydrogen gas bubbles in the reactor or hydrogen gas exists, but dissolved state.In the prior art
In, in Chinese patent CN103119133A disclosure of that, including narration：" hydrogen is with strip (slug) or the shape of bubble
Formula is present in the outside or inside that liquid is full of space region ", " hydrogen should exist to ensure to add hydrogen behaviour with sufficiently low concentration
Make the Continuous Liquid Phase in reactor, but concentration will be high enough to provide enough hydrogen for hydroprocessing hydrocarbon feed ".It is above old
It is there is (difference for having essence with the present invention) with gas or bubble shape to state bright hydrogen in that patent, and bubble form is deposited
Hydrogen, it is described to illustrate that technology such as background of invention one that the patent uses saves, needs using circulating hydrogen compressor, band
Come larger cost problem or directly outer row, a large amount of hydrogen is caused to waste, increase operating cost.In addition, Chinese patent
There is " Liquid product recycle oil " a kind of vocabulary in CN103805240A disclosure of that, but CN103805240A is that gas-liquid is inverse
The product circulation of flow reactor.Also, second reactor is not Liquid-phase reactor in CN103805240A, is gas-liquid conversed
The reactor of flowing, therefore, final reaction product property and reaction condition and pure Liquid-phase reactor are differentiated.
The beneficial effects of the invention are as follows：The circulating hydrogen compressor of conventional hydro is eliminated, while also eliminates conventional liquid phase
The product of hydrogen is added to recycle, oil hydrogenation technological process is simple, by the technique of the present invention, can significantly reduce cost of investment
And operating cost；This method is used for poly alpha olefin (PAO) synthetic oil hydrogenation and olefin hydrocarbon removal and aromatic hydrocarbons, can improve oil product color, carry
The oxidation stability of high PAO synthetic oils.
Description of the drawings
Fig. 1 is hydrogenation technique flow diagram of the present invention.
Fig. 2 is the front view of hydrogen make-up inner member of the present invention.
Fig. 3 is the vertical view of hydrogen make-up inner member of the present invention.
Wherein, reference numeral：
1st, hydrogen
2nd, feedstock oil
3rd, air and liquid mixer
4th, hydrogenation reactor
5th, Distallation systm
6th, purpose product
7th, hydrogen make-up inner member
8th, empty circles
9th, air inlet pipe
Specific embodiment
Technical scheme of the present invention is described in detail below in conjunction with specific embodiment, and listed illustrative embodiments are only
Make to illustrate and be used, be not intended as the limitation of the present invention.
A kind of method of synthetic oil Porous deproteinized bone, includes the following steps：
Oil product and hydrogen are carried out being mixed to form hydrogen oil mixture by step 1, which is sent into hydrogenation reaction
Device；
Step 2 carries out hydrogenation reaction to hydrogen oil mixture in hydrogenation reactor, obtains hydrogenation reaction product, add hydrogen anti-
It answers and hydrogen make-up inner member is equipped in device, hydrogen make-up inner member makes the hydrogenation reaction region of hydrogenation reactor, and there are contents always
Constant dissolved hydrogen；And
Hydrogenation reaction product is sent into Distallation systm by step 3, isolates the lubrication oil base of different viscosities index after cutting
Plinth oil；
Wherein, the hydrogen make-up inner member includes：
One empty circles, the empty circles are equipped with an air inlet；And
Multiple air inlet pipe, the multiple air inlet pipe are connected with the empty circles, and the multiple air inlet pipe is directed to justify
The heart, the top of the multiple air inlet pipe are closed, and the both sides of the multiple air inlet pipe are equipped with trepanning.
Further, the distance at the top of the trepanning distance of center circle air inlet pipe of the air inlet pipe side is three points of air inlet pipe pipe range
Two, the distance at the top of the trepanning distance of center circle air inlet pipe of the air inlet pipe opposite side is 1/3rd of air inlet pipe pipe range.
Further, the multiple air inlet pipe is uniformly arranged and length is identical.
Further, the open pore size of the air inlet pipe both sides is identical, is 2-10mm.
Further, the air inlet pipe top is apart from half of the center of circle for reactor radius.
Further, hydrogen reaches dissolving saturation state in the hydrogen oil mixture in step 1.
Further, it is from hydrogenation reactor by the feeding manner of hydrogen oil mixture feeding hydrogenation reactor in step 1
Bottom is fed.
Further, hydrogenation reaction is Continuous Liquid Phase hydrogenation reaction in step 2.
Further, hydrogenation conditions are in step 2：Reaction pressure 2.0MPa~6.0MPa, reaction temperature 220
DEG C~300 DEG C, volume space velocity 0.1h-1~2.0h-1。
Embodiment 1
The present embodiment provides a kind of methods of synthetic oil Porous deproteinized bone, include the following steps：
1) by the PAO4 feedstock oils 2 of synthesis (raw material A mainly produces PAO4, by-product low-viscosity oil) and hydrogen 1 in gas-liquid
Mixing is carried out in mixer 3 makes hydrogen 1 reach dissolving saturation state, forms the hydrogen oil mixture of pure liquid state, by hydrogen oil
Mixture is sent into hydrogenation reactor 4 from bottom；
2) in hydrogenation reactor 4, hydrogenation reaction is carried out to the hydrogen oil mixture, obtains hydrogenation reaction product, it is described
Hydrogenation reactor 4 include a catalyst bed, the catalyst bed includes hydrogen make-up inner member 7；The benefit
Gas inner member 7 is flushed with hydrogen to include：One empty circles 8, the empty circles 8 are equipped with an air inlet (being not drawn into figure) and five
Air inlet pipe 9, five air inlet pipe 9 are connected with the empty circles 8, and five air inlet pipe 9 are directed to the center of circle, and described five
The top of a air inlet pipe 9 is closed, and the both sides of five air inlet pipe 9 are equipped with trepanning (being not drawn into figure), the air inlet pipe 9
The distance at 9 top of trepanning distance of center circle air inlet pipe of side is 2/3rds of 9 pipe range of air inlet pipe, 9 opposite side of air inlet pipe
The distance at 9 top of trepanning distance of center circle air inlet pipe is 1/3rd of 9 pipe range of air inlet pipe；The open pore size of 9 both sides of air inlet pipe
It is identical, it is 2mm.The hydrogenation reaction process conditions are：Reaction pressure 4.0MPa, reaction temperature are 220 DEG C, and volume space velocity is
1.2h-1；
3) hydrogenation reaction product is sent into Distallation systm 5, isolates 6 base oil PAO4 of purpose product and other are evaporated
Point.
Raw material A property is listed in table 1, and 6 property of purpose product is listed in table 2.
As can be seen from Table 2, using the technology, product bromine number is 0, Saybolt color reaches No. 30, arene content 0,
Significantly improve the oxidation stability of synthetic lubricant base oil.
Embodiment 2
The present embodiment provides a kind of methods of synthetic oil Porous deproteinized bone, include the following steps：
1) by the PAO8 feedstock oils 2 of synthesis (raw material B mainly produces PAO8, by-product low-viscosity oil) and hydrogen 1 in gas-liquid
Mixing is carried out in mixer 3 makes hydrogen 1 reach dissolving saturation state, forms the hydrogen oil mixture of pure liquid state, by hydrogen oil
Mixture is sent into hydrogenation reactor 4 from bottom；
2) in hydrogenation reactor 4, hydrogenation reaction is carried out to the hydrogen oil mixture, obtains hydrogenation reaction product, it is described
Hydrogenation reactor 4 include two catalyst beds, the catalyst bed includes hydrogen make-up inner member 7；The benefit
Gas inner member 7 is flushed with hydrogen to include：One empty circles 8, the empty circles 8 are equipped with an air inlet and eight air inlet pipe 9, described
Eight air inlet pipe 9 are connected with the empty circles 8, and eight air inlet pipe 9 are directed to the center of circle, eight air inlet pipe 9
Top is closed, and the both sides of eight air inlet pipe 9 are equipped with trepanning, the trepanning distance of center circle air inlet pipe 9 of 9 side of air inlet pipe
The distance at top is 2/3rds of 9 pipe range of air inlet pipe, 9 top of trepanning distance of center circle air inlet pipe of 9 opposite side of air inlet pipe
Distance is 1/3rd of 9 pipe range of air inlet pipe, and the multiple air inlet pipe 9 is uniformly arranged and length is identical, 9 both sides of air inlet pipe
Open pore size it is identical, be 5mm.The hydrogenation reaction process conditions are：Reaction pressure 4.2MPa, reaction temperature are 245 DEG C,
Volume space velocity is 0.8h-1；
3) hydrogenation reaction product is sent into Distallation systm 5, isolates 6 base oil PAO8 of purpose product and other are evaporated
Point.
Raw material B properties are listed in table 1, and 6 property of purpose product is listed in table 2.
As can be seen from Table 2, using the technology, product bromine number is 0, Saybolt color reaches No. 30, arene content 0.22
ω %, hence it is evident that improve the oxidation stability of synthetic lubricant base oil.
Embodiment 3
The present embodiment provides a kind of methods of synthetic oil Porous deproteinized bone, include the following steps：
1) by the PAO40 feedstock oils 2 of synthesis (raw material C mainly produces PAO40, by-product low-viscosity oil) and hydrogen 1 in gas
Mixing is carried out in liquid mixer 3 makes hydrogen 1 reach dissolving saturation state, the hydrogen oil mixture of pure liquid state is formed, by the hydrogen
Oil mixture is sent into hydrogenation reactor 4 from bottom；
2) in hydrogenation reactor 4, hydrogenation reaction is carried out to the hydrogen oil mixture, obtains hydrogenation reaction product, it is described
Hydrogenation reactor 4 include two catalyst beds, the catalyst bed includes hydrogen make-up inner member 7；The benefit
Gas inner member 7 is flushed with hydrogen to include：One empty circles 8, the empty circles 8 are equipped with an air inlet and 12 air inlet pipe 9, institute
12 air inlet pipe 9 are stated with the empty circles 8 to be connected, 12 air inlet pipe 9 are directed to the center of circle, described 12 into
The top of tracheae 9 is closed, and the both sides of 12 air inlet pipe 9 are equipped with trepanning, the trepanning center of circle of 9 side of air inlet pipe
Distance away from 9 top of air inlet pipe is 2/3rds of 9 pipe range of air inlet pipe, the trepanning distance of center circle air inlet of 9 opposite side of air inlet pipe
The distance at 9 top of pipe is 1/3rd of 9 pipe range of air inlet pipe, and 12 air inlet pipe 9 are uniformly arranged and length is identical, described
The open pore size of 9 both sides of air inlet pipe is identical, is 10mm, 9 top of air inlet pipe is apart from half of the center of circle for reactor radius.Institute
The hydrogenation reaction process conditions stated are：Reaction pressure 5.0MPa, reaction temperature are 260 DEG C, volume space velocity 0.2h-1；
3) hydrogenation reaction product is sent into Distallation systm 5, isolates 6 base oil PAO40 of purpose product and other are evaporated
Point.
Raw material C properties are listed in table 1, and 6 property of purpose product is listed in table 2.
As can be seen from Table 2, using the technology, product bromine number is 0, Saybolt color reaches No. 30, ultraviolet absorptivity shows
Work becomes smaller, hence it is evident that improves the oxidation stability of synthetic lubricant base oil.
Comparative example 1
The synthetic base oil raw material D of same nature is handled, using this process and conventional single stage process, correction data
It is shown in Table 3.As can be seen from Table 3, comparable in process conditions, the indices of purpose product 6 are substantially suitable, but this work
The more conventional method of amounts of hydrogen used in process saves 80%.
The property of the raw materials used oil of 1 Examples 1 to 3 of table
| Project | Raw material A | Raw material B | Raw material C |
| Feedstock oil | PAO4 | PAO8 | PAO40 |
| Bromine number, gBr/100g | 2.85 | 2.31 | 1.74 |
| Saybolt color, number | 5 | -10 | -4 |
| Arene content, ω % | 0.35 | 0.85 | 0.95 |
| Ultraviolet absorptivity | |||
| 280nm | 1.536 | 2.930 | 2.678 |
| 290nm | 0.771 | 3.458 | 3.931 |
| 300nm | 0.365 | 3.341 | 3.389 |
| 360nm | 0.066 | 0.856 | 0.269 |
2 Examples 1 to 3 result of the test of table
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Bromine number, gBr/100g | 0 | 0 | 0 |
| Saybolt color, number | 30 | 30 | 30 |
| Arene content, ω % | 0 | 0.22 | 0.41 |
| Ultraviolet absorptivity | |||
| 280nm | / | 0.945 | 0.043 |
| 290nm | / | 0.468 | 0.016 |
| 300nm | / | 0.345 | 0.012 |
| 360nm | / | 0.016 | 0.002 |
3 comparative example of table, 1 raw material oil nature and result of the test
As can be seen from the above embodiments, it present invention eliminates the circulating hydrogen compressor of conventional hydro, while also eliminates
Conventional liquid phase adds the product of hydrogen to recycle, and oil hydrogenation technological process is simple, by the technique of the present invention, can significantly reduce
Cost of investment and operating cost；This method is used for poly alpha olefin (PAO) synthetic oil hydrogenation and olefin hydrocarbon removal and aromatic hydrocarbons, can improve oil product
Color improves the oxidation stability of PAO synthetic oils.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (9)
- A kind of 1. method of synthetic oil Porous deproteinized bone, which is characterized in that include the following steps：Oil product and hydrogen are carried out being mixed to form hydrogen oil mixture by step 1, which is sent into hydrogenation reactor；Step 2 carries out hydrogenation reaction to hydrogen oil mixture in hydrogenation reactor, obtains hydrogenation reaction product, hydrogenation reactor Interior to be equipped with hydrogen make-up inner member, hydrogen make-up inner member makes the hydrogenation reaction region of hydrogenation reactor, and there are content constants always Dissolved hydrogen；AndHydrogenation reaction product is sent into Distallation systm, isolates the lube base oil of different viscosities index after cutting by step 3；Wherein, the hydrogen make-up inner member includes：One empty circles, the empty circles are equipped with an air inlet；AndMultiple air inlet pipe, the multiple air inlet pipe are connected with the empty circles, and the multiple air inlet pipe is directed to the center of circle, institute The top for stating multiple air inlet pipe is closed, and the both sides of the multiple air inlet pipe are equipped with trepanning.
- 2. the method for synthetic oil Porous deproteinized bone according to claim 1, which is characterized in that the trepanning circle of the air inlet pipe side The heart is away from 2/3rds of the distance at the top of air inlet pipe for air inlet pipe pipe range, the trepanning distance of center circle air inlet pipe of the air inlet pipe opposite side The distance at top is 1/3rd of air inlet pipe pipe range.
- 3. the method for synthetic oil Porous deproteinized bone according to claim 1, which is characterized in that the multiple air inlet pipe is uniformly arranged And length is identical.
- 4. the method for synthetic oil Porous deproteinized bone according to claim 1, which is characterized in that the trepanning hole of the air inlet pipe both sides Diameter is identical, is 2-10mm.
- 5. the method for synthetic oil Porous deproteinized bone according to claim 1, which is characterized in that the air inlet pipe top is apart from the center of circle Half for reactor radius.
- 6. the method for synthetic oil Porous deproteinized bone according to claim 1, which is characterized in that in the hydrogen oil mixture in step 1 Hydrogen reaches dissolving saturation state.
- 7. the method for synthetic oil Porous deproteinized bone according to claim 1, which is characterized in that send hydrogen oil mixture in step 1 The feeding manner for entering hydrogenation reactor is to be fed from hydrogenation reactor bottom.
- 8. the method for synthetic oil Porous deproteinized bone according to claim 1, which is characterized in that hydrogenation reaction is continuous in step 2 Liquid-phase hydrogenatin is reacted.
- 9. the method for synthetic oil Porous deproteinized bone according to claim 1, which is characterized in that hydrogenation conditions in step 2 For：Reaction pressure 2.0MPa~6.0MPa, reaction temperature are 220 DEG C~300 DEG C, volume space velocity 0.1h-1~2.0h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611169547.XA CN108203599A (en) | 2016-12-16 | 2016-12-16 | Method for removing aromatic hydrocarbon from synthetic oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611169547.XA CN108203599A (en) | 2016-12-16 | 2016-12-16 | Method for removing aromatic hydrocarbon from synthetic oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108203599A true CN108203599A (en) | 2018-06-26 |
Family
ID=62602478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611169547.XA Pending CN108203599A (en) | 2016-12-16 | 2016-12-16 | Method for removing aromatic hydrocarbon from synthetic oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108203599A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110373227A (en) * | 2019-07-04 | 2019-10-25 | 上海米素环保科技有限公司 | A kind of hydrogen atmosphere protection inhibits the process for selective hydrogenation and device of coking |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178217A (en) * | 2013-05-22 | 2014-12-03 | 中石化洛阳工程有限公司 | Liquid phase hydrogenation method and reactor thereof |
| CN105602619A (en) * | 2015-12-18 | 2016-05-25 | 中国石油天然气股份有限公司 | Liquid-phase hydrogenation isomerization system and process and application thereof |
| CN105713656A (en) * | 2014-12-01 | 2016-06-29 | 中国石油天然气股份有限公司 | Micro-bubble intra-reactor hydrogen dissolving reactor and application method thereof |
| CN105733669A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Oil product hydrogenation method |
-
2016
- 2016-12-16 CN CN201611169547.XA patent/CN108203599A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178217A (en) * | 2013-05-22 | 2014-12-03 | 中石化洛阳工程有限公司 | Liquid phase hydrogenation method and reactor thereof |
| CN105713656A (en) * | 2014-12-01 | 2016-06-29 | 中国石油天然气股份有限公司 | Micro-bubble intra-reactor hydrogen dissolving reactor and application method thereof |
| CN105733669A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Oil product hydrogenation method |
| CN105602619A (en) * | 2015-12-18 | 2016-05-25 | 中国石油天然气股份有限公司 | Liquid-phase hydrogenation isomerization system and process and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110373227A (en) * | 2019-07-04 | 2019-10-25 | 上海米素环保科技有限公司 | A kind of hydrogen atmosphere protection inhibits the process for selective hydrogenation and device of coking |
| CN110373227B (en) * | 2019-07-04 | 2021-05-25 | 上海米素环保科技有限公司 | Hydrogenation reaction method and device for inhibiting coking under hydrogen atmosphere protection |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10683459B2 (en) | Liquid-phase hydroisomerization system and process therefor and use thereof | |
| CN101684415B (en) | Hydrocracking method for producing chemical materials to maximum with low cost | |
| KR20110121334A (en) | Manufacturing method of high grade base oil using unconverted oil | |
| CN111363580A (en) | Method and device for hydrotreating waste plastic | |
| CN111518589A (en) | Production process of food-grade white oil | |
| CN103773466A (en) | Method for producing lubricant base oil by hydrocracking-isodewaxing combination | |
| CN101942326B (en) | Method for producing low-aromatics solvent oil by hydrogenation | |
| CN101760236A (en) | Method for producing lube base oil | |
| CN108203599A (en) | Method for removing aromatic hydrocarbon from synthetic oil | |
| CN108659882B (en) | Heavy oil hydrogenation method and hydrogenation system thereof | |
| KR20230093025A (en) | Reaction system and reaction method of multi-phase combination | |
| CN113072975A (en) | System and process for producing lubricating oil base oil | |
| CN110616083B (en) | Process for producing crude white oil | |
| CN101892078A (en) | Preparation method of coal-based naphtha with high potential aromatic content for catalytic reforming, product and application thereof | |
| CN104611039B (en) | Inferior raw material method for hydrogen cracking | |
| CN103436290B (en) | Method for producing naphthenic base refrigerating machine oil base oil by using coal tar oil | |
| CN114686260B (en) | Method for producing naphthenic base rubber filling oil through hydrogenation | |
| CN105733669A (en) | Oil product hydrogenation method | |
| CN111378493B (en) | Hydrogenation process for producing API III + base oil from Fischer-Tropsch synthetic oil | |
| CN111378495B (en) | Fischer-Tropsch synthetic oil production API III+Hydrogenation method of base oil | |
| CN103102947A (en) | Production method for high-viscosity index lubricant base oil | |
| CN114437791A (en) | Low-pressure long-period hydrocracking process for Fischer-Tropsch synthetic oil | |
| CN210085379U (en) | Heterogeneous device for producing high-viscosity white oil by bottom reducing oil | |
| CN114437798B (en) | Shale oil hydrocracking method | |
| CN111073701B (en) | Processing system and method for high-viscosity poly-alpha-olefin synthetic oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180626 |
|
| RJ01 | Rejection of invention patent application after publication |