CN104923282B - A kind of super stabilizing processing method of high rare-earth content in-situ crystallization catalyst - Google Patents
A kind of super stabilizing processing method of high rare-earth content in-situ crystallization catalyst Download PDFInfo
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Abstract
The invention discloses a kind of super stabilizing processing method of high rare-earth content in-situ crystallization catalyst, this method is after the NaY types catalyst of in-situ crystallization is repeatedly exchanged through ammonium ion and rare earth ion, the high temperature hydrothermal calcine under different temperature gradient conditions, thus the super stabilizing catalyst prod that content of rare earth is high, lattice constant is less than 2.455nm, the features such as catalyst obtained using the present invention has high content of rare earth, silica alumina ratio height, activity, good stability and excellent coke selectivity are prepared.
Description
Technical field
The present invention relates to a kind of super stabilizing processing method of in-situ crystallization catalyst, more specifically, more particularly to it is a kind of
The super stabilizing processing method of high rare-earth content in-situ crystallization catalyst.
Background technology
From nineteen sixty synthetic zeolite catalysts cracking（FCC）Catalyst occurs to current, the preparation of Y type molecular sieve FCC catalyst
Technique can substantially be summarized as two types：(a) molecular sieve is manufactured separately, then compound with carrier；(b) molecular sieve is by natural high
Ridge soil in-situ crystallization, part kaolin is converted into Y zeolites, and part kaolin is used as carrier.
Former approach, the preparation of catalyst is exactly by active constituent, carrier（Filler and binding agent）It is beaten, passes through together
Spray drying forming, obtains 0-150 microns of particle diameter, the microspherical catalyst that 65-85 microns of average grain diameter.Active constituent changes to be various
The y-type zeolite of property, including REY, REHY, REUSY, USY etc..When the Y zeolites using high rare-earth content（RE2O3About 18-20m%）
When, because hydrogen transfer reaction is fast, cause catalyst coke yield high, octane number is low.Therefore, industrially by reducing zeolite
Rare-Earth Content simultaneously carries out super stabilizing processing to zeolite, i.e., the hydrothermal stability of zeolite is improved by improving Zeolite,
Hydrogen transfer reaction speed is reduced, improves product distribution, improve octane number.Stablize zeolitic frameworks aluminium because rare earth ion has
Effect, be difficult to remove zeolitic frameworks aluminium when zeolite rare earth ion content is higher, that is, be difficult to zeolite carry out super stabilizing processing
Improve silica alumina ratio.Therefore, the overstable gamma zeolite content of rare earth that the technique is obtained is low, typically about 0.5-5m%, such as USP4213307,
CN1065844A.Due to the technique carrier and molecular sieve are bonded together by binding agent it is industrial strong to catalyst to meet
The requirement of degree, when molecular sieve content is higher than 40m%, it is difficult to which intensity, which is made, meets desired product, is so contained when using low rare earth
When the super steady Y of amount is as active constituent, on the one hand due to overstable gamma zeolite activated centre（Activated aluminum quantity）It is low, on the other hand urge
Content of rare earth is low in agent, is 40 × 5%=2.0% when REO is higher, causes reaction conversion ratio low.It is of course possible to by improving zeolite
Content of rare earth improves catalyst activity, but as it was previously stated, reaction selectivity can be affected again.I.e. the technique is more difficult in reaction
Taken into account in selectivity and activity.
Later approach, kaolin in-situ crystallization prepares FCC catalyst technology, be using natural kaolin as initial feed,
Active component and host material are first prepared using one-step method simultaneously, then kaolin type FCC catalysis is prepared by modification
Agent.In preparation process, the crystallization product of the molecular sieve of type containing NaY is synthesized after kaolin microsphere is fired under hydrothermal conditions, this
The amorphous substance of crystallization product is carrier component, such as 4493902, EP0194101, EPA0369629 of USP,
CN1232862A etc..
The characteristics of catalyst prepared by the technology：1st, the high catalyst of molecular sieve content, example molecular sieve content can be made
Up to 60m%, while there is good catalyst strength, due to molecular sieve content height thus with high activity；2nd, catalyst
With very high specific surface area and excellent pore size distribution, thus with good reaction selectivity.Due to in-situ crystallization catalyst
These features so that the process catalyst has the ability of excellent processing heavy oil.Nonetheless, it is catalyzed to in-situ crystallization
In the modifying process of agent, need also exist for taking into account catalyst activity and selectivity consideration, its successive modified Main Means is also
Super stabilizing processing is carried out to product.In order to obtain compared with high silica alumina ratio, such as lattice constant is less than 2.460nm super stabilizing product, right
The molecular sieve catalyst post processing of in-situ crystallization synthesis gained NaY types, is also using low rare earth or without content of rare earth technique, such as
Shown in EPA0194101.CN1913965A, which reports situ catalytic agent content of rare earth, can reach 12%, but prepare low lattice constant
Super steady catalyst prod when content of rare earth less than 3%, lattice constant is in 2.450nm or so.For high rare-earth content, such as rare earth
Higher than 7m%, the super stabilizing handling process of catalyst is there is not yet document and pass patent report.
In addition, super stabilizing method is generally using the multiple cation exchange and high-temperature roasting reported such as above-mentioned document
Method.Cation typically uses various ammonium salts, such as ammonium chloride, ammonium nitrate and ammonium sulfate and rare earth ion, high temperature hydrothermal calcine temperature
Degree is general below 650 DEG C, and the roasting of typical process one temperature as described in CN1232862A is 550-600 DEG C, and two roasting temperature are 600-
650℃。
The content of the invention
It is an object of the invention to provide a kind of super stabilizing processing method of high rare-earth content in-situ crystallization catalyst, the party
Method is after the NaY types catalyst of in-situ crystallization is repeatedly exchanged through ammonium ion and rare earth ion, in different temperature gradient conditions
Lower high temperature hydrothermal calcine, thus prepares the super stabilizing catalyst prod that content of rare earth is high, lattice constant is less than 2.455nm.
To achieve the above object, processing method of the present invention includes following process step：
（1）Ammonium is exchanged：In-situ crystallization NaY types catalyst and ammonium salt are subjected to ion exchange, water/agent ratio with conventional method
（Weight ratio）For 3:1-5:1, ammonium salt consumption is：Ammonium salt/catalyst（Weight ratio）=0.2-0.4, filtering, filter cake deionized water
Elution, same method is exchanged once again, obtains Na2O content is less than 4.0m% NH4Y type catalyst；
（2）Rare earth exchanged：By step（1）Products therefrom carries out ion exchange, water/agent ratio with earth solution（Weight ratio）For
3:1-5:1, rare-earth usage（With RE2O3Meter）For the 4-10% of catalyst weight, filtered after exchange, obtain REY types and NH4Y types are urged
Agent mixture；
（3）Once it is calcined：By step（2）Gained mixture was in 500-600 DEG C of hydrothermal calcine 2-6 hours；
（4）Material mends rare earth after one roasting：By step（3）Mixture after roasting carries out ion exchange, water/agent ratio with ammonium salt
（Weight ratio）For 3:1-5:1, ammonium salt consumption is：Ammonium salt/catalyst（Weight ratio）=0.1-0.3, filtering, filter cake deionized water
After elution ion exchange, rare-earth usage are carried out with earth solution（With RE2O3Meter）For the 2-3% of catalyst weight, after exchange again
Filter to obtain filter cake；
（5）After baking：By step（4）Prior to 500-600 DEG C of gained filter cake hydrothermal calcine 1-2 hours, after be warming up to
800-850 DEG C is continued to be calcined 1-3 hours；
（6）Material is handled after two roastings：By step（5）Material after roasting carries out ion exchange, water/agent ratio with ammonium salt（Weight
Amount ratio）For 3:1-5:1, ammonium salt consumption is：Ammonium salt/catalyst（Weight ratio）=0.1-0.2, filtering, filter cake deionized water is drenched
Wash, dry, obtain content of rare earth 7-10%, lattice constant is urged for 2.445-2.455 nm high-activity high-selectivity in-situ crystallization
Agent.
In above-mentioned processing method, it is related to the step of ammonium ion is exchanged（1）、（4）、（6）In ammonium salt used be ammonium chloride, sulfuric acid
Ammonium, ammonium nitrate or ammonium phosphate.
In above-mentioned processing method, the step of being related to rare earth ion exchanged（2）、（4）In earth solution used be that lanthanum chloride is molten
Liquid, solution of cerium chloride by oxidation or lanthanum-cerium chloride mixed rare earth solution.
In above-mentioned processing method, the exchange of ammonium ion and rare earth ion is carried out according to the condition of prior art, the present invention
It is had no particular limits, conventional optimum condition is 60-90 DEG C of temperature, pH value 3.0-4.0, swap time is 20-60 points
Clock, pH value is adjusted with corresponding ammonium salt diluted acid, and such as ammonium chloride is adjusted with dilute HCl.
Compared with prior art, present invention be distinguished in that：By rare earth ion is before catalyst roasting and once roasts
Burn latter two steps to exchange in catalyst, the method being calcined using thermograde when being calcined for second carries out hydro-thermal to material
Roasting, the operation of thermograde roasting is first 500-600 DEG C of preroast, to avoid high-temperature water vapor from causing brokenly catalyst structure
It is bad, after be warming up to 800-850 DEG C of high-temperature roasting, to strengthen structure cell contraction, improve silica alumina ratio, be derived from content of rare earth high（Reach
To 7-10%）, lattice constant be 2.445-2.455nm catalyst prod.
The catalyst obtained by the present invention has high content of rare earth, silica alumina ratio height, activity, stability good and coke selectivity
Excellent the features such as, the coke yield lower than general Y-type rare earth catalyst is shown, referring specifically to table 2 and the evaluation number of table 3
According to.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Raw material specification used is as follows in example：
1st, original position NaY type molecular sieve catalysts
NaY type in-situ crystallization catalyst prods are prepared according to in-situ crystallization catalyst common process
I.e.：（1）Kaolin is spray-dried, and prepares the kaolin microsphere of 0-150 μm of particle diameter,（2）Kaolin microsphere is existed
Metakaolin microballoon is made in 700-900 DEG C of roasting, and sintering temperature of the present invention is 730 DEG C,（3）By kaolin microsphere in 900-1000
Spinel-type kaolin microsphere is made in DEG C roasting, and sintering temperature of the present invention is 940 DEG C,（4）By gained metakaolin microballoon and point
Spar soil microballoon presses 1:1 ratio mixing, in waterglass, carries out crystallization, is made in the presence of sodium hydroxide and directed agents
NaY type catalyst crystallization products.Relevant technique is shown in US4493902 and CN1232862A, CN1334318A.
Product crystallinity 46%, cell parameter 2.471nm.
2nd, watery hydrochloric acid：HCl concentration 4%, is formed by the allotment that adds water of the technical-grade hydrochloric acid of concentration 33 ~ 35%.
3rd, earth solution：Lanthanum-cerium chloride mixed rare earth solution, RE2O3330g/l, the g/ml of proportion 1.432, pH value 3.2.
4th, ammonium chloride：Technical grade solid ammonium chloride.
Example and comparative example use limits method：
1st, micro-activity：Micro fixed-bed reactor, test procatalyst is through 800 DEG C, 100% steam aging 4 hours.
2nd, activity stability：Micro fixed-bed reactor, test procatalyst through 800 DEG C, 100% steam aging 17 it is small
When.
3rd, reaction selectivity：ACE evaluating apparatus, test procatalyst is through 800 DEG C, 100% steam aging 17 hours.
Example 1
（1）Ammonium is exchanged
Add input in-situ crystallization NaY type catalyst 300g and chlorine under deionized water 1200g, stirring condition in stainless steel kettle
Change ammonium 90g, adjust pH value 3.0-4.0 with 4% dilute hydrochloric acid solution, exchanged 40 minutes under the conditions of 80 DEG C, filtering, filter cake is spent
Ion water wash, same method is exchanged once again, obtains Na2O content is less than 4.0m% NH4Y type catalyst.
（2）Rare earth exchanged
Above-mentioned product adds deionized water 1200g, adds RECl3Rare earth（RE2O3For the 8% of catalyst weight）Solution, in PH
Value 3.0-4.0, exchanges 40 minutes under the conditions of 80 DEG C, obtains REY types and NH4Y type catalyst mixtures.
（3）Once it is calcined
Said mixture hydrothermal calcine 4 hours under the conditions of 550 DEG C.
（4）Material mends rare earth after one roasting
Material adds deionized water 1200g, ammonium chloride 60g after an above-mentioned roasting, is exchanged under the conditions of pH value 3.0-4.0,80 DEG C
40 minutes, filtering, filter cake carried out ion exchange, rare-earth usage after being eluted with deionized water with earth solution（With RE2O3Meter）To urge
The 2% of agent weight, other conditions are same（2）.
（5）After baking
Above-mentioned filter cake is warming up to after 800 DEG C in 550 DEG C of hydrothermal calcines 2 hours and continues to be calcined 2 hours.
（6）Material ammonium is exchanged after two roastings
Material adds deionized water 1200g, ammonium chloride 30g after above-mentioned two roasting, is exchanged under the conditions of pH value 3.0-4.0,80 DEG C
40 minutes, filtering, filter cake was eluted with deionized water, is dried, is obtained catalyst A1.
Example 2
Super stabilizing modification is carried out to in-situ crystallization NaY types product by the method for example 1：Wherein step（5）Roasting temperature
Spending gradient is：Filter cake is calcined 2 hours in 550 DEG C, is warming up to after 850 DEG C and is continued to be calcined 2 hours, other conditions must be urged with example 1
Agent A2.
Example 3
（1）Ammonium is exchanged
Add input in-situ crystallization NaY type catalyst 300g and chlorine under deionized water 1200g, stirring condition in stainless steel kettle
Change ammonium 90g, adjust pH value 3.0-4.0 with 4% dilute hydrochloric acid solution, exchanged 40 minutes under the conditions of 80 DEG C, filtering, filter cake is spent
Ion water wash, same method is exchanged once again, obtains Na2O content is less than 4.0m% NH4Y type catalyst.
（2）Rare earth exchanged
Above-mentioned product adds deionized water 1200g, adds RECl3Rare earth（RE2O3For catalyst weight 6%）Solution, in pH value
3.0-4.0, exchanges 40 minutes under the conditions of 80 DEG C, obtains REY types and NH4Y type catalyst mixtures.
（3）Once it is calcined
Said mixture is calcined 4 hours at 550 DEG C.
（4）Material mends rare earth after one roasting
Material adds deionized water 1200g, ammonium chloride 60g after an above-mentioned roasting, is exchanged under the conditions of pH value 3.0-4.0,80 DEG C
40 minutes, filtering, filter cake carried out ion exchange, rare-earth usage after being eluted with deionized water with earth solution（With RE2O3Meter）To urge
The 3% of agent weight, other conditions are same（2）.
（5）After baking
Above-mentioned filter cake is calcined 2 hours in 550 DEG C, is warming up to after 800 DEG C and is continued to be calcined 2 hours.
（6）Material ammonium is exchanged after two roastings
Material adds deionized water 1200g, ammonium chloride 30g after above-mentioned two roasting, is exchanged under the conditions of pH value 3.0-4.0,80 DEG C
40 minutes, filtering, filter cake was eluted with deionized water, is dried, is obtained catalyst B1.
Example 4
Super stabilizing modification is carried out to in-situ crystallization NaY types product by the method for example 3：Wherein step（5）Roasting temperature
Spending gradient is：Filter cake is calcined 2 hours in 550 DEG C, is continuously heating to be calcined 2 hours after 850 DEG C, other conditions must be urged with example 3
Agent B2.
Comparative example
Comparative example typical process as described in CN1232862A is modified processing to catalyst.
（1）Ammonium is exchanged：Deionized water 1500g, NaY type in-situ crystallization product 300g, ammonium chloride 60g, PH3.0-3.5, temperature
90 DEG C of degree is exchanged 1 hour, is filtered, washing.
（2）Rare earth exchanged：One hands over material plus deionized water 1500g, and re chloride is exchanged（RE2O3For catalyst weight
3.2%）, PH3.5-4.0,90 DEG C exchange 1 hour, filter, washing.
（3）One roasting：Above-mentioned filter cake is calcined 1 hour at 550 DEG C.
（4）Mend rare earth exchanged：RE2O3For the 2.1% of catalyst weight, other conditions are same（2）.
（5）Two roastings：Above-mentioned filter cake is calcined 1 hour at 650 DEG C.
（6）Material ammonium is exchanged after two roastings：By step（1）Methods described ammonium sulfate 60g（Ammonium sulfate/agent=0.20）Exchange,
Catalyst C is obtained after drying；
The present invention of table 1 and contrast medium technics comparing
The present invention gained catalyst of table 2 is compared with comparative catalyst's physical and chemical performance
* silica alumina ratio is calculated according to lattice constant by Breck formula in table（Breck D W. Zeolite Molecular
Sieves. Wiley, 1974.）.
As shown by data in table 2, present invention gained catalyst is compared with contrast medium, and lattice constant and silica alumina ratio are substantially better than pair
Than agent, corresponding micro-activity and activity stability are also more preferable.
The catalyst of the present invention of table 3 and comparative catalyst's ACE device evaluation response performance comparisons
The as shown by data of table 3, present invention gained catalyst is compared with contrast medium, and conversion ratio and total liquid yield are significantly better than that
Contrast medium, and with low coke yield and excellent coke selectivity（Low burnt/turn ratio）.
Claims (4)
1. a kind of super stabilizing processing method of high rare-earth content in-situ crystallization catalyst, it is characterised in that：Including following processing step
Suddenly：
(1) ammonium is exchanged：In-situ crystallization NaY types catalyst and ammonium salt are subjected to ion exchange with conventional method, water/agent ratio is by weight
It is calculated as 3:1-5:1, ammonium salt consumption is：Ammonium salt/catalyst by weight=0.2-0.4, filtering, filter cake elutes with deionized water,
Same method is exchanged once again, obtains Na2O content is less than 4.0m% NH4Y type catalyst；
(2) rare earth exchanged：Step (1) products therefrom and earth solution are subjected to ion exchange, water/agent ratio by weight 3:1-
5:1, rare-earth usage is with RE2O3The 4-10% of catalyst weight is calculated as, is filtered after exchange, obtains REY types and NH4Y types catalyst is mixed
Compound；
(3) once it is calcined：By mixture obtained by step (2) in 500-600 DEG C of hydrothermal calcine 2-6 hours；
Material mends rare earth after (4) one roastings：Mixture after step (3) is calcined carries out ion exchange with ammonium salt, and water/agent ratio is by weight
Amount is calculated as 3:1-5:1, ammonium salt consumption is：Ammonium salt/catalyst by weight=0.1-0.3, filtering, filter cake elutes with deionized water
Ion exchange is carried out with earth solution afterwards, rare-earth usage is with RE2O3The 2-3% of catalyst weight is calculated as, is filtered again after exchange
Filter cake；
(5) after baking：By prior to 500-600 DEG C of filter cake hydrothermal calcine 1-2 hours obtained by step (4), after be warming up to 800-850
DEG C continue be calcined 1-3 hours；
Material is handled after (6) two roastings：Material after step (5) is calcined carries out ion exchange with ammonium salt, and water/agent ratio is by weight
For 3:1-5:1, ammonium salt consumption is：Ammonium salt/catalyst by weight=0.1-0.2, filtering, filter cake elutes with deionized water, does
It is dry, content of rare earth 7-10% is obtained, lattice constant is 2.445-2.455nm high-activity high-selectivity in-situ crystallization catalyst.
2. processing method according to claim 1, it is characterised in that：Ammonium salt used is in the step (1), (4), (6)
Ammonium chloride, ammonium sulfate, ammonium nitrate or ammonium phosphate.
3. processing method according to claim 1, it is characterised in that：Earth solution used is in the step (2), (4)
Lanthanum chloride solution, solution of cerium chloride by oxidation or lanthanum-cerium chloride mixed rare earth solution.
4. processing method according to claim 1, it is characterised in that：The step (1), (2), (4), the ion of (6) are handed over
Change and carried out under conditions of 60-90 DEG C of temperature, pH value 3.0-4.0, swap time is 20-60 minutes.
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| CN106927483B (en) * | 2015-12-29 | 2019-09-03 | 中国石油天然气股份有限公司 | Preparation method of modified Y-type molecular sieve |
| CN110871102B (en) * | 2018-08-29 | 2022-06-24 | 中国石油化工股份有限公司 | Preparation method of micro-mesoporous composite material containing Y-type molecular sieve |
| CN112206809A (en) * | 2019-07-09 | 2021-01-12 | 中国石油化工股份有限公司 | Rare earth-containing Y-type molecular sieve and preparation method thereof |
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