CN103028437A - Peptizing aluminum adhering agent, preparation method of peptizing aluminum adhering agent, catalytic cracking catalyst and preparation method of catalytic cracking catalyst - Google Patents
Peptizing aluminum adhering agent, preparation method of peptizing aluminum adhering agent, catalytic cracking catalyst and preparation method of catalytic cracking catalyst Download PDFInfo
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- CN103028437A CN103028437A CN2012101869763A CN201210186976A CN103028437A CN 103028437 A CN103028437 A CN 103028437A CN 2012101869763 A CN2012101869763 A CN 2012101869763A CN 201210186976 A CN201210186976 A CN 201210186976A CN 103028437 A CN103028437 A CN 103028437A
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Abstract
The invention provides a peptizing aluminum adhering agent and a preparation method of the peptizing aluminum adhering agent. The preparation method comprises the steps of: mixing and pulping an aluminum adhering agent and acid to obtain first slurry, adding alkali to regulate the pH value of the first slurry to be 5-8 to obtain second slurry, wherein the temperature of the second slurry is 50-95 DEG C; introducing the second slurry into a third peptizing kettle, adding acid to regulate pH value of the second slurry to be 2-4.9 to obtain third slurry, wherein the temperature of the third slurry does not exceed 30 DEG C; introducing the third slurry into a fourth peptizing kettle, adding alkali to regulate the pH value of the third slurry to be 5-8 to obtain fourth slurry, wherein the temperature of the fourth slurry is 50-95 DEG C; and introducing the fourth slurry into a fifth peptizing kettle, and adding acid to regulate the pH value of the fourth slurry to be 2-4.9, wherein the temperature of the fifth slurry does not exceed 30 DEG C. The invention also provides a catalytic cracking catalyst and a preparation method of the catalytic cracking catalyst. The catalytic cracking catalyst prepared by adopting the preparation method is good in repeatability and has the advantages of high molecular sieve utilization rate and high activity.
Description
Technical field
The present invention relates to a kind of peptization al binder and preparation method thereof and a kind of catalytic cracking catalyst and preparation method thereof.
Background technology
CN1098130A, CN1247885A, CN1246515A, CN1388213A, CN1690168A, CN1160436C all disclose some and have controlled the method for catalyst performance by control slurry viscosity or charging sequence etc.
At present China's catalytic cracking catalyst mainly uses al binder, and the semi-synthetic matrix catalytic cracking catalyst take aluminium colloidal sol and peptization boehmite as binding agent has the advantages that intensity is good, heavy oil cracking ability is strong.Boehmite refers to contain one to the hydrated alumina of two hydrones, is used for Cracking catalyst production and usually will passes through peptization.Peptization is the committed step that catalytic cracking catalyst is produced, the fluctuation of the peptization performance of boehmite and peptization degree can cause prepared catalyst mechanical strength and the fluctuation of pore volume, in order to guarantee the performance of prepared catalyst, usually employed boehmite is carried out the restriction of performance, such as to restrictions such as its solid content, alumina content, dephasign content.But even so, material quality is difficult to guarantee the performance of prepared binding agent.And prior art, for the boehmite that some β-gibbsite content is higher, often can't be for the preparation of Cracking catalyst.
Therefore, so that changing the method for preparing catalytic cracking catalyst that also can not cause the final catalyst physical and chemical performance that obtains to differ larger, the physico-chemical property of aluminium source (such as boehmite) will have the Research Significance of outbalance even how to develop a kind of.
Summary of the invention
Also can not cause the final catalyst physical and chemical performance that obtains to differ the larger method for preparing the peptization al binder even the technical problem to be solved in the present invention provides the physico-chemical property change of a kind of al binder raw material (such as boehmite), the other technical problem that the present invention will solve provides peptization al binder and the application in the Cracking catalyst preparation thereof of adopting method of the present invention to obtain.The catalytic cracking catalyst that the peptization al binder that adopts method of the present invention to obtain prepares has also that the molecular sieve utilization rate is high, the catalyst activity advantages of higher.
The application's applicant finds in research process unexpectedly, when preparation peptization al binder, to not only can reduce the harmful effect that the al binder material composition change prepares catalyst with the alkali neutralization and then with the acid neutralization after the intensification of the al binder after the acidifying under the lower temperature, the rugged catalyst quality, and can use the higher al binder Kaolinite Preparation of Catalyst of β-gibbsite content.Yet one uses cooling medium and cools off in same colloid generating kettle, heats with heat medium again for a moment, and not only workload is large, and efficient is low, and is unfavorable for industrial production.Finished thus the present invention.
The invention provides a kind of method for preparing the peptization al binder, the method comprises:
(1) in the first colloid generating kettle, al binder is mixed making beating with acid obtain the first slurries, the consumption of acid is so that the pH value of the first slurries is 2-4.9; Wherein, the temperature of controlling the first slurries is no more than 40 ℃;
(2) the first slurries are introduced in the second colloid generating kettle, the pH value that adding alkali is regulated the first slurries is 5-8, obtains the second slurries; Wherein, the temperature of controlling the second slurries is 50-95 ℃;
(3) the second slurries are introduced in the 3rd colloid generating kettle, the pH value that adds acid adjusting the second slurries is 2-4.9, obtains the 3rd slurries, and wherein, the temperature of controlling the 3rd slurries is no more than 30 ℃;
(4) the 3rd slurries are introduced in the 4th colloid generating kettle, the pH value that adding alkali is regulated the 3rd slurries is 5-8; Obtain the 4th slurries, wherein, the temperature of controlling the 4th slurries is 50-95 ℃;
(5) the 4th slurries are introduced in the 5th colloid generating kettle, the pH value that adds acid adjusting the 4th slurries is 2-4.9, obtains the 5th slurries, and wherein, the temperature of controlling the 5th slurries is no more than 30 ℃.
The invention provides a kind of peptization al binder that is prepared by the method for preparing the peptization al binder of the present invention.
The present invention also provides a kind of catalytic cracking catalyst, contains molecular sieve, clay and aluminium oxide in this catalytic cracking catalyst, and wherein, most or all are provided the aluminium oxide in the catalytic cracking catalyst by peptization al binder of the present invention.
The present invention also provides a kind of preparation method of catalytic cracking catalyst, and wherein, the method comprises: prepare a kind of binding agent, molecular sieve, clay and described binding agent are mixed making beating, then carry out successively spray-drying, washing, filtration and drying; Wherein, the preparation method of described binding agent is the method for preparing the peptization al binder of the present invention.
Adopt the preparation method of catalytic cracking catalyst of the present invention to prepare catalytic cracking catalyst, even the physico-chemical property of the al binder of different batches changes, can not cause the physico-chemical property of the catalytic cracking catalyst that obtains to differ larger yet, namely adopt method of the present invention to prepare the catalytic cracking catalyst good reproducibility and the catalytic cracking catalyst for preparing has that the molecular sieve utilization rate is high, the high advantage of catalyst activity.
Description of drawings
Fig. 1 is the schematic flow sheet of preparation peptization al binder of the present invention.
The specific embodiment
The invention provides a kind of method for preparing the peptization al binder, the method comprises:
(1) in the first colloid generating kettle, al binder is mixed making beating with acid obtain the first slurries, the consumption of acid is so that the pH value of the first slurries is 2-4.9; Wherein, the temperature of controlling the first slurries is no more than 40 ℃;
(2) the first slurries are introduced in the second colloid generating kettle, the pH value that adding alkali is regulated the first slurries is 5-8, obtains the second slurries; Wherein, the temperature of controlling the second slurries is 50-95 ℃;
(3) the second slurries are introduced in the 3rd colloid generating kettle, the pH value that adds acid adjusting the second slurries is 2-4.9, obtains the 3rd slurries, and wherein, the temperature of controlling the 3rd slurries is no more than 30 ℃;
(4) the 3rd slurries are introduced in the 4th colloid generating kettle, the pH value that adding alkali is regulated the 3rd slurries is 5-8; Obtain the 4th slurries, wherein, the temperature of controlling the 4th slurries is 50-95 ℃;
(5) the 4th slurries are introduced in the 5th colloid generating kettle, the pH value that adds acid adjusting the 4th slurries is 2-4.9, obtains the 5th slurries, and wherein, the temperature of controlling the 5th slurries is no more than 30 ℃.
Among the present invention, the first slurries are introduced in the second colloid generating kettle, the second slurries are introduced in the 3rd colloid generating kettle, the 3rd slurries are introduced in the 4th colloid generating kettle, the 4th slurries are introduced in the 5th colloid generating kettle all can be that part is introduced or all introduced, and in the general industry production in order to realize serialization, being generally part introduces, thereby can guarantee all has slurries in each colloid generating kettle, be conducive to realize serialization production.And among the present invention, all or partly introduce no matter be, can realize purpose of the present invention as long as guarantee the condition that reaches separately in each colloid generating kettle, therefore what of introducing amount the present invention do not emphasize in follow-up introduction, because can enough understanding according to the solution of the present invention, those skilled in the art how to implement, if for example the introducing in each colloid generating kettle is measured when more, the pH value that can regulate by adding more acid or alkali slurries, temperature can be regulated equally flexibly.In the concrete continuously production application process, generally in the first colloid generating kettle, add continuously al binder raw material, water and acid making beating, simultaneously the slurries in the first colloid generating kettle are introduced in the second colloid generating kettle, and in the second colloid generating kettle, add the alkali making beating, simultaneously the slurries of the second colloid generating kettle are introduced the 3rd colloid generating kettle; Equally, add the acid making beating when introducing the slurries from the second colloid generating kettle in the 3rd colloid generating kettle, simultaneously the slurries of the 3rd colloid generating kettle are introduced the 4th colloid generating kettle; The rest may be inferred for the operational circumstances of the 4th colloid generating kettle and the 5th colloid generating kettle, and those skilled in the art all can know this, no longer carry out expound at this.Wherein the 5th slurries that obtain in final the 5th colloid generating kettle can be directly used in the catalyst preparation, also can put into basin and store.
All can realize purpose of the present invention according to the aforesaid method of the present invention, for the active of catalytic cracking catalyst for preparing further improved and the preparation process good reproducibility, for the present invention, under the preferable case, the temperature of controlling the first slurries is no more than 30 ℃, further under the preferable case, control the temperature of the first slurries, the 3rd slurries, the 5th slurries and respectively do for oneself 0-25 ℃.
All can realize purpose of the present invention according to the aforesaid method of the present invention, for the active of catalytic cracking catalyst for preparing further improved and the preparation process good reproducibility, for the present invention, under the preferable case, the consumption of step (1), step (3), the middle acid of step (5) is the 2-4.5 so that the pH value of the first slurries, the 3rd slurries, the 5th slurries is respectively done for oneself respectively.
All can realize purpose of the present invention according to the aforesaid method of the present invention, for the active of catalytic cracking catalyst for preparing further improved and the preparation process good reproducibility, for the present invention, under the preferable case, control the temperature of the second slurries, the 4th slurries and respectively do for oneself 60-85 ℃.
All can realize purpose of the present invention according to the aforesaid method of the present invention, for the active of catalytic cracking catalyst for preparing further improved and the preparation process good reproducibility, for the present invention, under the preferable case, the consumption of alkali makes respectively the pH value of the second slurries, the 4th slurries 5-7.5 that respectively does for oneself in the step (2), step (4).
All can realize purpose of the present invention according to the aforesaid method of the present invention, optional wider range of the time of staying of slurries in each colloid generating kettle in colloid generating kettle separately, yet the long time of staying might cause the yield reducation of final catalyst or increase equipment volume, therefore, for the present invention, under the preferable case, the time of staying of the first slurries to the five slurries in the first colloid generating kettle to the five colloid generating kettles respectively did for oneself 10 minutes at least, be preferably 10-120 minute, more preferably 20-60 minute.
Among the present invention, optional wider range of the solid content of described the first slurries, for so that adopt method of the present invention well to realize the serialization steady production, the solid content of preferred the first slurries is the 5-40 % by weight, more preferably the 10-30 % by weight.Among the present invention, solid content (also claim non-volatile part content) refers to that the quality of solid matter that slurries were obtained in 800 ℃ of roastings in 1 hour again accounts for the ratio of the quality of slurries behind oven dry moisture under the 200-500 ℃ of condition, this is well known to those skilled in the art, and repeats no more.
The present invention adopts many stills continuous beating to prepare the peptization al binder, can comparatively easily as required, the material in the different colloid generating kettles be returned circulation.And, the present inventor finds in research process, the backflow of slurries is conducive to guarantee that the catalyst property of whole preparation process is steady, when particularly using the higher raw material of β gibbsite content, be conducive to improve product strength, therefore, preferred, the 4th slurries in the 4th colloid generating kettle are partly returned in the second colloid generating kettle, the slurries in the 5th colloid generating kettle are partly returned in the 3rd colloid generating kettle; Further preferred, the amount of returning of the 4th slurries is no more than 0.35:1 with the first slurry weight ratio of introducing in the second colloid generating kettle, and more preferably, the amount of returning of the 4th slurries is 0.2-0.35 times of the first slurry weight in introducing the second colloid generating kettle; The amount of returning of the 5th slurries is no more than 0.35:1 with the second slurry weight ratio of introducing in the 3rd colloid generating kettle, and more preferably the amount of returning of the 5th slurries is 0.2-0.35 times of the second slurry weight in introducing the 3rd colloid generating kettle.
Colloid generating kettle described in the present invention can be the colloid generating kettle of routine use, usually can adopt the reactor of jacketed or with the reactor of coil pipe as colloid generating kettle of the present invention, and generally speaking, for so that in the slurries mixing of materials even, preferred described reactor has agitating function.For the present invention, preferred adopt jacketed with the reactor of agitating function as the first colloid generating kettle, the 3rd colloid generating kettle, the 5th colloid generating kettle, thereby can lower the temperature to reactor by in chuck, passing into cooling medium (for example brine ice), employing with coil pipe or chuck with the reactor of agitating function as the second colloid generating kettle, the 4th colloid generating kettle, thereby can realize the second colloid generating kettle, the 4th colloid generating kettle heats, and adopts the reactor of jacketed as the second colloid generating kettle of the present invention, can heat by in chuck, passing into heat medium during the 4th colloid generating kettle.(also being in the embodiments of the invention) all selected in the specific implementation process of the present invention is that the reactor with agitating function of jacketed is tested, when wherein needing to heat (the temperature required room temperature that is higher than), heat by in chuck, passing into heat medium (such as water vapour), during cooling (temperature required be lower than room temperature), logically in the chuck cool off such as cooling medium (for example brine ice).Those skilled in the art all can know this, not repeat them here.
Among the present invention, optional wider range of the selection of the kind of described alkali, as long as it has the pH value that alkalescence can be used for regulating slurries of the present invention, for the present invention, be preferably inorganic base commonly used, one or more in ammoniacal liquor, NaOH or sodium hydrate aqueous solution and potassium hydroxide or the potassium hydroxide aqueous solution more preferably, ammoniacal liquor more preferably, the alkali same alkali that more preferably uses in each colloid generating kettle.In the specific implementation process, alkali is introduced (such as ammoniacal liquor) with the aqueous solution form of alkali usually, and the concentration of the aqueous solution of preferred bases is the 5-30 % by weight, is preferably the 15-25 % by weight.
Among the present invention, optional wider range of the selection of the kind of described acid, as long as it has the pH value that acidity can be used for regulating slurries of the present invention, for the present invention, be preferably inorganic acid commonly used, more preferably one or more in hydrochloric acid, nitric acid or aqueous solution of nitric acid, phosphoric acid or phosphate aqueous solution and sulfuric acid or the aqueous sulfuric acid; One or more in hydrochloric acid, nitric acid and the aqueous solution of nitric acid more preferably, the acid of more preferably using in each colloid generating kettle are same acid.In the specific implementation process, normally introduce described acid (example hydrochloric acid or aqueous solution of nitric acid) with the aqueous acid form, and preferably the concentration of aqueous acid is the 5-50 % by weight, is preferably the 20-40 % by weight.
According to the method for preparing the peptization al binder of the present invention, everyly can all can well be realized purpose of the present invention by the al binder of sour peptization, for the present invention, be preferably in boehmite, boehmite, gibbsite, bayerite and the η-aluminium oxide one or more, more preferably boehmite.
According to the method for preparing the peptization al binder of the present invention, because peptization al binder of the present invention is generally as the binding agent of Kaolinite Preparation of Catalyst, and generally speaking, may contain the additives such as clay, rare earth in the catalyst, therefore, in the process of preparation peptization al binder of the present invention, can be as required, in each colloid generating kettle, introduce the additives such as clay, rare earth, thereby so that namely contain the required auxiliary agent of catalyst in the peptization al binder for preparing.
Carry out briefly bright below in conjunction with accompanying drawing (Fig. 1) to the method for preparing the peptization al binder of the present invention, at first al binder, acid and water are sent in the first colloid generating kettle 1, al binder is mixed making beating with acid obtain the first slurries, the consumption of acid is so that the pH value of the first slurries is 2-4.9; Wherein, the temperature of controlling the first slurries is no more than 40 ℃; The first slurries are introduced from the first colloid generating kettle 1 in the second colloid generating kettle 2, and the pH value that adding alkali is regulated the first slurries is 5-8, obtains the second slurries; Wherein, the temperature of controlling the second slurries is 50-95 ℃; The second slurries are introduced from the second colloid generating kettle 2 in the 3rd colloid generating kettle 3, and the pH value that adds acid adjusting the second slurries is 2-4.5, obtains the 3rd slurries, and wherein, the temperature of controlling the 3rd slurries is no more than 30 ℃; The 3rd slurries are introduced from the 3rd colloid generating kettle 3 in the 4th colloid generating kettle 4, and the pH value that adding alkali is regulated the 3rd slurries is 5-8; Obtain the 4th slurries, wherein, the temperature of controlling the 4th slurries is 50-95 ℃; The 4th slurries are introduced from the 4th colloid generating kettle 4 in the 5th colloid generating kettle 5, and the pH value that adds acid adjusting the 4th slurries is 2-4.5, obtains the 5th slurries, and wherein, the temperature of controlling the 5th slurries is no more than 30 ℃, has realized thus the serialization production of peptization al binder.
The invention provides a kind of peptization al binder that is prepared by method of the present invention.
The present invention also provides a kind of catalytic cracking catalyst, contains molecular sieve, clay and aluminium oxide in this catalytic cracking catalyst, and wherein, most or all are provided the aluminium oxide in the catalytic cracking catalyst by peptization al binder of the present invention.
According to catalytic cracking catalyst of the present invention, under the preferable case, the 5-100 % by weight of the aluminium oxide in the catalytic cracking catalyst is provided by peptization al binder of the present invention.
According to catalytic cracking catalyst of the present invention, under the preferable case, take the gross weight of catalyst as benchmark, press the butt weighing scale, contain molecular sieve 10-50 % by weight in the catalytic cracking catalyst, clay 10-80 % by weight and aluminium oxide 10-40 % by weight.
According to catalytic cracking catalyst of the present invention, molecular sieve described in the present invention can be the various molecular sieves of prior art, for example can be in Y zeolite modification or unmodified, modification or unmodified ZSM-5 molecular sieve and modification or the unmodified beta-molecular sieve one or more, wherein, modified component is such as thinking in the modifying elements such as P, RE, Fe and Ni one or more, these are known for those skilled in the art, and the present invention gives unnecessary details no longer one by one at this.
According to catalytic cracking catalyst of the present invention, clay described in the present invention can be the various clays of prior art, for example can be in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and the bentonite one or more.
The invention provides a kind of preparation method of catalytic cracking catalyst, wherein, the method comprises: prepare a kind of binding agent, molecular sieve, clay and described binding agent are mixed making beating, then carry out successively spray-drying, washing, filtration and drying; Wherein, the preparation method of described binding agent is the method for preparing the peptization al binder of the present invention.
According to the preparation method of catalytic cracking catalyst of the present invention, under the preferable case, the 5-100 % by weight in the described binding agent is peptization al binder of the present invention.
According to the preparation method of catalytic cracking catalyst of the present invention, the kind of described molecular sieve and clay is described in detail aforementioned, does not repeat them here.
According to the preparation method of catalytic cracking catalyst of the present invention, making beating, spray-drying, washing, filtration and the dry technology that is well known to the skilled person do not repeat them here.
Below by embodiment the present invention is further described, but not thereby limiting the invention.
Among the present invention, specific area is the BET specific area, the pore volume of catalyst (also claiming water droplet method pore volume), abrasion index, heap than (apparent bulk density) respectively according to (" Petrochemical Engineering Analysis method (RIPP experimental technique) ", Yang Cui waits volume surely, Science Press, nineteen ninety publishes) in RIPP28-90, RIPP29-90, the method for RIPP31-90 measure.Refer to can be by the Al of sour peptization in the boehmite for the peptization index among the present invention
2O
3Weight account for total Al
2O
3Percentage, its assay method is prior art, the present invention does not repeat them here.
In each example and Comparative Examples, the content of element is measured (referring to " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publication) with x-ray fluorescence method in the material.
Used boehmite raw material is all available from Shandong Aluminium Industrial Corp in embodiment and the Comparative Examples.It is numbered N-1, N-2 and N-3, and wherein N-2 and N-1 are the qualified product that dispatches from the factory, but its catalyst processability is different, and β gibbsite content is higher among the N-3, and the peptization index is lower, and is specifically as shown in table 1.
Table 1
| Physico-chemical property | N-1 | N-2 | N-3 |
| Solid content, % by weight | 63 | 57 | 59 |
| β-gibbsite dephasign, % by weight | 3.1 | 3.0 | 9 |
| Na 2O, % by weight | 0.04 | 0.06 | 0.05 |
| Specific area, ml/g | 375.6 | 314.1 | 289.5 |
| The peptization index, % | 96 | 96 | 94 |
Embodiment 1
Test according to flow process shown in Figure 1:
1, preparation peptization al binder:
(1) with boehmite (N-1), water and hydrochloric acid (technical grade, 31 % by weight) mix making beating in introducing the first colloid generating kettle, wherein, the amount ratio of boehmite in the pulping process (N-1) and water, be 1:5 by weight, the temperature of slurries is controlled to be 20 ℃ in the first colloid generating kettle, and the pH value is 2.5-3.5, and the time of staying of slurries in the first colloid generating kettle is 20 minutes;
(2) the first slurries in the first colloid generating kettle and industrial ammonia (mass concentration 25%) are introduced in the second colloid generating kettle, the temperature of slurries is controlled to be 65 ℃ in the second colloid generating kettle, and the pH value is 5-6, and the time of staying of slurries in the second colloid generating kettle is 20 minutes;
(3) the second slurries in the second colloid generating kettle and hydrochloric acid (technical grade, 31 % by weight) are introduced in the 3rd colloid generating kettle, the temperature of slurries is controlled to be 20 ℃ in the 3rd colloid generating kettle, and the pH value is 2.5-3.5, and the time of staying of slurries in the 3rd colloid generating kettle is 20 minutes;
(4) the 3rd slurries in the 3rd colloid generating kettle and industrial ammonia (mass concentration 25%) are introduced in the 4th colloid generating kettle, the temperature of slurries is controlled to be 65 ℃ in the 4th colloid generating kettle, and the pH value is 5-6, and the time of staying of slurries in the 4th colloid generating kettle is 20 minutes;
(5) the 4th slurries in the 4th colloid generating kettle and hydrochloric acid (technical grade, 31 % by weight) are introduced in the 5th colloid generating kettle, the temperature of slurries is controlled to be 20 ℃ in the 5th colloid generating kettle, and the pH value is 2.5-3.5, and the time of staying of slurries in the 5th colloid generating kettle is 20 minutes;
2, preparation catalytic cracking catalyst:
With 44.44kg halloysite (Suzhou china clay company industrial products, solid content 45 % by weight), 25kg decationized Y sieve water joins in the 5th slurries that the step (5) of 86kg obtains, making beating 15min, adding ZSM-5 molecular sieve slurries 16.0kg(slurry solid content is 37.97 % by weight) and contain slurries (slurry solid content is 37.97 % by weight) the stirring 15min of REY molecular sieve (butt is 7.0kg), again to wherein adding the 7.5kg aluminium colloidal sol (commercial product that Sinopec Shandong catalyst branch company obtains, alumina content 20 % by weight), adding compound rare-earth solution 1kg(concentration in the whipping process is 300g/kg, rare earth element is La and Ce, La accounts for 65 % by weight, Ce accounts for 35 % by weight), stir 5min.Spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample C1.
The abrasion index of gained catalyst C1 is 1.1, and water droplet method pore volume is 0.43 ml/g, and heap is than 0.70 grams per milliliter.
3, catalyst activity evaluation:
According to micro-activity experiment method: Q/SH349912 this catalyst is estimated.Detailed process is: the 5 gram catalyst samples bed temperature of packing into is controlled in 460 ℃ the standard microreactor, 1.56 gram standard raw materials oil are at the uniform velocity reacted in the injecting reactor, the standard raw materials fuel oil meter is used huge port light diesel fuel (boiling range is 235-337 ℃) surely, reaction 70s, in the products therefrom, the percentage that the quality of gasoline+gas of＜240 ℃+coke accounts for combined feed is the micro-activity (MA) of catalyst, and the result is as shown in table 2.
Embodiment 2-10
Prepare catalytic cracking catalyst and carry out the micro-activity evaluation according to the method for embodiment 1, different is that operating condition changes, and specifically sees Table 2 and table 3.
Table 2
Table 3
In the table: a refers to the amount of returning the 4th slurries in the second colloid generating kettle in the 4th colloid generating kettle and the weight ratio of introducing the first slurries in the second colloid generating kettle; B refers to the amount of returning the 5th slurries in the 3rd colloid generating kettle in the 5th colloid generating kettle and the weight ratio of introducing the second slurries in the 3rd colloid generating kettle.
By the result of table 1 and table 2 as can be known, adopt method of the present invention to prepare catalytic cracking catalyst, although aluminium stone quality has fluctuation, but the catalyst physical property difference of using method preparation of the present invention is little, produce stable, and the catalyst activity that adopts method of the present invention to prepare is higher, and adopt method of the present invention, use the higher aluminium boehmite of β-gibbsite dephasign content also can prepare preferably catalyst (prior art generally can't be produced) of catalytic performance, this shows, method of the present invention is very suitable for suitability for industrialized production.
Comparative Examples 1
Under 26 ℃, use 40kg decationized Y sieve water with 8.64kg boehmite N-1(Shandong Aluminum Plant industrial products, solid content 63 % by weight) making beating, with hydrochloric acid (technical grade, 31 % by weight) its pH is transferred to 3, continue making beating 20min.44.44kg halloysite (Suzhou china clay company industrial products, solid content 45 % by weight) is added in the above-mentioned slurries making beating 15min, moisturizing 25kg.Adding ZSM-5 molecular sieve slurries 16.0kg(slurry solid content is 37.97 % by weight) and contain slurries (slurry solid content is 37.97 % by weight) the stirring 15min of REY molecular sieve butt 7.0kg, stir.Again to wherein adding the 7.5kg aluminium colloidal sol (commercial product that Sinopec Shandong catalyst branch company obtains, alumina content 20 % by weight), adding compound rare-earth solution 1kg(concentration in the whipping process is 300g/kg, rare earth element is La and Ce, La accounts for 65 % by weight, Ce accounts for 35 % by weight), stir 5min.Spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample D1.
The abrasion index of gained catalyst sample D1 is 1.3, and water droplet method pore volume is 0.40 ml/g, and heap is than 0.69 grams per milliliter.
Comparative Examples 2
Method according to Comparative Examples 1 prepares catalytic cracking catalyst, and different is that boehmite N-1 is replaced by boehmite N-2, obtains catalyst D2.
The abrasion index of gained catalyst sample D2 is 2.1, and water droplet method pore volume is 0.33 ml/g, and heap is than 0.76 grams per milliliter.
Result by Comparative Examples 1 and Comparative Examples 2 can illustrate, when adopting conventional peptization method, uses the catalyst prod performance difference of different boehmite raw materials larger.
Comparative Examples 3
According to the method for embodiment 1, different is operation under environment temperature (28 ℃), each colloid generating kettle does not carry out heating and cooling control temperature, use N-1 aluminium stone, and only use the first colloid generating kettle, the second colloid generating kettle and the 3rd colloid generating kettle, the slurries Kaolinite Preparation of Catalyst D3 that the 3rd colloid generating kettle is obtained.
Comparative Examples 4
Method according to Comparative Examples 3 prepares catalytic cracking catalyst, and different is that boehmite N-1 is replaced by boehmite N-2, obtains catalyst D4.
Comparative Examples 5
Under 26 ℃, with 8.64kg boehmite N-1 making beating, with hydrochloric acid (technical grade, 31 % by weight) its pH is transferred to 3.5 with 40kg decationized Y sieve water, pulled an oar again 20 minutes; Then add industrial ammonia (mass concentration 25%) 4.0kg, making its pH value is 8, pulls an oar 20 minutes, with hydrochloric acid slurries pH is transferred to 3.5 again, pulled an oar 20 minutes, then with ammoniacal liquor the pH value of slurries is adjusted to 9, stirring 20 minutes, is 3.0 with the salt acid for adjusting pH value again, pulls an oar 30 minutes; Then add 44.44kg halloysite (Suzhou china clay company industrial products, solid content 45 % by weight), pulled an oar 15 minutes, add water 25kg, then adding ZSM-5 molecular sieve slurries 16.0kg(concentration of slurry is 37.97 % by weight) and REY molecular sieve (butt) 7.0kg, stirred 15 minutes, again in stirring the lower 7.5kg of the adding aluminium colloidal sol (commercial product that catalyst branch company in Shandong obtains, alumina content 20 % by weight), 1kg compound rare-earth solution (concentration is 300g/kg, and La accounts for 65%, Ce and accounts for 35%), stirred 5 minutes, spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample D5.
Comparative Examples 6
Method according to Comparative Examples 5 prepares catalytic cracking catalyst, and different is that boehmite N-1 is replaced by boehmite N-2, obtains catalyst sample D6.
Table 4
Claims (16)
1. a method for preparing the peptization al binder is characterized in that, the method comprises:
(1) in the first colloid generating kettle, al binder is mixed making beating with acid obtain the first slurries, the consumption of acid is so that the pH value of the first slurries is 2-4.9; Wherein, the temperature of controlling the first slurries is no more than 40 ℃;
(2) the first slurries are introduced in the second colloid generating kettle, the pH value that adding alkali is regulated the first slurries is 5-8, obtains the second slurries; Wherein, the temperature of controlling the second slurries is 50-95 ℃;
(3) the second slurries are introduced in the 3rd colloid generating kettle, the pH value that adds acid adjusting the second slurries is 2-4.9, obtains the 3rd slurries, and wherein, the temperature of controlling the 3rd slurries is no more than 30 ℃;
(4) the 3rd slurries are introduced in the 4th colloid generating kettle, the pH value that adding alkali is regulated the 3rd slurries is 5-8; Obtain the 4th slurries, wherein, the temperature of controlling the 4th slurries is 50-95 ℃;
(5) the 4th slurries are introduced in the 5th colloid generating kettle, the pH value that adds acid adjusting the 4th slurries is 2-4.9, obtains the 5th slurries, and wherein, the temperature of controlling the 5th slurries is no more than 30 ℃.
2. method according to claim 1 wherein, is controlled the temperature of the first slurries, the 3rd slurries, the 5th slurries and is respectively done for oneself 0-25 ℃.
3. method according to claim 2, wherein, the consumption of the acid 2-4.5 so that the pH value of the first slurries, the 3rd slurries, the 5th slurries is respectively done for oneself respectively in step (1), step (3), the step (5).
4. method according to claim 1 wherein, is controlled the temperature of the second slurries, the 4th slurries and is respectively done for oneself 60-85 ℃.
5. in accordance with the method for claim 1, wherein, the consumption of alkali makes respectively the pH value of the second slurries, the 4th slurries 5-7.5 that respectively does for oneself in the step (2), step (4).
6. the described method of any one according to claim 1-5, wherein, the time of staying of the first slurries to the five slurries in the first colloid generating kettle to the five colloid generating kettles respectively did for oneself 10-120 minute.
7. the described method of any one according to claim 1-5, wherein, the solid content of the first slurries is the 5-40 % by weight.
8. the described method of any one according to claim 1-5, wherein, the method also comprises: the 4th slurries in the 4th colloid generating kettle are partly returned in the second colloid generating kettle, and wherein, the amount of returning of the 4th slurries is 0.2-0.35 times of the first slurry weight in introducing the second colloid generating kettle.
9. the described method of any one according to claim 1-5, wherein, the method also comprises: the 5th slurries in the 5th colloid generating kettle are partly returned in the 3rd colloid generating kettle, and wherein, the amount of returning of the 5th slurries is 0.2-0.35 times of the second slurry weight in introducing the 3rd colloid generating kettle.
10. the described method of any one according to claim 1-5, wherein, described alkali is one or more in ammoniacal liquor, NaOH or sodium hydrate aqueous solution and potassium hydroxide or the potassium hydroxide aqueous solution; Described acid is one or more in hydrochloric acid, nitric acid or aqueous solution of nitric acid, phosphoric acid or phosphate aqueous solution and sulfuric acid or the aqueous sulfuric acid.
11. the described method of any one according to claim 1-5, wherein, described al binder is one or more in boehmite, boehmite, gibbsite, bayerite and the η-aluminium oxide.
12. peptization al binder that is prepared by the described method of any one among the claim 1-11.
13. a catalytic cracking catalyst, this catalytic cracking catalyst contains molecular sieve, clay and aluminium oxide, it is characterized in that, most or all are provided the aluminium oxide in the catalytic cracking catalyst by the peptization al binder described in the claim 12.
14. catalytic cracking catalyst according to claim 13, wherein, the 5-100 % by weight of the aluminium oxide in the catalytic cracking catalyst is provided by the peptization al binder described in the claim 12.
15. according to claim 13 or 14 described catalytic cracking catalysts, wherein, take the gross weight of catalyst as benchmark, press the butt weighing scale, contain molecular sieve 10-50 % by weight in the catalytic cracking catalyst, clay 10-80 % by weight and aluminium oxide 10-40 % by weight.
16. the preparation method of a catalytic cracking catalyst, wherein, the method comprises: prepare a kind of binding agent, molecular sieve, clay and described binding agent are mixed making beating, then carry out successively spray-drying, washing, filtration and drying; It is characterized in that, the preparation method of described binding agent is the described method of any one among the claim 1-11.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105772074A (en) * | 2014-12-25 | 2016-07-20 | 中国石油天然气股份有限公司 | Preparation method for heavy oil catalytic cracking catalyst |
| CN108816273A (en) * | 2018-06-04 | 2018-11-16 | 中国中化股份有限公司 | A kind of preparation method of the hydrocracking catalyst of high light oil selectivity |
| CN110876948A (en) * | 2018-09-05 | 2020-03-13 | 中国石油化工股份有限公司 | Aluminum sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4010116A (en) * | 1974-10-15 | 1977-03-01 | Filtrol Corporation | Fluid cracking catalysts |
| CN1184078A (en) * | 1997-12-19 | 1998-06-10 | 中国石油化工总公司 | Preparation process of alumina |
| CN101624536A (en) * | 2008-07-10 | 2010-01-13 | 中国石油化工股份有限公司 | Method for preparing catalytic cracking catalyst |
-
2012
- 2012-06-07 CN CN201210186976.3A patent/CN103028437B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4010116A (en) * | 1974-10-15 | 1977-03-01 | Filtrol Corporation | Fluid cracking catalysts |
| CN1184078A (en) * | 1997-12-19 | 1998-06-10 | 中国石油化工总公司 | Preparation process of alumina |
| CN101624536A (en) * | 2008-07-10 | 2010-01-13 | 中国石油化工股份有限公司 | Method for preparing catalytic cracking catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105772074A (en) * | 2014-12-25 | 2016-07-20 | 中国石油天然气股份有限公司 | Preparation method for heavy oil catalytic cracking catalyst |
| CN105772074B (en) * | 2014-12-25 | 2018-07-13 | 中国石油天然气股份有限公司 | A kind of preparation method of catalyst for heavy oil catalytic cracking |
| CN108816273A (en) * | 2018-06-04 | 2018-11-16 | 中国中化股份有限公司 | A kind of preparation method of the hydrocracking catalyst of high light oil selectivity |
| CN108816273B (en) * | 2018-06-04 | 2021-04-09 | 中国中化股份有限公司 | Preparation method of hydrocracking catalyst with high light oil selectivity |
| CN110876948A (en) * | 2018-09-05 | 2020-03-13 | 中国石油化工股份有限公司 | Aluminum sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst |
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