CN107224991A - A kind of catalytic cracking improves octane number auxiliary agent and preparation method thereof - Google Patents
A kind of catalytic cracking improves octane number auxiliary agent and preparation method thereof Download PDFInfo
- Publication number
- CN107224991A CN107224991A CN201710654005.XA CN201710654005A CN107224991A CN 107224991 A CN107224991 A CN 107224991A CN 201710654005 A CN201710654005 A CN 201710654005A CN 107224991 A CN107224991 A CN 107224991A
- Authority
- CN
- China
- Prior art keywords
- auxiliary agent
- octane number
- catalytic cracking
- molecular sieve
- temperature
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses a kind of catalytic cracking and improves octane number auxiliary agent and preparation method thereof, and wherein catalytic cracking improves octane number auxiliary agent and is made up of following components according to percentage by weight：Silica alumina ratio is more than or equal to 200 in molecular sieve 0 70%, matrix 10 70%, nonmetallic active material 0 10%, binding agent 0 50%, and auxiliary agent 0 30%, the molecular sieve.The present invention prepares this kind of auxiliary agent by dipping, mashing, spray drying, roasting and aging.The persistence that catalytic cracking raising octane number auxiliary agent of the present invention possesses in high reactivity, hydrothermal stability and course of reaction is high, the slow characteristic of deactivation rate.
Description
Technical field
The invention belongs to catalyst technical field, and in particular to a kind of catalytic cracking improves octane number auxiliary agent and its system
Preparation Method.
Background technology
Gasoline in the cylinder normal combustion when flame propagation velocity be 10-20m/s, in detonating combustion up to 1500-
2000m/s, the latter can make temperature cylinder play liter, and gasoline combustion is incomplete, machine sharp pounding, so that power output declines,
Parts are damaged.Therefore, octane number is an important indicator for weighing motor petrol, main in the acquisition of China's light-end products
It is that, by catalytic cracking unit, but the octane number of catalytically cracked gasoline is relatively low, it is impossible to produce high-grade gasoline, and with environmental protection
It is required that raising, improve octane number be the task of top priority.
In order to pursue higher octane number, the catalytic cracking unit of oil plant typically now takes high temperature short contact
Operating condition and super stable molecular sieve catalyst, or gasoline octane is improved using a kind of synthetic zeolite catalysts cracking auxiliary agent of modification
Value, also there is patent report at present.
Type cracking/aromatization is selected as the active component of aromatisation using the ZSM-5 molecular sieve of Ga modifications such as USP4929337
Changing component makes alkane and cracking of olefins/aromatisation, selects type aromatisation component and alkane and alkene are changed into aromatic hydrocarbons.
USP4867863 describes a kind of method that RFCC improves octane number, and used catalyst contains 0.5-
5% HZSM-5 molecular sieves, the octane number of gasoline can be improved using this catalyst.
Also a kind of common selectivity for improving catalyst or auxiliary agent to low-carbon alkene, so as to improve octane number
Method.
A kind of catalyst as disclosed high zeolite content, high abrasion resistance strength in US2002/0049133A1.The catalyst
ZSM-5 zeolite containing 30-85w%, 6-24w% phosphorus (P2O5), and the Al less than 10w%2O3With the clay of surplus etc. its
His component, phosphorus therein is present in matrix.The catalyst is used in catalytic cracking process, can increase light olefin, especially propylene
Yield.
Although in the prior art, having there is the report that some catalytic cracking improve octane number auxiliary agent, these
The reactivity of auxiliary agent is relatively low, and the persistence in hydrothermal stability and course of reaction is not high, and deactivation rate is fast.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of catalytic cracking and improve octane number auxiliary agent and its preparation
Method, hydrothermal stability and reaction low with the reactivity for solving the raising octane number auxiliary agent of catalytic cracking in the prior art
During persistence it is not high, the problem of deactivation rate is fast.
In order to solve the above technical problems, the technical solution adopted by the present invention：A kind of catalytic cracking improves octane number and helped
Agent, it is characterised in that be made up of following components according to percentage by weight：
Molecular sieve 0-70%, matrix 10-70%, nonmetallic active material 0-10%, binding agent 0-50%, and auxiliary agent 0-
30%, silica alumina ratio is more than or equal to 200 in the molecular sieve.It is preferred that, silica alumina ratio is more than or equal to 350 in molecular sieve.
The molecular sieve of high silica alumina ratio is used in the present invention, can effectively make straight chain normal alkane isomerization or aromatisation,
So as to improve octane number in catalytic cracking process.The molecular sieve of high silica alumina ratio can effectively control hydrogen in catalytic cracking process
Transfer reaction, so as to reduce the yield losses that gasoline conversion is brought by liquefied gas as far as possible.
Further, the molecular sieve can for Y type molecular sieve, X-type molecular sieve, ZSM types molecular sieve, beta molecular sieve or
Any one or a few in person's erionite.
Further, the nonmetallic active material can for nonmetal oxide, Non-metal hydroxides, acidulants,
Any one or a few in nonmetallic salt or organic matter containing nonmetalloid.In the present invention, nonmetallic active matter
Matter promotes the cracking of macromolecular linear paraffin as active component, while controlling the hydrogen transfer reaction in cracking process, promotes alkane
Hydrocarbon isomerization, so as to improve octane number.
Further, the nonmetalloid in the nonmetallic active material can be IIIA, VA, VIA or VIIA
One kind in race's nonmetalloid.For example, nonmetalloid can be the boron in Group IIIA, the phosphorus in VA races or arsenic, Group VIA
In selenium or the iodine in VIIA races.And in the present invention, the preferable nonmetalloid of effect is boron or phosphorus.
Further, the auxiliary agent can be any one in organic acid, Organic Alcohol, organic ether or organic ester or several
Kind.Preferably, organic acid can be any one in oxalic acid, citric acid, and Organic Alcohol can be times in glycerine, ethylene glycol
Meaning is a kind of, and organic ester can be ethyl acetate.
Using active nonmetallic substance and Aid Portions, it is produced Synergy, optimize acid site quantity and acid is strong
Degree, and optimize the pore distribution of molecular sieve, and then improve the work that the catalytic cracking of the present invention improves octane number auxiliary agent
Property and anti-impurity pollution capacity.
Further, the binding agent is any one in Alumina gel or Ludox.
Using the sol bonded technology of unique aluminum, the catalytic cracking for substantially increasing the present invention improves octane number auxiliary agent
Wear strength, tear strength can reach≤1.5, the index of far smaller than current other like products, so as to reduce raising vapour
The consumption that oily octane enhancing additive is produced because being worn and torn with major catalyst in use.
A kind of catalytic cracking improves the preparation method of octane number auxiliary agent, it is characterised in that this method includes following step
Suddenly：
(1) molecular sieve, matrix, nonmetallic active material, binding agent, and auxiliary agent are weighed according to weight percentages of components,
It will be mixed to form mixture, using lapping device by mixture grind into powder, and the stirring that adds water forms slurries, the water
It is 1-10: 1 with mixture weight ratio, the slurries is stood more than 2 hours at a temperature of 0~100 DEG C；
(2) slurries in step (1) are stirred more than 1 hour at a temperature of 0~100 DEG C using agitator, is allowed to scattered
Uniformly；
(3) slurries in step (2) are spray-dried at a temperature of 100-300 DEG C, to form builder granule, will be helped
Agent particle is sieved, and obtains the target particles of builder granule particle diameter≤200 μm；
(4) target particles are carried out to roasting 0-5 hours at a temperature of 300-800 DEG C, builder granule is obtained；
(5) by builder granule at a certain temperature with chemical reagent aging certain time, be improved gasoline octane
It is worth auxiliary agent.
Further, the temperature of aging is 200~450 DEG C in step (5).
Further, the time of aging is 1-8 hours in step (5).
Further, chemical reagent includes deionized water, alkaline solution, Organic Alcohol, amine or phenols chemical combination in step (5)
Thing.
Using unique solvent aging technology in the present invention, because the acid site quantity of fresh auxiliary agent is more, acid strength also compares
It is higher, cause lytic activity higher, so during catalytic cracking reaction, carbon distribution is easily produced on auxiliary agent carrier, is caused
Auxiliary agent is inactivated quickly.Using aging technology, artificial reduction auxiliary agent initial activity, especially acid strength can slow down inactivation, raising is helped
Agent service life.The aging activity of builder granule is relevant with the alkalescence of ageing time, aging temperature and aging reagent.Builder granule
Ageing time it is too short, acid site quantity is more, and acid strength remains unchanged higher, and the lytic activity of builder granule remains unchanged higher；Auxiliary agent
Particle aging overlong time, the activity reduction of auxiliary agent, is unfavorable for improving octane number.Unsuitable too low, the temperature mistake of aging temperature
Low, ageing time is long；Builder granule aging temperature is too high also to influence the activity of builder granule；Aging technology improves gasoline
Lasting high activity in octane enhancing additive hydrothermal stability and course of reaction, the raising octane number for slowing down the present invention significantly is helped
Agent deactivation rate, extends the service life of auxiliary agent.
Beneficial effects of the present invention：
1st, the molecular sieve of high silica alumina ratio is used in the present invention, can effectively make straight chain normal alkane isomerization or aromatization
Change, so as to improve octane number in catalytic cracking process.The molecular sieve of high silica alumina ratio can effectively control catalytic cracking process
Middle hydrogen transfer reaction, so as to reduce the yield losses that gasoline conversion is brought by liquefied gas as far as possible.
2nd, using active nonmetallic substance and Aid Portions, it is produced Synergy, optimize acid site quantity and acid
Intensity, and optimize the pore distribution of molecular sieve, and then improve catalytic cracking raising octane number auxiliary agent of the invention
Active and anti-impurity pollution capacity.
3rd, using the sol bonded technology of unique aluminum, the catalytic cracking for substantially increasing the present invention improves octane number auxiliary agent
Wear strength, tear strength can reach≤1.5, far smaller than the index of other like products at present, so as to reduce raising
The consumption that octane number auxiliary agent is produced because being worn and torn with major catalyst in use.
4th, improve octane number auxiliary agent hydrothermal stability using unique solvent aging technology in the present invention and reacted
Lasting high activity in journey, slows down the raising octane number auxiliary agent deactivation rate of the present invention significantly.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
A kind of catalytic cracking improves octane number auxiliary agent, is made up of following components according to percentage by weight：Molecular sieve 0-
70%, matrix 10-70%, nonmetallic active material 0-10%, binding agent 0-50%, and auxiliary agent 0-30%, silicon in molecular sieve
Aluminum ratio is more than or equal to 200, it is preferred that silica alumina ratio is more than or equal to 350 in molecular sieve.
It should be noted that molecular sieve can for Y type molecular sieve, X-type molecular sieve, ZSM types molecular sieve, beta molecular sieve or
Any one in person's erionite.The present invention is not construed as limiting to the preprocessing process of molecular sieve, after being modified to them
Use, the molecular sieve of super steady type can also be selected.Preferably molecular sieve is ZSM types and beta molecular sieve, and molecular sieve in the present invention
Middle silica alumina ratio is higher, and preferably equal to or greater than 200.Using the molecular sieve of high silica alumina ratio, it can effectively make straight chain n-alkane different
Structure or aromatisation, so as to improve octane number in catalytic cracking process.The molecular sieve of high silica alumina ratio can effectively control to urge
Change hydrogen transfer reaction in cracking process, so as to reduce the yield losses that gasoline conversion is brought by liquefied gas as far as possible.Further
, silica alumina ratio is more than or equal to 350 in molecular sieve.
Matrix in the present invention can be alukalin, clay etc..The present invention to the modification of its matrix, activity processing,
Or impurity treatment and be not construed as limiting.Pickling, alkali cleaning can be carried out to matrix or using other chemical reagent at it
Reason.
Nonmetallic active material nonmetalloid can be the nonmetallic member of IIIA, VA, VIA or VIIA race in the present invention
One kind in element.For example, nonmetalloid can be Group IIIA in boron, the phosphorus in VA races or the selenium in arsenic, Group VIA or
Iodine in person VIIA races.And in the present invention, the preferable nonmetalloid of effect is boron or phosphorus.Promote big point as active component
The cracking of sub- linear paraffin, while controlling the hydrogen transfer reaction in cracking process, promotes alkane isomerization, so that it is pungent to improve gasoline
Alkane value.Due to play active function in the auxiliary agent be nonmetalloid in itself, therefore, the present invention is to the tool of nonmetallic active material
Body form is not limited, and can be nonmetal oxide, Non-metal hydroxides, acidulants, nonmetallic salt or containing non-
Any one in the organic matter of metallic element.Such as borax, phosphoric acid, arsenic acid or selenate, iodide.
Binding agent in the present invention is any one in Alumina gel or Ludox, it is preferred that binding agent is Alumina gel.Adopt
With the sol bonded technology of unique aluminum, the catalytic cracking for substantially increasing the present invention improves the wear-resistant strong of octane number auxiliary agent
Degree, tear strength can reach≤1.5, the index of far smaller than current other like products, so as to reduce raising octane number
The consumption that auxiliary agent is produced because being worn and torn with major catalyst in use.
Auxiliary agent in the present invention can be any one in organic acid, Organic Alcohol, organic ether or organic ester.Preferably,
Organic acid can be any one in oxalic acid, citric acid, and Organic Alcohol can be any one in glycerine, ethylene glycol, have
Machine ester can be ethyl acetate, and ethers can be ether.Its effect is that in preparation process, the addition of auxiliary agent can stir slurries
Mix more abundant, and form in roasting process more uniform pore size distribution.
Using active nonmetallic substance and Aid Portions in the present invention, it is produced Synergy, optimize acid site number
Amount and acid strength, and optimize the pore distribution of molecular sieve, and then improve the catalytic cracking raising octane number of the present invention
The active and anti-impurity pollution capacity of auxiliary agent.
A kind of catalytic cracking improves the preparation method of octane number auxiliary agent, it is characterised in that this method includes following step
Suddenly：
(1) molecular sieve, matrix, nonmetallic active material, binding agent, and auxiliary agent are weighed according to weight percentages of components,
Be mixed to form mixture, using lapping device by mixture grind into powder, and the stirring that adds water forms slurries, the water with
Mixture weight ratio is 1-10: 1, and the slurries are stood into more than 2 hours at a temperature of 0~100 DEG C；
(2) slurries in step (1) are stirred more than 1 hour at a temperature of 0~100 DEG C using agitator, is allowed to scattered
Uniformly；
(3) slurries in step (2) are spray-dried at a temperature of 100-300 DEG C, to form builder granule, will be helped
Agent particle is sieved, and obtains the target particles of builder granule particle diameter≤200 μm；
(4) target particles are carried out to roasting 0-5 hours at a temperature of 300-800 DEG C, builder granule is obtained；
(5) by builder granule at a certain temperature with chemical reagent aging certain time, be improved gasoline octane
It is worth auxiliary agent.
It should be noted that it is preferred that, the temperature of aging is 200~450 DEG C in step (5), and the time of aging is small for 1-8
When, the chemical reagent in ageing process includes deionized water, alkaline solution, Organic Alcohol, amine or phenolic compound.Adopted in the present invention
With unique solvent aging technology, because the acid site quantity of fresh auxiliary agent is more, acid strength is also higher, causes lytic activity ratio
It is higher, so during catalytic cracking reaction, carbon distribution is easily produced on auxiliary agent carrier, causes auxiliary agent to inactivate quickly.Using old
Change technology, artificial reduction auxiliary agent initial activity, especially acid strength, can slow down inactivation, improve auxiliary agent service life.Builder granule
Aging activity it is relevant with the alkalescence of ageing time, aging temperature and aging reagent.The ageing time of builder granule is too short, in acid
Calculation amount is more, and acid strength remains unchanged higher, and the lytic activity of builder granule remains unchanged higher；Builder granule ageing time is long, helps
The activity reduction of agent, is unfavorable for improving octane number.Aging temperature is unsuitable too low, and temperature is too low, and ageing time is long；Auxiliary agent
Particle aging temperature is too high also to influence the activity of builder granule；Aging technology improves octane number auxiliary agent hydrothermal stability
With the lasting high activity in course of reaction, slow down the raising octane number auxiliary agent deactivation rate of the present invention significantly, extend auxiliary agent
Service life.
Embodiment 1：
ZSM types molecular sieve 70%, alukalin 10%, borax 5%, Ludox 10%, and oxalic acid 5%, wherein ZSM
Silica alumina ratio 350 in type molecular sieve.
(1) ZSM type molecular sieve 70kg are weighed according to weight percentages of components, alukalin 10kg, borax 5kg, silicon is molten
Glue 10kg, and oxalic acid 5kg, are mixed to form mixture, using lapping device by mixture grind into powder, and add ion
Water 100kg is stirred to form slurries, and the slurries are stood into 5 hours at a temperature of 10 DEG C；
(2) slurries in step (1) are stirred 4 hours at a temperature of 10 DEG C using agitator, is allowed to be uniformly dispersed；
(3) slurries in step (2) are spray-dried at a temperature of 100 DEG C, to form builder granule, by auxiliary agent
Grain is sieved, and obtains the target particles of 200 μm of builder granule particle diameter；
(4) target particles are carried out to roasting 5 hours at a temperature of 300 DEG C, builder granule is obtained；
(5) builder granule is contacted into aging with deionized water, sodium hydroxide, ethanol, organic amine respectively at a temperature of 200 DEG C
8 hours, it is improved octane number auxiliary agent.
Embodiment 2：
Beta molecular sieve 10%, clay 25%, disodium hydrogen phosphate 10%, Alumina gel 25%, and glycerine 30%, wherein β
Silica alumina ratio 400 in type molecular sieve.
(1) beta molecular sieve 10kg, clay 25kg, disodium hydrogen phosphate 10kg, Alumina gel are weighed according to weight percentages of components
25kg, and glycerine 30kg, are mixed to form mixture, using lapping device by mixture grind into powder, and plus go
Ionized water 1000kg is stirred to form slurries, and the slurries are stood into 2 hours at a temperature of 100 DEG C；
(2) slurries in step (1) are stirred 1 hour at a temperature of 100 DEG C using agitator, is allowed to be uniformly dispersed；
(3) slurries in step (2) are spray-dried at a temperature of 300 DEG C, to form builder granule, by auxiliary agent
Grain is sieved, and obtains the target particles of 50 μm of builder granule particle diameter；
(4) target particles are carried out to roasting 0.5 hour at a temperature of 800 DEG C, builder granule is obtained；
(5) builder granule is contacted into aging with deionized water, sodium hydroxide, ethanol, organic amine respectively at a temperature of 450 DEG C
1 hour, it is improved octane number auxiliary agent.
Embodiment 3：
Y type molecular sieve 30%, alukalin 40%, boric acid 1%, Alumina gel 19%, and ethyl acetate 10%, wherein
Silica alumina ratio 300 in Y type molecular sieve.
(1) Y type molecular sieve 30kg, alukalin 40kg, boric acid 1kg, Alumina gel are weighed according to weight percentages of components
19kg, and ethyl acetate 10kg, are mixed to form mixture, using lapping device by mixture grind into powder, and add
Deionized water 500kg is stirred to form slurries, and the slurries are stood into 3 hours at a temperature of 50 DEG C；
(2) slurries in step (1) are stirred more than 2 hours at a temperature of 50 DEG C using agitator, is allowed to be uniformly dispersed；
(3) slurries in step (2) are spray-dried at a temperature of 200 DEG C, to form builder granule, by auxiliary agent
Grain is sieved, and obtains the target particles of 100 μm of builder granule particle diameter；
(4) target particles are carried out to roasting 3 hours at a temperature of 500 DEG C, builder granule is obtained；
(5) builder granule is contacted into aging with deionized water, sodium hydroxide, ethanol, organic amine respectively at a temperature of 300 DEG C
4 hours, it is improved octane number auxiliary agent.
Embodiment 4：
ZSM types molecular sieve 50%, clay 30%, sodium tripolyphosphate 5%, Ludox 5%, and organic ether 10%, wherein
Silica alumina ratio 450 in ZSM type molecular sieves.
(1) ZSM type molecular sieve 50kg are weighed according to weight percentages of components, clay 30kg, sodium tripolyphosphate 5kg, silicon is molten
Glue 5kg, and organic ether 10kg, are mixed to form mixture, using lapping device by mixture grind into powder, and plus go
Ionized water 800kg is stirred to form slurries, and the slurries are stood into 4 hours at a temperature of 25 DEG C；
(2) slurries in step (1) are stirred 3 hours at a temperature of 25 DEG C using agitator, is allowed to be uniformly dispersed；
(3) slurries in step (2) are spray-dried at a temperature of 200 DEG C, to form builder granule, by auxiliary agent
Grain is sieved, and obtains the target particles of 100 μm of builder granule particle diameter；
(4) target particles are carried out to roasting 2 hours at a temperature of 600 DEG C, builder granule is obtained；
(5) builder granule is contacted into aging with deionized water, sodium hydroxide, ethanol, organic amine respectively at a temperature of 400 DEG C
3 hours, it is improved octane number auxiliary agent.
Octane number auxiliary agent in embodiment 4 is added to Industrial Catalysis cracking experiment dress by the 6% of catalyst total amount
In putting, operating parameter is as follows：
When octane number auxiliary agent adds dosage to account for system reserve≤6%, compared with blank demarcation situation, in raw material and master
Under the conditions of operating operating mode essentially identical, octane number increase by more than 1.2, while the auxiliary agent is to diesel oil, gasoline and liquefied gas
Product quality is not influenceed, and total liquid yield is basically unchanged, and liquefied gas amplification is not more than 1.5%.Using octane number auxiliary agent to peace
Loopful is protected and had no adverse effects, and the process conditions, production operation to device do not result in harmful effect.Specific product distribution is as follows
Table：
| Yield distribution | ||
| Dry gas, wt% | Benchmark | Benchmark |
| Liquefied gas, wt% | Benchmark | +1.5 |
| Gasoline, wt% | Benchmark | -0.6 |
| Diesel oil, wt% | Benchmark | -0.9 |
| Slurry oil, wt% | Benchmark | Benchmark |
| Coke, wt% | Benchmark | Benchmark |
| Loss, wt% | Benchmark | Benchmark |
| Octane number | Benchmark | +1.2 |
| Propene yield, wt% | Benchmark | +0.6 |
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of catalytic cracking improves octane number auxiliary agent, it is characterised in that be made up of following components according to percentage by weight：
Molecular sieve 0-70%, matrix 10-70%, nonmetallic active material 0-10%, binding agent 0-50%, and auxiliary agent 0-
30%, silica alumina ratio is more than or equal to 200 in the molecular sieve.
2. a kind of catalytic cracking improves octane number auxiliary agent according to claim 1, it is characterised in that the molecular sieve can
Think any one or a few in Y type molecular sieve, X-type molecular sieve, ZSM types molecular sieve, beta molecular sieve or erionite.
3. a kind of catalytic cracking improves octane number auxiliary agent according to claim 1, it is characterised in that the nonmetallic work
Property material can for nonmetal oxide, Non-metal hydroxides, acidulants, nonmetallic salt or contain nonmetalloid
Any one or a few in organic matter.
4. a kind of catalytic cracking improves octane number auxiliary agent according to claim 3, it is characterised in that the nonmetallic work
Property material in nonmetalloid can be IIIA, VA, VIA or VIIA race nonmetalloid in one kind.
5. a kind of catalytic cracking improves octane number auxiliary agent according to claim 1, it is characterised in that the auxiliary agent can be with
For any one or a few in organic acid, Organic Alcohol, organic ether or organic ester.
6. a kind of catalytic cracking improves octane number auxiliary agent according to claim 1, it is characterised in that the binding agent is
Any one in Alumina gel or Ludox.
7. a kind of catalytic cracking improves the preparation method of octane number auxiliary agent according to claim 1-6, it is characterised in that
This method comprises the following steps：
(1) molecular sieve, matrix, nonmetallic active material, binding agent, and auxiliary agent are weighed according to weight percentages of components, will
It is mixed to form mixture, using lapping device by mixture grind into powder, and the stirring that adds water forms slurries, and the water is with mixing
Polymer weight ratio is 1-10: 1, and the slurries are stood into more than 2 hours at a temperature of 0~100 DEG C；
(2) slurries in step (1) are stirred more than 1 hour at a temperature of 0~100 DEG C using agitator, is allowed to be uniformly dispersed；
(3) slurries in step (2) are spray-dried at a temperature of 100-300 DEG C, to form builder granule, by auxiliary agent
Grain is sieved, and obtains the target particles of builder granule particle diameter≤200 μm；
(4) target particles are carried out to roasting 0-5 hours at a temperature of 300-800 DEG C, builder granule is obtained；
(5) by builder granule at a certain temperature with chemical reagent aging certain time, be improved octane number and help
Agent.
8. a kind of catalytic cracking improves the preparation method of octane number auxiliary agent according to claim 7, it is characterised in that step
Suddenly the temperature of aging is 200~450 DEG C in (5).
9. a kind of catalytic cracking improves the preparation method of octane number auxiliary agent according to claim 7, it is characterised in that step
Suddenly the time of aging is 1-8 hours in (5).
10. a kind of catalytic cracking improves the preparation method of octane number auxiliary agent according to claim 7, it is characterised in that
Chemical reagent includes deionized water, alkaline solution, Organic Alcohol, amine or phenolic compound in step (5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710654005.XA CN107224991B (en) | 2017-08-02 | 2017-08-02 | Auxiliary agent for improving gasoline octane number by catalytic cracking and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710654005.XA CN107224991B (en) | 2017-08-02 | 2017-08-02 | Auxiliary agent for improving gasoline octane number by catalytic cracking and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107224991A true CN107224991A (en) | 2017-10-03 |
| CN107224991B CN107224991B (en) | 2019-12-17 |
Family
ID=59958196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710654005.XA Active CN107224991B (en) | 2017-08-02 | 2017-08-02 | Auxiliary agent for improving gasoline octane number by catalytic cracking and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107224991B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686791A (en) * | 2019-03-12 | 2020-09-22 | 中国石油天然气股份有限公司 | Octane value auxiliary agent for catalytically cracked gasoline and preparation method thereof |
| CN114733557A (en) * | 2022-03-31 | 2022-07-12 | 青岛惠城环保科技股份有限公司 | Preparation method of octane number auxiliary agent for catalytically cracked gasoline |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851058A (en) * | 2011-06-30 | 2013-01-02 | 中国石油天然气股份有限公司 | Method for increasing octane number of catalytically cracked gasoline |
| CN102872902A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Catalytic cracking assistant for propylene yield increase |
| CN103007986A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration |
| CN103254925A (en) * | 2013-06-03 | 2013-08-21 | 湖北赛因化工有限公司 | Catalytic cracking propylene assistant and preparation method thereof |
| CN106179470A (en) * | 2016-08-08 | 2016-12-07 | 青岛惠城环保科技股份有限公司 | A kind of catalytic cracking improves the preparation method of octane number auxiliary agent |
-
2017
- 2017-08-02 CN CN201710654005.XA patent/CN107224991B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851058A (en) * | 2011-06-30 | 2013-01-02 | 中国石油天然气股份有限公司 | Method for increasing octane number of catalytically cracked gasoline |
| CN102872902A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Catalytic cracking assistant for propylene yield increase |
| CN103007986A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration |
| CN103254925A (en) * | 2013-06-03 | 2013-08-21 | 湖北赛因化工有限公司 | Catalytic cracking propylene assistant and preparation method thereof |
| CN106179470A (en) * | 2016-08-08 | 2016-12-07 | 青岛惠城环保科技股份有限公司 | A kind of catalytic cracking improves the preparation method of octane number auxiliary agent |
Non-Patent Citations (1)
| Title |
|---|
| 刘其武 等: "高硅ZSM－5在辛烷值助剂中的应用", 《工业催化》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686791A (en) * | 2019-03-12 | 2020-09-22 | 中国石油天然气股份有限公司 | Octane value auxiliary agent for catalytically cracked gasoline and preparation method thereof |
| CN111686791B (en) * | 2019-03-12 | 2023-04-25 | 中国石油天然气股份有限公司 | Catalytic cracking gasoline octane number auxiliary agent and preparation method thereof |
| CN114733557A (en) * | 2022-03-31 | 2022-07-12 | 青岛惠城环保科技股份有限公司 | Preparation method of octane number auxiliary agent for catalytically cracked gasoline |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107224991B (en) | 2019-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103827058B (en) | Alcohol is converted into the zeolite catalysis of Hydrocarbon | |
| EP2617697B1 (en) | Method for manufacturing aromatic hydrocarbon | |
| CN102049290B (en) | RFCC high octane gasoline additive and preparation method thereof | |
| CN101210187B (en) | Preparing method of catalyst for cracking heavy oil | |
| TW200409673A (en) | Catalyst for the production of light olefins | |
| CN101780417A (en) | Catalyst for preparing paraxylene and low-carbon olefin by methyl alcohol conversion, preparation method and application thereof | |
| CN107224991A (en) | A kind of catalytic cracking improves octane number auxiliary agent and preparation method thereof | |
| CN102220158B (en) | Method for reducing olefins in aromatic hydrocarbons | |
| CN101138740A (en) | Cracking catalyst containing nanometer rare-earth oxide and method of preparing the same | |
| JP2017500293A (en) | Unsupported heteropolyacid metal salt catalyst for dimerization and / or oligomerization of olefins | |
| US9776934B2 (en) | Method for producing monocyclic aromatic hydrocarbons | |
| CN101233213B (en) | Process for production of light olefins from hydrocarbon feedstock | |
| US9573864B2 (en) | Method of producing monocyclic aromatic hydrocarbons | |
| CN100363314C (en) | Process for polymerization preparation of diesel oil from C4 components containing butylene | |
| CN107398253A (en) | A kind of catalytic cracking fuel gas sulfur transferring assistant and preparation method thereof | |
| CN102816589B (en) | Hydrocarbon oil catalytic cracking method | |
| CN102041035B (en) | Reformate deolefination method without hydrogen | |
| CN108624354B (en) | Method for treating organic by-products in cyclohexanone production process | |
| CN102451753B (en) | Composite molecular sieve catalyst capable of improving octane number of gasoline and preparation method of composite molecular sieve catalyst | |
| CN103254925B (en) | Catalytic cracking propylene assistant and preparation method thereof | |
| CN107376986A (en) | A kind of bottom of towe oil catalytic cracking cracking auxiliary agent and preparation method thereof | |
| CN1261536C (en) | Method of reducing olefine and benzene content in gasoline | |
| CN112642466A (en) | Butane aromatization catalyst and preparation method and application thereof | |
| CN1076721C (en) | Process for alkylation of isomeric paraffin and olefin | |
| CN106607075A (en) | Fluid catalyst for preparing olefin and arene and application of fluid catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |