CN102166533A - Composite modified molecular sieve improving activity and hydrothermal stability and preparation method thereof - Google Patents
Composite modified molecular sieve improving activity and hydrothermal stability and preparation method thereof Download PDFInfo
- Publication number
- CN102166533A CN102166533A CN 201010114244 CN201010114244A CN102166533A CN 102166533 A CN102166533 A CN 102166533A CN 201010114244 CN201010114244 CN 201010114244 CN 201010114244 A CN201010114244 A CN 201010114244A CN 102166533 A CN102166533 A CN 102166533A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- preparation
- modified molecular
- phosphorus
- gram
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a composite modified molecular sieve improving activity and hydrothermal stability and a preparation method thereof. The preparation method is characterized by comprising the following steps of: adding the molecular sieve into phosphorus aqueous solution, reacting the molecular sieve for some time at a certain pH value and temperature and under a certain pressure, and filtering, drying and roasting the reaction product to obtain a phosphorus modified molecular sieve; and adding the phosphorus modified molecular sieve into the aqueous solution which contains rear-earth ions, reacting the molecular sieve for some time at a certain pH value and temperature and under a certain pressure, and filtering, washing, drying and roasting the reaction product to obtain the composite modified molecular sieve. The modified molecular sieve has a dry basis content of 88 to 99 weight percent, a silica alumina ratio of 15 to 250, 0.01 to 10 weight percent of phosphorus and 0.01 to 10 weight percent of rear earth. A model catalyst prepared through the composite modified molecular sieve has higher hydrothermal stability and micro activity than a model catalyst which contains an unmodified molecular sieve and a molecular sieve which is modified by other methods.
Description
Technical field
The invention belongs to molecular sieve modified technical field, particularly a kind of composite modified molecular sieve and preparation method who has improved active and hydrothermal stability.
Background technology
In recent years, the researcher of oil refining catalyst and manufacturer are devoted for years to the research that improves the FCC catalyst performance in the molecular sieve that adopts all kinds structure both at home and abroad, improve the productivity of low carbon olefin hydrocarbon of FCC apparatus.This is that steam cracking is to be undertaken by radical reaction owing to tradition system ethene and propylene main method, temperature height, to the ingredient requirement harshness.Yet the preparing low-carbon olefin by catalytically cracking cost is lower, is the focus of studying increased low carbon olefine output at present both at home and abroad.The function shape-selective molecular sieve is subjected to extensive concern as the main active component of such catalytic converting catalyst.
Since 1972, U.S. Mobil company has developed the ZSM-5 zeolite molecular sieve, and (USP 3,702,886) after, because it has higher silica alumina ratio, unique pore passage structure and excellent heat and hydrothermal stability, the ZSM-5 zeolite molecular sieve has obtained using extremely widely in petrochemical process such as the shape slective cracking (CN 1872415A) of hydro carbons, alkylation, isomerization, disproportionation, catalytic dewaxing, etherificate.Especially in conventional catalytic cracking catalyst or auxiliary agent, add productive rate and the octane number (USP5,997,728) that the ZSM-5 zeolite can increase substantially low-carbon alkene.
Yet the ZSM-5 zeolite molecular sieve is easy inactivation under the catalytic cracking hydrothermal condition, influences its stability and selectivity.So people have carried out a large amount of research to the modification of ZSM-5 zeolite molecular sieve.
USP 4,399, in 059 with diammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP) and NH
4After-ZSM-5 mixing and the oven dry, make phosphorous modified ZSM-5 through 500 ℃ of roastings.When being used for xylene isomerization reaction, this zeolite can significantly improve its contraposition product selectivity.
USP 5,171, disclose in 921 a kind ofly to flood modified zsm-5 zeolite with phosphorus compound, can be used as after the modification alkene or aliphatic hydrocarbon are converted into C
2～C
5The catalytic active component of alkene.
USP 3,972, and 382 and after USP 3,965,208 discloses HZSM-5 and adopt the Trimethyl phosphite modification, reaction selectivity improves.
CN85102828 reported and adopted dipping steam seasoning modified zsm-5 zeolite, and alkylation is produced p-methyl-ethylbenzene shape selective catalysis activity and improved greatly to vinyltoluene after the phosphorus modification.
CN97120271 has reported a kind of phosphorous faujasite hydrocarbon cracking catalyzer, described phosphorous faujasite be with faujasite and phosphorus-containing compound aqueous solution evenly after, drying prepares more than 0.5 hour in 450～600 ℃ of roastings, and catalytic activity is preferably arranged.
CN98117286 has reported aluminosilicate zeolite that a kind of 90-99.9 of containing is heavy and with P
2O
5Meter, the P-contained zeolite of the phosphorus of 0.1～10 heavy %, this zeolite have higher hydrocarbon activity of conversion, to the performance of heavy metals such as diesel oil selectivity and anti-preferably vanadium, nickel.
The molecular sieve that CN 1072201A, CN 1085825A, CN 1093101A, CN 1098130A and CN 91109945 disclose the phosphorus modification can improve the octane number of gasoline and the productive rate of alkene.
CN 1042201C and CN 1055301C report that also phosphorus modified molecular sieves can voluminous C
3 =～C
5 =, and make the productive rate of gasoline and octane number maintain higher level.
CN 1211469A and CN 1211470A have reported the combination of molecular sieve of a kind of producing more propylene and ethene, by the penta-basic cyclic molecular sieve of 85～95 heavy %, in the phosphorus of oxide 2～10 heavy %, in the alkaline-earth metal of oxide 0.3～5 heavy %, formed in the transition metal of oxide 0.3～5 heavy %.
CN 1072031C and CN 1072032C have also reported the penta-basic cyclic molecular sieve composite of a kind of producing more propylene and ethene (particularly ethene), by the penta-basic cyclic molecular sieve of 88～95 heavy %, in the phosphorus of oxide 2～8 heavy %, in the alkaline-earth metal of oxide 0.3～3 heavy %, formed in the transition metal of oxide 0～3 heavy %.This preparation method of composition is a step infusion process, and technology is simpler, good stability, and ethylene yield is significantly improved.
At present, the productive rate of the low-carbon alkene of the catalytic cracking catalyst of commercial Application, especially propylene is on the low side, can't satisfy the actual needs of oil refining and Chemical Manufacture, and the productive rate that therefore increases substantially propylene is significant.Modification to function shape slective cracking molecular sieve is the valid approach of catalytic cracking increased low carbon olefine output.
By the phosphorus modification to ZSM-5 Zeolite molecular sieve catalysis performance discover that the introducing of phosphorus has suppressed the dealuminization of ZSM-5 zeolitic frameworks under hydrothermal condition, significantly improved the acid reservation degree on the zeolite, thereby improved its catalytic activity and selectivity; In addition, realize the surface acidity of modulation zeolite simultaneously, need to introduce second kind of transition metal ions and carry out modification it for the hydrothermal stability that further significantly improves molecular sieve.
CN1796498A has reported a kind of auxiliary agent of propylene enhancing, wherein ZSM-5 is by phosphorus and is selected from Fe, one of Co or Ni's is metal-modified, this auxiliary agent is applied in the catalytic cracking process of petroleum hydrocarbon, when increasing liquefied gas yield and improving octane number, can improve the density of propylene in the liquefied gas greatly.
CN1651141A discloses a kind of aromatized catalyst, catalyst is by 50～90 weight % molecular sieves, 0～32 weight % carrier and 4～20 weight % binding agents are formed, wherein the used modifying element of ZSM-5 is zinc, phosphorus and rare earth metal, and this catalyst can be used for modifying inferior patrol production high octane gasoline component or aromatic hydrocarbons.
CN1915515A discloses the catalyst of a kind of olefin catalytic cracking to produce propylene, ethene, and employing 30～90% silica alumina ratios are 20～800 ZSM-5 molecular sieve, 0.01～6% rare earth oxide and 0.01～6% phosphorous oxides modifier.
After introducing rare-earth oxide in the ZSM-5 molecular sieve, rare-earth oxide has the effect of water-gas catalytic conversion to coking, can improve the anti-coking performance of catalyst.Rare-earth oxide and phosphorus have the stability action to framework of molecular sieve aluminium, can delay the speed that the aluminium atom comes off from framework of molecular sieve under water vapor acting, acidity-the chain carrier that has kept molecular sieve has for a long time improved the hydrothermal stability of molecular sieve.Rare-earth oxide can also act synergistically with phosphorous oxides, reduces the acidity of molecular sieve, reduces the generation of hydrogen transfer reaction, helps the raising of olefins yield.
Yet at present conventional phosphorus modified molecular sieves is when introducing second modified component by ion-exchange, and the P elements in the molecular sieve can run off in large quantities and can not realize the purpose of double elements modified molecular screen, thereby influences the stability and the catalytic activity of molecular sieve.Equally, when adopting conventional dipping or exchange process to prepare rare earth modified molecular sieve, rare earth only is adsorbed on the molecular sieve surface, easily runs off in last handling process, pollutes other components in the catalyst.
Summary of the invention
The objective of the invention is to provides the composite modified molecular sieve and the preparation method of a kind of high activity and hydrothermal stability at existing molecular screen material and technology.
A kind of preparation method who has improved the composite modified molecular sieve of active and hydrothermal stability, molecular sieve is joined the phosphorous aqueous solution, then after filtration, drying and roasting, it is characterized in that this method is that molecular sieve is joined in the phosphorous aqueous solution, control water and molecular sieve weight ratio are (2～5): 1, be 1～10 in the pH value (preferably 2～7), reaction temperature 70～200 ℃ (preferably 90～160 ℃) and 0.2～1.2MPa (preferably reacted 10～200 minutes under 0.2～0.8MPa) the reaction pressure condition, then after filtration, drying and roasting, obtain phosphorus modified molecular sieves, sintering temperature is 200～800 ℃, and the time is 0.5～10 hour; Phosphorus modified molecular sieves joined contain in the rare earth ion aqueous solution, control water and molecular sieve weight ratio are (2～10): 1, reaction temperature 0～100 ℃ of (preferably 60～90 ℃), reaction pressure are to react under 0.1～1MPa condition 30～300 minutes, washing then after filtration,, drying and roasting, sintering temperature is 400～800 ℃, time is 1～4 hour, obtains composite modified molecular sieve.
The present invention also provides a kind of composite modified molecular sieve that uses this preparation method to obtain, and it is characterized in that modified molecular screen to contain silica alumina ratio be the phosphorus of 15～250 molecular sieve 88～99 heavy %, 0.01～10 heavy % and rare earth in 0.01～10 heavy % of oxide.
In method provided by the present invention, filtration in the modifying process, drying and roasting all are to adopt normally used technical process and technical parameter in the prior art, the present invention is not limited especially, the baking temperature of recommending is 100～120 ℃, sintering temperature is 300～800 ℃, and roasting time is 0.5～10 hour.
The present invention is different from the modified condition of conventional phosphorus modifying method requirement, it is for high temperature and simultaneously with certain pressure, can further strengthen the diffusion of modified component in molecular sieve pore passage by high temperature and the synergy that has pressure, making modified component enter B acid position surperficial with it in the darker molecular sieve pore passage reacts, just high temperature or low temperature have pressure and all can not reach gratifying effect, and its prerequisite still need be with water as medium certainly.
The present invention need not limit the composition of molecular sieve kind in this method and composition thereof, phosphorus, decides as required.Described molecular sieve is one or more in ZSM type, β type, the MCM type molecular sieve preferably, preferred ZSM type and beta molecular sieve, and its silica alumina ratio is preferably 15～60.Use the modified molecular screen that method of modifying of the present invention obtains, generally containing contents on dry basis 88～99 heavy %, silica alumina ratio is 15～250 molecular sieve, the phosphorus of 0.01～10 heavy % and the rare earth of 0.01～10 heavy %, and this composite modified molecular sieve has good hydrothermal stability and activity.
In the method provided by the present invention the phosphorous aqueous solution is not limited especially, the used phosphorous aqueous solution of phosphorus modified molecular sieves all can usually.As being phosphoric acid solution, phosphorous acid solution, soluble phosphoric acid, the phosphite aqueous solution, organic phosphorus compound or the like, can be wherein one or more, soluble phosphoric acid, the phosphite aqueous solution can be the aqueous solution of phosphate such as ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphite.
The said rare earth ion aqueous solution that contains of the present invention can be RE phosphate, chlorate, nitrate, and rare earth can be one or more in lanthanum, cerium, praseodymium, the neodymium.
The present invention is different from the modified condition that conventional rare earth modified method requires, it is for high temperature and simultaneously with certain pressure, can further strengthen the diffusion of modified component in molecular sieve pore passage by high temperature and the synergy that has pressure, just high temperature or low temperature have pressure and all can not reach gratifying effect.The present invention also requires to carry out earlier the phosphorus modification, carries out rare earth modified then.
Advantage of the present invention is to be that this method can prevent a large amount of losses of phosphorus and rare earth modified molecular sieve phosphorus and rare earth component when carrying out post processing, and prepared composite modified molecular sieve and model catalyst thereof has fabulous hydrothermal stability and catalytic activity simultaneously.
The specific embodiment
The assay method of various embodiments of the present invention and Comparative Examples is:
1. elementary analysis adopts x ray fluorescence spectrometry (XRF) to measure, and used instrument is Japanese ZSXprimus type Xray fluorescence spectrometer of science.
2. estimation of stability changes by the relative crystallinity (ZSM-5%) before and after 800 ℃ * 4 hours and 800 ℃ * 17 hours hydrothermal agings and judges, degree of crystallinity is measured on the D/max-3C X-ray diffractometer of Japanese Rigaku company.
3. measure on the little anti-evaluation device of activity rating by the production of Beijing Hua Yang company, feedstock oil adopts the huge port light diesel fuel, assessing terms: catalyst was handled 4 hours, 17 hours under 800 ℃, 100% water vapour condition, catalyst loading amount 5 grams, 460 ℃ of reaction temperatures, in 70 seconds reaction time, oil ratio is 3.2.
Embodiment 1
Get 23.3 gram (NH
4)
2HPO
4Be dissolved in the 1000 gram distilled water, under the stirring condition ZSM-5 sieve sample 270 grams added in the solution, the pH value is adjusted to 4.In reaction temperature is 100 ℃, and reaction pressure is that the 0.2MPa stirring reaction filtered after 60 minutes, oven dry, and 500 ℃ of following roastings 4 hours, the gained sieve sample was designated as PZ-1 then.
Getting 100 gram PZ-1 molecular sieves and join and contain in the 26.6 gram lanthanum chloride solutions, is that 20 ℃, reaction pressure are that stirring reaction filtered after 250 minutes under the 1.0MPa in reaction temperature, dries, and 300 ℃ of following roastings 2 hours, obtains composite modified molecular sieve PZRE-1 then.Then kaolin (45%), aluminium colloidal sol (15%) and PZRE-1 (40%) are added making beating, 120 ℃ of dryings in the distilled water in above ratio, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as C-1, gets 20～40 order beaded catalysts and carries out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Embodiment 2
Get 46.6 gram (NH
4)
2HPO
4Be dissolved in the 1000 gram distilled water, under the stirring condition ZSM-5 sieve sample 270 grams added in the solution, the pH value is adjusted to 3.In reaction temperature is 120 ℃, and reaction pressure is that the 0.4MPa stirring reaction filtered after 120 minutes, oven dry, and 550 ℃ of following roastings 5 hours, the gained sieve sample was designated as PZ-2 then.
Getting 100 gram PZ-2 molecular sieves and join and contain in the 26.6 gram cerous nitrate aqueous solution, is that 40 ℃, reaction pressure are that stirring reaction filtered after 200 minutes under the 0.8MPa in reaction temperature, dries, and 400 ℃ of following roastings 2 hours, obtains composite modified molecular sieve PZRE-2 then.Then kaolin (45%), aluminium colloidal sol (15%) and PZRE-2 (40%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as C-2.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Embodiment 3
Get 69.7 gram (NH
4)
2HPO
4Be dissolved in the 1000 gram distilled water, under the stirring condition ZSM-5 sieve sample 270 grams added in the solution, the pH value is adjusted to 2.In reaction temperature is 140 ℃, and reaction pressure is that the 0.6MPa stirring reaction filtered after 200 minutes, oven dry, and 450 ℃ of following roastings 6 hours, the gained sieve sample was designated as PZ-3 then.
Getting 100 gram PZ-3 molecular sieves and join and contain in the 26.6 gram praseodymium nitrate aqueous solution, is that 60 ℃, reaction pressure are that stirring reaction filtered after 150 minutes under the 0.6MPa in reaction temperature, dries, and 500 ℃ of following roastings 2 hours, obtains composite modified molecular sieve PZRE-3 then.Then kaolin (45%), aluminium colloidal sol (15%) and PZRE-3 (40%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as C-3.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Embodiment 4
Get 139.4 gram (NH
4)
2HPO
4Be dissolved in the 1000 gram distilled water, under the stirring condition ZSM-5 sieve sample 270 grams added in the solution, the pH value is adjusted to 3.In reaction temperature is 160 ℃, and reaction pressure is that the 0.8MPa stirring reaction filtered after 200 minutes, oven dry, and 550 ℃ of following roastings 4 hours, the gained sieve sample was designated as PZ-4 then.
Getting 100 gram PZ-4 molecular sieves and join and contain in the 26.6 gram neodymium chloride aqueous solution, is that 80 ℃, reaction pressure are that stirring reaction filtered after 100 minutes under the 0.4MPa in reaction temperature, dries, and 500 ℃ of following roastings 2 hours, obtains composite modified molecular sieve PZRE-4 then.Then kaolin (45%), aluminium colloidal sol (15%) and PZRE-4 (40%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as C-4.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Embodiment 5
Get 232.4 gram NH
4H
2PO
4Be dissolved in the 1000 gram distilled water, under the stirring condition ZSM-5 sieve sample 270 grams added in the solution, the pH value is adjusted to 2.In reaction temperature is 180 ℃, and reaction pressure is that the 0.6MPa stirring reaction filtered after 60 minutes, oven dry, and 600 ℃ of following roastings 2 hours, the gained sieve sample was designated as PZ-5 then.
Getting 100 gram PZ-5 molecular sieves joins and contains in 5 gram praseodymium nitrates, 5 gram neodymium chlorides, 10 gram cerous nitrates and the 6.6 gram lanthanum chloride solutions, in reaction temperature is that 100 ℃, reaction pressure are that stirring reaction filtered after 100 minutes under the 0.2MPa, oven dry, 500 ℃ of following roastings 2 hours, obtain composite modified molecular sieve PZRE-5 then.Then kaolin (45%), aluminium colloidal sol (15%) and PZRE-5 (40%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as C-5.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Embodiment 6
Get 139.4 gram NH
4H
2PO
4Mixture be dissolved in the 1000 gram distilled water, under the stirring condition ZSM-5 sieve sample 270 gram is added in the solution, the pH value is adjusted to 2.In reaction temperature is 100 ℃, and reaction pressure is that the 0.4MPa stirring reaction filtered after 200 minutes, oven dry, and 600 ℃ of following roastings 6 hours, the gained sieve sample was designated as PZ-6 then.
Getting 100 gram PZ-6 molecular sieves and join and contain in the 13.3 gram cerous nitrate aqueous solution, is that 100 ℃, reaction pressure are that stirring reaction filtered after 100 minutes under the 0.2MPa in reaction temperature, dries, and 500 ℃ of following roastings 2 hours, obtains composite modified molecular sieve PZRE-6 then.Then kaolin (45%), aluminium colloidal sol (15%) and PZRE-6 (40%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as C-6.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Embodiment 7
Get 60 gram (NH
4)
2HPO
4With 79.4 gram NH
4H
2PO
4Mixture be dissolved in the 1000 gram distilled water, under the stirring condition ZSM-5 sieve sample 270 gram is added in the solution, the pH value is adjusted to 4.In reaction temperature is 140 ℃, and reaction pressure is that the 0.6MPa stirring reaction filtered after 200 minutes, oven dry, and 550 ℃ of following roastings 5.5 hours, the gained sieve sample was designated as PZ-7 then.
Getting 100 gram PZ-7 molecular sieves joins and contains in 19.9 gram cerous nitrates and the 20 gram lanthanum chloride solutions, in reaction temperature is that 100 ℃, reaction pressure are that stirring reaction filtered after 100 minutes under the 0.4MPa, oven dry 500 ℃ of following roastings 2 hours, obtains composite modified molecular sieve PZRE-7 then.Then kaolin (45%), aluminium colloidal sol (15%) and PZRE-7 (40%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as C-7.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Embodiment 8
Get 70 gram (NH
4)
2HPO
4With 69.4 gram NH
4H
2PO
4Mixture be dissolved in the 1000 gram distilled water, under the stirring condition ZSM-5 sieve sample 270 gram is added in the solution, the pH value is adjusted to 6.In reaction temperature is 160 ℃, and reaction pressure is that the 0.8MPa stirring reaction filtered after 200 minutes, oven dry, and 500 ℃ of following roastings 5 hours, the gained sieve sample was designated as PZ-8 then.
Getting 100 gram PZ-8 molecular sieves joins and contains in the 16.6 gram cerous nitrates and the 10 gram praseodymium nitrate aqueous solution, in reaction temperature is that 100 ℃, reaction pressure are that dipping filtered after 100 minutes under the 0.6MPa, oven dry 500 ℃ of following roastings 2 hours, obtains composite modified molecular sieve PZRE-8 then.Then kaolin (45%), aluminium colloidal sol (15%) and PZRE-8 (40%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as C-8.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Embodiment 9
Get 80 gram (NH
4)
2HPO
4With 59.4 gram NH
4H
2PO
4Mixture be dissolved in the 1000 gram distilled water, under the stirring condition HY sieve sample 270 gram is added in the solution, the pH value is adjusted to 5.In reaction temperature is 180 ℃, and reaction pressure is that the 0.6MPa stirring reaction filtered after 200 minutes, oven dry, and 450 ℃ of following roastings 4 hours, the gained sieve sample was designated as PY-9 then.
Getting 100 gram PY-9 molecular sieves joins and contains in the 3.3 gram praseodymium nitrates and the 10 gram neodymium phosphate aqueous solution, in reaction temperature is that 80 ℃, reaction pressure are that dipping filtered after 100 minutes under the 0.6MPa, oven dry 500 ℃ of following roastings 2 hours, obtains composite modified molecular sieve PYRE-9 then.Then kaolin (48%), aluminium colloidal sol (15%) and PYRE-9 (37%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as C-9.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Embodiment 10
Get 90 gram (NH
4)
2HPO
4With 49.4 gram NH
4H
2PO
4Mixture be dissolved in the 1000 gram distilled water, under the stirring condition MCM-41 sieve sample 270 gram is added in the solution, the pH value is adjusted to 3.In reaction temperature is 160 ℃, and reaction pressure is that the 0.6MPa stirring reaction filtered after 200 minutes, oven dry, and 400 ℃ of following roastings 3 hours, the gained sieve sample was designated as PM-10 then.
Getting 100 gram PM-10 molecular sieves joins and contains in the 19.9 gram cerous nitrates and the 20 gram neodymium phosphate aqueous solution, in reaction temperature is that 60 ℃, reaction pressure are that dipping filtered after 100 minutes under the 0.6MPa, oven dry 500 ℃ of following roastings 2 hours, obtains composite modified molecular sieve PMRE-10 then.Then kaolin (42%), aluminium colloidal sol (15%) and PMRE-10 (43%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as C-10.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Embodiment 11
Get 139.4 gram (NH
4)
2HPO
4Be dissolved in the 1000 gram distilled water, under the stirring condition beta-molecular sieve sample 270 grams added in the solution, the pH value is adjusted to 3.In reaction temperature is 180 ℃, and reaction pressure is that the 0.6MPa stirring reaction filtered after 200 minutes, oven dry, and 400 ℃ of following roastings 3 hours, the gained sieve sample was designated as P β-11 then.
Getting 100 gram P β-11 molecular sieves joins and contains in 5 gram praseodymium nitrates, 5 gram neodymium phosphates, 10 gram cerous nitrates and the 6.6 gram lanthanum chloride solutions, in reaction temperature is that 60 ℃, reaction pressure are that stirring reaction filtered after 100 minutes under the 0.6MPa, oven dry, 500 ℃ of following roastings 2 hours, obtain composite modified molecular sieve P β RE-11 then.Then kaolin (40%), aluminium colloidal sol (20%) and P β RE-11 (40%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as C-11.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Comparative Examples 1
Getting 100 gram PZ-4 molecular sieves and join and contain in the 26.6 gram neodymium chloride aqueous solution, is that stirring reaction filtered after 100 minutes under 80 ℃, normal pressure in reaction temperature, dries, and 500 ℃ of following roastings 2 hours, obtains composite modified molecular sieve PZRED-1 then.Then kaolin (45%), aluminium colloidal sol (15%) and PZRED-1 (40%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as CD-1.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Comparative Examples 2
Get 139.4 gram (NH
4)
2HPO
4Be dissolved in the 1000 gram distilled water, under the stirring condition ZSM-5 sieve sample 270 grams added in the solution, the pH value is adjusted to 3.In reaction temperature is 160 ℃, and stirring reaction filtered after 200 minutes under the normal pressure, oven dry, and 550 ℃ of following roastings 4 hours, the gained sieve sample was designated as PZD-2 then.
Getting 100 gram PZD-2 molecular sieves joins and contains in the 26.6 gram neodymium chloride aqueous solution, in reaction temperature is that 80 ℃, reaction pressure are that stirring reaction filtered after 100 minutes under the 0.4MPa, oven dry 500 ℃ of following roastings 2 hours, obtains composite modified molecular sieve PZRED-2 then.Then kaolin (45%), aluminium colloidal sol (15%) and PZRED-2 (40%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as CD-2.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Comparative Examples 3
Get 139.4 gram (NH
4)
2HPO
4Be dissolved in the 1000 gram distilled water, under the stirring condition ZSM-5 sieve sample 270 grams added in the solution, the pH value is adjusted to 3.In reaction temperature is 160 ℃, and stirring reaction filtered after 200 minutes under the normal pressure, oven dry, and 550 ℃ of following roastings 4 hours, the gained sieve sample was designated as PZD-3 then.
Getting 100 gram PZD-3 molecular sieves and join and contain in the 26.6 gram neodymium chloride aqueous solution, is 80 ℃ in reaction temperature, and stirring reaction filtered after 100 minutes under the normal pressure, dried, and 500 ℃ of following roastings 2 hours, obtained composite modified molecular sieve PZRED-3 then.Then kaolin (45%), aluminium colloidal sol (15%) and PZRED-3 (40%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as CD-3.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
Comparative Examples 4
Getting 1000 gram ZSM-5 molecular sieves and join and contain in the 266 gram neodymium chloride aqueous solution, is that 80 ℃, reaction pressure are that stirring reaction filtered after 100 minutes under the 0.4MPa in reaction temperature, dries, and 500 ℃ of following roastings 2 hours, obtains rare earth modified molecular sieve ZRED-4 then.
Get 139.4 gram (NH
4)
2HPO
4Be dissolved in the 1000 gram distilled water, under the stirring condition ZRED-4 sieve sample 270 grams added in the solution, the pH value is adjusted to 3.In reaction temperature is 160 ℃, and reaction pressure is that the 0.8MPa stirring reaction filtered after 200 minutes, oven dry, and 550 ℃ of following roastings 4 hours, the gained sieve sample was designated as PZRED-4 then.Then kaolin (45%), aluminium colloidal sol (15%) and PZRED-4 (40%) are added making beating, 120 ℃ of dryings in the distilled water by fixed proportion, 450 ℃ of roastings after 1 hour fragmentation sieve, the gained catalyst sample is designated as CD-4.Get 20～40 order beaded catalysts and carry out little investigation of living.The degree of crystallinity and the model catalyst micro-activity of the composition of sample, aging front and back see Table 1～3.
The hydrothermal stability of table 1 phosphorus modified molecular sieves
*Relative crystallinity * 100% before relative crystallinity/hydrothermal treatment consists after degree of crystallinity retention rate=hydrothermal treatment consists
The hydrothermal stability of table 2 double elements modified molecular screen
*Relative crystallinity * 100% before relative crystallinity/hydrothermal treatment consists after degree of crystallinity retention rate=hydrothermal treatment consists
The little active energy of table 3 modified molecular screen model catalyst
From table 1 and table 2 data as can be seen, the molecular sieve that adopts the method for modifying of embodiment 1～11 to carry out modification, its P elements does not run off substantially, and uses the method for modifying of Comparative Examples 1～3, and P elements runs off serious.By after 17 hours hydrothermal treatment consists, the molecular sieve that adopts the method for modifying of embodiment 1～11 to carry out modification all has higher relative crystallinity and crystallization reservation degree than the molecular sieve of other method modification.From table 3 data also as can be seen, adopt the molecular sieve model catalyst of the method modification of embodiment 1～11 all higher little active energy to be arranged than the molecular sieve catalyst of other method modification.
Claims (12)
1. one kind has been improved the preparation method of activity with the composite modified molecular sieve of hydrothermal stability, molecular sieve is joined the phosphorous aqueous solution, drying and roasting then after filtration,, it is characterized in that this method is that molecular sieve is joined in the phosphorous aqueous solution, control water and molecular sieve weight ratio are (2～5): 1, be 1～10 in the pH value, 70～200 ℃ of reaction temperatures and 0.2～1.2MPa, reacted under the reaction pressure condition 10～200 minutes, drying and roasting then after filtration,, obtain phosphorus modified molecular sieves, sintering temperature is 200～800 ℃, and the time is 0.5～10 hour.Phosphorus modified molecular sieves joined contain in the rare earth ion aqueous solution, control water and molecular sieve weight ratio are (2～10): 1,20～100 ℃ of reaction temperatures, reaction pressure are to react under 0.1～1.0MPa condition 30～300 minutes, washing then after filtration,, drying and roasting, sintering temperature is 400～800 ℃, time is 1～4 hour, obtains composite modified molecular sieve.
2. preparation method according to claim 1 is characterized in that molecular sieve is one or more in ZSM type, β type, Y type, the MCM type molecular sieve.
3. preparation method according to claim 1 is characterized in that the phosphorous aqueous solution is phosphoric acid solution, phosphorous acid or/and soluble phosphate, the phosphite aqueous solution.
4. preparation method according to claim 4 is characterized in that soluble phosphate is selected from one or more in ammonium phosphate, diammonium hydrogen phosphate, the ammonium dihydrogen phosphate (ADP).
5. preparation method according to claim 1, the pH value when it is characterized in that phosphorus modified molecular sieves is 2～7.
6. preparation method according to claim 1, the reaction temperature when it is characterized in that phosphorus modified molecular sieves are 90～160 ℃.
7. preparation method according to claim 1, the reaction pressure when it is characterized in that phosphorus modified molecular sieves are 0.2～0.8MPa.
8. preparation method according to claim 1, the sintering temperature when it is characterized in that phosphorus modified molecular sieves is 300～800 ℃.
9. preparation method according to claim 1, it is characterized in that containing the rare earth ion aqueous solution is RE phosphate, chlorate, nitrate.
10. preparation method according to claim 1 is characterized in that rare earth is one or more in lanthanum, cerium, praseodymium, the neodymium.
11. preparation method according to claim 1, the reaction temperature when it is characterized in that rare earth modified molecular sieve is 60～90 ℃.
12. a composite modified molecular sieve that makes according to the described preparation method of claim 1 is characterized in that modified molecular screen to contain silica alumina ratio is the phosphorus of 15～250 molecular sieve 88～99 heavy %, 0.01～10 heavy % and rare earth in 0.01～10 heavy % of oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010114244 CN102166533B (en) | 2010-02-25 | 2010-02-25 | Composite modified molecular sieve improving activity and hydrothermal stability and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010114244 CN102166533B (en) | 2010-02-25 | 2010-02-25 | Composite modified molecular sieve improving activity and hydrothermal stability and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102166533A true CN102166533A (en) | 2011-08-31 |
| CN102166533B CN102166533B (en) | 2013-07-31 |
Family
ID=44487963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010114244 Active CN102166533B (en) | 2010-02-25 | 2010-02-25 | Composite modified molecular sieve improving activity and hydrothermal stability and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102166533B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140269A (en) * | 2015-04-16 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of modified MFI structure zeolite and preparation method thereof |
| CN110605141A (en) * | 2018-06-15 | 2019-12-24 | 定州市荣鼎水环境生化技术有限公司 | Phosphorus-doped Cu-SSZ-13 catalyst and preparation method and application thereof |
| CN115624986A (en) * | 2020-06-24 | 2023-01-20 | 中国石油化工股份有限公司 | Phosphorus and metal-containing core-shell type molecular sieve and synthesis method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5171921A (en) * | 1991-04-26 | 1992-12-15 | Arco Chemical Technology, L.P. | Production of olefins |
| CN1211470A (en) * | 1997-09-17 | 1999-03-24 | 中国石油化工总公司 | Pentabasic cyclic molecular sieve composite for high output of ethylene and propylene |
| CN1915515A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalyst for producing propylene, ethane through catalytic cracking olefin |
| CN101537365A (en) * | 2008-03-19 | 2009-09-23 | 中国石油天然气股份有限公司 | Modified method for improving hydrothermal stability of molecular sieve in FCC catalyst with high efficiency |
-
2010
- 2010-02-25 CN CN 201010114244 patent/CN102166533B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5171921A (en) * | 1991-04-26 | 1992-12-15 | Arco Chemical Technology, L.P. | Production of olefins |
| CN1211470A (en) * | 1997-09-17 | 1999-03-24 | 中国石油化工总公司 | Pentabasic cyclic molecular sieve composite for high output of ethylene and propylene |
| CN1915515A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalyst for producing propylene, ethane through catalytic cracking olefin |
| CN101537365A (en) * | 2008-03-19 | 2009-09-23 | 中国石油天然气股份有限公司 | Modified method for improving hydrothermal stability of molecular sieve in FCC catalyst with high efficiency |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140269A (en) * | 2015-04-16 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of modified MFI structure zeolite and preparation method thereof |
| CN106140269B (en) * | 2015-04-16 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of modified MFI structure zeolite and preparation method thereof |
| CN110605141A (en) * | 2018-06-15 | 2019-12-24 | 定州市荣鼎水环境生化技术有限公司 | Phosphorus-doped Cu-SSZ-13 catalyst and preparation method and application thereof |
| CN115624986A (en) * | 2020-06-24 | 2023-01-20 | 中国石油化工股份有限公司 | Phosphorus and metal-containing core-shell type molecular sieve and synthesis method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102166533B (en) | 2013-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101537365B (en) | Modified method for improving hydrothermal stability of molecular sieve in FCC catalyst with high efficiency | |
| CN103447063B (en) | Heavy oil Efficient Conversion catalytic cracking catalyst and preparation method thereof | |
| EP2860157B1 (en) | Phosphorus-containing ultrastable y-type rare earth molecular sieve and preparation method therefor | |
| CN101837301B (en) | Catalytic cracking propylene catalyst with yield increase and preparation method | |
| CN100395312C (en) | Method for catalytic cracking petroleum hydrocarbons | |
| CN101745412B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN101823726B (en) | Modified Y molecular sieve | |
| CN102050462B (en) | Double-component modified molecular sieve with improved hydrothermal stability and preparation method | |
| CN102050458B (en) | Modified molecular sieve capable of improving sodium pollution resisting capability and preparation method of modified molecular sieve | |
| CN103566962B (en) | A kind of multi-functional catalyst composition | |
| CN102166533B (en) | Composite modified molecular sieve improving activity and hydrothermal stability and preparation method thereof | |
| CN102019195B (en) | Modified Y molecular sieve-containing catalytic cracking catalyst | |
| CN102166529A (en) | Catalyst for using C4 olefin to prepare ethylene and propylene by catalytic pyrolysis and application method thereof | |
| CN101590432B (en) | Modified clay and preparation method thereof | |
| CN113526522B (en) | Phosphorus modified MFI structure molecular sieve and preparation method thereof | |
| CN101683621B (en) | Catalyst for producing low-carbon olefins through catalytic cracking by fixed bed | |
| CN101745413B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN101733140B (en) | Preparation method of shape-selective molecular sieve combination | |
| CN114762836B (en) | Preparation method and preparation system of catalytic cracking catalyst of phosphorus-containing modified MFI structure molecular sieve | |
| CN114713277B (en) | Modified silicon-aluminum molecular sieve with MFI structure and preparation method thereof | |
| CN103771437B (en) | A kind of phosphorous modified beta molecular sieve | |
| CN100395311C (en) | Catalyst for cracking petroleum hydrocarbons, and preparation | |
| CN100351344C (en) | Catalytic conversion method for selective preparation of micromolecular olefin | |
| CN104108724A (en) | Method for synthesizing small crystal grain P-ZSM-5 molecular sieve by using low cost raw material | |
| CN111686786B (en) | Heteroatom modified Y-type zeolite with adjustable acidity and pore structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |