CN1078180C - Process for preparing Y-type molecular sieve - Google Patents
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- CN1078180C CN1078180C CN98117283A CN98117283A CN1078180C CN 1078180 C CN1078180 C CN 1078180C CN 98117283 A CN98117283 A CN 98117283A CN 98117283 A CN98117283 A CN 98117283A CN 1078180 C CN1078180 C CN 1078180C
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Abstract
The present invention provides a method for preparing NaY zeolite, which is characterized in that the method comprises the following steps: (1), a guide agent is prepared according to a method for preparing a guide agent adopted in the conventional method for preparing NaY zeolite; (2), the guide agent is uniformly mixed with water glass, waste slag containing SiO2 and Al2O3 in a catalyst plant, and aluminum salt and/or sodium aluminate, and the alkalinity of the mixture is adjusted to make the molar composition of obtained reaction mixture accord with the proportioning of (1.5 to 4.5) Na2: Al2O3: (5.5 to 12) SiO2: (120 to 300) H2O, wherein the Al2O3 in the guide agent accounts for 2 to 7% of the total amount of the Al2O3 of the mixture, the Al2O3 in the waste slag accounts for 0 to 60% of the total amount of Al2O3 of the mixture, and the SiO2 accounts for 15 to 50% of the total amount of the SiO2 in the mixture; (3), water-heat crystallization is carried out to the mixture obtained in the step (2) according to the conventional method, and the product is recovered. The method provided by the present invention has the advantages that the waste slag generated by the catalyst plant can be digested out, the environment pollution is reduced, the raw material is saved to a great extend, and the quality of the product of the obtained NaY zeolite is equal to the quality of the NaY zeolite prepared by the conventional method.
Description
The present invention relates to the particularly preparation method of y-type zeolite of faujusite, what also relate to silicon-aluminum containing class waste residue utilizes method again.
Y-type zeolite as the active component of catalytic cracking catalyst, is one of zeolite of consumption maximum mainly.USP313007 reports that it consists of 0.9 ± 0.2Na
2O: Al
2O
3: wSiO
2: xH
2O (w is 3～6, and x can reach 9), at present the industrial manufacture method that adopts is based on patent USP3639099, the USP3671191 of GRACE company basically, promptly prepares earlier mole to consist of (15～17) Na
2OAl
2O
3(14～16) SiO
2(200～350) H
2O is mixed with out mole with this directed agents and water glass, sodium aluminate, aluminium salt etc. again and consists of (3～6) Na
2OAl
2O
3(8～12) SiO
2(120～280) H
2The reaction mixture of O, and go out the NaY zeolite 100 ℃ of left and right sides crystallization.This external application roasting kaolin prepares faujusite also report, as USP3515511.
Particularly there is the catalyzer manufactory of catalyst of cracking petroleum kind in catalyzer manufactory, all produces a large amount of solid slags every year, and these waste residues mainly contain SiO
2, Al
2O
3, RE
2O
3, Na
2O and Fe
2O
3Deng composition, and contain Cl
-, SO
4 =, Ca
++, Mg
++, F
-, impurity such as P, As, Pb, the water content of waste residue-as surpass 50%, its physical aspect mainly is made up of the molecular sieve (being mainly y-type zeolite) of the cracking catalyst particle of various brands, various ion exchange form, silicon (aluminium) glue, aluminum oxide, kaolin etc., has become the blowdown rich and influential family of petrochemical industry.The technology that relates to controlling waste residue in the prior art and utilize is more, as adopt physical methods (as CN87103419, CN1051523A) such as shaping, briquetting with waste residue as material of construction and filler; From waste residue, extract the technology of useful component for another example, propose from the waste residue that contains rare earth, to extract rare earth such as CN1044635A, but can not be all effective to various components, can not complete digestion fall waste residue, even increase the amount of waste residue owing to treating processes.
Relating to silicon, aluminium mainly contains for the main waste residue of forming, the technology that liquid waste disposal technique particularly is prepared into zeolites: the mother liquor recycling of (1) synthetic zeolite, propose to synthesize the mother liquor heating that is produced among the JP6107411 and remove particulate matter, with being settled out silicon with waste liquid in the acid, and, use NaOH and H again with mother liquor mixing post-heating
2O regulates the composition proportioning makes it become water glass, can be used further to synthetic zeolite.It also is with sour silicon in the mother liquor to be precipitated out earlier that the mother liquor that usefulness such as DD227416, DD227686 is synthesized zeolites such as ZSM-5, Y, M comes the technology of synthetic faujasites, and similar, these technology all can't be handled the catalyst plant waste residue.(2) JP5155611 will contain SiO
2And Al
2O
3Inorganic or organic waste fusion and be added to the alkali of equivalent at least such as sodium hydroxide in boil and be used to prepare zeolite, waste residue is SiO preferably
2/ Al
2O
3=2～4 sludge or its incineration ash.JP5221628, JP6256012, JP6239612 are also substantially similarly.This method is not suitable for the catalyst plant waste residue, because very big catalyst plant waste residue elder generation fusion obviously is uneconomic for water content.(3) EP451112 will be less than 300 microns sial waste material with about 20% H
2SO
4Solvent and solute weight ratio 1.3～6 and 150～230 ℃ of following processing 0.25～0.75 hour, be cooled to 60～150 ℃ then, use alkali such as sodium-hydroxide treatment again, and in every liter, add 0.2～0.5 the gram flocculation agent, time obtain silicon-aluminium glue body in PH3.5～4.5, a ℃ following reaction obtains zeolite in PH8～13 and 60～200 for hydro-oxidation sodium and water, and zeolite type depends on the mixture composition.J5514412 adds flocculation agent and adjusts the basicity crystallization with silicate and sodium-hydroxide treatment aluminum oxide sludge to go out zeolite again.Characteristics are earlier with acid or alkaline purification and add flocculation agent.What difference was little with it is that USP4226837 dissolves the silicon-dioxide formation alkalimetal silicate that contains useless cigarette ash with alkali hydroxide soln down at 60～110 ℃, separate to be regardless of with gac or oxygenant and separate component, at room temperature with the alkali metal aluminate reaction and stir 8～48 hours crystallization down at 70～100 ℃ and obtain Y zeolite.
Known to the inventor, with forming and constituting all that the wet waste residue of catalyst plant sial class of more complicated does not directly appear in the newspapers as the raw material of preparation high silica alumina ratio NaY zeolite as yet without any pre-treatment, the improvement technology that the complete digestion of catalyst plant waste residue is fallen was not reported yet.
The purpose of this invention is to provide a kind of is that the method that catalyst plant effluxes waste residue is fallen in feedstock production NaY zeolite and complete digestion with the wet waste residue of catalyst plant siliceous, the aluminium class, to reduce the pollution of environment and to turn waste into wealth, guaranteeing to save starting material under the prerequisite that quality product does not reduce significantly simultaneously.
The method of the NaY of preparation zeolite provided by the present invention is made up of the following step:
(1) prepares directed agents according to the method for preparing directed agents that is adopted in the conventional NaY zeolite preparation method;
(2) with this directed agents and water glass, contain SiO
2And Al
2O
3Waste residue, aluminium salt and/or sodium metaaluminate mix, and adjust the basicity of mixture, the mole of gained reaction mixture is formed is met (1.5～4.5) Na
2O: Al
2O
3: (5.5～12) SiO
2: (100～300) H
2The proportioning of O, the wherein Al in the directed agents
2O
3Account for the total Al of said mixture
2O
32～8%, preferably 3.5～6.0% of amount; Al in the waste residue
2O
3Account for the total Al of said mixture
2O
30～60%, preferably 0～55% of amount; SiO in the waste residue
2Account for the total SiO of said mixture
215～50%, preferably 20～40% of amount; Na wherein
2O represents the basicity of mixture, and it does not comprise the part that is neutralized by acid;
(3) with (2) gained mixture hydrothermal crystallizing and reclaim product according to a conventional method.
Said directed agents (crystal seed) can prepare by the whole bag of tricks of preparation faujusite directed agents in the prior art in the step in the method provided by the present invention (1), but preferably the method for preparing directed agents that is adopted among the conventional preparation method according to the NaY zeolite of industrial common employing at present prepares, for example according to USP3639099, USP3671191, the method for preparing directed agents that is proposed among USP4166099 and the CN1081425A prepares, can not change existing NaY preparation technology like this and not need increase equipment, the mole compositing range of the directed agents of preparing according to these ordinary methods is (15～17) Na
2O: Al
2O
3: (14～16) SiO
2: (200～350) H
2O.
The said SiO that contains in the step in the method provided by the present invention (2)
2And Al
2O
3Waste residue be the waste residue that effluxes of catalyst plant catalyst plant that the catalyst of cracking petroleum kind is particularly arranged, its butt is formed SiO in (referring to the composition through gained resistates after 800 ℃ of roastings in 2 hours)
2And Al
2O
3Total content should be more than or equal to 50 heavy %, preferably more than or equal to 70 heavy %, more preferably more than or equal to 80 heavy %; Said waste residue can contain rare earth, iron, calcium, magnesium and Cl
-, SO
4 =, F
-Deng impurity; The water content of said waste residue has no particular limits, but preferably solid content weighs % more than or equal to 5; Its physical aspect mainly by the cracking catalyst particle of various brands, various ion exchange form (as Na
+, H
+, NH
4 +And rare earth ion) comprise that Y zeolite is (as NaY, REY, HY, REHY, NH
4Y, USY, REUSY etc.) and the ZSM-5 zeolite form in clay-type substance such as interior molecular sieve, silica gel or alumino silica gel, aluminum oxide and kaolin, metakaolins; The waste residue that joins in the synthetic system not only can mainly have been decided on its composition for system provides part silicon source but also can provide part aluminium source for system; Water glass that adds and the SiO in waste residue and the directed agents
2Common silicon source as synthetic NaY zeolite, the Al in the aluminium salt of interpolation and/or aluminate and waste residue and the directed agents
2O
3Common aluminium source as synthetic NaY zeolite.
Said aluminium salt can be Tai-Ace S 150, aluminum phosphate, aluminum chloride or aluminum nitrate in the step in the method provided by the present invention (2).The aluminate of tart aluminium salt and/or alkalescence also is used for the basicity of conditioned reaction system except being used to provide a part of aluminium source, the two can use separately, also can use simultaneously, in case of necessity can also exogenously added alkali or acid come the basicity of conditioned reaction system.
Total mole of the said mixture of step in the method provided by the present invention (2) consists of (1.5～4.5) Na
2O: Al
2O
3: (5.5～12) SiO
2: (100～300) H
2O, preferably (1.5～3.5) Na
2O: Al
2O
3: (6.0～9.5) SiO
2: (130～250) H
2O.
The condition of the said crystallization of step in the method provided by the present invention (3) is determined according to normal condition of the prior art, generally be 85～110 ℃ of following hydrothermal crystallizings 12～45 hours, industrial the most frequently used condition is 100 ℃ of left and right sides hydrothermal crystallizings 20～30 hours.
The advantage of method provided by the present invention is under the situation that does not change existing conventional NaY zeolite production technique and equipment substantially, can digest the waste residue that catalyst plant produces, reduce environmental pollution, and save starting material such as water glass, sodium aluminate, Tai-Ace S 150 significantly, waste residue can replace 15～40% silicon sources such as water glass, can replace aluminium sources such as 0～60% sodium aluminate, Tai-Ace S 150.The NaY zeolite quality that the quality of gained NaY zeolite product and ordinary method are prepared is suitable.
Fig. 1 is X-ray diffraction (XRD) the crystalline phase figure of embodiment 1 products obtained therefrom.
Fig. 2 is the electron scanning micrograph (magnification is 6.4K) of embodiment 1 products obtained therefrom.
The following examples will the present invention is further illustrated.
In each embodiment, the relative crystallinity of the NaY zeolite that synthesizes is measured according to RIPP146-90 standard method and (is seen " petrochemical complex analytical procedure (RIPP test method) ", Yang Cui waits volume surely, Science Press, nineteen ninety version), silica alumina ratio is pressed RIPP145-90 standard method and is measured (the same), chemical constitution presses RIPP134-90 and (the same) measured in RIPP111-90 standard method, the specific surface of zeolite and pore volume are measured by Chinese Industrial Standards (CIS) GB/T5816-1995 method, and the temperature failure temperature is measured with differential thermal analysis.
Embodiment 1
With 360 ml water glass (SiO
2Content=250 grams per liters, Na
2O content=80.7 grams per liters, Chang Ling oil-refining chemical factory catalyst plant is produced, down together) and 243.5 milliliters high basicity sodium aluminate solution (Al
2O
3Content=40 grams per liters, Na
2The O=287 grams per liter, Chang Ling oil-refining chemical factory catalyst plant is produced) mix, its mole of gained mixture consists of 16Na
2O: Al
2O
3: 15SiO
2: 320H
2O adds 100.6 ml deionized water with its ageing under room temperature (25 ℃) after 18 hours, the back that stirs is as directed agents.
(take between Chang Ling oil-refining chemical factory catalyst plant integrated car, the percentage composition of butt weight is Na to add 461 gram catalyst plant waste residues in 474 ml water glass
2O=10.5%, SiO
2=54.8%, Al
2O
3=16.1%, RE
2O
3=1.28%, SO
4 ==7.85%, Cl
-=1.50%, solid content is 13.6 heavy %, density 1.015 grams per milliliters) and 119.2 milliliters of above-mentioned directed agents, and 105.8 milliliters of alum liquor (Al
2O
3Content=90 grams per liters, down together) and 126.8 milliliters low basicity sodium aluminate solution (Al
2O
3Content=100 grams per liters, Na
2The O=150 grams per liter, Chang Ling oil-refining chemical factory catalyst plant is produced, down together), after stirring, the gained mixture packed in the stainless steel sealed reactor and 100 ℃ of following crystallization 24 hours, after filtration, after the washing, drying, the X-ray diffraction of products therefrom (XRD) thing phasor is seen Fig. 1, is indicated as the y-type zeolite structure, relative crystallinity is 88%, silica alumina ratio 5.17, temperature failure temperature are 958.66 ℃, 777 meters of BET surface-area
2/ gram, 0.356 milliliter/gram of pore volume, crystal morphology is seen Fig. 2.
Embodiment 2
In 362 ml water glass, add gained directed agents among 461 gram waste residues (with embodiment 1) and the 119.2 milliliters of embodiment 1, and 222 milliliters low basicity sodium aluminate solutions, adding 137 gram concentration then is the sulfuric acid of 25 heavy %, after stirring, the stainless steel sealed reactor and of packing into 100 ℃ of following crystallization 40 hours, after filtration, after the washing, drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, its relative crystallinity is 85%, silica alumina ratio 5.42,974.08 ℃ of temperature failure temperature.
Embodiment 3
In 482.6 ml water glass, add gained directed agents among 461 gram waste residues (with embodiment 1) and the 119.2 milliliters of embodiment 1, and 114.3 milliliters of alum liquors and 119.3 milliliters low basicity sodium aluminate solutions, after stirring, pack into stainless steel sealed reactor and 100 ℃ of following crystallization 18 hours, after washing after filtration,, the drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, and its relative crystallinity is 83%, silica alumina ratio 5.47.
Embodiment 4
In 269 ml water glass, add gained directed agents among 460.8 gram waste residues (with embodiment 1) and the 119.2 milliliters of embodiment 1, and 106 milliliters of alum liquors and 127 milliliters low basicity sodium aluminate solutions, after stirring, pack into stainless steel sealed reactor and 100 ℃ of following crystallization 22 hours, after filtration, after the washing, drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, its relative crystallinity is 85%, silica alumina ratio 4.97,952.19 ℃ of temperature failure temperature.
Embodiment 5
In 369.2 ml water glass, add gained directed agents among 485 gram waste residues (with embodiment 1) and the 116 milliliters of embodiment 1, and 81.5 milliliters of alum liquors and 125 milliliters low basicity sodium aluminate solutions, after stirring, pack into stainless steel sealed reactor and 100 ℃ of following crystallization 24 hours, after washing after filtration,, the drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, and its relative crystallinity is 85.1%, silica alumina ratio 5.14.
Embodiment 6
(take between Chang Ling oil-refining chemical factory catalyst plant integrated car, the percentage composition of butt weight is Na to add 404 gram waste residues in 273 ml water glass
2O=6.6%, SiO
2=84.2%, Al
2O
3=0, RE
2O
3=2.99%, Fe
2O
3=0.15%, SO
4 ==0.47%, Cl
-=2.0%, solid content is 11.7 heavy %) and 83 milliliters of embodiment 1 in the gained directed agents, and 254 milliliters of alum liquors, adding 85.5 gram concentration then is the sodium hydroxide solution of 40 heavy %, after stirring, and the stainless steel sealed reactor and of packing into 100 ℃ of following crystallization 24 hours, after washing after filtration,, the drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, and its relative crystallinity is 80%, silica alumina ratio 4.90.
Embodiment 7
(take between Chang Ling oil-refining chemical factory catalyst plant integrated car, the percentage composition of butt weight is Na to add 461 gram waste residues in 269 ml water glass
2O=6.74%, SiO
2=68.4%, Al
2O
3=18.4, RE
2O
3=2.6%, Fe
2O
3=0.2%, Ca=0.1%, Mg=0.05%, Pb=0.0074%, As=0.017%, F
-=0.0057%, solid content is 13.6 heavy %) and 119.3 milliliters of embodiment 1 in the gained directed agents, and 106 milliliters of alum liquors and 100 milliliters low basicity sodium aluminate solutions, after stirring, pack into stainless steel sealed reactor and 100 ℃ of following crystallization 24 hours, after filtration, after the washing, drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, its relative crystallinity is 81%, silica alumina ratio 5.13.
Embodiment 8
(take between Chang Ling oil-refining chemical factory catalyst plant integrated car, the percentage composition of butt weight is Na to add 382 gram waste residues in 311 ml water glass
2O=7.6%, SiO
2=77.4%, Al
2O
3=13.5%, RE
2O
3=1.37%, P=0.1%, F
-=0.1%, SO
4 ==6.5%, Fe
2O
3=0.1%, Cl
-=0.99%, solid content is 15.4 heavy %) and 103.5 milliliters of embodiment 1 in the gained directed agents, and 81.2 milliliters of alum liquors and 132.6 milliliters low basicity sodium aluminate solutions, after stirring, pack into stainless steel sealed reactor and 100 ℃ of following crystallization 28 hours, after filtration, after the washing, drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, its relative crystallinity is 84.7%, silica alumina ratio 5.12.
Embodiment 9
In 243 ml water glass, add gained directed agents among 412 gram waste residues (with embodiment 8) and the 103.5 milliliters of embodiment 1, and 81.2 milliliters of alum liquors and 132.6 milliliters low basicity sodium aluminate solutions, after stirring, pack into stainless steel sealed reactor and 100 ℃ of following crystallization 28 hours, after washing after filtration,, the drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, and its relative crystallinity is 84.7%, silica alumina ratio 5.32.
Embodiment 10
(take between Chang Ling oil-refining chemical factory catalyst plant integrated car, the percentage composition of butt weight is Na to add 382 gram waste residues in 311 ml water glass
2O=6.73%, SiO
2=68.6%, Al
2O
3=18.4%, RE
2O
3=1.299%, SO
4 ==7.85%, Fe
2O
3=0.1 5%, Cl
-=1.50%, solid content is 13.6 heavy %) and 103.5 milliliters of embodiment 1 in the gained directed agents, and 81.2 milliliters of alum liquors and 132.6 milliliters low basicity sodium aluminate solutions, after stirring, pack into stainless steel sealed reactor and 100 ℃ of following crystallization 28 hours, after filtration, after the washing, drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, its relative crystallinity is 92%, silica alumina ratio 5.13.
Embodiment 11
(take between Chang Ling oil-refining chemical factory catalyst plant integrated car, the percentage composition of butt weight is Na to add 378 gram waste residues in 341 ml water glass
2O=5.4%, SiO
2 ==78.0%, Al
2O
3=17.0%, SO
4 ==5.4%, Fe
2O
3=0.1%, RE
2O
3=0.14%, solid content is 14.9 heavy %) and 99 milliliters of embodiment 1 in the gained directed agents, and 66.5 milliliters of alum liquors and 115 milliliters low basicity sodium aluminate solutions, after stirring, pack into stainless steel sealed reactor and 100 ℃ of following crystallization 32 hours, after filtration, after the washing, drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, its relative crystallinity is 85%, silica alumina ratio 5.02.
Embodiment 12
(take between Chang Ling oil-refining chemical factory catalyst plant integrated car, the percentage composition of butt weight is Na to add 408 gram waste residues in 381.4 ml water glass
2O=12.8%, SiO
2=70.5%, Al
2O
3=0, RE
2O
3=0.14%, Fe
2O
3=0.12%, SO
4 ==4.7%, solid content is 14.7 heavy %) and 105.6 milliliters of embodiment 1 in the gained directed agents, and 127 milliliters of alum liquors and 177 milliliters low basicity sodium aluminate solutions, after stirring, pack into stainless steel sealed reactor and 100 ℃ of following crystallization 32 hours, after filtration, after the washing, drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, its relative crystallinity is 86.4%, silica alumina ratio 4.94.
Embodiment 13
In 318 ml water glass, add gained directed agents among 341 gram waste residues (with embodiment 12) and the 90 milliliters of embodiment 1, and 106 milliliters of alum liquors and 150 milliliters low basicity sodium aluminate solutions, after stirring, pack into stainless steel sealed reactor and 100 ℃ of following crystallization 24 hours, after washing after filtration,, the drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, and its relative crystallinity is 87.2%, silica alumina ratio 5.19.
Embodiment 14
(take between Chang Ling oil-refining chemical factory catalyst plant integrated car, the percentage composition of butt weight is Na to add 404 gram waste residues in 273 ml water glass
2O=6.7%, SiO
2=66.9%, Al
2O
3=11.6%, RE
2O
3=0.47%, SO
4 ==5.2%, Fe
2O
3=0.25%, solid content is 18.3 heavy %) and 85 milliliters of embodiment 1 in the gained directed agents, and 92 milliliters of alum liquors and 150 milliliters low basicity sodium aluminate solutions, stir, pack into stainless steel sealed reactor and 100 ℃ of following crystallization 32 hours, after filtration, after the washing, drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, its relative crystallinity is 87.8%, silica alumina ratio 5.0.
Embodiment 15
(take between Chang Ling oil-refining chemical factory catalyst plant integrated car, the percentage composition of butt weight is Na to add 1966.4 gram waste residues in 2566.5 ml water glass
2O=1.83%, SiO
2=76%, Al
2O
3=32.4%, RE
2O
3=0.28%, SO
4 ==1.14%, Fe
2O
3=0.046%, Cl
-=0.3%, solid content is 15.7 heavy %) and 683 milliliters of embodiment 1 in the gained directed agents, and 327 milliliters of alum liquors and 531 milliliters low basicity sodium aluminate solutions, after stirring, the stainless steel sealed reactor and of packing into 100 ℃ of following crystallization 28 hours, after washing after filtration,, the drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, and its relative crystallinity is 82.2%, and silica alumina ratio is 5.14, the temperature failure temperature is 958.66 ℃, and the BET surface-area is 690 meters
2/ gram, pore volume are 0.354 milliliter/gram.
Embodiment 16
(take between Chang Ling oil-refining chemical factory catalyst plant integrated car, the percentage composition of butt weight is Na to add 1416.5 gram waste residues in 715 ml waters
2O=8.76%, SiO
2=66.15%, Al
2O
3=21.41%, RE
2O
3=1.35%, SO
4 ==5.18%, Fe
2O
3=0.154%, Cl
-=1.22%, MgO=0.18%, solid content is 14.7 heavy %), gained directed agents in wherein adding 2073 ml water glass and 500 milliliters of embodiment 1 again, and 446 milliliters of alum liquors and 534.7 milliliters low basicity sodium aluminate solutions, after stirring, pack into stainless steel sealed reactor and 100 ℃ of following crystallization 27 hours, after washing after filtration,, the drying, the XRD analysis of products therefrom is indicated as the y-type zeolite structure, and its relative crystallinity is 82.2%, silica alumina ratio 5.02,958.66 ℃ of temperature failure temperature, 690 meters of BET surface-area
2/ gram, 0.354 milliliter/gram of pore volume.
Claims (12)
1. method for preparing the NaY zeolite is characterized in that this method is made up of the following step:
(1) prepares directed agents according to the method for preparing directed agents that is adopted in the conventional NaY zeolite preparation method;
(2) with this directed agents and water glass, contain SiO
2And Al
2O
3Waste residue, aluminium salt and/or sodium metaaluminate mix, and adjust the basicity of mixture, the mole of gained reaction mixture is formed is met (1.5～4.5) Na
2O: Al
2O
3: (5.5～12) SiO
2: (100～300) H
2The proportioning of O, the wherein Al in the directed agents
2O
3Account for the total Al of said mixture
2O
32～8% of amount; Al in the waste residue
2O
3Account for the total Al of said mixture
2O
30～60% of amount; SiO in the waste residue
2Account for the total SiO of said mixture
215～50% of amount; Na wherein
2O represents the basicity of mixture, and it does not comprise the part that is neutralized by acid;
(3) with (2) gained mixture hydrothermal crystallizing and reclaim product.
2. according to the process of claim 1 wherein that the mole compositing range of said directed agents is (15～17) Na in the step (1)
2O: Al
2O
3: (14～16) SiO
2: (200～350) H
2O.
3. according to the process of claim 1 wherein the said SiO of containing in the step (2)
2And Al
2O
3Waste residue be have the catalyst of cracking petroleum kind catalyst plant efflux waste residue, SiO during its butt is formed
2And Al
2O
3Total content more than or equal to 50 weight %.
4. according to the method for claim 3, SiO during wherein the butt of said waste residue is formed
2And Al
2O
3Total content more than or equal to 70 weight %.
5. according to the method for claim 3, SiO during wherein the butt of said waste residue is formed
2And Al
2O
3Total content more than or equal to 80 weight %.
6. according to the process of claim 1 wherein that the solid content of said waste residue is more than or equal to 5 weight %.
According to the process of claim 1 wherein the physical aspect of said waste residue comprise the catalyst of cracking petroleum particle, with Na
+, H
+, NH
4 +With rare earth ion be molecular sieve, silica gel or the alumino silica gel, the aluminum oxide that comprise y-type zeolite and ZSM-5 zeolite of ionic forms and the clay-type substance that comprises kaolin, metakaolin.
8. according to the process of claim 1 wherein that said aluminium salt is Tai-Ace S 150, aluminum phosphate, aluminum chloride or aluminum nitrate in the step (2).
9. according to the process of claim 1 wherein that total mole of the said mixture of step (2) consists of (1.5～3.5) Na
2O: Al
2O
3: (6.0～9.5) SiO
2: (130～250) H
2O.
10. according to the process of claim 1 wherein the Al in the directed agents in the step (2)
2O
3Account for the total Al of said mixture
2O
33.5～6.0% of amount.
11. according to the process of claim 1 wherein the Al in the waste residue in the step (2)
2O
3Account for the total Al of said mixture
2O
30～55% of amount; SiO in the waste residue
2Account for the total SiO of said mixture
220～40% of amount.
12. according to the process of claim 1 wherein that the condition of the said crystallization of step (3) is 85～110 ℃ of following hydrothermal crystallizings 12～45 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117283A CN1078180C (en) | 1998-08-14 | 1998-08-14 | Process for preparing Y-type molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117283A CN1078180C (en) | 1998-08-14 | 1998-08-14 | Process for preparing Y-type molecular sieve |
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| CN1245140A CN1245140A (en) | 2000-02-23 |
| CN1078180C true CN1078180C (en) | 2002-01-23 |
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| CN98117283A Expired - Lifetime CN1078180C (en) | 1998-08-14 | 1998-08-14 | Process for preparing Y-type molecular sieve |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767030B (en) * | 2008-12-31 | 2012-07-18 | 中国石油化工股份有限公司 | Preparation method of catalysis material containing ZSM-5 molecular sieve |
| CN101928010B (en) * | 2009-12-29 | 2012-07-04 | 大唐国际化工技术研究院有限公司 | Preparation method of NaY type molecular sieve |
| CN102233281B (en) * | 2010-04-30 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation of active carrier and application thereof |
| CN103058218B (en) * | 2011-10-21 | 2015-01-21 | 中国石油化工股份有限公司 | Preparation method of NaY molecular sieve |
| CN104402018B (en) * | 2014-11-10 | 2016-06-29 | 中国海洋石油总公司 | A kind of synthetic method of high-strength integral FAU type zeolite molecular sieve |
| CN105728015A (en) * | 2016-02-05 | 2016-07-06 | 青岛惠城环保科技股份有限公司 | Comprehensive utilization method for waste residues and waste liquor generated in catalytic cracking catalyst production |
| CN109485063B (en) * | 2018-12-10 | 2020-11-17 | 卓悦环保新材料（上海）有限公司 | Method for preparing Y molecular sieve from waste MTP catalyst and application of waste MTP catalyst |
| CN112717961B (en) * | 2019-10-28 | 2023-04-11 | 中国石油化工股份有限公司 | Filter residue and preparation method thereof, and catalytic cracking catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226837A (en) * | 1976-11-11 | 1980-10-07 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for converting silicon dioxide containing waste flue dust to crystalline zeolitic molecular sieves of type Y with a Faujasite structure |
| SU975573A1 (en) * | 1980-09-12 | 1982-11-23 | Предприятие П/Я Р-6518 | Process for producing zeolite of the faujasite type |
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- 1998-08-14 CN CN98117283A patent/CN1078180C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226837A (en) * | 1976-11-11 | 1980-10-07 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for converting silicon dioxide containing waste flue dust to crystalline zeolitic molecular sieves of type Y with a Faujasite structure |
| SU975573A1 (en) * | 1980-09-12 | 1982-11-23 | Предприятие П/Я Р-6518 | Process for producing zeolite of the faujasite type |
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| CN1245140A (en) | 2000-02-23 |
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