CN109465036A - A kind of activity of hydrocatalyst restoration methods - Google Patents
A kind of activity of hydrocatalyst restoration methods Download PDFInfo
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Abstract
The invention discloses a kind of activity of hydrocatalyst restoration methods, it include: that the hydrogenation catalyst of inactivation is mixed with acid organic reagent, organic dispersing agent, successively inactivation hydrogenation catalyst is regenerated using destructive distillation, processing of making charcoal, it is cooled to 80 DEG C~130 DEG C later, impregnation is carried out using enveloping agent solution；Hydrogenation catalyst by impregnation handles 1h~15h at 130 DEG C~220 DEG C, obtains the hydrogenation catalyst of activation recovering.The present invention organically combines the pretreatment, regeneration and activation recovering that inactivate hydrogenation catalyst, and the activity of hydrocatalyst metal component of inactivation can be made to be restored to the activated state in two class activated centres, the service performance of activation recovering degree and catalyst can be improved.Meanwhile the method for the present invention can also reduce energy consumption, reduce production cost, shorten the production cycle, be particularly conducive to the activation recovering of two class hydrogenation sites catalyst.
Description
Technical field
The present invention relates to a kind of activity of hydrocatalyst restoration methods, more particularly to two class activated centre hydrogenation catalysts
Method for activation recovering.
Technical background
With the development of economy with the raising of environmental requirement, the fuel demand amount in China is greatly increased, while fuel emission
Standard also will gradually integrate with America and Europe.EC regulations provide that European vehicle fuel in 2009 executes European V class standard, limitation oil
In sulfur content in 10g/g or less.The V vehicle fuel quality standard regulation sulfur content of state that China has been carried out needs to be reduced to 10 μ
G/g or less.
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.In recent years, the ultra-deep Hydrobon catalyst of domestic and international diesel oil mainly use organic complex technology adjust metal with
Interaction force between carrier improves active metal in the dispersity of carrier surface, mainly generates high activity II after curing
Class 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,
MoS2Disperse not to be very thin, be often formed by stacking by some biggish chips, vulcanize 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 class activated centres, makes units activity center all and has and is very high
Latent active makes the activity of active metal reach maximum value.
Hydrogenation catalyst is being oxidation state using preceding active metal component, and oxidized catalyst is lived before industrial application
Property metal needs be converted into sulphided state just catalytic activity with higher.With the operating of long-lasting catalytic, hydrogenation catalyst is deposited
In deactivation phenomenom.The deactivation mechanism of hydrogenation catalyst point poisoning, coking and sintering three classes.Coking is formed in catalyst surface
Carbonaceous is covered on activated centre, and a large amount of coking leads to hole plug, prevents activated centre in reactant molecule access aperture；Alkali
Property nitrogen such as pyridine compounds and their is chemisorbed on acid centre, so that catalyst is lost activity but also is blocked aperture and interior
Duct；Sintering then makes catalyst structure change and loss of activity center, refers to accumulation of metal or crystalline substance for hydrogenation catalyst
Body becomes larger.Acid-base neutralization caused by coking and impurity chemisorption belongs to temporary poisoning, can be restored by air burn
Activity, the process are the regeneration of catalyst, and regenerated catalyst can continue to use, to improve economic benefit.
Currently, a large amount of second classes activated centre hydrogenation catalyst technology of preparing is disclosed, as US5336654 discloses one kind
The method that hydrotreating catalyst is prepared using the salt of metal and the heteropoly acid impregnated carrier of metal.CN101491766A is disclosed
A kind of preparation method of hydrogenation catalyst introduces active component by two-stage method, and the metal component first introduced passes through calcination steps
Stronger with the effect of carrier, the active component introduced afterwards, no calcination steps are weaker with carrier function, in catalyst vulcanization and make
With in the process, the migration of the active metal weaker with carrier function can be inhibited poly- with the stronger active metal component of carrier function
Collection makes catalyst keep ideal activity stability.The regeneration that CN102463153A discloses a kind of carbon distribution decaying catalyst is multiple
Activating method is related to two class activated centre hydrogenation catalysts, under oxygen-containing gas effect, removes the carbon distribution of decaying catalyst, makes to urge
Carbon content in agent is calculated as 0.5%~2% with mass content；Then with containing alkaline matter solution and organic additive it is molten
Liquid contact, the last thermally treated catalyst for obtaining activation recovering.
Active metal is mainly supported on a catalyst support with metallic salt form in above-mentioned two classes site catalyst, together
Shi Tianjia organic compound, and without roasting, the activated centre of Lai Tigao catalyst is measured, and is obtained in two classes activity after inactivation
Activation recovering after heart hydrogenation catalyst inactivation.
The regeneration method of existing inactivation hydrogenation catalyst can not make its activation recovering to optimal effect.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of activity of hydrocatalyst restoration methods, and especially two classes are living
The activation recovering of property center hydrogenation catalyst.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of activity of hydrocatalyst restoration methods, comprising the following steps:
Step (1) mixes inactivation hydrogenation catalyst with acid organic reagent, organic dispersing agent, successively using destructive distillation, burning
Charcoal processing regenerates inactivation hydrogenation catalyst；
Hydrogenation catalyst after step (2), regeneration is cooled to 80 DEG C~130 DEG C, is carried out at dipping using enveloping agent solution
Reason；
Step (3), the hydrogenation catalyst by step (2) impregnation handle 1h~15h at 130 DEG C~220 DEG C, obtain
Obtain the hydrogenation catalyst of activation recovering.
In step (1), the inactivation hydrogenation catalyst refers to the hydrogenation catalyst based on two class activated centres through making
With and deactivated hydrogenation catalyst, the hydrogenation catalyst based on two class activated centres include carrier, hydrogenation active component
And organic additive；Wherein, the carrier is refractory porous oxide, and the refractory porous oxide is aluminium oxide, oxidation
At least one of silicon, amorphous silica-alumina, titanium oxide, molecular sieve etc.；Hydrogenation active component be one of W, Mo, Ni and Co or
Several, hydrogenation active component exists with metal salts, and hydrogenation active component content is 3wt%~50wt% in terms of oxide；
Organic additive is at least one of oxygen-containing organic compound, organic compounds containing nitrogen, organic compounds containing sulfur etc.；Organic additive
Content in hydrogenation catalyst is 0.2wt%~10wt%, preferably 0.5wt%~5wt%.
Specifically, hydrogenation catalyst can according to need selection commercial goods, can also be prepared by conventional method in that art,
It is also possible to regenerated catalyst of the decaying catalyst after regeneration.
The acid organic reagent is generally sulfur-bearing, nitrogenous or oxygen containing acidic organic compound；Specifically, described
Acid organic reagent is dimethyl disulfide, thioacetic acid, mercaptopropionic acid, dimethyl sulfoxide, amino-nonanoic acid, amion acetic acid, phosphinylidyne
Amine, antifebrin, N, N- dihydroxy ethyl aniline, thiocarbamide, semicarbazides, glutamic acid, oxalic acid, malonic acid, tartaric acid, citric acid, second
Glycol, glycerine, tetraethylene glycol, polyethylene glycol and one or more of with other materials similar in above-mentioned substance structure；It is excellent
It is selected as citric acid.
The dosage of the acid organic reagent, which is generally, inactivates the 0.01%~5% of hydrogenation catalyst weight, preferably
1%~3%.
The organic dispersing agent generally uses organic carboxylic ester, preferably fatty glyceride.Specifically, described has
Machine dispersing agent is sesame oil, safflower seed oil, palm oil, corn oil, cottonseed oil, peanut oil, rapeseed oil, soya-bean oil, walnut oil, coconut
Oil, olive oil, sunflower oil, lard, n-butyl acetate, ethyl acetate, 1,4 butanediol diacrylate, hexamethylene isopropyl propionate
One or more of Deng.
The organic dispersing agent dosage be inactivate hydrogenation catalyst weight 5%~50%, preferably 5%~20%.
The destructive distillation is heat treatment under conditions of no oxygen, and heat treatment condition is at 100 DEG C~200 DEG C
Reason 1~15 hour, is handled 3~6 hours preferably at 150~200 DEG C.The condition of the no oxygen is nitrogen atmosphere.
Using the interim regeneration method for controlling charcoal temperature and oxygen content, either shallow first is made charcoal for the processing of making charcoal
200 DEG C~300 DEG C, constant temperature 2h~8h, control oxygen content (volume fraction) is no more than 15%；Then make charcoal rise to 300~
400 DEG C of constant temperature, constant temperature 1h~8h, control oxygen content are no more than 21%；Last depth is made charcoal 400 DEG C~600 DEG C, and constant temperature 2h~
10h, control oxygen content are no more than 35%.
Preferably, either shallow is made charcoal 250 DEG C~280 DEG C, constant temperature 3h~6h first, and control oxygen content is no more than 10%；So
After make charcoal and rise to 350 DEG C~380 DEG C, constant temperature 2h~4h, control oxygen content 15%~21%；Last depth is made charcoal 450 DEG C
~550 DEG C, constant temperature 4h~8h, oxygen content is controlled 25%~30%.
In step (2), the amount of complex be inactivate hydrogenation catalyst weight 0.01%~5%, preferably 3%
~5%.The content (mass fraction) of complexing agent is 10~20% in the enveloping agent solution.
The complexing agent is identical as the organic additive of hydrogenation catalyst.
The complexing agent be organic compounds containing sulfur, oxygen-containing organic compound or organic compounds containing nitrogen and with it is above-mentioned
One or more of other materials similar in the structure of matter.
Organic compounds containing sulfur of the present invention be dimethyl disulfide, thioacetic acid, mercaptopropionic acid, dimethyl sulfoxide,
One or more of dodecyl mercaptan carbon.
The oxygen-containing organic compound for example oxalic acid, malonic acid, tartaric acid, citric acid, ethylene glycol, glycerine, tetraethylene glycol,
One or more of polyethylene glycol, glucose, fructose, lactose, maltose, sucrose.
The organic compounds containing nitrogen is alkyl amine substance, hydramine substance, amino acids substance, organic ammonium salt
One or more of substance, amide substance etc., specially ethylenediamine, ethanol amine, diethanol amine, triethanolamine, diisopropyl
Hydramine, tert-butylamine, lauryl amine, trioctylamine, three isopropyl acid ammoniums, N, N- diethyl ethylene diamine, amino-nonanoic acid, amion acetic acid, phosphinylidyne
Amine, antifebrin, N, N- dihydroxy ethyl aniline, thiocarbamide, semicarbazides, glutamic acid, rhodan ammonium.
In step (3), the hydrogenation catalyst by impregnation is in air atmosphere, oxygen denuded air atmosphere, inert gas gas
It is handled 1~15 hour at 130 DEG C~220 DEG C under the conditions of atmosphere or water vapour atmosphere etc..
Compared to the prior art, beneficial effects of the present invention:
1, the present invention has first passed through acid organic reagent dipping inactivation hydrogenation catalyst, makes to inactivate the alkali in hydrogenation catalyst
Property macromolecular mass and acid centre adsorption weaken, and play the role of complexing agent, to the activity in two class activated centres of formation
Metal forms protection；Meanwhile the destructive distillation before making charcoal, dispersing agent and remaining hydrocarbons are removed well, avoid regenerative process
In sharply exothermic phenomenon.
2, the present invention impregnates remaining hydrocarbon in inactivation hydrogenation catalyst, with hydrogenation catalyst microchannel by organic dispersing agent
Substance has the function that similar compatibility, avoids the hydrocarbons remained in hydrogenation catalyst duct to hydrogenation catalyst metal
Activated centre diffuses to form shielded layer, it is ensured that acid organic reagent is diffused into the metal active centres inside duct, is more advantageous to
Two class activated centre activation recoverings of the hydrogenation catalyst inside duct.
3, the catalyst after regeneration is immersed in enveloping agent solution and handled by the present invention, so that adding hydrogen living in catalyst
Property metal is more likely formed covalent form, can preferably promote the activation recovering of catalyst.
4, coke-burning regeneration process was divided into for three stages, can be good at control coke combustion: more subset it is carbon containing
Compound removes in the either shallow coke combustion of hypothermia and hypoxia；The carbon compound that less macromolecular mass and hardly possible are burnt up is in high temperature height
It is removed during oxygen content；By controlling the oxygen content of different phase, burn off object can be allowed sufficiently to remove, while being also avoided that
Sharply exothermic phenomenon in regenerative process, avoids accumulation of metal.
5, the present invention combines the regeneration for inactivating hydrogenation catalyst and activation recovering, makes two class activated centre hydrogenation catalysts
Activity be restored, even better than fresh dose, while also reducing energy consumption, reduce production cost, shorten the production cycle.
6, present invention process is simple, and using cheap industrial chemicals, and equipment is simple, strong operability, and hydrogen is added to urge
Agent catalytic activity with higher.
Specific embodiment
Embodiment uses fresh hydrogenation catalyst F-4A, which, using aluminium oxide as carrier, is activity with Mo-Ni
Component, using citric acid as organic additive, with MoO3The content for counting Mo is 24%, and the content of the Ni in terms of NiO is 3.0%, citric acid
Content be 3%.Two class activated centres inactivate after industrial operation a cycle, are denoted as hydrogenation catalyst F-4, carbon distribution 8.6%.
Raw material oil nature used is shown in Table 1.
The property of 1 feedstock oil of table
| Feedstock oil | Iranian VGO |
| Density (20 DEG C), g.cm-3 | 0.9056 |
| Boiling range (IBP/EBP), DEG C | 356/516 |
| Carbon/hydrogen, % | 86.45/12.75 |
| Sulphur, % | 2.56 |
| Nitrogen, μ g.g-1 | 2016 |
Embodiment 1
200 grams of hydrogenation catalyst F-4 of inactivation is taken, is impregnated in the mixed organic solvents of 2 grams of citric acids and 40 grams of soya-bean oil.
In nitrogen atmosphere, destructive distillation 4 hours at 180 DEG C.Processing of making charcoal is carried out again: rising to 260 DEG C, constant temperature 3h, controls oxygen content (body
Fraction) 8%；350 DEG C, constant temperature 4h are risen to again, control oxygen content 15%~20%；470 DEG C, constant temperature 6h are risen to again,
Oxygen content is controlled 25%~30%.After making charcoal, it is cooled to 130 DEG C.By the hydrogenation catalyst F-4 that makes charcoal that treated
It is immersed in enveloping agent solution (be dissolved in preparing in 50 grams of water by 8 grams of citric acids and obtain enveloping agent solution), then is warming up to 180 DEG C
When, constant temperature 4 hours, it is down to room temperature, obtains the hydrogenation catalyst F-4 of activation recovering.
Embodiment 2
200 grams of Hydrobon catalyst F-4 of inactivation is taken, the mixing for being impregnated in 2.6 grams of citric acids and 40 grams of soya-bean oil is organic molten
In liquid.In nitrogen atmosphere, destructive distillation 4 hours at 190 DEG C.Processing of making charcoal is carried out again: rising to 260 DEG C, constant temperature 3h, control oxygen contains
Amount is 8%；360 DEG C, constant temperature 4h are risen to again, control oxygen content 15%~20%；490 DEG C, constant temperature 6h are risen to again, control oxygen
Gas content is 25%~30%.After making charcoal, it is cooled to 130 DEG C.By making charcoal that treated, hydrogenation catalyst F-4 is immersed in
In enveloping agent solution (be dissolved in preparing in 50 grams of water by 7 grams of citric acids and obtain enveloping agent solution), then when being warming up to 200 DEG C, constant temperature 4
Hour, it is down to room temperature, obtains the hydrogenation catalyst F-4 of activation recovering.
Embodiment 3
200 grams of Hydrobon catalyst F-4 of inactivation is taken, the mixing for being impregnated in 6 grams of citric acids and 36 grams of palm oils is organic molten
In liquid.In nitrogen atmosphere, destructive distillation 3 hours at 180 DEG C.Processing of making charcoal is carried out again: rising to 260 DEG C, constant temperature 3h, control oxygen contains
Amount is 8%；350 DEG C, constant temperature 4h are risen to again, control oxygen content 15%~20%；470 DEG C, constant temperature 6h are risen to again, control oxygen
Gas content is 25%~30%.After making charcoal, it is cooled to 130 DEG C.By hydrogenation catalyst F-4 dipping drop of making charcoal that treated
It is permanent in enveloping agent solution (be dissolved in 10 grams of citric acids in 50 grams of water prepare obtain enveloping agent solution), then when being warming up to 210 DEG C
Temperature 4 hours, is down to room temperature, obtains the hydrogenation catalyst F-4 of activation recovering.
Embodiment 4
200 grams of Hydrobon catalyst F-4 of inactivation is taken, the mixed organic solvents of 4 grams of citric acids and 40 grams of soya-bean oil are impregnated in
In.In nitrogen atmosphere, destructive distillation 4 hours at 190 DEG C.Processing of making charcoal is carried out again: rising to 260 DEG C, constant temperature 3h, controls oxygen content
7%；350 DEG C, constant temperature 4h are risen to again, control oxygen content 15%~20%；450 DEG C, constant temperature 6h are risen to again, control oxygen
Gas content is cooled to 140 DEG C 25%~30%.After making charcoal, it is cooled to 140 DEG C.By making charcoal, treated plus hydrogen
8 grams of citric acids in enveloping agent solution (be dissolved in preparing in 50 grams of water and obtain enveloping agent solution) by catalyst F-4 dipping drop, then rises
When temperature is to 200 DEG C, constant temperature 4 hours, it is down to room temperature, obtains the hydrogenation catalyst F-4 of activation recovering.
Comparative example 1
Take inactivation 200 grams of hydrogenation catalyst F-4, regenerated in air atmosphere: 280 DEG C constant temperature calcining 3 hours, so
After be warming up to 450 DEG C and roast 3 hours, cool to room temperature, hydrogenation catalyst F-4 after regeneration dipping drop is in enveloping agent solution (by 8
Gram citric acid, which is dissolved in preparing in 50 grams of water, obtains enveloping agent solution) in, then when being warming up to 200 DEG C, constant temperature 4 hours, it is down to room temperature,
Obtain the catalyst F-4 of activation recovering.
The hydrogenation catalyst F- of 100 grams of fresh hydrogenation catalyst F-4A, comparative example 1, embodiment 1-4 activation recovering is taken respectively
4, activity rating is carried out after routinely in-situ presulfurization method is vulcanized again, catalyst process evaluation condition is shown in Table 2, catalyst
Activity Results are shown in Table 3.
2 catalyst process evaluation condition 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 | 1.20 |
| Reaction temperature, DEG C | 360 |
3 hydrotreating catalyst expression activitiy of table
| Number | Refined oil sulfur content, μ g/g | Refined oil nitrogen content, μ g/g |
| Comparative example 1 | 156 | 85 |
| Comparative example 2 | 115 | 73 |
| Embodiment 1 | 109 | 71 |
| Embodiment 2 | 111 | 73 |
| Embodiment 3 | 110 | 75 |
| Embodiment 4 | 105 | 71 |
Note: comparative example 2 is fresh hydrogenation catalyst F-4A.
Activity of hydrocatalyst restoration methods of the present invention, simple process reduce energy consumption, reduce production cost.It can by table 3
It is compared with finding out with existing catalyst regeneration techniques, inactivates hydrogenation catalyst through activity of hydrocatalyst restoration methods of the present invention
The activity of catalyst can effectively be restored after processing, catalyst activity also improves, and reaches fresh catalyst activity level.
Claims (10)
1. a kind of activity of hydrocatalyst restoration methods, it is characterised in that: the following steps are included:
Step (1) mixes inactivation hydrogenation catalyst with acid organic reagent, organic dispersing agent, successively uses that destructive distillation, make charcoal place
Reason regenerates inactivation hydrogenation catalyst；
Hydrogenation catalyst after step (2), regeneration is cooled to 80 DEG C~130 DEG C, carries out impregnation using enveloping agent solution；
Step (3), the hydrogenation catalyst by step (2) impregnation handle 1h~15h at 130 DEG C~220 DEG C, are lived
Property restore hydrogenation catalyst.
2. activity of hydrocatalyst restoration methods according to claim 1, it is characterised in that: in step (1), described adds
Hydrogen catalyst includes carrier, hydrogenation active component and organic additive, and wherein carrier is refractory porous oxide；Hydrogenation active component
For one or more of W, Mo, Ni and Co, hydrogenation active component content is 3wt%~50wt% in terms of oxide；There is machine aided
Agent is at least one of oxygen-containing organic compound, organic compounds containing nitrogen, organic compounds containing sulfur, and organic additive is urged adding hydrogen
Content in agent is 0.2wt%~10wt%.
3. activity of hydrocatalyst restoration methods according to claim 2, it is characterised in that: the refractory porous oxidation
Object is at least one of aluminium oxide, silica, amorphous silica-alumina, titanium oxide, molecular sieve.
4. activity of hydrocatalyst restoration methods according to claim 2, it is characterised in that: organic additive is in hydrogenation catalyst
Content in agent is 0.5wt%~5wt%.
5. activity of hydrocatalyst restoration methods according to claim 1, it is characterised in that: in step (1), the acid
Property organic reagent be sulfur-bearing, nitrogenous or oxygen containing acidic organic compound, acid organic reagent dosage is inactivation hydrogenation catalyst
The 0.01%~5% of weight, preferably 1%~3%；The organic dispersing agent dosage is inactivation hydrogenation catalyst weight
5%~50%, preferably 5%~20%.
6. activity of hydrocatalyst restoration methods according to claim 5, it is characterised in that: the acid organic reagent
For dimethyl disulfide, thioacetic acid, mercaptopropionic acid, dimethyl sulfoxide, amino-nonanoic acid, amion acetic acid, carbamide, antifebrin,
N, N- dihydroxy ethyl aniline, thiocarbamide, semicarbazides, glutamic acid, oxalic acid, malonic acid, tartaric acid, citric acid, ethylene glycol, glycerine,
One or more of tetraethylene glycol, polyethylene glycol；
The organic dispersing agent is sesame oil, safflower seed oil, palm oil, corn oil, cottonseed oil, peanut oil, rapeseed oil, beans
Oil, walnut oil, coconut oil, olive oil, sunflower oil, lard, n-butyl acetate, ethyl acetate, 1,4- butanediol diacrylate
One or more of ester, hexamethylene isopropyl propionate.
7. activity of hydrocatalyst restoration methods according to claim 1, it is characterised in that: in step (1), described is dry
It evaporates to be heat-treated 1~15 hour at 100 DEG C~200 DEG C under the conditions of no oxygen；
Using interim regeneration method, either shallow first is made charcoal 200 DEG C~300 DEG C, constant temperature 2h~8h, is controlled for the processing of making charcoal
Oxygen content is no more than 15%；Then it makes charcoal and rises in 300~400 DEG C of constant temperature, constant temperature 1h~8h, control oxygen content and be no more than
21%；Last depth is made charcoal 400 DEG C~600 DEG C, constant temperature 2h~10h, and control oxygen content is being no more than 35%.
8. according to the method described in claim 1, it is characterized by: in step (1), the destructive distillation are as follows: in the item of no oxygen
Under part, it is heat-treated 3~6 hours at 150~200 DEG C；
The processing of making charcoal are as follows: either shallow is made charcoal 250 DEG C~280 DEG C, constant temperature 3h~6h first, and control oxygen content is no more than
10%；Then it makes charcoal and rises to 350 DEG C~380 DEG C, constant temperature 2h~4h, control oxygen content 15%~21%；Last depth is burnt
450 DEG C~550 DEG C of charcoal, constant temperature 4h~8h, oxygen content is controlled 25%~30%.
9. activity of hydrocatalyst restoration methods according to claim 1, it is characterised in that: in step (2), the network
Mixture is organic compounds containing sulfur, oxygen-containing organic compound or organic compounds containing nitrogen；Amount of complex is inactivation hydrogenation catalyst
The 0.01%~5% of agent weight.
10. activity of hydrocatalyst restoration methods according to claim 1, it is characterised in that: described in step (2)
Organic compounds containing sulfur is one of dimethyl disulfide, thioacetic acid, mercaptopropionic acid, dimethyl sulfoxide, dodecyl mercaptan carbon
Or it is several；The oxygen-containing organic compound be oxalic acid, malonic acid, tartaric acid, citric acid, ethylene glycol, glycerine, tetraethylene glycol,
One or more of polyethylene glycol, glucose, fructose, lactose, maltose, sucrose；The organic compounds containing nitrogen is hydrocarbon
One or more of base amine substance, hydramine substance, amino acids substance, organic ammonium salt substance, amide substance, it is excellent
It is selected as ethylenediamine, ethanol amine, diethanol amine, triethanolamine, diisopropanolamine (DIPA), tert-butylamine, lauryl amine, trioctylamine, three isopropyl acids
Ammonium, N, N- diethyl ethylene diamine, amino-nonanoic acid, amion acetic acid, carbamide, antifebrin, N, N- dihydroxy ethyl aniline, thiocarbamide,
One or more of semicarbazides, glutamic acid, rhodan ammonium.
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| CN112746170A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Treatment process of deactivated hydrogenation catalyst containing molecular sieve carrier |
| CN112746172A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Treatment method of deactivated hydrogenation catalyst |
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| CN110204447B (en) * | 2019-05-31 | 2022-04-22 | 万华化学集团股份有限公司 | Regeneration method of catalyst in continuous production process of 4, 4' -diaminodicyclohexyl methane |
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| CN112746170B (en) * | 2019-10-29 | 2023-01-10 | 中国石油化工股份有限公司 | Treatment process of deactivated hydrogenation catalyst containing molecular sieve carrier |
| CN112746170A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Treatment process of deactivated hydrogenation catalyst containing molecular sieve carrier |
| CN112746172A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Treatment method of deactivated hydrogenation catalyst |
| CN112746172B (en) * | 2019-10-29 | 2023-01-10 | 中国石油化工股份有限公司 | Treatment method of deactivated hydrogenation catalyst |
| CN111068686A (en) * | 2019-12-31 | 2020-04-28 | 山东金滢新材料有限公司 | Method for preparing nickel-based catalyst from residual oil hydrogenation deactivated catalyst |
| CN111068686B (en) * | 2019-12-31 | 2020-12-29 | 山东金滢新材料有限公司 | Method for preparing nickel-based catalyst from residual oil hydrogenation deactivated catalyst |
| CN113976143A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Regeneration method of deactivated hydrogenation catalyst containing iron deposition |
| CN113976143B (en) * | 2020-07-27 | 2023-07-28 | 中国石油化工股份有限公司 | Regeneration method of iron-containing deposition deactivated hydrogenation catalyst |
| CN112337501A (en) * | 2020-10-28 | 2021-02-09 | 中海油天津化工研究设计院有限公司 | Preparation method of vulcanization type regenerated hydrogenation catalyst |
| CN114377692A (en) * | 2021-12-21 | 2022-04-22 | 中海油天津化工研究设计院有限公司 | Regeneration method for treating hydrogenation catalyst iron poisoning |
| CN115957829A (en) * | 2022-12-26 | 2023-04-14 | 本源精化环保科技有限公司 | Regeneration method of supported catalyst for hydrogenation reduction |
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