CN1609175A - Hydroprocessing catalyst and its prepn process - Google Patents

Hydroprocessing catalyst and its prepn process Download PDF

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Publication number
CN1609175A
CN1609175A CN 200310104902 CN200310104902A CN1609175A CN 1609175 A CN1609175 A CN 1609175A CN 200310104902 CN200310104902 CN 200310104902 CN 200310104902 A CN200310104902 A CN 200310104902A CN 1609175 A CN1609175 A CN 1609175A
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molecular screen
catalyzer
sio
agent
ton
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CN1277613C (en
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刘全杰
徐会青
童广明
廖士纲
刘平
姚春雷
谢庆华
谢亮亮
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 is hydroprocessing catalyst and its preparation process. The catalyst includes one kind of molecular sieve with TON type structure and active metal component, and the molecular sieve has the features of surface Si/Al ratio higher than the bulk Si/Al ratio, proper acidity and channel structure for paraffin hydrocarbon to generate shape-selective cracking-isomerizing reaction, etc. The catalyst is used in hydroprocessing intermediate fraction oil and heavy fraction product, and has the features of high activity, high isomerizing selectivity, low cracking performance, etc.

Description

A kind of hydrotreating catalyst and preparation method thereof
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, particularly diesel oil, lube oil hydrogenation are handled Catalysts and its preparation method.
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 diesel oil, lubricated wet goods centre and the heavy 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, makes wax component generation selective catalytic cracking, generates the hydro carbons than small molecules, thereby the condensation point of base oil depression of pour point or diesel oil is reduced.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 the purpose product yield is low, by product value is low.In lubricant base hydrogenation process, isomerization dewaxing can 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.In the diesel oil hydrogenation process, isomerization dewaxing can improve the yield of diesel oil greatly when reducing condensation point of diesel oil.
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 grades all are that report relates to isomerization dewaxing technology production lubricant base, 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 because isomerization reaction is very strict to the pore structure and the requirement of acid matter of material, for commaterial, cause to cause the serious difference of catalytic performance owing to treating processes is different, particularly for the isomerization reaction of macromole hydrocarbon in the subtle change of material physical and chemical performance.
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 taking place isomerizedly simultaneously some paraffinic hydrocarbon components that are difficult for taking place isomerization reactions to be carried out suitable cracking, make cracking and isomerization reaction reach balance, base oil character is done the trick.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 dispersion effect of molecular sieve is poor, and characteristics are given full play to, and embodies the good synergistic of not coming out.
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 a kind of molecular sieve of the TON of having type constitutional features.Because the molecular sieve that uses has suitable pore passage structure and acid matter, can make paraffinic hydrocarbon select shape cracking-isomerization reaction simultaneously, is used for lube oil hydrotreating process, has 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, TON structure molecular screen, hydrogenation metal component, and selectable adjuvant component.Wherein TON structure molecular screen content is 10%～90% of total catalyst weight, is preferably 30%～80%, more preferably 40%～70%.Inorganic refractory oxide is molecular sieve and/or unformed oxide compound, is 5w%～80w% in final catalyzer content, is preferably 10w%～60w%, more preferably 15w%～40w%; Additive is boron, fluorine, chlorine or phosphorus, and content is 0～10w%, is preferably 0.1w%～5w%; Active metal component be in Pt, Pd, Ru, Rh, nickel, cobalt, molybdenum and the tungsten one or more, content is 0.1w%～30w%, is preferably 0.2w%～10w%.
Wherein TON type structure molecular screen has following feature, epiphase SiO 2/ Al 2O 3Mol ratio is 50～200, epiphase SiO 2/ Al 2O 3Mol ratio is than body phase SiO 2/ Al 2O 3Mol ratio is high by 5～50, and more long-pending than epiphase is 150m 2/ g～500m 2/ g, pore volume are 0.15ml/g～0.50ml/g, mean pore size 2.0nm～10.0nm, and B acid amount is 0.05mmol/g～0.5mmol/g, L acid amount is 0.05mmol/g～0.5mmol/g.Molecular sieve character is preferably, epiphase SiO 2/ Al 2O 3Mol ratio is 80～120, epiphase SiO 2/ Al 2O 3Mol ratio is than body phase SiO 2/ Al 2O 3Mol ratio is high by 15～30, and more long-pending than epiphase is 200m 2/ g～300m 2/ g, pore volume are 0.20ml/g～0.40ml/g, mean pore size 3.0nm～6.0nm, and B acid amount is 0.1mmol/g～0.3mmol/g, L acid amount is 0.1mmol/g～0.2mmol/g.
Catalyzer of the present invention can adopt conventional catalyst preparation process, as pickling process etc.Wherein in the preparation process of TON type molecular sieve, template is a double template, and preferably adds auxiliary agent and adopt the segmentation crystallization method, and concrete preparation process is:
(a) preparation is a kind of is selected from the even gel that IIIA in the periodic table of elements, IVA element compound, mineral alkali, organic lamina membranacea agent and water are formed by at least a;
(b) gel of heating steps (a) preparation under the condition of crystallization, makes the gel crystallization complete, through aftertreatment, obtains molecular screen primary powder, obtains final zeolite product through removing processes such as lamina membranacea agent, ammonium exchange, dealumination complement silicon then.
The molecular sieve that catalyzer of the present invention relates to has TON type structure, have suitable pore structure and surface properties, particularly use the epiphase silica alumina ratio to be higher than body phase silica alumina ratio and Surface L acid amount and the suitable TON type molecular sieve of B acid amount, make catalyzer when having greater activity, has higher isomery selectivity, and the cracking rate is low, the product yield height.Compare with the correlation technique document, be used for lube oil hydrotreating process, when obtaining ejusdem generis base oil, adopt catalyzer of the present invention, can make temperature of reaction reduce by 10 ℃～more than 50 ℃, air speed improves 10%～80%.Or under same operational condition, adopt catalyzer of the present invention, can make to obtain the product yield raising more than 5%, low 1 ℃～10 ℃ of the pour point of product.
Description of drawings
Fig. 1 is the XRD figure of embodiment 1 sample E-1.
Fig. 2 is the XRD figure of embodiment 2 sample E-2.
Fig. 3 is the XRD figure of embodiment 3 sample E-3.
Fig. 4 is the XRD figure of comparative example 1 sample C-1.
Fig. 5 is the XRD figure of the SAPO-11 sample that obtains in the comparative example 2.
Embodiment
Adopt the concrete steps of immersion process for preparing catalyzer of the present invention to be:
(1) abundant together mixing such as TON type molecular sieve, 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.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.
In the process of preparation TON structure molecular screen provided by the invention, other raw material and operational condition can be determined by prior art, as the raw material and the operational condition of various TON structure molecular screens (ZSM-22, Theta-1, ISI-1, KZ-2 and NU-10) preparation process employing in the prior art.It changes part and is: the described template of step (a) is a double template, promptly is made up of two kinds of template, and wherein the master module agent is a diamine compounds, can be C 2-C 10Diamines, be preferably C 5-C 8Diamines, hexanediamine more preferably; The auxiliary template agent is generally nitrogen-containing heterocycle compound, is preferably pyrrole derivative, more preferably tetramethyleneimine.Said auxiliary agent can be C 5-C 10Alkane, be preferably C 5-C 8Normal paraffin or naphthenic hydrocarbon, C more preferably 5-C 7Naphthenic hydrocarbon.IVA element compound in the said periodic table of elements, 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, silica-gel powder, active silica, silicate, vaporific silicon, white carbon black, silicon sol and siliceous organism etc. are preferably silicate, silicon sol and silica-gel powder, more preferably silica-gel powder.Said IIIA element can be boron, aluminium, gallium, indium etc., is preferably aluminium.The 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, for example AlCl 3, Al 2(SO 4) 3, Al (NO 3) 3Deng.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.A) preparation method of said gel carries out thorough mixing with required material, obtains the homogeneous phase colloidal mixture.The composition of gained gel has the listed feature of table 1.
The mole of hydrogel is formed before table 1 crystallization of the present invention
Mol ratio is general more preferably preferred
SiO 2/Al 2O 3???????30～∝??????????50～500?????????80～300
M +/SiO 2???????????0.01～1.0???????0.05～0.8???????0.1～0.5
OH -/SiO 2??????????0.01～1.0???????0.05～0.8???????0.1～0.5
H 2O/SiO 2??????????10～200?????????20～150?????????30～100
Master module agent RN/SiO 20.01～1.0 0.05～0.8 0.3～0.7
Auxilliary template PY/SiO 20～0.5 0.02～0.3 0.03～0.1
Auxiliary agent CH/SiO 20～0.5 0.05～0.3 0.08～0.15
M wherein +Be the monovalence metallic cation, RN is the master module agent, and PY is auxilliary template, and CH is an auxiliary agent
Said crystallization is to carry out in the high-pressure reactor of autogenous pressure in the step (b), and crystallization can be that the single hop crystallization also can be the segmentation crystallization.During the single hop crystallization, general crystallization temperature is 120 ℃～180 ℃, is preferably 130 ℃～170 ℃, and crystallization time is 8～96h, and being preferably is 24～60h.During for the segmentation crystallization, for two sections crystallization, first section crystallization temperature is 80 ℃～100 ℃, and preferred 85 ℃～95 ℃, crystallization time is 4h～48h, is preferably 8h～36h.Second section crystallization temperature is 120 ℃～180 ℃, and preferred 130 ℃～170 ℃, crystallization time is 8h～48h, is preferably 12～24h.For three sections crystallization, first section crystallization temperature is 80 ℃～100 ℃, and preferred 85 ℃～95 ℃, crystallization time is 4h～36h, is preferably 8h～24h.Second section crystallization temperature is 100 ℃～140 ℃, and preferred 110 ℃～130 ℃, crystallization time is 4h～24h, is preferably 12～24h.The 3rd section crystallization temperature is 140 ℃～180 ℃, and preferred 150 ℃～170 ℃, crystallization time is 12h～96h, is preferably 24h～48h.Said aftertreatment refers to through processing such as collection, washing and dryings, can adopt method commonly used at present to carry out, and for example collects and uses method of pumping filtration, uses deionized water wash, makes the sample thorough drying at 100 ℃～250 ℃ then.
Dried molecular sieve obtains final zeolite product through processes such as removed template method, ion-exchange, dealuminzation, benefit silicon, wherein the condition of each step can adopt the normal condition in this area, the present invention will select certain treatment process by special methods synthetic TON type structure molecular screen, and adopt the treatment step of particular order to make the finished product have good use properties.The actual conditions in each step is as follows.Removing of template can be adopted existing any method, for example processes such as high-temperature roasting or organic solvent extraction under air atmosphere.The ion-exchange process, solutions employed is for containing NH 4 +Ion, NH 4 +Volumetric molar concentration is 0.05mol/L～10mol/L, 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, used solution are acidic solution, wherein contain at least a be selected from mineral acid and at least a middle organic acid such as oxalic acid, acetate, citric acid that is selected from nitric acid, hydrochloric acid and the sulfuric acid etc., and mineral acid and organic acid mol ratio are 10: 1～1: 1, H in the solution +Volumetric molar concentration is 0.05mol/L～10mol/L, 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 the used solution of silicon process for containing the soluble silicon compound solution, be preferably ammonium fluosilicate solution.Strength of solution is 1w%～10w%, and temperature is normal temperature～200 ℃, and pressure is normal pressure～5MPa, and the time is 0.5h～12h, and the mass ratio of solution and molecular sieve is 5～10.
Give further instruction below by embodiment to technology of the present invention.
Embodiment 1～3
The preparation method of the TON type molecular sieve that catalyzer of the present invention relates to.
Get quantitative water and place beaker, add silicon source, aluminium source and alkali successively, thorough mixing, add master module agent, auxilliary template and auxiliary agent more successively, together add after also three kinds of organism can being mixed, behind the thorough mixing, move into autoclave and carry out crystallization, obtain sample E-1, E-2, E-3 and C-1 respectively through aftertreatment.Sample E-1, E-2, E-3 removed the lamina membranacea agent in 2 hours at 550 ℃ of constant temperature; Ammonium exchange twice, condition is for being that 10% ammonium nitrate solution of 5 times of molecular sieve weight exchanges 4 hours at 80 ℃ with weight, then 550 ℃ of roastings 4 hours; Be that 0.5mol/L and tartrate volumetric molar concentration are the mixed acid solution of 0.2mol/L with the nitric acid volumetric molar concentration then, handled 4 hours that solution usage is 8 times of molecular sieve weight at 90 ℃; With concentration is the (NH of 3w% 4) 2SiF 6The aqueous solution was handled 4 hours at 85 ℃, and solution usage is 10 times of molecular sieve weight, through filtration, washing, 110 ℃ of dryings 2 hours and 450 ℃ of roastings 2 hours final molecular sieve.C-1 crosses and removes that the exchange of lamina membranacea agent and ammonium is handled and processing 2 hours under 550 ℃ and 100% water vapor conditions.Gel composition, crystallization condition and the product property of each embodiment see Table 2.
Gel composition, crystallization condition and the product property of each embodiment of table 2
The embodiment numbering ????1① ????2② ????3③ Comparative example 1
?SiO 2/Al 2O 3 ????80 ????100 ????150 ????100
?M +/SiO 2 ????0.2 ????0.6 ????0.1 ????0.3
?OH -/SiO 2 ????0.2 ????0.3 ????0.3 ????0.2
?RN/SiO 2 ????0.3 ????0.6 ????0.2 ????0.3
?H 2O/SiO 2 ????45 ????120 ????60 ????40
?PY/SiO 2 ????0.1 ????0.2 ????0.4 ????-
?CH/SiO 2 ????0.05 ????0.1 ????0.5 ????-
Crystallization temperature, ℃ ????160 ????80+170 ????70+100+150 ????190
Crystallization time, h ????48 ????12+24 ????24+6+12 ????72
Yield, w% ????86 ????90 ????95 ????81
Molecular sieve character
Product structure ????TON ????TON ????TON ????TON
Degree of crystallinity, % ????106 ????110 ????128 ????100
Body phase SiO 2/Al 2O 3Mol ratio ????76 ????90 ????137 ????104
Epiphase SiO 2/Al 2O 3Mol ratio ????96 ????112 ????164 ????106
Specific surface, m 2/g ????278 ????274 ????265 ????263
Specific pore volume, ml/g ????0.20 ????0.20 ????0.20 ????0.18
Mean pore size, nm ????2.7 ????2.6 ????2.6 ????2.4
B acid amount, mmol/g ????0.212 ????0.206 ????0.187 ????0.179
L acid amount, mmol/g ????0.140 ????0.139 ????0.136 ????0.09
Annotate: 1. silicon source: silicon sol, aluminium source: Al 2(SO 4) 3, alkali: KOH, master module agent: hexanediamine, auxilliary template: tetramethyleneimine, auxiliary agent: hexanaphthene;
2. silicon source: silica-gel powder, aluminium source: Al (OH) 3, alkali: NaOH, master module agent: octamethylenediamine, auxilliary template: N-crassitude, auxiliary agent: Skellysolve A+hexanaphthene (mol ratio 1: 1);
3. silicon source: tetraethoxy, aluminium source: aluminium colloidal sol, alkali: KOH, master module agent: heptamethylene diamine, auxilliary template: N-ethyl pyrrolidine, auxiliary agent: octane;
Comparative example 1 raw material is with 2. identical.
From embodiment as can be seen, the method for the TON of preparation structure molecular screen provided by the invention is compared with correlation technique, and crystallization time obviously shortens, crystallization temperature reduces, product yield and degree of crystallinity height, particularly molecular sieve epiphase silica alumina ratio be than body phase silica alumina ratio height, B acid obviously reduce and the L acidic group this is constant.
Comparative example 2
A kind of preparation method of comparative catalyst 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 5) 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.
Comparative example 3
A kind of preparation method of comparative catalyst of the present invention
Preparation of catalysts is with comparative example 2, and the TON type molecular sieve 650g that removes with comparative example 1 preparation replaces the SAPO-11 molecular sieve, obtains comparative catalyst of the present invention, is numbered C-3, its appreciation condition and the results are shown in Table 3 and table 4.
Embodiment 4
A kind of preparation method of catalyzer of the present invention
Preparation of catalysts is with comparative example 2, the TON type molecular sieve 650g that removes with embodiment 1 preparation replaces the SAPO-11 molecular sieve, only contains Pt in the dipping solution, makes the catalyzer of the present invention that contains 0.6w%Pt at last, be numbered E-4, its appreciation condition and the results are shown in Table 3 and table 4.
Embodiment 5
A kind of preparation method of catalyzer of the present invention
Preparation of catalysts is with comparative example 2, and the TON type molecular sieve 650g that removes with embodiment 2 preparations replaces the SAPO-11 molecular sieve, obtains catalyzer of the present invention, is numbered E-5, its appreciation condition and the results are shown in Table 3 and table 4.
Embodiment 6
A kind of preparation method of catalyzer among the present invention
The preparation of carrier removes with molecular sieve E-3 replacement E-2 with embodiment 5, 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-6 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.
Embodiment 7
A kind of preparation method of catalyzer among the present invention
The preparation of carrier removes the molecular sieve with 400g molecular sieve replacement 600g with embodiment 4, 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-7 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 3861.1
Sulphur, μ g/g 4.0
Nitrogen, μ g/g 1.2
Viscosity, mm/s 2, 40 ℃ 29.69
100℃??????????????????????????5.47
Pour point, ℃ 21
C/H?????????????????????????????????????????85.82/14.08
Flash-point (opening), ℃ 198
Wax content, % 9.8
Boiling range, ℃ (D1160)
IBP/10％????????????????????????????????????227/399
30％/50％???????????????????????????????????428/441
70％/90％?????????????????????????????455/469
95％/EBP??????????????????????????????477/500
Table 4 catalyst runs condition and result
Catalyzer numbering C-2 C-3 E-4 E-5 E-6 E-7
Processing condition
Reaction pressure, MPa 10 10 10 10 10 10
Volume space velocity, h -10.9 0.9 0.9 0.9 0.9 0.9
Hydrogen to oil volume ratio 800 800 800 800 800 800
Temperature of reaction, ℃ 375 340 310 310 315 320
C 5 +Liquid is received, and % 96.1 92.3 97.3 96.4 97.0 97.5
Product distributes, %
C 5～130℃???????????1.8??????6.2??????5.1??????4.6??????5.5??????4.6
130℃～280℃?????????5.2??????4.7??????3.9??????3.7??????4.0??????3.2
280℃～350℃?????????8.6??????5.6??????6.0??????6.6??????6.3??????5.1
350℃ +??????????????80.5?????75.8?????82.3?????82.5?????81.2?????84.6
350 ℃ +Neutral oil character
Viscosity, 40 ℃, mm 2/ s 32.38 36.22 36.35 38.22 36.42 36.38
Viscosity index 110 102 105 96 104 108
Pour point, ℃-6-21-21-24-28-18
Comparative example 4
A kind of preparation method of comparative catalyst of the present invention
Preparation of catalysts is with comparative example 2, the TON type molecular sieve that removes with comparative example 1 preparation replaces the SAPO-11 molecular sieve, only contains Ni in the steeping fluid, obtains containing the comparative catalyst of the present invention of 2.4w%Ni at last, be numbered C-4, its appreciation condition and the results are shown in Table 3 and table 5.
Embodiment 8
A kind of preparation method of catalyzer of the present invention
Preparation of catalysts is with comparative example 4, removes TON type molecular sieve with embodiment 1 preparation and replaces TON type molecular sieve than example 1 preparation, obtains containing the catalyzer of the present invention of 2.2w%Ni at last, is numbered E-8, its appreciation condition and the results are shown in Table 3 and table 5.
Embodiment 9
A kind of preparation method of catalyzer of the present invention
Preparation of catalysts is with embodiment 8, removes with the steeping fluid that contains Ni and B to replace the steeping fluid that only contains Ni, obtains containing the catalyzer of the present invention of 2.2w%Ni and 2.6w%B at last, is numbered E-9, its appreciation condition and the results are shown in Table 3 and table 5.
Embodiment 10
A kind of preparation method of catalyzer of the present invention
Preparation of catalysts is with embodiment 8, removes with the steeping fluid that contains Ni, B and P to replace the steeping fluid that only contains Ni, obtains containing the catalyzer of the present invention of 2.8w%Ni, 1.4w%B and 1.0w%P at last, is numbered E-10, its appreciation condition and the results are shown in Table 3 and table 5.
Table 4 catalyst runs condition and result
Catalyzer numbering C-4 E-8 E-9 E-10
Processing condition
Reaction pressure, MPa 10 10 10 10
Volume space velocity, h -10.6 0.6 0.6 0.6
Hydrogen to oil volume ratio 800 800 800 800
Temperature of reaction, ℃ 350 355 360 360
C 5 +Liquid is received, and % 86.6 90.7 92.3 93.9
Product distributes, %
C 5～130℃???????????5.3??????4.5??????4.0??????3.5
130℃～280℃?????????2.6??????2.7??????3.5??????3.8
280℃～350℃?????????8.3??????8.2??????8.3??????9.1
350℃ +??????????????70.4?????75.3?????76.5?????77.5
350 ℃ +Neutral oil character
Viscosity, 40 ℃, mm 2/ s 37.42 37.23 36.64 36.79
Viscosity index 92 96 100 96
Pour point, ℃-18-20-21-19
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 body phase SiO of molecular sieve 2/ Al 2O 3Adopt plasma emission spectrum (ICP) method to measure, the epiphase silica alumina ratio adopts x-ray photoelectron spectroscopy (XPS) method to measure.The amount in B acid and L acid site is that pyridine-TPD is at 1700cm by in fourier-transform infrared (FT-IR) spectrum -1-1350cm -1Peak area obtains.

Claims (10)

1, a kind of hydrotreating catalyst, contain the refractory oxide carrier, the TON structure molecular screen, the hydrogenation metal component, and selectable adjuvant component, wherein TON structure molecular screen content is 10%～90% of total catalyst weight, inorganic refractory oxide content is 5w%～80w%, auxiliary agent content is 0～10w%, and the hydrogenation metal component concentration is 0.1w%～30w%; It is characterized in that described TON type structure molecular screen has following feature, epiphase SiO 2/ Al 2O 3Mol ratio is 50～200, epiphase SiO 2/ Al 2O 3Mol ratio is than body phase SiO 2/ Al 2O 3Mol ratio is high by 5～50.
2,, it is characterized in that described TON type structure molecular screen has following feature, epiphase SiO according to the described catalyzer of claim 1 2/ Al 2O 3Mol ratio is 80～120.
3,, it is characterized in that the epiphase SiO of described TON type structure molecular screen according to claim 1 or 2 described catalyzer 2/ Al 2O 3Mol ratio is than body phase SiO 2/ Al 2O 3Mol ratio is high by 15～30.
4,, it is characterized in that the long-pending 150m of being of ratio epiphase of described TON type structure molecular screen according to claim 1 or 2 described catalyzer 2/ g～500m 2/ g, pore volume are 0.15ml/g～0.50ml/g, mean pore size 2.0nm～10.0nm.
5,, it is characterized in that the long-pending 200m of being of ratio epiphase of described TON type structure molecular screen according to claim 1 or 2 described catalyzer 2/ g～300m 2/ g, pore volume are 0.20ml/g～0.40ml/g, mean pore size 3.0nm～6.0nm.
6, according to claim 1 or 2 described catalyzer, it is characterized in that the B acid amount of described TON type structure molecular screen is 0.05mmol/g～0.5mmol/g, L acid amount is 0.05mmol/g～0.5mmol/g.
7, according to claim 1 or 2 described catalyzer, it is characterized in that the B acid amount of described TON type structure molecular screen is 0.1mmol/g～0.3mmol/g, L acid amount is 0.1mmol/g～0.2mmol/g.
8, according to the described catalyzer of claim 1, it is characterized in that described TON structure molecular screen content is 30%～80% of total catalyst weight, inorganic refractory oxide is molecular sieve and/or unformed oxide compound, and content is 10w%～60w%, and auxiliary agent is boron, fluorine, chlorine or phosphorus; The hydrogenation metal component be in Pt, Pd, Ru, Rh, nickel, cobalt, molybdenum and the tungsten one or more.
9, the described Preparation of catalysts method of a kind of claim 1 adopts immersion process for preparing, adds respective substance according to each component concentration of catalyzer, it is characterized in that TON type molecular sieve wherein adopts following process preparation:
(a) preparation is a kind of is selected from the even gel that IIIA in the periodic table of elements, IVA element compound, mineral alkali, organic lamina membranacea agent and water are formed by at least a;
(b) gel of heating steps (a) preparation under the condition of crystallization, makes the gel crystallization complete, through aftertreatment, obtains molecular screen primary powder, obtains final zeolite product through removing lamina membranacea agent, ammonium exchange, dealumination complement silicon process then;
Wherein the template described in the step (a) is a double template: the master module agent is a diamine compounds, and the auxiliary template agent is a nitrogen-containing heterocycle compound.
10, in accordance with the method for claim 9, it is characterized in that adding C in the gel in step (a) 5-C 10Alkane be auxiliary agent, described master module agent is C 2-C 10Diamines, the auxiliary template agent is a pyrrole derivative.
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