CN106566589A - Method for processing high-wax-content lubricant base oil - Google Patents

Abstract

The invention relates to a method for processing high-wax-content lubricant base oil. According to the method, a wax-containing mixed oil raw material with the wax content not smaller than 50 wt% and hydrogen are mixed to enter a hydroisomerization reactor, and the mixture firstly passes through a first bed layer containing mesoporous-micropore composite molecular sieve based catalysts to be subjected to primary hydroisomerization; then, the mixture passes through a second bed layer containing ten-membered ring one-dimension duct molecular sieve based catalysts to be subjected to deep hydroisomerization; a reaction product enters a supplement refined reactor to react with a noble metal catalyst, the arene deep saturation reaction is conducted, and the oil color degree and oxidation stability are improved; and then the product is subjected to fractional distillation, and light lubricant and heavy lubricant base oil are obtained. By means of the method, the high-wax raw materials can be subjected to sufficient hydroisomerization, and the method has the beneficial effects that the product pour point is low, and the base oil yield is high.

Description

A kind of method for processing high wax content lube base oil

Technical field

The present invention relates to a kind of method for processing high wax content lube base oil, belongs to lube base oil processing neck Domain.

Background technology

Fischer-tropsch wax is a kind of heavy product of Fiscber-Tropscb synthesis, is with the impurity contents such as relatively low S, N, higher viscosity The very good material of production high-quality lube base oil.In recent years, with the continuous popularization of F- T synthesis technology, Fischer-Tropsch wax it is comprehensive Close using the attention for also constantly causing people.

United States Patent (USP) US2004/0065584A1 and European patent WO2004/033595A1 are described with the hydrocarbon of F- T synthesis Class is raw material, through multistep hydrogenation, prepares the process of heavy lubricating oil base oil, dewaxing catalyst by ZSM-48 (including EU-2, The structure identical molecular sieve such as EU-11, ZBM-30) and a kind of hydrogenation component composition.United States Patent (USP) US 7,198,710 is described A kind of process route for being prepared lube base oil in the F- T synthesis wax oil of 750 ℉ -900 ℉ by boiling range, will alkane point Light component and heavy constituent are cut into, two kinds of raw materials carry out respectively isomerization reaction on the molecular sieve catalyst of medium pore sizes, then Weight base oil is carried out into atomization process so as to which pour point and cloud point are less than or equal to target pour point and cloud point.Patent WO97/21788 Fischer-Tropsch wax is carried out into hydroisomerizing and hydrocracking reaction in bifunctional catalyst first, afterwards separates product with 700 °F, it is high Boiling point fraction (700 °F of ＞) removes n-alkane therein through traditional solvent dewaxing, then obtains through rectification under vacuum again The lube base oil of different viscosities index.Used catalyst is SiO₂-Al₂O₃The Co-Mo-Ni series catalysts of upper load.Patent EP0323092 describes the method that Fischer-Tropsch wax is converted into the lubricating oil with high viscosity index (HVI) and low pour point, and wax is first violent Under conditions of through hydrotreating (R-1), then in presence of hydrogen through hydroisomerizing (R-2), used catalyst is specified Load the 8th group of metal fluoride on alumina.Hydroisomerization form is again through dewaxing (D-1) production high-quality lubrication oil base Plinth oil.United States Patent (USP) US7704379 and Chinese patent CN 1703490A, disclose one kind and Fischer-Tropsch wax are changed into into high-quality profit Lubricant base oil, first by beta-molecular sieve catalyst, is then used by average diameter 0.50nm to 0.65nm, maximum gauge and most Minor diameter difference is less than 0.05nm, the one-dimensional mesoporous molecular sieve with approximately circular opening structure.Both catalyst all by a kind of or More 8th group of metal compositions.Chinese patent CN 103831135A disclose a kind of Fischer Tropsch waxes selective isomerization catalyst, Its special type is the molecular sieve SAPO- that catalyst is modified by non-noble metal j element in precious metals pt or Pd oxides, transition metal 11 and heteropoly acid composition.Patent CN 103102956A discloses a kind of hydrogenation producer of base oil of high viscosity index lubricant Method, with one or more content of wax in hydrotreating distillate, the frivolous oil of hydrotreating, Fischer Tropsch waxes or hydrocracking tail oil Oil is feedstock oil, and raw material and hydrogen are mixed into hydroisomerization reactor, and product is fractionated, obtain light lubricating oil and Heavy grease, heavy grease at least partly loops back hydroisomerizing dewaxing reactor.Patent CN 102533329A is disclosed A kind of method for producing lube base oil by Fischer Tropsch waxes, raw material first passes through hydrofinishing and then through two-stage hydroisomerizing Obtain isomery oil, then through isolated lube base oil, isomery section used catalyst be mesoporous molecular sieve ZSM-5, One or more carried noble metal catalysis in ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, SAPO-11 and SAPO-11 Agent.

Above patent takes different process and different catalysts to process the lube base oil original of Fischer-Tropsch wax grade height wax content Material, for how effectively proposing effective method using Fischer-Tropsch wax, but there is macromolecular macromolecular wax isomerization The big selectivity of difficulty is low, the not high problem of reaction selectivity and base oil yield.

The content of the invention

The purpose of the present invention overcomes the deficiencies in the prior art, there is provided a kind of processing of high wax content Lube basic oil material feedstocks Method, the conversion ratio for improving wax by two sections of step isomerization handling process improves selectivity simultaneously, with wax high conversion rate, base The characteristics of plinth oil yield is high.

Find under study for action, Fischer-Tropsch wax is being processed using traditional molecular sieve catalyst with MTT and TON topological structures Deng wax content higher raw material when, the conversion ratio of wax is very low, and needing to improve temperature increases the conversion ratio of wax, but simultaneously because temperature The too high yield that can reduce base oil.Using MCM-41 or SBA-15 and ZSM-22 or ZSM-23 eutectics be combined to it is mesoporous-micro- When high wax content raw material is processed with higher wax conversion ratio, but liquid receives lower slightly to hole composite molecular sieve catalyst.Therefore, we The two is filled in same reactor by novelty according to certain level with mode, coordinates the appropriate hydrogenation technique can be efficient Process the raw material of high wax content, with wax high conversion rate, it is selective good the characteristics of.

The present invention is achieved especially by technical scheme below：

A kind of method for processing high wax content Lube basic oil material feedstocks, the content of wax miscella of wax content ≮ 50wt% is former Material is mixed into hydroisomerization reactor with hydrogen, first passes around equipped with mesoporous-microporocomposite composite molecular sieve catalyst first Layer, carries out preliminary hydroisomerizing；Then depth is carried out through the second bed equipped with ten-ring one-dimensional channels molecular sieve catalyst Hydroisomerizing；The volume ratio of the first bed catalyst and the second bed catalyst is 1～3:3；Product enters post-refining Reactor, with noble metal catalyst reaction, carries out aromatic hydrocarbons depth saturated reaction, improves oil product oxidation stability；Then Product obtains light lubricating oil and heavy lubricant base stock through fractionation.Hydroisomerizing section is divided into two reaction beds, and first Bed loads mesoporous-microporocomposite composite molecular sieve catalyst, is adapted to Long carbon chain wax molecule isomery；Second bed filling ten-ring is one-dimensional Duct molecular sieve catalyst, is adapted to the hydroisomerizing compared with short carbon chain wax molecule；So that it is guaranteed that the abundant hydroisomerizing of high wax stock, It is low with product pour point, the characteristics of base oil yield is high.

In above-mentioned technical proposal, described content of wax miscella raw material be Fischer-Tropsch wax or Fischer-Tropsch wax with hydrocracking tail oil, The miscella of hydrogenation distillate.

Described mesoporous-microporocomposite composite molecular sieve is by micropore ZSM-23 or ZSM-22 (core) and mesostructured material (shell) or SBA-15 (shell) are compounded to form composite molecular screen ZM and ZS with core shell structure by the way of eutectic；

Described ten-ring one-dimensional channels molecular sieve refers to ZSM-22 or ZSM-23；

Described molecular sieve catalytic agent carrier is the complex carrier of molecular sieve and aluminum oxide composition, active metal be Pt and/ Or Pd；

The operating condition of described hydroisomerization reactor be 5～20MPa of pressure, 300 DEG C～380 DEG C of temperature, hydrogen oil body Product ratio 300～1000:1,0.5～2.0h of volume space velocity^-1。

Compared with prior art, the present invention prepares lube base oil to the inventive method using the feedstock oil of high wax content, Particularly hydroisomerizing section is divided into two reaction beds, and the first bed filling mesoporous-microporocomposite composite molecular sieve catalyst is adapted to length Carbochain wax molecule isomery；Second bed loads ten-ring one-dimensional channels molecular sieve catalyst, is adapted to adding compared with short carbon chain wax molecule Hydrogen isomery is the characteristics of base oil yield is high and whole so that it is guaranteed that the abundant hydroisomerizing of high wax stock, low with product pour point Body technology is simple.

Specific embodiment

Technical solution of the present invention is described further with reference to specific embodiment, but does not limit the guarantor of the inventive method Shield scope.

Wherein embodiment 1-8 is catalyst preparation example, and embodiment 9-10 is the inventive method hydroisomerizing section first Layer, the second bed use the embodiment of different catalysts, and comparative example 1-2 is hydroisomerizing section only with a kind of feelings of catalyst Condition.

It is raw materials used for Fischer-Tropsch wax and hydrocracking tail oil miscella in embodiment 9-10 and comparative example 1-2, main character Such as following table：

The raw material main character of table 1

Embodiment 1

(1) ZSM-22 Zeolite synthesis

ZSM-22 Zeolite synthesis are carried out according to patent US4556477.1) by 28.6g Ludox (30wt%SiO₂) and 29.8g deionized water is well mixed；2) by 1g aluminum sulfate (17.2wt%Al₂O₃), 2.3g potassium hydroxide and 52.3g deionized waters It is well mixed；1) and 2) 3) solution is mixed into 15min, then 5g hexamethylene diamines is added into mixed solution, stirring；4) 3) solution is put in the autoclave with stirring, 160 DEG C is heated to, stirring, reaction 72h；5) and then through washing, mistake Filter, by filter cake and is dried 10h and obtains SiO at 110 DEG C₂/Al₂O₃The ZSM-22 molecular screen primary powders of mol ratio about 60.

(2) it is molecular sieve modified：

1) by ZSM-22 original powder roasting 6h at 600 DEG C；2) with the NH of 0.3mol/L₄NO₃The aqueous solution molecular sieve is carried out from Son is exchanged.Give-and-take conditions are：Solid-liquid mass ratio is 1:10,90 DEG C of exchange temperature, swap time 2h；3) exchange solution after terminating Washed, filtered to filtrate in neutrality；4) filter cake is dried into 6h in 110 DEG C, obtains H-ZSM-22.

Embodiment 2

(1) ZSM-23 synthesis

The synthesis of ZSM-23 is according to method disclosed in United States Patent (USP) US4076842：1) by 3.3g sodium metaaluminate (43.1wt% Al₂O₃, 33.1wt%Na₂O and 24.7wt%H₂O), 30g deionized waters and 0.34gNaOH (the 50wt% aqueous solution) mixing, stirring Uniformly, it is subsequently adding 18.2g pyrrolidines to continue to stir；2) by 164.8g Ludox (30%SiO₂, 70%H₂O) add above-mentioned molten Liquid, stirs until forming gel；3) above-mentioned gel is put into into heating in autoclave, stirring, and in 180 DEG C of continuous crystallizations 7 My god；4) filter cake is dried about 16 hours by product through washing, filtering to filtrate in neutrality at 110 DEG C, obtains SiO₂/ Al₂O₃The ZSM-23 molecular screen original powder of mol ratio about 60.

(2) molecular sieve modified method obtains H-ZSM-23 according to the method for embodiment 1.

Embodiment 3

Composite molecular screen ZM synthesizes

16g cetyl trimethylammonium bromides (CTAB) are weighed, 777g deionized waters are added, is stirred to dissolving, Ran Houyi Secondary addition 33.3g Ludox (30%SiO₂, 70%H₂O), 1.25g aluminum sulfate, 40g ZSM-23 molecular screens original powder, are well mixed, It is eventually adding a certain amount of NaOH and adjusts pH value of solution to 10～11, continues to stir 2h.Reactant liquor is fitted in crystallizing kettle, 120 DEG C Crystallization 24h；The cooling of product Jing, washing, drying, obtain composite molecular screen original powder ZM.Composite molecular screen intermediary hole MCM-41 Molecular sieve accounts for 20wt%.

Take 100g composite molecular screen ZM and be put into 2L beakers, add 1L deionized waters, be subsequently adding 24gNH₄NO₃, stir and add Heat keeps 4h to 90 DEG C；Then filter, be washed to neutrality, in 120 DEG C of dryings 2 hours, then 550 DEG C of roastings 4 hours, obtained H-ZM。

Embodiment 4

Composite molecular screen ZS synthesizes

24g triblock copolymers PEO-PPOX-PEO (P123) is weighed, adds 577g to go Ionized water, stirs to dissolving, then sequentially adds 33.3g Ludox (30%SiO₂, 70%H₂O), 1.25g aluminum sulfate, 40g ZSM-23 molecular screen original powder, is well mixed, and is eventually adding a certain amount of HCl and adjusts pH value of solution to 2～4, continues to stir 2h.Will be mixed Close slurries to be fitted in crystallizing kettle, 100 DEG C of crystallization 24h；The cooling of product Jing, washing, drying, obtain composite molecular screen original powder ZS.Wherein, composite molecular screen intermediary hole SBA-15 molecular sieves account for 20wt%.

Take 100g composite molecular screen ZS and be put into 2L beakers, add 1L deionized waters, be subsequently adding 24gNH₄NO₃, stir and add Heat keeps 4h to 90 DEG C；Then filter, be washed to neutrality, in 120 DEG C of dryings 2 hours, then 550 DEG C of roastings 4 hours, obtained H-ZS。

Embodiment 5

Pt-ZSM-22 catalyst preparations

1) by 82.4g H-ZSM-22,160g SB powder (butt 75wt%, Al₂O₃Content ＞ 99%), 2.4g Methyl celluloses Element mixing；2) 142g5wt% dilute nitric acid solutions are configured；3) by 2) with 1) kneading 40min in kneading machine, then extruded moulding, Extrude the bunge bedstraw herb of a diameter of 2.0 × 1.8mm；4) will obtain after bunge bedstraw herb type carrier is dried 6h at 120 DEG C in N₂Under atmosphere, 400 DEG C of roasting 6h, then change blowing air, are warming up to 550 DEG C of roasting 4h；5) 50g carriers are taken, then by 30g Pt contents 0.67wt% chloroplatinic acid aqueous solutions are added drop-wise on carrier, and room temperature volumetric dipping 8h is dried 6h after 110 DEG C, then in 350 DEG C roasting 4h.

Embodiment 6

Pt-ZSM-23 catalyst preparations

1) by 82.4g H-ZSM-23,160g SB powder (butt 75wt%, Al₂O₃Content ＞ 99%), 2.4g Methyl celluloses Element mixing；2) 142g5wt% dilute nitric acid solutions are configured；3) by 2) with 1) kneading 40min in kneading machine, then extruded moulding, Extrude the bunge bedstraw herb of a diameter of 2.0 × 1.8mm；4) will obtain after bunge bedstraw herb type carrier is dried 6h at 120 DEG C in N₂Under atmosphere, 400 DEG C of roasting 6h, then change blowing air, are warming up to 550 DEG C of roasting 4h；5) 50g carriers are taken, then by 30g Pt contents 0.67wt% chloroplatinic acid aqueous solutions are added drop-wise on carrier, and room temperature volumetric dipping 8h is dried 6h after 110 DEG C, then in 350 DEG C roasting 4h.

Embodiment 7

Pd-ZM catalyst preparations

1) by 90g H-ZM, 147g SB powder (butt 75wt%, Al₂O₃Content ＞ 99%), the mixing of 2.4g methylcellulose； 2) 142g5wt% dilute nitric acid solutions are configured；3) by 2) with 1) kneading 40min in kneading machine, then extruded moulding, extrudes diameter For the bunge bedstraw herb of 2.0 × 1.8mm；4) will obtain after bunge bedstraw herb type carrier is dried 6h at 120 DEG C in N₂Under atmosphere, 400 DEG C of roastings 6h, then changes blowing air, is warming up to 550 DEG C of roasting 4h；5) 50g carriers are taken, then by 30g Pd content 0.67wt% chloroplatinic acids The aqueous solution is added drop-wise on carrier, and room temperature volumetric dipping 8h is dried 6h after 110 DEG C, then in 400 DEG C of roasting 4h.

Embodiment 8

Pd-ZS catalyst preparations

1) by 90g H-ZS, 147g SB powder (butt 75wt%, Al₂O₃Content ＞ 99%), the mixing of 2.4g methylcellulose； 2) 142g5wt% dilute nitric acid solutions are configured；3) by 2) with 1) kneading 40min in kneading machine, then extruded moulding, extrudes diameter For the bunge bedstraw herb of 2.0 × 1.8mm；4) will obtain after bunge bedstraw herb type carrier is dried 6h at 120 DEG C in N₂Under atmosphere, 400 DEG C of roastings 6h, then changes blowing air, is warming up to 550 DEG C of roasting 4h；5) 50g carriers are taken, then by 30g Pd content 0.67wt% chloroplatinic acids The aqueous solution is added drop-wise on carrier, and room temperature volumetric dipping 8h is dried 6h after 110 DEG C, then in 400 DEG C of roasting 4h.

Embodiment 9

Post-refining catalyst preparation

Prepared by post-refining catalyst reference Chinese patent CN101850265A methods, 1) with the production of Wenzhou catalyst plant NaY zeolite 120g is put in the 1L aqueous solution of 120gNH4NO3 and 2mL red fuming nitric acid (RFNA)s, is warming up to 85 DEG C, is filtered after stirring 3h, is washed Wash, dry.2) to step 1) product that obtains carries out hydro-thermal process, 650 DEG C of water partial pressure 0.25MPa, temperature；3) by step 2) To product repeat step 1) 2) after, product is dried 12h at 110 DEG C, makes HY zeolite molecular sieves；4) with contain equivalent to The chlorine palladium acid of 3.6gPd and the chloroplatinic acid equivalent to 2.4gPt are made into the 1190mL aqueous solution, and the PVP solution 60mL of 5g/L is added In above-mentioned solution, 2h is stirred, add the HCHO solution 150mL that concentration is 2%, stirring reduction 5h, noble metal glue is obtained after reduction Body；6) by step 5) precious metal colloid that obtains is sprayed on the mixed carrier surface that step 4 is obtained, and needs stirring to carry during sprinkling Body powder, dries 60h under normal temperature, normal pressure, keeps air humidity 60%, then heats up 1 DEG C per 3min, and temperature is risen to into 55 DEG C, 20h is dried, then heat up 1 DEG C per 5min, temperature is risen to into 100 DEG C, 48h is dried, need first to vacuumize during drying, Ran Houtong Enter nitrogen, be maintained at nitrogen atmosphere；7) the aluminum oxide 285g of Shandong Aluminum Plant's production, and step 6 are weighed) the product machinery that obtains is mixed It is even, add the aqueous solution of nitric acid of 1300mL4%, and add 20g citric acids and 20g sesbania powders, be sufficiently mixed it is uniform, extrusion into Type, is shaped asBunge bedstraw herb, be to slowly warm up to dry 16h under 110 DEG C, nitrogen atmosphere, then heat up in an oxygen-free atmosphere To 550 DEG C of roasting 3h, catalyst is obtained.

Embodiment 10

The catalyst of 50mL embodiments 5 is loaded into 100mL high-pressure hydrogenation evaluating apparatus first reactors bottom bed, is then filled Fill out 10mLInert ceramic balls, then in the catalyst of top bed filling 40mL embodiments 7.Second reactor filling 110mL is implemented Post-refining catalyst prepared by example 9；Catalyst packing finishes laggard luggage and puts nitrogen purging, pressure testing.Then use hydrogen instead to blow Sweep, device pressure is raised to into 6MPa, hydrogen flowing quantity is adjusted to 50L/h, and beds are warming up to the heating rate of 50 DEG C/h 150 DEG C, catalyst is dried after 2h, is warming up to 310 DEG C with 25 DEG C/h heating rates and is stopped 2h, carries out catalyst reduction, reduction After end two it is counter be cooled to 220 DEG C, start into feedstock oil, inlet amount is 100mL/h, while one it is counter be warming up to 330 DEG C, heat up speed 25 DEG C/h of rate.

Gas-liquid separation is carried out through high-pressure separator after two anti-hydrogenation products coolings out, product liquid enters products pot.

Embodiment 11

One anti-upper and lower two beds load respectively embodiment 8 and the catalyst of embodiment 6, the other the same as in Example 10.

Comparative example 1

One anti-upper and lower two beds load the catalyst of embodiment 6, the other the same as in Example 10.

Comparative example 2

One anti-upper and lower two beds load the catalyst of embodiment 8, the other the same as in Example 10.

Liquid is received and calculated：

Liquid yield=(product liquid rewinding amount (weight)/liquid charging stock inlet amount (weight)) * 100%

Product pour point is analyzed：Detected using ASTM D97 methods

Base oil yield：Distillation (ASTM D7213) is simulated to product, according to simulation distillation curve, recovered (distilled) temperature ＞ Oil distillate based on 320 DEG C of components, i.e.,：320 DEG C of component weight percent content * liquid of base oil yield=recovered (distilled) temperature ＞ are received Rate

Evaluation result is shown in Table (2).

The evaluation result of table 2

Project	Hydrogenation products pour point, DEG C	Liquid is received, %	Base oil yield, %
				Embodiment 10	-38	93.2	83.9
Embodiment 11	-42	92.7	82.5
				Comparative example 1	-27	93.9	84.5
Comparative example 2	-43	89.2	77.6

Claims (7)

1. the method for the high wax content lube base oil of a kind of processing, it is characterised in that mix the content of wax of wax content ≮ 50wt% Close oily raw material and be mixed into hydroisomerization reactor with hydrogen, first pass around equipped with mesoporous-microporocomposite composite molecular sieve catalyst First bed, carries out preliminary hydroisomerizing；Then enter through the second bed equipped with ten-ring one-dimensional channels molecular sieve catalyst Row deep hydrogenation isomery；Product enters post-refining reactor, with noble metal catalyst reaction, carries out aromatic hydrocarbons depth saturation Reaction, improves oil product oxidation stability；Then product obtains light lubricating oil and heavy lubricant base through fractionation Oil.

2. method according to claim 1, it is characterised in that described content of wax miscella raw material is Fischer-Tropsch wax or Fischer-Tropsch wax With hydrocracking tail oil, the miscella of hydrogenation distillate.

3. method according to claim 1, it is characterised in that mesoporous-microporocomposite composite molecular sieve be with micropore ZSM-23 or ZSM-22 is core, is compounded to form with core shell structure by the way of eutectic as shell with mesostructured material or SBA-15 Composite molecular screen.

4. method according to claim 1, it is characterised in that ten-ring one-dimensional channels molecular sieve is ZSM-22 or ZSM- 23。

5. method according to claim 1, it is characterised in that the carrier of molecular sieve catalyst is molecular sieve and aluminum oxide group Into complex carrier, active metal be Pt and/or Pd.

6. method according to claim 1, it is characterised in that the volume of the first bed catalyst and the second bed catalyst Than for 1～3:3.

7. method according to claim 1, it is characterised in that the operating condition of hydroisomerization reactor be pressure 5～ 20MPa, 300 DEG C～380 DEG C of temperature, hydrogen to oil volume ratio 300～1000:1,0.5～2.0h of volume space velocity^-1。