CN1768954A - Method for reproducing deactivation catalyst of carbon deposit - Google Patents
Method for reproducing deactivation catalyst of carbon deposit Download PDFInfo
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- CN1768954A CN1768954A CN 200410050722 CN200410050722A CN1768954A CN 1768954 A CN1768954 A CN 1768954A CN 200410050722 CN200410050722 CN 200410050722 CN 200410050722 A CN200410050722 A CN 200410050722A CN 1768954 A CN1768954 A CN 1768954A
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Abstract
The invention discloses a method for regenerating the carbon-accumulated inactive catalyst. The invention first uses organic solution to treat the carbon-accumulated inactive catalyst, then processes the regeneration treatment. Said organic solution is formed by at least one of organic alcohol, ester, aether, aromatic hydrocarbons, hydroxybenzene, alcohol amine, alcohol ether, alcohol ester, ketone, organic carboxyl acid, and Dutch liquid. The invention is characterized in that: after the regeneration treatment, processing the organic solution treatment to reduce the contet of accumulated carbon of the catalyst, especially the content of amorphous accumulated carbon, to apply the control on the temperature of regeneration, reduce the regeneration time and the bad effect on the property of catalyst caused by the heat emission in the regeneration treatment, to improve the activity of regenerated catalyst. Said treating method can apply the catalyst which has large heat emission in the regeneration treatment, especially for the inactive hydrogenation catalyst which needs oxidizing removing accumulated-carbon method to be regenerated, as hydrogenation refined catalyst, hydrogenation crack catalyst and the residual oil hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of renovation process of coking deactivation catalyst, particularly the renovation process of coking deactivation 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 decaying catalysts 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 the decaying 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 performance of catalyst is caused negative effect.
But in existing relevant decaying catalyst Recycling Patents, most of patents consider emphatically how to prevent that decaying catalyst from concentrating or the problem of excessive exotherms in regenerative process.As patent USP5,037,785 suggestion is under oxygen containing gas, and the method that adopts the laser irradiation is to the catalyst decoking; Patent USP4,202,865 suggestions are annotated oxygen with batch (-type); Patent USP4,780,195 and USP4,417,975 grades think that then adding a certain amount of water in atmosphere prevents sintering of catalyst etc.Relevant then rare by the patent of the inactivation carbon deposited catalyst being handled the too much problem of heat release when solving decaying catalyst regeneration.
Patent USP5 was once arranged, and 916,835 pairs of heterogeneous decaying catalysts of titaniferous that are used for epoxidation of ethylene adopt materials such as water, alcohol, ester, nitrile, ether, aromatic hydrocarbons, ketone to handle, and have 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 renovation process of coking deactivation catalyst.This method can reduce the thermal discharge of catalyst in the coke-burning regeneration process, has improved the activity of regenerated catalyst.
The renovation process of coking deactivation catalyst of the present invention comprises following process: with organic solution the coking deactivation catalyst is handled earlier, removed its carbon deposit, the processing of regenerating then as far as possible.Contain in alcohol, ester, ether, aromatic hydrocarbons, phenol, hydramine, alcohol ether, alcohol ester, ketone, carboxylic acid and the ethlyene dichloride one or more in this organic solution.
In the described organic solution, 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 ethanol, 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, comprise phenmethylol, phenylpropanol etc.The carbon atom number of ester, ether, aromatic hydrocarbons, phenol, hydramine, alcohol ether, alcohol ester, ketone, carboxylic acid is selected from respectively from forming the needed carbon atom of simple structure to C
14, be preferably C
12Below in one or more, wherein contain straight chain, side chain and cycloalkane compound, comprise simple function group, two functional group's classes etc., as Ethyl formate, butyl butyrate, diisobutyl ether, glycol dimethyl ether, tert-butyl benzene, butyl benzene, propylene glycol ester, butylphenol, nonanone, 2,3-pentanedione, ethanedioic acid, propylene glycol carbonate, butyric acid, succinic acid, ethyl pelargonate, monoethanolamine, ethylene glycol monobutyl ether etc.Ethlyene dichloride comprises tetrachloro-ethylene, trichloro-ethylene, dichloroethylene etc.When selecting above-mentioned organic solution, can select in the above-claimed cpd one or more arbitrarily, be preferably type to each compound, carbon chain lengths, functional group what etc. carry out reasonably combined, make the purpose that dissimilar carbon deposits remove on the catalyst such as selecting inhomogeneity compound, the compound of different carbon chain lengths and/or the compound of different functional groups, reaching.In the organic solution of the present invention, select organic matter nontoxic or that toxicity is less as far as possible.
For when reducing cost, guarantee regeneration effect, in the described organic solution, preferably contain benzene and/or ethanol.
In addition, also lower-cost gasoline and/or kerosene can be joined in the described organic solution.
In the described organic solution, the content of benzene, ethanol, gasoline and kerosene accounts for 0%～98% of total organic solution volume, and more preferably 20～98%, be preferably 80～95%, the content of other organic compounds accounts for 2%～100% of total organic solution volume, and more preferably 2～80%, be preferably 5～20%.In the described organic solution in containing benzene, ethanol, gasoline and kerosene one or more, preferably also contain other organic compounds, as in alcohol (except that ethanol), ester, ether, aromatic hydrocarbons (except that benzene), phenol, hydramine, alcohol ether, alcohol ester, ketone, carboxylic acid and the ethlyene dichloride one or more.Like this, not only can make the cost of organic solution lower, and it is also fine to remove the effect of carbon deposit.
The generation of catalyst surface carbon deposit is the chemical process of a complexity, and 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 the carbon deposit of class graphite shape structure, have attached to catalyst surface, that also have relatively poor with binding ability catalyst, these carbon deposits are amorphous carbon deposit, can before regeneration, make it to remove, can reach the purpose of carbon deposit content on effective reduction decaying catalyst like this by organic solution processing of the present invention.
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 before decaying catalyst regeneration, handle with organic solution earlier, can make bond fission between catalyst-carbon deposit, can reduce the carbon deposit content on the decaying catalyst significantly, temperature when helping controlling its regeneration, the negative effect that excessive exotherms causes catalyst performance when preventing to regenerate has also reduced the recovery time simultaneously, improves the efficient of catalyst regeneration.
In the present invention, employed solvent 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 catalyst of heat release when processing method of the present invention is applicable to regeneration is specially adapted to the inactivation hydrogenation catalyst that needs employing oxidation burn off carbon deposit method to regenerate.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 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.
In the present invention, decaying catalyst can be placed in any suitable reactor it is handled.
Among the present invention, the coking deactivation catalyst is handled, meaned in the presence of organic solution the processing method of coking deactivation catalyst is combined for soaking, distill and adding one or more that pine for, be preferably and soak and method that distillation combines.Infusion method is there be not the coking deactivation beds to put for a long time with solution, and the time is more than the 2h, to be preferably 10-20h.The way of distillation is that solution temperature is raised to its azeotropic temperature, with solution vapor catalyst is carried out decatize, and the time is more than the 1h, to be preferably 1.5-5h.Heating is meant that the 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 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 the most frequently used to decaying catalyst.Wherein can select a kind of four step method of reproduction, concrete steps are as follows: the catalyst that will the handle regenerating unit of packing at first, first usefulness inert gas is (as N
2, Ar etc.) device is replaced, then oxygen content is transferred to 0.5v%～10.0v%, be preferably 1.0v%～5.0v%, catalyst is carried out the substep coke-burning regeneration.Generally can divide four-stage to regenerate, the major control condition in each stage is as follows, first section: at 100～140 ℃, be preferably 110～120 ℃, constant temperature 1～3h; Second section:, be preferably 170～220 ℃, constant temperature 1～3h at 150～240 ℃; The 3rd section:, be preferably 260～320 ℃, constant temperature 1～2h at 250～350 ℃; The 4th section:, be preferably 480～510 ℃, constant temperature 2～4h at 450～550 ℃.
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 determined at and carry out on the D/max2500 type X-ray diffractometer that Japanese 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 575ml organic solution (wherein the volume ratio of ethanol and benzene is 1: 1, and the concrete consumption of each solvent sees Table 1) to the 100ml hydrofinishing MoNiP/Al behind the industrial operation
2O
3Decaying catalyst (be numbered A, carbon deposit content is 10.21wt%) is handled respectively, and the catalyst after the processing continues distillation 30min 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 hydrofinishing MoNiP/Al
2O
3The result of variations of decaying catalyst carbon deposit content after organic solution is handled
| Organic solution is formed | Treatment conditions | Residue carbon deposit content, wt% | Thermogravimetric result: account for the content of residue carbon deposit, wt% | ||
| Amorphous | Class graphite shape | ||||
| 575ml ethanol and benzene | - | Distillation 2h | 9.87 | 54 | 46 |
| 489ml ethanol and benzene | The 86ml butyl butyrate | 7.65 | 40 | 60 | |
| 489ml ethanol and benzene | The 86ml diisobutyl ether | 7.23 | 37 | 63 | |
| 489ml ethanol and benzene | The 86ml butanone | 7.46 | 39 | 61 | |
| 575ml ethanol and benzene | - | Soak 16h, redistillation 2h | 9.45 | 52 | 48 |
| 489ml ethanol and benzene | The 86ml glycol dimethyl ether | 7.25 | 37 | 63 | |
| 489ml ethanol and benzene | The 86ml cyclohexanol | 6.93 | 35 | 65 | |
| 489ml ethanol and benzene | The 86ml monoethanolamine | 7.12 | 36 | 64 | |
In the carbon deposit on this Hydrobon catalyst, the shared large percentage of class graphite shape carbon deposit, this part carbon deposit is difficult to be removed.As can be seen from Table 1, the adding of organic solution can reach the effect that reduces catalyst surface carbon deposit (and hydrocarbon).Adding the carbon deposit that removes after the organic solution mainly is impalpable structure.Add the kind difference of organic solution, will influence the efficient that carbon deposit removes.In addition, the immersion of certain hour may be softening with the carbon deposit on the catalyst, removes the better effects if of carbon deposit.
Above-mentioned 500ml inactivation Hydrobon catalyst A 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 220 ℃ of constant temperature 1h; At 320 ℃ of constant temperature 1h; At 500 ℃ of constant temperature 4h.The 15ml catalyst of so regeneration is packed in the microreactor, carries out activity rating by following condition:
Feedstock oil: 950ppm 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 185ppm in the oil sample of processing back.
Above-mentioned 500ml inactivation hydrofinishing A is packed in the flask, add 500ml ethanol, 500ml benzene and 175ml cyclohexanol, redistillation 2h behind the immersion 16h adopts with inactivation Hydrobon catalyst A the same terms then and regenerates and activity rating, found that nitrogen content is 152ppm in the oil sample.
This explanation adopts organic solution that decaying catalyst is handled, and can improve the activity of regeneration rear catalyst.
Embodiment 2
In the flask of 1000ml, add variety classes organic solution (total amount is 575ml, and wherein monoethanolamine accounts for the 15v% of total amount) to the 100ml residuum hydrodesulfurization MoNi/Al behind the industrial operation
2O
3Decaying catalyst (be numbered B, carbon deposit content is 8.55wt%) is handled respectively, and the catalyst after the processing continues to handle 30min 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 2.
Table 2 residuum hydrodesulfurization MoNi/Al
2O
3The result of variations of decaying catalyst carbon deposit content after organic solution is handled
| Organic solution is formed | Treatment conditions | Residue carbon deposit content, wt% | Thermogravimetric result: account for the content of residue carbon deposit, wt% | ||
| Amorphous | Class graphite shape | ||||
| 489ml ethanol | The 86ml monoethanolamine | Distillation 2h | 7.12 | 68 | 32 |
| 489ml benzene | The 86ml monoethanolamine | 7.35 | 69 | 31 | |
| 489ml ethanol: benzene=1: 1 (v%) | The 86ml monoethanolamine | 6.95 | 67 | 33 | |
| 489ml gasoline | The 86ml monoethanolamine | Soak 2h | 7.54 | 70 | 30 |
| 489ml kerosene | The 86ml monoethanolamine | 7.36 | 69 | 31 | |
| 489ml gasoline: kerosene=1: 1 (v%) | The 86ml monoethanolamine | 7.01 | 68 | 32 | |
As can be seen from Table 2, use different solvents, adopt different treatment conditions, under the situation that organic solution exists, all can reach the purpose that carbon deposit in the carbon deposited catalyst (especially amorphous carbon deposit) is reduced.
Certainly, owing to the solvent that uses, the treatment conditions difference of employing, treatment effect is also variant.
Embodiment 3
In the flask of 1000ml, add the 575ml organic solution (mixed solution that contains gasoline, hexylene glycol, ethanedioic acid and Ethyl formate, wherein the volume ratio of hexylene glycol, ethanedioic acid and Ethyl formate is 1: 1: 1) the 100ml deactivated commercial hydrocracking catalysts behind the industrial operation (is numbered C, carbon deposit content is 9.96wt%) handle respectively, catalyst after the processing continues distillation 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 hydrocracking WNi/Al
2O
3The result of variations of+USY decaying catalyst carbon deposit content after organic solution is handled
| Organic solution is formed | Treatment conditions | Residue carbon deposit content, wt% | Thermogravimetric result: account for the content of residue carbon deposit, wt% | ||
| Gasoline, ml | Hexylene glycol, ethanedioic acid and Ethyl formate (1: 1: 1), ml | ||||
| Amorphous | Class graphite shape | ||||
| 575.00 | - | Distillation 2h | 9.27 | 48 | 52 |
| 563.50 | 11.50 | 8.84 | 45 | 55 | |
| 546.25 | 28.75 | 7.85 | 39 | 61 | |
| 488.75 | 86.25 | 7.45 | 35 | 65 | |
| 460.00 | 115.00 | 7.23 | 33 | 67 | |
| 345.00 | 230.00 | 7.15 | 33 | 67 | |
| 230.00 | 345.00 | 7.08 | 32 | 68 | |
| 115.00 | 460.00 | 6.94 | 31 | 69 | |
| - | 575.00 | 6.82 | 31 | 69 | |
Embodiment 4
Adding 575ml organic solution (specifically composition and content see Table 4) in the flask of 1000ml handles respectively the 100ml deactivated commercial hydrocracking catalysts C behind the industrial operation, catalyst after the processing continues distillation 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 4.
Table 4 hydrocracking WNi/Al
2O
3The result of variations of+USY decaying catalyst carbon deposit content after organic solution is handled
| Organic solution is formed | Treatment conditions | Residue carbon deposit content, wt% | Thermogravimetric result: account for the content of residue carbon deposit, wt% | ||
| Benzene and ethanol (volume ratio is 1: 1), ml | Propylene-glycol ethyl ether, propylene glycol carbonate and ethlyene dichloride (volume ratio is 1: 1: 1), ml | ||||
| Amorphous | Class graphite shape | ||||
| 575.00 | - | Heating 2h | 9.04 | 46 | 54 |
| 563.50 | 11.50 | 8.44 | 42 | 58 | |
| 546.25 | 28.75 | 7.32 | 33 | 67 | |
| 488.75 | 86.25 | 6.97 | 30 | 70 | |
| 460.00 | 115.00 | 6.75 | 27 | 73 | |
| 345.00 | 230.00 | 6.63 | 26 | 74 | |
| 230.00 | 345.00 | 6.55 | 26 | 74 | |
| 115.00 | 460.00 | 6.45 | 24 | 76 | |
| - | 575.00 | 6.45 | 24 | 76 | |
From table 3 and table 4 as can be seen, the content of gasoline in the organic solution (or benzene and alcohol mixture) is different, and the removal efficiency of carbon deposit is also different on the catalyst.Along with the minimizing of gasoline (or benzene and alcohol mixture) content, treatment effect strengthens.But gasoline (or benzene and alcohol mixture) adds too many, and the carbon deposit that can remove can not remove fully, addition very little, too big variation does not take place in the carbon deposit removal efficiency along with the minimizing of its addition.
This shows, from effect of the present invention and regeneration originally, in the organic solution in gasoline, kerosene, benzene, the ethanol one or more content be preferably between the 80-95v%, the content of other organic compounds is 5-20v%.
Embodiment 5
Above-mentioned 200ml deactivated commercial hydrocracking catalysts C 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 5.0v%, 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 2h; At 300 ℃ of constant temperature 1.5h; At 500 ℃ of constant temperature 3h, obtain catalyst C1.Carry out X-ray diffraction (XRD) analysis then, the results are shown in Table 5.
Above-mentioned 200ml deactivated commercial hydrocracking catalysts C is packed in the flask, add 600ml gasoline, 100ml hexylene glycol, 100ml ethanedioic acid and 100ml Ethyl formate, distillation 2h obtains catalyst C2.Carry out XRD analysis then, the results are shown in Table 5.
The XRD analysis result of table 5 catalyst C1 and C2
| The catalyst numbering | Crystalline phase | The Y zeolite relative crystallinity, % |
| C1 | γ-Al 2O 3, Y zeolite, a large amount of NiWO 4、 WO 3、W 19O 55Isoreactivity accumulation of metal thing | 100 |
| C2 | γ-Al 2O 3, Y zeolite, minor N iWO 4 | 131 |
The Y zeolite relative crystallinity is that the degree of crystallinity with Y zeolite among the catalyst C1 is 100% in the table 5, and the degree of crystallinity of Y zeolite is the degree of crystallinity of Y zeolite among the relative catalyst C1 among the catalyst C2.
As can be seen from Table 5, the catalyst of handling through organic solution after the regeneration, obviously makes the gathering of reactive metal on the catalyst reduce, and the degree of crystallinity that makes Y zeolite is than the regenerated catalyst height after organic solution processing of the present invention.This has considerable meaning to the activity that keeps regenerated catalyst.
Embodiment 6
In the flask of 1000ml, add 575ml organic solution (its concrete composition and consumption see Table 6) to the 100ml residuum hydrogenating and metal-eliminating MoNi/Al behind the industrial operation
2O
3Decaying catalyst (be numbered D, carbon deposit content is 15.93wt%) is handled respectively, and the catalyst after the processing continues distillation 30min 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 6.
Table 6 residuum hydrogenating and metal-eliminating MoNi/Al
2O
3The result of variations of decaying catalyst carbon deposit content after distillation is handled
| Organic solution is formed | Treatment conditions | Residue carbon deposit content, wt% | Thermogravimetric result: account for the content of residue carbon deposit, wt% | ||
| Amorphous | Class graphite shape | ||||
| 575ml gasoline: kerosene=1: 1 (v%) | - | Soak 16h, redistillation 2h | 11.25 | 65 | 35 |
| 489ml gasoline: kerosene=1: 1 (v%) | The 86ml ethyl butyrate | 9.24 | 57 | 43 | |
| 489ml gasoline: kerosene=1: 1 (v%) | 43ml ethyl butyrate 43ml phenol | 8.35 | 54 | 46 | |
| 489ml gasoline: kerosene=1: 1 (v%) | The positive valeric acid of 29ml ethyl butyrate 29ml phenol 28ml | 8.26 | 52 | 48 | |
As can be seen from Table 6, the composition difference of organic solution, the removal efficiency of carbon deposit is also different on the catalyst.Add multiple organic compound simultaneously and will help removing of carbon deposit.In real work, can adjust, to reach best result of use the kind and the relative amount of the organic solution that adds.
Above-mentioned 100ml inactivation residual oil hydrocatalyst D is carried out differential scanning calorimetric (DSC) analyze, the results are shown in Table 7.
Above-mentioned 100ml inactivation residual oil hydrocatalyst D is packed in the flask, add 250ml gasoline, 250ml kerosene, 25ml ethyl butyrate, 25ml phenol and the positive valeric acid of 25ml, soak redistillation 2h behind the 16h, obtain catalyst D1.Carry out dsc analysis then, the results are shown in Table 7.
The DSC result of table 7 catalyst D and D1
| The catalyst numbering | D | D1 |
| The heat release summit temperature, ℃ | 240 360 527 | 215 330 517 |
| The exothermic peak area, W/g | 0.33 0.65 0.44 | 0.16 0.56 0.40 |
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 unformed carbon deposit, 450-550 ℃ peak then is the heat release of graphite mould 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 7, through the catalyst D1 that organic solution is handled, the heat release when regeneration, the heat release of especially unformed class carbon deposit obviously reduces.This just means that D1 can reduce constant temperature time in low-temperature zone when regeneration, thereby accelerates the reproduction speed of catalyst.
Claims (17)
1, a kind of renovation process of coking deactivation catalyst comprises regeneration process, it is characterized in that: the coking deactivation catalyst is handled the processing of regenerating then with organic solution earlier; Described organic solution contains one or more in alcohol, ester, ether, aromatic hydrocarbons, phenol, hydramine, alcohol ether, alcohol ester, ketone, carboxylic acid and the ethlyene dichloride.
2,, it is characterized in that in the described organic solution that alcohol is fatty alcohol and/or aralkyl alcohol according to the described renovation process of claim 1; 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 respectively
14Below in one or more, wherein contain straight chain, side chain and cycloalkane compound, ethlyene dichloride is selected from one or more in tetrachloro-ethylene, trichloro-ethylene and the dichloroethylene.
3,, it is characterized in that in the described organic solution that it is C that described fatty alcohol is selected from carbon atom number according to the described renovation process of claim 1
2-C
10In one or more; It is C that described aralkyl alcohol is selected from carbon atom number
7-C
12In one or more; It is C that ester, ether, aromatic hydrocarbons, phenol, hydramine, alcohol ether, alcohol ester, ketone, carboxylic acid are selected from carbon atom number respectively
12Below in one or more.
4,, it is characterized in that in the described organic solution, described fatty alcohol is selected from one or more in ethanol, n-hexyl alcohol, isohexyl alcohol, cyclohexanol and the hexylene glycol according to the described renovation process of claim 1; Described aralkyl alcohol is selected from phenmethylol and phenylpropanol etc.; Ester, ether, aromatic hydrocarbons, phenol, hydramine, alcohol ether, alcohol ester, ketone and carboxylic acid are selected from Ethyl formate, butyl butyrate, diisobutyl ether, glycol dimethyl ether, tert-butyl benzene, butyl benzene, propylene glycol ester, butylphenol, nonanone, 2, one or more in 3-pentanedione, ethanedioic acid, propylene glycol carbonate, butyric acid, succinic acid, ethyl pelargonate, monoethanolamine, the ethylene glycol monobutyl ether.
5,, it is characterized in that containing in the described organic solution benzene and/or ethanol according to the described renovation process of claim 1.
6,, it is characterized in that containing in the described organic solution gasoline and/or kerosene according to the arbitrary described renovation process of claim 1～5.
7,, it is characterized in that in the described organic solution, the content of benzene, ethanol, gasoline and kerosene accounts for 20%～98% of total organic solution volume according to the described renovation process of claim 6.
8,, it is characterized in that in the described organic solution, the content of benzene, ethanol, gasoline and kerosene accounts for 80～95% of total organic solution volume according to the described renovation process of claim 7.
9,, it is characterized in that containing in the described organic solution compound of inhomogeneity compound, different carbon chain lengths and/or the compound of different functional groups according to the described renovation process of claim 1.
10,, it is characterized in that described coking deactivation catalyst is a hydrogenation catalyst according to the described processing method of claim 1.
11,, it is characterized in that described hydrogenation catalyst is Hydrobon catalyst, hydrocracking catalyst or catalyst for hydrotreatment of residual oil according to the described processing method of claim 10.
12,, it is characterized in that described processing method is to soak, distill and add one or more that pine for according to the described processing method of claim 1.
13,, it is characterized in that described processing method is the method for soaking and distillation combines according to the described processing method of claim 1.
According to claim 12 or 13 described processing methods, it is characterized in that in the described infusion method that 14, soak time is 2-20h; In the described way of distillation, the processing time is 1-5h; In the described heating, temperature is controlled at and is lower than azeotropic temperature, and the processing time is 1-5h.
15,, it is characterized in that in the described infusion method that soak time is 10-20h according to the described processing method of claim 14; In the described way of distillation, the processing time is 1.5-5h; In the described heating, temperature is controlled at and is lower than azeotropic temperature 10-50 ℃, and the processing time is 3-5h.
16, according to the described processing method of claim 1, it is characterized in that described regenerative process is specific as follows: the catalyst that organic solution the was handled regenerating unit of packing at first, with inert gas device is replaced, then oxygen content is transferred to 0.5v%～10.0v%, decaying catalyst is carried out the substep coke-burning regeneration, and described substep coke-burning regeneration divides four-stage to carry out, and the major control condition in each stage is as follows, first section: at 100～140 ℃, constant temperature 1～3h; Second section: at 150～240 ℃, constant temperature 1～3h; The 3rd section: at 250～350 ℃, constant temperature 1～2h; The 4th section: at 450～550 ℃, constant temperature 2～4h.
17, according to the described processing method of claim 16, it is characterized in that in the described regenerative process that the substep coke-burning regeneration divides four-stage to carry out, the major control condition in each stage is as follows: first section temperature is 110～120 ℃; Second section temperature is 170～220 ℃; The 3rd section temperature is 260～320 ℃; The 4th section temperature is 480～510 ℃.
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| CN1195583C (en) * | 2002-10-10 | 2005-04-06 | 中国石油化工股份有限公司 | Catalyst reactivating method |
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