CN102806096A - Rare earth-containing Y-type molecular sieve cracking catalyst and preparation method thereof - Google Patents
Rare earth-containing Y-type molecular sieve cracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a rare earth-containing Y-type molecular sieve cracking catalyst. The preparation method comprises the steps: (1), mixing NaY molecular sieve without ion exchange and a matrix, pulping, spray-drying and molding to obtain a catalyst precursor; (2), firstly calcining the catalyst precursor at 20-400 DEG C; performing ammonium ion exchange on the calcined product; (3), performing second calcining and at least one rare-earth ion exchange on the product after ammonium ion exchange, wherein the rare-earth ion exchange is performed after the second calcining; the temperature of the ammonium ion exchange is more than that of the rare-earth ion exchange; and the second calcining temperature is more than that of the first calcining temperature. The invention also relates to a Y-type molecular sieve cracking catalyst obtained by the method. The rare earth-containing Y-type molecular sieve cracking catalyst obtained by the method provided by the invention has big total hole volume and specific surface area and has good wearing resistance.
Description
Technical field
The present invention relates to a kind of preparation method who contains the Y zeolite Cracking catalyst of rare earth, and by the Y zeolite Cracking catalyst that contains rare earth of this method preparation.
Background technology
Along with feedstock oil becomes heavy day by day, the continuous reinforcement of people's environmental consciousness has caused not only requiring catalytic cracking catalyst to have good reaction selectivity, activity and stable, and also requires more and more harsher for the Preparation of catalysts flow process.
In the production of catalytic cracking catalyst; The preparation flow of traditional Cracking catalyst that contains zeolite roughly can be divided into two types: one type is to exchange flow process earlier, adds matrix after zeolite elder generation's ion-exchange soon or the modification again and removes spray drying forming (being with or not being with roasting); Another kind of is that the back exchanges flow process, is about to go to carry out ion-exchange or modification processing again behind the zeolite adding matrix elder generation spray drying forming without exchange.
CN1065844A discloses a kind of preparation method of superstable Y type zeolite containing less rare-earth elements; What adopted is " two the hand over two roastings " technology that exchanges earlier in the flow process; Concrete, this method comprises: the NaY zeolite of (1) silica alumina ratio >=4.5 and the hybrid ionic exchange reaction of ammonium ion and rare earth ion; (2) (1) step gains being carried out hydrothermally stable handles; (3) an amount of silicon-containing compound is added in the entry, the silicone content that makes gained liquid is 0.02-0.5 weight %, and with 10-15: the liquid-solid ratio of 1 (weight ratio) adds (2) step gains; Mix, under room temperature-100 ℃ and stirring condition, dripping concentration with the speed of 1-5 ml/min is the inorganic acid of 0.01-3N; 2.8-3.3 is constant to be as the criterion the addition of acid so that the pH value of mixed liquor remains on, above-mentioned add sour process also can be under 50-100 ℃ and stirring condition, dropping concentration is the organic acid of 0.5-4N; 4-4.5 is constant to be as the criterion the organic acid addition so that the pH value of mixed liquor remains on, and after stopping to add acid, continues reaction 1-3 hour; Filter washing; (4) (3) step gains are carried out hydrothermal treatment consists.
Though the zeolite of the method for above-mentioned patent application preparation has good structural stability and activity stability; With this zeolite is that the Cracking catalyst of active component has active high, selectivity is good and activity stability is good characteristics; Yet, because different, the sterically hindered difference in the residing position of sodium in the active component particularly in the catalyst will make that the sodium content in molecular sieve and the catalyst meets the demands; Just must be with excessive ammonium salt, this has just inevitably caused the pollution of environment; And; Zeolite needs to add the matrix spray-drying and processes catalyst after modification well; Also need exchange the sodium content that reduces in the matrix this moment with excessive ammonium salt, also need a large amount of decationizing water to wash simultaneously in the process of each exchange, this has just wasted great amount of water resources.
CN101670295A discloses a kind of production of cracking catalyst; What adopted is back exchange flow process; This method comprise with Y zeolite mix with matrix, making beating, spray-dired step; Wherein, said Y zeolite is the NaY molecular sieve, comprises that also the catalyst powder that spray-drying is obtained contacts the step of carrying out ion-exchange, reclaiming catalyst with exchange ion; Said ion-exchange can be for contacting catalyst powder with the solution that contains exchange ion, said exchange ion is one or more in ammonium ion, rare earth ion and the transition metal ions.
Though the method for above-mentioned patent application has overcome the excessive use of ammonium salt that exists in traditional flow process of exchange earlier and the defective of waste water resource; But, have total pore volume and specific area is less, wear resistence is relatively poor defective according to the Cracking catalyst of the method for above-mentioned patent application preparation.
Summary of the invention
To the objective of the invention is the above-mentioned defective that exists in the existing Y zeolite Preparation of catalysts method in order overcoming, a kind of preparation method who contains the Y zeolite Cracking catalyst of rare earth to be provided.
The invention provides a kind of preparation method who contains the Y zeolite Cracking catalyst of rare earth, this method comprises: (1) will mix with matrix without the NaY molecular sieve of ion-exchange, making beating and spray drying forming, obtains catalyst precarsor; (2) said catalyst precarsor is carried out first roasting at 200 ℃ under less than 400 ℃ temperature, and the product that obtains after said first roasting is carried out ammonium ion exchange; And the product that (3) obtain after with said ammonium ion exchange carries out at least one time second roasting and at least rare earth ion exchanged, and said rare earth ion exchanged is carried out after said second roasting; The temperature of said ammonium ion exchange is higher than the temperature of said rare earth ion exchanged, and the temperature of said ammonium ion exchange is 100-200 ℃; The temperature of said second roasting is higher than the temperature of said first roasting.
The present invention also provides the Y zeolite Cracking catalyst that contains rare earth by method for preparing.
According to said method provided by the invention; Carry out ammonium ion exchange earlier through making by the catalyst precarsor of processing without the NaY molecular sieve of ion-exchange; Carry out rare earth ion exchanged again; Suitably control simultaneously the temperature of first roasting and the temperature of second roasting; Can make have bigger total pore volume and specific area, the Y zeolite Cracking catalyst that contains rare earth of wear resistence preferably, thereby overcome total pore volume that catalyst that the preparation method according to existing Cracking catalyst makes exists and the defective that specific area is less, wear resistence is relatively poor.And the catalyst of method according to the present invention preparation is used for RFCC, has higher yield of gasoline and conversion ratio, and coking yield and heavy oil yield are lower.
In addition; What said method provided by the invention adopted is back exchange flow process, and therefore, method according to the present invention has not only overcome the excessive use of ammonium salt that exists in traditional flow process of exchange earlier and the defective of waste water resource; And; Compare with the filter process after the NaY molecular sieve being carried out ion-exchange, have higher operating efficiency to carry out ion-exchange filter process afterwards by the catalyst precarsor of processing without the NaY molecular sieve of ion-exchange, thereby improved the production efficiency of catalyst.
In addition; In said method provided by the invention; Use more a spot of ammonium salt and rare-earth salts to carry out ion-exchange; Can reach the sodium oxide content in the catalyst is reduced to lower level, make that the utilization rate of rare-earth salts and ammonium salt is higher, thereby reduced the pressure of production cost and follow-up waste disposal.
Description of drawings
Fig. 1 representes the graph of pore diameter distribution of the Y zeolite Cracking catalyst C1, DC1 and the DC3 that contain rare earth of embodiment 1, Comparative Examples 1 and Comparative Examples 3 preparations.
The specific embodiment
The preparation method who contains the Y zeolite Cracking catalyst of rare earth according to the present invention may further comprise the steps:
(1) will mix with matrix without the NaY molecular sieve of ion-exchange, making beating and spray drying forming, obtain catalyst precarsor;
(2) said catalyst precarsor is carried out first roasting at 200 ℃ under less than 400 ℃ temperature, and the product that obtains after said first roasting is carried out ammonium ion exchange; And
(3) product that obtains after the said ammonium ion exchange is carried out at least one time second roasting and at least rare earth ion exchanged, said rare earth ion exchanged is carried out after said second roasting;
The temperature of said ammonium ion exchange is higher than the temperature of said rare earth ion exchanged, and the temperature of said ammonium ion exchange is 100-200 ℃; The temperature of said second roasting is higher than the temperature of said first roasting.
According to said method provided by the invention, the purpose that said catalyst precarsor is carried out said first roasting is in order to strengthen the intensity of said catalyst precarsor, with the active component in the guard catalyst better.When the temperature of said first roasting is more than 400 ℃ the time, later stage catalyst exchange degree is reduced, the too high not only energy consumption of sintering temperature strengthens, and can make catalyst generation sintering, thereby causes active reduction of catalytic cracking reaction of catalyst; And when the temperature of said first roasting be below 200 ℃ the time, then can not reach the Expected Results of roasting.Yet the purpose of said second roasting is for the further activation of sodium that will not exchanged, and is come out by rare earth ion exchanged to impel sodium, improves the efficient of ion-exchange.Therefore, as long as the temperature that makes the temperature of said second roasting be higher than said first roasting can realize the object of the invention.
Under preferable case, the temperature of said second roasting is than the high 10-400 of temperature ℃ of said first roasting, more preferably 100-300 ℃.
According to said method provided by the invention; For the catalytic cracking reaction of the Y zeolite Cracking catalyst that contains rare earth that improves final preparation active; The temperature of said first roasting is preferably 250-390 ℃, more preferably 260-390 ℃, further is preferably 300-390 ℃.
According to said method provided by the invention, the time of said first roasting does not have special qualification, is preferably 0.1-2 hour, more preferably 0.5-1 hour.
According to said method provided by the invention, said ammonium ion exchange is carried out in 100-200 ℃ temperature range, and the temperature of said ammonium ion exchange is higher than the temperature of said rare earth ion exchanged.When the temperature of said ammonium ion exchange is lower than 100 ℃, relatively low according to the catalytic cracking reaction activity of the catalyst of this method preparation.
Under preferable case, the temperature of said ammonium ion exchange more preferably 30-170 ℃, further is preferably 50-150 ℃ than the high 20-180 of temperature ℃ of said rare earth ion exchanged.
According to said method provided by the invention, the temperature of said ammonium ion exchange is preferably 110-190 ℃, more preferably 120-180 ℃, further is preferably 140-180 ℃; The time of said ammonium ion exchange is preferably 0.1-1.5 hour, more preferably 0.5-1.5 hour.
According to said method provided by the invention, said ammonium ion exchange can be carried out under the pressure of 0.1-1.6MPa.Under the preferable case, said ammonium ion exchange is carried out under high pressure (as greater than 0.1MPa to 1.6MPa), for example can in autoclave, carry out, and the pressure in the said autoclave is preferably 0.15-1.25MPa, more preferably 0.35-1.2MPa.
According to said method provided by the invention, said ammonium ion exchange is to realize through product that obtains after first roasting and ammonium salt solution are mixed to contact.Through said ammonium ion exchange, the sodium in the said catalyst precarsor is substituted by ammonium ion, thereby can improve the acidity of catalyst, play the effect of stabilizing catalyst activity component structure simultaneously.In said ammonium ion exchange process, the usage ratio of the product that obtains after first roasting, ammonium salt and water does not have special qualification, can be at the catalyst in the ammonium ion exchange process of routine: ammonium salt: suitably select in the usage ratio of water.Under preferable case, the weight ratio of the product that obtains after first roasting, ammonium salt and water can be 100: 5-8: 100-2000 is preferably 100: 6-7: 200-1000.
According to said method provided by the invention, said ammonium salt does not have special qualification, can in the ammonium salt of routine, suitably select.Under preferable case, said ammonium salt is to be selected from ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium acetate, ammonium phosphate, ammonium dihydrogen phosphate (ADP) and the ammonium hydrogen phosphate one or more, more preferably one or more in ammonium sulfate, ammonium chloride and the ammonium nitrate.
According to said method provided by the invention, the temperature of said second roasting does not have special qualification, as long as make the temperature of said second roasting be higher than the temperature of said first roasting.Under preferable case, the temperature of said second roasting is 400-650 ℃, more preferably 450-650 ℃, further is preferably 500-650 ℃; The time of said second roasting is 0.1-5 hour, more preferably 0.5-4 hour, further is preferably 1-3 hour.
According to said method provided by the invention, said rare earth ion exchanged is to mix to contact with rare earths salt and realize through passing through the product that obtains after said second roasting.Through said rare earth ion exchanged, further exchange out the sodium in the product that obtains after said second roasting with rare earth ion, be reduced to lower level with the Na content in the Y zeolite Cracking catalyst that will finally prepare.In the present invention, condition, the product after second roasting and the mixed proportion of rare-earth salts that the Na content in the Y zeolite Cracking catalyst of final preparation can be through regulating said rare earth ion exchanged and the enforcement number of times of rare earth ion exchanged are realized.In the present invention, through said method can realize with in the said Y zeolite Cracking catalyst with Na
2The Na content of O meter is controlled to be below the 0.2 weight %, more preferably below the 0.1 weight %.
According to said method provided by the invention, the enforcement number of times of said rare earth ion exchanged is many more, and the Na content in the Y zeolite Cracking catalyst of final preparation is few more, yet the rare-earth salts that is consumed is many more.Therefore, take all factors into consideration the performance and the production cost of the Y zeolite Cracking catalyst of final preparation, the enforcement number of times of said rare earth ion exchanged is preferably 1-2.In the present invention; Because said rare earth ion exchanged is carried out after said second roasting; Also promptly whenever carry out once all carrying out said successively second roasting before the said rare earth ion exchanged; Therefore, be under the situation of 1-2 at the enforcement number of times of said rare earth ion exchanged, the enforcement number of times of said second roasting also is 1-2.
According to said method provided by the invention, said rare earth ion exchanged can be carried out according to the ionic liquid phase exchange process of routine.The temperature of said rare earth ion exchanged is preferably 5-100 ℃, and more preferably 30-90 ℃, further be preferably 40-90 ℃, further be preferably 50-90 ℃; The time of said rare earth ion exchanged can be 0.1-4 hour, is preferably 0.5-3 hour, more preferably 0.5-2 hour, further is preferably 0.5-1.5 hour.
According to said method provided by the invention; In said rare earth ion exchanged process; The usage ratio of the product that obtains after second roasting, rare-earth salts and water does not have special qualification, can be at the catalyst in the rare earth ion exchanged process of routine: rare-earth salts: suitably select in the usage ratio of water.Under preferable case, the weight ratio of the product that obtains after second roasting, rare-earth salts and water can be 100: 0.5-3.5: 100-2000 is preferably 100: 2-3: 200-1000.
According to said method provided by the invention, said rare-earth salts does not have special qualification, and the water-solubility rare-earth salt of various routines all can be used among the present invention and realizes said purpose of the present invention.Under preferable case, said rare-earth salts is one or more in rare earth chloride, carbonated rare earth and the nitric acid rare earth.Rare earth element in the said rare-earth salts can be for well known to a person skilled in the art various rare earth elements, for example can be for being selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium and the neptunium one or more.
According to said method provided by the invention, said NaY molecular sieve without ion-exchange can be commercially available or prepare through any existing method.Said NaY molecular sieve without ion-exchange is after crystallization is synthetic; Remove mother liquor, can directly be used to prepare catalyst, or after washing, mix making beating preparation catalyst again with matrix; Said washing is included under the normal temperature condition with molecular sieve weight 5-10 decationized Y sieve water or the washing of neutral deionized water doubly; Filter then, for example molecular sieve is mixed with water and kept filtration then 5-120 minute.The relative crystallinity of said NaY molecular sieve without ion-exchange is not less than 50%.
According to said method provided by the invention, said matrix can be the conventional various matrix of using in the preparation field of Cracking catalyst, for example can be in clay, aluminium oxide, alumina precursor, Ludox and the Alusil one or more.Said clay for example can be for kaolin, halloysite, imvite, diatomite, galapectite, saponite, tiredly take off in soil, sepiolite, attapulgite, hydrotalcite and the bentonite one or more, most preferably is kaolin.Said aluminium oxide for example can be in gama-alumina, η-aluminium oxide, θ-aluminium oxide and the χ-aluminium oxide one or more.Said alumina precursor for example can be for boehmite, have a diaspore structure hydrated alumina, have in gibbsite structure hydrated alumina, the hydrated alumina with bayerite structure and the aluminium colloidal sol one or more, most preferably is aluminium colloidal sol and/or boehmite.
According to said method provided by the invention; In the process of said NaY molecular sieve without ion-exchange being mixed making beating with matrix; Weight with respect to 100 weight portions in the said catalyst precarsor of butt; Said NaY molecular sieve without ion-exchange can be the 4-50 weight portion in the consumption of butt, is preferably the 5-45 weight portion; Said matrix can be the 50-96 weight portion in the consumption of butt, is preferably the 55-95 weight portion.In the present invention, the weight in butt is meant in the weight of roasting after 1 hour under about 800 ℃ condition.
According to said method provided by the invention, the method that will mix and pull an oar with matrix without the NaY molecular sieve of ion-exchange is compared with among the existing catalytic cracking catalyst preparation method molecular sieve and matrix being mixed with the method for making beating, does not have special requirement.For example, can be with kaolin or other clay and the making beating of aluminium colloidal sol, aluminium oxide and hydrochloric acid making beating mix making beating with two kinds of slurries mixing then again with without the NaY molecular sieve of ion-exchange or without the NaY molecular sieve pulp of ion-exchange, obtain the catalyst colloid.
According to said method provided by the invention, said spray-dired method does not have special requirement, can carry out according to the spray drying process that existing Cracking catalyst prepares in the process.
According to said method provided by the invention, in order to collect the Y zeolite Cracking catalyst, said method is filtered, is washed and drying after can also being included in each ion-exchange.Said washing can according in the production of existing NaY molecular sieve or the washing methods in the Catalyst Production carry out.Usually, said washing comprises the product that after ion-exchange, obtains is contacted with water or salt solution mix, preferably mixes contacting with water.Said water is preferably the water of decationized Y sieve or the water of exhaustion of yin ion.Said drying can be implemented according to the method for routine, for example can be spray-drying, roller drying, expansion drying or pneumatic conveying drying.
The present invention also provides the Y zeolite Cracking catalyst that contains rare earth by method for preparing.
Below will be described further the present invention, but protection scope of the present invention is not limited in this through embodiment.
Embodiment 1
Present embodiment is used to explain said Y zeolite Cracking catalyst that contains rare earth provided by the invention and preparation method thereof.
(1) preparation catalyst precarsor
3000g kaolin (in butt, available from Suzhou kaolin company), 300g aluminium colloidal sol (in aluminium oxide, available from catalyst Shandong branch company of China Petrochemical Industry) and 4500g decationized Y sieve water are mixed, and making beating obtains slurries M1; 1600g boehmite (in aluminium oxide, available from Shandong Aluminum Plant), 10000g decationized Y sieve water and 310ml hydrochloric acid (HCl content is 36 weight %) are mixed, and making beating obtains slurries M2; M1 and M2 are mixed, stir, under 60-70 ℃, left standstill aging 1 hour; Under agitation add the NaY molecular sieve (in butt, available from China Petrochemical Industry catalyst Shandong branch company) of 1550g, stir without ion-exchange; Carry out spray drying forming then, obtain catalyst precarsor.
(2) ion-exchange for the first time
With catalyst precarsor of preparation in (1) of 150g 350 ℃ of following roastings 1 hour; To pass through the catalyst precarsor of this roasting afterwards pulls an oar with the decationizing water of 1500mL; And to the aqueous solution that contains 9g ammonium sulfate that wherein adds 100mL, join then in the autoclave, reaction is 1 hour under 180 ℃, 1.1MPa; Filter then, wash and drying, obtain catalyst A 1.
(3) ion-exchange for the second time
With the catalyst A 1 of 150g 500 ℃ of following roastings 2 hours; To pass through the catalyst of this roasting afterwards pulls an oar with the decationizing water of 1500mL; And to the aqueous solution that contains 4.5g lanthanum chloride (available from Shanghai Supreme Being sun chemical industry Co., Ltd) that wherein adds 100mL; Reacted 1 hour down at 90 ℃, filter then, wash and drying, obtain catalyst B 1.
(4) ion-exchange for the third time
With the catalyst B 1 of 150g 500 ℃ of following roastings 0.5 hour; To pass through the catalyst of this roasting afterwards pulls an oar with the decationizing water of 15mL; And to the aqueous solution that contains 4.5g lanthanum chloride (available from Shanghai Supreme Being sun chemical industry Co., Ltd) that wherein adds 100mL; Reacted 1 hour down at 90 ℃, filter then, wash and drying, obtain containing the Y zeolite Cracking catalyst products C 1 of rare earth.
Comparative Examples 1
The Y zeolite Cracking catalyst that contains rare earth according to the method preparation of embodiment 1; Different is that in the ion-exchange first time of step (2), the temperature of ion-exchange is 90 ℃; Pressure is normal pressure, thereby makes the Y zeolite Cracking catalyst product DC1 that contains rare earth.
Comparative Examples 2
Method according to embodiment 1 prepares the Y zeolite Cracking catalyst that contains rare earth, and different is that in the ion-exchange first time of step (2), sintering temperature is 400 ℃, thereby makes the Y zeolite Cracking catalyst product DC2 that contains rare earth.
Comparative Examples 3
Method according to embodiment 1 prepares the Y zeolite Cracking catalyst that contains rare earth, and different is that in the ion-exchange first time of step (2), sintering temperature is 500 ℃, thereby makes the Y zeolite Cracking catalyst product DC3 that contains rare earth.
Embodiment 2
Present embodiment is used to explain said Y zeolite Cracking catalyst that contains rare earth provided by the invention and preparation method thereof.
(1) preparation catalyst precarsor
3000g kaolin (in butt, available from Suzhou kaolin company), 1500g decationized Y sieve water and 452ml hydrochloric acid (HCl content is 36 weight %) are mixed making beating; Add 2000g boehmite (in aluminium oxide, available from Shandong Aluminum Plant) then, stirred 1 hour; Under 60-70 ℃, left standstill aging 1 hour; Under agitation add the NaY molecular sieve (in butt, available from China Petrochemical Industry catalyst Shandong branch company) of 3550g, stir without ion-exchange; Carry out spray drying forming then, obtain catalyst precarsor.
(2) ion-exchange for the first time
With catalyst precarsor of preparation in (1) of 150g 390 ℃ of following roastings 0.5 hour; To pass through the catalyst precarsor of this roasting afterwards pulls an oar with the decationizing water of 1500mL; And to the aqueous solution that contains 10g ammonium nitrate that wherein adds 100mL, join then in the autoclave, reaction is 2 hours under 100 ℃, 0.35MPa; Filter then, wash and drying, obtain catalyst A 2.
(3) ion-exchange for the second time
With the catalyst A 2 of 150g 650 ℃ of following roastings 0.5 hour; To pass through the catalyst of this roasting afterwards pulls an oar with the decationizing water of 1500mL; And to the aqueous solution that contains 4g cerous nitrate (available from Zibo Rui Bokang rare earth material Co., Ltd) that wherein adds 100mL; Reacted 2 hours down at 60 ℃, filter then, wash and drying, obtain catalyst B 2.
(4) ion-exchange for the third time
With the catalyst B 2 of 150g 650 ℃ of following roastings 0.5 hour; To pass through the catalyst of this roasting afterwards pulls an oar with the decationizing water of 15mL; And to the aqueous solution that contains 4g cerous nitrate (available from Zibo Rui Bokang rare earth material Co., Ltd) that wherein adds 100mL; Reacted 2 hours down at 60 ℃, filter then, wash and drying, obtain containing the Y zeolite Cracking catalyst products C 2 of rare earth.
Embodiment 3
Present embodiment is used to explain said Y zeolite Cracking catalyst that contains rare earth provided by the invention and preparation method thereof.
(1) preparation catalyst precarsor
2200g kaolin (in butt, available from Suzhou kaolin company), 246g aluminium colloidal sol (in aluminium oxide, available from catalyst Shandong branch company of China Petrochemical Industry) and 3100g decationized Y sieve water are mixed, and making beating obtains slurries M3; 1210g boehmite (in aluminium oxide, available from Shandong Aluminum Plant), 6890g decationized Y sieve water and 238ml hydrochloric acid (HCl content is 36 weight %) are mixed, and making beating obtains slurries M4; M3 and M4 are mixed, stir, under 60-70 ℃, left standstill aging 1 hour, under agitation add the NaY molecular sieve (in butt) of 2398g, stir, carry out spray drying forming then, obtain catalyst precarsor without ion-exchange.
(2) ion-exchange for the first time
With catalyst precarsor of preparation in (1) of 150g 300 ℃ of following roastings 3 hours; To pass through the catalyst precarsor of this roasting afterwards pulls an oar with the decationizing water of 1500mL; And to the aqueous solution that contains 10.5g ammonium chloride that wherein adds 100mL, join then in the autoclave, reaction is 3 hours under 200 ℃, 1.6MPa; Filter then, wash and drying, obtain catalyst A 3.
(3) ion-exchange for the second time
With the catalyst A 3 of 150g 550 ℃ of following roastings 1 hour; To pass through the catalyst of this roasting afterwards pulls an oar with the decationizing water of 1500mL; And to the aqueous solution that contains 3g neodymium nitrate (available from Zibo Rui Bokang rare earth material Co., Ltd) that wherein adds 100mL; Reacted 3 hours down at 30 ℃, filter then, wash and drying, obtain catalyst B 3.
(4) ion-exchange for the third time
With the catalyst B 3 of 150g 550 ℃ of following roastings 1 hour; To pass through the catalyst of this roasting afterwards pulls an oar with the decationizing water of 15mL; And to the aqueous solution that contains 3g neodymium nitrate (available from Zibo Rui Bokang rare earth material Co., Ltd) that wherein adds 100mL; Reacted 3 hours down at 30 ℃, filter then, wash and drying, obtain containing the Y zeolite Cracking catalyst products C 3 of rare earth.
Test case 1
The Y zeolite Cracking catalyst C1-C3 that contains rare earth for preparing among embodiment 1-3 and the Comparative Examples 1-3 and the physico-chemical parameter of DC1-DC3 are detected:
(1) according to RIPP 117-90 standard method (see volumes such as " petrochemical industry analytical method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publishes) detect in the said Y zeolite Cracking catalyst that contains rare earth with Na
2The sodium content of O meter.
(2) according to RIPP 131-90 standard method (see volumes such as " petrochemical industry analytical method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publishes) detect in the said Y zeolite Cracking catalyst that contains rare earth with RE
2O
3The content of rare earth of meter.
(3) (see volumes such as " petrochemical industry analytical method " (RIPP test method) Yang Cuiding according to RIPP 146-90 standard method; Science Press; Nineteen ninety publishes) detect the said relative crystallinity (also being degree of crystallinity reservation degree) that contains the Y zeolite Cracking catalyst of rare earth, the degree of crystallinity of the degree of crystallinity/catalyst precarsor of the Y zeolite Cracking catalyst of relative crystallinity=contain rare earth.
(4) detect the said lattice constant that contains the Y zeolite Cracking catalyst of rare earth according to RIPP 145-90 standard method (seeing volumes such as " petrochemical industry analytical method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publication).
(5) adopt the U.S. Autosorb-1 of Kang Ta company nitrogen adsorption desorption appearance to detect the said specific area that contains the Y zeolite Cracking catalyst of rare earth according to the GB/T5816-1995 method, sample need outgas 6 hours down at 300 ℃ before test.
(6) detect the said total pore volume that contains the Y zeolite Cracking catalyst of rare earth according to RIPP151-90 standard method (see " petrochemical industry analytical method " (RIPP test method), Yang Cui delimits the organizational structure, Science Press, nineteen ninety publication).
(7) (see " petrochemical industry analytical method " (RIPP test method) according to RIPP 29-90 standard method; Yang Cui delimits the organizational structure; Science Press; Nineteen ninety publishes) the said abrasion index (be used for characterizing wear resistence, the more little then wear resistence of abrasion index is good more) that contains the Y zeolite Cracking catalyst of rare earth of detection.
The result of above-mentioned detection is as shown in table 1 below.
Table 1
Can find out that from table 1 sodium content that prepared according to the methods of the invention contains the Y zeolite Cracking catalyst of rare earth is below the 0.2 weight %, have bigger specific area and total pore volume and wear resistence preferably.
Test case 2
(see " petrochemical industry analytical method " (RIPP test method) according to the RIPP151-90 standard method; Yang Cui delimits the organizational structure; Science Press; The nineteen ninety publication) test contains the pore-size distribution of Y zeolite Cracking catalyst C1, DC1 and the DC3 of rare earth, and the pore-size distribution result adopts BJH (Barrett-Joyner-Halenda) model to be obtained by the desorption curve calculation, and measured graph of pore diameter distribution is as shown in Figure 1.
Can find out that by Fig. 1 the Y zeolite Cracking catalyst that prepared according to the methods of the invention contains rare earth has more macroporous structure.
Test case 3
With the Y zeolite Cracking catalyst C1-C3 that contains rare earth and the DC1-DC3 that prepare among embodiment 1-3 and the Comparative Examples 1-3 feedstock oil is carried out catalytic cracking reaction respectively, and detect the catalytic cracking reaction activity of each catalyst, its detection method is following:
The said Y zeolite Cracking catalyst that contains rare earth after under 800 ℃, 100% water vapor conditions aging 8 hours, is loaded in the riser reactor, and useful load is 9.0g.Then, it is 3 to be added in the said reactor with agent weight of oil ratio that force is mixed three heavy oil (performance parameter is as shown in table 2 below), and oil inlet quantity is 2.4g; Reacted 75 seconds down at 500 ℃; And according to the composition of the standard method of RIPP92-90 (see volumes such as " petrochemical industry analytical method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publishes) analytical reactions product; And calculate conversion ratio and micro-activity according to following formula, the result is as shown in table 3 below:
Conversion ratio (%)=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield
Table 3
Table 4
Can find out from the data of last table 3; In above-mentioned catalytic cracking reaction process; The Y zeolite Cracking catalyst that prepared according to the methods of the invention contains rare earth has higher catalytic cracking reaction activity, and is concrete, with respect to the Y zeolite Cracking catalyst DC1-DC3 that contains rare earth; The Y zeolite Cracking catalyst C1-C3 that contains rare earth of method according to the present invention preparation can obtain higher yield of gasoline and conversion ratio, and coking yield and heavy oil yield are lower.
The above specific embodiment only is used to describe preferred implementation of the present invention; But; The present invention is not limited to the detail in the above-mentioned embodiment; In technical conceive scope of the present invention, can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Claims (11)
1. preparation method who contains the Y zeolite Cracking catalyst of rare earth, this method may further comprise the steps:
(1) will mix with matrix without the NaY molecular sieve of ion-exchange, making beating and spray drying forming, obtain catalyst precarsor;
(2) said catalyst precarsor is carried out first roasting at 200 ℃ under less than 400 ℃ temperature, and the product that obtains after said first roasting is carried out ammonium ion exchange; And
(3) product that obtains after the said ammonium ion exchange is carried out at least one time second roasting and at least rare earth ion exchanged, said rare earth ion exchanged is carried out after said second roasting;
The temperature of said ammonium ion exchange is higher than the temperature of said rare earth ion exchanged, and the temperature of said ammonium ion exchange is 100-200 ℃; The temperature of said second roasting is higher than the temperature of said first roasting.
2. method according to claim 1, wherein, the temperature of said second roasting is than the high 10-400 of temperature ℃ of said first roasting.
3. method according to claim 2, wherein, the temperature of said second roasting is than the high 100-300 of temperature ℃ of said first roasting.
4. according to any described method among the claim 1-3, wherein, the temperature of first roasting is 250-390 ℃, and the temperature of second roasting is 400-650 ℃.
5. method according to claim 1, wherein, the temperature of said ammonium ion exchange is than the high 20-180 of temperature ℃ of said rare earth ion exchanged.
6. according to claim 1 or 5 described methods, wherein, the temperature of said ammonium ion exchange is 110-190 ℃, and pressure is 0.1-1.6MPa, and the time is 0.1-1.5 hour.
7. according to claim 1 or 5 described methods, wherein, the temperature of said rare earth ion exchanged is 5-100 ℃, and the time is 0.1-4 hour.
8. method according to claim 1, wherein, in said ammonium ion exchange process, the weight ratio of the product that obtains after first roasting, ammonium salt and water is 100: 5-8: 100-2000.
9. method according to claim 1, wherein, in said rare earth ion exchanged process, the weight ratio of the product that obtains after second roasting, rare-earth salts and water is 100: 0.5-3.5: 100-2000.
10. method according to claim 1; Wherein, in step (1), with respect to the said catalyst precarsor of 100 weight portions; Said NaY molecular sieve without ion-exchange is the 4-50 weight portion in the consumption of butt, and said matrix is the 50-96 weight portion in the consumption of butt.
11. the Y zeolite Cracking catalyst that contains rare earth by any described method preparation among the claim 1-10.
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