CN105562120B - A kind of Cracking catalyst in batches plus agent, continuous ageing method - Google Patents
A kind of Cracking catalyst in batches plus agent, continuous ageing method Download PDFInfo
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Abstract
Agent, continuous ageing method, this method is added to implement including adding in the catalyst treatment device of agent tank, aging device and piece-rate system in batches the present invention relates to a kind of Cracking catalyst, including：(1) will plus after agent tank vacuumizes, so that the Cracking catalyst after sieving is pumped into adding agent tank；(2) agent tank will be added to boost to 200kPa or more, and will make that the Cracking catalyst in agent tank will be added to be delivered under the action of fluidized wind in aging device；(3) in the presence of fluidizing agent, Cracking catalyst is made to carry out hydrothermal aging in aging device；(4) catalyst hydrothermal aging to be cracked repeats implementation steps (1) to (3) to after to a certain degree, to realize in batches plus agent and continuous ageing；(5) material for passing through hydrothermal aging in aging device is subjected to gas solid separation, the solid catalyst isolated is made to continue to fluidize in aging device, the gas isolated injection piece-rate system is made to be detached.The method efficient stable provided by the invention and energy preferably simulation industry poising agent property.
Description
Technical field
The present invention relates to the processing methods of catalytic cracking catalyst in PETROLEUM PROCESSING field, and in particular, to a kind of cracking
Catalyst adds agent, continuous ageing method in batches.
Background technology
Catalytic cracking is a kind of important secondary processing process, is the effective means of heavy oil lighting.Primary raw material is bad
Reduced fuel oil, and product is then liquefied gas, gasoline, the diesel oil etc. of high added value.Quiet run of the catalyst to product yield, device
And it plays an important role in terms of environmental protection.Since fresh catalyst activity is higher, direct use can cause catalytic cracking
The negative effects such as coke output increases in product, and octane number declines, so, the research work in laboratory, either technique
Exploitation, catalyst preparation and evaluation, raw material of industry Technological adaptability investigation etc. are required to carry out hydrothermal aging to used catalyst
Or heavy metal pollution, every physical and chemical performance of the catalyst after aging are more nearly with the poising agent in commercial plant, experiment
Acquired results are relatively reliable, have better directive significance to industrial production.
CN102527449A discloses a kind of aging method and equipment of typical catalytic cracking catalyst, this method packet
It includes：(1) in catalyst aging device, vapor and high temperature catalyst contact reduce catalyst activity, the gas in catalyst aging device
Body and its entrained catalyst detach at the top of catalyst aging device, and gas enters aftertreatment systems, and catalyst returns old
Change device bottom；(2) introduce fuel in dilute phase burner, the catalyst of aging device bottom enter in dilute phase burner with it is oxygenous
Body, fuel mixing carry out combustion reaction, and gas and catalyst after combustion reaction is complete enter the middle part of aging device；(3) it is catalyzed
After agent activity is reduced to targeted activity, device is stopped work, and catalyst is drawn off.Using the catalyst aging method of the patent application, urge
Agent hydro-thermal reaction reduce catalyst activity and catalyst heating separately reaction, can easily control respectively its operating condition and
Reaction speed, the catalyst activity after aging are evenly distributed.
Catalytic cracking industrial process is along with the process that is gradually reduced of catalyst activity, the activity of fresh molecular sieve catalyst
It is higher, generally 90 or more, but due to catalytic cracking reaction during, temperature is higher in regenerator, anti-scorch steam, stripping steam
Under the action of vapour, the inactivation of catalyst will certainly be caused, in addition catalyst stack less present in device operation, it is therefore necessary to periodically
The fresh makeup catalyst into FCC apparatus, to maintain the catalyst activity in device in a stable level, activity at this time
Referred to as " running balance catalyst activity ", some refineries in order to maintain higher catalyst activity, also can use periodically unload agent with
The way of fresh makeup catalyst.Therefore, it is said on stricti jurise, the running balance agent of commercial plant is the catalyst of all ages and classes
Mixture, micro-activity have certain gradient.It is actual catalysis reaction be different micro-activities catalyst mixture with
The cracking reaction of hydrocarbon ils contact.
Since the activity distribution of the catalyst used in laboratory has essential difference, commercial plant with commercial plant poising agent
Running balance agent be all ages and classes catalyst mixture, micro-activity has certain gradient, and catalyst is old in hydro-thermal
During change happens is that crystal structure cave in and the process of super stabilizing, the specific reaction of the catalyst of different ageing times
Performance gap is larger.And the aging equipment that laboratory is all at present, it is essentially all old using the identical ageing time of same batch
Catalyst after change, catalyst activity is relatively uniform, is distributed without gradient.This is to the research of oil Refining Technologies on molecular level and urges
The careful investigation of agent performance is made troubles.And relevant experiment can only be by being added poising agent or mix and convert different activities catalyst
It realizes, convenience is poor, and is often subject to the restriction of various conditions, therefore there is an urgent need for a kind of simulation all ages and classes, different micro-
The laboratory aging method of anti-activity industrial operation poising agent.
Invention content
The object of the present invention is to provide a kind of efficient stable and the cracking catalysis of energy preferably simulation industry poising agent property
Agent adds agent, continuous ageing method in batches.
The present invention provides a kind of Cracking catalyst in batches plus agent, continuous ageing method, this method including add agent tank,
Implement in aging device and the catalyst treatment device of piece-rate system, the described method comprises the following steps：
(1) after agent tank being added to vacuumize, the Cracking catalyst after sieving is made to be pumped into described plus agent tank；
(2) agent tank will be added to boost to 200kPa or more, and will make the Cracking catalyst in described plus agent tank in fluidisation wind action
Under be delivered in aging device；
(3) in the presence of fluidizing agent, the Cracking catalyst is made to carry out hydrothermal aging in the aging device；
(4) catalyst hydrothermal aging to be cracked repeats implementation steps (1) to (3) to after to a certain degree, with realize in batches plus
Agent and continuous ageing；
(5) material for passing through hydrothermal aging in aging device is subjected to gas solid separation, makes the solid catalyst isolated old
Change and continue to fluidize in device, the gas isolated injection piece-rate system is made to be detached.
The Cracking catalyst provided by the invention in batches plus agent, continuous ageing method the advantages of include：
(a) method and apparatus is provided using the present invention, every physico-chemical property of the Cracking catalyst of institute's aging with
Running balance agent property is very close, especially the micro pore volume of catalyst, specific surface area, SEM crystalline phases and running balance agent base
This is consistent.Under operating condition and experimental rig unanimous circumstances, experiment obtained by the catalyst of method aging of the present invention
As a result with industrial result more close to thus can more efficiently instructing commerical test.
(b) catalyst after mix and convert batch aging used by generally use catalytic cracking simulation operation poising agent is compared,
Method of the present invention is simple to operate, can solve the problems, such as age distribution by an aging, has stronger facility
Property and flexibility.
(c) catalyst treatment device used by method of the present invention can utilize the common aging equipment in laboratory
It is slightly transformed, avoids the input of newly-built equipment, there is preferable economy.
(d) catalyst treatment device of the present invention can be with the hydrothermal deactivation in Laboratory Weathering Devices, metal
The parallel operation of the catalyst treatments process such as pollution, catalyst structure is independent of each other.There is stronger adaptability to different aging equipments.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 be the Cracking catalyst provided by the invention in batches plus agent, continuous ageing method flow diagram.
Reference sign
1 stainless steel barrel, 2 fluidization air inlet valve
3 add agent transfer valve 4 plus agent tank
5 blow valve, 6 vacuum pump
7 fluidizing agent, 8 aging device
9 settler, 10 overhead line
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The Cracking catalyst provided by the invention adds agent, continuous ageing method including adding agent tank, aging device in batches
Implement in the catalyst treatment device of piece-rate system.Specifically, the Cracking catalyst in batches plus agent, continuous ageing method
Include the following steps：
(1) after agent tank being added to vacuumize, the Cracking catalyst after sieving is made to be pumped into described plus agent tank；
(2) agent tank will be added to boost to 200kPa or more, and will make the Cracking catalyst in described plus agent tank in fluidisation wind action
Under be delivered in aging device；
(3) in the presence of fluidizing agent, the Cracking catalyst is made to carry out hydrothermal aging in the aging device；
(4) catalyst hydrothermal aging to be cracked repeats implementation steps (1) to (3) to after to a certain degree, with realize in batches plus
Agent and continuous ageing；
(5) material for passing through hydrothermal aging in aging device is subjected to gas solid separation, makes the solid catalyst isolated old
Change and continue to fluidize in device, the gas isolated injection piece-rate system is made to be detached.
In the method provided by the invention, it is preferable that described plus agent tank volume is the aging device treating capacity
120-150%.
In step (1), be by the purpose that described plus agent tank vacuumizes in order to make plus agent tank generates negative pressure, and it is negative using this
Cracking catalyst after sieving is pumped into described plus agent tank by pressure.As long as the absolute pressure after described plus agent tank vacuumizes can
There is provided enough negative pressure enables Cracking catalyst to be pumped into described plus agent tank.It, will described plus agent under preferable case
It is 10kPa or less that tank, which is evacuated to absolute pressure,.In the present invention, described plus agent tank is vacuumized can be by conventional method
Implement, such as vacuum pump pair may be used, agent tank is added to vacuumize.
In step (2), it is to enable to add the Cracking catalyst in agent tank that agent tank will be added, which to boost to 200kPa or more,
As the fluidized wind generated by pressure difference enters in aging device.Preferably, agent tank will be added to boost to 200-300kPa.In the present invention
In, it will add the boosting of agent tank that can implement by conventional method, such as can be by adding the side for injecting fluidization air in agent tank
Formula is pressurizeed.
In step (3), the condition of the hydrothermal aging may include：Temperature is 550-810 DEG C, preferably 600-750
℃；Pressure is 0.01-0.5MPa (G), preferably 0.01-0.1MPa (G)；Catalyst residence times are 1-15min, preferably 1-
5min。
In step (3), the fluidizing agent can be vapor and optional nitrogen or air, wherein vapor
The 10 volume % or more of the fluidizing agent, preferably 50 volume % or more can be accounted for.Preferably, oxygen accounts for the fluidizing agent
21 volume % or more, more preferable 10 volume % or less.
In step (3), the void tower linear speed of the aging device can be 0.02-1.5m/s, and mean temperature can be 550-
750℃.The void tower linear speed of the aging device refers to the gas linear velocity of void tower when catalyst is not present.The mean temperature is
Refer to the arithmetic mean of instantaneous value of the three temperature measuring point measured temperatures in aging device upper, middle and lower.The void tower linear speed of the aging device can pass through tune
The amount of fluidizing agent is saved to control.
In the method provided by the invention, the amount of the first Cracking catalyst being added in aging device is known as the aging
The amount of the initial plus dosage of device, the catalyst being added after the Cracking catalyst being added for the first time into aging device referred to as adds in batches
Dosage.In the preferred case, the initial plus dosage of the aging device is the 10-50% of the aging device treating capacity, adds agent in batches
Amount initially adds the 5-10% of dosage to be every two hours added.In one embodiment, the initial plus dosage of the aging device is
10-50kg, preferably 10-30kg；It is 0.5-5kg/2h, preferably 0.5-2kg/2h to add agent rate.
In the method provided by the invention, the degree of the Cracking catalyst hydrothermal aging described in step (4) can be with
According to industrial operation poising agent to be simulated activity and age distribution and determine.In step (4), in implementation steps again
(1) to during (3), the addition of the raw catelyst in phases-time can be calculated according to the requirement of aging condition, led to
Cross plus the differential pressure level-sensing device control in agent tank plus dosage, realize catalyst be added at times, in batch to plus agent tank, and realize
Continuous ageing is handled.
In step (4), the gas solid separation can be implemented in the settler being set at the top of the aging device, described
The void tower linear speed of settler can be 0.05-15m/s, and mean temperature can be 350-600 DEG C.The void tower linear speed of the settler
It refer to the gas linear velocity of void tower when catalyst not being added.The mean temperature refers to that settler up and down surveyed by two temperature measuring points
The arithmetic mean of instantaneous value of temperature.
The method provided by the invention is suitable for different types of Cracking catalyst.Different types of Cracking catalyst can
To be the different Cracking catalyst of granular size and/or the different Cracking catalyst of apparent bulk density.The Cracking catalyst
In active component can select different types of zeolite, the zeolite can be selected from y-type zeolite, the height with five-membered ring structure
At least one of silicone zeolite and ferrierite, the zeolite can contain rare earth and/or phosphorus, can not also contain rare earth and phosphorus.Its
In, the y-type zeolite can be HY zeolites, ultrastable etc..Method Cracking catalyst to be dealt with of the present invention
It can be the mixture of single catalyst or two or more catalyst.
Method of the present invention can be with the hydrothermal aging of fresh catalyst, the hydrothermal aging of fresh catalyst and metal
Pollution and gold-attempt belong to the techniques serial operations such as passivation, with the property of more preferable simulation industrial operation poising agent.
Below in conjunction with attached drawing, the invention will be further described, but protection scope of the present invention is not therefore by any limit
System.
Fig. 1 be the Cracking catalyst provided by the invention in batches plus agent, continuous ageing method flow diagram.Such as
Shown in Fig. 1, add the in batches agent, continuous ageing method of the Cracking catalyst provided by the invention include：When initially adding agent, close
It closes and adds 4 top blow valve 5 of agent tank, bottom fluidization air inlet valve 2 and add agent transfer valve 3, agent tank 4 will be added to take out with vacuum pump 6
Cracking catalyst sucking in stainless steel barrel 1 is added agent tank 4 by vacuum using negative pressure.Then, vacuum pump 6 is closed, it is empty to open fluidisation
Gas inlet valve 2 after being raised to certain pressure, opens catalyst transport valve 3, Cracking catalyst is i.e. by adding agent to adding agent tank 4 to pressurize
Tank 4 enters in aging device main body 8, and is passed through fluidizing agent 7 in aging device bottom, and Cracking catalyst is made to be sent out in aging device 8
The gas of unboiled water heat inactivation, generation realizes gas solid separation with catalyst by the settler 9 (such as chimney filter) being arranged at the top of aging device,
Gas enters subsequent separation system from overhead line 10.In the present invention, in order to simulate activity and the year of industrial operation poising agent
Age is distributed, and the quantitative agent feeding after separated in time can be automatically brought into operation by controlling material position to realize, add dosage then can root
It is calculated according to required aging condition.
With reference to embodiment, the present invention will be further described, but is not limiting upon the present invention.Following embodiment and right
Catalyst used by ratio 1 is the ASC-2 Cracking catalyst of sinopec catalyst Co. asphalt in Shenli Refinery production, property
Parameter is as shown in table 1.The catalyst used in laboratory reference example is industrial operation poising agent, is purchased from the sinopec Yangtze petrochemical industry Qingjian River
Petrochemical industry, trade mark ASC-1, nature parameters are as shown in table 1.
Table 1
Embodiment 1
The present embodiment be used for illustrate the Cracking catalyst provided by the invention in batches plus agent, continuous ageing method.
Cracking catalyst is carried out using technological process shown in FIG. 1 to add agent and continuous ageing in batches, specifically, initial
When adding agent, close plus agent tank 4 (for the 150% of aging device treating capacity) top blow valve 5, bottom fluidization air inlet valve 2 and
Add agent transfer valve 3, with vacuum pump 6 will plus agent tank 4 vacuumize, it is 9kPa to be evacuated to absolute pressure, using negative pressure by stainless steel
Cracking catalyst sucking in bucket 1 plus agent tank 4.Then, vacuum pump 6 is closed, fluidization air inlet valve 2 is opened, is added to agent tank 4 is added
Pressure opens catalyst transport valve 3, Cracking catalyst is i.e. by adding agent tank 4 to enter aging device main body 8 after boosting to 200kPa
In, wherein aging device initial plus dosage is aging device treating capacity 10%, and initially plus dosage is 10kg adds the agent rate to be
1kg/2h.It is passed through fluidizing agent 7 in aging device bottom, it is 0.02m/s to make the void tower linear speed of aging device, and mean temperature is 550 DEG C,
Wherein, fluidizing agent contains 10 volume % vapor and 90 volume % air, and oxygen content is about 18.9 bodies in fluidizing agent
Product %.Make Cracking catalyst that hydrothermal aging occur under conditions of temperature is 550 DEG C, pressure is 0.01MPa in aging device 8.
The gas that is generated in aging device and catalyst realize gas solid separation by the chimney filter 9 being arranged at the top of aging device, and gas is from head tube
Line 10 enters subsequent separation system, and the void tower linear speed of chimney filter 9 is 0.2m/s, and mean temperature is 400 DEG C.
Initially plus after agent and burin-in process (i.e. catalyst residence times) 600min, repeatedly as procedure described above to adding agent
Cracking catalyst is added portionwise in tank 4 and injects in aging device 8 progress continuous ageing processing, wherein subsequent batch adds the dosage to be
Every two hours it is added initial plus dosage 10%.So obtain simulation industrial operation poising agent A1.
Embodiment 2
The present embodiment be used for illustrate the Cracking catalyst provided by the invention in batches plus agent, continuous ageing method.
Cracking catalyst is carried out using technological process shown in FIG. 1 to add agent and continuous ageing in batches, specifically, initial
When adding agent, close plus agent tank 4 (for the 150% of aging device treating capacity) top blow valve 5, bottom fluidization air inlet valve 2 and
Add agent transfer valve 3, with vacuum pump 6 will plus agent tank 4 vacuumize, it is 9kPa to be evacuated to absolute pressure, using negative pressure by stainless steel
Cracking catalyst sucking in bucket 1 plus agent tank 4.Then, vacuum pump 6 is closed, fluidization air inlet valve 2 is opened, is added to agent tank 4 is added
Pressure opens catalyst transport valve 3, Cracking catalyst is i.e. by adding agent tank 4 to enter aging device main body 8 after boosting to 300kPa
In, wherein aging device initial plus dosage is aging device treating capacity 50%, and initially plus dosage is 50kg adds the agent rate to be
2.5kg/2h.It is passed through fluidizing agent 7 in aging device bottom, it is 1.5m/s, mean temperature 750 to make the void tower linear speed of aging device
DEG C, wherein fluidizing agent is vapor (oxygen content 0).Temperature is 750 DEG C, pressure is 0.5MPa's in aging device 8
Under the conditions of make Cracking catalyst occur hydrothermal aging.The gas generated in aging device passes through setting at the top of aging device with catalyst
Chimney filter 9 realizes that gas solid separation, gas enter subsequent separation system from overhead line 10, and the void tower linear speed of chimney filter 9 is 15m/s, is put down
Equal temperature is 600 DEG C.
Initially plus after agent and burin-in process (i.e. catalyst residence times) 600min, repeatedly as procedure described above to adding agent
Cracking catalyst is added portionwise in tank 4 and injects in aging device 8 progress continuous ageing processing, wherein subsequent batch adds the dosage to be
Every two hours it is added initial plus dosage 5%.So obtain simulation industrial operation poising agent A2.
Embodiment 3
The present embodiment be used for illustrate the Cracking catalyst provided by the invention in batches plus agent, continuous ageing method.
Cracking catalyst is carried out using technological process shown in FIG. 1 to add agent and continuous ageing in batches, specifically, initial
When adding agent, close plus agent tank 4 (for the 150% of aging device treating capacity) top blow valve 5, bottom fluidization air inlet valve 2 and
Add agent transfer valve 3, with vacuum pump 6 will plus agent tank 4 vacuumize, it is 9kPa to be evacuated to absolute pressure, using negative pressure by stainless steel
Cracking catalyst sucking in bucket 1 plus agent tank 4.Then, vacuum pump 6 is closed, fluidization air inlet valve 2 is opened, is added to agent tank 4 is added
Pressure opens catalyst transport valve 3, Cracking catalyst is i.e. by adding agent tank 4 to enter aging device main body 8 after boosting to 250kPa
In, wherein aging device initial plus dosage is aging device treating capacity 30%, and initially plus dosage is 30kg adds the agent rate to be
1.5kg/2h.It is passed through fluidizing agent 7 in aging device bottom, it is 0.5m/s, mean temperature 650 to make the void tower linear speed of aging device
DEG C, wherein fluidizing agent contains 50 volume % vapor and 50 volume % air, and oxygen content is about 10.5 in fluidizing agent
Volume %.Make Cracking catalyst that hydrothermal aging occur under conditions of temperature is 650 DEG C, pressure is 0.3MPa in aging device 8.
The gas that is generated in aging device and catalyst realize gas solid separation by the chimney filter 9 being arranged at the top of aging device, and gas is from head tube
Line 10 enters subsequent separation system, and the void tower linear speed of chimney filter 9 is 5m/s, and mean temperature is 500 DEG C.
Initially plus after agent and burin-in process (i.e. catalyst residence times) 600min, repeatedly as procedure described above to adding agent
Cracking catalyst is added portionwise in tank 4 and injects in aging device 8 progress continuous ageing processing, wherein subsequent batch adds the dosage to be
Every two hours it is added initial plus dosage 5%.So obtain simulation industrial operation poising agent A3.
Comparative example 1
Hydrothermal aging conventionally is carried out to catalytic cracking catalyst, specifically, disposably by 60Kg catalyst
It is added in aging device, is warming up to 700 DEG C, pressure 0.1MPa, is passed through fluidizing agent in aging device bottom, makes the void tower of aging device
Linear speed is 0.5m/s, and mean temperature is 700 DEG C, wherein fluidizing agent is 100 volume % vapor, in temperature in aging device
Make Cracking catalyst that hydrothermal aging occur under conditions of being 0.1MPa for 700 DEG C, pressure.The gas generated in aging device and catalysis
Agent realizes that gas solid separation, gas enter subsequent separation system from overhead line by the chimney filter being arranged at the top of aging device, chimney filter
Void tower linear speed is 5m/s, and mean temperature is 550 DEG C.So obtain simulation industrial operation poising agent D1.
Experimental example
Following experimental example is used to evaluate industrial operation poising agent or simulate the property of industrial operation poising agent, each experiment
Feedstock oil is straight-run gas oil used by example, and property is as shown in table 2.
Table 2
| Feedstock oil title | Straight-run gas oil |
| Density (20 DEG C)/(kg/m3) | 945 |
| Carbon residue/% | 2.2 |
| Condensation point/DEG C | 48 |
| Constituent content | |
| Carbon/% | 85.12 |
| Hydrogen/% | 11.77 |
| Sulphur/% | 2.8 |
| Total nitrogen/% | 0.2 |
| Basic nitrogen/(μ g/g) | 0.0654 |
| Hydrocarbon system's composition/% | |
| Saturated hydrocarbons | 47.1 |
| Aromatic hydrocarbons | 48.6 |
| Colloid | 3.1 |
| Asphalitine | / |
| Tenor/(μ g/g) | |
| Fe | 24.9 |
| Ni | 1.1 |
| Cu | <0.1 |
| V | 3.2 |
| Na | 6.8 |
| Ca | 5.5 |
| Boiling range/DEG C | |
| Initial boiling point | 350 |
| 5% | 462 |
| 10% | 490 |
| 30% | 515 |
| 50% | 532 |
| Terminal yield/% is evaporated eventually | 60 |
| Distillation end point temperature/DEG C | 540 |
Laboratory reference example
Using industrial operation poising agent, evaluation test is carried out in Research Institute of Petro-Chemical Engineering's kitty cracker,
Used reaction condition, product distribution and product property are as shown in table 3.
Experimental example 1-3 and comparative experimental example 1
The simulation using reaction condition identical with laboratory reference example and feedstock oil prepared by embodiment 1-3 and comparative example 1
Industrial operation poising agent is evaluated, and evaluation result is as shown in table 3.
Table 3
| Test number | Laboratory reference example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Reaction condition |
| Reaction temperature/DEG C | 515 | 515 | 515 | 515 | 515 |
| Reaction pressure/MPa | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
| Regeneration temperature/DEG C | 685 | 685 | 685 | 685 | 685 |
| Inlet amount/(kg/h) | 10 | 10 | 10 | 10 | 10 |
| Atomizing steam amount/% | 5 | 5 | 5 | 5 | 5 |
| Agent oil quality ratio | 6 | 6 | 6 | 6 | 6 |
| Residence time/s | 1.67 | 1.67 | 1.67 | 1.67 | 1.67 |
| Product yield/% | |||||
| Dry gas | 3.05 | 3.19 | 3.00 | 2.89 | 2.38 |
| Liquefied gas | 16.58 | 16 | 16.63 | 16.05 | 14.96 |
| Gasoline | 42.26 | 41.72 | 42.06 | 43.01 | 43.62 |
| Light diesel fuel | 24.15 | 25.5 | 24.35 | 24.26 | 26.95 |
| Heavy oil | 5.85 | 5.34 | 5.55 | 5.96 | 4.34 |
| Coke | 7.58 | 7.64 | 7.87 | 7.32 | 7.33 |
| Loss | 0.53 | 0.61 | 0.54 | 0.51 | 0.42 |
| Conversion ratio/% | 70 | 69.16 | 70.1 | 69.78 | 68.71 |
| Octane number | |||||
| RON | 92.1 | 92.5 | 91.8 | 92.3 | 93.5 |
| MON | 82.3 | 83 | 82.1 | 82.6 | 84 |
As can be seen from Table 3, since the catalyst aging age is similar in comparative example 1, so size distribution has preferably
Consistency, in addition 0-20 μm of catalyst fines lose a part by chimney filter in ageing process, so catalyst particle
Content is less, and average grain diameter is larger.And embodiment using it is of the present invention in batches plus agent, continuous ageing method, it is obtained
Catalyst grain size distribution and industrial operation poising agent are more similar.
As can be seen from Table 3, processed catalyst according to the method described in the present invention, whether physical and chemical performance or reality
Border reactivity worth, is all more nearly with poising agent, and illustrating can preferably mould using catalyst aging method of the present invention
The property of quasi- industrial operation poising agent, the test result of obtained experimental result and industrial operation poising agent is closer, thus according to
The Cracking catalyst that method aging of the present invention obtains is in laboratory evaluation, industrial result evaluation and test and catalytic mechanism research
Aspect has more advantage.
Claims (11)
1. a kind of Cracking catalyst adds agent, continuous ageing method in batches, this method is including adding agent tank, aging device and segregative line
Implement in the catalyst treatment device of system, the described method comprises the following steps：
(1) after agent tank being added to vacuumize, the Cracking catalyst after sieving is made to be pumped into described plus agent tank；
(2) agent tank will be added to boost to 200kPa or more, and will keep the Cracking catalyst in described plus agent tank defeated under the action of fluidized wind
It send to aging device；
(3) in the presence of fluidizing agent, the Cracking catalyst is made to carry out hydrothermal aging in the aging device；
(4) catalyst hydrothermal aging to be cracked repeats implementation steps (1) to (3) to after to a certain degree, with realize in batches plus agent and
Continuous ageing；
(5) material for passing through hydrothermal aging in aging device is subjected to gas solid separation, makes the solid catalyst isolated in aging device
Inside continue to fluidize, the gas isolated injection piece-rate system is made to be detached.
2. according to the method described in claim 1, wherein, described plus agent tank volume is the 120- of the aging device treating capacity
150%.
3. method according to claim 1 or 2, wherein in step (1), described plus agent tank is evacuated to absolute pressure
Power is 10kPa or less.
4. according to the method described in claim 1, wherein, in step (2), agent tank will be added to boost to 200-300kPa.
5. according to the method described in claim 1, wherein, in step (3), the condition of the hydrothermal aging includes：Temperature is
550-810 DEG C, pressure 0.01-0.5MPa.
6. according to the method described in claim 1, wherein, in step (3), the fluidizing agent is vapor and optional
Nitrogen or air, wherein vapor accounts for the 10 volume % or more of the fluidizing agent.
7. according to the method described in claim 1, wherein, the initial plus dosage of the aging device is the aging device treating capacity
10-50%, in batches plus dosage is that initial plus dosage 5-10% is every two hours added.
8. according to the method described in claim 7, wherein, the initial plus dosage of the aging device is 10-50kg, adds the agent rate to be
0.5-5kg/2h。
9. according to the method described in claim 1, wherein, in step (3), the void tower linear speed of the aging device is 0.02-
1.5m/s, mean temperature are 550-750 DEG C.
10. according to the method described in claim 1, wherein, in step (4), the gas solid separation is being set to the aging
Implement in settler at the top of device, the void tower linear speed of the settler is 0.05-15m/s, and mean temperature is 350-600 DEG C.
11. according to the method described in claim 1, wherein, the active component in the Cracking catalyst is selected from y-type zeolite, tool
There are at least one of silica-rich zeolite and the ferrierite of five-membered ring structure.
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| JP2011079909A (en) * | 2009-10-05 | 2011-04-21 | Idemitsu Kosan Co Ltd | Fluid catalytic cracking method |
| CN102527449A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Aging method and equipment of catalytic cracking catalyst |
| CN102950031A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Method and equipment for quickly stabilizing activity of catalytic cracking catalyst |
| CN102989519A (en) * | 2011-09-15 | 2013-03-27 | 中国石油化工股份有限公司 | Catalytic cracking catalyst continuous aging method and device |
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| JP2011079909A (en) * | 2009-10-05 | 2011-04-21 | Idemitsu Kosan Co Ltd | Fluid catalytic cracking method |
| CN102527449A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Aging method and equipment of catalytic cracking catalyst |
| CN102950031A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Method and equipment for quickly stabilizing activity of catalytic cracking catalyst |
| CN102989519A (en) * | 2011-09-15 | 2013-03-27 | 中国石油化工股份有限公司 | Catalytic cracking catalyst continuous aging method and device |
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