CN109174207B - A kind of activity of hydrocatalyst restores and vulcanization process - Google Patents

Abstract

The present invention provides a kind of recovery of activity of hydrocatalyst and vulcanization process, are pre-processed with acid organic reagent and hydrogenation catalyst of the carboxylate mixed liquor to inactivation, then carry out destructive distillation to hydrogenation catalyst, carry out coke-burning regeneration to the hydrogenation catalyst after destructive distillation；With the mixed liquor of organic complexing agent and unsaturated organic solvent, the hydrogenation catalyst after coke-burning regeneration is impregnated；Then vulcanizing treatment is carried out to the hydrogenation catalyst after dipping, then processing is passivated to the hydrogenation catalyst after vulcanizing treatment；A kind of activity of hydrocatalyst of the present invention restores and vulcanization process, not only effectively improves the activity of regenerated catalyst, but also shorten the production cycle of catalyst regeneration in the prior art and vulcanization, reduces energy consumption, advantageously reduce production cost.

Description

A kind of activity of hydrocatalyst restores and vulcanization process

Technical field

The present invention relates to a kind of recovery of activity of hydrocatalyst and vulcanization process, especially two class activated centre hydrogenation catalysts Vulcanize outside the activation recovering and device of agent.

Background technique

With the development of economy with the raising of environmental requirement, the fuel emission standard in China will gradually integrate with America and Europe, together When demand also greatly increase.EC regulations provide that European vehicle fuel in 2009 executes European V class standard, limit in oil Sulfur content is in 10g/g or less.State V vehicle fuel quality standard of the China to implement, sulfur content need to be reduced to 10 μ g/g with Under.

Hydrogen addition technology and mating catalyst are the guarantees of V ideal fuels of producing country, and hydrogenation catalyst is the core of hydrogen addition technology Heart technology.The ultra-deep Hydrobon catalyst of recent domestic diesel oil mainly uses organic complex technology to adjust metal and carry Interaction force between body improves active metal in the dispersity of carrier surface, mainly generates II class of high activity after curing Activated centre, to improve the activated centre number and its latent active of active metal sulphided state.

Studies have shown that the feature in the second class activated centre is exactly that interaction between activated centre and carrier matrix is weaker, MoS2 disperses not to be very thin, is often formed by stacking by some biggish chips, vulcanizes relatively sufficiently, with the in conventional carriers A kind of activity is compared, and the activity of the second class activity phase greatly improves.Therefore the second class should be made living as far as possible in Catalyst Design Property centric quantity increases and has good dispersibility, can prepare the catalyst of high activity.STARS technology is exactly at material gain With first catalyst technology of this principle.The technology use from previous different method, both guarantee to have quantity very big and disperse Good activated centre, also ensuring that all activated centres all is two classes, and making units activity center all has very high latent active, The activity of active metal is set to reach maximum value.

Two class activated centre hydrogenation catalyst technologies of preparing are a large amount of open in the conventional method, as US5336654 is disclosed It is a kind of by with the heteropoly acid of the salt of metal and metal come impregnated carrier, the method for preparing hydrotreating catalyst. CN101491766A discloses a kind of preparation method of hydrogenation catalyst, and active component is introduced by two-stage method, the gold first introduced It is stronger by the effect of calcination steps and carrier to belong to component, the active component introduced afterwards, no calcination steps, with carrier function compared with It is weak, in catalyst vulcanization and use process, can inhibit with the stronger active metal component of carrier function and carrier function compared with The migration of weak active metal is assembled, and catalyst is made to keep ideal activity stability.

In addition, hydrogenation catalyst using preceding active metal component be oxidation state, oxidized catalyst before industrial application, Its active metal need to be converted into sulphided state just catalytic activity with higher.With the operating of long-lasting catalytic, hydrogenation catalyst There is deactivation phenomenoms for agent.The deactivation mechanism of hydrogenation catalyst point poisoning, coking and sintering three classes.Coking is in catalyst surface Carbonaceous is formed, is covered on activated centre, a large amount of coking leads to hole plug, prevents in reactant molecule access aperture in activity The heart；Basic nitrogen such as pyridine compounds and their is chemisorbed on acid centre, and catalyst is not only made to lose activity but also plugging hole Mouth and inner duct；Sintering then makes catalyst structure change and loss of activity center, refers to that metal is poly- for hydrogenation catalyst Collection or crystal become larger.Acid-base neutralization caused by coking and impurity chemisorption belongs to temporary poisoning, can pass through air burn And activity recovery, the process are the regeneration of catalyst, regenerated catalyst can continue to use, to improve economic benefit. Therefore, how activation recovering more efficiently to be carried out to two class activated centre hydrogenation catalysts, become in order to which a urgent need solves The problem of.

CN102463153A is related to two class activated centre hydrogenation catalysts, under oxygen-containing gas effect, except de-inactivation is catalyzed The carbon distribution of agent makes the carbon content in catalyst be calculated as 0.5%~2% with mass content；Then with containing alkaline matter solution and The solution of organic additive contacts, the last thermally treated catalyst for obtaining activation recovering.

CN102151588A carries out the outer coke burning regeneration of device of decarburization and/or desulfurization process using regenerated catalyst is treated, right Hydrogenation catalyst to be regenerated carries out limited the step of burning processing；And carry out the technique step of active metal redisperse processing Suddenly.

CN104624248A is related to a kind of heavy oil, the regeneration of catalyst for hydrotreatment of residual oil and activation method, including following Process: (1) de-oiling of inactivation heavy oil hydrogenating treatment catalyst is pre-processed；(2) oxidation burning sulphur is carried out to decaying catalyst to make charcoal Regeneration treatment；(3) regenerated catalyst is contacted into activation with the compound dipping solution of organic compound；(4) it will be catalyzed after activation Agent is dried, and obtains the catalyst of regeneration activating.

In addition, in the prior art, there are also catalyst used in other application field and its regeneration techniques, such as apply Number the inactivation load type palladium that dimethylnaphthalene is dehydrogenated to for dimethyl hydrogenated naphthalene is disclosed for the patent document of US19900539619 The process for reactivation of catalyst, by lower than 200 DEG C at a temperature of, contacted with polar organic solvent with catalyst, with Improve the activity of palladium catalyst；But it is relatively simple to the treatment process of catalyst in this method, it is active to regenerated catalyst to mention High level is limited；In addition, palladium catalyst handled in this application is dehydrogenation, active constituent, application field situation, Catalytic process, reactivation processing method, are all different with two class activated centre hydrogenation catalysts.

Above-mentioned patent carries out activation recovering for two class site catalysts, but corresponding treatment process is relatively simple, To the active raising limitation of regenerated catalyst；And no matter in carrying out pretreatment or dipping process to decaying catalyst, It not can relate to the diffusion problem of pretreating agent or maceration extract in catalyst microchannel, be unfavorable for further increasing on catalyst The distribution of active metal, so that the active raising degree of regenerated catalyst is lower.

Further, since the catalyst after regeneration also needs individually to be vulcanized before being put into use, for the second class activity For the industrial application of center catalyst, so that the whole production cycle is longer, and energy consumption is higher；Therefore, it improving, restoring catalysis While agent activity, how be also faced with will vulcanize the problem of being organically combined outside the regeneration of hydrogenation catalyst and device, constitute one A complete activity of hydrocatalyst restores and the technical process of vulcanization, to shorten the whole production cycle, reduces production energy consumption.

Summary of the invention

In view of this, the present invention is directed to propose a kind of activity of hydrocatalyst restores and vulcanization process, especially for two Class activated centre hydrogenation catalyst, to solve the problems, such as that it is lower to improve degree for regenerated catalyst activity in the prior art.

In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:

A kind of activity of hydrocatalyst restores and vulcanization process, with acid organic reagent and carboxylate mixed liquor to inactivation Hydrogenation catalyst is pre-processed, then carries out destructive distillation to hydrogenation catalyst, carries out coke-burning regeneration to the hydrogenation catalyst after destructive distillation； With the mixed liquor of organic complexing agent and unsaturated organic solvent, the hydrogenation catalyst after coke-burning regeneration is impregnated；Then right Hydrogenation catalyst after dipping carries out vulcanizing treatment, then is passivated processing to the hydrogenation catalyst after vulcanizing treatment.

Further, the pretreated process carries out in the reaction kettle for being provided with microwave generating apparatus, microwave power It is 0.1-2.0W/g with hydrogenation catalyst mass ratio, after microwave generating apparatus every unlatching 0.5-2 minutes, closes 0.5-2 minutes, Continue -2 hours 30 minutes.

Further, the carboxylate is aliphatic carboxylic acid esters, including n-butyl acetate, ethyl acetate, 1,4-butanediol At least one of diacrylate, M Cr；

The acidity organic reagent is the acidic organic compound containing at least one of element sulphur, oxygen element element, institute State acid organic reagent include thioacetic acid, mercaptopropionic acid, oxalic acid, malonic acid, tartaric acid, citric acid, ethylene glycol, glycerine, At least one of tetraethylene glycol.

Further, the unsaturated organic solvent include conjugated diene, in unsaturated aliphatic carboxylate at least It is a kind of.

Further, the conjugated diene include pentadiene, cyclopentadiene, 1,3- cyclohexadiene, 1,3- hexadiene, At least one of 2,5- dimethyl -2,4- hexadiene；

The unsaturated aliphatic carboxylate is vegetable fat, including sesame oil, safflower seed oil, palm oil, corn oil, cotton At least one of seed oil, peanut oil, rapeseed oil, soya-bean oil, walnut oil, coconut oil, olive oil, sunflower oil.

Further, a kind of activity of hydrocatalyst recovery and vulcanization process, comprising the following steps:

S1, the mixed liquor for preparing acid organic reagent and carboxylate, oxytropism organic reagent add with carboxylate mixed liquor Enter and inactivate hydrogenation catalyst, carries out microwave treatment, then destructive distillation is carried out to hydrogenation catalyst；

S2, to the hydrogenation catalyst after destructive distillation, regenerated using the method for making charcoal；

S3, organic complexing agent and unsaturated organic solvent are mixed, to organic complexing agent and unsaturated organic solvent mixing In liquid, it is added by step S2 treated hydrogenation catalyst, is impregnated；

S4, vulcanizing agent is heated, when vulcanizing agent is heated to 125 DEG C~150 DEG C, is added into vulcanizing agent by step Hydrogenation catalyst after rapid S3 dipping, and 1h~15h is handled at 130 DEG C~180 DEG C；

S5, it organic compound is added in by step S4 treated hydrogenation catalyst is passivated, and 120 will be risen to DEG C~250 DEG C, constant temperature handles 1h~8h.

Further, the hydrogenation catalyst includes carrier component, hydrogenation active component and organic additive, the vehicle group It is divided at least one of refractory porous oxide, including aluminium oxide, silica, amorphous silica-alumina, titanium oxide, molecular sieve；Institute Stating hydrogenation active component includes at least one of W, Mo, Ni and Co, and hydrogenation active component exists with metal salts, with oxidation Object meter, hydrogenation active component content are 3wt%~50wt%；The organic additive includes oxygen-containing organic compound, nitrogenous organic At least one of compound, organic compounds containing sulfur, content of the organic additive in hydrogenation catalyst are 0.01%~5%.

Further, the destructive distillation in step S1 be heat treatment process, heat treatment condition be oxygen-free environment, 120 DEG C~ It is handled 1~15 hour at a temperature of 200 DEG C.

Further, in step S2, the method for making charcoal carries out coke-burning regeneration using control charcoal temperature and oxygen content；

It is described make charcoal method include make charcoal stage A, the stage B that makes charcoal, make charcoal at least one of stage C.

Further, the stage A that makes charcoal are as follows: 200 DEG C~300 DEG C of charcoal temperature, constant temperature 2h~8h, oxygen content control In volume fraction less than 15%；

The stage B that makes charcoal are as follows: 300~400 DEG C of charcoal temperature, constant temperature 1h~8h, oxygen content is controlled in volume fraction Less than 21%；

The stage C that makes charcoal are as follows: 400 DEG C~600 DEG C of charcoal temperature, constant temperature 2h~10h, Control for Oxygen Content is in volume fraction Less than 35%.

Compared with the existing technology, a kind of activity of hydrocatalyst of the present invention restores and vulcanization process is with following excellent Gesture:

The present invention provides the treatment process of complete set for decaying catalyst, and entire technique constitutes complete and continuous mistake The treatment process of catalyst living, makes decaying catalyst that can direct plunge into production and application after treatment, no longer needs to carry out other Treatment process not only contributes to improve catalyst activity recovery extent, it is ensured that the continuity of decaying catalyst processing section, and And avoid and carry out relatively complicated step-by-step processing in prior art to catalyst, be conducive to shorten the whole production cycle, reduce Production cost reduces production energy consumption.

In addition, the present invention to decaying catalyst into preprocessing process, by using acid organic reagent and carboxylate Mixed liquor impregnates decaying catalyst, microwave treatment is carried out while dipping, so that can be right before coke-burning regeneration Catalyst microchannel is preferably pre-processed, and is conducive to the hole appearance for improving regenerated catalyst and its activity, is made charcoal convenient for subsequent The progress of regeneration and vulcanization.

The present invention is organically contacted coke-burning regeneration, sulfidation processes together by complexing treatment process simultaneously, It is compounded by the way that organic complexing agent is carried out mixing with unsaturated organic solvent, catalyst is impregnated, organic network is not only made Mixture is fully dispersed in catalyst microchannel, comes into full contact with the activated centre of catalyst, improves catalyst activity, and The specific gravity in the activated centre in catalyst containing lone pair electrons is improved, so that the activated centre of catalyst is more likely formed covalent shape State can advantageously promote the activation recovering of catalyst, be conducive to the progress of subsequent sulfuration process, the catalyst after improving vulcanization Activity.

Detailed description of the invention

The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:

Fig. 1 is returning during coke-burning regeneration in a kind of activity of hydrocatalyst recovery of the present invention and vulcanization process Rotary kiln structural schematic diagram；

Fig. 2 is A-A of the present invention in Fig. 1 to schematic cross-section；

Fig. 3 is B-B direction schematic cross-section of the present invention in Fig. 1；

Fig. 4 is C-C of the present invention in Fig. 1 to schematic cross-section；

Fig. 5 is that the weir plate structure of rotary kiln in a kind of activity of hydrocatalyst recovery of the present invention and vulcanization process is shown It is intended to；

Fig. 6 is that the column structure of rotary kiln in a kind of activity of hydrocatalyst recovery of the present invention and vulcanization process shows It is intended to；

Fig. 7 is the bulk cargo pawl structure of rotary kiln in a kind of activity of hydrocatalyst recovery of the present invention and vulcanization process Schematic diagram.

Description of symbols:

First furnace body 1, weir plate 11, the first connecting pin 111, cylinder 12, second connection end 121 meet material end 122, back material end 123, the second furnace body 2, bulk cargo pawl 21；Third connecting pin 211, plate body 212, pawl structure 213, third furnace body 3, transition part 4.

Specific embodiment

With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention is further described, Obviously, described embodiment is only a part of the embodiments of the present invention, rather than whole embodiments.Based in the present invention Embodiment, those of ordinary skill in the art's every other embodiment obtained under the premise of not making the creative labor, It shall fall within the protection scope of the present invention.

It should be noted that the understanding for the ease of those skilled in the art to the content of present invention, in the present invention, not In the case where being individually explained, it is related to the percentage of substance dosage or the percentage of constituent content, is quality percentage Number, and " catalyst " refers both to " hydrogenation catalyst ".

The present invention proposes that a kind of activity of hydrocatalyst restores and vulcanizes for two class site catalysts after inactivation Method is pre-processed with acid organic reagent and hydrogenation catalyst of the carboxylate mixed liquor to inactivation, then to hydrogenation catalyst Destructive distillation is carried out, coke-burning regeneration is carried out to the hydrogenation catalyst after destructive distillation；With the mixing of organic complexing agent and unsaturated organic solvent Liquid impregnates the hydrogenation catalyst after coke-burning regeneration；Then vulcanizing treatment is carried out to the hydrogenation catalyst after dipping, then right Hydrogenation catalyst after vulcanizing treatment is passivated processing.

A kind of activity of hydrocatalyst restores and vulcanization process, specifically includes the following steps:

S1, the mixed liquor for preparing acid organic reagent and carboxylate, oxytropism organic reagent add with carboxylate mixed liquor Enter and inactivate hydrogenation catalyst, carries out microwave treatment, then destructive distillation is carried out to hydrogenation catalyst；

S2, to the hydrogenation catalyst after destructive distillation, regenerated using the method for making charcoal；

S3, organic complexing agent and unsaturated organic solvent are mixed, to organic complexing agent and unsaturated organic solvent mixing In liquid, it is added by step S2 treated hydrogenation catalyst, is impregnated；

S4, vulcanizing agent is heated, when vulcanizing agent is heated to 125 DEG C~150 DEG C, is added into vulcanizing agent by step Hydrogenation catalyst after rapid S3 dipping, and 1h~15h is handled at 130 DEG C~180 DEG C；

S5, it organic compound is added in by step S4 treated hydrogenation catalyst is passivated, and 120 will be risen to DEG C~250 DEG C, constant temperature handles 1h~8h.

The present invention provides the treatment process of complete set, i.e. catalyst pretreatment-coke-burning regeneration-for the catalyst of inactivation Complexing processing-vulcanizing treatment-passivation protection, entire technique constitute the treatment process of complete and continuous decaying catalyst, make to lose Catalyst living can direct plunge into production and application after treatment, no longer need to carry out other treatment processes, not only contribute to improve Catalyst activity recovery extent, it is ensured that the continuity of decaying catalyst processing section, and avoid in prior art to urging Agent carries out relatively complicated step-by-step processing, is conducive to shorten the whole production cycle, reduces production cost, reduces production energy consumption.

Wherein, the hydrogenation catalyst is two class site catalysts, including carrier component, hydrogenation active component and is had Machine aided agent, the carrier component are refractory porous oxide, including aluminium oxide, silica, amorphous silica-alumina, titanium oxide, molecule At least one of sieve；The hydrogenation active component includes at least one of W, Mo, Ni and Co, and hydrogenation active component is with metal Salt form exists, and in terms of oxide, hydrogenation active component content is 3wt%~50wt%；The organic additive includes oxygen-containing having At least one of machine compound, organic compounds containing nitrogen, organic compounds containing sulfur, organic additive containing in hydrogenation catalyst Amount is 0.01%~5%.It is and existing in view of the specific preparation method and concrete composition substance of the hydrogenation catalyst in the present invention Two class site catalysts in technology are identical, no longer repeated in the present invention.

Scientific research personnel of the invention emphatically studies decaying catalyst regeneration and vulcanizing treatment, wherein is locating in advance During reason, i.e., to catalyst except alkali removes the process of carbon, by using acid organic reagent, not only to remaining in catalyst micropore Alkaline macromolecular mass in road is removed, and eliminates the suction-operated of alkaline macromolecular mass and metal active centres, and Preferable protection is formed to the active metal in two class activated centres；It, can be to remaining in catalyst simultaneously by using carboxylate Hydrocarbons in microchannel are dissolved, and are conducive to improve dispersibility of the acid organic reagent in catalyst microchannel Can, enhance the removing to alkaline macromolecular mass and acts on.

Wherein, the acid organic reagent is the acid organic compound containing at least one of element sulphur, oxygen element element Object, the acidity organic reagent includes thioacetic acid, mercaptopropionic acid, oxalic acid, malonic acid, tartaric acid, citric acid, ethylene glycol, third At least one of triol, tetraethylene glycol, acid organic reagent dosage are inactivate hydrogenation catalyst weight 1%~5%；The carboxylic Acid esters is in aliphatic carboxylic acid esters, including n-butyl acetate, ethyl acetate, 1,4-butanediol diacrylate, M Cr At least one, organic dispersing agent dosage be inactivate hydrogenation catalyst weight 5%~50%, preferably 5%~20%.

As a preferred solution of the present invention, the carboxylate is unsaturated aliphatic carboxylate, including 1,4-butanediol two At least one of acrylate, M Cr.

The pretreated process carries out in the reaction kettle for being provided with microwave generating apparatus, microwave power and hydrogenation catalyst Agent mass ratio is 0.1-2.0W/g, after microwave generating apparatus every unlatching 0.5-2 minutes, closes 0.5-2 minutes, continues 30 points Clock -2 hours.

Before coke-burning regeneration, the destructive distillation of progress is heat treatment process, heat treatment condition be oxygen-free environment, 120 DEG C~ It handles 1~15 hour at a temperature of 200 DEG C, is handled 3~6 hours preferably at 150~200 DEG C.By being carried out before coke-burning regeneration Destructive distillation processing, so as to preferably be detached from away volatile substances remaining in catalyst, avoids in coke-burning regeneration mistake The sharply exothermic phenomenon being likely to occur in journey.

Wherein, the coke combustion carries out in rotary kiln, in order to ensure catalyst can equably carry out coke combustion, Raising is made charcoal efficiency.As shown in attached drawing 1-7, the present invention is also correspondingly improved rotary kiln, and particular content is as follows:

The rotary kiln can carry out temperature programmed control, and rotary kiln is evenly arranged with more with cavity, and in the cavity on wall A temperature control point is monitored the make charcoal temperature in stages of difference, steady to temperature value and its temperature to meet difference stage of making charcoal The requirement for condition of pledging love.Thermocouple temperature measuring point is provided at the center of rotary kiln, for detecting rotary kiln inside cavity gas phase temperature；Institute It states and is additionally provided with gas vent on rotary kiln, and gas outlet is provided with Analysis of Carbon Dioxide Concentration instrument；The rotary kiln On be additionally provided with feeder, provide and make charcoal with gas into rotary kiln cavity in coke combustion, described make charcoal includes oxygen with gas bag Gas and nitrogen, and control and adjust by gas flowmeter the ratio of oxygen and nitrogen contain oxygen with meeting difference stage of making charcoal The requirement of amount；

In rotary kiln during feeding, making charcoal, discharge, it is contemplated that the reunion situation of catalyst, is urged at heat dispersion Agent and oxygen contact situation etc., the rotary kiln includes the first furnace body 1, the second furnace body 2, third furnace body 3, the second furnace body 2 It is connect respectively with the first furnace body 1, third furnace body 3；First furnace body 1, the second furnace body 2, third furnace body 3 all have cavity structure, and The cavity structure of each furnace body is connected to, and collectively forms the cavity of rotary kiln；Feed inlet, third are provided on first furnace body 1 Discharge port is provided on furnace body 3；

At least two weir plates 11 are provided on the inner wall of first furnace body 1, the weir plate 11 passes through the first connecting pin 111 It is connect with the inner wall of the first furnace body 1, in the side far from the first connecting pin 111, is provided with multiple blades (not on the weir plate 11 Diagram), with the rotation of rotary kiln, weir plate and blade are rotated also with rotary kiln, at this time the cut direction and rotary kiln of blade Rotation direction it is identical, for radially being separated to catalyst feed in the first furnace body；On two weirs of arbitrary neighborhood Between plate 11, several cylinders 12 are additionally provided on the inner wall of the first furnace body 1, cylinder 12 passes through second connection end 121 and first The inner wall of furnace body 1 connects, and the cross section of the cylinder 12 can be round, rectangular, trapezoidal or triangle；Preferably, cylinder 12 close to catalyst feed enter direction be provided with meet material end 122, far from catalyst feed enter direction be provided with Back material end 123, the end face for meeting material end 122 are less than the end face at back material end 123, i.e. the cross section of cylinder 12 is preferably trapezoidal or triangle Shape；Further, it also can be set blade on the cylinder 12, the cut end of blade and met material end 122 and cooperate, jointly the Catalyst feed is separated in the axial direction of one furnace body；In practical coke combustion, catalyst feed initially enters the first furnace Body 1, and there are certain agglomerations for catalyst at this time, by the way that weir plate 11, cylinder 12 are arranged on the inner wall of the first furnace body 1, Material is separated on radially, axially respectively, to alleviate the reunion situation of catalyst；

The internal diameter of second furnace body 2 is greater than the internal diameter of the first furnace body 1, and with increasing for catalyst input amount, catalyst is from the One furnace body 1 enters the second furnace body 2, preferably, carrying out round and smooth mistake by transition part 4 between the first furnace body 1 and the second furnace body 2 Cross connection, and be provided with cylinder 12 on the transition part 4 between the first furnace body 1 and the second furnace body 2, and with the column on the first furnace body 1 12 structure of body is consistent, for further separating to the catalyst feed for entering the second furnace body 2；

Multiple bulk cargo pawls 21 are provided on the inner wall of second furnace body 2, the bulk cargo pawl 21 includes plate body 212, and plate body 212 is logical Third connecting pin 211 is crossed to connect with the inner wall of the second furnace body 2；In the side far from third connecting pin 211, it is arranged on plate body 212 There is pawl structure 213；To which with the rotation of rotary kiln, catalyst is spread out by bulk cargo pawl 21, is not only made by the second furnace body 2 Catalyst comes into full contact in coke combustion with oxygen, guarantees that catalyst carries out more sufficient coke combustion, and be conducive to Heat transfer between material can shorten the heating time in coke combustion so that heat is more uniformly spread, more into one Step, also ensures that the heat for generation of making charcoal can be taken away by gas phase in time, avoids the generation of hot spot in catalyst feed, caused The occurrence of catalyst damage；

With the progress made charcoal, need that the regenerated catalyst after making charcoal is discharged from third furnace body 3, in order to ensure catalyst It can be more swimmingly discharged from third furnace body 3, improve discharging speed, pass through transition between third furnace body 3 and the second furnace body 2 Portion 4 carries out rounding off connection, and 3 inner wall of third furnace body is smooth inner wall, the internal diameter of third furnace body 3 greater than, equal to or be less than The internal diameter of second furnace body 2；Preferably, internal diameter of the internal diameter of third furnace body 3 less than the second furnace body 2；Catalysis after coke-burning regeneration Agent material is arranged into third furnace body 3, and from third furnace body 3 by the transition part 4 between third furnace body 3 and the second furnace body 2 Out.

In addition, the present invention in coke combustion, i.e. in the step S2 of the method, is contained using control charcoal temperature and oxygen Amount carries out coke-burning regeneration；Wherein, the method for making charcoal includes make charcoal stage A, the stage B that makes charcoal, at least one in the stage C that makes charcoal It is a；

Specifically, the stage A that makes charcoal are as follows: 200 DEG C~300 DEG C of charcoal temperature, constant temperature 2h~8h, oxygen content is controlled in volume Score is less than 15%；Preferably 250 DEG C~280 DEG C of charcoal temperature, constant temperature 3h~6h, oxygen content control are less than in volume fraction 10%；

Make charcoal stage B are as follows: 300~400 DEG C of charcoal temperature, constant temperature 1h~8h, oxygen content control is less than in volume fraction 21%；Preferably 350 DEG C~380 DEG C of charcoal temperature, constant temperature 2h~4h, oxygen content are controlled in volume fraction 15%~21%；

Make charcoal stage C are as follows: 400 DEG C~600 DEG C of charcoal temperature, constant temperature 2h~10h, Control for Oxygen Content is less than in volume fraction 35%；Preferably 450 DEG C~550 DEG C of charcoal temperature, constant temperature 4h~8h, Control for Oxygen Content is in volume fraction 25%~30%.

It wherein, is that removing is burnt to carbon deposit due to there is most suitable effect in coke combustion, it is contemplated that inactivation is urged Relationship in agent between carbon content and coke combustion, researcher of the invention is according to work throughout the year in the actual production process Skill experience, and examine and prove by subsequent many experiments proposes one kind and makes charcoal technique, specifically with of the present invention one Kind activity of hydrocatalyst restores and vulcanization process combines, and realizes and carries out further technological improvement, i.e. institute to the step S2 Step S2 is stated to specifically include:

S201, carbon content detection is carried out to the hydrogenation catalyst after destructive distillation；

Wherein, the process of carbon content detection, use conventional coke on regenerated catalyst measuring method in the prior art are all Such as volumetric determination coke on regenerated catalyst, high-frequency welded H steel measures coke on regenerated catalyst etc., in view of the measurement of coke on regenerated catalyst Method is the prior art, herein without repeating；

S202, judge coke on regenerated catalyst whether less than 3.5%；It is that then coke combustion only carries out the stage B that makes charcoal, it is no, then Carry out step S203；

Wherein, when coke on regenerated catalyst is less than 3.5%, remaining carbon deposit is less in the catalyst after illustrating destructive distillation；This hair It is bright after destructive distillation, catalyst to carbon content less than 3.5%, only according to making charcoal, stage B carries out coke combustion；On the one hand, in order to Energy consumption in coke combustion is reduced to the full extent, on the other hand energy-saving and emission-reduction avoid the occurrence of the catalysis less to carbon content The case where agent is excessively made charcoal, caused catalyst damage occurs,

S203, judge whether coke on regenerated catalyst is greater than 5.1%；It is that then coke combustion is made charcoal rank according to the stage A- of making charcoal Section C- make charcoal stage B make charcoal method progress；It is no, then coke combustion according to the stage A- of making charcoal make charcoal stage B make charcoal method into Row.

Wherein, when coke on regenerated catalyst is greater than 5.1%, still remain a large amount of product in the catalyst after illustrating destructive distillation Charcoal；The present invention is greater than 5.1% catalyst to carbon content, first makes charcoal according to the stage A of making charcoal, then according to making charcoal after destructive distillation Stage, C made charcoal, and finally made charcoal according to the stage B of making charcoal, i.e., makes charcoal the making charcoal of stage B according to the stage A- of the making charcoal stage C- that makes charcoal Method is made charcoal；By utilizing three different coke combustions, 5.1% catalyst is greater than for carbon content, it can be fine Control coke combustion so that being removed in the stage A that makes charcoal to subset carbon compound remaining in catalyst, so The carbon compound of macromolecular mass carbon compound remaining in catalyst or more difficult burn off is carried out in the stage C that makes charcoal afterwards Removing, finally by making charcoal, stage B maintains condition of more smoothly making charcoal, and continues to remove to remaining carbon compound, Sufficiently to carry out burn off to carbon compound remaining in decaying catalyst, while also being mentioned for the hot environment in the stage C that makes charcoal The buffering course for having supplied a cooling, avoids long-lasting catalytic from occurring damage situations under high temperature environment；

In addition, the present invention after destructive distillation, to the catalyst of 3.5%≤carbon content≤5.1%, is first burnt according to the stage A that makes charcoal Then charcoal is made charcoal according to the stage B of making charcoal, i.e., make charcoal according to the make charcoal method of making charcoal of stage B of the stage A- of making charcoal；Pass through two-stage Coke combustion, the carbon compound different to micel situation in the catalyst of 3.5%≤carbon content≤5.1% carry out sublevel Section processing, can preferably control the progress of coke combustion, avoid the sharply exothermic phenomenon in coke combustion.

In addition, the present invention in coke combustion, by controlling the oxygen content of different phase, can promote burn off object sufficiently de- It removes, while the sharply exothermic phenomenon in regenerative process can also be avoided well, active metal is avoided to assemble.

For the complexing processing after catalyst regeneration, there is solvent to carry out at dipping catalyst using complexing agent and unsaturation Reason；Wherein organic complexing agent is the organic compound containing at least one of element sulphur, nitrogen, oxygen element element, including two Two sulphur of methyl, thioacetic acid, mercaptopropionic acid, dimethyl sulfoxide, dodecyl mercaptan carbon, oxalic acid, malonic acid, tartaric acid, citric acid, Ethylene glycol, glycerine, tetraethylene glycol, polyethylene glycol, glucose, fructose, lactose, maltose, sucrose, ethylenediamine, ethanol amine, diethyl Hydramine, triethanolamine, diisopropanolamine (DIPA), tert-butylamine, lauryl amine, trioctylamine, three isopropyl acid ammoniums, N, N- diethyl ethylene diamine, ammonia Base n-nonanoic acid, amion acetic acid, carbamide, antifebrin, N, N- dihydroxy ethyl aniline, thiocarbamide, semicarbazides, glutamic acid, rhodan ammonium At least one of；Organic complexing agent dosage is inactivate hydrogenation catalyst weight 1%~5%；

The unsaturation organic solvent includes at least one of conjugated diene, unsaturated aliphatic carboxylate；It is described Conjugated diene includes pentadiene, cyclopentadiene, 1,3- cyclohexadiene, 1,3- hexadiene, 2,5- dimethyl -2,4- hexadiene At least one of；The unsaturated aliphatic carboxylate is vegetable fat, including sesame oil, safflower seed oil, palm oil, corn Oil, at least one of cottonseed oil, peanut oil, rapeseed oil, soya-bean oil, walnut oil, coconut oil, olive oil, sunflower oil；It is unsaturated The dosage of organic solvent be inactivate hydrogenation catalyst weight 1%~50%, preferably 5%~30%.

By the way that using unsaturated organic solvent as solution, organic complexing agent not only contributes to improve organic network as solute Dispersion performance of the mixture in catalyst micropore, so that the active metal in catalyst is come into full contact with organic complexing agent, To improve catalyst activity, and unsaturated organic solvent and organic complexing agent be jointly to catalyst action, so that catalyst Active metal is more likely formed covalent form, can advantageously promote the activation recovering of catalyst.

In sulfidation, preferably handled 2~8 hours at 130 DEG C~180 DEG C, the processing is in air atmosphere, oxygen deprivation It is carried out under the conditions of air atmosphere, inert gas atmosphere or water vapour atmosphere；The vulcanizing agent dosage is that hydrogenation catalyst is theoretical Need the 90%~150% of sulfur content；Vulcanizing agent is at least one of elemental sulfur, polysulfides, preferably elemental sulfur and polysulfide Object is closed to be used in mixed way；When elemental sulfur and polysulfides are used in mixed way, weight ratio is 1:0.2~1:1, preferably 1:0.3~1: 0.6.Since elemental sulfur, polysulfides are nonhazardous substance, so as to avoid contact of the people with noxious material, reduction pair The damage of human body, and make the catalyst catalytic activity with higher after vulcanization.

In passivating process, the organic compound is vegetable fat, including sesame oil, safflower seed oil, palm oil, corn Oil, at least one of cottonseed oil, peanut oil, rapeseed oil, soya-bean oil, walnut oil, coconut oil, olive oil, sunflower oil are described to have The dosage of machine compound be inactivate hydrogenation catalyst weight 1%~40%, preferably 5%~20%；The passivation preferably exists It is handled 4~6 hours at 160 DEG C~220 DEG C；The processing is in air atmosphere, oxygen denuded air atmosphere, inert gas atmosphere or water vapour It is carried out under atmospheric condition.By finally to the Passivation Treatment of catalyst, being protected to catalyst so that catalyst storage, During transport and filling, no longer needs to carry out nitrogen protection, be not only convenient for production operation, and advantageously reduce and be produced into This.

By the related description to the method for the present invention, a kind of activity of hydrocatalyst restores and vulcanization process, tool Body the following steps are included:

S01, the mixed liquor for preparing acid organic reagent and carboxylate, in oxytropism organic reagent and carboxylate mixed liquor, Inactivation hydrogenation catalyst is added, carries out microwave treatment, then destructive distillation is carried out to hydrogenation catalyst；

S02, carbon content detection is carried out to the hydrogenation catalyst after destructive distillation；

S03, judge coke on regenerated catalyst whether less than 3.5%；It is that then coke combustion only carries out the stage B that makes charcoal, it is no, then Carry out step S04；

S04, judge whether coke on regenerated catalyst is greater than 5.1%；It is that then coke combustion is made charcoal the stage according to the stage A- of making charcoal C- make charcoal stage B make charcoal method progress；It is no, then coke combustion according to the stage A- of making charcoal make charcoal stage B make charcoal method carry out；

S05, organic complexing agent and unsaturated organic solvent are mixed, to organic complexing agent and unsaturated organic solvent mixing In liquid, it is added by hydrogenation catalyst of making charcoal that treated, is impregnated；

S06, vulcanizing agent is heated, when vulcanizing agent is heated to 125 DEG C~150 DEG C, is added and passes through into vulcanizing agent Hydrogenation catalyst after step S05 dipping, and 1h~15h is handled at 130 DEG C~180 DEG C；

S07, it organic compound is added in by step S06 treated hydrogenation catalyst is passivated, and will rise to 120 DEG C~250 DEG C, constant temperature handles 1h~8h.

In addition, in the present invention, the insatiable hunger either used in the carboxylate used in pretreatment or complexation process And the organic compound used in organic solvent and passivating process, since it all has more stable physico-chemical property, Yi Ji All have preferable dispersion performance in catalyst microchannel, can be come into full contact with catalyst, thus to catalyst into In row treatment process, adequately protection is provided to two class activated centre of catalyst and is restored, is conducive to improve in sulfidation The sulphur reservation degree of catalyst so that sulfidation is more uniform, facilitate catalyst go into operation use when uniform heat release.

The key point in present invention process will be described in detail by experimental example below:

First it should be noted that the data in following experimental examples are to be obtained by inventor by many experiments, as space is limited, A part therein is only shown in the description, and those of ordinary skill in the art can understand and implement this hair under this data Bright, remainder data all has trend identical with following experiment conclusions and can obtain identical conclusion, repeats no more hereinafter.

Experimental example 1

In experimentation of the invention, inventor uses it was unexpectedly observed that before carrying out regeneration treatment to catalyst Acid organic reagent carries out mixing with carboxylate and compounds, and impregnates to decaying catalyst, not only makes the active metal reunited Again it scatter, and the hydrocarbons remained in hydrogenation catalyst microchannel and alkaline macromolecular can be effectively removed Group, to increase the Kong Rong of catalyst.

Specific experiment process is as follows: being grouped to a batch of inactivation hydrogenation catalyst F-4, every group of inactivation catalysis Agent quality is 1kg；1 is organized as a comparison with untreated decaying catalyst；Only to carry out the catalyst of coke-burning regeneration as contrast groups 2；To remaining catalyst group, different dippings is taken to be impregnated with agent to decaying catalyst, then destructive distillation is carried out to catalyst, is burnt Charcoal regeneration；Its Kong Rong is detected to each group catalyst one by one later, experimental result is as shown in table 1.

Wherein, the corresponding same operation condition of each group is all the same；Specifically, dip operation duration 2 hours；Retorting operation It is handled 4 hours at oxygen-free environment, 180 DEG C；Make charcoal operate according to the stage A- of making charcoal make charcoal stage B make charcoal method carry out, Its operating parameter takes median.

As shown in Table 1, acid organic reagent carries out mixing with carboxylate and compounds, after decaying catalyst dipping, Catalyst regeneration is carried out again, and the Kong Rong of obtained regenerated catalyst is obviously increased, and with statistical significance, (p is less than its data 0.01)。

The hole of 1 catalyst of table is showed mercy condition

The related experiment carried out by experimental example 1 illustrates that acid organic reagent and carboxylate mixed liquor carry out catalyst After dipping, the active metal reunited not only is made to scatter again, but also big for the alkalinity for being blocked in catalyst microchannel point Sub- group, hydrocarbons etc. are removed, so that blocked catalyst duct has obtained preferable dredging and recovery.

Experimental example 2

In experimentation of the invention, compounded inventors have found that acid organic reagent is mixed with carboxylate, to inactivation While catalyst is impregnated, the Kong Rong of catalyst can be effectively improved using the microwave of appropriate power.

Detailed process is as follows: in dipping process, microwave generating apparatus being arranged on the reaction kettle of dipping, and adjusts micro- Wave generating device power 1kW, it is every to open 1 minute, it closes 1 minute, microwave action is carried out to the catalyst in reaction kettle, 2 hours Dipping terminates afterwards, simultaneously closes off microwave generating apparatus；Remaining operating procedure, parameter, condition are identical as experimental example 1；Through burning After charcoal regeneration, its Kong Rong is detected to each group catalyst one by one, experimental result is as shown in table 2；Wherein, contrast groups 1 in table 2, right It is more identical as contrast groups 1, the contrast groups 2 in experimental example 1 than group 2.

Inactivation is urged with the result of table 2 it is found that acid organic reagent carries out mixing with carboxylate and compounds by analytical table 1 Agent carries out microwave treatment while dipping, then carries out catalyst regeneration, and the hole of obtained regenerated catalyst has significant increasing Add, and its data has statistical significance (p is less than 0.01).

Under 2 microwave treatment of table, the hole of catalyst is showed mercy condition

Since decaying catalyst is after coke-burning regeneration, although catalyst microchannel is dredged, its catalytic activity is still It is old lower, catalyst activity is often improved using the process of ex situ presulfiding in the prior art；But often ignore in the prior art The quantity accounting in the activated centre in the catalyst after coke-burning regeneration with lone pair electrons is lower, if after coke-burning regeneration directly Vulcanized, then the state of cure (vulcanization) in activated centre is lower in catalyst, and the covalent form that is formed of activated centre and sulphur atom compared with It is unstable, so that the degree that catalyst activity restores is lower.Therefore, in order to before vulcanization, so that catalyst is accounted for quantity The relatively high activated centre containing lone pair electrons, the present invention also carry out catalyst after coke-burning regeneration, before vulcanizing treatment Complexing processing not only contributes to improve catalyst activity recovery extent, and organically by catalyst regeneration and catalyst vulcanization It links together, forms a complete catalyst treatment technique, avoid relatively complicated to catalyst progress in prior art Step-by-step processing, be conducive to shorten the whole production cycle, reduce production cost, reduce production energy consumption.

About the exploration of catalyst " coke-burning regeneration-complexing processing-vulcanizing treatment " this technique, especially with respect to " complexing The exploration of processing " technical process, inventor have carried out a large amount of experimentation, as space is limited, have tested to part Experiment content It is shown and illustrates in example 3.

Experimental example 3

In experimentation of the invention, inventor to the catalyst after coke-burning regeneration it was unexpectedly observed that vulcanize Before processing, mixing is carried out with unsaturated organic solvent using organic complexing agent and is compounded, especially organic complexing agent and conjugation two When alkene or unsaturated aliphatic carboxylate carry out mixing compounding, catalyst is impregnated, not only organic complexing agent is existed It is fully dispersed in catalyst microchannel, it is come into full contact with the activated centre of catalyst, improves catalyst activity, and improve The specific gravity in the activated centre in catalyst containing lone pair electrons, so that the activated centre of catalyst is more likely formed covalent form, it can The activation recovering for advantageously promoting catalyst is conducive to the progress of subsequent sulfuration process, and the catalyst activity after improving vulcanization is extensive Multiple degree.

Specific experiment process is as follows: being grouped to a batch of inactivation hydrogenation catalyst F-4, every group of inactivation catalysis Agent quality is 1kg；With mercaptopropionic acid 25g, the mixed liquor of 1,4-butanediol diacrylate 130g carries out decaying catalyst micro- Wave impregnation, destructive distillation, coke-burning regeneration；Different complexing processing is taken to carry out complexing processing (containing blank to each group catalyst with agent Group), fresh catalyst 1kg is in addition taken, after carrying out vulcanization to fresh catalyst and each group catalyst, in catalyst activity After stablizing 72 hours, use Iranian vacuum gas for raw material (its parameter index is shown in Table 3), under the conditions of identical catalyst reaction (its reaction condition is shown in Table 4), compares the activity of fresh catalyst, each group regenerated catalyst respectively, and experimental result is as shown in table 5.

3 feedstock oil parameter of table

Feedstock oil	Iranian VGO
		Density (20 DEG C), g.cm-3	0.9156
Boiling range (IBP/EBP), DEG C	356/521
		Carbon/hydrogen, %	86.45/12.55
Sulphur, μ g.g-1	27600
		Nitrogen, μ g.g-1	2160

4 reaction condition parameter of table

Feedstock oil	Iranian VGO
		Hydrogen partial pressure, MPa	14.0
Hydrogen to oil volume ratio	600
		Volume space velocity when liquid, h-1	1.30
Reaction temperature, DEG C	365

It should be noted that the operating condition of the corresponding same operation of each group is consistent；Wherein microwave dipping, destructive distillation, burning Operations parameter during charcoal is identical as experimental example 2；In addition, sulfidation is vulcanization conventional in the prior art Journey, herein without repeating.

As shown in Table 5, before carrying out vulcanizing treatment to the catalyst after coke-burning regeneration, organic complexing agent is used It carries out mixing with unsaturated organic solvent to compound, especially organic complexing agent and conjugated diene and/or unsaturated aliphatic carboxylic After acid esters carries out mixing compounding, catalyst is impregnated, then carries out vulcanizing treatment, the catalysis of obtained regenerated catalyst is living Property be significantly increased, or even basically reached the catalytic activity level of fresh catalyst, and its data has statistical significance (p Less than 0.01).

5 catalyst activity situation of table

A specific embodiment of the invention is further described with reference to embodiments, is not therefore limited the present invention System is within the scope of the embodiment described.

Embodiment 1

Inactivation hydrogenation catalyst F-4 (1kg) is taken, is impregnated in the mixed liquor of thioacetic acid 10g and n-butyl acetate 50g, While dipping, adjusting microwave sounding device power is 0.1kW, every to open 0.5 minute, is tied after closing 0.5 minute, 2 hours Beam microwave action and dipping.In nitrogen environment, destructive distillation 15 hours at 120 DEG C；After destructive distillation, the carbon content for detecting catalyst is 5.3%, catalyst is put into rotary kiln, is warming up to 200 DEG C, constant temperature 8h, oxygen content is controlled in 15% (volume fraction), then 400 DEG C, constant temperature 10h are warming up to, Control for Oxygen Content is in 35% (volume fraction), then is warming up to 300 DEG C, constant temperature 8h, oxygen content Control is in 21% (volume fraction)；10gN is taken, N- diethyl ethylene diamine is mixed with 10g cyclopentadiene, to urging after coke-burning regeneration Agent dipping；150g elemental sulfur is taken to be heated to 125 DEG C, treated that catalyst impregnates to complexing, and handles at 130 DEG C 15h；10g safflower seed oil is added into catalyst, temperature is adjusted to 120 DEG C, and constant temperature handles 8h, then is down to room temperature, obtains again Raw catalyst.Its Kong Rong is detected to regenerated catalyst obtained, the results are shown in Table 6.

Embodiment 2

Inactivation hydrogenation catalyst F-4 (1kg) is taken, is impregnated in the mixed liquor of tartaric acid 50g and ethyl acetate 500g, is soaking While stain, adjusting microwave sounding device power is 2kW, every to open 2 minutes, terminates microwave action after closing 2 minutes, 30 minutes And dipping.In nitrogen environment, destructive distillation 1 hour at 200 DEG C；After destructive distillation, the carbon content for detecting catalyst is 5.0%, will be catalyzed Agent is put into rotary kiln, is warming up to 300 DEG C, constant temperature 2h, and oxygen content is controlled in 8% (volume fraction), then is warming up to 400 DEG C, Constant temperature 1h, oxygen content are controlled in 16% (volume fraction)；50g dodecyl mercaptan carbon is taken to mix with 500g sunflower oil, to burning Catalyst dipping after charcoal regeneration；80g elemental sulfur and 80g butyl polysulfides are taken, is heated to 150 DEG C, after complexing processing Catalyst impregnated, and handle 1h at 180 DEG C；400g sunflower oil is added into catalyst, temperature is adjusted to 250 DEG C, constant temperature handles 1h, then is down to room temperature, obtains regenerated catalyst.Its Kong Rong is detected to regenerated catalyst obtained, as a result such as Shown in table 6.

Embodiment 3

Inactivation hydrogenation catalyst F-4 (1kg) is taken, is impregnated in the mixed liquor of glycerine 30g and M Cr 100g, In While dipping, adjusting microwave sounding device power is 1.2kW, every to open 1.5 minutes, is terminated after closing 1 minute, 1 hour micro- Wave effect and dipping.In nitrogen environment, destructive distillation 8 hours at 150 DEG C；After destructive distillation, the carbon content for detecting catalyst is 4.8%, Catalyst is put into rotary kiln, is warming up to 260 DEG C, constant temperature 5h, oxygen content is controlled in 10% (volume fraction), then is warming up to 350 DEG C, constant temperature 5h, oxygen content is controlled in 18% (volume fraction)；Take 20g citric acid, 50g 1,3- hexadiene, 50g soya-bean oil Mixing impregnates the catalyst after coke-burning regeneration；It takes 140g myrcenyl polysulfides to be heated to 140 DEG C, complexing is handled Catalyst afterwards is impregnated, and handles 10h at 160 DEG C；200g sesame oil is added into catalyst, temperature is adjusted to 200 DEG C, constant temperature handles 5h, then is down to room temperature, obtains regenerated catalyst.Its Kong Rong is detected to regenerated catalyst obtained, as a result such as Shown in table 6.

Embodiment 4

Inactivation hydrogenation catalyst F-4 (1kg) is taken, mercaptopropionic acid 20g and 1,4-butanediol diacrylate 200g are impregnated in Mixed liquor in, dipping while, adjustings microwave sounding device power be 0.8kW, it is every open 1 minute, closing 1 minute, 1.5 Terminate microwave action and dipping after hour.In nitrogen environment, destructive distillation 10 hours at 160 DEG C；After destructive distillation, the carbon of catalyst is detected Content is 4.2%, and catalyst is put into rotary kiln, is warming up to 240 DEG C, constant temperature 6h, oxygen content control is in 12% (volume point Number), then 360 DEG C are warming up to, constant temperature 6h, oxygen content is controlled in 20% (volume fraction)；30g dimethyl sulfoxide, 80g 2 are taken, 5- dimethyl-2,4-hexadiene, the mixing of 160g peanut oil, impregnate the catalyst after coke-burning regeneration；Take 100g elemental sulfur and 40g Cyclohexyl polysulfides is heated to 145 DEG C, and to complexing, treated that catalyst impregnates, and handles 12h at 150 DEG C； 240g peanut oil is added into catalyst, temperature is adjusted to 180 DEG C, and constant temperature handles 6h, then is down to room temperature, obtains regeneration catalyzing Agent.Its Kong Rong is detected to regenerated catalyst obtained, the results are shown in Table 6.

Comparative example 1

Inactivation hydrogenation catalyst F-4 is handled using the technical solution of CN104624248A, specifically:

Take inactivation hydrogenation catalyst F-4, be put into tubular reactor, using toluene and ethyl alcohol by 4: 1 (volumes) mix as Solvent, in 2 hours of 80 DEG C of continuous flushings.Gained sample in tube furnace at 100 DEG C through nitrogen purge 1 hour after, in air Carry out oxidation under atmosphere and burn the processing of sulphur coke-burning regeneration, 150 DEG C constant temperature 1 hour, at 250 DEG C, constant temperature is burnt sulphur 2 hours, at 400 DEG C Constant temperature is made charcoal 3 hours；The aqueous impregnation solution of DTPA and diammonium hydrogen phosphate are prepared, DTPA concentration is the 7wt% of aqueous impregnation solution, phosphorus Sour two ammonium concentration of hydrogen is the 2wt% of aqueous impregnation solution, using isometric saturation infusion process by the maceration extract according to common process pair Catalyst after coke-burning regeneration is sprayed, the closed placement 48h at 60 DEG C, after 160 DEG C of processing in dry 2 hours, is obtained Regenerated catalyst.Its Kong Rong is detected to regenerated catalyst obtained, the results are shown in Table 6.

Comparative example 2

Inactivation hydrogenation catalyst F-4 is handled using the technical solution of embodiment 3 in CN102310006A, specifically Are as follows:

Inactivation hydrogenation catalyst F-4 (1kg) is taken, is regenerated in air atmosphere.320 DEG C constant temperature calcining 4 hours, then It is warming up to 550 DEG C to roast 3 hours, cool down 200 DEG C.Elemental sulfur 100g is mixed with (NH4) 2S of 50g, heat is carried out at 150 DEG C Mixing.When will heat mixed vulcanizing agent impregnation catalyst agent again, and handled 5 hours at 200 DEG C, then cooling to 80 DEG C, it is added 200g organic solvent (organic solvent be coking kerosene fraction), the ratio of carbon atom number 9~12 is not less than 50% in organic solvent, Constant temperature 4 hours, then it is down to room temperature, obtain regenerated catalyst.Its Kong Rong is detected to regenerated catalyst obtained, as a result such as table 6 It is shown.

Comparative example 3

Inactivation hydrogenation catalyst F-4 (1kg) is taken, mercaptopropionic acid 20g and 1,4-butanediol diacrylate 200g are impregnated in Mixed liquor in, impregnate 1.5 hours.In nitrogen environment, destructive distillation 10 hours at 160 DEG C；After destructive distillation, the carbon for detecting catalyst contains Amount is 4.6%, and catalyst is put into rotary kiln, is warming up to 240 DEG C, constant temperature 6h, oxygen content control is in 12% (volume point Number), then 360 DEG C are warming up to, constant temperature 6h, oxygen content is controlled in 20% (volume fraction)；30g dimethyl sulfoxide, 80g 2 are taken, 5- dimethyl-2,4-hexadiene, the mixing of 160g peanut oil, impregnate the catalyst after coke-burning regeneration；Take 100g elemental sulfur and 40g Cyclohexyl polysulfides is heated to 145 DEG C, and to complexing, treated that catalyst impregnates, and handles 12h at 150 DEG C； 240g peanut oil is added into catalyst, temperature is adjusted to 180 DEG C, and constant temperature handles 6h, then is down to room temperature, obtains regeneration catalyzing Agent.Its Kong Rong is detected to regenerated catalyst obtained, the results are shown in Table 6.

Comparative example 4

Inactivation hydrogenation catalyst F-4 (1kg) is taken, mercaptopropionic acid 20g and 1,4-butanediol diacrylate 200g are impregnated in Mixed liquor in, dipping while, adjustings microwave sounding device power be 0.8kW, it is every open 1 minute, closing 1 minute, 1.5 Terminate microwave action and dipping after hour.In nitrogen environment, destructive distillation 10 hours at 160 DEG C；After destructive distillation, the carbon of catalyst is detected Content is 4.2%, and catalyst is put into rotary kiln, is warming up to 240 DEG C, constant temperature 6h, oxygen content control is in 12% (volume point Number), then 360 DEG C are warming up to, constant temperature 6h, oxygen content is controlled in 20% (volume fraction)；Take 100g elemental sulfur and 40g cyclohexyl Polysulfides is heated to 145 DEG C, impregnates to the catalyst after coke-burning regeneration, and handles 12h at 150 DEG C；To catalysis 240g peanut oil is added in agent, temperature is adjusted to 180 DEG C, and constant temperature handles 6h, then is down to room temperature, obtains regenerated catalyst.It is right Regenerated catalyst obtained detects its Kong Rong, and the results are shown in Table 6.

Comparative example 5

Inactivation hydrogenation catalyst F-4 (1kg) is taken, catalyst is put into rotary kiln, is warming up to 240 DEG C, constant temperature 6h, oxygen Content is controlled in 12% (volume fraction), then is warming up to 360 DEG C, constant temperature 6h, and oxygen content is controlled in 20% (volume fraction)；It takes 30g dimethyl sulfoxide, 80g 2,5- dimethyl-2,4-hexadiene, the mixing of 160g peanut oil, soak the catalyst after coke-burning regeneration Stain；100g elemental sulfur and 40g cyclohexyl polysulfides are taken, is heated to 145 DEG C, treated that catalyst soaks to complexing Stain, and 12h is handled at 150 DEG C；240g peanut oil is added into catalyst, temperature is adjusted to 180 DEG C, and constant temperature handles 6h, then It is down to room temperature, obtains regenerated catalyst.Its Kong Rong is detected to regenerated catalyst obtained, the results are shown in Table 6.

The hole of each regenerated catalyst is showed mercy condition in 6 embodiment of table and comparative example

As the data in table 6 it is found that the Kong Rong of regenerated catalyst made from embodiment 1-4 is compared to inactivation hydrogenation catalyst F- 4, comparative example 1-5 is improved, and has statistical significance (p < 0.01).

Further, the Kong Rong of regenerated catalyst made from comparative example 3,4 is higher than comparative example 1,2 (p < 0.01), but low It is higher than comparative example 2 (p < 0.01) in embodiment 1-4 (p < 0.01), the Kong Rong that regenerated catalyst is made in comparative example 5, but is lower than Comparative example 1 and embodiment 1-4 (p < 0.01), this illustrates that the method in the present invention, each step are all indispensable, and this The combination of a little preparation steps can obtain unexpected technical effect.

Use Iranian vacuum gas for raw material (its parameter index is shown in Table 3), (it is anti-under the conditions of identical catalyst reaction It answers condition to be shown in Table 4), compares the activity of fresh catalyst, embodiment 1-4, comparative example 1-5 respectively, experimental result is as shown in table 7.

The active situation of each regenerated catalyst in 7 embodiment of table and comparative example

	Sulfur content, μ g/g	Nitrogen content, μ g/g
			Fresh catalyst	96.1	68.7
Embodiment 1	102.2	76.6
			Embodiment 2	101.7	74.8
Embodiment 3	97.5	70.3
			Embodiment 4	98.0	69.4
Comparative example 1	133.8	96.9
			Comparative example 2	147.6	95.4
Comparative example 3	119.1	86.3
			Comparative example 4	125.9	91.7
Comparative example 5	113.5	80.0

As the data in table 7 it is found that the activity of regenerated catalyst made from embodiment 1-4 is mentioned compared to comparative example 1-5 Regenerated catalyst made from height or even individual embodiments close to fresh catalyst level, and have statistical significance (p < 0.01).

Further, the activity of regenerated catalyst made from comparative example 3-5 is above comparative example 1,2 (p < 0.01), but low In embodiment 1-4 (p < 0.01), this illustrates the method in the present invention, and each step is all indispensable, and these preparation steps Combination can obtain unexpected technical effect.

In addition, according to the data of table 6, table 7, by analyzing embodiment 1-4, it can be seen that when the carboxylate is When unsaturated aliphatic carboxylate, specially 1,4-butanediol diacrylate, M Cr, i.e. embodiment 3 or embodiment 4 Regenerated catalyst obtained is showed mercy in condition and catalyst activity index in hole, is superior to made from embodiment 1 and embodiment 2 Regenerated catalyst.

For catalyst, activity improves research in " coke-burning regeneration-complexing processing-vulcanizing treatment " this technique, especially About the combined situation of the unsaturated organic solvent in complexing treatment process, inventor has carried out a large amount of research, by following Separate embodiment is illustrated:

Embodiment 5-13, the embodiment of comparative example 6-8 and condition are substantially same as Example 4, except that in network The unsaturated organic solvent closed in treatment process is different, concrete condition and the results are shown in Table 8.

Table 8

It is analyzed by the data to table 8, it can be seen that the present invention is using conjugated diene and/or unsaturated lipid Regenerated catalyst obtained when aliphatic carboxylic acid's ester is as solvent, compared to regenerated catalyst made from other unsaturated solvents, In Tool is significantly improved in catalyst activity index, and its data has statistical significance (p < 0.01).

In addition, in the case where temporary indefinite specific mechanism, researcher of the invention process through a large number of experiments It was unexpectedly observed that, compared to other solvents, regenerated catalyst obtained has when conjugated diene is only used only as solvent Better activity index, and its data has statistical significance (p < 0.05)；

In addition to this, more exceed that the application researcher is unexpected to be, using pentadiene, cyclopentadiene, 1, When 3- cyclohexadiene, 1,3- hexadiene, the multiple combinations in 2,5- dimethyl-2,4-hexadiene are as solvent, especially with Wherein any three kinds of combinations are used as solvent, and compared to other combinations, regenerated catalyst obtained has preferably activity Index, and its data has statistical significance (p < 0.05).

The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (9)

1. a kind of activity of hydrocatalyst restores and vulcanization process, which is characterized in that mixed with acid organic reagent with carboxylate Liquid pre-processes the hydrogenation catalyst of inactivation, then to hydrogenation catalyst carry out destructive distillation, to the hydrogenation catalyst after destructive distillation into Row coke-burning regeneration；With the mixed liquor of organic complexing agent and unsaturated organic solvent, the hydrogenation catalyst after coke-burning regeneration is carried out Dipping；Then vulcanizing treatment is carried out to the hydrogenation catalyst after dipping, then the hydrogenation catalyst after vulcanizing treatment is passivated Processing；The pretreatment is microwave treatment；The unsaturation organic solvent includes conjugated diene, and the acidity organic reagent is Acidic organic compound containing at least one of element sulphur, oxygen element element.

2. a kind of activity of hydrocatalyst as described in claim 1 restores and vulcanization process, which is characterized in that the pretreatment Process carried out in the reaction kettle for being provided with microwave generating apparatus, microwave power and hydrogenation catalyst mass ratio are 0.1- 2.0W/g after microwave generating apparatus every unlatching 0.5-2 minutes, closes 0.5-2 minutes, continues -2 hours 30 minutes.

3. a kind of activity of hydrocatalyst as described in claim 1 restores and vulcanization process, which is characterized in that the carboxylate For aliphatic carboxylic acid esters, including in n-butyl acetate, ethyl acetate, 1,4-butanediol diacrylate, M Cr extremely Few one kind；

The acidity organic reagent includes thioacetic acid, mercaptopropionic acid, oxalic acid, malonic acid, tartaric acid, at least one in citric acid Kind.

4. a kind of activity of hydrocatalyst as described in claim 1 restores and vulcanization process, which is characterized in that the unsaturation Organic solvent includes conjugated diene and unsaturated aliphatic carboxylate.

5. a kind of activity of hydrocatalyst as claimed in claim 4 restores and vulcanization process, which is characterized in that the conjugation two Alkene include pentadiene, cyclopentadiene, 1,3- cyclohexadiene, 1,3- hexadiene, in 2,5- dimethyl -2,4- hexadiene extremely Few one kind；

The unsaturated aliphatic carboxylate is vegetable fat, including sesame oil, safflower seed oil, palm oil, corn oil, cottonseed At least one of oil, peanut oil, rapeseed oil, soya-bean oil, walnut oil, coconut oil, olive oil, sunflower oil.

6. a kind of activity of hydrocatalyst as described in claim 1 restores and vulcanization process, which is characterized in that including following step It is rapid:

S1, the mixed liquor for preparing acid organic reagent and carboxylate, oxytropism organic reagent are added and lose with carboxylate mixed liquor Hydrogenation catalyst living carries out microwave treatment, then carries out destructive distillation to hydrogenation catalyst；

S2, to the hydrogenation catalyst after destructive distillation, regenerated using the method for making charcoal；

S3, organic complexing agent and unsaturated organic solvent are mixed, into organic complexing agent and unsaturated organic solvent mixed liquor, It is added by step S2 treated hydrogenation catalyst, is impregnated；

S4, vulcanizing agent is heated, when vulcanizing agent is heated to 125 DEG C ~ 150 DEG C, is added into vulcanizing agent and passes through step S3 Hydrogenation catalyst after dipping, and 1h ~ 15h is handled at 130 DEG C ~ 180 DEG C；

S5, organic compound be added in by step S4 treated hydrogenation catalyst be passivated, and will rise to 120 DEG C ~ 250 DEG C, constant temperature handles 1h ~ 8h.

7. a kind of activity of hydrocatalyst as claimed in claim 6 restores and vulcanization process, which is characterized in that described plus hydrogen is urged Agent includes carrier component, hydrogenation active component and organic additive, and the carrier component is refractory porous oxide, including oxidation At least one of aluminium, silica, amorphous silica-alumina, titanium oxide, molecular sieve；The hydrogenation active component include W, Mo, Ni and At least one of Co, hydrogenation active component exist with metal salts, and in terms of oxide, hydrogenation active component content is 3wt% ~50wt%；The organic additive includes oxygen-containing organic compound, organic compounds containing nitrogen, at least one in organic compounds containing sulfur Kind, content of the organic additive in hydrogenation catalyst is 0.01% ~ 5%.

8. a kind of activity of hydrocatalyst as claimed in claim 6 restores and vulcanization process, which is characterized in that in step S1 Destructive distillation is heat treatment process, and heat treatment condition is to handle 1 ~ 15 hour at a temperature of oxygen-free environment, 120 DEG C ~ 200 DEG C.

9. a kind of activity of hydrocatalyst as claimed in claim 6 restores and vulcanization process, which is characterized in that in step S2, The method of making charcoal carries out coke-burning regeneration using control charcoal temperature and oxygen content；

It is described make charcoal method include make charcoal stage A, the stage B that makes charcoal, make charcoal at least one of stage C；

The stage A that makes charcoal are as follows: 200 DEG C ~ 300 DEG C of charcoal temperature, constant temperature 2h ~ 8h, oxygen content control is less than in volume fraction 15%；

The stage B that makes charcoal are as follows: 300 ~ 400 DEG C of charcoal temperature, constant temperature 1h ~ 8h, oxygen content control is less than in volume fraction 21%；

The stage C that makes charcoal are as follows: 400 DEG C ~ 600 DEG C of charcoal temperature, constant temperature 2h ~ 10h, Control for Oxygen Content is less than in volume fraction 35%。