CN106179487B

CN106179487B - Regeneration method containing noble metal and TON type molecular sieve catalysts

Info

Publication number: CN106179487B
Application number: CN201510210485.1A
Authority: CN
Inventors: 徐会青; 刘全杰; 贾立明; 王伟
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2015-04-29
Filing date: 2015-04-29
Publication date: 2018-06-19
Anticipated expiration: 2035-04-29
Also published as: CN106179487A

Abstract

The invention discloses a kind of regeneration methods containing noble metal and TON type molecular sieve catalysts.The catalyst includes TON types molecular sieve and the VIIIth race's noble metal component, regenerative process include：Deactivation catalyst of carbon deposit first is handled with organic solvent, then using infusion process load containing lanthanum compound and zinc compound, the atomic ratio for impregnating metal platinum in the lanthanum and catalyst loaded on rear catalyst is 6:1~1:1, the atomic ratio of metal platinum is 10 in the zinc and catalyst that load on catalyst:1~1:1, the first roasting is then carried out under oxygen-containing gas effect, then carries out reduction treatment, the second roasting is carried out under oxygen-containing gas effect again, the maximum temperature of first roasting process is not higher than 450 DEG C, and the second calcination process is washed after completing through aqueous slkali soaking, most afterwards through being dried to obtain regenerated catalyst.The method of the present invention is not only able to, at low temperature effectively except carbon deposition removal, ensure that catalyst pore structure is not destroyed, and noble metal dispersion can be made good, the performance of regenerated catalyst is restored very well.

Description

Regeneration method containing noble metal and TON type molecular sieve catalysts

Technical field

The present invention relates to a kind of regeneration method containing noble metal and TON type molecular sieve catalysts, more specifically to one The regeneration method of catalyst for hydroisomerizing of the kind containing noble metal and TON type molecular sieves, especially paraffin hydrocarbon hysomer are urged The regeneration method of agent, the catalyst recovery process that the hydroisomerization dewaxing process particularly suitable for lubricating oil uses.

Background technology

The hydrogen that faces that Isodewaxing Technology is mainly used in diesel oil, wax oil and other specialty oils is handled, and is reduced with reaching Normal paraffin content improves the purpose of oil quality.The technology also has important meaning to the low temperature flow for improving diesel oil.One As for, wax content is higher in straight-run diesel oil or secondary processing diesel oil, therefore its condensation point or cold filter plugging point are unqualified, reduce diesel oil Yield, n-alkane can be effectively converted into the isoparaffin of low condensation point by hydroisomerization, and it is high by 16 to retain its The characteristics of alkane value.The special type oil of high quality is produced as the tail oil for being hydrocracked or modifying about VGO, hydroisomerization is even more to close Key technology.By the isomerization of long-chain normal paraffin, the fraction oil ingredient of low pour point, high viscosity index (HVI), low volatility can be produced, So exploitation isomerization dewaxing catalyst regeneration techniques are not only with good economic efficiency, but also its social effect is quite important With it is far-reaching.

Activity can continuously decrease the catalyst that oil-refining chemical process uses in use, i.e. catalyst inactivation, conclude Reason of getting up is generally divided into coking and deactivation（Catalyst pores is caused to block）, poisoning and deactivation（Acidity of catalyst center is caused to be poisoned）With Sintering deactivation（Cause the change of catalyst crystalline phases）Deng.The main reason for industrial hydrogenation catalyst inactivation is coke generation and metal It blocks, active metal component migration or aggregation, the variation of phase composition, number of active center is reduced, carrier is sintered, zeolite structured collapses With collapse etc..The decaying catalyst for caused by carbon deposit can restore its activity with regeneration method, and metal deposit is polluted Caused by decaying catalyst, it is impossible to regeneration be allowed to activity recovery, can only discard.

Catalyst regeneration is divided into two kinds of in-situ regeneration and ex-situ regeneration, and in-situ regeneration typical media is nitrogen and air, is use up Amount does not have to vapor and air, because vapor can promote accumulation of metal on catalyst, zeolite crystalline structure to be destroyed.Due to In-situ regeneration shortcoming is too many, seldom carries out catalyst regeneration using which.It is industrial at present, particularly large-scale reactor In catalyst all use ex-situ regeneration technique.The major advantage of catalyst device outer regeneration technology be in catalyst regeneration process not Hot-spot is also easy to produce, catalyst activity recovery extent is higher；The number of days that goes into operation of device can be increased；And device reaction system Without the corrosion for bearing sulfurous gas in regeneration gas again.

The essence of ex-situ regeneration patented technology is the contact with oxygen-containing gas by decaying catalyst, removes the product on surface Charcoal makes catalyst regeneration by way of making charcoal.Compared with fresh catalyst, the Kong Rong of regenerated catalyst, specific surface have A degree of decline, and the fall of activity is also larger.

In order to improve the activity of regenerated catalyst, certain methods are also elaborated in patented technology, to urging after regeneration Agent is post-processed, and as CN1187215A propositions contact catalyst with additive and is activated, and is done under certain condition later The dry catalyst so that the additive is remained substantially in catalyst, the additive be selected from least two hydroxyls and 2 ~ At least one compound of the compound of 10 carbon atoms and the ether of these compounds.WO01/02092 describe it is a kind of by with Under type by the used catalyst regeneration based on additive and activation method：This is catalyzed at being 500 DEG C in maximum temperature Agent is contacted with oxygen-containing gas, is then made its activation by being contacted with organic additive, is dried using certain temperature, to ensure extremely Few 50% additive is maintained in the catalyst.Preferred additive be selected from comprising at least two oxygen-containing parts and 2 ~ The compound and the compound as derived from these compounds of 10 carbon atoms.Mentioned example includes acid, aliphatic diol, fat Race's glycol ethers, carbohydrate and oxygenatedchemicals.CN1890351A the methods are：By catalyst with acid and boiling point be 80 ~ 500 DEG C with And solubility in water is at least the organic additive contact of 5g/L, dries under certain condition so that the institute of at least 50wt% Additive is stated to retain in the catalyst.Above-mentioned ex-situ regeneration method is since high temperature to be passed through is made charcoal step, then again with organic Additive treating, this method are not suitable for using noble metal and molecular screen material as in the isomerization dewaxing catalyst of active component.

The active metal that isomerization dewaxing catalyst uses is generally noble metal, and carrier is generally a kind of using TON molecular sieves Catalyst containing noble metal and molecular sieve simultaneously.The catalyst has suitable acid centre and high hydrogenation activity, makes it Selective hydrocracking and hydroisomerization function reach good balance, can make the wax isomerization reactivity of catalyst in this way It is greatly improved with selectivity, is in particular in that yield dewaxed oil and viscosity index (VI) are improved, pour point is substantially reduced.

Isomerization dewaxing catalyst includes the following the main reason for activity declines in hydroisomerization dewaxing reaction：（1） Carbon deposit covers the active sites of catalyst or plugs the duct of catalyst on catalyst；（2）The chemical combination such as sulphur, nitrogen in raw material Object makes catalyst poisoning；（3）The aggregation of metal or the destruction of carrier structure；（4）Metal or nonmetallic deposition in raw material, Such as silicon, arsenic, iron etc..Since isomerization dewaxing catalyst is a kind of macromolecule sieve content noble metal catalyst, molecular sieve is a kind of Metastable state crystallizes, under certain condition（Such as high temperature, illumination, long-time etc.）More stable structure can be converted into（Generally ZSM-5 molecular sieve structure）, the reactivity worth of original catalyst can be lost, easilys lead to crystallization of molecular sieves structure at high temperature Destruction, and be easy to cause the aggregation of metal, once accumulation of metal, it is impossible into the chlorine of row metal as reforming catalyst Change update（At high temperature, chlorine and vapor are very big to the destruction of molecular sieve structure）Even if using organic additive etc. after making charcoal Conventional method processing, it is also difficult to it be made to be disperseed well again.It can be seen that conventional catalyst high temperature coke-burning regeneration method The performance of the isomerization dewaxing catalyst will seriously be destroyed.So general noble metal catalyst（Such as reforming catalyst）Regeneration Method is not suitable for the regeneration of isomerization dewaxing catalyst, in entire regenerative process, it is necessary to stringent control catalyst particle surface Temperature is excessively high, and ensures that oxidation is thorough, specially requires regeneration temperature and oxygen-containing is strictly controlled in catalyst regeneration process thus Amount.So isomerization dewaxing catalyst regeneration key is to find a carbon deposit that can be as possible on Removal of catalyst, while again can Inhibit to molecular sieve destruction and reduce the operating condition of accumulation of metal.

In existing related deactivation catalyst of carbon deposit Recycling Patents, most of patents consider how to prevent inactivation from urging emphatically Agent is concentrated in regenerative process or the problem of excessive exotherms.If US5,037,785 suggests under oxygen containing gas, using laser The method of irradiation devokes catalyst, US4,202, the 865 intermittent note oxygen of suggestion, US4,780,195 and US4, and 417,975 etc. Then think to add a certain amount of water in atmosphere to prevent sintering of catalyst etc..CN1768956A thinks that the carbon deposit on catalyst can It is obtained preferably with being handled by distinct methods as a result, temperature when being conducive to control its regeneration, reduces high temperature to catalyst The influence of performance improves the activity of regenerated catalyst.Its processing mode is first to add in carbon deposit cleaner such as propylene glycol monomethyl ether acetic acid The organic solvents such as ester, propylene-glycol ethyl ether, dipropylene glycol methyl ether, propylene glycol monomethyl ether carry out washing by soaking to decaying catalyst.But This method solvent dosage is excessive, and the macromolecular by-product in detergent is also difficult to detach.And this method is first removed with organic solvent The carbon deposit that easily removes of part is removed, to reduce the heat released in coke-burning regeneration, but finally there is still a need for high temperature coke combustion, still So there are problems that isomerization dewaxing catalyst is encountered in high temperature regeneration, particularly aggregation, molecular sieve structure quilt occur for metal platinum The problems such as destruction.

Invention content

In order to overcome shortcoming of the prior art, urged the present invention provides one kind containing noble metal and TON type molecular sieves The regeneration method of agent is particularly suitable for the molecular sieve of type containing TON and the catalyst recovery process of the VIIIth race's noble metal component, especially It is the regeneration method of paraffin hydrocarbon catalyst for hydroisomerizing.Regeneration method using the present invention is not only able to effectively remove at low temperature Carbon deposition removal ensures that catalyst pore structure is not destroyed, and can effectively avoid the aggregation of noble metal, metal platinum is made to obtain well Dispersion, makes the performance of regenerated catalyst can restore to fresh catalyst level.

The present invention provides a kind of regeneration method containing noble metal and TON type molecular sieve catalysts, which includes TON Type molecular sieve and the VIIIth race's noble metal component, regenerative process include：Deactivation catalyst of carbon deposit first is handled with organic solvent, then is used Infusion process load impregnates the atom of metal platinum in the lanthanum and catalyst loaded on rear catalyst containing lanthanum compound and zinc compound Than being 6:1~1:1, the atomic ratio of metal platinum is 10 in the zinc and catalyst that load on catalyst:1~1:1, then in oxygen-containing gas Effect is lower to carry out the first roasting, reduction treatment is carried out after the completion of the first roasting, then the second roasting is carried out under oxygen-containing gas effect, The maximum temperature of first roasting process is not higher than 450 DEG C, and the second calcination process is washed after completing through aqueous slkali soaking, most afterwards through dry It is dry to obtain regenerated catalyst.

Involved TON types molecular sieve can be ZSM-22, SSZ-32, Nu-10, KZ-2 and ISI- in the method for the present invention One or more of 1, ZSM-22 molecular sieves are preferably comprised, noble metal component is selected from group VIII metal platinum.It can also contain resistance to Molten porous inorganic oxide, for example, it is one or more in aluminium oxide, silica, titanium oxide, zirconium oxide etc..With the weight of catalyst On the basis of amount, the content of TON type molecular sieves is 10wt% ~ 90wt%, and preferably 30wt% ~ 80wt%, the content of noble metal is 0.05 wt The wt % of % ~ 5.0, refractory porous inorganic oxide are surplus.

In the method for the present invention, decaying catalyst is first handled with organic solvent, used in organic solvent can be general One or more of benzene, ethyl alcohol, gasoline, kerosene can be used, leaching may be used in the method for organic solvent processing decaying catalyst The common methods such as bubble, distillation.The volume ratio of organic solvent and catalyst can be 8:1~1:1.

In the method for the present invention, when infusion process load is containing lanthanum compound and zinc compound, a step infusion process may be used, Step impregnation method, preferably a step infusion process can also be used.When using a step infusion process, the maceration extract used in infusion process is adopted With dissolved with the aqueous solution containing lanthanum compound and zinc compound, wherein, can be lanthanum nitrate, lanthanum acetate, sulphur containing lanthanum compound One or more in the solubility lanthanum salt such as sour lanthanum, the concentration containing lanthanum compound is calculated as 1.0wt% ~ 10wt% with lanthanum element, containing zinc Compound water solution can be one or more in the soluble zinc salts such as zinc nitrate, zinc acetate, zinc chloride, zinc sulfate, containing zinc The concentration of compound is calculated as 10wt% ~ 30wt% with Zn-ef ficiency.

When using step impregnation method, conventional step impregnation method may be used and loaded containing the water-soluble of lanthanum compound Liquid and zinc compound can first load the aqueous solution containing lanthanum compound, can also first load zinc compound.Step impregnation Maceration extract includes two kinds of solution of aqueous solution of aqueous solution and zinc compound containing lanthanum compound, the aqueous solution containing lanthanum compound Concentration 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 Zn-ef ficiency.

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

In the method for the present invention, the roasting condition of the first roasting and the second roasting can be the same or different.Described One roasting condition be：The catalyst is contacted with oxygen-containing gas, 300 DEG C ~ 450 DEG C of temperature, preferably 320 DEG C ~ 420 DEG C, Time of contact is 1.0h ~ 10h, preferably 2.0h ~ 8h.The condition of described second roasting is：By the catalyst with it is oxygenous Body contacts, 300 DEG C ~ 450 DEG C of temperature, preferably 320 DEG C ~ 420 DEG C, and time of contact is 1.0h ~ 10h, preferably 2.0h ~ 8h.Contain Oxygen content can be 0.2v% ~ 25v%, preferably 0.5v% ~ 10v% in carrier of oxygen.

In the method for the present invention, the reduction treatment may be used reducibility gas commonly used in the art and be gone back It is former, it is preferred to use hydrogen is restored, and hydrogen uses the hydrogen feed of 99.9 v % of purity ＞, the operation of the reduction treatment Condition is：The catalyst is contacted with hydrogen, temperature be 100 DEG C ~ 500 DEG C, preferably 200 DEG C ~ 450 DEG C, the time for 1.0h ~ 15.0h, preferably 5.0h ~ 10.0h, Hydrogen Vapor Pressure are 0.5 MPa ~ 6.0MPa, preferably 1.0 MPa ~ 4.0MPa.

In the method for the present invention, the aqueous slkali may be used aqueous slkali commonly used in the art, preferably NaOH solution or KOH solution.A concentration of 0.1wt% ~ 20wt% of the aqueous slkali, preferably 1.0wt% ~ 10wt%, soaking time can be 0.5h ~ 20.0h, preferably 1.0h ~ 15.0h, more preferably 5.0h ~ 10.0h, impregnate and wash temperature is room temperature.After washing Catalyst again through be dried, drying temperature can be 60 DEG C ~ 200 DEG C, preferably 70 DEG C ~ 160 DEG C, more preferably 80 DEG C ~ 120 DEG C, drying time can be 1 .0h ~ 20h, preferably 3.0h ~ 15h, more preferably 5 .0h ~ 10h.

The method of the present invention has the following advantages that：

（1）First decaying catalyst is handled with organic solvent, the carbon deposit content on decaying catalyst can be reduced, favorably Temperature when its regeneration is controlled, heat release is excessive when preventing from regenerating or excessively concentrates, and avoids the mistake thermal response of catalyst, causes to urge Agent property changes, as the structure of molecular sieve is destroyed or the enrichment of carried metal causes to bear to the property of catalyst Face is rung.

（2）Regeneration temperature and oxygen content are strictly controlled in the coke combustion of the first roasting, this is because containing in catalyst There are the TON type molecular sieves of higher proportion, due to the particularity of its molecular sieve（It is easily converted to the more stable ZSM-5 molecules of structure Sieve structure）, charcoal temperature is excessively high, seriously affects the crystallinity of molecular sieve, and researches show that charcoal temperatures in 420 DEG C of procatalyst Structure there is no a significant change, but when 450 DEG C of charcoal temperature, apparent variation has occurred in the structure of catalyst, is urged with fresh Agent is compared, and relative crystallinity drops to 97%（Fig. 1 is fresh dose of XRD diagram）, so in burning process is aoxidized, temperature of making charcoal Degree is a key factor.When charcoal temperature is relatively low, carbon deposit elimination factor is relatively low, but with the raising of charcoal temperature, can cause The aggregation of active metal and the structure for destroying molecular sieve, make the performance of catalyst be a greater impact.In entire regenerative process, The temperature that must be strictly controlled catalyst particle surface is excessively high, and ensures that oxidation is thorough, but due to during making charcoal, urging Carbon in agent also releases heat during burning, exists so considering to ensure that catalyst is not burned control temperature Not higher than 450 DEG C.

（3）Loaded on the catalyst after being handled through organic solvent it is a certain amount of containing lanthanum compound and zinc compound, And the first roasting is carried out at a lower temperature.Due to easily being restored at high temperature containing lanthanum compound and zinc compound by carbon, And lanthanum/zinc is met oxygen and is easily oxidized, and active oxygen can be generated in oxidation process, active oxygen being capable of quick oxidation catalyst On carbon distribution generation carbon dioxide, be not only able to remove effectively carbon deposit in this way, and in the first roasting process lanthanum/zinc with losing Platinum on catalyst living, which forms Pt-Zn-La complex chemical compounds, to be disperseed, and roasted using reduction treatment and second, can be more The effective aggregation for avoiding noble metal, improves the dispersion of noble metal platinum, while avoids the destruction of TON type molecular sieve structures, burns For catalyst after charcoal regeneration except dezincify by the way of alkali cleaning, the catalyst after the regeneration obtained in this way not only can guarantee catalyst Pore structure is not destroyed, and Pt metal has preferably dispersion, and can be also prevented from metal La and Pt in the process and be lost in, Due to the synergistic effect of La-Pt, the hydrogenation/dehydrogenation reactivity of catalyst can be improved, makes the performance recovery of catalyst to fresh Levels of catalysts.

Description of the drawings

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

Fig. 2 is the XRD spectra of deactivator FD-1（Crystallinity ~ 99%）；

Fig. 3 is the XRD spectra of R-420（Crystallinity ~ 99%）；

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

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

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

Specific embodiment

The preparation process of catalyst, but it is not considered that the present invention only office are further illustrated the present invention below by embodiment It is limited in following embodiment.In the present invention, wt% is mass fraction, and v% is volume fraction.

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

1 feedstock oil main character of table

Density（20℃）, kg/m³	861.1
		Sulphur, μ g/g	4.0
Nitrogen, μ g/g	1.2
		Viscosity（40℃）, 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 present invention relates to FD-1 decaying catalysts hydrogen is added to split in Sinopec Qilu Petrochemical for FD-1 fresh catalysts Change the deactivator after tail oil isomerization dewaxing device industrial operation.The physico-chemical property of FD-1 decaying catalysts is as follows：Specific surface area is 103m²/ g, Kong Rongwei 0.28mL/g, Pt content 0.45wt%, C content are 7.24 wt %.The composition and property that fresh dose of FD-1 It is as follows：Specific surface area is 235m²The content of/g, Kong Rongwei 0.35mL/g, Pt content 0.50wt%, ZSM-22 molecular sieve is 70wt%。

The physico-chemical property of FD-2 decaying catalysts of the present invention is as follows：Specific surface area is 110m²/ g, Kong Rongwei 0.26 ML/g, Pt content 0.45wt%, C content are 8.12wt %.The composition and property that fresh dose of FD-2 are as follows：Specific surface area is 245m²The content of/g, Kong Rongwei 0.36mL/g, Pt content 0.50wt%, NU-10 molecular sieve is 50wt%.

The physico-chemical property of FD-3 decaying catalysts of the present invention is as follows：Specific surface area is 120m²/ g, Kong Rongwei 0.27mL/g, Pt content 0.44wt%, C content are 10.02wt %.The composition and property that fresh dose of FD-3 are as follows：Specific surface area is 270m²The content of/g, Kong Rongwei 0.37mL/g, Pt content 0.50wt%, 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 solutions are added in the flask of 2000mL（Wherein ethyl alcohol and benzene volume ratio are 2:1）, industry is transported 200mL decaying catalyst FD-1 processing after turning, it is Ca-1 to distill the catalyst number after 2.0h.

Take 27.8g lanthanum nitrates（Lanthanum content 3.0wt%）, 5.2g zinc nitrates（Zn contents 10.0wt%）Prepare the leaching containing lanthanum/zinc Stain liquid takes Ca-1 catalyst 100g to carry out saturation dipping, and the atomic ratio that La and Pt, Zn and Pt is made is respectively 3:1 and 4:1 contains The catalyst sample of lanthanum/zinc, then the heating rate with 3 DEG C/min are warming up to 350 DEG C of constant temperature 5h.Gained catalyst number is Ea- 1。

Above-mentioned catalyst Ea-1 carries out the first calcination process under air atmosphere, and actual conditions are：With the heating of 3 DEG C/min Speed is warming up to 350 DEG C of constant temperature 5h.First calcined catalyst is being subjected to reduction treatment, actual conditions under an atmosphere of hydrogen It is：Hydrogen Vapor Pressure is 3.5Mpa, and reduction temperature is 430 DEG C, recovery time 6.0h.By the catalyst after reduction treatment in air Second calcination process under atmosphere, actual conditions are：With the heating rate of 3 DEG C/min, it is warming up to 410 DEG C of constant temperature 3h, gained catalysis Agent number is Ea-2.

Take 8.5wt%（In terms of NaOH）Sodium hydrate aqueous solution 300g adds in the above-mentioned catalyst Ea-2 of 100g, soaks at room temperature 10.0h is steeped, then through 120 DEG C of dry 10h, obtains catalyst E-1 of the present invention, specific 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 acetates（Lanthanum content 8.0wt%）Maceration extract is configured to, Ca-1 catalyst is prepared according to 1 method of embodiment 100g carries out saturation dipping, and the atomic ratio that La and Pt is made is 5:1 sample containing lanthanum catalyst after drying and roasting, takes 3.9g zinc acetate（Zn contents 10.0wt%）Be configured to maceration extract, take it is above-mentioned carry out supersaturated dipping containing lanthanum catalyst, be made Zn with The atomic ratio of Pt is 3:1 catalyst sample containing lanthanum/zinc, then the heating rate with 3 DEG C/min are warming up to 420 DEG C of constant temperature 4h. Gained catalyst number is Eb-1.

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

Take 7.5wt%（In terms of NaOH）Sodium hydrate aqueous solution 300g adds in the above-mentioned catalyst Eb-2 of 100g, soaks at room temperature 10h is steeped, then through 120 DEG C of dry 10h, obtains catalyst E-2 of the present invention, specific 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 solvents are added in the flask of 2000mL（Wherein gasoline and kerosene volume ratio are 1:1）, it is right Decaying catalyst FD-1 processing after 200mL industrial operations, it is Cb-1 to distill the catalyst number after 2.0h.

Take 83.4g lanthanum sulfates（Lanthanum content 2.0wt%）, 7.8g zinc nitrates（Zn contents 20.0wt%）Prepare the leaching containing lanthanum/zinc Stain liquid takes Cb-1 catalyst 100g to carry out saturation dipping, and the atomic ratio that La and Pt, Zn and Pt is made is respectively 6:1 and 8:1 contains The catalyst sample of lanthanum/zinc, then the heating rate with 3 DEG C/min are warming up to 350 DEG C of constant temperature 5h.Gained catalyst number is Ec- 1。

Above-mentioned catalyst Ec-1 carries out the first calcination process under air atmosphere, and actual conditions are：With the heating of 3 DEG C/min Speed is warming up to 350 DEG C of constant temperature 5h.First calcined catalyst is subjected to reduction treatment under an atmosphere of hydrogen, actual conditions are： Hydrogen Vapor Pressure is 2.5MPa, and reduction temperature is 450 DEG C, recovery time 7.0h；By the catalyst after reduction treatment in air atmosphere The second calcination process of lower progress is enclosed, actual conditions are：With the heating rate of 3 DEG C/min, it is warming up to 350 DEG C of constant temperature 3.0h.Gained Catalyst number is Ec-2.

Take 15wt%（In terms of NaOH）Sodium hydrate aqueous solution 300g adds in the above-mentioned catalyst Ec-2 of 100g, impregnates at room temperature 10h, then through 120 DEG C of dry 10.0h, catalyst E-3 of the present invention is obtained, specific 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.

For the preparation process of catalyst E-4 ~ E-6 of the present invention with embodiment 1, the difference lies in be catalyzed with inactivation used Agent, lanthanum and zinc solution and roasting are different with the temperature of reduction, and the catalyst E-4 ~ E-6 of the present invention prepared is specific to handle Condition is shown in Table 2, and reaction result is shown in Table 3.

Comparative example 1

It is prepared by comparative catalyst C-1 of the present invention.

The preparation method is the same as that of Example 1 for catalyst, and the difference lies in catalyst not to use containing lanthanum compound, number C- 1, physico-chemical property is shown in Table 2, and reaction result is shown in Table 3.

Comparative example 2

It is prepared by comparative catalyst C-2 of the present invention.

The preparation method is the same as that of Example 1 for catalyst, the difference lies in catalyst without using zinc compound, number C- 2, specific treatment conditions are shown in Table 2, and reaction result is shown in Table 3.

Comparative example 3

It is prepared by comparative catalyst C-3 of the present invention.

The preparation method is the same as that of Example 1 for catalyst, although the difference lies in catalyst by being handled containing lanthanum/zinc solution, But only roasted by a calcination process without reduction treatment and second, number C-3, specific treatment conditions are shown in Table 2, reaction result is shown in Table 3.

Comparative example 4

It is prepared by comparative catalyst C-4 of the present invention.

The preparation method is the same as that of Example 1 for catalyst, although being handled the difference lies in catalyst by lanthanum/zinc solution, again By the first roasting, reduction treatment and the second roasting, but without alkaline solution treatment, number C-4, specific treatment conditions 2 are shown in Table, reaction result is shown in Table 3.

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

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

Number	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-4^③	3.2	400℃×5h	410℃×4h	2.5
					E-5	3.8	410℃×5h	370℃×2h	5.0
E-6^④	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：Ethyl alcohol/benzene, 2. gasoline/kerosene, 3. FD-2 decaying catalysts, 4. FD-3 decaying catalysts

3 evaluating catalyst condition of table and result

Table 3 continues evaluating catalyst condition and result

The evaluation result of table 3 is shown, compared with comparative catalyst, using the regenerated catalyst of the method for the present invention, for moistening In the hydroprocessing processes of lubricant oil fraction, when lube base oil pour point is close, C₅ ⁺Liquid, which is received, improves more than 10wt%, lubricating oil Base oil yield improves 15wt% or so, and the viscosity index (VI) of product improves nearly 12 units, illustrates urging after the method for the present invention regeneration During crude lube stock is handled, effect has to be significantly improved agent.

By Fig. 1 to Fig. 5 as it can be seen that the crystallinity of fresh dose of FD-1, which is set to 100%, XDR structures, sees Fig. 1, the structure of deactivator See Fig. 2, different charcoal temperatures（420 DEG C, 450 DEG C and 500 DEG C）The XRD characterization result of obtained sample is shown in Fig. 3 ~ Fig. 5, from Fig. 3 Result can be seen that：There is no significant change in the structure of 420 DEG C of procatalyst, but when charcoal temperature 450 in charcoal temperature DEG C when, some changes have occurred in the structure of catalyst, and when charcoal temperature reaches 500 DEG C, the structure of catalyst has occurred significantly Variation.Therefore, the present invention claims the charcoal temperature control of the first roasting not higher than 450 DEG C, preferably not higher than 420 DEG C.

Claims

1. a kind of regeneration method containing noble metal and TON type molecular sieve catalysts, which includes TON types molecular sieve and the VIIIth Race's noble metal component, which is characterized in that regenerative process includes：Deactivation catalyst of carbon deposit first is handled with organic solvent, then using leaching The load of stain method impregnates the atomic ratio of metal platinum in the lanthanum and catalyst loaded on rear catalyst containing lanthanum compound and zinc compound It is 6:1~1:1, the atomic ratio of metal platinum is 10 in the zinc and catalyst that load on catalyst:1~1:1, then in oxygen-containing gas Effect is lower to carry out the first roasting, reduction treatment is carried out after the completion of the first roasting, then the second roasting is carried out under oxygen-containing gas effect, The maximum temperature of first roasting process is not higher than 450 DEG C, through aqueous slkali soaking, washing after the completion of the second calcination process, most passes through afterwards It is dried to obtain regenerated catalyst.

2. according to the method for claim 1, it is characterised in that：In the catalyst, noble metal component is platinum, TON types Molecular sieve is one or more of ZSM-22, Nu-10, KZ-2 and ISI-1.

3. according to the method for claim 1, it is characterised in that：In the catalyst, TON types molecular sieve, your gold contained Belong to platinum and refractory porous inorganic oxide, on the basis of the weight of catalyst, the content of molecular sieve is 10wt%~90wt%, your gold The content of category is the wt% of 0.05wt%~5.0, and surplus is refractory porous inorganic oxide.

4. according to the method for claim 3, it is characterised in that：On the basis of the weight of catalyst, the content of molecular sieve is 30wt%~80wt%.

5. according to the method for claim 1, it is characterised in that：The catalyst is hydroisomerization dewaxing catalyst.

6. according to the method for claim 1, it is characterised in that：After infusion process load is containing lanthanum compound and zinc compound, The atomic ratio of platinum is 4 in the lanthanum and decaying catalyst that are loaded on catalyst:1~2:1, the zinc loaded on catalyst is catalyzed with inactivation The atomic ratio of platinum is 8 in agent:1~3:1.

7. according to the method for claim 1, it is characterised in that：Decaying catalyst is first handled with organic solvent, wherein Organic solvent used is one or more in ethyl alcohol, benzene, gasoline and kerosene.

8. according to the method for claim 1, it is characterised in that：Decaying catalyst is first handled with organic solvent, wherein The method of organic solvent processing decaying catalyst is using the method impregnated or distilled.

9. according to the method for claim 1, it is characterised in that：The volume ratio of organic solvent and decaying catalyst is 8:1~ 1:1。

10. according to the method for claim 1, it is characterised in that：Infusion process load is containing lanthanum compound and zinc compound Method is a step infusion process, and maceration extract is used dissolved with the aqueous solution containing lanthanum compound and zinc compound, wherein, chemical combination containing lanthanum The concentration of object is calculated as 1.0wt%~10wt% with lanthanum element, and the concentration of zinc compound is calculated as 10wt%~30wt% with Zn-ef ficiency.

11. according to the method for claim 1, it is characterised in that：Infusion process load is containing lanthanum compound and zinc compound Method is step impregnation method, and maceration extract includes the aqueous solution of aqueous solution and zinc compound containing lanthanum compound, containing lanthanum compound The concentration of aqueous solution 1.0wt%~10wt% is calculated as with lanthanum element, the concentration of the aqueous solution of zinc compound is calculated as with Zn-ef ficiency 10wt%~30wt%.

12. according to the method described in claim 10 or 11, it is characterised in that：It is lanthanum nitrate containing lanthanum compound, lanthanum acetate, sulfuric acid One or more in lanthanum, zinc compound is zinc nitrate, one or more in zinc acetate, zinc chloride, zinc sulfate.

13. according to the method for claim 1, it is characterised in that：The condition of described first roasting is：By the catalyst It is contacted with oxygen-containing gas, temperature is 300 DEG C~450 DEG C, and the time is 1.0h~10h.

14. according to the method for claim 13, it is characterised in that：The condition of described first roasting is：By the catalysis Agent is contacted with oxygen-containing gas, and temperature is 320 DEG C~420 DEG C, and the time is 2.0h~8.0h.

15. according to the method for claim 1, it is characterised in that：The condition of described second roasting is：By the catalyst It is contacted with oxygen-containing gas, temperature is 300 DEG C~450 DEG C, and the time is 1.0h~10h.

16. according to the method for claim 15, it is characterised in that：The condition of described second roasting is：By the catalysis Agent is contacted with oxygen-containing gas, and temperature is 320 DEG C~420 DEG C, and the time is 2.0h~8.0h.

17. according to the method described in any one in claim 1,13-16, it is characterised in that：Oxygen in the oxygen-containing gas Content is 0.2v%~25v%.

18. according to the method for claim 17, it is characterised in that：In the oxygen-containing gas oxygen content for 0.5v%~ 10v%。

19. according to the method for claim 1, it is characterised in that：The operating condition of the reduction treatment is：It is urged described Agent is contacted with hydrogen, and temperature is 100 DEG C~500 DEG C, and the time is 1h~15h, and Hydrogen Vapor Pressure is 0.5MPa~6.0MPa.

20. according to the method for claim 19, it is characterised in that：The operating condition of the reduction treatment is：By described in Catalyst is contacted with hydrogen, and temperature is 200 DEG C~450 DEG C, and the time is 5h~10h, and Hydrogen Vapor Pressure is 1.0MPa~4.0MPa.

21. according to the method for claim 1, it is characterised in that：The aqueous slkali is NaOH solution or KOH solution.

22. according to the method described in claims 1 or 21, it is characterised in that：A concentration of 0.1 wt % of the aqueous slkali~ 20 wt %。

23. according to the method for claim 22, it is characterised in that：A concentration of 1 .0wt %~10 of the aqueous slkali wt %。

24. according to the method for claim 1, it is characterised in that：The condition of the drying is as follows：Temperature is 60~200 DEG C, the time is 1~20h.

25. according to the method for claim 24, it is characterised in that：The condition of the drying is as follows：Temperature is 70~160 DEG C, the time is 3~15h.

26. according to the method for claim 25, it is characterised in that：The condition of the drying is as follows：Temperature is 80~120 DEG C, the time is 5~10h.