CN104588038B - A kind of renovation process inactivating heavy oil hydrogenating treatment catalyst - Google Patents
A kind of renovation process inactivating heavy oil hydrogenating treatment catalyst Download PDFInfo
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- CN104588038B CN104588038B CN201310532049.7A CN201310532049A CN104588038B CN 104588038 B CN104588038 B CN 104588038B CN 201310532049 A CN201310532049 A CN 201310532049A CN 104588038 B CN104588038 B CN 104588038B
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Abstract
The invention discloses a kind of renovation process inactivating heavy oil hydrogenating treatment catalyst.The method includes: is placed in by inactivation heavy oil hydrogenating treatment catalyst in supercritical fluid system response device, makes mixed liquor and supercritical fluid CO with organic solvent, dispersant and organic acid2In the presence of heavy oil hydrogenating treatment catalyst is processed, then hydrothermal treatment, the catalyst after being regenerated.The method is produced the problem of a large amount of pollution when being and not only solve decaying catalyst regeneration, and makes the mechanical performance of catalyst and hydrogenation activity well be recovered, and technology is easily implemented.
Description
Technical field
The present invention relates to a kind of renovation process inactivating hydrogenation catalyst, the method is particularly well-suited to inactivate at heavy-oil hydrogenation
The regeneration of reason catalyst.
Background technology
Day by day become at crude oil be heavily deteriorated, under the ever-increasing situation of ultra-clean demand for fuel, hydrogen addition technology increasingly has
Captivation.Hydrogenation catalyst in use, due to strong adsorbent make active center poisoning, that active site is deposited thing is (burnt
Charcoal and metal) cover, catalyst aperture reduces/blocks and the activity factor such as phase sintering causes and loses its original activity.Inactivation
Hydrogenation catalyst mostly is black, and the material such as oil, colloid is contained on surface, and catalyst itself has valency containing Co, Ni, Mo, V, W, Fe etc.
The metal of value.Inactivation hydrogenation catalyst can be used by regeneration method, reduce directly discharge the pollution of environment and
The waste of resource.
The regeneration of hydrogenation catalyst refers to that catalyst activity and selectivity after using drops to a certain degree, by suitably
Process make a kind of operating process that its activity and selectivity even mechanical strength is restored, it is the use extending catalyst
Life-span, a kind of important means of reduction production cost.The renovation process of conventional decaying catalyst mainly has oxidizing process and solvent method
Two kinds.Oxidizing process ignition temperature is high, is easily destroyed the structure of catalyst or changes the chemical composition of catalyst.Solvent method uses molten
Solvable Jiao on agent catalyst-solvent under certain operating conditions, solvent load is relatively big and reclaims more difficulty.
Supercritical fluid refers to be in the fluid of more than critical temperature and critical pressure.It has the property of gas and liquid concurrently
Matter, had both had liquid and had had the feature of bigger dissolubility to solute, had again the characteristic that gas easily spreads and moves, its mass transfer
Speed is much higher than liquid phase process.Therefore, supercritical fluid is able in fields such as extraction, separation, microgranule preparation and chemical reactions
Application.
At present, using treatment with supercritical fluid decaying catalyst main purpose is to remove the Organic substance of catalyst surface deposition
Matter.CN1762600A discloses a kind of method of reproducing catalyst by supercritical fluid.The method is by unsaturation organic compound
In thing hydrogenation reaction the catalyst of inactivation in one of double extraction kettles in parallel with CO2Or CO2-cosolvent contacts continuously, utilizes
CO2Extraction carrys out regenerated catalyst.The method is thought under supercritical situation, CO2And cosolvent is to adsorbing at precious metal catalyst
The organic impurities causing catalysqt deactivation in agent has good dissolubility without catalyst carrier is had harmful effect.But
For heavy oil or residual oil inactivated hydrotreating catalyst, owing to its surface deposits more carbon deposit and W metal, V, Fe etc.,
Use this supercritical process that the activity of heavy oil or catalyst for hydrotreatment of residual oil can not be made very well to be recovered.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of renovation process inactivating heavy oil hydrogenating treatment catalyst.
The method is produced the problem of a large amount of pollution when being and not only solve decaying catalyst regeneration, and makes the mechanical performance of catalyst
Well being recovered with hydrogenation activity, technology is easily implemented.
The present invention inactivates the renovation process of heavy oil hydrogenating treatment catalyst, including:
(1) inactivation heavy oil hydrogenating treatment catalyst is placed in supercritical fluid system response device；
(2) mixed liquor is made with organic solvent, dispersant and organic acid；Described organic acid is acetic acid, citric acid, grass
One or more in acid, tartaric acid, addition is 0.1 ~ 5g/mL organic solvent, preferably 0.5 ~ 4g/mL organic solvent；
(3) in supercritical fluid system response device, temperature is 40 ~ 100 DEG C, and pressure is 8 ~ 25MPa, is passed through in reactor
Liquid CO2And mixed liquor prepared by above-mentioned steps (2), heavy oil hydrogenating treatment catalyst is processed；
(4) catalyst after the process of step (3) gained carries out hydrothermal treatment consists, in hydrothermal treatment device at hydro-thermal
Catalyst after reason, after being regenerated；Wherein said hydrothermal conditions is as follows: temperature is 400 DEG C ~ 600 DEG C, and processing pressure is
0.15～0.35MPa, the process time is 1～8h.
In step (1), inactivation heavy oil hydrogenating treatment catalyst, particularly catalyst for heavy oil hydrogenation demetal, hydrodesulfurization are urged
Agent or hydrogenation conversion catalyst.
Organic solvent described in step (2) is selected from ketones solvent, such as one or more in acetone, butanone.Described
Dispersant is one or more in Polyethylene Glycol, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polypropylene amine, and addition is that 0.5 ~ 5g/mL has
Machine solvent, preferably 1 ~ 3 g/mL organic solvent.The molecular weight of described dispersant is 200 ~ 2000.Described organic acid be acetic acid,
One or more in citric acid, oxalic acid, tartaric acid, addition is that 0.1 ~ 5g/mL organic solvent, preferably 0.5 ~ 4g/mL are organic
Solvent.
Reaction temperature described in step (3) preferably 40 ~ 90 DEG C, pressure preferably 9 ~ 15MPa.Liquid CO2Flow be 5 ~
80mL/min, preferably 10 ~ 50mL/min, the flow of step (2) mixed liquor is 10 ~ 100 mL/min, preferably 10 ~ 50mL/min.
Extraction time comprehensively determines according to catalyst inactivation, decaying catalyst treating capacity and operating condition.
The method of the regeneration of deactivated heavy oil hydrogenating treatment catalyst that the present invention provides, uses CO2Supercritical fluids system, and dividing
In the presence of the mixed liquor of powder, organic acid and organic solvent, inactivation heavy oil hydrogenating treatment catalyst is processed, not only can
Effectively remove heavy oil and the part carbon deposit of the residual on decaying catalyst surface, the feelings that simultaneously substantially can also keep at catalyst strength
Under condition, improve the dispersion again of W metal, V, Fe and the active metal of deposition further, and in follow-up hydrothermal treatment step
In further activated catalyst, not only avoid the loss of active metal, but also make the activity of active metal be recovered
Take full advantage of again the metal of deposition simultaneously.Additionally, follow-up hydrothermal treatment process, moreover it is possible to reduce the coke content of catalyst surface
And sulfur content, and improve catalyst pore structure.The inventive method can make the mechanical strength of catalyst revert to the 80% of fresh dose with
On, hydrogenation activity reverts to more than the 70% of fresh dose.
Detailed description of the invention
It is addressed further under the technical characteristic of the present invention below by embodiment, but is not limited to embodiment.Wt% is that quality is divided
Number.
Embodiment 1
Measure the HDS catalyst A-N(wherein MoO of certain volume3: 13wt%, NiO:2.3wt%, alumina content is
82.7wt%), drawing off that to obtain catalyst A-S(carbon content be 22.48% after residual hydrogenation equipment operates, sulfur content is 4.86%),
Its weight is 10g, is placed in the basketry of Multifunction super critical fluid system.Use PEG400 as organic point
Powder, citric acid, as weak acid, is dissolved in the acetone solvent of 1L, and wherein the addition of PEG400 is 500g, citric acid
Addition be 500g, be configured to mixed liquor.If consumption not can be by this proportional arrangement.
Temperature in Multifunction super critical fluid system response device is set as 90 DEG C, and pressure is set as 10MPa, to reactor
Inside it is passed through liquid CO2And the mixed liquor of above-mentioned preparation, decaying catalyst is processed, until the liquid phase put into is near colorless
Time, stop supercritical processing apparatus.The catalyst in basketry is taken out after cooling.Wherein CO2Flow be 20mL/min, mixed liquor
Flow be 20mL/min.
By the catalyst after supercritical device processes, it is placed in hydrothermal treatment device and carries out hydrothermal treatment consists, process
Temperature is 550 DEG C, processing pressure 0.23MPa, processes time 4h, the catalyst A-1 after hydrothermal treatment consists.Repeat with this condition
Repeatedly, sample is saved bit by bit.
Embodiment 2
Other condition is with embodiment 1, and simply the addition of citric acid is 1000g, and hydrothermal treatment consists temperature is 600 DEG C, processes
Obtain catalyst A-2.With this condition repeatedly, sample is saved bit by bit.
Embodiment 3
Measure the HDM catalyst B-N(wherein MoO of certain volume3: 5wt%, NiO:1.0 wt%, alumina content is
95wt%), drawing off that to obtain catalyst B-S(carbon content be 9.50% after residual hydrogenation equipment operates, sulfur content is 12.93%), its
Weight is 15g, is placed in the basketry of Multifunction super critical fluid system.Use polyethylene glycol 200 as organic dispersion
Agent, glacial acetic acid, as weak acid, joins in acetone and the butanone (volume ratio 1:1) of 1L, and wherein the addition of polyethylene glycol 200 is
100g, the addition of glacial acetic acid is 3500g, is configured to mixed liquor, if consumption not can be by this proportional arrangement.
Temperature in Multifunction super critical fluid system response device is set as 120 DEG C, and pressure is set as 13MPa, to reaction
Liquid CO it is passed through in device2And the mixed liquor of above-mentioned preparation, decaying catalyst is processed, until the liquid phase put into is approximation nothing
During color, stop supercritical processing apparatus.The catalyst in basketry is taken out after cooling.Wherein CO2Flow be 10mL/min, mixing
The flow of solvent is 30mL/min.
By the catalyst after supercritical device processes, it is placed in hydrothermal treatment device and carries out hydrothermal treatment consists, process
Temperature is 500 DEG C, processing pressure 0.30MPa, processes time 6h, the catalyst B-1 after hydrothermal treatment consists.Repeat with this condition
Repeatedly, sample is saved bit by bit.
Embodiment 4
Other condition, with embodiment 3, is only to increase citric acid 500g, and first supercritical processing temperature changes 100 DEG C into, hydrothermal treatment consists
Temperature is 450 DEG C, processes and obtains catalyst B-2.With this condition repeatedly, sample is saved bit by bit.
Comparative example 1
Measuring the HDS catalyst A-N of certain volume, draw off and obtain catalyst A-S after residual hydrogenation equipment operates, it is heavy
Amount is 10g, is placed in the basketry of Multifunction super critical fluid system.By in Multifunction super critical fluid system response device
Temperature is set as 90 DEG C, and pressure is set as 10MPa, is passed through liquid CO in reactor2And organic solvent-acetone, to inactivation catalysis
Agent processes, and during until the liquid phase put into is near colorless, stops supercritical processing apparatus.Urging in basketry is taken out after cooling
Agent A-R1.Wherein CO2Flow be 20mL/min, the flow of acetone is 20mL/min.With this condition repeatedly, sample is saved bit by bit
Product.
Comparative example 2
Measuring the HDS catalyst A-N of certain volume, draw off and obtain catalyst A-S after residual hydrogenation equipment operates, it is heavy
Amount is 10g, is placed in the basketry of Multifunction super critical fluid system.By in Multifunction super critical fluid system response device
Temperature is set as 90 DEG C, and pressure is set as 10MPa, is passed through liquid CO in reactor2And organic solvent-acetone, to inactivation catalysis
Agent processes, and during until the liquid phase put into is near colorless, stops supercritical processing apparatus.Urging in basketry is taken out after cooling
Agent.Wherein CO2Flow be 20mL/min, the flow of acetone is 20mL/min.
By the catalyst after supercritical device processes, it is placed in hydrothermal treatment device and carries out hydrothermal treatment consists, process
Temperature is 550 DEG C, processing pressure 0.23MPa, processes time 4h, the catalyst A-R2 after hydrothermal treatment consists.With this condition weight
The most repeatedly, sample is saved bit by bit.
Comparative example 3
Measuring the HDS catalyst A-N of certain volume, draw off and obtain catalyst A-S after residual hydrogenation equipment operates, it is heavy
Amount is 10g, is placed in the basketry of Multifunction super critical fluid system.Use citric acid as weak acid, be dissolved into 1L's
In acetone solvent, wherein the addition of citric acid is 500g, is configured to mixed liquor.If consumption can be joined in this ratio not
Put.
Temperature in Multifunction super critical fluid system response device is set as 90 DEG C, and pressure is set as 10MPa, to reactor
Inside it is passed through liquid CO2And the mixed liquor of above-mentioned preparation, decaying catalyst is processed, until the liquid phase put into is near colorless
Time, stop supercritical processing apparatus.The catalyst A-R3 in basketry is taken out after cooling.Wherein CO2Flow be 20mL/min, mixed
The flow closing liquid is 20mL/min.With this condition repeatedly, sample is saved bit by bit.
Comparative example 4
Measuring the HDM catalyst B-N of certain volume, draw off and obtain catalyst B-S after residual hydrogenation equipment operates, it is heavy
Amount is 15g, is placed in the basketry of Multifunction super critical fluid system.
Temperature in Multifunction super critical fluid system response device is set as 120 DEG C, and pressure is set as 13MPa, to reaction
Liquid CO it is passed through in device2And mixed liquor prepared by acetone and butanone (volume ratio 1:1), decaying catalyst is processed, until
When the liquid phase put into is near colorless, stop supercritical processing apparatus.The catalyst B-R2 in basketry is taken out after cooling.Wherein
CO2Flow be 10mL/min, the flow of mixed solvent is 30mL/min.With this condition repeatedly, sample is saved bit by bit.
Above-mentioned fresh catalyst and the catalyst after regeneration are analyzed, and live in batch autoclave
Property evaluate, raw materials used oil nature is shown in Table 1, and appreciation condition is shown in Table 2, and the physico-chemical property of catalyst is shown in Table 3, and evaluation result is shown in Table 4.
Table 1 raw oil character
Table 2 process conditions
Table 3 catalyst property
Table 3 continues
Table 4 evaluation result
| Project | A-N | A-1 | A-2 | Comparative example A-R1 | Comparative example A-R2 | Comparative example A-R3 |
| Relatively de-(Ni+V) rate | 100 | 80 | 84 | 52 | 65 | 61 |
| Desulfurization degree relatively | 100 | 83 | 89 | 58 | 70 | 65 |
| Relatively take off carbon yield | 100 | 79 | 83 | 53 | 66 | 62 |
Continued 4
| Project | B-N | B-1 | B-2 | Comparative example B-R1 |
| Relatively de-(Ni+V) rate | 100 | 73 | 79 | 50 |
| Desulfurization degree relatively | 100 | 80 | 85 | 55 |
| Relatively take off carbon yield | 100 | 75 | 80 | 50 |
Data from table 3 and table 4 are it can be seen that use regeneration methods of the invention, and specific surface area and pore volume recovery are preferable,
C and S is effectively removed, and intensity reduces seldom, and active metallic content is higher, and activation recovering is higher.
Claims (6)
1. inactivate a renovation process for heavy oil hydrogenating treatment catalyst, including:
(1) inactivation heavy oil hydrogenating treatment catalyst is placed in supercritical fluid system response device；
(2) mixed liquor is made with organic solvent, dispersant and organic acid；Described organic acid is acetic acid, citric acid, oxalic acid, wine
One or more in stone acid, addition is 0.1 ~ 5g/mL organic solvent；Wherein, described organic solvent is selected from acetone, butanone
In one or more；Described dispersant is the one in Polyethylene Glycol, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polypropylene amine or several
Kind, addition is 0.5 ~ 5g/mL organic solvent；The molecular weight of described dispersant is 200 ~ 2000；
(3) in supercritical fluid system response device, temperature is 40 ~ 100 DEG C, and pressure is 8 ~ 25MPa, is passed through liquid in reactor
CO2And mixed liquor prepared by above-mentioned steps (2), heavy oil hydrogenating treatment catalyst is processed；
(4) catalyst after the process of step (3) gained carries out hydrothermal treatment consists, through hydrothermal treatment consists in hydrothermal treatment device
After, the catalyst after being regenerated；Wherein said hydrothermal conditions is as follows: temperature is 400 DEG C ~ 600 DEG C, and processing pressure is
0.15～0.35MPa, the process time is 1～8h.
The most in accordance with the method for claim 1, it is characterised in that in step (1), heavy oil hydrogenating treatment catalyst is heavy-oil hydrogenation
Catalyst for demetalation, Hydrobon catalyst or hydrogenation conversion catalyst.
The most in accordance with the method for claim 1, it is characterised in that the dispersant addition described in step (2) is 1 ~ 3g/mL
Organic solvent.
The most in accordance with the method for claim 1, it is characterised in that described organic acid addition is that 0.5 ~ 4g/mL is organic molten
Agent.
The most in accordance with the method for claim 1, it is characterised in that the reaction temperature described in step (3) is 40 ~ 90 DEG C, pressure
It is 9 ~ 15MPa.
The most in accordance with the method for claim 1, it is characterised in that in step (3), described liquid CO2Flow be 5 ~ 80mL/
Min, the flow of step (2) gained mixed liquor is 10 ~ 100 mL/min.
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| CN113019470A (en) * | 2021-03-18 | 2021-06-25 | 上海大学材料基因组工程(萍乡)研究院 | Method for activating transition metal catalyst |
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| CN1078105C (en) * | 1998-03-30 | 2002-01-23 | 中国科学院山西煤炭化学研究所 | In-situ regeneration process of fisher-tropsch synthesis catalyst |
| US6753286B2 (en) * | 2002-01-29 | 2004-06-22 | Exxonmobil Research And Engineering Company | Supported catalyst regeneration |
| CN100337753C (en) * | 2004-10-22 | 2007-09-19 | 中国石油化工股份有限公司 | Method for reproducing catalyst by supercritical fluid |
| CN100395030C (en) * | 2004-10-22 | 2008-06-18 | 中国石油化工股份有限公司 | Process for reproducing catalyst by supercritical fluid |
| CN100423835C (en) * | 2007-03-16 | 2008-10-08 | 中国石化扬子石油化工有限公司 | Method for reactivating palledium/carbon catalyst |
| CN102382676A (en) * | 2010-08-25 | 2012-03-21 | 中国石油化工股份有限公司 | Alkylation method |
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