CN1107700C - Method of regenerating hydrogenation cracking catalyst - Google Patents
Method of regenerating hydrogenation cracking catalyst Download PDFInfo
- Publication number
- CN1107700C CN1107700C CN 00110722 CN00110722A CN1107700C CN 1107700 C CN1107700 C CN 1107700C CN 00110722 CN00110722 CN 00110722 CN 00110722 A CN00110722 A CN 00110722A CN 1107700 C CN1107700 C CN 1107700C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hours
- temperature
- atmosphere
- regenerating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention discloses a regeneration method of a hydrocracking catalyst, particularly a regeneration method of a hydrocracking catalyst containing a molecular sieve component. Firstly, the catalyst is reduced to convert sulphur reacting with active metal into hydrogen sulphide to escape; secondly, the catalyst is oxidated to eliminate coke. The catalyst regenerated by combining the two steps, which can prevent acid component collapse, for example, molecular sieve collapse, from being caused by sulphuric acid generated in the regeneration process to a large extent, is favorable for the activity of the catalyst.
Description
The present invention relates to a process for regenerating a used hydrocracking catalyst, in particular a hydrocracking catalyst containing a molecular sieve component.
Now, the world oil refining industry is faced with the contradiction between heavy crude oil and the relatively reduced fuel oil demand of the market, and the continuously increased demand for light oil products, especially for middle distillate products, which makes refiners have to consider converting more heavy distillate into good quality middle distillate. Hydrocracking is a better way to solve the above contradictions and complete the above oil refining process. Meanwhile, with the hydrocracking function of producing high quality reformed material and ethylene material, the hydrocracking technology will be developed further.
Hydrocracking catalysts are the core of hydrocracking technology. It generally consists of two parts: active metals providing hydrogenation function, such as tungsten, molybdenum, cobalt, nickel, etc., and acidic carriers providing cracking active sites, such as amorphous silica-alumina, molecular sieves, alumina, etc., sometimes with small amounts of other materials added to optimize catalyst performance. The catalyst will gradually decrease in activity during long-term operation, and after this occurs, the catalyst will usually be maintained in activity by raising the temperature, and when the temperature is not raised enough to ensure further increase in temperature due to the equipment capacity and catalyst performance, the operation will have to be stopped and the catalyst will be regenerated. At present, in the industry, the adoption of the regeneration technology outside the device is overwhelmingly dominant, and the regeneration inside the device is less. It is generally believed that the deactivation of the catalyst is largely caused by the deposition of coke on the surface of the catalyst, so that the removal of coke from the catalyst is the primary consideration in the regeneration of the hydrogenation catalyst, for example, in the method of patent US5,015,611, which is to burn off the coke on the catalyst in an oxygen-containing atmosphere to restore the activity of the catalyst. Of course, in the regeneration process, except carbon deposit, other components on the catalyst must contact with the regeneration gas, and some components even interact with the regeneration gas, so that the important significance of ensuring that the physicochemical properties of the regenerated catalyst and the fresh catalyst are relatively close to each other as far as possible is realized for recovering the activity of the catalyst.
Before use, the catalyst must be sulfurized to exert optimal efficiency, so that the active metal on the catalyst still exists in a sulfurized state after the used catalyst is gradually deactivated in the long-term operation process. The coke in the deactivated catalyst, which contains, in addition to a large amount of carbon, nitrogen, sulfur, oxygen, etc., will inevitably be converted to their respective oxides and removed from the catalyst during the regeneration process; at the same time, the sulfided active metal on the catalyst will also be oxidized, as shown in the followingformula:
in the presence of oxygen, the sulfur dioxide produced on the catalyst will also be partially oxidized to sulfur trioxide:
if water or water vapor exists in the regeneration atmosphere, the generated sulfur dioxide and sulfur trioxide automatically become sulfurous acid and sulfuric acid:
molecular sieves, which are commonly used as supports for hydrocracking catalysts, have a relatively high heat resistance, but due to the presence of a large number of hydroxyl groups on the surface of the molecular sieves, they are particularly sensitive to acidic atmospheres, such as sulfur dioxide and sulfur trioxide produced in the above-described processes, and the molecular sieve framework is susceptible to collapse due to attack by these acidic gases, especially at high temperatures. Meanwhile, in the process of disassembling the catalyst and the like, interlayer water, structural water and the like which are difficult to remove and generated by the strong water absorption capacity of the molecular sieve just meet the generation process of sulfurous acid and sulfuric acid. The fact that the molecular sieve is partially collapsed during regeneration due to the action of these acidic substances has been proved by many experiments.
The negative effect of molecular sieve collapse on catalyst activity is evident. One solution to this problem is to control the generation of sulfur dioxide and sulfur trioxide during the regeneration process. The conversion of sulfur in the carbon deposits to oxidized sulfur seems unavoidable, but the amount produced is small. In contrast, sulfur dioxide and sulfur trioxide produced by oxidation of the metal in the sulfided state are only those portions that need to be carefully controlled. If the generation of the partial oxidation state sulfur can be solved, the purpose of greatly preventing the molecular sieve from collapsing can be achieved. In addition, the removal of interlayer water and structural water which are difficult to remove in the molecular sieve also has a positive effect on preventing the molecular sieve on the catalyst from collapsing.
Therefore, the invention aims to provide a method for regenerating a hydrocracking catalyst, which prevents a molecular sieve in the catalyst from collapsing during regeneration, thereby ensuring that the performance of the regenerated hydrocracking catalyst is recovered to the maximum extent.
The method comprises the following steps:
1) contacting the deactivated hydrocracking catalyst with a hydrogen-containing gas at an elevated temperature to convert sulfided metal on the catalyst to reduced metal and to convert sulfur on the catalyst that reacts with the active metal to hydrogen sulfide for removal;
2) the catalyst thus treated is then subjected to an oxidation treatment to convert the metals on the catalyst to an oxidized state and to remove coke to restore the catalyst activity.
In order to further prevent the molecular sieve on the catalyst from collapsing in the regeneration process, the temperature can be increased in an inert atmosphere before the first step, and interlayer water and structural water which are difficult to remove in the molecular sieve are removed;
the specific operation process for removing interlayer water and structural water which are difficult to remove in the molecular sieve can be as follows: raising the temperature to 120 ℃ in an inert atmosphere for at least 1 hour, preferably 2 to 3 hours, and then raising the temperature to 450 ℃ for 0.5 to 1.5 hours, preferably 1 hour;
the specific operation process in the step 1) may be: the catalyst is reduced in an atmosphere containing hydrogen in the range of 3-30 v%, preferably 10-20 v%, at a temperature of 200-280 deg.C, preferably 210-240 deg.C for at least 2 hours, preferably 2-5 hours, and then the original atmosphere is kept at room temperature. The operating pressure is not a necessary control condition in this step, and it is generally carried out at one atmospheric pressure from the viewpoint of operation. There will also be some coke removal during this step.
The specific operation process in the step 2) may be: the entire system was initially purged with inert gas until the concentration of hydrogen in the purged gas was no greater than 0.2 v%, and then the atmosphere was switched to an oxygen-containing gas. The oxygen content introduced at the start is strictly controlled, less than 0.1 v%, preferably less than 0.05 v%, so that the reduced metal on the catalyst is converted to the oxidized metal under milder conditions for a period of at least 2 hours, preferably from 2 to 6 hours. The catalyst may then be subjected to stepwise charking regeneration with a stepwise increase in oxygen content of 0.5 to 2.0 v%, preferably 1.0 to 1.5 v%. The main control steps are as follows: keeping the temperature at 250 ℃ at 220 ℃ and preferably at 240 ℃ for at least 2 hours, preferably 2-6 hours; keeping the temperature at 350 ℃ and preferably at 320 ℃ and 290 ℃ for at least 1 hour, preferably 1-4 hours; the temperature is maintained at 450 ℃ and 550 ℃, preferably 470 ℃ and 490 ℃ for at least 2 hours, preferably 2-4 hours.
The regeneration process of the present invention is particularly useful for hydrocracking catalysts. In particular to a hydrocracking catalyst which takes metal components selected from VIB, VIIB and VIII groups, such as Co, Mo, W, Ni and the like as hydrogenation active components and is loaded on a carrier containing a molecular sieve. The catalyst is generally cylindrical, spherical or multi-lobed in shape, having a diameter of 0.5 to 3.5 mm and a length of 1.5 to 10.0 mm.
In the present invention, the deactivated catalyst is placed in a reactor having any suitable configuration. Except for the indicated hydrogen or oxygen, the atmosphere used is an inert gas such as nitrogen or argon, and the purity is more than 99.99 v%. It should be noted that, particularly at the constant temperature in step 2), the bed temperature of the catalyst should be controlled as much as possible to prevent the catalyst from sintering due to too fast a steady rise.
Compared with the prior art, the method provided by the invention is used for regenerating the catalyst through a two-step method or three-step method regeneration process. The combination of the two or three steps with the regenerated catalyst can greatly prevent the collapse of the molecular sieve framework on the catalyst carrier caused by acidic substances such as sulfur dioxide, sulfur trioxide, sulfurous acid, sulfuric acid and the like generated in the regeneration process, thereby being beneficial to the activity of the catalyst. While also preventing undesirable deposits of sulfur on the catalyst and corrosion of the regeneration equipment by these acidic species.
The process of the invention is further illustrated by the following examples.
Example 1
WNi/Al with properties shown in table I2O3+ USY hydrocracking catalyst, containing 58% by weight of USY molecular sieve in the fresh catalyst, was used in a hydrocracking process for the production of naphtha. The temperature was raised to 130 ℃ for 2 hours in a nitrogen atmosphere and then to 450 ℃ for 1 hour. After cooling to 210 ℃, H containing 15 v% of hydrogen is introduced2/N2Reducing the gas for 2 hours, and then keeping the original atmosphere to be cooled to room temperature. Followed by N2The entire system was purged for 2 hours and then the atmosphere was switched to O containing 0.03 v% oxygen2/N2The mixture was purged continuously for 3 hours. Subsequently, the catalyst was subjected to stepwise charking regeneration with a stepwise increase in the oxygen content of the atmosphere to 1.0 v%. The main temperature control steps are as follows: the temperature is kept constant at 230 ℃ for 5 hours, at 300 ℃ for 4 hours and at 470 ℃ for 4 hours, so that the regeneration process of the catalyst is completed. The results are shown in Table I.
TABLE comparison of the before and after Properties of a deactivated hydrocracking catalyst
Comparative catalyst analysis method of regenerated catalyst of deactivated catalyst WO3W% 24.4224.3724.47 inorganic analysis NiO,% 5.525.485.39 inorganic analysis relative crystallinity,% 1009683X-ray diffraction method
Meanwhile, the catalyst contains 1.5 v% of oxygen O directly in the atmosphere2/N2Keeping the temperature at 120 ℃ for 2 hours, at 230 ℃ for 5 hours, at 300 ℃ for 4 hours, and at 470 ℃ for 4 hoursThe regeneration results of the comparative catalysts of (a) are also given in table one. Table one shows that the present invention has the effect of preventing the molecular sieve in the hydrocracking catalyst from collapsing during the regeneration process.
Example 2
MoNiP/USY + Al with properties shown in table II2O3The hydrocracking catalyst contains 43% of USY molecular sieve and is used for the hydrocracking process of distillate oil in one-stage series production. H containing 15 v% of hydrogen is introduced2/N2After the gas is reduced for 4 hours at the constant temperature of 240 ℃, the original atmosphere is kept to be reduced to the room temperature. Followed by N2The entire system was purged for 3 hours and then the atmosphere was switched to O containing 0.05 v% oxygen2/N2The mixture was purged continuously for 3 hours. Subsequently, the catalyst was subjected to stepwise charking regeneration with a stepwise increase in the oxygen content of the atmosphere to 1.5 v%. The main temperature control steps are as follows: the temperature is kept constant at 240 ℃ for 3 hours, at 320 ℃ for 2 hours and at 490 ℃ for 3 hours, so that the regeneration process of the catalyst is completed. The results are shown in Table II.
TABLE comparison of the Properties before and after regeneration of a deactivated cracking catalyst
Deactivated catalyst regenerated catalyst comparative catalyst analysis method MoO3，w％ 19.27 19.1318.68 inorganic analysis NiO, w% 5.615.475.36 inorganic analysis P2O5W% 1.481.431.56 relative crystallinity by inorganic analysis,% 1009485X-ray diffraction method
At the same time, the catalyst is directly in the presence of 1.5% by volume of oxygen-containing O2/N2The results of the regeneration of the comparative catalyst, which was carried out in an atmosphere of 120 ℃ for 2 hours, 240 ℃ for 3 hours, 320 ℃ for 2 hours and 490 ℃ for 3 hours, are also shownin Table II. Table two shows that the present invention has the effect of preventing the molecular sieve in the hydrocracking catalyst from collapsing during the regeneration process.
Claims (6)
1. A method for regenerating a hydrocracking catalyst, characterized by comprising the steps of:
1) contacting the deactivated hydrocracking catalyst with a hydrogen-containing gas at an elevated temperature to convert sulfided metal on the catalyst to reduced metal and to convert sulfur on the catalyst, which reacts with the active metal, to hydrogen sulfide for removal; the specific operating conditions are as follows: reducing the catalyst at 200-280 ℃ in an atmosphere containing 3-30 v% of hydrogen for at least 2 hours, and then keeping the original atmosphere to be cooled to room temperature;
2) oxidizing the treated catalyst to convert the metal in the catalyst into oxide state and eliminating coke to restore the activity of the catalyst; the specific operating conditions are as follows: purging the whole system by using inert gas until the concentration of hydrogen in the purged gas is not more than 0.2 v%, and then switching the atmosphere to oxygen-containing gas; the oxygen content introduced at the beginning is strictly controlled to be less than 0.1 v%, the duration is at least 2 hours, then, the oxygen content can be gradually increased to 0.5-2.0 v%, the catalyst is subjected to fractional coke burning regeneration, and the main control steps are as follows: keeping the temperature constant at 250 ℃ for at least 2 hours at 220 ℃, keeping the temperature constant at 350 ℃ for at least 1 hour at 290 ℃ and keeping the temperature constant at 550 ℃ for at least 2 hours at 450 ℃.
2. The method for regenerating a hydrocracking catalyst according to claim 1, wherein before said step 1), the temperature is first raised in an inert atmosphere to remove interlayer water and structural water which are difficult to remove in the molecular sieve.
3. The process for regenerating a hydrocracking catalyst according to claim 1, wherein said step 1) is carried out by the specific operation of: the catalyst is reduced in an atmosphere containing 10-20 v% of hydrogen at the temperature of 210-240 ℃ for 2-5 hours, and then the original atmosphere is kept to be reduced to the room temperature.
4. The process for regenerating a hydrocracking catalyst according to claim 1, wherein said step 2) is carried out by the specific operation of: purging the whole system by using inert gas until the concentration of hydrogen in the purged gas is not more than 0.2 v%, and then switching the atmosphere to oxygen-containing gas; the oxygen content introduced at the beginning is strictly controlled to be less than 0.05 v%, the duration is 2-6 hours, and then the oxygen content can be gradually increased to 1.0-1.5 v%, and the catalyst is subjected to fractional carbonization regeneration; the main control steps are as follows: the temperature is kept constant at 230-240 ℃ for 2-6 hours, at 300-320 ℃ for 1-4 hours, and at 470-490 ℃ for 2-4 hours.
5. The method for regenerating a hydrocracking catalyst according to claim 1, wherein the hydrocracking catalyst is a hydrocracking catalyst comprising a metal component selected from the group consisting of group VIB, group VIIB and group VIII as a hydrogenation active component and supported on a carrier containing a molecular sieve.
6. The method for regenerating a hydrocracking catalyst according to claim 2, wherein said specific operation for removing interlayer water and structural water which are difficult to remove in the molecular sieve is: raising the temperature to 120-150 ℃ in inert atmosphere, keeping the temperature constant for at least 1 hour, then raising the temperature to 420-480 ℃, and keeping the temperature constant for at least 0.5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00110722 CN1107700C (en) | 2000-07-24 | 2000-07-24 | Method of regenerating hydrogenation cracking catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00110722 CN1107700C (en) | 2000-07-24 | 2000-07-24 | Method of regenerating hydrogenation cracking catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1335359A CN1335359A (en) | 2002-02-13 |
| CN1107700C true CN1107700C (en) | 2003-05-07 |
Family
ID=4580701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00110722 Expired - Fee Related CN1107700C (en) | 2000-07-24 | 2000-07-24 | Method of regenerating hydrogenation cracking catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1107700C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363469C (en) * | 2004-11-30 | 2008-01-23 | 中国石油化工股份有限公司 | Regenerating method for hydrogenating catalyst |
| US8137535B2 (en) * | 2008-01-29 | 2012-03-20 | Kellogg Brown & Root Llc | Method for adjusting catalyst activity |
| CN101992131B (en) * | 2009-08-27 | 2013-03-06 | 中国石油化工股份有限公司 | Method for regenerating hydrogenation catalyst, regenerated hydrogenation catalyst and application thereof |
| CN106669788B (en) * | 2015-11-11 | 2019-07-12 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN106669710B (en) * | 2015-11-11 | 2019-02-22 | 中国石油化工股份有限公司 | A kind of regeneration method of catalytic diesel oil hydrocracking catalyst |
| CN112717999A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Regeneration method of hydrocracking catalyst |
| CN112718019A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Method for recovering activity of hydrocracking catalyst |
| CN113426494A (en) * | 2021-06-24 | 2021-09-24 | 陕西延长石油（集团）有限责任公司 | Method for reactivating and regenerating waste catalytic cracking catalyst |
-
2000
- 2000-07-24 CN CN 00110722 patent/CN1107700C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1335359A (en) | 2002-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4454240A (en) | Catalyst regeneration process including metal contaminants removal | |
| KR101890044B1 (en) | Regeneration catalyst for hydrotreating heavy oil or residue and preparation method thereof | |
| EP0244014B1 (en) | Method for the regeneration of spent alumina-based catalysts | |
| US8106250B2 (en) | Process for removing silicon compounds from hydrocarbon streams | |
| CN1120051C (en) | Catalyst regeneration process | |
| CN1107700C (en) | Method of regenerating hydrogenation cracking catalyst | |
| JP3110525B2 (en) | Method for regenerating hydrocarbon oil hydrotreating catalyst | |
| CA1050915A (en) | Demetallization of high metals feedstocks using regenerated catalyst | |
| GB2157968A (en) | Catalyst rejuvenation process | |
| CN109926105A (en) | A kind of regeneration method of hydrogenation catalyst | |
| CA1087591A (en) | Catalyst demetallization with a reductive so.sub.2 wash | |
| JP4773274B2 (en) | Regeneration method for heavy oil hydrotreating catalyst | |
| EP0026508B1 (en) | Process and apparatus for the demetallization of a hydrocarbon oil | |
| US3228993A (en) | Catalytic hydrogenation process employing a reduced nickel- molybdenum-alumina catalyst | |
| RU2666355C2 (en) | Used hydro-treating catalyst regeneration method | |
| CA2412363C (en) | Method for presulfiding and preconditioning of residuum hydroconversion catalyst | |
| CN107344124B (en) | In-situ regeneration method of solid super acidic catalyst | |
| CA1129364A (en) | On-line regeneration of hydrodesulfurization catalyst | |
| CN112547080B (en) | Method for recycling supported hydrogenation catalyst | |
| US20020098971A1 (en) | Regeneration method of heterogeneous catalysts and adsorbents | |
| CN114425393B (en) | Preparation method of catalyst | |
| CN108097275B (en) | Start-up method of semi-regenerated catalytic reforming catalyst | |
| US4293403A (en) | Catalyst demetallization by converting the metal poisons to a sulfur containing metal compound having a defined low amount of sulfur | |
| US3172864A (en) | Activation of deactivatex hydro- benitkimcation catalysts | |
| CN109988596B (en) | Start-up method of semi-regenerated catalytic reforming catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030507 Termination date: 20110724 |