CN101745373B - Catalytic cracking additive - Google Patents
Catalytic cracking additive Download PDFInfo
- Publication number
- CN101745373B CN101745373B CN2008102276627A CN200810227662A CN101745373B CN 101745373 B CN101745373 B CN 101745373B CN 2008102276627 A CN2008102276627 A CN 2008102276627A CN 200810227662 A CN200810227662 A CN 200810227662A CN 101745373 B CN101745373 B CN 101745373B
- Authority
- CN
- China
- Prior art keywords
- hole
- volume
- weight
- aluminium oxide
- auxiliary agent
- 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.)
- Active
Links
Images
Abstract
The invention provides a catalytic cracking additive. By taking the weight of the additive as reference, the additive contains 0.5 to 50 percent of alumina with stepped pore distribution based on the weight of alumina, 5 to 50 percent of binder based on the weight of oxides and 0 to 60 weight percent of clay. The alumina with stepped pore distribution consists of 10 to 90 weight percent of macropore alumina and 10 to 90 weight percent of micropore alumina. Based on the volume of 2 to 100-nanometer pores, in the macropore alumina, the volume of the 2 to 5-nanometer pores accounts for 20 to 35 percent; the volume of the 5 to 10-nanometer pores accounts for 25 to 45 percent; and the volume of the 10 to 60-nanometer pores accounts for 20 to 50 percent; and in the micropore alumina, the volume of the 2 to 5-nanometer pores accounts for 50 to 70 percent; the volume of the 5 to 10-nanometer pores accounts for 15 to 30 percent; and the volume of the 10 to 60-nanometer pores accounts for 10 to 20 percent. The catalytic cracking additive is used for heavy oil catalytic cracking, can improve heavy oil conversion capacity, and ensures high yield of light oil and good coke selectivity.
Description
Technical field
The present invention relates to a kind of hydrocarbon oil catalytic cracking co-catalyst.
Background technology
Catalytic cracking is the important means of refinery's processing of heavy oil, in the refinery critical role is arranged, the main means of be not only oil plant heavy oil balance, producing clean fuel, the focus of the energy efficiency of oil plant especially.The constantly soaring processing cost that has increased considerably the refinery of crude oil price in order to reduce cost, increases economic well-being of workers and staff; The refinery processes poor oil at a low price on the one hand; On the other hand heavy oil is carried out deep processing, therefore increasing oil plant turns to the focus of catalytic cracking the degree of depth of mink cell focus to transform, and pursues and improves working ability; Have more high value added product; In the hope of maximizing the benefits, this requires Cracking catalyst that high ability of residuum conversion is arranged, and has the lower dry gas and the productive rate of coke.
CN1255530, US5164073 adopt to have than the natural material of macropore volume such as concavo-convex rod, palygorskite, diatomite etc. as the catalyst substrates material, to improve the heavy oil conversion performance of catalyst; EP0550271A1, US5051385, US5997729 add siliceous material in the preparation process of aluminium-based catalyst, like waterglass, generate the performance that unformed big mesoporous aluminosilicate improves Cracking catalyst.
CN1209442C discloses a kind of Cracking catalyst and preparation method thereof; Macroporous aluminium oxide 5～60 heavy %, zeolite 5～60 heavy %, binding agent 5～40 heavy %, clay 5～85 heavy % in containing in the catalyst, the average pore diameter of said middle macroporous aluminium oxide is not less than 3 nanometers.Said big mesoporous aluminas can be boehmite or/and boehmite at the dehydration product below 900 ℃.The preparation method of said catalytic cracking catalyst after zeolite and middle macroporous aluminium oxide, binding agent, clay are mixed, makes through spraying, roasting, washing, drying.
Summary of the invention
The technical problem that the present invention will solve provides a kind of assistant for calalytic cracking of alumina-containing matrix, and this auxiliary agent can improve heavy oil cracking ability, improves yield of light oil.The other technical problem that the present invention will solve provides said Preparation of catalysts and methods for using them.
The present invention provides a kind of assistant for calalytic cracking, is benchmark with the weight of auxiliary agent, contains the aluminium oxide with stepped pore distribution in aluminium oxide 0.5 weight %～50 weight %, in the binding agent of oxide 5 weight %～50 weight % and the clay of 0-60 weight %; Said aluminium oxide with stepped pore distribution is made up of the macroporous aluminium oxide of 10～90 weight % and the aperture aluminium oxide of 10～90 weight %; Pore volume with 2～100nm hole is a benchmark, and in the said macroporous aluminium oxide, the pore volume in 2～5nm hole accounts for 20～35%, and the pore volume in 5～10nm hole accounts for 25～45%, and the volume in 10～60nm hole accounts for 20～50%; The pore volume in 2～5nm hole accounts for 50～70% in the said little porous aluminum oxide, and the pore volume in 5～10nm hole accounts for 15～30%, and the pore volume in 10～60nm hole accounts for 10～20%.
The present invention also provides a kind of preparation method of catalyst aid provided by the invention; Comprise the step of the aluminium oxide that will have stepped pore distribution, binding agent, clay mixing, making beating, spray shaping, wherein said aluminium oxide with stepped pore distribution is made up of the macroporous aluminium oxide of 10～90 weight % and the aperture aluminium oxide of 10～90 weight %; Pore volume with 2～60nm hole is a benchmark, and in the said macroporous aluminium oxide, the pore volume in 2～5nm hole accounts for 25～35%, and the pore volume in 5～10nm hole accounts for 25～45%, and the pore volume in 10～60nm hole accounts for 20～50%; The pore volume in 2～5nm hole accounts for 50～70% in the said little porous aluminum oxide, and the pore volume in 5～10nm hole accounts for 15～30%, and the volume in 10～60nm hole accounts for 10～20%.
The present invention also provides the application process of auxiliary agent provided by the invention, is included under the condition of catalytic cracking the step that mixture that auxiliary agent provided by the invention and catalytic cracking major catalyst are formed contacts with heavy oil.
Auxiliary agent provided by the invention is behind hydrothermal aging; In the larger aperture scope, has stepped pore distribution; Except pore size distribution with 4nm place; Near 9nm and 60nm, have relatively the pore size distribution of concentrating, and specific area and pore volume are higher, help the big molecule of heavy oil and change into value product.Catalyst aid of the present invention is used for RFCC, can improve heavy oil conversion performance, improves yield of light oil, and has coke selectivity preferably.For example: with the cracking additive that contains aluminium sol adhesive that 30 weight % have stepped pore distribution aluminium oxide, 5 weight %, 30 weight % molecular sieves, 35 weight % provided by the invention and industrial catalyst MLC-500 by weight the mixed that is 15: 85; Through 17 hours 100% steam agings; Be to carry out heavy oil catalytic cracking reaction under 6 the condition in 500 ℃ of oil ratios; React under similarity condition than the MLC-500 catalyst, the heavy oil yield reduces 3.07 percentage points, and yield of light oil increases by 1.73 percentage points; The burnt commentaries on classics than reducing to 0.094,5 percentage points of conversion ratio raisings by 0.1.It is thus clear that assistant for calalytic cracking provided by the invention can more effectively become high-value product with heavy oil transformation, can improve heavy oil cracking ability and conversion ratio, improve the light oil productive rate and have coke selectivity (changeing than expression) preferably with Jiao.
Description of drawings
Accompanying drawing 1 is the pore size distribution figure of the used big or small porous aluminum oxide of the present invention.
Accompanying drawing 2 is hydrothermal aging pore size distribution figure after 17 hours under the fresh attitude of catalyst that provides of embodiment 1 and 800 ℃, 100 water vapour atmospheres.
Accompanying drawing 3 is hydrothermal aging pore size distribution figure after 17 hours under the fresh attitude of catalyst and 800 ℃, 100 water vapour atmospheres of Comparative Examples 1 preparation.
The specific embodiment
In the assistant for calalytic cracking provided by the invention, contain the alumina host with stepped pore distribution, said aluminium oxide with stepped pore distribution is made up of macroporous aluminium oxide and aperture aluminium oxide; Pore volume with 2～100nm hole is a benchmark, and in the said macroporous aluminium oxide, the pore volume in 2～5nm hole accounts for 20～35%; The pore volume in 5～10nm hole accounts for 25～45 weight %, and the pore volume in 10～60nm hole accounts for 20～50%, and remaining is the pore volume content in 60～100nm hole; Under the preferable case; The pore volume in 2～5nm hole accounts for 20～30% in the said macroporous aluminium oxide, and the pore volume in 5～10nm hole accounts for 25～40%, and the pore volume in 10～60nm hole accounts for 25～45%; The pore volume in 2～5nm hole accounts for 50～70% in the said little porous aluminum oxide; The pore volume in 5～10nm hole accounts for 15～30%, and the pore volume in 10～60nm hole accounts for 10～20%, and remaining is the pore volume content in 60～100nm hole; Under the preferable case; The pore volume in 2～5nm hole accounts for 52～68% in the said little porous aluminum oxide, and the pore volume in 5～10nm hole accounts for 15～30%, and the pore volume in 10～60nm hole accounts for 11～18%.Volume with 2～100nm hole is a benchmark, and the pore volume in 60～100nm hole preferably is no more than 10% in the described macroporous aluminium oxide, and the pore volume in 60～100nm hole is no more than 5% in the said little porous aluminum oxide.The hole of wherein said 2～5nm is meant that the aperture is more than or equal to 2nm; Hole less than 5nm; The hole of 5～10nm is meant the aperture more than or equal to the hole of 5nm less than 10nm, and the hole of 10～60nm is meant that the aperture is more than or equal to 10nm; Less than the hole of 60nm, 2～100nm is meant that the aperture is more than or equal to the hole of 2nm smaller or equal to 100nm.The specific area of described macroporous aluminium oxide preferably is not less than 350m
2G
-1, pore volume preferably is not less than 0.70mlg
-1Weight with catalyst is benchmark, and described content with aluminium oxide of stepped pore distribution is preferably 1 weight %～35 weight %, and more preferably 3 weight %～30 weight % further are preferably 5 weight %～20 weight %; In the shoulder hole aluminium oxide, the content of said macroporous aluminium oxide is preferably 15～85 weight %, and the aperture alumina content is preferably 15～85 weight %.Said macroporous aluminium oxide and little porous aluminum oxide can be commercially available, or through existing method preparation.
In the assistant for calalytic cracking provided by the invention; The pore size distribution of under 800 ℃, 100% water vapour atmosphere, measuring with low-temperature nitrogen adsorption method after aging 17 hours; Pore volume with 2～100nm hole is a benchmark; The pore volume in 5～10nm hole accounts for 8～30% in the said auxiliary agent, is preferably 12～28%, and more preferably 15～26%; The volume in 10～60nm hole preferably accounts for 30～50% in the said auxiliary agent; The volume in 5～60nm hole preferably accounts for 50～75% in the said auxiliary agent, and the volume in the hole of 60～100nm preferably is no more than 20%.5～10nm hole is 0.2～2 with the ratio of the volume in 2～5nm hole in the said auxiliary agent, is preferably 0.4～1.8, and 10～60nm hole is preferably 1～3.5 with the ratio of the volume in 2～5nm hole, and 5～10nm hole is preferably 0.3～0.7 with the ratio of 10～60nm pore volume.
Binding agent of the present invention is selected from one or more in the binding agent commonly used in the assistant for calalytic cracking; Being preferably aluminium oxide, hydrated alumina, aluminium colloidal sol, Ludox, sial coagulates/and colloidal sol, aluminum phosphate coagulates/in colloidal sol and their precursor or the various modifier one or more, more preferably one or more in Ludox, boehmite and the aluminium colloidal sol.
In the assistant for calalytic cracking provided by the invention, also can contain molecular sieve, the content of preferred molecular sieve is no more than 70 weight %, and more preferably the content of molecular sieve is no more than 50 weight %.Said molecular sieve can be one or more in zeolite molecular sieve and the non-zeolite molecular sieve.Said zeolite molecular sieve for example has zeolite, Beta zeolite, the y-type zeolite molecular sieve of MFI structure.Said Y zeolite is selected from the Y zeolite of prepared in various methods, modification, for example REY, REHY, REUSY, USY.
Clay according to the invention is selected from one or more in the clay that is usually used in Cracking catalyst and auxiliary agent, for example one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite.These clays are that those of ordinary skills are known.Said clay content is preferably 10～50 weight %, more preferably 25～40 weight %.
Can also contain modified component in the assistant for calalytic cracking provided by the invention, one or more in phosphorous oxides, rare earth oxide, zirconia, silica-alumina and the titanium oxide for example, this is well known to those skilled in the art, and the present invention repeats no more.
Among the assistant for calalytic cracking preparation method provided by the present invention; Clay, binding agent, aluminium oxide with stepped pore distribution are mixed making beating; Spray-drying; Can carry out according to the preparation method of existing Cracking catalyst or auxiliary agent, for example the method among patent CN1098130A, CN1362472A, CN1727442A, CN1132898C or the CN1727445A.The said aluminium oxide that will have stepped pore distribution mixes making beating with clay, binding agent, can macroporous aluminium oxide and aperture aluminium oxide be prepared slurries respectively, mixes making beating with other component again after then two strands of slurries being mixed; Perhaps two strands of slurries are mixed making beating with binding agent and clay respectively; Also can macroporous aluminium oxide and aperture aluminium oxide solid be introduced in the slurries of clay and binding agent at the same time or separately and pull an oar.When also containing molecular sieve in the prepared catalyst, can introduce molecular sieve in any step of making beating, for example, introducing perhaps introduces simultaneously after having the aluminium oxide of stepped pore distribution with kaolin, aluminium oxide with stepped pore distribution.After preferably clay, binding agent, the aluminium oxide with stepped pore distribution, molecular sieve being prepared slurries respectively, more various slurries are mixed making beating.Wherein can also introduce acid in the mixed process, make mixture be the peptization state, said acid is preferably introduced after introducing macroporous aluminium oxide and aperture aluminium oxide, and acid is preferably 0.12～0.28 with the mol ratio of macroporous aluminium oxide and aperture aluminium oxide sum.Said acid is hydrochloric acid, nitric acid for example.The solid content of preferred prepared catalyst slurry is 5～45 weight %.
In the method for preparing catalyst provided by the invention, also can comprise the catalyst microballoon washing that spray-drying is obtained, dry step.Said washing, drying are prior art, and the present invention does not have specific (special) requirements.
Assistant for calalytic cracking provided by the invention is applicable to hydrocarbon oil catalytic cracking, is particularly suitable for RFCC, and said heavy oil is decompressed wax oil, vacuum gas oil (VGO), propane deasphalting oil, reduced crude, decompression residuum for example.When catalytic cracking catalyst of the present invention is used for hydrocarbon oil catalytic cracking, hydrocarbon ils is contacted with the catalyst mixture that contains auxiliary agent of the present invention, under the condition of catalytic cracking, carry out catalytic cracking reaction.Contain auxiliary agent provided by the invention and major catalyst in the said catalyst mixture, wherein the content of auxiliary agent is 1～99 weight %, is preferably 1～30 weight %; The weight ratio of auxiliary agent and major catalyst is 1: 99～30: 70, preferred 5: 95～20: 80; Said major catalyst is existing catalytic cracking catalyst commonly used, for example contain the Y zeolite Cracking catalyst, contain the Cracking catalyst of MFI structural zeolite, these catalyst are known for those skilled in the art.Also can contain other cracking additive in the catalyst mixture, for example the CO combustion adjuvant.Assistant for calalytic cracking provided by the invention is close with the major catalyst physical property, can with the major catalyst physical mixed after add catalytic cracking unit, also can add catalytic cracking unit separately, the device in mix with major catalyst.
Following embodiment will further specify the present invention, but therefore not limit the present invention.
In an embodiment with Comparative Examples in:
Zeolite REY, DASY2.0, REHY, ZRP-1; Provide by catalyst Shandong branch company of China Petrochemical Industry; Aluminium colloidal sol is provided by catalyst Shandong branch company of China Petrochemical Industry; Its alumina content is 21.5 weight %, and kaolin is Chinese Suzhou kaolin, and macroporous aluminium oxide, little porous aluminum oxide are provided by Shandong Aluminum Plant.Used chemical reagent does not indicate especially among Comparative Examples and the embodiment, and its specification is a chemical pure.Catalyst C1 trade names MLC-500, the trade names of catalyst C2 are GOR-II, are catalyst Shandong branch company of China Petrochemical Industry product.
In each Comparative Examples and embodiment, the pore size distribution of catalyst is measured { referring to " petrochemical industry analytical method (RIPP test method) ", volumes such as Yang Cuiding, Science Press, nineteen ninety publication } with low-temperature nitrogen adsorption method.
In water, add 1750 gram kaolin (in butt, high territory solid content 76 weight %), stirred 15 minutes; Add the 1250 little porous aluminum oxides of gram (in butt) and stir, add macroporous aluminium oxide 250 grams (in butt) again, stirred 15 minutes; Adding 820ml concentration is 31 weight % hcl acidifyings, makes the aluminium oxide peptization, stirs 30 minutes; Add molecular sieve pulp again and (wherein contain REY molecular sieve 1500 grams (in butt) in the slurries; The content of molecular sieve is 30 weight % in the molecular sieve pulp) stir, add aluminium colloidal sol 250 grams (in aluminium oxide, the content of aluminium oxide is 21.5 weight % in the aluminium colloidal sol) at last; Obtain the catalyst aid slurries after the stirring, spray shaping obtains the catalyst aid microballoon.Wherein to make the solid content of the catalyst aid slurries of formation be 30 weight % to the consumption of each component.
Resulting auxiliary agent microballoon in 400 ℃ of roastings 2 hours, is got auxiliary agent microballoon 1000 gram then and mixed with 1 liter of oronain solution and wash (the 2 weight % that the oronain amount is the catalyst butt), filtration, drying, obtain assistant for calalytic cracking of the present invention.
Embodiment 2～9
Method according to embodiment 1 prepares auxiliary agent, and wherein each raw material consumption is seen table 1, and wherein the raw material consumption is in butt weight.
Table 1
| The embodiment numbering | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| The auxiliary agent numbering | A1 | A2 | A3 | A4 | A5 | A6 | A7 | A8 | A9 |
| Macroporous aluminium oxide A, gram | 250 | 500 | 750 | 1000 | 1250 | 1000 | |||
| Macroporous aluminium oxide B, gram | 1000 | 1600 | |||||||
| Macroporous aluminium oxide C, gram | 600 | ||||||||
| Aperture aluminium oxide A, gram | 1250 | 1000 | 750 | 500 | 250 | 400 | |||
| Aperture aluminium oxide B, gram | 200 | ||||||||
| Aperture aluminium oxide C, gram | 2000 | 900 | |||||||
| The hydrochloric acid addition, ml | 820 | 820 | 820 | 820 | 820 | 2130 | 420 | 750 | 1130 |
| Aluminium colloidal sol (in aluminium oxide), gram | 250 | 250 | 250 | 250 | 250 | 250 | 250 | 0 | 250 |
| Ludox (in silica), gram | 0 | 0 | 0 | 0 | 0 | 0 | 800 | ||
| Kaolin, gram | 1750 | 1750 | 1750 | 1750 | 1750 | 500 | 1500 | 1000 | 2250 |
| REY, gram | 1500 | 1500 | 1500 | 1500 | 1500 | 0 | 0 | 0 | |
| DASY2.0, gram | 0 | 0 | 0 | 0 | 0 | 1250 | 0 | 2000 | |
| REHY, gram | 0 | 0 | 0 | 0 | 0 | 0 | 2250 | 0 | |
| The catalyst aid abrasion index | 1.1 | 1.2 | 1.8 | 2.0 | 3.0 | 2.4 | 1.5 | 2.1 | |
| Catalyst aid water droplet method pore volume, milliliter/gram | 0.34 | 0.36 | 0.40 | 0.45 | 0.48 | 0.43 | 0.37 | 0.40 |
Table 2 is seen in the pore size distribution of the embodiment of the invention 1～9 big pore aluminium oxide, little porous aluminum oxide and prepared catalyst aid.Wherein macroporous aluminium oxide and little porous aluminum oxide are measured pore size distribution and pore volume with low-temperature nitrogen adsorption method then prior to 400 ℃ of roastings 1 hour; Embodiment and Comparative Examples catalyst aid are measured pore size distribution and pore volume with low-temperature nitrogen adsorption method after aging 17 hours down in 800 ℃, 100% water vapour atmosphere.
Table 2
Comparative Examples 1～3
According to method preparation contrast catalyst aid B1～B3 of embodiment 1, it feeds intake and sees table 3, and table 2 is seen in pore size distribution.Used boehmite average pore size 3.86nm.
Table 3
| The embodiment numbering | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| The auxiliary agent numbering | B1 | B2 | B3 |
| Boehmite, (in aluminium oxide) gram | 1500 | 400 | 2500 |
| The hydrochloric acid addition, ml | 820 | 220 | 630 |
| Aluminium colloidal sol, gram (in aluminium oxide) | 250 | 0 | 250 |
| Ludox, gram (in silica) | 0 | 850 | 0 |
| Kaolin, gram | 1750 | 1500 | 2250 |
| REY, gram | 1500 | 0 | 0 |
| DASY2.0, gram | 0 | 2250 | 0 |
Visible by table 2, have more 5～10nm hole behind the auxiliary agent hydrothermal aging that embodiment 1～9 provides.
Comparative Examples 4
Get industrial catalyst C1 (trade names MLC-500, catalyst Shandong branch company of China Petrochemical Industry product, down with) aging 17 hours of 800 ℃, 100% steam, go up the catalytic performance of investigating aging back auxiliary agent at ACE device (a kind of small fixed flowing bed).Raw materials used oiliness matter is seen table 4.Appreciation condition and result see table 5.
Get auxiliary agent that instance 1,3,5 provides and industrial catalyst C1 by weight 10: 90 physical mixed, aging 17 hours of 800 ℃, 100% steam are gone up the catalytic performance of investigating aging rear catalyst at ACE device (a kind of small fixed flowing bed).Feedstock oil character is seen table 4.Appreciation condition and result see table 5.
Comparative Examples 5
Get auxiliary agent B 1 that Comparative Examples 1 provides and industrial catalyst C1 by weight 10: 90 physical mixed, aging 17 hours of 800 ℃, 100% steam are gone up the catalytic performance of investigating aging rear catalyst at ACE device (a kind of small fixed flowing bed).Feedstock oil character is seen table 3.Appreciation condition and result see table 5.
Table 4
Table 5
Visible by table 5, auxiliary agent provided by the invention is used for RFCC, can improve heavy oil conversion performance, coke selectivity and liquid and receive (gasoline+diesel oil+yield of liquefied gas).
Embodiment 11～12
Get auxiliary agent A 2 that instance 2 provides and industrial catalyst C1 respectively by weight 5: 95,15: 85 physical mixed, aging 17 hours of 800 ℃, 100% steam are gone up the catalytic performance of investigating aging rear catalyst at ACE device (a kind of small fixed flowing bed).Feedstock oil character is seen table 3.Appreciation condition and result see table 5.
Comparative Examples 6
Get industrial catalyst C2 in aging 8 hours of 800 ℃, 100% steam, go up the catalytic performance of investigating aging rear catalyst at ACE device (small fixed flowing bed).Raw materials used oiliness matter is seen table 3.Appreciation condition and result see table 6.
Table 6
Visible by table 6, auxiliary agent provided by the invention all can show good heavy oil conversion performance and coke selectivity with different ratios and major catalyst blending, can adjust flexibly according to the needs of products distribution.
Embodiment 13～14
Get auxiliary agent A 7 that instance 6,7 provides, A9 respectively with industrial catalyst C2 by weight 5: 95 physical mixed, aging 8 hours of 800 ℃, 100% steam are gone up the catalytic performance of investigating aging rear catalyst at ACE device (a kind of small fixed flowing bed).Feedstock oil character is seen table 4.Appreciation condition and result see table 7.
Comparative Examples 7～8
Get auxiliary agent B 2 that Comparative Examples 2,3 provides, B3 respectively with industrial catalyst C2 by weight 5: 95 physical mixed, aging 8 hours of 800 ℃, 100% steam are gone up the catalytic performance of investigating aging rear catalyst at ACE device (a kind of small fixed flowing bed).Feedstock oil character is seen table 4.Appreciation condition and result see table 7.
Table 7
Visible by table 7, contrast medium B2 has reduced total heavy oil conversion performance; Contrast medium B3 improves coke output, and its heavy oil cracking ability is relatively poor.Auxiliary agent provided by the invention does not increase coke output when improving heavy oil conversion performance, can effectively heavy oil transformation be become high-value product, increases the yield of gasoline and diesel oil.
Claims (12)
1. assistant for calalytic cracking is a benchmark with the weight of auxiliary agent, contains the aluminium oxide with stepped pore distribution in aluminium oxide 0.5 weight %～50 weight %, in the binding agent of oxide 5 weight %～50 weight % and the clay of 0-60 weight %; Said aluminium oxide with stepped pore distribution is made up of the macroporous aluminium oxide of 10～90 weight % and the aperture aluminium oxide of 10～90 weight %; Volume with 2～100nm hole is a benchmark, and in the said macroporous aluminium oxide, the pore volume in 2～5nm hole accounts for 20～35%, and the pore volume in 5～10nm hole accounts for 25～45%, and the volume in 10～60nm hole accounts for 20～50%; The pore volume in 2～5nm hole accounts for 50～70% in the said little porous aluminum oxide, and the volume in 5～10nm hole accounts for 15～30%, and the volume in 10～60nm hole accounts for 10～20%; The hole of wherein said 2～5nm is meant the aperture more than or equal to 2nm, less than the hole of 5nm, and the hole of 5～10nm; Be meant that the aperture is more than or equal to the hole of 5nm less than 10nm; The hole of 10～60nm is meant the aperture more than or equal to 10nm, and less than the hole of 60nm, 2～100nm is meant that the aperture is more than or equal to the hole of 2nm smaller or equal to 100nm.
2. according to the described auxiliary agent of claim 1, it is characterized in that, is benchmark with the pore volume in 2～100nm hole, and the pore volume in 5～10nm hole accounts for 8～30% in the auxiliary agent.
3. according to the described auxiliary agent of claim 2, it is characterized in that the pore volume in 5～10nm hole accounts for 15～26% in the auxiliary agent.
4. according to the described auxiliary agent of claim 1, it is characterized in that 5～10nm hole is 0.2～2 with the ratio of the volume in 2～5nm hole in the said auxiliary agent.
5. according to the described auxiliary agent of claim 1, it is characterized in that 10～60nm hole is 1～3.5 with the ratio of the volume in 2～5nm hole in the said auxiliary agent.
6. according to the described auxiliary agent of claim 1, it is characterized in that 5～10nm hole is 0.3～0.7 with the ratio of 10～60nm pore volume in the said auxiliary agent.
7. according to the described auxiliary agent of claim 1, it is characterized in that the volume in 5～60nm hole accounts for 50～75% in the auxiliary agent, the volume in the hole of 60～100nm is no more than 20%.
8. according to the described auxiliary agent of claim 7, it is characterized in that said aluminium oxide with stepped pore distribution contains the macroporous aluminium oxide of 15～85 weight %, contain the little porous aluminum oxide of 15～85 weight %.
9. the preparation method of each described assistant for calalytic cracking of claim 1～7; Comprise the step of the aluminium oxide that will have stepped pore distribution, binding agent, clay mixing, making beating, spray shaping, wherein said aluminium oxide with stepped pore distribution is made up of the macroporous aluminium oxide of 10～90 weight % and the aperture aluminium oxide of 10～90 weight %; Volume with 2～100nm hole is a benchmark, and in the said macroporous aluminium oxide, the pore volume in 2～5nm hole accounts for 20～35%, and the pore volume in 5～10nm hole accounts for 25～45 weight %, and the volume in 10～60nm hole accounts for 20～50%; The pore volume in 2～5nm hole accounts for 50～70% in the said little porous aluminum oxide, and the volume in 5～10nm hole accounts for 15～30%, and the volume in 10～60nm hole accounts for 10～20%; The hole of wherein said 2～5nm is meant the aperture more than or equal to 2nm, less than the hole of 5nm, and the hole of 5～10nm; Be meant that the aperture is more than or equal to the hole of 5nm less than 10nm; The hole of 10～60nm is meant the aperture more than or equal to 10nm, and less than the hole of 60nm, 2～100nm is meant that the aperture is more than or equal to the hole of 2nm smaller or equal to 100nm.
10. the preparation method of the described assistant for calalytic cracking of claim 8; Comprise the step of the aluminium oxide that will have stepped pore distribution, binding agent, clay mixing, making beating, spray shaping, wherein said aluminium oxide with stepped pore distribution is made up of the macroporous aluminium oxide of 15～85 weight % and the aperture aluminium oxide of 15～85 weight %; Volume with 2～100nm hole is a benchmark, and in the said macroporous aluminium oxide, the pore volume in 2～5nm hole accounts for 20～35%, and the pore volume in 5～10nm hole accounts for 25～45 weight %, and the volume in 10～60nm hole accounts for 20～50%; The pore volume in 2～5nm hole accounts for 50～70% in the said little porous aluminum oxide, and the volume in 5～10nm hole accounts for 15～30%, and the volume in 10～60nm hole accounts for 10～20%; The hole of wherein said 2～5nm is meant the aperture more than or equal to 2nm, less than the hole of 5nm, and the hole of 5～10nm; Be meant that the aperture is more than or equal to the hole of 5nm less than 10nm; The hole of 10～60nm is meant the aperture more than or equal to 10nm, and less than the hole of 60nm, 2～100nm is meant that the aperture is more than or equal to the hole of 2nm smaller or equal to 100nm.
11. the application process of each said auxiliary agent of claim 1～8 in catalytic cracking; It is characterized in that, comprise the step that catalyst mixture that said auxiliary agent or said auxiliary agent and catalytic cracking major catalyst are formed and heavy oil contact under catalytic cracking condition.
12., it is characterized in that the content of auxiliary agent is 1～30 weight % in the said catalyst mixture according to the described method of claim 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102276627A CN101745373B (en) | 2008-11-28 | 2008-11-28 | Catalytic cracking additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102276627A CN101745373B (en) | 2008-11-28 | 2008-11-28 | Catalytic cracking additive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101745373A CN101745373A (en) | 2010-06-23 |
| CN101745373B true CN101745373B (en) | 2012-05-23 |
Family
ID=42473365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102276627A Active CN101745373B (en) | 2008-11-28 | 2008-11-28 | Catalytic cracking additive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101745373B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007990B (en) * | 2011-09-22 | 2014-12-03 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
| CN107303479B (en) * | 2016-04-19 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of phosphorus Aluminum sol and its preparation method and application and catalytic cracking catalyst and preparation method thereof |
| CN108014775B (en) * | 2017-11-22 | 2021-03-16 | 青岛惠城环保科技股份有限公司 | Preparation method of catalytic cracking calcium-resistant catalyst |
| CN111744483B (en) | 2019-03-28 | 2021-09-07 | 中国石油化工股份有限公司 | Aluminum oxide, preparation method and application thereof |
| CN110252385A (en) * | 2019-06-17 | 2019-09-20 | 青岛惠城环保科技股份有限公司 | A kind of catalytic cracking catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260240A (en) * | 1989-12-29 | 1993-11-09 | Chevron Research And Technology Company | Process for the demetallization of FCC catalyst |
| CN1083512A (en) * | 1993-08-26 | 1994-03-09 | 中国石化兰州炼油化工总厂 | A kind of preparation method who comprises the catalytic cracking catalyst of molecular sieve |
| CN1296860A (en) * | 1999-11-17 | 2001-05-30 | 中国石化集团齐鲁石油化工公司 | Process for preparing catalyst containing small-grain Y-molecular sieve |
| CN1436835A (en) * | 2002-02-07 | 2003-08-20 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and its prepn |
| CN1854252A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Petroleum hydrocabon cracking catalyst and its production |
-
2008
- 2008-11-28 CN CN2008102276627A patent/CN101745373B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260240A (en) * | 1989-12-29 | 1993-11-09 | Chevron Research And Technology Company | Process for the demetallization of FCC catalyst |
| CN1083512A (en) * | 1993-08-26 | 1994-03-09 | 中国石化兰州炼油化工总厂 | A kind of preparation method who comprises the catalytic cracking catalyst of molecular sieve |
| CN1296860A (en) * | 1999-11-17 | 2001-05-30 | 中国石化集团齐鲁石油化工公司 | Process for preparing catalyst containing small-grain Y-molecular sieve |
| CN1436835A (en) * | 2002-02-07 | 2003-08-20 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and its prepn |
| CN1854252A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Petroleum hydrocabon cracking catalyst and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101745373A (en) | 2010-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101745417B (en) | Catalytic cracking catalyst | |
| JP5053098B2 (en) | Catalyst and method for cracking hydrocarbons | |
| CN102079986B (en) | Cracking method of heavy hydrocarbon oil | |
| CN101462741B (en) | Method for preparing ZSM-5 zeolite by in situ crystallization | |
| CN102078821B (en) | Cracking catalyst containing mesoporous silica-alumina materials | |
| CN100496711C (en) | Cracking catalyst and its preparing process | |
| CN101745418A (en) | Catalytic cracking catalyst, preparation and application thereof | |
| CN106807434B (en) | A kind of preparation method of porous active catalysis material | |
| CN101745373B (en) | Catalytic cracking additive | |
| CA2240608C (en) | Catalyst for cracking heavy oil | |
| CN105813740A (en) | Phosphorus-containing fcc catalyst | |
| CN101462740A (en) | Method for preparing ZSM-5 zeolite by in situ crystallization | |
| CN101210187A (en) | Catalyst for cracking heavy oil | |
| CN112371167B (en) | Catalyst for producing high-octane component gasoline and preparation method and application thereof | |
| TW201138954A (en) | Process for making improved zeolite catalysts from peptized aluminas | |
| CN109304212A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| JP3949778B2 (en) | Catalytic cracking catalyst | |
| CN100537030C (en) | Catalytic cracking additive for promoting liquid gas propylene concentration | |
| CN104014361A (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN101767029B (en) | Heavy oil cracking catalyst and application thereof | |
| CN109746039B (en) | Hierarchical pore silicon-aluminum catalytic material and preparation method and application thereof | |
| CN111686785A (en) | Heavy oil catalytic cracking catalyst and preparation method thereof | |
| CN109675616B (en) | Catalytic conversion catalyst for producing more butene, preparation method of catalytic conversion catalyst and catalytic conversion method for producing more butene | |
| CN110636901A (en) | Bottoms upgrading and low coke fcc catalyst | |
| CN1104955C (en) | Once-exchanging once-calcining phosphoreted Y-zeolite cracking catalyst and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |