CN100340342C - Carbon deposit cleaning agent and its application in reproduction of carbon deposit deactivation catalyst - Google Patents
Carbon deposit cleaning agent and its application in reproduction of carbon deposit deactivation catalyst Download PDFInfo
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- CN100340342C CN100340342C CNB2004100507243A CN200410050724A CN100340342C CN 100340342 C CN100340342 C CN 100340342C CN B2004100507243 A CNB2004100507243 A CN B2004100507243A CN 200410050724 A CN200410050724 A CN 200410050724A CN 100340342 C CN100340342 C CN 100340342C
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Abstract
The present invention discloses a carbon deposit cleaning agent and an application thereof in the regeneration process of deactivated catalysts. The carbon deposit cleaning agent comprises the following components: 5 to 95v% of ethyl acetate, 5 to 95v% of acetone, 0 to 90v% of butanol and 0 to 90v% of ethanol. The carbon deposit cleaning agent of the present invention is used for processing the deactivated catalysts to be generated and then regenerated. Carbon deposit content on the deactivated catalysts can be greatly reduced, and the present invention is favorable for controlling the temperature of the regeneration of the deactivated catalysts, reducing the influence on catalyst performance and increasing the activity of the regenerated catalysts. The carbon deposit cleaning agent of the present invention is suitable for catalysts with obvious heat release in regeneration and especially suitable for deactivated hydrogenation catalysts and methane aromatization catalysts requiring an oxidation carbon deposit burning method.
Description
Technical field
The present invention relates to a kind of carbon deposit cleaner and the application in the decaying catalyst regenerative process thereof, be specially adapted to the regeneration of inactivation hydrogenation catalyst.
Background technology
Loss is active gradually in the long-term operation process for the catalyst that the oil-refining chemical process is used, and tracing it to its cause is owing to the deposition of carbon deposit at catalyst surface causes to a great extent.These coking deactivation catalyst are by the regeneration of oxidation burn off carbon deposit, and activity can partially or completely be restored, and still can continue to use in industrial production.The catalyst that has even the use of can repeatedly regenerating have reached energy savings, increase the purpose of benefit.
During coking deactivation catalyst coke-burning regeneration, carbon deposit will react with oxygen and be removed, and produce a large amount of heat simultaneously.If heat release too much or too concentrated, atmosphere can't be taken away the heat that produces, and will cause the mistake thermal response of catalyst, causes catalyst property to change, and the character of catalyst is caused negative effect.
But in existing relevant coking deactivation catalyst regeneration patent, most of patents consider emphatically how to prevent that decaying catalyst from concentrating or the problem of excessive exotherms in regenerative process.As USP 5,037,785 suggestions are under oxygen containing gas, and the method that adopts the laser irradiation is to the catalyst decoking; USP 4,202, and 865 suggestions are annotated oxygen with batch (-type); USP 4,780,195 and USP 4,417,975 grades think then that in atmosphere adding a certain amount of water prevents sintering of catalyst etc.The patent of the relevant too much problem of heat release by the coking deactivation catalyst treatment being solved decaying catalyst when regeneration is then rare.
Once the heterogeneous decaying catalyst of titaniferous that had 5,916,835 couples of patent USP to be used for epoxidation of ethylene adopts materials such as water, alcohol, ester, nitrile, ether, aromatic hydrocarbons, ketone to handle, and has reached the purpose of recovering catalyst activity.The non-molecular sieve Ti-Si catalyst that this patent is related, in epoxidation of ethylene process (approximately 100-200 ℃ and 10-500 pound/square inch), usually generate two in the ethylene oligomerization course of reaction, trimer or with oxide generation two, three polyethers.Because their molecule is bigger, the diffusion rate in the catalyst duct is slower, easily blocks the duct, and reactant can't be arrived on the active sites, causes catalyst activity reduction.Used catalyst is handled through materials such as moisture, pure, ester, nitrile, ether, aromatic hydrocarbons, ketone, and most of activity of catalyst is restored.But because of the reason of the titaniferous heterogeneous catalyst inactivation that is used for epoxidation of ethylene in the catalyst of coking deactivation and the above-mentioned patent is obviously different, so the reaction principle of said method can't be applied to catalyst because of coking deactivation.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of carbon deposit cleaner and the application in the decaying catalyst regenerative process thereof, be specially adapted to the regeneration of inactivation hydrogenation catalyst.After this carbon deposit cleaner is handled, can reduce catalyst liberated heat in the coke-burning regeneration process, improve the activity of regenerated catalyst.
Carbon deposit cleaner of the present invention comprises following component:
Ethyl acetate 5-95v% is preferably 5-20v%;
Acetone 5-95v% is preferably 5-30v%;
Ethanol 0-90v% is preferably 5-85v%;
Benzene 0-90v% is preferably 5-85v%;
The total volume percent of wherein said ethyl acetate, acetone, ethanol, benzene is 100%.
When adopting ethyl acetate and acetone in the above-mentioned carbon deposit cleaner, have the ability that reduces carbon deposit content in the decaying catalyst admirably, but consider that the cost of ethyl acetate and acetone, especially ethyl acetate is higher.In order to reduce the cost of carbon deposit cleaner, in the carbon deposit cleaner of the present invention except containing lower-cost ethanol and benzene, also can add gasoline, kerosene or its mixture, the content of gasoline and kerosene is ethyl acetate and acetone cumulative volume 2-20 times, is preferably 5-10 doubly.Employing contains the carbon deposit cleaner of one or more components in benzene, ethanol, gasoline and the kerosene, not only makes the organic solution cost relatively low, reduces regeneration cost, and it is also fine to remove the effect of carbon deposit.
The organic matter that also can contain other in the carbon deposit cleaner of the present invention, be selected from organic alcohol, ester, ether, aromatic hydrocarbons, phenol, hydramine, alcohol ether, alcohol ester, ketone, carboxylic acid and the ethlyene dichloride one or more, its content is ethyl acetate and acetone volume 0.5-5 times, is preferably 1-3 doubly.
Described organic alcohol can be fatty alcohol, also can be aralkyl alcohol.It is C that described fatty alcohol is selected from carbon atom number
1-C
12, be preferably C
2-C
10In one or more, wherein contain the alcohols of straight chain, side chain and band, comprise single alcohol, glycol etc., as n-hexyl alcohol, isohexyl alcohol, cyclohexanol, hexylene glycol etc.; It is C that described aralkyl alcohol is selected from carbon atom number
7-C
14, be preferably C
7-C
12In one or more, as phenmethylol, phenylpropanol etc.Ester, ether, aromatic hydrocarbons, phenol, hydramine, alcohol ether, alcohol ester, ketone and carboxylic acid are selected from carbon atom number for from forming the needed carbon number of simple structure to C
14(be C
14Below), be preferably C
12Below in one or more, the hydrocarbon compound of wherein containing straight chain, side chain and band, comprise simple function group, two functional group's classes etc., as butyl butyrate, diisobutyl ether, glycol dimethyl ether, butyl benzene, butylphenol, butanone, 2,3-pentanedione, butyric acid, succinic acid monoethanolamine, ethylene glycol monobutyl ether etc.Ethlyene dichloride comprises tetrachloro-ethylene, trichloro-ethylene, dichloroethylene etc.
The application of carbon deposit cleaner of the present invention in the coking deactivation catalyst regeneration process comprises following process: the coking deactivation catalyst is handled with above-mentioned carbon deposit cleaner earlier, removes its carbon deposit as far as possible, and then regenerates.
Among the present invention, decaying catalyst is handled, can be adopted in infusion method, the way of distillation and the heating one or more with carbon deposit cleaner.Infusion method is there be not the inactivation beds to put for a long time with above-mentioned carbon deposit cleaner, and the time is more than the 2h, to be preferably 2～20h, is preferably 10-20h.The way of distillation is that above-mentioned carbon deposit cleaner temperature is raised to its azeotropic temperature, with its steam decaying catalyst is carried out decatize, and the time is more than the 1h, to be preferably 1～5h, is preferably 1.5-5h.Heating is meant that the carbon deposit cleaner solution temperature that will soak catalyst is raised to and is higher than room temperature but is lower than azeotropic temperature that solution temperature is preferably and is lower than azeotropic temperature 10-50 ℃, is preferably 20-30 ℃, and the processing time is more than the 1h, to be preferably 1～5h, is preferably 3-5h.
Regenerative process of the present invention can be the regenerative process of conventional coking deactivation catalyst, generally decides on the character of carbon deposit on catalyst property and the catalyst, can adopt multiple renovation process.Adopt under the oxygen-containing atmosphere under different temperatures constant temperature so that regeneration is modal to decaying catalyst.Wherein can select a kind of four step method of reproduction, concrete steps are as follows: elder generation replaces device with inert gas, oxygen content is progressively increased to be 0.5-10.0v% then, is preferably 1.0-5.0v%, and catalyst is carried out the substep coke-burning regeneration.Generally can divide four-stage to regenerate, each stage major control condition is: at 100-140 ℃, constant temperature is 1-3 hour in the time of best 110-120 ℃; At 150-240 ℃, constant temperature is 1-3 hour in the time of best 170-220 ℃; At 250-350 ℃, constant temperature is 1-2 hour in the time of best 260-320 ℃; At 450-550 ℃, constant temperature is 2-4 hour in the time of best 480-510 ℃.
The generation of catalyst surface carbon deposit is the chemical process of a complexity.The composition of carbon deposit depends on the degree of the type of catalyst, the composition that is processed raw material, temperature, process time, carbon deposit and the condition that subsequently carbon deposited catalyst purged etc.As in hydrogenation process, because reaction is carried out under HTHP usually, itself carbon deposit content is higher, and fine and close class graphite shape structure carbon deposit is more in the carbon deposit, so reproduction ratio difficulty, regeneration techniques is also always among continuous research.In the carbon deposit of inactivation hydrogenation catalyst, except class graphite shape structure carbon deposit, have attached to catalyst surface, that also have relatively poor with binding ability catalyst, these carbon deposits are amorphous carbon deposit, can make it before regeneration, to remove by adopting some solvent, can reach the purpose of carbon deposit content on effective reduction decaying catalyst like this.
On structure, the carbon deposit on the decaying catalyst comprises amorphous and class graphite shape two class formations of X ray.Along with the harshness of processing conditions, the shared ratio of class graphite shape structure increases in the carbon deposit.Carry out thermogravimetric when experiment at the simulation regeneration condition and find, the weightlessness of 150-320 ℃ of existence can be used for characterizing what of amorphous carbon deposit, 450-550 ℃ of contribution that then belongs to class graphite shape carbon deposit.By two temperature range weightlessness what, can characterize the variation of different structure coke content on the catalyst.
Characteristics of the present invention are to adopt the carbon deposit cleaner of specific composition to handle decaying catalyst, the processing of regenerating then can reduce the carbon deposit content on the decaying catalyst significantly, the temperature when helping controlling its regeneration, minimizing improves the activity of regenerated catalyst to the influence of catalyst performance.
In the present invention, employed carbon deposit cleaner not only can reduce the carbon deposit on the decaying catalyst, and to catalyst property do not have influence, toxicity is less.
The specific embodiment
The tangible coking deactivation catalyst of heat release when carbon deposit cleaner of the present invention is applicable to regeneration as hydrogenation catalyst and methane aromatization catalyst, is specially adapted to need to adopt the inactivation hydrogenation catalyst of oxidation burn off carbon deposit method regeneration.Hydrogenation catalyst generally is to be carrier with inorganic refractory oxide or inorganic refractory oxide and zeolite, and inorganic refractory oxide generally is selected from aluminium oxide, silica, alumina silicate etc.Reactive metal in the hydrogenation catalyst is selected from one or more in VIB, VIIB, the VIII family metal.The shape of hydrogenation catalyst generally is cylindrical, spherical or leafy shape, and diameter is the 0.5-3.5 millimeter, and length is the 1.5-10.0 millimeter.Hydrogenation catalyst generally is used for the processes such as hydrofinishing, hydrocracking and residual hydrocracking of oil product.
Be described in further detail method of the present invention below by embodiment.
Carbon deposit Determination on content in the embodiment of the invention is to measure on German ELEMENFAV VARIOEL type elemental analyser, and experiment condition is: get 5mg catalyst fines sample at Ar/O
2Be heated to 1100 ℃ under the air-flow, the gas of generation carries out C, S and analyzes.
Amorphous carbon deposit in the embodiment of the invention and class graphite shape carbon deposit Determination on content are to carry out on 951 type thermogravimetric analyzers of du pont company production.Experiment condition is: under the 50ml/min air atmosphere, heat up with 10 ℃/min.
XRD analysis in the embodiment of the invention and relative crystallinity are to carry out on the D/max2500 type X-ray diffractometer that Japan company of science produces, voltage 40kV, electric current 80mA, 6 °/min scanning.
DSC experiment in the embodiment of the invention is to carry out on the DSC951 type DSC instrument that E.I.Du Pont Company produces, and experiment condition is: the 15mg catalyst fines, the speed with 10 ℃/min in the air atmosphere of 30ml/min heats up.
Embodiment 1
In the flask of 1000ml, add carbon deposit cleaner (specifically composition and content see Table 1) to the 100ml inactivation residuum hydrodesulfurization MoNiP/Al behind the industrial operation
2O
3Catalyst (be numbered A, carbon deposit content is 11.45wt%) is handled respectively, and the catalyst after the processing continues to handle with absolute ethyl alcohol, measures the content of amorphous and class graphite shape carbon deposit then with the thermogravimetric instrument, and it the results are shown in Table 1.
Table 1 residuum hydrodesulfurization MoNiP/Al
2O
3Decaying catalyst is the result of variations of carbon deposit content after treatment
| Carbon deposit cleaner is formed | Treatment conditions | Residue carbon deposit content, wt% | Thermogravimetric result: account for the content of residue carbon deposit, wt% | ||
| Amorphous | Class graphite shape | ||||
| - | 431ml kerosene 144ml gasoline | Soak 16h, redistillation 2h | 8.87 | 55 | 45 |
| 25ml benzene 490ml ethanol 30ml acetone 50ml ethyl acetate | - | Directly distill 2h | 7.38 | 43 | 57 |
| 15ml benzene 20ml ethanol 25ml acetone 50ml ethyl acetate | 489ml gasoline | 7.37 | 43 | 57 | |
| 490ml benzene 20ml ethanol 100ml acetone 33ml ethyl acetate | - | Soak 16h, redistillation 2h | 7.50 | 45 | 55 |
| 15ml benzene 20ml ethanol 25ml acetone 50ml ethyl acetate | 600ml kerosene 200ml gasoline | 7.22 | 41 | 59 | |
| 250ml acetone 250ml ethyl acetate 25ml benzene | - | 6.94 | 39 | 61 | |
| 25ml ethanol 150ml acetone 100ml ethyl acetate | - | 7.05 | 40 | 60 | |
| 120ml benzene 120ml ethanol 120ml acetone 120ml ethyl acetate | - | 7.10 | 40 | 60 | |
| 200ml benzene 200ml ethanol 100ml acetone 70ml ethyl acetate | - | 7.15 | 39 | 61 | |
As can be seen from Table 1, compare with the decaying catalyst of only handling with kerosene and gasoline, the coke content of the catalyst of handling with carbon deposit cleaner of the present invention all significantly reduces, and it is fairly obvious that the relative amount of especially amorphous carbon deposit reduces amplitude.
Also can find out from table 1, the higher carbon deposit cleaner better effects if of ethyl acetate content, but exist cost higher, increase the problem of catalyst regeneration cost.Contain a large amount of benzene, ethanol in carbon deposit cleaner, especially when gasoline, kerosene equal solvent, can reduce the cost of regeneration significantly, the cleaning performance of carbon deposit is also fine simultaneously.
Above-mentioned 100ml inactivation residual oil hydrocatalyst A is carried out differential scanning calorimetric (DSC) analyze, the results are shown in Table 2.
Above-mentioned 100ml inactivation residual oil hydrocatalyst A is packed in the flask, add 600ml gasoline, 200ml kerosene, soak redistillation 2h behind the 16h, obtain catalyst A 1.Carry out dsc analysis then, the results are shown in Table 2.
Above-mentioned 100ml inactivation residual oil hydrocatalyst A is packed in the flask, add 600ml gasoline, 200ml kerosene, 15ml benzene, 20ml ethanol, 25ml acetone, the 50ml ethyl acetate soaks redistillation 2h behind the 16h, obtains catalyst A 2.Carry out dsc analysis then, the results are shown in Table 2.
The DSC result of table 2 catalyst A, A1 and A2
| The catalyst numbering | A | A1 | A2 |
| The heat release summit temperature, ℃ | 235 354 509 | 250 325 517 | 218 368 529 |
| The exothermic peak area, W/g | 0.33 0.65 0.44 | 0.31 0.67 0.40 | 0.18 0.60 0.39 |
On the DSC of inactivation hydrogenation catalyst spectrogram, can see the exothermic peak of two kinds of carbon deposits apparent in viewly, 200-280 ℃ heat release is the contribution of amorphous carbon deposit, 450-550 ℃ peak then is the heat release of graphite shape carbon deposit.In addition, the heat release between 300-400 ℃ is the heat release of reactive metal sulphided state.As can be seen from Table 2, the catalyst A 1 that process 600ml gasoline, 200ml kerosene were handled, heat release when regeneration, reduce to some extent than catalyst without this solution-treated, but compare with the catalyst A 2 that adopts carbon deposit cleaner of the present invention to handle, heat release during regeneration, the especially heat release of amorphous-type carbon deposit are obviously still many.Illustrate and adopt carbon deposit cleaner of the present invention that decaying catalyst is handled, can reach the purpose of heat release when reducing decaying catalyst regeneration really.This just means that A2 can reduce constant temperature time in low-temperature zone when regeneration, thereby accelerates the reproduction speed of catalyst.
Embodiment 2
In the flask of 1000ml, add carbon deposit cleaner (specifically composition and content see Table 3) the 100ml Mo/HZSM-5 methane aromatization catalyst behind the industrial operation (is numbered B, carbon deposit content is 10.84wt%) handle respectively, catalyst after the processing continues to handle 30min with absolute ethyl alcohol, measure the content of amorphous and class graphite shape carbon deposit then with the thermogravimetric instrument, it the results are shown in Table 3.
Table 3 methane aromatizing Mo/HZSM-5 catalyst is the result of variations of carbon deposit content after treatment
| Carbon deposit cleaner | Solvent | Treatment conditions | Residue carbon deposit content, wt% | Thermogravimetric result: account for the content of residue carbon deposit, wt% | |
| Amorphous | Class graphite shape | ||||
| - | 431ml kerosene 144ml gasoline | Soak 16h, directly distill 2h | 10.21 | 86 | 14 |
| 15ml benzene 20ml ethanol 25ml acetone 50ml ethyl acetate 10ml monoethanolamine | 489ml kerosene | 8.19 | 82 | 18 | |
| 25ml acetone 50ml ethyl acetate 150ml diisobutyl ether 15ml phenol | 400ml gasoline | Heating 3h | 8.24 | 82 | 18 |
| 250ml benzene 250ml ethanol 25ml acetone 20ml ethyl acetate 30ml diisobutyl ether | - | 8.13 | 81 | 19 | |
As can be seen from Table 3, contain other in the carbon deposit cleaner of the present invention and be selected from least a organic matter in organic alcohol, ester, ether, aromatic hydrocarbons, phenol, hydramine, alcohol ether, alcohol ester, ketone, carboxylic acid and the ethlyene dichloride, more help reducing the carbon deposit on the non-hydrogenation catalyst, especially have special effect removing the impalpable structure carbon deposit.
Above-mentioned 100ml inactivation methane aromatization catalyst B is regenerated in the following ways:
The regenerating unit of at first catalyst being packed into is used N earlier
2Device is replaced, then oxygen content is transferred to 2.0v%, catalyst is carried out the substep coke-burning regeneration.Each stage major control condition is: at 120 ℃, and constant temperature 1h; At 200 ℃ of constant temperature 1h; At 300 ℃ of constant temperature 1h; At 500 ℃ of constant temperature 4h, obtain catalyst B 1.Carry out X-ray diffraction (XRD) analysis then, the results are shown in Table 4.
Above-mentioned 100ml inactivation methane aromatization catalyst B is packed in the flask, add 250ml benzene, 250ml ethanol, 25ml acetone, the 20ml ethyl acetate, the 30ml diisobutyl ether soaks 16h, redistillation 2h, adopt the condition identical to regenerate then with catalyst B 1 after, obtain catalyst B 2.Carry out XRD analysis then, the results are shown in Table 4.
The XRD analysis result of table 4 catalyst B 1 and B2
| The catalyst numbering | Crystalline phase | The type ZSM 5 molecular sieve relative crystallinity, % |
| B1 | MoO 3，ZSM-5 | 100 |
| B2 | ZSM-5 | 106 |
Type ZSM 5 molecular sieve relative crystallinity in the table 4 is that the degree of crystallinity with the type ZSM 5 molecular sieve in the catalyst B 1 is defined as 100%, and the degree of crystallinity of the type ZSM 5 molecular sieve in the catalyst B 2 is the degree of crystallinity of relative catalyst B 1.
As can be seen from Table 4, through containing the decaying catalyst that the carbon deposit cleaner solution-treated is crossed, the gathering of reactive metal does not appear on the regeneration rear catalyst, and it is better that the degree of crystallinity of while type ZSM 5 molecular sieve keeps, illustrate and adopt this method to handle, can reduce the loss in activated centre on the catalyst.This has considerable meaning to the activity that keeps regenerated catalyst.
Embodiment 3
With the 100ml hydrofinishing MoNiP/Al behind the industrial operation
2O
3Decaying catalyst (be numbered C, carbon deposit content is 10.21wt%) is regenerated in the following ways:
The regenerating unit of at first catalyst being packed into is used N earlier
2Device is replaced, then oxygen content is transferred to 2.0v%, catalyst is carried out the substep coke-burning regeneration.Each stage major control condition is: at 120 ℃, and constant temperature 3h; At 200 ℃ of constant temperature 2h; At 300 ℃ of constant temperature 1.5h; At 500 ℃ of constant temperature 3h.
The 15ml catalyst of so regeneration is packed in the microreactor, carries out activity rating by following condition:
Feedstock oil: 950 μ g/g pyridine/lam-oil; Volume space velocity: 2.0h
-1Temperature: 360 ℃: reaction pressure: 4.0MPa; Hydrogen flow rate: 100ml/min.Stablize sample analysis after 12 hours.Nitrogen content is 185 μ g/g in the oil sample of processing back.
Above-mentioned 500ml inactivation Hydrobon catalyst C is packed in the flask, add 250ml benzene, 250ml ethanol, 25ml acetone, the 20ml ethyl acetate, 30ml diisobutyl ether, redistillation 2h behind the immersion 16h, adopt with catalyst C the same terms then and regenerate and activity rating, found that nitrogen content is 137 μ g/g in the oil sample.
This explanation adopts the carbon deposit cleaner that contains ethyl acetate, acetone, ethanol and benzene that decaying catalyst is handled, and can improve the activity of regeneration rear catalyst.
Claims (13)
1, a kind of carbon deposit cleaner comprises following component:
Ethyl acetate 5-95v%;
Acetone 5-95v%;
Ethanol 0-90v%;
Benzene 0-90v%;
The total volume percent of wherein said ethyl acetate, acetone, ethanol, benzene is 100%.
2, according to the described carbon deposit cleaner of claim 1, comprise following component:
Ethyl acetate 5-20v%;
Acetone 5-30v%;
Ethanol 5-85v%;
Benzene 5-85v%;
The total volume percent of wherein said ethyl acetate, acetone, ethanol, benzene is 100%.
3, according to claim 1 or 2 described carbon deposit cleaners, it is characterized in that also containing in the described carbon deposit cleaner gasoline, kerosene or its mixture, its content is ethyl acetate and acetone cumulative volume 2-20 times.
4, according to the described carbon deposit cleaner of claim 3, the content that it is characterized in that described gasoline, kerosene or its mixture is ethyl acetate and acetone cumulative volume 5-10 times.
5, according to the described carbon deposit cleaner of claim 3, it is characterized in that also containing in the described carbon deposit cleaner other organic matters, this organic matter is selected from one or more in organic alcohol, ester, ether, aromatic hydrocarbons, phenol, hydramine, alcohol ether, alcohol ester, ketone, carboxylic acid and the ethlyene dichloride, and its content is ethyl acetate and acetone cumulative volume 0.5-5 times.
6,, it is characterized in that described organic content is ethyl acetate and acetone cumulative volume 1-3 times according to the described carbon deposit cleaner of claim 5.
7,, it is characterized in that described organic alcohol is fatty alcohol and/or aralkyl alcohol according to the described carbon deposit cleaner of claim 5; It is C that described fatty alcohol is selected from carbon atom number
1-C
12In one or more, wherein contain the alcohols of straight chain, side chain and band; It is C that described aralkyl alcohol is selected from carbon atom number
7-C
14In one or more; It is C that ester, ether, aromatic hydrocarbons, phenol, hydramine, alcohol ether, alcohol ester, ketone and carboxylic acid are selected from carbon atom number
14Below in one or more.
8, the application of the arbitrary described carbon deposit cleaner of claim 1～7 in the coking deactivation catalyst regeneration process comprises following process: the coking deactivation catalyst is handled the processing of regenerating then earlier with described carbon deposit cleaner.
9,, it is characterized in that method that carbon deposit cleaner is handled decaying catalyst is selected from one or more in infusion method, the way of distillation and the heating according to the described application of claim 8.
10,, it is characterized in that the method that carbon deposit cleaner is handled decaying catalyst is the method for soaking and distillation combines according to the described application of claim 8.
11,, it is characterized in that in the described infusion method processing time 2h-20h according to the described application of claim 9; In the described way of distillation, the processing time is 1h-5h; In the described heating, the temperature of carbon deposit cleaner is lower than azeotropic temperature, and the processing time is 1h-5h.
12, according to the described application of claim 8, it is characterized in that described regeneration process is as follows: the regenerating unit of packing into of the catalyst after will cleaning with carbon deposit cleaner, with inert gas device is replaced earlier, then oxygen content is progressively increased and be 0.5-10.0v% catalyst to be carried out the substep coke-burning regeneration; Described substep coke-burning regeneration divides four-stage, and each stage major control condition is as follows, first section: constant temperature is 1-3 hour in the time of 100-140 ℃; Second section: constant temperature is 1-3 hour in the time of 150-240 ℃; The 3rd section: constant temperature is 1-2 hour in the time of 250-350 ℃; The 4th section: constant temperature is 2-4 hour in the time of 450-550 ℃.
13,, it is characterized in that described coking deactivation catalyst is hydrogenation catalyst or methane aromatization catalyst according to the described application of claim 8.
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