CN104611023A - Method for producing special lubricating oil base oil - Google Patents
Method for producing special lubricating oil base oil Download PDFInfo
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- CN104611023A CN104611023A CN201310540470.2A CN201310540470A CN104611023A CN 104611023 A CN104611023 A CN 104611023A CN 201310540470 A CN201310540470 A CN 201310540470A CN 104611023 A CN104611023 A CN 104611023A
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- hydrodewaxing
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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- 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
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/14—White oil, eating oil
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- 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
The present invention discloses a method for producing special lubricating oil base oil. According to the method of the present invention, a wax oil raw material and hydrogen gas are mixed and then sequentially pass through at least two hydrogenation reaction zones connected in series, wherein each hydrogenation reaction zone sequentially comprises a refining dewaxing catalyst composite bed layer filled with a hydrodewaxing catalyst and a hydrorefining catalyst in a mixed manner and a hydrodewaxing catalyst bed layer according to the material flowing direction, and the reaction effluent obtained from the last hydrogenation reaction zone is subjected to separation and fractionation to obtain the lubricating oil base oil, the white oil and other products. With the method of the present invention, the temperature decrease during the hydrodewaxing process and the temperature increase during the hydrogenation process are subjected to reasonable combination utilization, such that the low freezing point lubricating oil base oil is produced while the hot spot temperature of the device is reduced and the operation period is prolonged; and the cold hydrogen consumption or the heating furnace fuel gas loss is reduced, and the operating cost is saved.
Description
Technical field
The present invention relates to a kind of production method of special lubricating oil base oil, especially a kind ofly to be loaded and grating technology by catalyzer compound, be used for producing the method for hydrotreating of special lubricating oil base oil.
Background technology
Lubricant is the very important petroleum products of a class, is the key factor of brought into motion parts, although its product only accounts for about 2% of crude runs, but because of varying of its working conditions, kind is nearly hundreds of, and strict to specification of quality, and lubricating oil just belongs to the one of lubricant.For miscellaneous lubricating oil, can not often kind all go independent production, for this reason, produce to simplify it, each state all adopts the lubricant base first made and meet certain standard, then carries out being in harmonious proportion and adding additive according to the needs in market, with obtained various product.
As can be seen here, although the kind of lubricating oil is a lot, but be all that main body is made with base oil, and for the lubricant base produced from crude oil, paraffin base oil oil series, intermediate base base oil series and naphthenic base oils can be divided into serial according to standard.In addition, basis oil properties is except belonging to relevant with the base of crude oil, also depend on working method used to a great extent, the hydrogen addition technology such as extensively adopted can make the quality of lubricant base have greatly improved, and comprises some main character such as viscosity, viscosity index, condensation point and colourity.
Such as, so for selected crude oil, the basic character of above-mentioned cited lubricating oil, can select suitable method of hydrotreating to adjust it, selects conventional Hydrofining Technology can improve the colourity etc. of product; Hydrocracking technology can improve the viscosity, viscosity index etc. of product; Shape slective cracking and selective isomerization can improve the condensation point etc. of product, therefore, if think the lubricant base blend component of production high quality and favourable price, select which kind of hydrogen addition technology to be the crucial part of success or failure.And the selective isomerization technique of current industrial extensive employing, select precious metal as the active ingredient of catalyzer, cost is relatively higher, and the adaptability of raw material is relatively poor, and shape slective cracking technology can make up these deficiencies, shape slective cracking technology, also known as hydrodewaxing, refers in the presence of hydrogen, the raw material of the content of wax by the dual-function catalyst surface containing active metal and molecular sieve, thus reduces wax molecule content wherein.Its dewaxing principle is under certain operating conditions, raw material is mixed with hydrogen contact with Hydrodewaxing catalyst, paraffinic hydrocarbons in raw material, band short-side chain alkane, be cracked into small molecules the naphthenic hydrocarbon of belt length side chain and the contour condensation point compositional selecting of the aromatic hydrocarbons of belt length side chain, and other component does not change substantially, finally reach the object of the condensation point reducing oil product, feature exclusive in its technique is reaction process is thermo-negative reaction, according to the difference of the pour point depression degree of depth, show temperature drop in various degree, consume lower because it has reaction process hydrogen, adaptability to raw material is strong, energy consumption is lower, technical process is simple, process integration or the independent plurality of advantages such as to use can be formed with other hydrogenation process, therefore be widely used.
CN201010222066.7 discloses a kind of method that cycloalkyl distillate hydrogenation produces lubricant base.With cycloalkyl distillate for raw material, the one-stage serial hydrogenation technique of hydrotreatment-hydrodewaxing-hydrofinishing is adopted to produce lubricant base.The method successfully make use of the characteristic of different catalysts, has produced low pour point, the lubricant base of good security.But because all kinds of catalyzer independently loads, certain contradiction is created to the balance that yield and the depression effeCt of lubricating oil distillate improve, reduces the life-span of Hydrodewaxing catalyst.
CN200410050735.1 discloses a kind of production method by paraffinic crude distillate or lubricant base direct production white oil.Adopt one-stage serial technique, by different catalyzer gratings, different catalysts combination loading, integrates the technological process of hydrofining, hydrodewaxing, hydrofinishing.Technique of the present invention is simple, easy to operate, and condition relaxes, and catalyzer has very strong sulfur resistive, nitrogen ability, does not have strict restriction to the sulphur of stock oil, nitrogen content.But also do not utilize the temperature drop of hydrodewaxing process and the temperature rise of hydrogenation process fully, plant energy consumption is comparatively large, and hot(test)-spot temperature is higher, and running period is limited.
CN98121075.9 discloses a kind of method of being produced high-grade low-freezing diesel oil by distillate.The method adopts hydrofining and hydrodewaxing one-stage serial flow process, and comprising Hydrobon catalyst and Hydrodewaxing catalyst two beds, hydrodewaxing adopts Ni/ZSM-5 catalyzer.The method is comparatively large at the temperature drop of Hydrodewaxing catalyst bed, and the yield of diesel oil distillate and the raising of depression effeCt are subject to a definite limitation, reduce the work-ing life of Hydrodewaxing catalyst.
CN200910188163.6 discloses a kind of method of diesel oil hydrogenation pour point depression.The method is character by adjusting catalyzer thus to have diesel oil depression effeCt good, the feature that diesel oil distillate yield is high, but owing to still adopting the combination process of hydrofining and hydrodewaxing series connection, the contradiction between depression effeCt and diesel oil distillate yield still exists.
CN201010514141.7 discloses a kind of method of diesel hydro-pour-reducing.Although the method improves the average reaction temperature of Hydrodewaxing catalyst, utilize the temperature rise of finishing agent, increase the utilization ratio of pour point depression catalyzer, the temperature of reaction of each bed outlet is still relatively high, receives certain restriction running period.
Summary of the invention
For prior art Problems existing, the invention provides a kind of production method of special lubricating oil base oil.The mixed catalyst that hydrodewaxing and hydrofining compound (mixing) load by the inventive method and Hydrodewaxing catalyst carry out grating, temperature rise in the temperature drop of hydrodewaxing process and hydrogenation process is reasonably combined utilization, while the low Solidification Point Lube Base Oils of production, reduce the hot(test)-spot temperature of device, extend running period; Employing the art of this patent can also make up the problem that conventional compound filling process runs in addition, optimizes the effect of mixed packing, is fully mated by dissimilar catalyzer; In addition reduce the consumption of cold hydrogen or the combustion gas loss of process furnace, save process cost, the special lubricating oil base oil aromaticity content produced in addition is lower, and the severity etc. that can reduce the techniques such as follow-up solvent treatment even saves some related process.
The invention provides a kind of production method of special lubricating oil base oil, comprise following content:
After wax oil raw material mixes with hydrogen, successively by the hydroconversion reaction zones of at least two series connection, comprise by the refining pour point depression catalyzer composite bed of Hydrodewaxing catalyst and Hydrobon catalyst mixed packing and Hydrodewaxing catalyst bed successively by each hydroconversion reaction zone, Flow of Goods and Materials direction; The reaction effluent that last hydroconversion reaction zone obtains is through being separated and after fractionation, obtaining the product such as lubricant base, white oil.
According to method of the present invention, wherein in each described hydroconversion reaction zone, wax oil raw material and hydrogen, first by the refining pour point depression catalyzer composite bed by Hydrodewaxing catalyst and Hydrobon catalyst mixed packing, carry out hydrogenating desulfurization, hydrodenitrification, aromatic saturation and pour point depression reaction; Reaction effluent by Hydrodewaxing catalyst bed, carries out the reaction of degree of depth pour point depression again.
According to method of hydrotreating of the present invention, described wax oil raw material is conventional lube stock, and boiling range is generally 250 ~ 550 DEG C, and condensation point is generally all more than-10 DEG C, and preferred condensation point is more than-5 DEG C.The nitrogen content of described lube stock, at 1000 below μ g/g, is generally 50 ~ 800 μ g/g, most preferably is 100 ~ 500 μ g/g.If the organic nitrogen content in wax oil raw material is too high, if nitrogen content is when 1000 more than μ g/g, before the refining pour point depression catalyzer composite bed of wax oil raw material by the first hydroconversion reaction zone, in advance by a hydrofining or hydrodenitrogenation catalyst bed, part denitrogenation can be carried out.The wax oil etc. of the various straight run that described lube stock can obtain for processing naphthenic base crude, intermediate base crude oil or paraffinic crude or secondary processing, the straight-run gas oil component of the naphthenic base crude of preferred time processing, processing LIAOHE CRUDE or the various vacuum gas oils (VGO) that obtain of Kelamayi Crude Oil can be selected from, as one or several in Liaohe River VGO, Kelamayi VGO.When production object is different, also can be selected from the various vacuum gas oils (VGO) that processing paraffinic crude obtains, as one or more in grand celebration VGO, long celebrating VGO.Doing of wax oil raw material is generally 500 ~ 550 DEG C, preferably 510 ~ 540 DEG C.
Described Hydrodewaxing catalyst adopts the catalyzer containing shape slective cracking molecular sieve, comprises the metal component of carrier and institute's load.Described catalyzer generally with shape slective cracking molecular sieve and tackiness agent for carrier, with group VIB and/or group VIII metal for hydrogenation active metals component.Described shape slective cracking molecular sieve is hydrogen type molecular sieve, described molecular sieve can be selected from Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieve one or more, preferred ZSM-5 molecular sieve; The silica alumina ratio of described shape slective cracking molecular sieve is generally 10 ~ 150, is preferably 20 ~ 120.
Described group VIB metal is Mo and/or W, and described group VIII metal is Co and/or Ni.With the weight of catalyzer for benchmark, hydrogenation active metals component is with the content of oxide basis for 1% ~ 16%, and the content of shape slective cracking molecular sieve is 50% ~ 85%, and the content of tackiness agent is 10% ~ 40%.The bulk density of Hydrodewaxing catalyst is generally at 0.65 ~ 0.75gcm
-3, its normal use temperature scope is generally 380 DEG C ~ 410 DEG C.Described Hydrodewaxing catalyst can select existing various commercial catalysts, the Hydrodewaxing catalysts such as FDW-1, FDW-3 that such as Fushun Petrochemical Research Institute (FRIPP) develops; Also can be prepared by the general knowledge of this area as required, such as, can prepare satisfactory Hydrodewaxing catalyst with reference to content disclosed in CN1952074A, CN1352231A, CN101143333A, CN102451748A.
Described Hydrobon catalyst comprises the hydrogenation metal of carrier and institute's load.With the weight of catalyzer for benchmark, generally include metal component of group VIB in the periodic table of elements, as tungsten and/or molybdenum with oxide basis for 10% ~ 35%, be preferably 15% ~ 30%; Group VIII metal as nickel and/or cobalt with oxide basis for 1% ~ 7%, be preferably 1.5% ~ 6%.Carrier is inorganic refractory oxide, is generally selected from aluminum oxide, amorphous silicon aluminium, silicon-dioxide, titanium oxide etc.Hydrobon catalyst can select the modified acquisition of existing various hydrocracking pre-treatment commercial catalysts, such as Fushun Petrochemical Research Institute (FRIPP) develop 3936,3996, the hydrogenation catalyst modification such as FF-26, FF-36, FF-46 preparation; Also can be prepared by the general knowledge of this area as required.
Described Hydrobon catalyst the aluminum oxide of salic to be a kind of crystalline phase be pseudo-boehmite, content is 40w% ~ 80w%.According to the alumina supporter of this technology special preparation, containing macroporous aluminium oxide tackiness agent in Hydrobon catalyst, take catalyst weight as benchmark, macroporous aluminium oxide content is generally 60w% ~ 85w%, preferred 65w% ~ 80w%; The pore volume of described macroporous aluminium oxide is 1.0 ~ 1.7mL/g, is preferably >1.2 ~ 1.7mL/g(and is greater than 1.2 to 1.7 mL/g); Specific surface area is 200 ~ 550m
2/ g, is preferably 300 ~ 500m
2/ g.
In method of the present invention, selected Hydrobon catalyst is when catalyst/support is shaping, preferably be particularly suitable for the sour peptizing techniques of this technique, mineral acid and organic acid mixing acid are joined in moulding process, enhance the character such as the specific surface area of catalyzer, intensity, also simplify the Production Flow Chart of catalyzer in addition, reduce production cost, also can ensure the stability of macroporous aluminium oxide simultaneously, make the pore volume that prepared catalyst/support keeps higher.This technology can be that gained is prepared in the modification when shaping of current industry-wide catalyzer.Adopt catalyzer prepared by this technology, on catalyzer face shaping, be also optimized process simultaneously, be preferably prepared into tooth ball shape catalyst, be convenient to transport, filling and mixing.
Recited above through modified Hydrobon catalyst, due to the change of carrying alumina volume property, when reaching the same reaction degree of depth, its activity will be weaker than about 10 DEG C conventional of Hydrobon catalyst, and normal use temperature scope is elevated to 380 DEG C ~ 400 DEG C.This kind of modified catalyst is compared with Hydrodewaxing catalyst, and in mixing process, bulk density requires that difference is less than 0.05gcm
-3.
The operational condition of the refining pour point depression catalyzer composite bed of described hydrodewaxing and Hydrobon catalyst composition is: reaction pressure 8.0 ~ 20.0 MPa, hydrogen to oil volume ratio 700:1 ~ 1600:1, volume space velocity is 0.1 ~ 10.0 h
-1, temperature of reaction 270 DEG C ~ 460 DEG C; Preferred operations condition is reaction pressure 10.0 ~ 15.0 MPa, hydrogen to oil volume ratio 800:1 ~ 1200:1, volume space velocity 0.3 ~ 8.0 h
-1, temperature of reaction 315 DEG C ~ 425 DEG C.
The operational condition of described Hydrodewaxing catalyst bed is: reaction pressure 8.0 ~ 20.0 MPa, hydrogen to oil volume ratio 600:1 ~ 1500:1, and volume space velocity is 0.1 ~ 10.0 h
-1, temperature of reaction 260 DEG C ~ 455 DEG C; Preferred operations condition is reaction pressure 10.0 ~ 15.0 MPa, hydrogen to oil volume ratio 700:1 ~ 1100:1, volume space velocity 0.3 ~ 8.0 h
-1, temperature of reaction 310 DEG C ~ 420 DEG C.
According to method of the present invention, wherein in each hydroconversion reaction zone, described Hydrodewaxing catalyst bed and be 1:10 ~ 10:1 by the admission space ratio of the refining pour point depression beds of Hydrodewaxing catalyst and Hydrobon catalyst mixed packing, is preferably 1:5 ~ 5:1.
In described refining pour point depression catalyzer composite bed, Hydrodewaxing catalyst and Hydrobon catalyst compound are loaded, and admission space is than being 1:10 ~ 10:1, preferred 1:5 ~ 5:1.
For described at least two hydroconversion reaction zones, wherein said refining pour point depression catalyzer composite bed and Hydrodewaxing catalyst bed, can be separately positioned in two or more beds of a reactor; Or can be separately positioned in the hydrogenator of two or more series connection.
Compared with prior art, the inventive method has the following advantages:
1, in the inventive method, in each hydroconversion reaction zone, first stock oil by refining pour point depression beds, process wax oil raw material, carry out hydrogenating desulfurization, hydrodenitrification, aromatic saturation and pour point depression reaction, this reaction shows as the synergistic effect of heat absorption and heat release.Stock oil after the process of pour point depression process is again by Hydrodewaxing catalyst bed, and carry out the reaction of degree of depth pour point depression, this reaction shows as thermo-negative reaction, and all in all, because hydrogenation reaction shows as thermopositive reaction, this process produces temperature rise; And hydrodewaxing reaction is for selecting the reaction of type molecular sieve cracking, heat effect shows as thermo-negative reaction, and process produces temperature drop; These two kinds of catalyzer are carried out the filling of grating compound, its respective heat release and endothermic effect can be made full use of, the comprehensive utilization of the heat of realization response process, excessive temperature rise and temperature drop effect can not be produced, and affect depression effeCt, thus the hot(test)-spot temperature of whole beds is reduced, both can ensure the yield of lubricant base, also achieve better depression effeCt.And wax oil raw material is first and refining pour point depression catalyst exposure, adaptability to raw material is stronger, in addition Hydrodewaxing catalyst is adopted to carry out grating, compared with the selective isomerization of current industrial widespread use, also have the advantage that catalyzer cost is low, and the lubricant base aromaticity content produced is lower, viscosity is high, can use as special lubricating oil base oil, in addition because the aromatic saturation effect of unifining process can also reduce the severity etc. of the techniques such as follow-up solvent treatment.
2, at process aspect, in each hydroconversion reaction zone, substantially identical effect is all shown.Thus at least two hydroconversion reaction zones of series connection, described hydrogenation reaction shows as comprehensive cumulative effect of optimization.Compared with prior art, the present invention is on the basis of not changing device flow process, by means of only compound filling and the grading composition of catalyzer, from local by the high temperature dot of device and the effective Appropriate application of low warm spot, reduce the hot(test)-spot temperature of device, reasonably decrease the bulk temperature gradient of device, extend the work-ing life of catalyzer, decrease the output of byproduct, improve economic benefit.In addition this combination is compared with the hydrodewaxing combination process of routine, heat due to reaction process obtains and more reasonably utilizes, can beat less between two reaction zones or not liquid hydrogen injection, therefore also reduce the consumption of cold hydrogen and the combustion gas loss of process furnace, save process cost.
3, in the present invention special select suitable Hydrobon catalyst and technique with the use of, there is very large adaptability and advantage.During by itself and Hydrodewaxing catalyst mixed packing, can reach more excellent and load in mixture effect, when avoiding the catalyst mix filling caused because of excessive, the out-of-shape of density variation, the problem of size distribution inequality, the reactive behavior reducing Hydrobon catalyst that modification is simultaneously also suitable, better can mate with Hydrodewaxing catalyst like this, make the two quite active, to play the effect that it is maximum separately in same temperature ranges stated, while reduction product condensation point, can also improve the quality of products.In addition, if be provided with hydrodenitrification reactor before mixing bed, also can reduce denitrification reactor outlet and the temperature head mixing bed inlet, decrease the consumption of cold hydrogen, improve the safety coefficient of plant running, reach more excellent Temperature Matching effect.
Accompanying drawing explanation
Fig. 1 is the grading loading schematic diagram of a kind of embodiment of the inventive method; Single reactor layering is selected to load the operating method with two hydroconversion reaction zones.
Embodiment
Be described in detail below in conjunction with the production method of accompanying drawing to a kind of special lubricating oil base oil of the present invention.
As shown in Figure 1, base oil production method flow process of the present invention is as follows:
Stock oil 1 enters reactor 3 with hydrogen 2 after reactor inlet mixes, from top to bottom successively by the hydrodewaxing of connecting step by step and hydrorefined composite catalyst bed 4, Hydrodewaxing catalyst bed 5, hydrodewaxing and hydrorefined composite bed 6 and Hydrodewaxing catalyst bed 7, obtain reaction effluent 8 and after water filling 9, enter into high-pressure separator 10 from reactor bottom discharge, top obtains gas 11 by circulating hydrogen compressor 12, and hydrogen or cold hydrogen use as a supplement to obtain recycle hydrogen 14 after mixing with new hydrogen 13; The liquid phase that middle and lower part obtains enters light pressure separator 17, and top is discharged low point of gas 18 and gone subsequent disposal, and middle and lower part obtains liquid phase 20 and enters subsequent fractionation system; The sour water 15 of discharging bottom high-pressure separator 10 mixes rear disacidify water treatment device with the sour water 19 of discharging bottom light pressure separator 17 and carries out following process.
Next by specific embodiment, base oil production method of the present invention is further described.The character of used catalyst in embodiment is listed in table 1.Raw materials used oil properties is listed in table 2.
The main physico-chemical property of table 1 catalyzer and active contrast.
| Catalyzer | FF-46 | FF-46G | FDW-3 |
| Catalyst type | Hydrofining | Hydrofining | Hydrodewaxing |
| Wherein macroporous aluminium oxide, % | 5 | 29 | |
| Pore volume, cm 3/g | 0.50 | 1.25 | — |
| Specific surface area, m 2/g | 200 | 210 | — |
| Catalyst physical properties | |||
| Shape | Tooth ball | Tooth ball | Tooth ball |
| Diameter, mm | 2.5 | 2.5 | 2.5 |
| Physical strength, N/cm | ≮150 | ≮130 | ≮100 |
| Active ingredient | Mo-Ni | Mo-Ni | Ni |
| Metal content, % | 29.0 | 22.2 | 2.0 |
| Nature packing density, t/m 3 | 0.88～0.98 | 0.65～0.75 | 0.65～0.75 |
| Mean pore size/nm | 4.44 | 7.75 | — |
| Temperature when reaching the same reaction degree of depth/DEG C | 371 | 380 | — |
| Normal use temperature (just-latter stage)/DEG C | 370～390 | 380～400 | 380～400 |
Comparative example 1
Comparative example 1 is the device adopting hydrofining, hydrodewaxing one-stage serial flow process production lubricant base.Comprise Hydrobon catalyst bed and Hydrodewaxing catalyst bed.Comparative example 1 produces the lubricant base of the identical trade mark with embodiment 1.The catalyzer used, stock oil and lube product condensation point are all identical with embodiment 1.Operation result lists in table 3.
Comparative example 2
Comparative example 2 is the device adopting hydrofining, hydrodewaxing one-stage serial flow process production lubricant base.Control substantially identical base oil yield with embodiment 1, the product condensation point produced is different.The catalyzer that comparative example 2 uses, stock oil and base oil product yield are all identical with embodiment 1, and catalyst loading is with comparative example 1.Operation result lists in table 3.
Embodiment 1
Adopt the technical process shown in Fig. 1, utilize and load in mixture and grating serial flow production lubricant base.Embodiment 1 comprises the hydroconversion reaction zone of two series connection, and in the refining pour point depression catalyzer composite bed of each reaction zone, Hydrodewaxing catalyst is 1:2 with the mixed volume ratio of Hydrobon catalyst, and the total consumption of catalyzer is all identical with comparative example 2 with comparative example 1.The Hydrobon catalyst used in embodiment 1 is FF-46 catalyzer, and Hydrodewaxing catalyst is FDW-3 catalyzer, and described catalyzer is the commercial catalyst of Fushun Petrochemical Research Institute's development and production.
Operational condition and test-results list in table 3.
Embodiment 2
Adopt the technical process shown in Fig. 1, utilize and load in mixture and grating serial flow production lubricant base.Embodiment 1 comprises the hydroconversion reaction zone of two series connection, and in the refining pour point depression catalyzer composite bed of each reaction zone, Hydrodewaxing catalyst is 1:2 with the mixed volume ratio of Hydrobon catalyst, and the total consumption of catalyzer is all identical with comparative example 2 with comparative example 1.The Hydrobon catalyst used in embodiment 2 is FF-46G catalyzer, and Hydrodewaxing catalyst is FDW-3 catalyzer, and described catalyzer is the commercial catalyst of Fushun Petrochemical Research Institute's development and production.
Operational condition and test-results list in table 3.
Table 2 stock oil property list.
| Project | Stock oil |
| Source | Decompressed wax oil |
| Density (20 DEG C)/gcm -3 | 0.9410 |
| Boiling range scope/DEG C | 309～525 |
| Nitrogen/μ gg -1 | 1900 |
| Sulphur/μ gg -1 | 2800 |
| Condensation point/DEG C | 4 |
Table 3 process conditions and result.
| Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | |
| Catalyzer forms | FF-46/FDW-3 | FF-46/FDW-3 | (FF-46+FDW-3)/FDW-3 | (FF-46G+FDW-3)/FDW-3 |
| Reaction pressure/MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Average reaction temperature/DEG C | 385/380 | 385/375 | 386*/380/386*/380 | 390*/380/390*/380 |
| LHSV/h -1 | 2.0/2.0 | 2.0/2.0 | 4.0**/4.0/4.0**/4.0 | 4.0**/4.0/4.0**/4.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Base oil condensation point/DEG C | -13 | -6 | -14 | -15 |
| > 350 DEG C of yields, wt% | 66.4 | 70.5 | 71.5 | 72.7 |
| Base oil viscosity index | 27 | 38 | 27 | 21 |
| Bed vertex temperature/DEG C | 400 | 401 | 396 | 393 |
| Cold hydrogen consumption/benchmark | 0.97 | 1.81 | 1.0 | 0.96 |
* average reaction temperature is the weighted mean temperature of refining pour point depression beds;
* volume space velocity is the volume space velocity of refining pour point depression beds.
As can be seen from above embodiment, the modified catalyst that embodiment 2 uses, there is mixed effect more excellent, hot(test)-spot temperature is lower, the feature that base oil yield is higher simultaneously, in addition, the maximum feature of the inventive method is, for processing wax oil raw material, special lubricating oil base oil can be produced, such as transformer oil, refrigerator oil, rubber filling material etc., there is adaptability to raw material stronger, the feature that catalyzer cost is low, the lubricant base foreign matter content produced is few, the condensation point of raw material can be reduced when ensureing certain base oil yield, the white oil that goes out of by-product and petroleum naphtha also can be the industrial chemicals of high-quality and make up the drawback of conventional mixed packing simultaneously, in addition also to have hot(test)-spot temperature low for the inventive method, and running period is long, the feature that cold hydrogen consumption is low, the lubricant base aromaticity content produced is lower, and the severity that can reduce the techniques such as follow-up solvent treatment even saves some related process, for enterprise, while completing quality products production task, human and material resources and energy consumption have very large advantage.
Claims (11)
1. the production method of a special lubricating oil base oil, comprise following content: after wax oil raw material mixes with hydrogen, successively by the hydroconversion reaction zone of at least two series connection, by Flow of Goods and Materials direction, each hydroconversion reaction zone comprises by the refining pour point depression composite catalyst bed of Hydrodewaxing catalyst and Hydrobon catalyst mixed packing and Hydrodewaxing catalyst bed successively; The reaction effluent that last hydroconversion reaction zone obtains is through being separated and after fractionation, obtaining the product such as lubricant base, white oil.
2. in accordance with the method for claim 1, it is characterized in that, described wax oil raw material condensation point more than-10 DEG C, preferably more than-5 DEG C; Nitrogen content, at 1000 below μ g/g, is preferably 100 ~ 500 μ g/g.
3. in accordance with the method for claim 1, it is characterized in that, the nitrogen content of described wax oil raw material is at 1000 more than μ g/g, pass through the refining pour point depression catalyzer composite bed of the first hydroconversion reaction zone at wax oil raw material before, in advance by a hydrofining or hydrodenitrogenation catalyst bed, carry out part denitrogenation.
4. in accordance with the method for claim 1, it is characterized in that, doing of described wax oil raw material is 500 ~ 550 DEG C, preferably 510 ~ 540 DEG C.
5. in accordance with the method for claim 1, it is characterized in that, in described each hydroconversion reaction zone, Hydrodewaxing catalyst bed and the admission space ratio by the refining pour point depression composite catalyst bed of Hydrodewaxing catalyst and Hydrobon catalyst mixed packing are 1:10 ~ 10:1.
6. in accordance with the method for claim 1, it is characterized in that, in described composite catalyst bed, Hydrodewaxing catalyst and Hydrobon catalyst mixed packing, admission space is than being 1:10 ~ 10:1.
7. in accordance with the method for claim 1, it is characterized in that, the operational condition of described Hydrodewaxing catalyst bed is: reaction pressure 8.0 ~ 20.0 MPa, hydrogen to oil volume ratio 600:1 ~ 1500:1, and volume space velocity is 0.1 ~ 10.0 h
-1, temperature of reaction 260 DEG C ~ 455 DEG C; The operational condition of described composite bed is: reaction pressure 8.0 ~ 20.0 MPa, hydrogen to oil volume ratio 700:1 ~ 1600:1, and volume space velocity is 0.1 ~ 10.0 h
-1, temperature of reaction 270 DEG C ~ 460 DEG C.
8. in accordance with the method for claim 1, it is characterized in that, described Hydrodewaxing catalyst with shape slective cracking molecular sieve and tackiness agent for carrier, with group VIB and/or group VIII metal for hydrogenation active metals component, with the weight of catalyzer for benchmark, hydrogenation active metals is with the content of oxide basis for 1% ~ 16%, and the content of shape slective cracking molecular sieve is 50% ~ 85%, and the content of tackiness agent is 10% ~ 40%.
9. according to the method described in claim 1 or 8, it is characterized in that, the bulk density of described Hydrodewaxing catalyst is 0.65 ~ 0.75gcm
-3, the bulk density of described Hydrobon catalyst is 0.65 ~ 0.75gcm
-3, wherein the difference of the bulk density of Hydrobon catalyst and Hydrodewaxing catalyst is less than or equal to 0.05 gcm
-3.
10. in accordance with the method for claim 1, it is characterized in that, with the weight of catalyzer for benchmark, described Hydrobon catalyst tungsten and/or molybdenum are with oxide basis 10% ~ 35%, nickel and/or cobalt are with oxide basis 1% ~ 7%, carrier is inorganic refractory oxide, is selected from one or more in aluminum oxide, amorphous silicon aluminium, silicon-dioxide, titanium oxide.
11. in accordance with the method for claim 10, it is characterized in that, containing macroporous aluminium oxide in described Hydrobon catalyst, take catalyst weight as benchmark, macroporous aluminium oxide content is 60w% ~ 85w%, preferred 65w% ~ 80w%; The pore volume of described macroporous aluminium oxide is 1.0 ~ 1.7mL/g, is preferably greater than 1.2 to 1.7 mL/g; Specific surface area is 200 ~ 550m
2/ g, is preferably 300 ~ 500m
2/ g.
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| CN109423351A (en) * | 2017-08-22 | 2019-03-05 | 中国石油天然气股份有限公司 | Low-temperature switch oil and preparation method thereof |
| CN113969186A (en) * | 2020-07-23 | 2022-01-25 | 中国石油化工股份有限公司 | Method for producing refrigerator oil |
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