CN106179487A - Containing noble metal and the renovation process of TON type molecular sieve catalyst - Google Patents

Abstract

The invention discloses a kind of containing noble metal with the renovation process of TON type molecular sieve catalyst.This catalyst includes TON type molecular sieve and the VIIIth race's noble metal component, regenerative process includes: first process deactivation catalyst of carbon deposit with organic solvent, use infusion process load containing lanthanum compound and zinc compound again, on dipping rear catalyst, the lanthanum of load is 6:1 ~ 1:1 with the atomic ratio of metal platinum in catalyst, on catalyst, the zinc of load is 10:1 ~ 1:1 with the atomic ratio of metal platinum in catalyst, then under oxygen-containing gas effect, carry out the first roasting, then reduction treatment is carried out, the second roasting is carried out again under oxygen-containing gas effect, the maximum temperature of the first roasting process is not higher than 450 DEG C, second calcination process is washed through aqueous slkali soaking after completing, last drying obtains regenerated catalyst.The inventive method is not only able to the most effectively remove carbon deposit, it is ensured that catalyst pore structure is not destroyed, and noble metal dispersion can be made good, and the performance of regenerated catalyst is recovered very well.

Description

Containing noble metal and TON The renovation process of type molecular sieve catalyst

Technical field

The present invention relates to a kind of containing noble metal with the renovation process of TON type molecular sieve catalyst, more specifically, relate to a kind of containing noble metal with the renovation process of the catalyst for hydroisomerizing of TON type molecular sieve, the especially renovation process of paraffin hydrocarbon catalyst for hydroisomerizing, is particularly suitable for the catalyst recovery process that the hydroisomerization dewaxing process of lubricating oil uses.

Background technology

Isodewaxing Technology is mainly used in the hydrogen that faces of diesel oil, wax oil and other specialty oils and processes, and to reduce normal paraffin content, improves the purpose of oil quality.This technology also has important meaning to the low temperature flow improving diesel oil.In general, in straight-run diesel oil or secondary processing diesel oil, wax content is higher, and therefore its condensation point or cold filter plugging point are defective, reduces the productivity of diesel oil, n-alkane can be converted into the isoparaffin of low condensation point by hydroisomerization effectively, and can also retain the feature of its high cetane number.High-quality extraordinary oil, hydroisomerization key technology especially is produced as the tail oil being hydrocracked about VGO or modifying.By the isomerization of long-chain normal paraffin, can produce the distillate component of low pour point, high viscosity index (HVI), low volatility, so exploitation isomerization dewaxing catalyst regeneration techniques not only has good economic benefit, and its social meaning is the most important and far-reaching.

The catalyst in use activity that oil-refining chemical process uses can be gradually lowered, i.e. catalysqt deactivation, is summed up reason and is generally divided into coking and deactivation (causing catalyst pores to block), poisoning and deactivation (causing acidity of catalyst center to be poisoned) and sintering deactivation (causing the change of catalyst crystalline phases) etc..The main cause of industry hydrogenation catalyst inactivation is that coke generates and metal blocking, active metal component migrates or gatherings, the change of phase composition, number of active center reduces, carrier sinters, zeolite structured subsides and collapse etc..The decaying catalyst caused for carbon deposit can recover its activity by regeneration method, and metal deposit is polluted to the decaying catalyst caused, it is impossible to regeneration is allowed to activity recovery, can only discard.

Catalyst regeneration is divided into in-situ regeneration and ex-situ regeneration two kinds, and in-situ regeneration typical media is nitrogen and air, as far as possible without steam and air, because steam can promote accumulation of metal on catalyst, zeolite crystalline structure to be destroyed.Owing to in-situ regeneration shortcoming is too many, which is seldom used to carry out catalyst regeneration.The most industrial, the catalyst in the most large-scale reactor all uses ex-situ regeneration technique.The major advantage of catalyst device outer regeneration technology is to be not likely to produce hot-spot in catalyst regeneration process, and catalyst activity recovery extent is higher；The natural law that goes into operation of device can be increased；And device reaction system is without bearing the corrosion of sulfurous gas in regeneration gas again.

The essence of ex-situ regeneration patented technology is contacting by decaying catalyst and oxygen-containing gas, removes the carbon deposit on surface, i.e. makes catalyst regenerate by the way of making charcoal.Compared with fresh catalyst, the pore volume of regenerated catalyst, specific surface have a certain degree of decline, and the fall of activity is the biggest.

In order to improve the activity of regenerated catalyst, also certain methods is elaborated in patented technology, catalyst after regeneration is carried out post processing, propose to contact catalyst with additive such as CN1187215A and activate, being dried described catalyst the most under certain condition so that described additive remains substantially in catalyst, described additive is at least one compound of the compound selected from least two hydroxyl and 2 ~ 10 carbon atoms and the ether of these compounds.WO01/02092 describes a kind of in the following manner by the method for the regeneration of used catalyst based on additive with activation: contacted with oxygen-containing gas by this catalyst at maximum temperature is 500 DEG C, it is made to activate by contacting with organic additive subsequently, it is dried through uniform temperature again, to ensure that the described additive of at least 50% is maintained in this catalyst.Preferably additive is selected from comprising the oxygen-containing part of at least two and the compound of 2 ~ 10 carbon atoms and the compound derived by these compounds.Mentioned example includes acid, aliphatic diol, aliphatic diol ether, saccharide and oxygenatedchemicals.Method described in CN1890351A is: be 80 ~ 500 DEG C by catalyst and acid and boiling point and dissolubility in water is at least the organic additive of 5g/L and contact, dry under certain condition so that the described additive reservation of at least 50wt% in the catalyst.Above-mentioned ex-situ regeneration method, owing to make charcoal step through high temperature, processes with organic additive the most again, and the method is not suitable for noble metal and molecular screen material in the isomerization dewaxing catalyst as active component.

The active metal that isomerization dewaxing catalyst uses is generally noble metal, and carrier typically uses TON molecular sieve, is a kind of catalyst simultaneously containing noble metal and molecular sieve.This catalyst has suitable acid centre and high hydrogenation activity, its selective hydrocracking and hydroisomerization function is made to reach well to balance, wax isomerization reactivity and the selectivity that so can make catalyst are greatly improved, being in particular in that yield dewaxed oil and viscosity index (VI) are all improved, pour point is substantially reduced.

Isomerization dewaxing catalyst main cause of activity decrease in hydroisomerization dewaxing reacts include following some: on (1) catalyst, carbon deposit covers the active sites of catalyst or plugs the duct of catalyst；(2) compound such as the sulfur in raw material, nitrogen makes catalyst poisoning；(3) gathering of metal or the destruction of carrier structure；(4) metal or nonmetallic deposition, such as silicon, arsenic, ferrum etc. in raw material.Owing to isomerization dewaxing catalyst is a kind of macromolecule sieve content noble metal catalyst, molecular sieve is a kind of metastable state crystallization, (such as high temperature under certain condition, illumination, long-time etc.) more stable structure (generally ZSM-5 molecular sieve structure) can be converted into, the reactivity worth of original catalyst can be lost, at high temperature easily lead to crystallization of molecular sieves structural damage, and it is easily caused the gathering of metal, once accumulation of metal, the chlorination that can not carry out metal as reforming catalyst updates (at high temperature, chlorine and steam are very big to the destruction of molecular sieve structure), even if using the conventional methods such as organic additive to process after making charcoal, it also is difficult to make it be disperseed the most well.As can be seen here, conventional catalyst high temperature coke-burning regeneration method will the performance of this isomerization dewaxing catalyst of heavy damage.So general noble metal catalyst (such as reforming catalyst) renovation process is not suitable for the regeneration of isomerization dewaxing catalyst, in whole regenerative process, the temperature that must strictly control catalyst particle surface is too high, and ensure oxidation thoroughly, specially require strict control regeneration temperature and oxygen content in catalyst regeneration process for this.So isomerization dewaxing catalyst regeneration it is critical only that and finds a carbon deposit can tried one's best on Removal of catalyst, can suppress again molecular sieve to be destroyed and reduces the operating condition of accumulation of metal simultaneously.

In existing relevant deactivation catalyst of carbon deposit Recycling Patents, most of patents consider how emphatically to prevent decaying catalyst from concentrating in regenerative process or the problem of excessive exotherms.Such as US5,037,785 suggestion is under oxygen containing gas, and catalyst is devoked by the method using laser to irradiate, US4,202,865 suggestion batch (-type)s note oxygen, US4,780,195 and US4,417,975 grades are then thought and are added a certain amount of water in atmosphere to prevent sintering of catalyst etc..CN1768956A thinks that the carbon deposit on catalyst can process to obtain more preferable result by distinct methods, is conducive to controlling temperature during its regeneration, reduces the high temperature impact on catalyst performance, improves the activity of regenerated catalyst.Its processing mode is to be initially charged the carbon deposit cleaner such as organic solvent such as propylene glycol methyl ether acetate, propylene-glycol ethyl ether, dipropylene glycol methyl ether, propylene glycol monomethyl ether decaying catalyst is carried out washing by soaking.But the method solvent load is excessive, the macromole by-product in detergent is also difficult to separate.And the carbon deposit that the method first easily removes with organic solvent removing unit partial volume, to reduce the liberated heat when coke-burning regeneration, but finally remain a need for high temperature coke combustion, yet suffer from the problems such as the problem that isomerization dewaxing catalyst runs into, particularly metal platinum are assembled, molecular sieve structure is destroyed when high temperature regeneration.

Summary of the invention

In order to overcome weak point of the prior art, the invention provides a kind of containing noble metal with the renovation process of TON type molecular sieve catalyst, it is particularly suited for containing TON type molecular sieve and the catalyst recovery process of the VIIIth race's noble metal component, the particularly renovation process of paraffin hydrocarbon catalyst for hydroisomerizing.Regeneration methods of the invention is used to be not only able to the most effectively remove carbon deposit, ensure that catalyst pore structure is not destroyed, and the gathering of noble metal can be prevented effectively from, make metal platinum well be disperseed, make the performance of regenerated catalyst can recover to fresh catalyst level.

The invention provides a kind of containing noble metal with the renovation process of TON type molecular sieve catalyst, this catalyst includes TON type molecular sieve and the VIIIth race's noble metal component, regenerative process includes: first process deactivation catalyst of carbon deposit with organic solvent, use infusion process load containing lanthanum compound and zinc compound again, on dipping rear catalyst, the lanthanum of load is 6:1 ~ 1:1 with the atomic ratio of metal platinum in catalyst, on catalyst, the zinc of load is 10:1 ~ 1:1 with the atomic ratio of metal platinum in catalyst, then under oxygen-containing gas effect, carry out the first roasting, first roasting carries out reduction treatment after completing, the second roasting is carried out again under oxygen-containing gas effect, the maximum temperature of the first roasting process is not higher than 450 DEG C, second calcination process is washed through aqueous slkali soaking after completing, last drying obtains regenerated catalyst.

TON type molecular sieve involved in the method for the present invention can be one or more in ZSM-22, SSZ-32, Nu-10, KZ-2 and ISI-1, preferably comprises ZSM-22 molecular sieve, and noble metal component is selected from group VIII metal platinum.One or more in refractory porous inorganic oxide, such as aluminium oxide, silicon oxide, titanium oxide, zirconium oxide etc. can also be contained.On the basis of the weight of catalyst, the content of TON type molecular sieve is 10wt% ~ 90wt%, preferably 30wt% ~ 80wt%, and the content of noble metal is 0.05 wt % ~ 5.0 wt %, and refractory porous inorganic oxide is surplus.

In the inventive method, decaying catalyst first processes with organic solvent, organic solvent wherein used typically can use one or more in benzene, ethanol, gasoline, kerosene, and organic solvent processes the method that the method for decaying catalyst can use immersion, distillation etc. to commonly use.Organic solvent can be 8:1 ~ 1:1 with the volume ratio of catalyst.

In the inventive method, when infusion process load is containing lanthanum compound and zinc compound, a step infusion process can be used, it would however also be possible to employ step impregnation method, preferably one step infusion process.When using a step infusion process, impregnation liquid used by infusion process uses and is dissolved with the aqueous solution containing lanthanum compound and zinc compound, wherein, can be one or more in the solubility lanthanum salt such as Lanthanum (III) nitrate, lanthanum acetate, lanthanum sulfate containing lanthanum compound, concentration containing lanthanum compound is calculated as 1.0wt% ~ 10wt% with lanthanum element, zinc compound aqueous solution can be one or more in the soluble zinc salts such as zinc nitrate, zinc acetate, zinc chloride, zinc sulfate, and the concentration of zinc compound is calculated as 10wt% ~ 30wt% with zinc element.

When using step impregnation method, the step impregnation method of routine can be used to carry out the load aqueous solution containing lanthanum compound and zinc compound, can first load the aqueous solution containing lanthanum compound, it is also possible to first load zinc compound.The impregnation liquid of step impregnation includes two kinds of solution of aqueous solution of the aqueous solution containing lanthanum compound and zinc compound, the concentration of the aqueous solution containing lanthanum compound is calculated as 1.0wt% ~ 10wt% with lanthanum element, and the concentration of the aqueous solution of zinc compound is calculated as 10wt% ~ 30wt% with zinc element.

After infusion process load is containing lanthanum compound and zinc compound, on catalyst, the lanthanum of load is 4:1 ~ 2:1 with the atomic ratio of platinum in decaying catalyst, and on catalyst, the zinc of load is 8:1 ~ 3:1 with the atomic ratio of platinum in decaying catalyst.

In the inventive method, the roasting condition of the first roasting and the second roasting can be the same or different.The condition of the first described roasting is: contacted with oxygen-containing gas by described catalyst, temperature 300 DEG C ~ 450 DEG C, and preferably 320 DEG C ~ 420 DEG C, time of contact is 1.0h ~ 10h, preferably 2.0h ~ 8h.The condition of the second described roasting is: contacted with oxygen-containing gas by described catalyst, temperature 300 DEG C ~ 450 DEG C, and preferably 320 DEG C ~ 420 DEG C, time of contact is 1.0h ~ 10h, preferably 2.0h ~ 8h.In oxygen-containing gas, oxygen content can be 0.2v% ~ 25v%, preferably 0.5v% ~ 10v%.

In the inventive method, described reduction treatment can use reducibility gas commonly used in the art to reduce, preferably employing hydrogen to reduce, hydrogen uses the hydrogen feed of purity ＞ 99.9 v %, and the operating condition of described reduction treatment is: contacted with hydrogen by described catalyst, temperature is 100 DEG C ~ 500 DEG C, being preferably 200 DEG C ~ 450 DEG C, the time is 1.0h ~ 15.0h, preferably 5.0h ~ 10.0h, Hydrogen Vapor Pressure is 0.5 MPa ~ 6.0MPa, preferably 1.0 MPa ~ 4.0MPa.

In the inventive method, described aqueous slkali can use aqueous slkali commonly used in the art, preferably NaOH solution or KOH solution.The concentration of described aqueous slkali is 0.1wt% ~ 20wt%, preferably 1.0wt% ~ 10wt%, and soak time can be 0.5h ~ 20.0h, preferably 1.0h ~ 15.0h, more preferably 5.0h ~ 10.0h, soaks and wash temperature is room temperature.Catalyst after washing drying again processes, and baking temperature can be 60 DEG C ~ 200 DEG C, preferably 70 DEG C ~ 160 DEG C, more preferably 80 DEG C ~ 120 DEG C, and drying time can be 1 .0h ~ 20h, preferably 3.0h ~ 15h, more preferably 5 .0h ~ 10h.

The inventive method has the advantage that

(1) first with organic solvent, decaying catalyst is processed, the carbon deposit content on decaying catalyst can be reduced, be conducive to controlling temperature during its regeneration, when preventing from regenerating, heat release too much or is excessively concentrated, avoid the mistake thermal response of catalyst, causing catalyst property to change, the structure such as molecular sieve is destroyed, or the character of catalyst is adversely affected by the enrichment of carried metal.

(2) strict control regeneration temperature and oxygen content in the coke combustion of the first roasting, this is the TON type molecular sieve owing to containing higher proportion in catalyst, particularity (being easily converted to the ZSM-5 molecular sieve structure that structure is more stable) due to its molecular sieve, charcoal temperature is too high, have a strong impact on the degree of crystallinity of molecular sieve, research display charcoal temperature does not has significant change in the structure of the procatalyst of 420 DEG C, but when charcoal temperature 450 DEG C, the structure of catalyst there occurs significantly change, compared with fresh catalyst, it is the XRD figure of fresh dose that relative crystallinity drops to 97%(Fig. 1), so in oxidation burning process, charcoal temperature is a key factor.When charcoal temperature is relatively low, carbon deposit elimination factor is relatively low, but along with the rising of charcoal temperature, can cause assembling and the structure of saboteur's sieve of active metal, make the performance of catalyst be a greater impact.In whole regenerative process, the temperature that must strictly control catalyst particle surface is too high, and ensure that oxidation is thoroughly, but due to during making charcoal, carbon on catalyst also releases heat during burning, so considering for guaranteeing that catalyst is not burned control temperature at not higher than 450 DEG C.

(3) load a certain amount of containing lanthanum compound with zinc compound on the catalyst after processing through organic solvent, and carry out the first roasting at a lower temperature.nullOwing at high temperature easily being reduced by carbon containing lanthanum compound and zinc compound，And lanthanum/zinc is met oxygen and is easily oxidized，Active oxygen can be produced in oxidizing process，Active oxygen quickly can generate carbon dioxide by the carbon distribution on oxidation catalyst，So it is not only able to effectively remove carbon deposit，And lanthanum/zinc and the formation Pt-Zn-La complex chemical compound of the platinum on decaying catalyst disperse in the first roasting process，The most again through reduction treatment and the second roasting，Can more effectively avoid the gathering of noble metal，Improve the dispersion of noble metal platinum，Avoid the destruction of TON type molecular sieve structure simultaneously，Catalyst after coke-burning regeneration uses the mode of alkali cleaning to remove zinc，Catalyst after the regeneration so obtained not only can guarantee that catalyst pore structure is not destroyed，Pt metal has preferably dispersion，And metal La Yu Pt can be also prevented from the process and run off，Synergism due to La-Pt，The hydrogenation/dehydrogenation reactivity of catalyst can be improved，Make the performance recovery of catalyst to fresh catalyst level.

Accompanying drawing explanation

Fig. 1 is the XRD spectra (100%) of fresh dose of FD-1；

Fig. 2 XRD spectra (degree of crystallinity ~ 99%) for deactivator FD-1；

Fig. 3 XRD spectra (degree of crystallinity ~ 99%) for R-420；

Fig. 4 is the XRD spectra (degree of crystallinity ~ 97%) of R-450；

Fig. 5 is the XRD spectra (degree of crystallinity ~ 92%) of R-500.

Wherein, the R-in Fig. 3-5 refers to that the sintering temperature of FD-1 deactivator, such as R-420 represent FD-1 deactivator digitized representation relative crystallinity after 420 DEG C of calcination process, in bracket.

Detailed description of the invention

Further illustrate the preparation process of catalyst of the present invention below by embodiment, but invention should not be deemed limited in below example.In the present invention, wt% is mass fraction, and v% is volume fraction.

Regenerated catalyst of the present invention is to use the medium-sized fixed bed reactors of 200mL to be evaluated, loaded catalyst is 100mL, before Jin Liao, catalyst is carried out prereduction, the noble metal on catalyst is made to be changed into reduction-state, reducing condition is as follows: in presence of hydrogen, temperature 300 DEG C ~ 500 DEG C, pressure 0.5MPa ~ 10MPa, time 1.0h ~ 12.0h, evaluates the raw oil main character used and is shown in Table 1.

Table 1 raw oil main character

Density (20 DEG C), kg/m3	861.1
		Sulfur, μ g/g	4.0
Nitrogen, μ g/g	1.2
		Viscosity (40 DEG C), mm/s2	29.69
Pour point, DEG C	21
		Wax content, wt%	9.8
Boiling range, DEG C (D1160)
		IBP/10%	227/399
30%/50%	428/441
		70%/90%	455/469
95%/EBP	477/500

The FD-1 decaying catalyst that the present invention relates to is FD-1 fresh catalyst deactivator after Sinopec Qilu Petrochemical hydrocracking tail oil isomerization dewaxing device industrial operation.The physico-chemical property of FD-1 decaying catalyst is as follows: specific surface area is 103m²/ g, pore volume is 0.28mL/g, Pt content 0.45wt%, and C content is 7.24 wt %.Composition and character that FD-1 is fresh dose are as follows: specific surface area is 235m²/ g, pore volume is 0.35mL/g, Pt content 0.50wt%, and the content of ZSM-22 molecular sieve is 70wt%.

The physico-chemical property of the FD-2 decaying catalyst that the present invention relates to is as follows: specific surface area is 110m²/ g, pore volume is 0.26 mL/g, Pt content 0.45wt%, and C content is 8.12wt %.Composition and character that FD-2 is fresh dose are as follows: specific surface area is 245m²/ g, pore volume is 0.36mL/g, Pt content 0.50wt%, and the content of NU-10 molecular sieve is 50wt%.

The physico-chemical property of the FD-3 decaying catalyst that the present invention relates to is as follows: specific surface area is 120m²/ g, pore volume is 0.27mL/g, Pt content 0.44wt%, and C content is 10.02wt %.Composition and character that FD-3 is fresh dose are as follows: specific surface area is 270m²/ g, pore volume is 0.37mL/g, Pt content 0.50wt%, and the content of SSZ-32 molecular sieve is 40wt%.

Wherein FD-2 and FD-3 is laboratory rapid deactivation agent.

Embodiment 1

The preparation of catalyst E-1 of the present invention.

1450mL organic solution (wherein ethanol and benzene volume ratio are 2:1) is added, to the 200mL decaying catalyst FD-1 process after industrial operation, the numbered Ca-1 of catalyst after distillation 2.0h in the flask of 2000mL.

Take 27.8g Lanthanum (III) nitrate (lanthanum content 3.0wt%), 5.2g zinc nitrate (the Zn content 10.0wt%) preparation impregnation liquid containing lanthanum/zinc, take Ca-1 catalyst 100g and carry out saturated dipping, prepared La Yu Pt, the atomic ratio of Zn Yu Pt are respectively the catalyst sample containing lanthanum/zinc of 3:1 and 4:1, again with the programming rate of 3 DEG C/min, it is warming up to 350 DEG C of constant temperature 5h.The numbered Ea-1 of gained catalyst.

Above-mentioned catalyst Ea-1 carries out the first calcination process under air atmosphere, and actual conditions is: with the programming rate of 3 DEG C/min, is warming up to 350 DEG C of constant temperature 5h.First calcined catalyst is being carried out reduction treatment under an atmosphere of hydrogen, and actual conditions is: Hydrogen Vapor Pressure is 3.5Mpa, and reduction temperature is 430 DEG C, and the recovery time is 6.0h.By second calcination process under air atmosphere of the catalyst after reduction treatment, actual conditions is: with the programming rate of 3 DEG C/min, is warming up to 410 DEG C of constant temperature 3h, the numbered Ea-2 of gained catalyst.

Take 8.5wt%(in terms of NaOH) sodium hydrate aqueous solution 300g, add 100g above-mentioned catalyst Ea-2, soak 10.0h under room temperature, then through 120 DEG C of dry 10h, obtain catalyst E-1 of the present invention, its concrete treatment conditions are shown in Table 2, and reaction result is shown in Table 3.

Embodiment 2

The preparation of catalyst E-2 of the present invention.

Take 17.4g lanthanum acetate (lanthanum content 8.0wt%) and be configured to impregnation liquid, Ca-1 catalyst 100g is prepared according to embodiment 1 method, carry out saturated dipping, prepare La Yu Pt atomic ratio be 5:1 containing lanthanum catalyst sample, after drying and roasting, take 3.9g zinc acetate (Zn content 10.0wt%) and be configured to impregnation liquid, take and above-mentioned carry out supersaturation dipping containing lanthanum catalyst, prepare the catalyst sample containing lanthanum/zinc that atomic ratio is 3:1 of Zn Yu Pt, again with the programming rate of 3 DEG C/min, it is warming up to 420 DEG C of constant temperature 4h.The numbered Eb-1 of gained catalyst.

Above-mentioned catalyst Eb-1 carries out the first calcination process under air atmosphere, and actual conditions is: with the programming rate of 3 DEG C/min, is warming up to 420 DEG C of constant temperature 4h.First calcined catalyst carries out reduction treatment under an atmosphere of hydrogen, and actual conditions is: Hydrogen Vapor Pressure is 4.5Mpa, and reduction temperature is 480 DEG C, and the recovery time is 5h；By second calcination process under air atmosphere of the catalyst after reduction treatment, actual conditions is: with the programming rate of 3 DEG C/min, is warming up to 450 DEG C of constant temperature 3h, the numbered Eb-2 of gained catalyst.

Take 7.5wt%(in terms of NaOH) sodium hydrate aqueous solution 300g, add 100g above-mentioned catalyst Eb-2, soak 10h under room temperature, then through 120 DEG C of dry 10h, obtain catalyst E-2 of the present invention, its concrete treatment conditions are shown in Table 2, and reaction result is shown in Table 3.

Embodiment 3

The preparation of catalyst E-3 of the present invention.

1450mL organic solvent (wherein gasoline and kerosene volume ratio are 1:1) is added, to decaying catalyst FD-1 process after 200mL industrial operation, the numbered Cb-1 of catalyst after distillation 2.0h in the flask of 2000mL.

Take 83.4g lanthanum sulfate (lanthanum content 2.0wt%), 7.8g zinc nitrate (the Zn content 20.0wt%) preparation impregnation liquid containing lanthanum/zinc, take Cb-1 catalyst 100g and carry out saturated dipping, prepared La Yu Pt, the atomic ratio of Zn Yu Pt are respectively the catalyst sample containing lanthanum/zinc of 6:1 and 8:1, again with the programming rate of 3 DEG C/min, it is warming up to 350 DEG C of constant temperature 5h.The numbered Ec-1 of gained catalyst.

Above-mentioned catalyst Ec-1 carries out the first calcination process under air atmosphere, and actual conditions is: with the programming rate of 3 DEG C/min, is warming up to 350 DEG C of constant temperature 5h.First calcined catalyst carries out reduction treatment under an atmosphere of hydrogen, and actual conditions is: Hydrogen Vapor Pressure is 2.5MPa, and reduction temperature is 450 DEG C, and the recovery time is 7.0h；Catalyst after reduction treatment carries out under air atmosphere the second calcination process, and actual conditions is: with the programming rate of 3 DEG C/min, is warming up to 350 DEG C of constant temperature 3.0h.The numbered Ec-2 of gained catalyst.

Take 15wt%(in terms of NaOH) sodium hydrate aqueous solution 300g, add 100g above-mentioned catalyst Ec-2, soak 10h under room temperature, then through 120 DEG C of dry 10.0h, obtain catalyst E-3 of the present invention, its concrete treatment conditions are shown in Table 2, and reaction result is shown in Table 3.

Embodiment 4 ~ 6

The preparation of catalyst E-4 ~ E-6 of the present invention.

The preparation process of catalyst E-4 ~ E-6 of the present invention is with embodiment 1, difference is with decaying catalyst used, lanthanum and zinc solution and roasting different with the temperature of reduction, catalyst E-4 ~ the E-6 of the present invention prepared, its concrete treatment conditions are shown in Table 2, and reaction result is shown in Table 3.

Comparative example 1

Prepared by comparative catalyst C-1 of the present invention.

The preparation method of catalyst is with embodiment 1, and difference is that catalyst does not use containing lanthanum compound, numbered C-1, and its physico-chemical property is shown in Table 2, and reaction result is shown in Table 3.

Comparative example 2

Prepared by comparative catalyst C-2 of the present invention.

The preparation method of catalyst is with embodiment 1, and difference is that catalyst does not use zinc compound, numbered C-2, and its concrete treatment conditions are shown in Table 2, and reaction result is shown in Table 3.

Comparative example 3

Prepared by comparative catalyst C-3 of the present invention.

The preparation method of catalyst, with embodiment 1, processes containing lanthanum/zinc solution although difference is that catalyst passes through, but only through a calcination process, without reduction treatment and the second roasting, numbered C-3, its concrete treatment conditions is shown in Table 2, and reaction result is shown in Table 3.

Comparative example 4

Prepared by comparative catalyst C-4 of the present invention.

The preparation method of catalyst is with embodiment 1, although difference is that catalyst processes through lanthanum/zinc solution, again through the first roasting, reduction treatment and the second roasting, but without alkaline solution treatment, numbered C-4, its concrete treatment conditions are shown in Table 2, and reaction result is shown in Table 3.

The each embodiment of table 2 and the treatment conditions of comparative example

Table 2 continues the treatment conditions of each embodiment and comparative example

Numbering	Hydrogen Vapor Pressure, MPa	Reduction temperature	Second roasting	Naoh concentration, wt%
					E-1	3.5	430℃×6h	410℃×3h	8.5
E-2	4.5	480℃×5h	450℃×3h	7.5
					E-3	2.5	450℃×7h	350℃×3h	15
E-4③	3.2	400℃×5h	410℃×4h	2.5
					E-5	3.8	410℃×5h	370℃×2h	5.0
E-6④	4.0	270℃×10h	400℃×5h	13.5
					C-1	3.5	410℃×6h	420℃×3h	8.5
C-2	3.5	410℃×6h	420℃×3h	8.5
					C-3	--	--	--	8.5
C-4	3.5	410℃×6h	420℃×3h	--

Note: Ethanol/benzene, 2. gasoline/kerosene, 3. FD-2 decaying catalyst, 4. FD-3 decaying catalyst

Table 3 evaluating catalyst condition and result

Table 3 continues evaluating catalyst condition and result

The evaluation result of table 3 shows, compared with comparative catalyst, uses the catalyst of the inventive method regeneration, in the hydroprocessing processes of lube cut, when lube base oil pour point is close, C₅ ⁺Liquid is received and is improved more than 10wt%, and lube base oil yield improves about 15wt%, and the viscosity index (VI) of product improves nearly 12 units, illustrate the catalyst after the inventive method regeneration during process crude lube stock, effect has and significantly improves.

From Fig. 1 to Fig. 5, the degree of crystallinity that FD-1 is fresh dose is set to 100%, its XDR structure is shown in Fig. 1, the structure of deactivator is shown in Fig. 2, the XRD characterization result of the sample that different charcoal temperatures (420 DEG C, 450 DEG C and 500 DEG C) obtain is shown in Fig. 3 ~ Fig. 5, from the result of Fig. 3 it can be seen that there is no significant change at charcoal temperature in the structure of the procatalyst of 420 DEG C, but when charcoal temperature 450 DEG C, the structure of catalyst there occurs that some change, when charcoal temperature reaches 500 DEG C, the structure of catalyst there occurs significantly change.Therefore, the charcoal temperature of application claims the first roasting controls not higher than 450 DEG C, the most not higher than 420 DEG C.

Claims (18)

1. null1. one kind contains noble metal and the renovation process of TON type molecular sieve catalyst，This catalyst includes TON type molecular sieve and the VIIIth race's noble metal component，It is characterized in that，Regenerative process includes: first process deactivation catalyst of carbon deposit with organic solvent，Use infusion process load containing lanthanum compound and zinc compound again，On dipping rear catalyst, the lanthanum of load is 6:1 ~ 1:1 with the atomic ratio of metal platinum in catalyst，On catalyst, the zinc of load is 10:1 ~ 1:1 with the atomic ratio of metal platinum in catalyst，Then under oxygen-containing gas effect, carry out the first roasting，First roasting carries out reduction treatment after completing，The second roasting is carried out again under oxygen-containing gas effect，The maximum temperature of the first roasting process is not higher than 450 DEG C，Second calcination process complete after through aqueous slkali soaking、Washing，Last drying obtains regenerated catalyst.
2. The most in accordance with the method for claim 1, it is characterised in that: in described catalyst, noble metal component is platinum, and TON type molecular sieve is one or more in ZSM-22, SSZ-32, Nu-10, KZ-2 and ISI-1.
3. The most in accordance with the method for claim 1, it is characterized in that: in described catalyst, containing TON type molecular sieve, noble metal platinum and refractory porous inorganic oxide, on the basis of the weight of catalyst, the content of molecular sieve is 10wt% ~ 90wt%, being preferably 30wt% ~ 80wt%, the content of noble metal is 0.05wt% ~ 5.0 wt%, and surplus is refractory porous inorganic oxide.
4. The most in accordance with the method for claim 1, it is characterised in that: described catalyst is hydroisomerization dewaxing catalyst.
5. The most in accordance with the method for claim 1, it is characterized in that: after infusion process load is containing lanthanum compound and zinc compound, on catalyst, the lanthanum of load is 4:1 ~ 2:1 with the atomic ratio of platinum in decaying catalyst, and on catalyst, the zinc of load is 8:1 ~ 3:1 with the atomic ratio of platinum in decaying catalyst.
6. The most in accordance with the method for claim 1, it is characterised in that: decaying catalyst first processes with organic solvent, one or more in ethanol, benzene, gasoline and kerosene of organic solvent wherein used.
7. The most in accordance with the method for claim 1, it is characterised in that: decaying catalyst first processes with organic solvent, and wherein organic solvent processes the method that the method employing of decaying catalyst is soaked or distilled.
8. The most in accordance with the method for claim 1, it is characterised in that: organic solvent is 8:1 ~ 1:1 with the volume ratio of decaying catalyst.
9. The most in accordance with the method for claim 1, it is characterized in that: the infusion process load method containing lanthanum compound and zinc compound is a step infusion process, impregnation liquid uses and is dissolved with the aqueous solution containing lanthanum compound and zinc compound, wherein, concentration containing lanthanum compound is calculated as 1.0wt% ~ 10wt% with lanthanum element, and the concentration of zinc compound is calculated as 10wt% ~ 30wt% with zinc element.
10. The most in accordance with the method for claim 1, it is characterized in that: the infusion process load method containing lanthanum compound and zinc compound is step impregnation method, impregnation liquid includes the aqueous solution of the aqueous solution containing lanthanum compound and zinc compound, the concentration of the aqueous solution containing lanthanum compound is calculated as 1.0wt% ~ 10wt% with lanthanum element, and the concentration of the aqueous solution of zinc compound is calculated as 10wt% ~ 30wt% with zinc element.
11. 11. according to the method described in claim 9 or 10, it is characterised in that: being one or more in Lanthanum (III) nitrate, lanthanum acetate, lanthanum sulfate containing lanthanum compound, zinc compound is one or more in zinc nitrate, zinc acetate, zinc chloride, zinc sulfate.
12. 12. in accordance with the method for claim 1, it is characterised in that: the condition of the first described roasting is: contacted with oxygen-containing gas by described catalyst, and temperature is 300 DEG C ~ 450 DEG C, preferably 320 DEG C ~ 420 DEG C, and the time is 1.0h ~ 10h, preferably 2.0h ~ 8.0h.
13. 13. in accordance with the method for claim 1, it is characterised in that: the condition of the second described roasting is: contacted with oxygen-containing gas by described catalyst, and temperature is 300 DEG C ~ 450 DEG C, preferably 320 DEG C ~ 420 DEG C, and the time is 1.0h ~ 10h, preferably 2.0h ~ 8.0h.
14. 14. according to the method described in claim 1 or 12 or 13, it is characterised in that: in described oxygen-containing gas, oxygen content is 0.2v% ~ 25v%, preferably 0.5v% ~ 10v%.
15. 15. in accordance with the method for claim 1, it is characterized in that: the operating condition of described reduction treatment is: contacted with hydrogen by described catalyst, temperature is 100 DEG C ~ 500 DEG C, it is preferably 200 DEG C ~ 450 DEG C, time is 1h ~ 15h, being preferably 5h ~ 10h, Hydrogen Vapor Pressure is 0.5MPa ~ 6.0MPa, preferably 1.0MPa ~ 4.0MPa.
16. 16. in accordance with the method for claim 1, it is characterised in that: described aqueous slkali is NaOH solution or KOH solution.
17. 17. according to the method described in claim 1 or 16, it is characterised in that: the concentration of described aqueous slkali is 0.1 wt % ~ 20 wt %, preferably 1 .0wt % ~ 10 wt %.
18. 18. in accordance with the method for claim 1, it is characterised in that: the described condition being dried is as follows: temperature is 60 ~ 200 DEG C, preferably 70 ~ 160 DEG C, more preferably 80 ~ 120 DEG C, time 1 ~ 20h, preferably 3 ~ 15h, more preferably 5 ~ 10h.