CN1219034C - Lube oil hydrogenation treating catalyst and preparing method thereof - Google Patents

Lube oil hydrogenation treating catalyst and preparing method thereof Download PDF

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CN1219034C
CN1219034C CN 03133556 CN03133556A CN1219034C CN 1219034 C CN1219034 C CN 1219034C CN 03133556 CN03133556 CN 03133556 CN 03133556 A CN03133556 A CN 03133556A CN 1219034 C CN1219034 C CN 1219034C
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molecular sieve
solution
catalyzer
pressure
ton
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CN1552822A (en
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刘全杰
徐会青
孙万付
周勇
杨军
王伟
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The present invention relates to a hydrotreating catalyst of lubricating oil and a making method of the hydrotreating catalyst. The hydrotreating catalyst of lubricating oil comprises active metal and a compound molecular sieve having the characteristics of TON structure and MFI structure. The molecular sieve simultaneously has the characteristics of the TON structure and the MFI structure, thereby enabling paraffin hydrocarbons to react in a form-selecting cracking-isomerization mode. The hydrotreating catalyst of lubricating oil is used for the hydrotreating process of lubricating oil fractions. The present invention has the characteristics of low reaction temperature, high yield of base oil, low product pour point, high viscosity index, etc.

Description

A kind of lube oil hydrogenation is handled Catalysts and its preparation method
Technical field
The present invention relates to a kind of lube oil hydrogenation and handle Catalysts and its preparation method.More particularly, the present invention relates to a kind of hydrotreating catalyst that comprises a kind of TON of having and two kinds of constitutional features composite molecular screens of MFI and preparation method thereof, catalyzer of the present invention is specially adapted to lubricating oil distillate hydrotreatment process.
Background technology
Owing to contain the higher macromole straight chain of a large amount of fusing points or few branched paraffin (being commonly referred to wax) in the lubricating oil distillate, so its pour point is higher, viscosity index is low and poor performance at low temperatures.Improve these performances, will remove high melting-point wax wherein is all or part of.Process for dewaxing commonly used at present mainly contains solvent dewaxing, catalytic dewaxing and isomerization dewaxing.
Solvent dewaxing is exactly to utilize the solubility property of wax in solvent to remove, and the shortcoming of this method is that solvent selects a large amount of organic solvent of difficulty, waste, harmful and contaminate environment, facility investment and process cost height and quality product limited by raw material.Catalytic dewaxing just is to use has the catalyzer of selecting shape cracking function, make wax component generation selective catalytic cracking in the lubricating oil distillate, generation is than the hydro carbons of small molecules, thereby make the base oil depression of pour point, for example P.4247388 U.S. Pat just is to use the method for catalytic dewaxing with USP.4659311, the shortcoming of this method is because the macromolecular cpd of a large amount of high values is converted into the small-molecule substance of low value, makes that base oil yield is low, the viscosity index loss is big, by product value is low.Compare with preceding two kinds of process for dewaxing, isomerization dewaxing is to make macromole wax generation isomerization reaction generate isoparaffin, and isoparaffin pour point and the higher viscosity index lower than having with the wax phase of same molecular amount, and still be retained in the lubricating oil distillate, thereby base oil yield is greatly enhanced.
The purpose of isomerization dewaxing is exactly to make high melting-point wax be converted into the lower isoparaffin of fusing point, but the alkane fusing point that isomerisation degree is high is higher on the contrary, so isomerisation degree that just must control wax molecule, this has just proposed strict requirement to the acid matter of acidic components and pore structure and hydrogenation component.Acidic components will have the moderate acid sites of intensity and have the pore structure of space constraint effect in general, and active metal component has hydrogenation/dehydrogenation activity fast, prevent the further isomery and even the cracking of uncle's carbonium ion.
At present a lot of about the report of isomerization dewaxing catalyst, for example, U.S. Pat P5990371,5833,837,5817907,5149421,5135638,5110445,4919788,4419420,4601993,4599162,4518485 etc. all is that report relates to the isomerization dewaxing technology and produces lubricant base, and use therein acidic components mainly contain mordenite, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, SSZ-32, Nu-10, KZ-2 and ISI-1, ZSM-22 etc.These materials can both make paraffinic hydrocarbon generation isomerization reaction to a certain extent, but for some reactions, particularly for the reaction of some mixtures, lubricating oil distillate for example, owing to wherein contain very complicated component, not that identical molecule is participated in reaction, so some adaptability problems will occur for molecular sieve with homogeneous structural, to a kind of molecule can fine coupling catalytic material, just may not be very desirable for other component.
Molecular sieve for different structure, owing to have its unique pore passage structure and physico-chemical property, so be fit to different purposes, for example the MFI structure molecular screen has three-dimensional zigzag duct, less (the 0.65nm * 0.51nm), be applied to micromolecular conversion and macromolecular selective splitting process in aperture more; The TON structure molecular screen has suitable aperture, and (structure in 0.56nm * 0.56nm) and one dimension straight hole road in the isomerization reaction of hydrocarbon molecules, has unique effect.
In the 1980s, the high silicon Si-Al zeolite molecular sieve that one class is new is found, this class zeolite is owing to have very unique TON structure and physico-chemical property, paraffinic hydrocarbon isomerization aspect there is good performance, its XRD result has table 1 feature, for example THA-1, Nu-10, KZ-2, ISI-1 and ZSM-22 etc.An other class has MFI structure high-silica zeolite, because its special Z font pore passage structure, selects aspect the shape cracking very suitablely at straight-chain paraffin, and its XRD result has table 2 feature, for example ZSM-5 etc.
For lubricating oil distillate, because existing, paraffinic hydrocarbon cause its condensation point higher, low temperature flowability is poor, if only pass through the isomerization reaction of wax component, often can not make its condensation point reach the ideal effect, and may cause viscosity index to reduce, if, base oil character is done the trick taking place isomerizedly simultaneously some paraffinic hydrocarbon components that are difficult for taking place isomerization reactions to be carried out suitable cracking.So just wish that a catalyzer has the shape of selecting cracking and isomerized multi-functional simultaneously, if adopt multiple molecular sieve to carry out mechanically mixing, the poor dispersion of molecular sieve often can not make separately characteristics give full play to, and embodies the good synergistic of not coming out.
The XRD result of table 1 TON structure molecular screen
d hkl(nm) I/I 0
1.090±0.02 0.870±0.016 0.694±0.010 0.458±0.007 0.436±0.007 0.368±0.005 0.362±0.005 0.347±0.004 0.252±0.002 M-W VW VW VW VS VS S M W-VW
The XRD result of table 2 MFI structure molecular screen
d hkl(nm) I/I 0
1.114±0.004 0.999±0.005 0.972±0.004 0.599±0.006 0.558±0.004 0.437±0.006 0.386±0.002 0.382±0.004 0.375±0.004 0.373±0.004 0.365±0.005 0.332±0.006 0.305±0.007 0.298±0.006 S M VW VW VW VW VS VS S-M S W VW VW W-VW
The represented relative intensity of symbol is worth as follows in the form: VS, 80%-100%; S, 60%-80%; M, 40%-60%; W, 20%-4%0; VW,＜20%.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of paraffinic hydrocarbon and select shape cracking-isomerization dual-function catalyst and preparation method thereof.Specifically, this catalyzer comprises the NEW TYPE OF COMPOSITE molecular sieve of a kind of TON of having and two kinds of constitutional featuress of MFI, called after MT-1 here, and grain-size is less than 0.8 micron.Because the molecular sieve that uses has the feature (see Table 1, table 2) of TON and MFI structure, and crystal grain is less, be used for lube oil hydrotreating process, can make paraffinic hydrocarbon select shape cracking-isomerization reaction simultaneously, have lubricant base yield height, viscosity index height and the low characteristics of pour point.
Hydrotreating catalyst of the present invention contains the refractory oxide carrier, composite molecular screen, and hydrogenation metal component and auxiliary agent.Wherein composite molecular screen content is 10%～90% of total catalyst weight, is preferably 30%～80%, more preferably 40%～70%.This composite molecular screen has TON and two kinds of structures of MFI, and the TON/MFI weight ratio is 0.05～20: 1, is preferably 1～10: 1, and skeleton SiO 2/ Al 2O 3Mol ratio is 50～200, and degree of crystallinity is 80～100%, and specific surface area is 200m 2/ g～300m 2/ g, pore volume are 0.20ml/g～0.30ml/g, mean pore size 3.0nm～6.0nm, micropore (＜1.7nm) pore volume 0.10ml/g～0.20ml/g.
Catalyzer of the present invention can adopt conventional immersion process for preparing, and wherein the preparation process of composite molecular screen is:
(a) preparation is a kind of is selected from IV in the periodic table of elements by at least a AThe even gel that element compound, mineral alkali, organic masterplate agent, crystal seed, salt and water are formed.
(b) gel of heating steps (a) preparation under the condition of static crystallization, makes the gel crystallization complete, through aftertreatment, obtains the composite structure crystalline molecular sieve.
(c) the composite structure crystalline molecular sieve that obtains of step (b) carries out modification and handles, and obtains the composite molecular screen of suitable this catalyzer.
Compare with the correlation technique document, the composite molecular screen that catalyzer of the present invention uses has TON and two kinds of constitutional featuress of MFI, can satisfy the needs of differential responses thing simultaneously to material requirements, different components is all reacted according to the ideal mode, in addition, because this composite molecular screen crystal grain is less, thereby has improved reactive activity and selectivity.For example be used for lubricating oil distillate hydrotreatment process, compare with associated catalysts, when obtaining ejusdem generis base oil, adopt catalyzer of the present invention, temperature of reaction is reduced more than 20 ℃, air speed improves more than 20%.And under same operational condition, adopt catalyzer of the present invention, and can make to obtain the product yield raising more than 5%, the pour point of product is lower simultaneously.
Description of drawings
Fig. 1. be the XRD figure of comparative example 1 sample C-1a.
Fig. 2. be the XRD figure of comparative example 1 sample C-1b.
Fig. 3. be the XRD figure of embodiment 1 sample MT-1S (molecular screen primary powder).
Fig. 4. be the SEM figure of embodiment 1 sample MT-1S (molecular screen primary powder).
Fig. 5. be the XRD figure of embodiment 1 sample MT-1 (modified molecular screen).
Fig. 6. be the XRD figure of embodiment 2 sample MT-2 (molecular screen primary powder).
Fig. 7. be the XRD figure of comparative example 2 sample SAPO-11 (modified molecular screen).
Fig. 8. be the XRD figure of comparative example 3 sample TON (modified molecular screen).
Fig. 9. be the XRD figure of comparative example 3 sample MFI (modified molecular screen).
Embodiment
Adopt the concrete steps of immersion process for preparing catalyzer of the present invention to be:
(1) abundant together mixing such as composite molecular screen, additive, other inorganic refractory oxide, extrusion aid, water, peptizing agent pinched into plastic paste, extruded moulding obtains support of the catalyst through last handling processes such as super-dry, roastings.
(2) supported active metal component and auxiliary agent on the carrier by last handling processes such as drying, activation, obtain catalyzer of the present invention.
Inorganic refractory oxide can be molecular sieve and/or unformed oxide compound, as in amorphous silicon aluminium, silicon titanium, aluminum oxide, silicon oxide or the molecular sieve one or more, be preferably in amorphous silicon aluminium, titanium aluminium, silicon oxide, magnesium oxide, zinc oxide and the aluminum oxide one or more, more preferably silicon oxide and/or aluminum oxide most preferably are aluminum oxide; Content is 5w%～80w%, is preferably 10w%～60w%, more preferably 15w%～40w%; Additive is meant the material that can improve catalyst property, is preferably boron, fluorine, chlorine and phosphorus, and content is 0.1w%～10w%, is preferably 0.2w%～5w%, more preferably 0.2w%～2w%; Peptizing agent refers to mineral acid and/or organic acid, is preferably one or more mixtures in nitric acid, hydrochloric acid, sulfuric acid, formic acid, acetate, oxalic acid, the citric acid; Extrusion aid is meant the material that helps extrusion molding, is preferably sesbania powder, starch, carboxymethyl cellulose, carbon black, Graphite Powder 99, citric acid.
Active metal component is meant in the periodictable among the VIB and VIII family element one or more, be preferably in Pt, Pd, Ru, Rh, nickel, cobalt, molybdenum and the tungsten one or more, be more preferably Pt or/and Pd most preferably is Pd, bullion content is generally 0.1w%～5w%.Active component solution commonly used is the aqueous solution that contains the reactive metal soluble compound, for example platinum acid chloride solution, platinum amine complex solution, palladium amine complex solution, palladium nitrate solution, palladium chloride solution and organic coordination compound solution thereof; Carrying method can adopt the mode of at present all loaded metals, and for example pickling process or ion exchange method are preferably pickling process.
The operational condition of processes such as the drying of catalyzer and carrier, roasting and activation can be same as the prior art, for example drying conditions is normal temperature～300 ℃ maintenance 1h～48h, roasting condition is 400 ℃～800 ℃ and keeps 0.5h～10h that activation condition is 350 ℃～600 ℃ and keeps 1h～8h.
The concrete preparation process of composite molecular screen is as follows:
Composite molecular screen of the present invention has TON and two kinds of molecular sieve structures of MFI, the principal feature of building-up process is to have in static state to finish under crystal seed and the salt acting in conjunction, need not stir, crystal seed and halogenide can promote the crystallization of molecular sieve, crystallization time is shortened greatly, and the selection and the prior art of other condition and various raw materials are similar.Wherein said salt can be selected from one or more of basic metal or alkaline-earth metal salt, is preferably alkali metal halide, more preferably KF or NaCl etc.Said crystal seed can be selected from one or more of molecular sieve with TON or MFI structure, is preferably to have the TON structure molecular screen, and content (with respect to gel weight) is 0.01%～1%, is preferably 0.1%～0.5%, and more preferably 0.3%～0.5%.
In the process of preparation molecular sieve provided by the invention, other raw material and operational condition can be determined by prior art, IV in the common said periodic table of elements of step (a) AElement compound, can be selected from the compound of silicon or germanium one or more, be preferably the compound of silicon, can be all silicon-containing compounds that can be used in other molecular sieve of preparation, for example, active silica, silicate, silicon sol and siliceous organism etc. are preferably silicate, silicon sol and siliceous organism, more preferably silicon sol.Said mineral alkali can be all alkaline matters, and the oxyhydroxide of for example alkali-metal oxyhydroxide, carbonate, alkaline-earth metal and ammoniacal liquor etc. are preferably alkali-metal oxyhydroxide, more preferably potassium hydroxide.Said aluminium source can be to be selected from activated alumina and precursor, aluminum soluble salt and the organic aluminum contained compound one or more, for example clay, hydrated aluminum oxide, aluminium colloidal sol, aluminate, aluminium salt and aluminiferous organism, be preferably aluminate and aluminium salt, more preferably aluminium salt.Said organic directed agents is ammonium salt or amine organism, is preferably the amine organism, and more preferably hexanediamine and octamethylenediamine most preferably are octamethylenediamine.
The preparation method of the said gel of step (a) carries out thorough mixing with required material, obtains the homogeneous phase colloidal mixture.The mol ratio of each material is generally in the gained gel:
0.8～2.0M 2O/1.0～5.0R/0.01～1.0Al 2O 3/10SiO 2/0.1～2.0NX/50～600H 2O+0.01w％～1w％S，
Be preferably:
1.0～1.5M 2O/2.0～4.0R/0.05～0.5Al 2O 3/10SiO 2/0.2～1.0NX/100～500H 2O+0.05w％～0.5w％S，
More preferably:
1.1～1.4M 2O/2.5～3.5R/0.1～0.2Al 2O 3/10SiO 2/0.2～0.5NX/300～400H 2O+0.1w％～0.3w％S，
Wherein R is a structure directing agent, and M is the monovalent base metal ion, and NX is a halogenide, and S is a crystal seed, and content is the weight with respect to gel.
Said crystallization is to carry out in the high-pressure reactor of autogenous pressure in the step (b), and crystallization temperature is 120～200 ℃, is preferably 150～180 ℃, more preferably 160～170 ℃; Crystallization time is 10～240 hours, is preferably 24～96 hours, more preferably 48～72 hours; The method of aftertreatment can be any conventional molecular sieve aftertreatment means, for example collects, washs and drying etc.The XRD result of the molecular sieve that obtains has table 1 and table 2 feature, its anhydrous consisting of: 0.1～0.6M 2O/0.01～1.0Al 2O 3/ 10SiO 2
Be preferably: 0.1～0.3M 2O/0.1～0.2Al 2O 3/ 10SiO 2
Here, M is a monovalent metallic ion.
In the said molecular sieve modified treating processes, used organic solvent can be to be selected from acetone, C in the step (c) 1～C 3Alcohols and C 1～C 3In the organic acid one or more are preferably C 1～C 3Alcohols, more preferably methyl alcohol.Treatment temp can be normal temperature～500 ℃, is preferably 80 ℃～200 ℃, more preferably is in reflux conditions at solvent.Processing pressure is the pressure of liquid phase for keeping solvent, is preferably autogenous pressure.Treatment time is generally 0.5h～48h, is preferably 1h～12h, more preferably 2h～4h.Consumption of organic solvent (ratio of liquid/stereoplasm amount) is generally 0.5～50, is preferably 2～20, and more preferably 5～10.
Said ion-exchange process in the process, solutions employed is introduced cationic compound solution for containing needs, is preferably H +Or/and NH 4 +The solution of ionic compound more preferably contains NH 4 +The solution of ionic compound, for example NH 4NO 3, (NH 4) 2SO 4And NH 4Cl solution etc.The solution quality percentage concentration is 1w%～50w%, is preferably 2w%～20w%, more preferably 5w%～15w%.Temperature is normal temperature～200 ℃, is preferably 30 ℃～150 ℃, more preferably 50 ℃～100 ℃.Pressure is the pressure of liquid phase for keeping solution, is preferably normal pressure.Time is 1h～24h, is preferably 1h～12h, more preferably 2h～8h.Gu the liquid/mass ratio of solution and molecular sieve is 5～20, is preferably 5～10.
Said dealumination process in the process, used solution is acidic solution, is preferably inorganic acid solution, for example nitric acid, hydrochloric acid and sulfuric acid, more preferably nitric acid.H in the solution +Volumetric molar concentration is 0.05mol/L～10mol/L, is preferably 0.2mol/L～2mol/L.Temperature is normal temperature～300 ℃, is preferably 50 ℃～200 ℃, more preferably 70 ℃～100 ℃.Pressure is normal pressure～5MPa, is preferably the autogenous pressure of encloses container, more preferably normal pressure.Time is 0.5h～8h, is preferably 1h～6h, more preferably 2h～4h.The mass ratio of solution and molecular sieve is 5～10.
Said benefit silicon process in the process, used solution is preferably ammonium fluosilicate solution for containing the soluble silicon compound solution.Strength of solution is 1w%～10w%, is preferably 2w%～5w%.Temperature is normal temperature～200 ℃, is preferably 50 ℃～100 ℃, more preferably 70 ℃～80 ℃.Pressure is normal pressure～5MPa, is preferably the autogenous pressure of encloses container, more preferably normal pressure.Time is 0.5h～12h, is preferably 1h～8h, more preferably 2h～4h.The mass ratio of solution and molecular sieve is 5～10.
Catalyzer of the present invention is to adopt 100 milliliters of medium-sized fixed-bed reactor to estimate, loaded catalyst is 100 milliliters, catalyzer being reduced to handle before the charging makes loaded metal exist with simple substance form, reductive condition is: hydrogen pressure 1MPa～10Mpa, 200 ℃～500 ℃ of temperature, 1 hour～24 hours time, preferably hydrogen pressure 4MPa～6MPa, 300 ℃～400 ℃ of temperature, 4 hours～12 hours time.Reaction conditions is: hydrogen pressure 5MPa～20MPa, 260 ℃～400 ℃ of temperature, volume space velocity 0.4h -1～2.0h -1, hydrogen to oil volume ratio 300～2000, optimum condition is: hydrogen pressure 8MPa～16MPa, 280 ℃～360 ℃ of temperature, volume space velocity 0.8h -1～1.2h -1, hydrogen to oil volume ratio 500～1000.
Give further instruction below by embodiment to technology of the present invention.
Comparative Examples 1
Get the TON type molecular sieve that obtains according to United States Patent (USP) 4902406 embodiment 1 disclosed method, be numbered C-1a, its XRD sees Fig. 1.MFI type molecular sieve according to Chinese patent CN1187462A embodiment 1 disclosed method obtains is numbered C-1b, and its XRD sees Fig. 2.
XRD result adopts D/MAX-RA type x-ray diffractometer of science, and source of radiation is the copper target, the filtering of graphite monocrystalline, operation tube voltage 35KV, tube current 30～50mA, sweep velocity (2 θ) be 4 degree/minute, sweep limit is 4～35 degree.The surface-area of molecular sieve adopts ASAP 2400, and cryogenic nitrogen absorption (77K) calculates according to BET formula.The SiO of molecular sieve 2/ Al 2O 3, La 2O 3/ Al 2O 3Adopt plasma emission spectrum (ICP) method to measure.
A kind of preparation method of embodiment 1 molecular sieve MT-1 of the present invention
The preparation process of molecular sieve mainly comprises:
(a) preparation process of gel is: with the KOH of 17.75 grams 82%, and 37.8 grams 1,8-octamethylenediamine, 4 gram AlCl 3, 200 gram SiO 2Content is 30% silicon sol, 0.5 gram SiO 2/ Al 2O 3Be 44, crystal grain is crystal seed (0.06% with respect to gel weight) less than 1 micron TON structure molecular screen, and 2.9 gram KF and 577 gram water mixed according to a definite sequence, through 20 minutes vigorous stirring, obtain homogeneous gel shape mixture, the mole that obtains gel consists of:
1.3K 2O/3.00R/0.15Al 2O 3/10SiO 2/0.5KF/400H 2O+0.06w％S
R=1,8-octamethylenediamine, S are crystal seed.
(b) crystallization process: the gel that step (a) obtains is transferred in the stainless steel autogenous pressure reactor, made reactor be elevated to 165 ℃ from room temperature in two hours, static constant temperature stops heating, reactor naturally cooling after 48 hours.
(c) aftertreatment: open reactor, can see that upper solution clarification, crystallisate all accumulate in the still bottom, through suction filtration, deionized water wash 3 times, 110 ℃ of dryings 4 hours obtain the former powder of crystalline molecular sieve, are numbered MT-1S.
(d) SiO of sample MT-1S 2/ Al 2O 3Be 58, XRD figure 3, SEM sees Fig. 4.Found out to have two kinds of structure knots of MFI and TON molecular sieve in the product and exist by Fig. 3, wherein the ratio of the content of MFI and TON structure molecular screen is 0.5, and Fig. 4 shows that zeolite crystal is of a size of about 0.8 micron.
(e) above-mentioned synthesis of molecular sieve modifying process is:
1. be in the 10 adding flasks with methyl alcohol (2000 gram) by weight with molecular sieve (200 gram), heat-up rate with 1.5 ℃/min under stirring condition seethes with excitement to solution, refluxed 3 hours, after the end through filtration, washing and 110 ℃ of dryings 4 hours, obtain removing the molecular sieve of organic lamina membranacea agent.
2. get molecular sieve 150 grams that step (1) obtains and place 2000 ml beakers, add 1500 milliliters of hydrochloric acid solns that volumetric molar concentration is 0.5mol/L, under agitation, be warmed up to 75 ℃, constant temperature 4 hours, product through filtration, washing, 110 ℃ of dryings 4 hours, obtain the dealuminzation molecular sieve.
3. get molecular sieve 100 grams that step (2) obtains and place 2000 milliliters of three-necked bottles, add (the NH that 2000 ml concns are 3.5w% 4) 2SiF 6The aqueous solution under agitation, is warmed up to 90 ℃, constant temperature 1 hour, product through filtration, washing, 110 ℃ of dryings 2 hours and 450 ℃ of roastings 2 hours, obtain modified molecular screen, be numbered MT-1, its SiO 2/ Al 2O 3Be 66, XRD figure 5 is found out by Fig. 5, and the degree of crystallinity of molecular sieve is 92% (with respect to former powder), and wherein the ratio of the content of MFI structure and TON structure molecular screen does not become 0.5 substantially, and the specific surface area of molecular sieve is 263m 2/ g, pore volume are 0.24ml/g, mean pore size 4.1nm, micropore (＜1.7nm) pore volume 0.14.
A kind of preparation method of embodiment 2 molecular sieve MT-2 of the present invention
The preparation process of molecular sieve mainly comprises:
(a) preparation process of gel is: with embodiment 1, remove the KOH that adds 20.50 grams 82%, 20.5 grams 1,6-hexanediamine replace 37.8 grams 1,8-octamethylenediamine, 10 gram Al 2(SO 4) 3.18H 2O replaces 4 gram AlCl 3, 5.8 gram KF, 1.0 gram TON molecular sieves (0.15w% is with respect to gel weight) and 400 gram water mix according to a definite sequence, through 20 minutes vigorous stirring, obtain homogeneous gel shape mixture, and the mole that obtains gel consists of:
1.5K 2O/2.01R/0.08Al 2O 3/10SiO 2/1.0KF/300H 2O
R=1, the 6-hexanediamine
(b) crystallization process: with embodiment 1.
(c) aftertreatment: with embodiment 1, obtain the former powder of crystalline molecular sieve, be numbered MT-2S.
(d) characterize: the SiO of MT-2S 2/ Al 2O 3Be 104, the XRD of sample the results are shown in Figure 6.Found out to have TON and two kinds of configuration molecular sieves of MFI feature in the product by Fig. 6, wherein the ratio of the content of TON structure and MFI structure molecular screen is 5.0.
(e) the MT-2S molecular sieve is handled through the modification with embodiment 1, obtains modified molecular screen, is numbered MT-2, its SiO 2/ Al 2O 3Be 128, the degree of crystallinity of molecular sieve is 96% (with respect to former powder), and wherein the ratio of the content of TON structure and MFI structure molecular screen does not become 5.0 substantially.The specific surface area of molecular sieve is 270m 2/ g, pore volume are 0.24ml/g, mean pore size 4.2nm, micropore (＜1.7nm) pore volume 0.13.A kind of preparation method of comparative example 2 comparative catalysts of the present invention
(1) gets according to United States Patent (USP) 4,440,871 embodiment, 15 disclosed methods, the SAPO-11 molecular sieve (see figure 7) 650g that obtains, pseudo-boehmite (butt 72w%) 280g, 210g SB powder and sesbania powder 20g mix, add 270ml water and 22ml concentrated nitric acid (66.5w%) fully mixed pinching on rolling machine then, make it to become the paste plastic, extruding diameter on banded extruder is the Herba Galii Bungei type bar of 1.5mm, Herba Galii Bungei type bar is following dry 8 hours at 110 ℃, in air atmosphere 500 ℃ then, roasting 6 hours makes carrier;
(2) get the carrier that 200 gram steps (1) obtain, use and contain Pt (NH 3) 4Cl 2And Pd (NH 3) 4(NO 3) 2Solution carry out saturated dipping, then 110 ℃ dry 6 hours down, 380 ℃ of roastings are 6 hours in air atmosphere, make the comparative catalyst of the present invention who contains 0.4w%Pt, 0.8w%Pd, are numbered C-2, its appreciation condition and the results are shown in Table 3 and table 4.
A kind of preparation method of comparative example 3 comparative catalysts of the present invention
Get the TON type molecular sieve (see figure 8) 217g that obtains according to United States Patent (USP) 4902406 embodiment 1 disclosed method, with the MFI type molecular sieve (see figure 9) 108g (MFI/TON=0.5) that obtains according to Chinese patent 1187462A embodiment 1 disclosed method, method with comparative example 2, obtain the comparative catalyst, be numbered C-3, its appreciation condition and the results are shown in Table 3 and table 4.
A kind of preparation method of embodiment 3 catalyzer of the present invention
Get the MT-1 molecular sieve 650g of embodiment 1 preparation,, obtain catalyzer of the present invention, be numbered E-3, its appreciation condition and the results are shown in Table 3 and table 4 with the method for comparative example 2.
A kind of preparation method of embodiment 4 catalyzer of the present invention
Get the MT-2 molecular sieve 650g of embodiment 2 preparation,, obtain catalyzer of the present invention, be numbered E-4, its appreciation condition and the results are shown in Table 3 and table 4 with the method for comparative example 2.
A kind of preparation method of catalyzer among embodiment 5 the present invention
Carrier is with embodiment 3, and the carrier that obtains uses and contains Pd (NH 3) 4(NO 3) 2And NH 4The solution of F carries out saturated dipping, then 110 ℃ dry 6 hours down, 500 ℃ of roastings are 4 hours in air atmosphere, make the catalyzer E-5 of the present invention that contains 0.6w%Pd and 0.4w% fluorine, its appreciation condition and the results are shown in Table 3 and table 4.
A kind of preparation method of catalyzer among embodiment 6 the present invention
Carrier is with embodiment 3, and the carrier that obtains contains Pd (NH with 400 milliliters 3) 4(NO 3) 2, NH 4F and H 3BO 3Solution in carry out supersaturation dipping, then 90 ℃ dry 12 hours down, 450 ℃ of roastings are 4 hours in air atmosphere, make the catalyzer E-6 of the present invention that contains 1.5w%Pd, 0.2w%F and 1.0w%B, its appreciation condition and the results are shown in Table 3 and table 4.
Table 3 stock oil character
Density (20 ℃), kg/m 3Sulphur, μ g/g nitrogen, μ g/g viscosity, mm/s 240 ℃ of 100 ℃ of pour points, ℃ C/H flash-point (opening), ℃ wax content, the % boiling range, ℃ (D1160) IBP/10% 30%/50% 70%/90% 95%/EBP 861.1 4.0 1.2 29.69 5.47 21 85.82/14.08 198 9.8 227/399 428/441 455/469 477/500
Table 4 catalyst runs condition and result
The catalyzer numbering C-2 C-3 E-3 E-4 E-5 E-6
The processing condition reaction pressure, MPa volume space velocity, h -1The hydrogen to oil volume ratio temperature of reaction, ℃ C 5 +Liquid is received, and the % product distributes, % C 5～130℃ 130℃～280℃ 280℃～350℃ 350℃ +350℃ +Neutral oil character viscosity, 40 ℃, mm 2/ s viscosity index pour point, ℃ 15.6 0.6 800 370 96.1 2.6 7.2 11.5 74.8 32.38 110 -18 10 0.9 800 340 95.8 4.7 2.3 10.6 78.2 36.22 102 -21 10 0.9 800 310 96.5 5.1 1.9 7.0 82.5 36.35 105 -24 10 0.9 800 310 97.2 4.9 1.7 6.6 84.0 38.22 96 -21 10 0.9 800 315 96.8 4.5 2.4 6.9 83.0 36.42 104 -28 10 0.9 800 320 97.0 4.6 2.7 5.1 84.6 36.38 108 -25

Claims (10)

1, a kind of lube oil hydrogenation is handled catalyzer, contain refractory oxide, hydrogenation metal component and auxiliary agent, it is characterized in that containing composite molecular screen, wherein composite molecular screen content is 10%～90% of total catalyst weight, composite molecular screen has TON and two kinds of structures of MFI, the TON/MFI weight ratio is 0.05～20: 1, skeleton SiO 2/ Al 2O 3Mol ratio is 50～200, and degree of crystallinity is 80～100%.
2, according to the described catalyzer of claim 1, it is characterized in that composite molecular screen content is 30%～80%, composite molecular screen TON/MFI weight ratio is 1～10: 1, specific surface area is 200m 2/ g～300m 2/ g, pore volume are 0.20ml/g～0.30ml/g, mean pore size 3.0nm～6.0nm.
3, according to the described catalyzer of claim 1, it is characterized in that described inorganic refractory oxide is molecular sieve and/or unformed oxide compound, be 5w%～80w% in final catalyzer content; Additive is boron, fluorine, chlorine or phosphorus, and content is 0.1w%～10w%; Active metal component be in Pt, Pd, Ru, Rh, nickel, cobalt, molybdenum and the tungsten one or more, bullion content is 0.1w%～5w%.
4, the described Preparation of catalysts method of a kind of claim 1 adopts immersion process for preparing, it is characterized in that wherein the preparation process of composite molecular screen is:
(a) preparation is a kind of is selected from IV in the periodic table of elements by at least a AThe even gel that element compound, mineral alkali, organic formwork agent, crystal seed, salt and water are formed;
(b) gel of heating steps (a) preparation under the condition of static crystallization, makes the gel crystallization complete, through aftertreatment, obtains the composite structure crystalline molecular sieve;
(c) the composite structure crystalline molecular sieve that obtains of step (b) carries out modification and handles, and obtains the composite molecular screen of suitable this catalyzer.
5, in accordance with the method for claim 4, the step that it is characterized in that described immersion process for preparing catalyzer is:
(1) composite molecular screen, additive, other inorganic refractory oxide, extrusion aid, water and peptizing agent are fully mixed together pinch into plastic paste, extruded moulding obtains support of the catalyst through last handling processes such as super-dry, roastings;
(2) supported active metal component and auxiliary agent on the carrier by last handling processes such as drying, activation, obtain final catalyzer.
6, in accordance with the method for claim 5, the operational condition of drying, roasting and reactivation process that it is characterized in that described catalyzer and carrier is as follows: drying conditions is that normal temperature～300 ℃ keep 1h～48h, roasting condition is 400 ℃～800 ℃ and keeps 0.5h～10h that activation condition is 350 ℃～600 ℃ and keeps 1h～8h.
7, in accordance with the method for claim 4, the mol ratio that it is characterized in that each material in the said even gel of step (a) is:
0.8～2.0M 2O/1.0～5.0R/0.01～1.0Al 2O 3/ 10SiO 2/ 0.1～2.0NX/50～600H 2O+0.01w%～1w%S wherein R is a structure directing agent, is selected from the amine organism, and M is the monovalent base metal ion, and NX is a halogenide, and S is a crystal seed, and crystal seed is selected from one or more of molecular sieve with TON or MFI structure, and content is the weight with respect to gel.
8, in accordance with the method for claim 4, it is characterized in that said crystallization is to carry out in the step (b) in the high-pressure reactor of autogenous pressure, crystallization temperature is 120～200 ℃, and crystallization time is 10～240 hours, and the method for aftertreatment comprises collection, washing and dry.
9, in accordance with the method for claim 4, it is characterized in that in the step (c) that said molecular sieve modified treating processes comprises organic solvent treatment and ion-exchange, dealuminzation, benefit silicon process, wherein the organic solvent treating processes is: organic solvent is selected from acetone, C 1～C 3Alcohols and C 1～C 3In the organic acid one or more, treatment temp are normal temperature～500 ℃, and processing pressure is the pressure of liquid phase for keeping solvent, and the treatment time is 0.5h～48h, and organic solvent and molecular sieve consumption weight ratio are 0.5～50.
10, in accordance with the method for claim 9, it is characterized in that described ion-exchange process is: with containing H +Or/and NH 4 +The solution-treated of ionic compound, solution quality percentage concentration are 1w%～50w%, and temperature is normal temperature～200 ℃, and pressure is the pressure of liquid phase for keeping solution, and the time is 1h～24h, Gu the liquid/mass ratio of solution and molecular sieve is 5～20; Dealumination process is: use H +Volumetric molar concentration is that the inorganic acid solution of 0.05mol/L～10mol/L is handled, and temperature is normal temperature～300 ℃, and pressure is normal pressure～5MPa, and the time is 0.5h～8h, and the mass ratio of solution and molecular sieve is 5～10; Mend silicon and dealuminzation and carry out simultaneously or carry out respectively, benefit silicon process is: handle with containing the soluble silicon compound solution, strength of solution is 1w%～10w%, temperature is normal temperature～200 ℃, pressure is normal pressure～5MPa, and the time is 0.5h～12h, and the mass ratio of solution and molecular sieve is 5～10.
CN 03133556 2003-05-31 2003-05-31 Lube oil hydrogenation treating catalyst and preparing method thereof Expired - Lifetime CN1219034C (en)

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CN100457868C (en) * 2005-10-19 2009-02-04 中国石油化工股份有限公司 Hydrodewaxing catalyst for lubricant oil and its preparing method
CN104117387B (en) * 2013-04-23 2016-07-06 上海碧科清洁能源技术有限公司 A kind of ZSM-22/ZSM-5 mixed molecular sieve catalyst and preparation thereof and application
CN104549462B (en) * 2013-10-23 2017-05-17 中国石油化工股份有限公司 Alkane isomerization catalyst and preparation method and application thereof
CN104549461B (en) * 2013-10-23 2017-03-29 中国石油化工股份有限公司 A kind of 22 composite molecular screens of MCM 22/ZSM and its preparation method and application
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CN107570206A (en) * 2016-07-04 2018-01-12 中国石油天然气股份有限公司 Diesel oil hydrogenation pour point depression catalyst and preparation method thereof
CN107570207A (en) * 2016-07-04 2018-01-12 中国石油天然气股份有限公司 Non-noble metal distillate oil hydroisomerization catalyst and preparation method thereof

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