CN1245091A - Process for regenerating deactivated catalyst containing Y-type zeolite - Google Patents
Process for regenerating deactivated catalyst containing Y-type zeolite Download PDFInfo
- Publication number
- CN1245091A CN1245091A CN98117284A CN98117284A CN1245091A CN 1245091 A CN1245091 A CN 1245091A CN 98117284 A CN98117284 A CN 98117284A CN 98117284 A CN98117284 A CN 98117284A CN 1245091 A CN1245091 A CN 1245091A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- zeolite
- activity
- deactivated catalyst
- decaying
- 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.)
- Granted
Links
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A process for regenerating the deactivated catalyst containing Y-zeolite features that the said deactivated catalyst is treated in the aqueous solution containing Na2O source and unforced chosen NaCl at 80-110 deg.C for 10-30 hr (90-100 deg.C for 14-24hr is preferable). The weight ratio of deactivated catalyst: Na2O : Na2Cl : H2O is 1 : (0.01-0.3) : (0-0.1) : (0.3-3). Its advantages include simple process, low cost and high quality of product, including high content of molecular sieve, high activity and low content of V. The regenerated catalyst can be reused as cracking catalyst.
Description
The present invention relates to a kind of Retreatment method that contains the decaying catalyst of y-type zeolite, particularly contain the Retreatment method of fluid catalytic cracking (FCC) equilibrium catalyst of y-type zeolite.
A kind of catalysis material that the y-type zeolite amount of being to use is bigger, its topmost application are in the catalytic cracking and hydrocracking process of petroleum hydrocarbon.In the catalytic cracking process of petroleum hydrocarbon, the microspherical catalyst that contains Y zeolite and carrier material under high temperature and the hydrothermal condition in reactor and regenerator through cycle operation repeatedly after, because the deposition of the continuous avalanche of molecular sieve structure and destruction and heavy metal and poisoning wherein, this activity of such catalysts and selectivity are reduced gradually, until not using at last.Though constantly have fresh catalyst to replenish motion device, still need from device, to draw off the seriously equilibrium catalyst of inactivation of a part when inactivation is serious.How the inactivation poising agent that this part draws off utilizes again, is the problem that people relatively are concerned about always.
That had reported some inactivation Cracking catalyst in the prior art utilizes method again, for example is used as the raw material of construction material etc., but most worthy is that its effective regeneration is recovered active (reactivation), it can be got back to continue in the device to use.
Described a kind of method of regeneration of spent FCC catalyst among the CN1037857A, this method is that dead catalyst is handled with ammonium salt (not fluorine-containing) aqueous solution earlier, again with NH
4The F aqueous solution is handled, and then through 450～550 ℃ of roastings, can make activity of such catalysts obtain part and recover.This method can not obviously be improved the character of catalyst, and produces fluorine containing waste water.
A kind of renovation process of waste molecular sieve cracking catalyzer is disclosed among the CN1072617A, this method be with dead catalyst and ammonium sulfate by ammonium sulfate: catalyst=0.25～1.5: 1 weight ratio is mixed, then 250～600 ℃ of roastings more than 10 minutes, product of roasting is through water logging, filtration, washing, perhaps, get regenerated catalyst after the drying again through ion-exchange.This method biases toward the extrusion rate of emphasizing heavy metal on the catalyst, and the activity of regeneration rear catalyst is not significantly recovered, because the sulfuric acid that the ammonium sulfate pyrolytic produces is to the destruction of molecular sieve, even its activity decreases on the contrary.
The inactivation of catalytic cracking poising agent is except poisoning owing to the pollution of heavy metal, the more important thing is because the structural breakdown of molecular sieve wherein causes the content of molecular sieve to reduce, activated centre quantity reduces, the physical property of Y zeolite and don't destruction catalyst is (as granular size and distribution if therefore can regrow out in the hole of inactivation poising agent, tear strength etc.), will bring good result for the utilization again of inactivation poising agent.
USP5,182, proposed in 243 a kind of the FCC poising agent to be converted into the method for the FCC catalyst that activity with expectation and selectivity keep its physical property simultaneously, the basic ideas of this method are the Y zeolites in the destruction of balance agent and do not destroy carrier, and the Y zeolite regrows out in carrier.To obtain necessary activity of industrial operation and selectivity.The concrete steps of this method are: the poising agent that will contain the Y zeolite is with a kind of Na of containing
2O source, SiO
2The mixture in the aluminium source of source, limpid amorphous crystal seed (in fact being exactly directed agents) and optional selection was handled 6～30 hours down at 70～110 ℃, laid equal stress on and newly grew the Y zeolite of no more than 70 heavy % to destroy the molecular sieve that contained originally in the catalyst.This method is the same during NaY with preparation to need to prepare directed agents (limpid amorphous crystal seed), so process is comparatively complicated.
The objective of the invention is to provide on the basis of existing technology a kind of Retreatment method of decaying catalyst of the Y of containing zeolite, make and the y-type zeolite content in the decaying catalyst is increased through comparatively simple method, thereby improve its activity, can keep the decaying catalyst original physical properties again simultaneously.
The Retreatment method of the decaying catalyst of the Y of containing zeolite provided by the present invention comprises: with said decaying catalyst with a kind of Na of containing
2The aqueous solution of the NaCl of O source and optional selection was handled 10～30 hours down at 80～110 ℃, preferably handled 14～24 hours down at 90～100 ℃, wherein decaying catalyst: Na
2O: NaCl: H
2The weight ratio of O is 1: (0.01～0.3): (0～0.1): (0.3～3).
In the method provided by the invention the decaying catalyst of the said Y of containing zeolite be in the catalytic cracking process conventional that use and drawn off from device because of inactivation, handle the equilibrium catalyst that removes carbon deposit through making charcoal.
Said Na in the method provided by the invention
2The O source can be NaOH, or contained alkali in the NaY synthesis mother liquid, also can be alkaline aqueous solutions such as waterglass.Under back two kinds of situations,, can add the NaOH of appropriate amount again if basicity is not enough.
The Retreatment method of the decaying catalyst of the Y of containing zeolite provided by the present invention can also comprise the step of the catalyst through above-mentioned processing being carried out again ammonium or rare earth ion exchanged.
Retreatment method and the USP5 that contains the decaying catalyst of Y zeolite provided by the invention, 182,, 243 method is compared, and can not need to prepare directed agents (limpid amorphous crystal seed), and treatment fluid also can not contain SiO
2The source, thus simple to operate, and cost reduces.Increased molecular sieve content (the X-ray diffraction peak intensity obviously increases) and handle the back products obtained therefrom again, improved activity, reduced the content of heavy metal (vanadium), and its physical property is not significantly damaged, and can continue to re-use as Cracking catalyst.
Fig. 1 a is X-ray diffraction (XRD) figure of the inclined to one side Y-15 poising agent of Yanshan Petrochemical.
Fig. 1 b schemes for the X-ray diffraction (XRD) of the inclined to one side Y-15 poising agent of Yanshan Petrochemical that process method of the present invention is handled.
Fig. 2 a is the electron scanning micrograph (amplifying 100 times) of the inclined to one side Y-15 poising agent of Yanshan Petrochemical.
Fig. 2 b is the electron scanning micrograph (amplifying 100 times) of the inclined to one side Y-15 poising agent of Yanshan Petrochemical of process method processing of the present invention.
Fig. 3 a is the electron scanning micrograph (amplifying 100 times) of Jiujiang oil plant CRC-1 poising agent.
Fig. 3 b is the electron scanning micrograph (amplifying 100 times) of Jiujiang oil plant CRC-1 poising agent of process method processing of the present invention.
The following examples will the present invention is described further.
Wherein, each analytical method is referring to " petrochemical industry analytical method (RIPP test method) " (volume such as Yang Cuiding, Science Press, nineteen ninety publishes): the elementary analysis using plasma emission spectrographic determination (RIPP129-90 standard method) of catalyst, size distribution (size consist) adopts the elutriation Particle Size Analyzer to measure (RIPP30-90 standard method), apparent bulk density adopts sedimentation to measure (RIPP31-90 standard method), micro-activity adopts RIPP92-90 standard method (catalytic cracking poising agent mat activity test method) to measure, relative crystallinity adopts the RIPP146-90 standard method to measure, and specific area adopts Chinese Industrial Standards (CIS) GB/T 5816-1995 method to measure.The n-tetradecane lytic activity of catalyst adopts the pulse micro-inverse-chromatogram arrangement that has reactor to estimate, reaction temperature is 460 ℃, the catalyst loading amount is 0.1 gram, and the n-tetradecane sample size is 0.5 microlitre, with the conversion ratio of the n-tetradecane n-tetradecane lytic activity as catalyst.
The character of used inactivation poising agent is listed in the table 1 among each embodiment.Table 1
| Title | Jiujiang oil plant CRC-1 poising agent | The inclined to one side Y-15 poising agent of Yanshan Petrochemical | |
| Size distribution (%) | ????＜20μm | ????0.5 | ????0.2 |
| ????20～40μm | ????20.3 | ????4.1 | |
| ????40～80μm | ????62.8 | ????72.7 | |
| ????＞80μm | ????16.4 | ????22.0 | |
| Elementary analysis (ppm) | ????Sb | ????1499 | ????6100 |
| ????Ni | ????5914 | ????4900 | |
| ????V | ????911 | ????1200 | |
| ????Fe | ????6635 | ????3800 | |
| ????Cu | ????67 | ????100 | |
| ????Na | ????2009 | ????2700 | |
| Apparent bulk density (g/cm 3) | ????0.858 | ????-- | |
| Specific area (m 2/g) | ????64 | ????80 | |
| The n-tetradecane lytic activity | ????66 | ????67 | |
| Micro-activity | ????54 | ????53 | |
Embodiment 1
The inclined to one side Y-15 poising agent of 100g Yanshan Petrochemical (is taken from Yanshan Petrochemical company Dongfanghong oil plant two catalysis workshops, Y-15 catalyst activity component is a rare earth Y type molecular sieve partially, carrier is a full synthesis carrier not argillaceous) put into the sodium hydroxide solution of 100ml 40%, in the sealed reaction jar, be warming up to 90 ℃ and handled 16 hours, after filtration, wash with water and dry catalyst after obtaining handling.The X-ray diffraction (XRD) of catalyst analysis (seeing Fig. 1 a, Fig. 1 b) shows that its XRD diffraction peak intensity of the catalyst after the processing obviously strengthens before and after handling, and relative crystallinity has increased by 100%, shows that wherein the Y zeolite content obviously increases; The sieve analysis result shows that its size distribution situation of catalyst after the processing does not have marked change (seeing Table 2); The ESEM morphology analysis shows its granule-morphology of catalyst after the processing remain unchanged (seeing Fig. 2 a, Fig. 2 b); Content of vanadium the analysis showed that the content of vanadium of handling rear catalyst obviously reduces (seeing Table 2).
With the catalyst after the above-mentioned processing according to catalyst: ammonium sulfate: the weight ratio of deionized water=1: 0.25: 4 is 80 ℃ of washing exchanges 0.5 hour down, and repeats once this ammonium exchange again.Press RECl afterwards
3: catalyst: the weight ratio of deionized water=0.1: 1: 4 80 ℃ down with mixed chlorinated rare earth solution exchange 0.5 hour, filter and drying after, the mat activity test result shows that the micro-activity of carrying out this exchange rear catalyst is 65.The n-tetradecane lytic activity that carries out this exchange rear catalyst is 97.
Contrast: after will be not carrying out ammonium exchange and rare earth exchanged according to the method described above through the inclined to one side Y-15 poising agent of Yanshan Petrochemical of NaOH solution-treated, the n-tetradecane lytic activity of gained catalyst is 74.
Table 2: the performance after the inclined to one side Y-15 poising agent process of the Yanshan Petrochemical NaOH solution-treated
| Size distribution (%) | ????＜20μm | ????1.2 |
| ????20～40μm | ????7.3 | |
| ????40～80μm | ????72.8 | |
| ????＞80μm | ????18.7 | |
| Vanadium (V) content, ppm | ????700 | |
| The relative crystallinity recruitment | ????100％ | |
Embodiment 2
The inclined to one side Y-15 poising agent of 100g Yanshan Petrochemical (with embodiment 1) is put into the sodium hydroxide solution of 100ml 35%, add 5 gram NaCl again, stir, in the sealed reaction jar, be warming up to 98 ℃ and handled 15 hours, after filtration, wash with water and dry catalyst after obtaining handling.XRD analysis shows that its relative crystallinity has increased by 110%, and elementary analysis shows that its content of vanadium is 600ppm, and carrying out after ammonium exchange and the rare earth exchanged its n-tetradecane according to the same procedure among the embodiment 1 again, to split Jie's activity be 99%.
Embodiment 3
100g Jiujiang oil plant CRC-1 poising agent (is taken from oil plant catalytic cracking workshop, Jiujiang, CRC-1 catalyst activity component is a rare earth Y type molecular sieve, carrier is for containing kaolinic semi-synthetic carrier) and 5 restrain the sodium hydroxide solution that NaCl put into 200ml 20% and stir, in the sealed reaction jar, be warming up to 95 ℃ and handled 16 hours, after filtration, wash with water and dry catalyst after obtaining handling.The ESEM morphology analysis shows that its granule-morphology of catalyst after the processing and size distribution remain unchanged and (sees Fig. 3 a, Fig. 3 b), XRD analysis shows that its relative crystallinity has increased by 104%, elementary analysis shows that its content of vanadium is 500ppm, and carrying out after ammonium exchange and the rare earth exchanged its n-tetradecane according to the same procedure among the embodiment 1 again, to split Jie's activity be 95%.
Embodiment 4
The sodium hydroxide solution of 100g Jiujiang oil plant CRC-1 poising agent being put into 100ml 25% stirs, and is warming up to 90 ℃ and handled 24 hours in the sealed reaction jar, after filtration, wash with water and dry catalyst after obtaining handling.XRD analysis shows that its relative crystallinity has increased by 80%, and carrying out after ammonium exchange and the rare earth exchanged its n-tetradecane according to the same procedure among the embodiment 1 again, to split Jie's activity be 94%.
Embodiment 5
The mother liquor that 100g Jiujiang oil plant CRC-1 poising agent is put into after the 50ml NaY crystallization (is taken from catalyst plant molecular sieve two workshops, Zhou village, SiO
2Content is 50 grams per liters, Na
2O content is 25 grams per liters) stir, in the sealed reaction jar, be warming up to 90 ℃ and handled 16 hours, after filtration, wash with water and dry catalyst after obtaining handling.XRD analysis shows that its relative crystallinity has increased by 30%, and elementary analysis shows that its content of vanadium is 800ppm, and carrying out after ammonium exchange and the rare earth exchanged its n-tetradecane according to the same procedure among the embodiment 1 again, to split Jie's activity be 95%.These results show that the mother liquor after also available NaY synthesizes replaces NaOH solution.
Claims (5)
1. Retreatment method that contains the decaying catalyst of Y zeolite is characterized in that this method comprises: with said decaying catalyst with a kind of Na of containing
2The aqueous solution of the NaCl of O source and optional selection was handled 10～30 hours down at 80～110 ℃, wherein decaying catalyst: Na
2O: NaCl: H
2The weight ratio of O is 1: (0.01～0.3): (0～0.1): (0.3～3).
According to the process of claim 1 wherein the decaying catalyst of the said Y of containing zeolite be in the catalytic cracking process conventional that use and drawn off from device because of inactivation, handle the equilibrium catalyst that removes carbon deposit through making charcoal.
3. according to the process of claim 1 wherein said Na
2The O source is NaOH, or contained alkali in the NaY synthesis mother liquid, or waterglass.
4. according to the process of claim 1 wherein that the condition of handling is to handle 14～24 hours down at 90～100 ℃.
5. according to the method for claim 1, this method also comprises the step of the catalyst through said processing being carried out again ammonium or rare earth ion exchanged.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117284A CN1078100C (en) | 1998-08-14 | 1998-08-14 | Process for regenerating deactivated catalyst containing Y-type zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117284A CN1078100C (en) | 1998-08-14 | 1998-08-14 | Process for regenerating deactivated catalyst containing Y-type zeolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1245091A true CN1245091A (en) | 2000-02-23 |
| CN1078100C CN1078100C (en) | 2002-01-23 |
Family
ID=5225446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98117284A Expired - Lifetime CN1078100C (en) | 1998-08-14 | 1998-08-14 | Process for regenerating deactivated catalyst containing Y-type zeolite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1078100C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101757944B (en) * | 2008-12-25 | 2012-05-30 | 中国石油化工股份有限公司 | Cracking additive for increasing production of liquid gas and preparation method thereof |
| CN109305767A (en) * | 2017-11-16 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of method that harmlessness disposing FCC dead catalyst prepares geo-polymer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4784980A (en) * | 1987-07-15 | 1988-11-15 | Amoco Corporation | Process for preparing zeolite A from spent cracking catalyst |
| AU8976891A (en) * | 1990-12-21 | 1992-06-25 | Alcoa Of Australia Limited | Conversion process |
| US5182243A (en) * | 1991-11-01 | 1993-01-26 | Englehard Corporation | Process for preparing fluidized cracking catalysts from equilibrium fluidized cracking catalysts |
| CN1035104C (en) * | 1991-11-27 | 1997-06-11 | 中国科学院化工冶金研究所 | Regenerating method for waste molecular sieve cracking catalyzer |
-
1998
- 1998-08-14 CN CN98117284A patent/CN1078100C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101757944B (en) * | 2008-12-25 | 2012-05-30 | 中国石油化工股份有限公司 | Cracking additive for increasing production of liquid gas and preparation method thereof |
| CN109305767A (en) * | 2017-11-16 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of method that harmlessness disposing FCC dead catalyst prepares geo-polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1078100C (en) | 2002-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1170634C (en) | Prepn of high-silicon Y-Zeolite | |
| US20120156116A1 (en) | Process For Metal Recovery From Catalyst Waste | |
| US4692236A (en) | Catalytic cracking process for heavy oil with mixture of alumina and zeolite | |
| CN1506161A (en) | Ultrastable rare earth Y molecular sieve active component and preparation method thereof | |
| CN1036899C (en) | Modified aluminas and the use thereof in FCC catalysts | |
| CN1078100C (en) | Process for regenerating deactivated catalyst containing Y-type zeolite | |
| CZ294677B6 (en) | Process for increasing the activity of zeolite containing particulate solids | |
| CN1730614A (en) | Catalytic cracking catalyst and its preparation method | |
| CN1209288C (en) | Modified faujasite | |
| CN1064072C (en) | Catalyst containing modified kaoling for cracking hydrocarbons | |
| CN1245448A (en) | Process for zeolitic catalyst reactivation | |
| CN1214977C (en) | Method for preparing zeolite molecular sieve with high activity and stability | |
| CN1132695C (en) | Process for preparing superstable gamma-type molecular sieve | |
| CN1382525A (en) | Process for preparing rare-earth type high-silicon gamma-zeolite | |
| CN1060100C (en) | Reactivation method of cracking catalyst containing molecular sieve | |
| CN1239678C (en) | Catalytic cracking catalyst demetallated reactivating process | |
| CN1031030A (en) | The preparation of low content of rare earth super-stable Y molecular sieves | |
| CN109292927A (en) | A kind of waste acidity recovery regenerative agent and its preparation, application method | |
| CN1027739C (en) | Hydrocarbon cracking catalyzer composite containing vanadium fixing agent | |
| CN1062750A (en) | The cracking catalyst of phosphorous and hyperastable Y-type RE zeolite | |
| CN111514849B (en) | Dechlorination adsorbent, preparation method thereof, regeneration method thereof and application of dechlorination adsorbent in removal of organic chlorine | |
| CN1060304A (en) | The phosphorated hydrocarbon cracking catalyzer | |
| US6190562B1 (en) | Method for treating a liquid stream contaminated with an iodine-containing compound using a cation-exchanged crystalline manganese phosphate | |
| CN100404432C (en) | Method for reducing ammonia nitrogen pollution in zeolite modification process | |
| CN1624079A (en) | Hydrocarbon cracking catalyst containing modified faujasite |
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 | ||
| CX01 | Expiry of patent term |
Granted publication date: 20020123 |
|
| CX01 | Expiry of patent term |