CN109852417A - A kind of production method of naphthenic base specialty oil - Google Patents
A kind of production method of naphthenic base specialty oil Download PDFInfo
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Abstract
The present invention provides a kind of production method of naphthenic base specialty oil.Using naphthenic base distillate as raw material, using two sections of extraordinary oil of serial hydrogenation technique production naphthenic base of hydrotreating-depth post-refining.Enter depth post-refining reaction zone after hydrotreating reaction effluent stripping, depth post-refining reaction zone loads two kinds of post-refining catalyst, different types of naphthenic base specialty oil is produced using different post-refining catalyst combination modes according to the different characteristics of raw material.The method of the present invention process is simple, adaptability to raw material is wide, can be adapted for various raw materials plus hydrogen production good security specialty oil process.
Description
Technical field
The present invention relates to a kind of production methods of naphthenic base specialty oil, specifically a kind of to be produced using hydrogenation technique
The method of naphthenic base specialty oil.
Background technique
Traditional lube base oil production is using solvent process, and main two steps are removed using solvent refining
The undesirable components such as aromatic hydrocarbons and solvent dewaxing are to guarantee the low temperature fluidity of base oil.In addition, generally also to carry out carclazyte or
Hydrofining.
Crude oil can be used characterization factor K and classify, and it is paraffinic base crude oil that characterization factor K, which is greater than 12.1,；Characterization factor K exists
11.5~12.1 be intermediate base crude；Characterization factor K is naphthene base crude less than 11.5.The Determination of Alkane Content one of paraffinic base distillate
As more than 50%, it is excellent that the higher i.e. viscosity temperature characteristic of viscosity index (VI) can be produced using traditional lube base oil production technology
Lube base oil.Due to worldwide crude oil in poor quality, so that being suitable for conventionally produced high viscosity index (HVI) lubrication
The paraffinic base crude oil quantity of oil base oil gradually decreases, and therefore, it is very rapid that hydrogenation method produces Lubricating Oil Technique development.Hydrogenation method
Technique refers to using hydrotreating or hydrocracking process-hydrodewaxing or isomerization dewaxing-hydrofinishing process integration production profit
The process of lubricant base oil, its advantage is that feed flexibility is big, base oil yield is high, by-product value is high etc..Naphthene base crude
It is big with density and viscosity, the features such as aromatic hydrocarbons and naphthene content are high, and condensation point is low.Hydrogenation method production oil for electrical appliances, cold can be used
Freeze machine oil and rubber filling oil etc. not require viscosity temperature characteristic, and the lube base oil of crude resources can be made full use of.In
Between the property of base oil be between above two crude oil, the lube base oil of medium viscosity index can only be produced.
CN200410029869.5 describes a kind of hydrotreating-hydrodewaxing-hydrofinishing production lube base oil
Method, after the hydrotreatment products of this method must carry out vapor-liquid separation, product liquid just can enter hydrodewaxing process.
A kind of method that CN97196410.6 describes hydrotreating-hydrodewaxing-hydrofinishing production lube base oil, this method
Raw material solvent refining must be carried out before carrying out hydrotreating, with reach material viscosity index be greater than 75 requirement.It adds hydrogen
Processing product must also carry out gas-liquid separation, and by the hydrogen sulfide and ammonia removal in hydrotreated material, product liquid just be can enter
Hydrodewaxing process.CN97122140.5 discloses a kind of method of solvent refining-hydrotreating production lube base oil, should
The viscosity index (VI) of raw material can be significantly increased in method, but is not suitable for the production of naphthenic base distillate feedstock and wants to viscosity index (VI)
Seek the process of not high naphthenic lube oil and base oil.
Isomerization dewaxing is a kind of common method for improving lube base oil viscosity index (VI), but this method generally should be with paraffin
Base oil distillate oil is raw material, does not have positive effect to naphthene base crude distillate.Product stability is poor after isomerization dewaxing, must be into
One step post-refining, therefore production process is more complex, higher cost.
In conclusion the suitable process process of the extraordinary oil of hydrogenation method production naphthenic base need to be according to the characteristics of raw material and naphthenic base
The requirement of extraordinary oil product determines.The prior art is unable to satisfy naphthenic base distillate or frivolous oil plus hydrogen produces specialty oil
It is required that.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides that a kind of adaptability to raw material is strong, process flow is simple, flexible production
The method of the extraordinary oil of naphthenic base.Naphthenic base distillate through hydrogenated processing-depth post-refining refining reaction, it is raw through suitable rectifying
The method of the more good naphthenic base special type oil product of yield and quality.
A kind of production method of naphthenic base specialty oil of the invention, including the following contents:
(1) after naphthenic base distillate is mixed with hydrogen, into hydrotreating reaction area, it is anti-that progress is contacted with Hydrobon catalyst
It answers；
(2) after the generation oil that step (1) obtains is mixed with hydrogen, mixed hydrogen is carried out into mixed hydrogen tank, gained is saturated the liquid phase of molten hydrogen
Effluent is contacted with hydrofining catalyst and is reacted into post-refining reaction zone；
(3) post-refining reaction effluent obtained by step (2) carries out gas-liquid separation, and liquid obtains corresponding special type by fractionation
Oil product fraction.
In the present invention, the naphthenic base fraction can be naphthenic base distillate, frivolous coal tar, coal tar hydrocracking
At least one of tail oil or catalytic cracking diesel oil fraction.The arene content of naphthenic base fraction is generally 30~100 wt%, and 20 DEG C
Density is generally 0.923~0.955 g/cm3.The boiling range of naphthenic base distillate feedstock is any model within the scope of 200~600 DEG C
It encloses, the temperature difference of general initial boiling point to the end point of distillation is between 100~400 DEG C.
Hydrobon catalyst as described in step (1) is the conventional hydro catalyst for refining of this field, such as can be bavin
Oily Hydrobon catalyst or pretreating catalyst by hydrocracking.Hydrobon catalyst is generally with VI B race and/or the VIIIth race gold
Belonging to is active component, and using aluminium oxide or silicon-containing alumina as carrier, group VIB metal is generally Mo and/or W, group VIII metal
Generally Co and/or Ni.With the poidometer of catalyst, group VIB tenor is calculated as 10wt%~50wt% with oxide, and the VIIIth
Race's tenor is calculated as 3~15 wt% with oxide；Its property is as follows: specific surface area is 100~350m2/ g, Kong Rongwei 0.15
~0.6mL/g.Selectable commercial catalyst has China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute's development
Exploitation 3936,3996, the Hydrobon catalysts such as FF-16, FF-26, FF-36, FF-46, FF-56, FF-66.It is also possible to
The function of World Catalyst company exploitation is similar to catalyst, such as HC-K, HC-P catalyst of Uop Inc., the TK- of Topsoe company
555, TK-565 catalyst and KF-847, KF-848 of AKZO company etc..
The operating condition in hydrotreating reaction area are as follows: 10.0~20.0MPa of reaction pressure, 300~420 DEG C of reaction temperature,
Hydrogen to oil volume ratio 200~2000,0.1~3.0h of volume space velocity-1；Preferably, 10.0~18.0MPa of reaction pressure, hydrogen oil volume
Than 500~1500,0.2~2.0h of volume space velocity-1, 320~400 DEG C of reaction temperature.
Hydrotreatment products are directly entered the processing of hydrofining reaction zone, hydrofining catalysis in step (2)
Agent is the Typical precious metal hydrogenation catalyst of this field.The hydrofining catalyst contains carrier and is carried on carrier
On active metal component, the active metal component be Pt and/or Pd, the carrier contain small crystal grain Y-shaped molecular sieve, oxidation
Aluminium and amorphous silica-alumina, the average grain diameter of the small crystal grain Y-shaped molecular sieve are 200-700nm, SiO2/Al2O3Molar ratio is
40-120, relative crystallinity >=95%, specific surface area 900-1200m2The Kong Rong of the secondary pore of/g, 1.7-10nm accounts for total pore volume
50% or more.
The average grain diameter of the small crystal grain Y-shaped molecular sieve be 200-700nm, specifically, for example, can for 200nm,
Appointing in 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm and these point values
Arbitrary value in two ranges constituted of anticipating.In the preferred case, the average grain diameter of the small crystal grain Y-shaped molecular sieve is
300-500nm.In the present invention, the average grain diameter of the small crystal grain Y-shaped molecular sieve is according to SEM(scanning electron microscope)
Method detection.
The SiO of the small crystal grain Y-shaped molecular sieve2/Al2O3Molar ratio is 40-120, specifically, such as can for 40,50,
60,70,80,90,100,110,120 and these point values in the range that is constituted of any two in arbitrary value.
Relative crystallinity >=95% of the small crystal grain Y-shaped molecular sieve, preferably 95-120%, more preferably 98-115%.?
In the present invention, the relative crystallinity of the small crystal grain Y-shaped molecular sieve is detected according to x-ray diffraction method.
The specific surface area of the small crystal grain Y-shaped molecular sieve is 900-1200m2/ g specifically, such as can be 900m2/g、
920m2/g、950m2/g、980m2/g、1000m2/g、1020m2/g、1050m2/g、1080m2/g、1100m2/g、1120m2/g、
1150m2/g、1180m2/g、1200m2The arbitrary value in range that any two in/g and these point values are constituted.At this
In invention, the specific surface area of the small crystal grain Y-shaped molecular sieve is detected according to low temperature liquid nitrogen physisorphtion.
The small crystal grain Y-shaped molecular sieve has more secondary pore, specifically, in the small crystal grain Y-shaped molecular sieve,
The Kong Rong of the secondary pore of 1.7-10nm accounts for 50% of total pore volume or more, preferably 50-80%, further preferably 60-80%.At this
In invention, the Kong Rong of the secondary pore of the small crystal grain Y-shaped molecular sieve is detected according to low temperature liquid nitrogen physisorphtion.
The lattice constant of the small crystal grain Y-shaped molecular sieve can be 2.425-2.435nm, such as 2.425nm, 2.426nm,
2.427nm, 2.428nm, 2.429nm, 2.43nm, 2.431nm, 2.432nm, 2.433nm, 2.434nm, 2.435nm and this
The arbitrary value in range that any two in a little point values are constituted.In the present invention, the structure cell of the small crystal grain Y-shaped molecular sieve
Constant is detected according to x-ray diffraction method.
The Kong Rongke of the small crystal grain Y-shaped molecular sieve with for 0.5-0.8mL/g, such as 0.5mL/g, 0.55mL/g,
The range that any two in 0.6mL/g, 0.65mL/g, 0.7mL/g, 0.75mL/g, 0.8mL/g and these point values are constituted
In arbitrary value.In the present invention, the Kong Rong of the small crystal grain Y-shaped molecular sieve is detected according to low temperature liquid nitrogen physisorphtion.
In the present invention, the property of the hydrofining catalyst is as follows: specific surface area can be 350-550m2/
G, preferably 380-500m2/g；Kong Rongke is with for 0.5-1mL/g, preferably 0.5-0.9mL/g.
In the hydrofining catalyst, on the basis of the total weight of catalyst, the active metal component
Content can be 0.1-2 weight %, preferably 0.2-1.5 weight %；The content of the carrier can be 98-99.9 weight %, preferably
For 98.5-99.8 weight %.
In the carrier, on the basis of the total weight of the carrier, the content of the small crystal grain Y-shaped molecular sieve can be
5-40 weight %, preferably 10-25 weight %；The content of the aluminium oxide can be 10-40 weight %, preferably 15-30 weight %；
The content of the amorphous silica-alumina can be 20-65 weight %, preferably 30-60 weight %.
The specific surface area of hydrofining catalyst is 900~1200m20.5~0.80mL/g of/g, Kong Rong, wherein 1.7
The Kong Rong of the secondary mesoporous of~10nm accounts for 50% of total pore volume or more, preferably 50%~80%, further preferably 60%~80%.
In the present invention, the hydrofining catalyst can choose suitable commercial catalyst, can also basis
Prepared by the conventional method of this field, be such as made according to the method reported in CN104588073A.Specifically, described plus hydrogen is mended
Fill catalyst for refining preparation method may include: by small crystal grain Y-shaped molecular sieve, amorphous silicon aluminium and made of aluminium oxide glue
Mixture mechanical mixture, molding, then dry and roasting, are made catalyst carrier；Using infusion process in supported on carriers Pt and/or
Pd obtains hydrofining catalyst through dry and roasting.
The preparation method of the small crystal grain Y-shaped molecular sieve may comprise steps of:
(1) Na is made in small crystal grain NaY molecular sieve2O content≤2.5 weight % little crystal grain NH4NaY molecular sieve；
(2) by little crystal grain NH4NaY molecular sieve carries out hydro-thermal process, then carries out dealumination complement silicon with hexafluorosilicic acid aqueous ammonium；
(3) molecular sieve for obtaining step (3), which is used, contains NH4 +And H+The mixed solution of sum is handled, and is washed out and is dried, obtains small
Grain Y-molecular sieve.
The property of the small crystal grain NaY molecular sieve is as follows: SiO2/Al2O3Molar ratio is greater than 6 and is not higher than 9, preferably
6.5-9 further preferably 7-8；Average grain diameter is 200-700nm, preferably 300-500nm；Specific surface area is 800-
1000m2/ g, preferably 850-950m2/g；Hole holds 0.3-0.45mL/g, relative crystallinity 90-130%, and lattice constant is
2.46-2.47, after being roasted 3 hours in 650 DEG C of air relative crystallinity be 90% or more, preferably 90-110%, more preferably
90-105%。
On the basis of the quality of hydrofining catalyst, wherein the content of Pt and/or Pd is generally 0.1%~2%,
Remaining is carrier.On the basis of quality, composition generally includes the catalyst carrier: small crystal grain Y-shaped molecular sieve 5%~40%,
Amorphous silica-alumina 20%~65%, aluminium oxide are l0%~40%.The post-refining catalyst can choose suitable commodity and urge
Agent can also be prepared according to the conventional method of this field, as disclosed a kind of post-refining in CN104588073A
The preparation method of catalyst.
The process conditions of hydrofining are general are as follows: 4.0~20.0MPa of reaction pressure, preferably 10.0~15.0 MPa；
0.3~6.0 h of volume space velocity when liquid-1, preferably 0.5~3.0 h-1；150~380 DEG C of average reaction temperature, preferably 200~360
℃。
In the present invention, post-refining reaction zone preferably includes two concatenated conversion zones, i.e. the first post-refining section and
Two post-refining sections.It corresponds, the catalyst in the first post-refining section is post-refining catalyst A, the second supplement essence
Catalyst in section processed is post-refining catalyst B, the percentage composition x of the active metal component in the hydrogenation catalyst A1
Higher than the percentage composition x of the active metal component in the hydrogenation catalyst B2, small-grain Y in the hydrogenation catalyst A
Percentage composition y of the percentage composition of type molecular sieve lower than the small crystal grain Y-shaped molecular sieve in the hydrogenation catalyst B2.Excellent
In the embodiment of choosing, x1Compare x2It is 0.1~1.5 percentage point high, it is preferably 0.5~1.5 percentage point high；y1Compare y2Low 5~50
Percentage point is 10~40 percentage points preferably low.
In the first post-refining section and the second post-refining section, used post-refining catalyst in metal due to containing
The difference of amount and small crystal grain Y-shaped molecular sieve content, and it is respectively provided with different property.Post-refining catalyst A is then because have
Relatively high tenor and relatively low Y type molecular sieve content, and Hydrogenation is higher, lytic activity is on the weak side.Add hydrogen
The hydrogenation products of processing section again with post-refining catalyst A haptoreaction when, wherein existing by the unsaturated aromatic hydrocarbons of partial hydrogenation
Under lower reaction temperature, since the cracking activity of catalyst is restricted, and acid saturation function is strong, and further progress adds
Hydrogen, most carbon-carbon double bonds obtain saturation to obtain the extraordinary oil of naphthenic base, to improve the yield of purpose product.
Post-refining catalyst B has relatively low tenor and higher Y type molecular sieve content, thus catalyst
Cracking performance it is higher.The few ring or polycyclic naphthene for generating the belt length side chain contained in oil distillate are refined by A catalyst make-up
Further with post-refining catalyst B haptoreaction, chain rupture or isomerization reaction occur hydrocarbon for the side chain on cycloalkane, while few
The unsaturated polycyclic aromatic hydrocarbon of amount can complete double bond saturated reaction.
As it can be seen that the catalyst grading composition that the post-refining stage uses in the present invention, realizes thick in distillate well
Cycloaromatics adds hydrogen saturation and remains into ideal composition, and the chain rupture or isomerization of long side chain reduce the mesh of pour point on cyclic hydrocarbon
's.So that hydrogenation method can be used in directly producing the high extraordinary oil product of good security, purpose product yield.
In a preferred embodiment, the process conditions of the first post-refining section and the second post-refining section should preferably be fitted
Answering property adjusts, preferably the average reaction temperature of the second post-refining section it is higher by 10 than the average reaction temperature of the first post-refining section~
It is 150 DEG C, 30~120 DEG C preferably low.In further preferred embodiment, the average response of the first post-refining conversion zone
Temperature is generally 150~350 DEG C, preferably 180~330 DEG C；The average reaction temperature of second post-refining conversion zone be 180~
380 DEG C, preferably 220~350 DEG C.
In the present invention, the first post-refining section and the second post-refining section be can be set in a reactor, Huo Zhefen
It She Zhi not be in more than two reactors.
Specialty oil production method of the present invention uses two-stage process process, and hydrotreatment stage generates oil and only need to simply strip,
It can be used as post-refining section feeding, process greatly simplifies.The present invention evaporates naphthenic base by the catalyst of the suitable performance of selection
Divide hydroprocessing processes to simplify, and can guarantee product quality.Adaptability to raw material of the present invention is strong, special according to the difference of raw material
Point can produce different types of specialty oil, technique mistake using different hydrofining catalyst grading composition modes
Journey is flexible.And noble metal hydrogenation post-refining reaction zone reaction temperature gradient uniformity advantageously reduces energy consumption, produces extraordinary oil
Product significantly simplify process flow, save investment.
Hydrotreating reaction area includes that a kind of catalyst is Hydrobon catalyst.Hydrobon catalyst have desulfurization,
Denitrogenation and aromatic hydrocarbons are saturated function.When raw material is naphthenic base distillate or frivolous coal tar, production transformer oil, refrigerator oil and rubber
The lube base oil that glue filling oil etc. does not require viscosity temperature characteristic, when, hydrotreating reaction area can be only hydrotreating
Catalyst；The product in above-mentioned hydrotreating reaction area need to remove H therein through stripping separation2S and NH3, hydrogen can be added into being equipped with
The reaction zone of post-refining catalyst is saturated aromatic hydrocarbons, and after the pour point for reducing product, post-refining product is obtained through product separation process
To the extraordinary oil product of various good securities.
Post-refining catalyst used in the present invention, using small crystal grain Y-shaped molecular sieve as acidic components, the Y type point
Sub- sifter device has the characteristics of more high silica alumina ratio, high-crystallinity, secondary pore, bigger serface, with amorphous silica-alumina and plus hydrogen work
Property metal component Pt and Pd cooperate, not only promote the performance of aromatic hydrogenation saturated activity, be more advantageous to the selection of aromatic hydrocarbons
Property open loop and chain rupture, and be conducive to the diffusion of reaction product, while holding charcoal ability and also greatly enhancing, to improve catalyst
Activity, selectivity and stability.The catalyst is especially suitable as cycloalkanes based raw material, and especially viscosity height, condensed-nuclei aromatics contains
In the hydrogenation dearomatization hydrocarbon reaction for measuring high cycloalkanes based raw material.
In the present invention, in post-refining reaction zone, it is preferred to use two different post-refining catalyst.First supplement
The catalyst A used in refining stage then because having relatively high tenor and lower Y type molecular sieve content, and adds
Hydrogen performance is partially strong, and its suitable lytic activity also adds hydrogen saturation to have important catalytic action condensed-nuclei aromatics.And second
The catalyst B used in post-refining section has relatively high Y type molecular sieve content and relatively low tenor, thus
Show as inclined lytic activity.For naphthenic base fraction, the inclined cracking performance of catalyst B can be to the aromatic hydrocarbons with side chain alkane
Effective chain rupture or isomerization reaction are carried out, pour point is further decreased.Therefore, part is had occurred and that in the first post-refining section
The cyclic hydrocarbon for adding hydrogen and generating can add hydrogen full under lower reaction temperature in the whole aromatic rings of the second post-refining section completion
With to obtain the good extraordinary oil product of stability.
Detailed description of the invention
Fig. 1 is the process flow diagram of the method for the present invention.
Specific embodiment
More detailed description is done to method of the invention below by way of specific embodiment.
As shown in Figure 1, naphthenic base feedstock oil passes through pipeline 1, circulating hydrogen passes through pipeline 2, enters after the two mixing and add hydrogen
Finishing reactor 3 carries out the reactions such as removing sulphur, nitrogen and aromatic hydrocarbons saturation.Hydrofining reaction effluent enters gas-liquid by pipeline 4
Separator 5 carries out gas-liquid separation, and gained hydrogen-rich gas introduces after pipeline 6 and the processing of optional depriving hydrogen sulphide with pipeline 7
Supplement hydrogen is mixed to get circulating hydrogen；Gained liquid generates oil and passes through pipeline 8, with after the hydrogen of pipeline 13 mixes, enters
Mixed hydrogen tank 9 carries out sufficiently mixing hydrogen, and the effluent that gained is saturated molten hydrogen enters the first post-refining reactor 11 through pipeline 10, with height
Active hydrogenation post-refining catalyst A contact, carries out depth aromatic hydrogenation saturated reaction.The warp of effluent obtained by first post-refining
It crosses pipeline 12 and enters the second post-refining reactor 14, haptoreaction is carried out with low activity hydrofining catalyst B, to ring
The long side chain chain rupture of alkane or isomerization reduce pour point and not fully saturated aromatic hydrocarbons is saturated, while keeping the complete of cycloalkane annular
It is whole, in favor of the low temperature flow of purpose product.Second post-refining reaction effluent enters gas-liquid separator by pipeline 15
16(or flash column), it obtains gas and is discharged after purification through pipeline 17.16 gained liquid through line 18 of gas-liquid separator enters
Fractionating column 19, gas are discharged by pipeline 20, and gained different size specialty oil can pass through pipeline 21,22 and 23 rows respectively
Out.
Unless otherwise instructed, related % is mass percent below.Wherein, the Saybolt color of solvent naphtha uses
GB/T3555, arene content use the analysis method or analytical standard of GB/T 17474.
Embodiment 1
Process as shown in Figure 1, hydrotreating reaction area use Hydrobon catalyst, in post-refining reaction zone catalyst regardless of
Section, and only with a kind of catalyst A.Be listed in Tables 1 and 2 respectively using the property of catalyst, obtain extraordinary oil distillate property
It is shown in Table 4.
Embodiment is prepared using post-refining catalyst all in accordance with method disclosed in CN104588073A.
Embodiment 2
With embodiment 1, post-refining reaction zone is interior to be used only catalyst B for hydrotreating part.Extraordinary oil can be equally obtained to evaporate
Point property is shown in Table 4.
Embodiment 3
With embodiment 1, two post-refining sections are divided into post-refining reaction, and using catalyst A and are urged for hydrotreating part
The grading distribution scheme of agent B.Process conditions also have matching simultaneously.Extraordinary oil distillate property is shown in Table 4.
Embodiment 4
With embodiment 3, change the grade sequence ligand of post-refining catalyst.Extraordinary oil distillate property can equally be obtained and be shown in Table 4.
Comparative example 1
This comparative example is identical using naphthenic base based raw material, and technical process first passes through hydrotreating catalyst for raw material and handles, then into
Row conventional hydro pour point depression and hydrofining, result are specifically also shown in Table 4.The comparison number of embodiment and comparative example from table 4
According to it is found that cycloalkanes based raw material using hydrotreating catalyst is first passed through, then carries out hydrodewaxing again and hydrofining is raw
The stability of the specialty oil of production is poor, and purpose product yield is lower.
Institute's column data from table 4 obtains extraordinary oil it is found that for the prior art that raw material adds hydrogen under different condition
Moral character matter is different, and the grading method of catalyst of embodiment 3 is optimal.
It can be seen that naphthene base crude oil raw material in the present invention from the data of embodiment 1-4 and comparative example and pass through hydrotreating, depth
The process of degree supplement hydrofinishing, can obtain the extraordinary oil product of pour point qualification.And wherein, post-refining reaction zone
The stability of the scheme matched using catalyst grade, gained special type oil product is more preferable, has and more preferably adds hydrogen effect.
1 raw material oil nature of table
The physico-chemical property of 2 Hydrobon catalyst of table
3 post-refining catalyst property of table
4 process conditions of table and result
Claims (18)
1. a kind of production method of naphthenic base specialty oil, including the following contents:
(1) after naphthenic base distillate is mixed with hydrogen, into hydrotreating reaction area, it is anti-that progress is contacted with Hydrobon catalyst
It answers；
(2) after the generation oil that step (1) obtains is mixed with hydrogen, mixed hydrogen is carried out into mixed hydrogen tank, gained is saturated the liquid phase of molten hydrogen
Effluent contacts with hydrofining catalyst into post-refining reaction zone and carries out hydrogenation reaction；
(3) post-refining reaction effluent obtained by step (2) carries out gas-liquid separation, and liquid obtains corresponding special type by fractionation
Oil product fraction.
2. according to the method for claim 1, which is characterized in that the hydrofining catalyst contains carrier and bears
The active metal component being loaded on carrier, the active metal component are Pt and/or Pd, and the carrier contains small-grain Y-type point
Son sieve, aluminium oxide and amorphous silica-alumina, the average grain diameter of the small crystal grain Y-shaped molecular sieve are 200-700nm, SiO2/
Al2O3Molar ratio is 40-120, relative crystallinity >=95%, specific surface area 900-1200m2The secondary pore of/g, 1.7-10nm
Kong Rong accounts for 50% of total pore volume or more.
3. according to the method for claim 2, which is characterized in that the relative crystallinity of the small crystal grain Y-shaped molecular sieve is 95-
120%。
4. according to the method for claim 2, which is characterized in that in the small crystal grain Y-shaped molecular sieve, the two of 1.7-10nm
The Kong Rong of secondary aperture accounts for the 50-80% of total pore volume, preferably 60-80%.
5. according to the method for claim 2, which is characterized in that the lattice constant of the small crystal grain Y-shaped molecular sieve is
2.425-2.435nm。
6. according to the method for claim 2, which is characterized in that the Kong Rongwei 0.5- of the small crystal grain Y-shaped molecular sieve
0.8mL/g。
7. according to the method for claim 2, which is characterized in that total with catalyst in the hydrofining catalyst
On the basis of weight, the content of the active metal component is 0.1-2 weight %, preferably 0.2-1.5 weight %；The carrier contains
Amount is 98-99.9 weight %, preferably 98.5-99.8 weight %.
8. according to the method for claim 7, which is characterized in that described on the basis of the total weight of carrier in the carrier
The content of small crystal grain Y-shaped molecular sieve is 5-40 weight %, preferably 10-25 weight %；The content of the aluminium oxide is 10-40 weight
Measure %, preferably 15-30 weight %；The content of the amorphous silica-alumina can be 20-65 weight %, preferably 30-60 weight %.
9. according to the method for claim 7, which is characterized in that the specific surface area of hydrofining catalyst be 900~
1200m20.5~0.80mL/g of/g, Kong Rong, wherein the Kong Rong of the secondary mesoporous of 1.7~10nm accounts for 50% of total pore volume or more.
10. according to the method for claim 1, which is characterized in that the Hydrobon catalyst is with VI B race and/or
VIII race's metal is active component, using aluminium oxide or silicon-containing alumina as carrier；With the poidometer of catalyst, group VIB metal contains
Amount is calculated as 10wt%~50wt% with oxide, and group VIII metal content is calculated as 3~15 wt% with oxide.
11. according to the method for claim 1, which is characterized in that the operating condition in hydrotreating reaction area are as follows: reaction pressure
10.0~20.0MPa, 300~420 DEG C of reaction temperature, hydrogen to oil volume ratio 200~2000,0.1~3.0h of volume space velocity-1。
12. according to the method for claim 1, which is characterized in that the process conditions of post-refining are as follows: hydrogen partial pressure 4.0~
20.0MPa, 0.3~6.0 h of volume space velocity when liquid-1, 150~380 DEG C of average reaction temperature.
13. according to any method of claim 2-9, which is characterized in that post-refining reaction zone includes being sequentially connected in series
Two conversion zones, i.e. the first post-refining section and the second post-refining section；It corresponds, the catalysis in the first post-refining section
Agent is post-refining catalyst A, and the catalyst in the second post-refining section is post-refining catalyst B, the hydrogenation catalyst A
In active metal component percentage composition x1Higher than the percentage composition of the active metal component in the hydrogenation catalyst B
x2, the percentage composition of the small crystal grain Y-shaped molecular sieve in the hydrogenation catalyst A is lower than the small crystalline substance in the hydrogenation catalyst B
The percentage composition y of grain Y type molecular sieve2。
14. according to the method for claim 13, which is characterized in that x1Compare x2It is 0.1~1.5 percentage point high, it is preferably high by 0.5
~1.5 percentage points；y1Compare y2It is low 5~50 percentage points, 10~40 percentage points preferably low.
15. according to the method for claim 14, the average reaction temperature of the second post-refining section is than the first post-refining section
Average reaction temperature it is 10~150 DEG C high, it is 30~120 DEG C preferably low.
16. according to the method for claim 15, which is characterized in that the average reaction temperature of the first post-refining conversion zone is
150~350 DEG C, preferably 180~330 DEG C；The average reaction temperature of second post-refining conversion zone is 180~380 DEG C, preferably
220~350 DEG C.
17. according to the method for claim 1, which is characterized in that the arene content of the naphthenic base fraction is 30~100
Wt%, 20 DEG C of density are 0.923~0.955 g/cm3。
18. according to method described in claim 1 or 17, which is characterized in that the naphthenic base fraction be naphthenic base distillate,
At least one of frivolous coal tar, coal tar hydrocracking tail oil or catalytic cracking diesel oil fraction.
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| CN1944587A (en) * | 2005-10-08 | 2007-04-11 | 中国石油化工股份有限公司 | Method for producing food grade white oil by hydrogenating tail oil |
| CN102311785A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for hydrogenating naphthenic base distillate to produce lubricating oil basic oil |
| CN104588073A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Hydrogenation dearomatization catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1944587A (en) * | 2005-10-08 | 2007-04-11 | 中国石油化工股份有限公司 | Method for producing food grade white oil by hydrogenating tail oil |
| CN102311785A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for hydrogenating naphthenic base distillate to produce lubricating oil basic oil |
| CN104588073A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Hydrogenation dearomatization catalyst and preparation method thereof |
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| CN115806837A (en) * | 2021-09-15 | 2023-03-17 | 中国石油化工股份有限公司 | Hydrocracking method for producing low-carbon light hydrocarbon and naphthenic base special oil |
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