CN102806097B - Rare-earth-containing Y type molecular sieve cracking catalyst and method for preparing same - Google Patents
Rare-earth-containing Y type molecular sieve cracking catalyst and method for preparing same Download PDFInfo
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Abstract
The invention discloses a method for preparing a rare-earth-containing Y type molecular sieve cracking catalyst, comprising the following steps: (1) mixing a NaY molecular sieve which is not subjected to ion exchange with a matrix, pulping, and molding by spraying and drying to obtain a catalyst precursor; (2) calcinating the catalyst precursor for the first time at the temperature which is more than or equal to 200 DEG C and less than 400 DEG C, and subjecting the product obtained by calcinating to ammonium ion exchange; and (3) calcinating the product obtained by subjecting the product obtained by calcinating to ammonium ion exchange for at least one time, and then subjecting the product to rare earth ion exchange for at least one time, wherein the temperature for calcinating for the second time is higher than that for calcinating for the first time. The invention also discloses the rare-earth-containing Y type molecular sieve cracking catalyst prepared by adopting the method. The rare-earth-containing Y type molecular sieve cracking catalyst prepared by adopting the method has the characteristics of a large total pore volume, a large specific surface area and better abrasion resistance.
Description
Technical field
The present invention relates to a kind of preparation method of the Y zeolite Cracking catalyst containing rare earth, and the Y zeolite Cracking catalyst containing rare earth prepared by the method.
Background technology
Along with feedstock oil becomes heavy day by day, the continuous reinforcement of people's environmental consciousness, result in and not only require that catalytic cracking catalyst has good reaction selectivity, activity and stability, and also requires more and more harsher for the preparation flow of catalyst.
In the production of catalytic cracking catalyst, the preparation flow of traditional Cracking catalyst containing zeolite roughly can be divided into two classes: a class, for first to exchange flow process, removes spray drying forming (with or without roasting) by the first ion-exchange of zeolite or the modified matrix that adds again; Another kind of is rear exchange flow process, goes to carry out ion-exchange or modification after being about to add the first spray drying forming of matrix without the zeolite exchanged again.
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 " technique first exchanged in flow process, concrete, the 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) hydrothermally stable process is carried out to (1) step gains, (3) appropriate silicon-containing compound is added to the water, the silicone content of gained liquid is made to be 0.02-0.5 % by weight, (2) step gains are added with the liquid-solid ratio of 10-15: 1 (weight ratio), mix, under the condition that room temperature-100 DEG C also stirs, the inorganic acid that concentration is 0.01-3N is dripped with the speed of 1-5 ml/min, 2.8-3.3 is constant is as the criterion to make the pH value of mixed liquor remain on for the addition of acid, under the condition that above-mentioned acid adding process also also can stir at 50-100 DEG C, dripping concentration is the organic acid of 0.5-4N, 4-4.5 is constant is as the criterion to make the pH value of mixed liquor remain on for organic acid addition, after stopping acid adding, continue reaction 1-3 hour, filter, washing, (4) (3) step gains are carried out hydrothermal treatment consists.
Although zeolite prepared by the method for above-mentioned patent application has good structural stability and activity stability, the Cracking catalyst being active component with this zeolite has active high, selective good and feature that activity stability is good, but, because the position in catalyst particularly in active component residing for sodium is different, sterically hindered difference, sodium content in molecular sieve and catalyst is met the demands, just must with excessive ammonium salt, this just inevitably causes the pollution of environment; And, zeolite needs to add matrix spraying dry and makes catalyst after modification well, now also need to carry out exchanging the sodium content reduced in matrix with excessive ammonium salt, also need a large amount of decationizing water to wash in each process exchanged, this just wastes a large amount of water resources simultaneously.
CN101670295A discloses a kind of production of cracking catalyst, what adopted is rear exchange flow process, the method comprise Y zeolite mixed with matrix, pull an oar, spray-dired step, wherein, described Y zeolite is NaY molecular sieve, also comprises the catalyst powder obtained by spraying dry and contacts the step of carrying out ion-exchange, reclaiming catalyst with exchange ion; Described ion-exchange can be contacted with the solution containing exchange ion by catalyst powder, and described exchange ion is one or more in ammonium ion, rare earth ion and transition metal ions.
Although the method for above-mentioned patent application overcomes traditional defect first exchanging the excessive use of ammonium salt and the waste water resource existed in flow process, but, according to the defect that Cracking catalyst exists total pore volume and specific area is less, wear resistence is poor prepared by the method for above-mentioned patent application.
Summary of the invention
The object of the invention is the above-mentioned defect existed in the preparation method in order to overcome existing Y zeolite catalyst, a kind of preparation method of the Y zeolite Cracking catalyst containing rare earth is provided.
The invention provides a kind of preparation method of the Y zeolite Cracking catalyst containing rare earth, the method comprises: the NaY molecular sieve without ion-exchange mixes with matrix by (1), pull an oar and spray drying forming, obtains catalyst precarsor; (2) described catalyst precarsor is carried out the first roasting under 200 DEG C to the temperature being less than 400 DEG C, and the product obtained after described first roasting is carried out ammonium ion exchange; And the product obtained after described ammonium ion exchange is carried out the second roasting and at least one times rare earth ion exchanged at least one times by (3), described rare earth ion exchanged is carried out after described second roasting, and the temperature of described second roasting is higher than the temperature of described first roasting.
Present invention also offers the Y zeolite Cracking catalyst containing rare earth prepared by said method.
According to described method provided by the invention, first ammonium ion exchange is carried out by making the catalyst precarsor be made up of the NaY molecular sieve without ion-exchange, carry out rare earth ion exchanged again, suitably control the temperature of the first roasting and the temperature of the second roasting simultaneously, the Y zeolite Cracking catalyst containing rare earth with larger total pore volume and specific area, preferably wear resistence can be obtained, thus overcome the total pore volume that the catalyst that obtains according to the preparation method of existing Cracking catalyst exists and the defect that specific area is less, wear resistence is poor.And catalyst prepared by method according to the present invention, for RFCC, has higher yield of gasoline and conversion ratio, and coking yield and heavy oil yield lower.
In addition, what described method provided by the invention adopted is rear exchange flow process, therefore, method according to the present invention not only overcomes traditional defect first exchanging the excessive use of ammonium salt and the waste water resource existed in flow process, and, with carry out NaY molecular sieve compared with the filter process after ion-exchange, to the catalyst precarsor be made up of the NaY molecular sieve without the ion-exchange filter process carried out after ion-exchange, there is higher operating efficiency, thus improve the production efficiency of catalyst.
In addition, in described method provided by the invention, the ammonium salt of small amount and rare-earth salts is used to carry out ion-exchange, can reach and the sodium oxide content in catalyst is reduced to lower level, make the utilization rate of rare-earth salts and ammonium salt higher, thus reduce the pressure of production cost and follow-up refuse process.
Accompanying drawing explanation
Fig. 1 represent prepared by embodiment 1 and comparative example 2 containing the Y zeolite Cracking catalyst C1 of rare earth and the graph of pore diameter distribution of DC2.
Detailed description of the invention
The preparation method of the Y zeolite Cracking catalyst containing rare earth according to the present invention comprises the following steps:
(1) NaY molecular sieve without ion-exchange mixed with matrix, pull an oar and spray drying forming, obtain catalyst precarsor;
(2) described catalyst precarsor is carried out the first roasting under 200 DEG C to the temperature being less than 400 DEG C, and the product obtained after described first roasting is carried out ammonium ion exchange; And
(3) product obtained after described ammonium ion exchange is carried out the second roasting and at least one times rare earth ion exchanged at least one times, described rare earth ion exchanged is carried out after described second roasting, and the temperature of described second roasting is higher than the temperature of described first roasting.
According to described method provided by the invention, the object of carrying out described first roasting to described catalyst precarsor is the intensity in order to strengthen described catalyst precarsor, with the active component in guard catalyst better.When the temperature of described first roasting is more than 400 DEG C, later stage catalyst can be made to exchange degree and reduce, the too high not only energy consumption of sintering temperature strengthens, and catalyst can be made to sinter, thus causes the catalytic cracking reaction activity of catalyst to reduce; And when the temperature of described first roasting is below 200 DEG C, then can not reach the Expected Results of roasting.But the object of described second roasting is to be activated further by the sodium be not swapped out, to impel sodium by rare earth ion exchanged out, improve the efficiency of ion-exchange.Therefore, as long as make the temperature of described second roasting can realize object of the present invention higher than the temperature of described first roasting.
In the preferred case, the temperature of described second roasting, than the temperature height 10-400 DEG C of described first roasting, is more preferably 100-300 DEG C.
According to described method provided by the invention, in order to the catalytic cracking reaction of the Y zeolite Cracking catalyst containing rare earth improving final preparation is active, the temperature of described first roasting is preferably 250-390 DEG C, is more preferably 260-390 DEG C, more preferably 300-390 DEG C.
According to described method provided by the invention, the time of described first roasting, there is no particular limitation, is preferably 0.1-2 hour, is more preferably 0.5-1 hour.
According to described method provided by the invention, described ammonium ion exchange can be carried out according to the liquid-phase ion exchange of routine.There is no particular limitation for the condition of described ammonium ion exchange, and conventional ammonium ion exchange condition is all applicable to the present invention.In the preferred case, the temperature of described ammonium ion exchange can be 5-100 DEG C, is preferably 30-90 DEG C, is more preferably 40-90 DEG C, more preferably 50-90 DEG C; The time of described ammonium ion exchange can be 0.1-4 hour, is preferably 0.5-3 hour, is more preferably 0.5-2 hour, more preferably 0.5-1.5 hour.
According to described method provided by the invention, described ammonium ion exchange is by the product obtained after the first roasting and ammonium salt solution being carried out mixing to contact realizing.By described ammonium ion exchange, the sodium in described catalyst precarsor is substituted by ammonium ion, thus the acidity of catalyst can be improved, play the effect of stabilizing catalyst activity component structure simultaneously.In described ammonium ion exchange process, there is no particular limitation for the usage ratio of the product obtained after the first roasting, ammonium salt and water, can catalyst in the ammonium ion exchange process of routine: ammonium salt: suitably select in the usage ratio of water.In the preferred case, the weight ratio of the product obtained after the first roasting, ammonium salt and water can be 100: 5-8: 100-2000, is preferably 100: 6-7: 200-1000.
According to described method provided by the invention, there is no particular limitation for described ammonium salt, suitably can select in the ammonium salt of routine.In the preferred case, described ammonium salt be selected from ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium acetate, ammonium phosphate, ammonium dihydrogen phosphate (ADP) and ammonium hydrogen phosphate one or more, be more preferably in ammonium sulfate, ammonium chloride and ammonium nitrate one or more.
According to described method provided by the invention, there is no particular limitation for the temperature of described second roasting, as long as make the temperature of described second roasting higher than the temperature of described first roasting.In the preferred case, the temperature of described second roasting is 400-650 DEG C, is more preferably 450-650 DEG C, more preferably 500-650 DEG C; The time of described second roasting is 0.1-5 hour, is more preferably 0.5-4 hour, more preferably 1-3 hour.
According to described method provided by the invention, described rare earth ion exchanged is by the product obtained after described second roasting and rare earths salt being carried out mixing to contact realizing.By described rare earth ion exchanged, the sodium in the product obtained after being swapped out described second roasting further with rare earth ion, to be reduced to lower level by the Na content in the Y zeolite finally prepared Cracking catalyst.In the present invention, the Na content in the Y zeolite Cracking catalyst of final preparation can be realized by the product after regulating the condition of described rare earth ion exchanged, the second roasting and the mixed proportion of rare-earth salts and the enforcement number of times of rare earth ion exchanged.In the present invention, by described method can realize by described Y zeolite Cracking catalyst with Na
2the Na content of O meter controls to be less than 0.2 % by weight, is more preferably less than 0.1 % by weight.
According to described method provided by the invention, the enforcement number of times of described rare earth ion exchanged is more, and the Na content in the Y zeolite Cracking catalyst of final preparation is fewer, but the rare-earth salts consumed is more.Therefore, consider performance and the production cost of the Y zeolite Cracking catalyst of final preparation, the enforcement number of times of described rare earth ion exchanged is preferably 2-3.In the present invention, because described rare earth ion exchanged is carried out after described second roasting, also described second roasting successively is all carried out before namely often carrying out once described rare earth ion exchanged, therefore, when the enforcement number of times of described rare earth ion exchanged is 2-3, the enforcement number of times of described second roasting is also 2-3.
According to described method provided by the invention, described rare earth ion exchanged can be carried out according to the liquid-phase ion exchange of routine.There is no particular limitation for the condition of described rare earth ion exchanged, and the condition of conventional rare earth ion exchanged is all applicable to the present invention.In the preferred case, the temperature of described rare earth ion exchanged can be 5-100 DEG C, is preferably 30-90 DEG C, is more preferably 40-90 DEG C, more preferably 50-90 DEG C; The time of described rare earth ion exchanged can be 0.1-4 hour, is preferably 0.5-3 hour, is more preferably 0.5-2 hour, more preferably 0.5-1.5 hour.In the present invention, the condition of described ammonium ion exchange and described rare earth ion exchanged can be the same or different.
According to described method provided by the invention, in described rare earth ion exchanged process, there is no particular limitation for the usage ratio of the product obtained after the second roasting, rare-earth salts and water, can catalyst in the rare earth ion exchanged process of routine: rare-earth salts: suitably select in the usage ratio of water.In the preferred case, the weight ratio of the product obtained after the 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 described method provided by the invention, there is no particular limitation for described rare-earth salts, and the water-solubility rare-earth salt of various routine all to can be used in the present invention and realizes described object of the present invention.In the preferred case, described rare-earth salts is one or more in rare earth chloride, carbonated rare earth and nitric acid rare earth.The various rare earth elements that rare earth element in described rare-earth salts can be known to the skilled person, such as can for being selected from one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium and neptunium.
According to described method provided by the invention, the described NaY molecular sieve without ion-exchange can be commercially available or be prepared by any existing method.The described NaY molecular sieve without ion-exchange is after crystallization synthesis, remove mother liquor, Kaolinite Preparation of Catalyst can be directly used in, or mix with matrix Kaolinite Preparation of Catalyst of pulling an oar again after washing, described washing uses the decationized Y sieve water of molecular sieve 5-10 times or neutral deionised water under being included in normal temperature condition, then filter, such as, molecular sieve mixed with water and keep 5-120 minute, then filtering.The relative crystallinity of the described NaY molecular sieve without ion-exchange is not less than 50%.
According to described method provided by the invention, described matrix can be the conventional various matrix used in the preparation field of Cracking catalyst, such as, can be one or more in clay, aluminium oxide, alumina precursor, Ludox and Alusil.Described clay can be such as one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, tired de-soil, sepiolite, attapulgite, hydrotalcite and bentonite, most preferably is kaolin.Described aluminas is as being one or more in gama-alumina, η-aluminium oxide, θ-aluminium oxide and χ-aluminium oxide.Described alumina precursor such as can for boehmite, there is a diaspore structure hydrated alumina, have in gibbsite structure hydrated alumina, the hydrated alumina with boehmite structure and Alumina gel one or more, most preferably be Alumina gel and/or boehmite.
According to described method provided by the invention, the described NaY molecular sieve without ion-exchange is being mixed in the process of pulling an oar with matrix, relative to 100 weight portions in the weight of the described catalyst precarsor of butt, the described NaY molecular sieve without ion-exchange can be 4-50 weight portion in the consumption of butt, is preferably 5-45 weight portion; Described matrix can be 50-96 weight portion in the consumption of butt, is preferably 55-95 weight portion.In the present invention, the weight of roasting after 1 hour under the condition of about 800 DEG C is referred in the weight of butt.
According to described method provided by the invention, the method NaY molecular sieve without ion-exchange being mixed with matrix and pull an oar, compares with the method for pulling an oar with being mixed with matrix by molecular sieve in existing catalytic cracking catalyst preparation method, does not have special requirement.Such as, kaolin or other clay and Alumina gel can be pulled an oar, aluminium oxide and hydrochloric acid are pulled an oar, and then two kinds of slurries mixing are mixed with the NaY molecular sieve without ion-exchange or the NaY molecular sieve slurries without ion-exchange again and pull an oar, obtain catalyst colloid.
According to described method provided by the invention, the not special requirement of described spray-dired method, can carry out according to the spray drying process in existing Cracking catalyst preparation process.
According to described method provided by the invention, in order to collect Y zeolite Cracking catalyst, described method carries out after can also being included in each ion-exchange filtering, washing and drying.Washing methods during described washing can be produced according to existing NaY molecular sieve or in Catalyst Production carries out.Usually, described washing comprises the product obtained after ion-exchange to mix with water or salting liquid and contacts, and preferably mixes with water and contacts.Described water is preferably the water of decationized Y sieve or the water of exhaustion of yin ion.Described drying can be implemented according to the method for routine, such as, can be spraying dry, roller drying, expansion drying or pneumatic conveying drying.
Present invention also offers the Y zeolite Cracking catalyst containing rare earth prepared by said method.
Below will the invention will be further described by embodiment, but protection scope of the present invention is not limited in this.
Embodiment 1
The present embodiment is for illustration of described Y zeolite Cracking catalyst containing rare earth provided by the invention and preparation method thereof.
(1) Kaolinite Preparation of Catalyst precursor
3000g kaolin (in butt, purchased from Kaolin of Suzhou company), 300g Alumina gel (in aluminium oxide, purchased from catalyst asphalt in Shenli Refinery of China Petrochemical Industry) and 4500g decationized Y sieve water are mixed, making beating obtains slurries M1; 1600g boehmite (in aluminium oxide, purchased from Shandong Aluminum Plant), 10000g decationized Y sieve water and 310ml hydrochloric acid (HCl content is 36 % by weight) are mixed, making beating obtains slurries M2; M1 and M2 is mixed, stir, aging 1 hour is left standstill at 60-70 DEG C, under agitation add the NaY molecular sieve of 1550g without ion-exchange (in butt, purchased from catalyst asphalt in Shenli Refinery of China Petrochemical Industry), stir, then carry out spray drying forming, obtain catalyst precarsor.
(2) first time ion-exchange
By the roasting 1 hour at 350 DEG C of the catalyst precarsor of preparation in (1) of 150g, afterwards the decationizing water of the catalyst precarsor 1500mL through this roasting is pulled an oar, and add the aqueous solution containing 9g ammonium sulfate of 100mL wherein, react 1 hour at 90 DEG C, then carry out filtering, washing and drying, obtain catalyst A 1.
(3) second time ion-exchange
By the roasting 2 hours at 500 DEG C of the catalyst A 1 of 150g, afterwards the decationizing water of the catalyst 1500mL through this roasting is pulled an oar, and add the aqueous solution containing 4.5g lanthanum chloride (purchased from Shanghai Di Yang Chemical Co., Ltd.) of 100mL wherein, react 1 hour at 90 DEG C, then carry out filtering, washing and drying, obtain catalyst B 1.
(4) third time ion-exchange
By the roasting 2 hours at 500 DEG C of the catalyst B 1 of 150g, afterwards the decationizing water of the catalyst 15mL through this roasting is pulled an oar, and add the aqueous solution containing 4.5g lanthanum chloride (purchased from Shanghai Di Yang Chemical Co., Ltd.) of 100mL wherein, react 1 hour at 90 DEG C, then carry out filtering, washing and drying, obtain the Y zeolite Cracking catalyst products C 1 containing rare earth.
Comparative example 1
Contain the Y zeolite Cracking catalyst of rare earth according to the method preparation of embodiment 1, difference is, in the first time ion-exchange of step (2), sintering temperature is 400 DEG C, thus the obtained Y zeolite Cracking catalyst product DC1 containing rare earth.
Comparative example 2
Contain the Y zeolite Cracking catalyst of rare earth according to the method preparation of embodiment 1, difference is, in the first time ion-exchange of step (2), sintering temperature is 500 DEG C, thus the obtained Y zeolite Cracking catalyst product DC2 containing rare earth.
Embodiment 2
The present embodiment is for illustration of described Y zeolite Cracking catalyst containing rare earth provided by the invention and preparation method thereof.
(1) Kaolinite Preparation of Catalyst precursor
By 3000g kaolin (in butt, purchased from Kaolin of Suzhou company), 1500g decationized Y sieve water and 452ml hydrochloric acid (HCl content is 36 % by weight) mixing, making beating, then 2000g boehmite is added (in aluminium oxide, purchased from Shandong Aluminum Plant), stir 1 hour, aging 1 hour is left standstill at 60-70 DEG C, under agitation add the NaY molecular sieve of 3550g without ion-exchange (in butt, purchased from catalyst asphalt in Shenli Refinery of China Petrochemical Industry), stir, then carry out spray drying forming, obtain catalyst precarsor.
(2) first time ion-exchange
By the roasting 0.5 hour at 390 DEG C of the catalyst precarsor of preparation in (1) of 150g, afterwards the decationizing water of the catalyst precarsor 1500mL through this roasting is pulled an oar, and add the aqueous solution containing 10g ammonium nitrate of 100mL wherein, react 2 hours at 60 DEG C, then carry out filtering, washing and drying, obtain catalyst A 2.
(3) second time ion-exchange
By the roasting 0.5 hour at 650 DEG C of the catalyst A 2 of 150g, afterwards the decationizing water of the catalyst 1500mL through this roasting is pulled an oar, and add the aqueous solution containing 4g cerous nitrate (purchased from Zibo Rui Bokang rare earth material Co., Ltd) of 100mL wherein, react 2 hours at 60 DEG C, then carry out filtering, washing and drying, obtain catalyst B 2.
(4) third time ion-exchange
By the roasting 0.5 hour at 650 DEG C of the catalyst B 2 of 150g, afterwards the decationizing water of the catalyst 15mL through this roasting is pulled an oar, and add the aqueous solution containing 4g cerous nitrate (purchased from Zibo Rui Bokang rare earth material Co., Ltd) of 100mL wherein, react 2 hours at 60 DEG C, then carry out filtering, washing and drying, obtain the Y zeolite Cracking catalyst products C 2 containing rare earth.
Embodiment 3
The present embodiment is for illustration of described Y zeolite Cracking catalyst containing rare earth provided by the invention and preparation method thereof.
(1) Kaolinite Preparation of Catalyst precursor
2200g kaolin (in butt, purchased from Kaolin of Suzhou company), 246g Alumina gel (in aluminium oxide, purchased from catalyst asphalt in Shenli Refinery of China Petrochemical Industry) and 3100g decationized Y sieve water are mixed, making beating obtains slurries M3; 1210g boehmite (in aluminium oxide, purchased from Shandong Aluminum Plant), 6890g decationized Y sieve water and 238ml hydrochloric acid (HCl content is 36 % by weight) are mixed, making beating obtains slurries M4; M3 and M4 is mixed, stirs, at 60-70 DEG C, leave standstill aging 1 hour, under agitation add the NaY molecular sieve (in butt) of 2398g without ion-exchange, stir, then carry out spray drying forming, obtain catalyst precarsor.
(2) first time ion-exchange
By the roasting 3 hours at 300 DEG C of the catalyst precarsor of preparation in (1) of 150g, afterwards the decationizing water of the catalyst precarsor 1500mL through this roasting is pulled an oar, and add the aqueous solution containing 10.5g ammonium chloride of 100mL wherein, react 3 hours at 30 DEG C, then carry out filtering, washing and drying, obtain catalyst A 3.
(3) second time ion-exchange
By the roasting 1 hour at 550 DEG C of the catalyst A 3 of 150g, afterwards the decationizing water of the catalyst 1500mL through this roasting is pulled an oar, and add the aqueous solution containing 3g neodymium nitrate (purchased from Zibo Rui Bokang rare earth material Co., Ltd) of 100mL wherein, react 3 hours at 30 DEG C, then carry out filtering, washing and drying, obtain catalyst B 3.
(4) third time ion-exchange
By the roasting 1 hour at 550 DEG C of the catalyst B 3 of 150g, afterwards the decationizing water of the catalyst 15mL through this roasting is pulled an oar, and add the aqueous solution containing 3g neodymium nitrate (purchased from Zibo Rui Bokang rare earth material Co., Ltd) of 100mL wherein, react 3 hours at 30 DEG C, then carry out filtering, washing and drying, obtain the Y zeolite Cracking catalyst products C 3 containing rare earth.
Test case 1
To detecting containing the Y zeolite Cracking catalyst C1-C3 of rare earth and the physico-chemical parameter of DC1-DC2 of preparing in embodiment 1-3 and comparative example 1-2:
(1) according to RIPP 117-90 standard method (see volumes such as " Petrochemical Engineering Analysis method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publishes) detect described containing in the Y zeolite Cracking catalyst of rare earth with Na
2the sodium content of O meter.
(2) according to RIPP 131-90 standard method (see volumes such as " Petrochemical Engineering Analysis method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publishes) detect described containing in the Y zeolite Cracking catalyst of rare earth with RE
2o
3the content of rare earth of meter.
(3) according to RIPP 146-90 standard method (see volumes such as " Petrochemical Engineering Analysis method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publishes) detect the relative crystallinity (also i.e. degree of crystallinity reservation degree) of the described Y zeolite Cracking catalyst containing rare earth, relative crystallinity=containing the degree of crystallinity of the degree of crystallinity/catalyst precarsor of the Y zeolite Cracking catalyst of rare earth.
(4) according to RIPP 145-90 standard method (see volumes such as " Petrochemical Engineering Analysis method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publishes) detect the described lattice constant containing the Y zeolite Cracking catalyst of rare earth.
(5) adopt U.S. Kang Ta company Autosorb-1 nitrogen adsorption desorption instrument to detect the specific area of the described Y zeolite Cracking catalyst containing rare earth according to GB/T5816-1995 method, sample to need at 300 DEG C degassed 6 hours before testing.
(6) according to RIPP151-90 standard method (see " Petrochemical Engineering Analysis method " (RIPP test method), Yang Cui delimits the organizational structure, Science Press, nineteen ninety publishes) detect the described total pore volume containing the Y zeolite Cracking catalyst of rare earth.
(7) according to RIPP 29-90 standard method (see " Petrochemical Engineering Analysis method " (RIPP test method), Yang Cui delimits the organizational structure, Science Press, nineteen ninety publishes) detect the described abrasion index (be used for characterizing wear resistence, the less then wear resistence of abrasion index is better) containing the Y zeolite Cracking catalyst of rare earth.
The result of above-mentioned detection is as shown in table 1 below.
Table 1
As can be seen from Table 1, prepared according to the methods of the invention is less than 0.2 % by weight containing the sodium content of Y zeolite Cracking catalyst of rare earth, has larger specific area and total pore volume and wear resistence preferably.
Test case 2
According to RIPP151-90 standard method (see " Petrochemical Engineering Analysis method " (RIPP test method), Yang Cui delimits the organizational structure, Science Press, nineteen ninety publishes) test containing the Y zeolite Cracking catalyst C1 of rare earth and the pore-size distribution of DC2, pore-size distribution result adopts BJH (Barrett-Joyner-Halenda) model to be calculated by desorption curve, and measured graph of pore diameter distribution as shown in Figure 1.
As seen from Figure 1, prepared according to the methods of the invention has more macroporous structure containing the Y zeolite Cracking catalyst of rare earth.
Test case 3
Carry out catalytic cracking reaction with the Y zeolite Cracking catalyst C1-C3 containing rare earth prepared in embodiment 1-3 and comparative example 1-2 and DC1-DC2 to feedstock oil respectively, and the catalytic cracking reaction detecting each catalyst is active, its detection method is as follows:
By the described Y zeolite Cracking catalyst containing rare earth 800 DEG C, under 100% water vapor conditions after aging 8 hours, be loaded in riser reactor, useful load is 9.0g.Then, be 3 be added in described reactor by mixed for force three heavy oil (performance parameter is as shown in table 2 below) with agent weight of oil ratio, oil inlet quantity is 2.4g, react 75 seconds at 500 DEG C, and according to the composition of the standard method of RIPP 92-90 (see volumes such as " Petrochemical Engineering Analysis method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publishes) analytical reactions product, and go out conversion ratio and micro-activity according to following formulae discovery, result is as shown in table 3 below:
Conversion ratio (%)=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield
Table 2
Table 3
As can be seen from the data of upper table 3, in above-mentioned catalytic cracking reaction process, prepared according to the methods of the invention has higher catalytic cracking reaction activity containing the Y zeolite Cracking catalyst of rare earth, concrete, relative to the Y zeolite Cracking catalyst DC1-DC2 containing rare earth, prepared by method according to the present invention can obtain higher yield of gasoline and conversion ratio containing the Y zeolite Cracking catalyst C1-C3 of rare earth, and coking yield and heavy oil yield lower.
Above detailed description of the invention is only for describing the preferred embodiment of the present invention; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive 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 (9)
1., containing a preparation method for the Y zeolite Cracking catalyst of rare earth, the method comprises the following steps:
(1) NaY molecular sieve without ion-exchange mixed with matrix, pull an oar and spray drying forming, obtain catalyst precarsor;
(2) described catalyst precarsor is carried out the first roasting at the temperature of 200 DEG C to 390 DEG C, and the product obtained after described first roasting is carried out ammonium ion exchange; And
(3) product obtained after described ammonium ion exchange is carried out the second roasting and at least one times rare earth ion exchanged at least one times, described rare earth ion exchanged is carried out after described second roasting, the temperature of described second roasting is higher than the temperature of described first roasting, and the temperature of described second roasting is than the temperature height 100-400 DEG C of described first roasting.
2. method according to claim 1, wherein, the temperature of described second roasting is than the temperature height 100-300 DEG C of described first roasting.
3. method according to claim 1 and 2, wherein, the temperature of described first roasting is 250-390 DEG C, and the temperature of described second roasting is 400-650 DEG C.
4. method according to claim 1, wherein, the temperature of described ammonium ion exchange is 5-100 DEG C, and the time is 0.1-4 hour.
5. the method according to claim 1 or 4, wherein, in described ammonium ion exchange process, the weight ratio of the product obtained after the first roasting, ammonium salt and water is 100:5-8:100-2000.
6. method according to claim 1, wherein, the temperature of described rare earth ion exchanged is 5-100 DEG C, and the time is 0.1-4 hour.
7. the method according to claim 1 or 6, wherein, in described rare earth ion exchanged process, the weight ratio of the product obtained after the second roasting, rare-earth salts and water is 100:0.5-3.5:100-2000.
8. method according to claim 1, wherein, in step (1), relative to the described catalyst precarsor of 100 weight portions, the described NaY molecular sieve without ion-exchange in the consumption of butt for 4-50 weight portion, described matrix in the consumption of butt for 50-96 weight portion.
9. the Y zeolite Cracking catalyst containing rare earth prepared by the method in claim 1-8 described in any one.
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