CN103896302B - A kind of si molecular sieves and preparation method thereof - Google Patents
A kind of si molecular sieves and preparation method thereof Download PDFInfo
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Abstract
A kind of si molecular sieves, it is characterized in that this molecular sieve has MFI crystalline structure, its pore volume is greater than 0.3cm
3/ g, total specific surface area 200 ~ 400m
2/ g, outer surface area 30 ~ 150m
2/ g, and the ratio that outer surface area accounts for total specific surface area is 10% ~ 55%; This molecular sieve is at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity that records under the condition of 1 hour is at least 75mg/g molecular sieve, N
2there is under Static Adsorption test the micropore size of 0.9 ~ 1.5nm scope.
Description
Technical field
The present invention relates to a kind of silicone zeolite molecular sieve and preparation method thereof, more specifically to a kind of method utilizing the oximes catalyst preparing silicone zeolite molecular sieve of inactivation.
Background technology
Si molecular sieves, also referred to as total silicon zeolite, is the molecular sieve that skeleton is all made up of silica element.Wherein Silicalite-1(S-1) molecular sieve has ZSM-5(MFI) silica zeolite of the framework of molecular sieve of structure.Directly as the material of membrane sepn, also can form hetero-atom molecular-sieve by utilizing the part silicon in other hybrid atom MCM-41 skeleton, having a extensive future.
Disclosing si molecular sieves S-1 and synthetic method thereof in US4061724, have MFI crystalline structure, do not have aluminium source in its raw materials, only have silicon source, alkali source, template and water, is the si molecular sieves of directly synthesis.In the existing technology preparing si molecular sieves, as JP59164617 and Catal.Rev.-Sci.Eng., 1997,39(4): in 395 ~ 424, do silicon source with organosilicon acid esters, during synthesis in early stage, organosilicon acid esters needs hydrolysis also need heat except alcohol, makes early stage generated time relatively long; Meanwhile, due to Si itself to lead brilliant ability weak, make the crystallization time preparing si molecular sieves also longer.In the last few years, although improve through certain, effect was not also very good.
CN1338427A discloses a kind of si molecular sieves of MFI crystalline structure, and it is characterized in that grain surface is empty male and fomale(M&F), BET specific surface area is 430 ~ 500m
2/ g and Extra specific surface area is 5 ~ 100m
2/ g, the absorption of its nitrogen absorption under low temperature is propped up and is propped up at P/P with desorption
0hysteresis loop is there is between=0.45 ~ 0.98.
TS-1 molecular sieve is introduced by transition metal titanium to have a kind of novel titanosilicate with superior catalytic selective oxidation performance formed in the framework of molecular sieve of ZSM-5 structure.TS-1 not only has the catalysed oxidn of titanium, but also there is ZSM-5 molecular sieve select shape effect and excellent stability, this molecular sieve is prepared in the technique of cyclohexanone-oxime at pimelinketone catalytic ammoxidation and is successfully achieved industrial application.But after operation for some time, catalytic performance can be deteriorated usually, occurs deactivation phenomenom.Inactivation is divided into again temporary inactivation and permanent inactivation.The catalysis of temporary inactivation can make it recuperation section or all active through regeneration, permanent inactivation then cannot by regeneration activity recovery (as regenerate rear activity lower than initial activity 50% situation).Oximes catalyzer TS-1 cannot recycle after there is permanent deactivation at present, adopts the mode process of piling up landfill.Like this, valuable land resources and inventory space is occupied.
Summary of the invention
Contriver finds through large quantifier elimination, when the MFI crystalline structure HTS of inactivation after roasting with the acid solution combination treatment of volumetric molar concentration >0.1mol/L, reclaim the product obtained, there is special physical chemical characteristics, and its relative crystallinity is higher, benzene adsorptive capacity is larger.Based on this, complete the present invention.
Therefore, an object of the present invention is to provide a kind of si molecular sieves with special physical chemical characteristics, and two of object is to provide the preparation method of above-mentioned si molecular sieves.
Si molecular sieves provided by the invention, it is characterized in that this molecular sieve has MFI crystalline structure, its pore volume is greater than 0.3cm
3/ g, total specific surface area 200 ~ 400m
2/ g, outer surface area 30 ~ 150m
2/ g, and the ratio that outer surface area accounts for total specific surface area is 10% ~ 55%; This molecular sieve is at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity that records under the condition of 1 hour is at least 75mg/g molecular sieve, N
2there is under Static Adsorption test the micropore size of 0.9 ~ 1.5nm scope.
Present invention also offers the preparation method of above-mentioned si molecular sieves, it is characterized in that the HTS of the MFI crystalline structure of inactivation after roasting, mix with the acid solution of volumetric molar concentration >0.1mol/L again and pull an oar and process 0.5 ~ 36 hour at 10 ~ 200 DEG C, reclaim product and obtain si molecular sieves, wherein, with SiO
2meter MFI crystalline structure HTS with in the molar ratio of the acid of H+ for 100:(5 ~ 200).
Si molecular sieves provided by the invention, has special physical chemical characteristics.Method provided by the invention, using the MFI crystalline structure HTS of inactivation as the raw materials of si molecular sieves, turns waste into wealth, and the yield of gained zeolite product and benzene adsorptive capacity higher.
Embodiment
Si molecular sieves provided by the invention, it is characterized in that this molecular sieve has MFI crystalline structure, its pore volume is greater than 0.3cm
3/ g, total specific surface area 200 ~ 400m
2/ g, outer surface area 30 ~ 150m
2/ g, and the ratio that outer surface area accounts for total specific surface area is 10% ~ 55%; This molecular sieve is at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity that records under the condition of 1 hour is at least 75mg/g molecular sieve, N
2there is under Static Adsorption test the micropore size of 0.9 ~ 1.5nm scope.
In the present invention, its total specific surface area of the si molecular sieves provided refers to BET specific surface area, and external surface area refers to the surface-area of the outside surface of si molecular sieves, also referred to as outer surface area, all can record according to ASTMD4222-98 standard method.
Si molecular sieves of the present invention, Si is with SiO
2the mass percentage >99% of meter, preferred >99.5%, further preferred >99.9%.Generally can contain a small amount of Ti, with TiO
2the mass percentage <1% of meter, preferred <0.5%, further preferred <0.1%.
Si molecular sieves of the present invention, has MFI crystalline structure, and its pore volume is greater than 0.3cm
3/ g, such as, pore volume is at 0.3 ~ 0.5cm
3/ g.Total specific surface area 200 ~ 400m
2/ g, outer surface area 30 ~ 150m
2/ g, and the ratio that outer surface area accounts for total specific surface area is 10% ~ 55%, preferably, the ratio that outer surface area accounts for total specific surface area is 10% ~ 35%.
Si molecular sieves of the present invention, at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity that records under the condition of 1 hour is at least 75mg/g molecular sieve, and preferably, being at least 100mg/g molecular sieve, such as, is 100 ~ 130mg/g molecular sieve.
Si molecular sieves of the present invention, its micropore size is except near 0.4 ~ 0.7nm(0.55nm) have pore size distribution specific to typical MFI topological framework molecular sieve in scope except, within the scope of 0.9 ~ 1.5nm, also have distribution.Here it should be noted that, if when within the scope of 0.9 ~ 1.5nm, micropore size distribution accounts for the ratio <1% of total pore size distribution amount, then the pore distribution of this part is ignored, namely think does not have micropore to distribute within the scope of 0.9 ~ 1.5nm, and this is that those skilled in the art are in common knowledge.So the present invention is said at N
2the micropore size under Static Adsorption test with 0.9 ~ 1.5nm scope refers to that micropore size distribution accounts for ratio>=1% of total pore size distribution amount within the scope of 0.9 ~ 1.5nm; The present invention is preferred, and within the scope of 0.4 ~ 0.7nm, micropore size distribution accounts for ratio≤95% of total pore size distribution amount, and within the scope of 0.9 ~ 1.5nm, micropore size distribution accounts for ratio>=5% of total pore size distribution amount; Preferred, within the scope of 0.4 ~ 0.7nm, micropore size distribution accounts for ratio≤90% of total pore size distribution amount, and within the scope of 0.9 ~ 1.5nm, micropore size distribution accounts for ratio>=10% of total pore size distribution amount; Most preferred, within the scope of 0.4 ~ 0.7nm, micropore size distribution accounts for ratio≤85% of total pore size distribution amount, and within the scope of 0.9 ~ 1.5nm, micropore size distribution accounts for ratio>=15% of total pore size distribution amount, such as 15 ~ 30%.The testing method of micropore size is well known to those skilled in the art, as adopted N
2the method tests such as Static Adsorption.
Present invention also offers the preparation method of above-mentioned si molecular sieves, it is characterized in that the HTS of the MFI crystalline structure of inactivation after roasting, mix with the acid solution of volumetric molar concentration >0.1mol/L again and pull an oar and process 0.5 ~ 36 hour at 10 ~ 200 DEG C, reclaim product and obtain si molecular sieves, wherein, with SiO
2meter MFI crystalline structure HTS with H
+the molar ratio of the acid of meter is 100:(5 ~ 200).
Preparation method provided by the invention, be preferably adopt the HTS of inactivation to be raw material, the HTS that usually can not continue to meet operation activity more all belongs to available raw material.Such as, the pimelinketone oximate catalyzer (particle diameter is at 100 ~ 500nm for titanium-silicon molecular sieve TS-1, powdery) of inactivation is as main raw material.The HTS of said inactivation, for pimelinketone oximate catalyzer, refer to adopt the conventional regeneration processes such as solvent wash or roasting cannot make it activation recovering to initial activity 50% when the pimelinketone oximate catalyzer of inactivation (initial activity refers at reaction conditions, the average activity of catalyzer within 1h.As in actual rings hexanone oximation reaction, the initial activity of general catalyzer will reach more than 95%).Decaying catalyst after the oximate catalyzer of inactivation can derive from industrial deactivator or carry out Ammoximation reaction in the lab.Certainly, from the angle of preparation effect, method of the present invention also can adopt fresh HTS as raw material, just from can not be suitable the angle of cost control, method provided by the invention, mainly using the HTS of inactivation as raw material, turn waste into wealth, saved cost.The si molecular sieves that the inventive method obtains, due to be preferably with the HTS of inactivation for raw material, therefore, in product si molecular sieves, generally can contain a small amount of Ti, usually with TiO
2the mass percentage <1% of meter, preferred <0.5%, further preferred <0.1%.
In method provided by the invention, the roasting of the HTS of inactivation is the preparation process of necessity of preparation method provided by the invention, but the process of baking operation is ordinary method, by those skilled in the art is familiar with, to have no special requirements at this, said roasting can 300 ~ 800 DEG C of temperature ranges, such as 550 ~ 600 DEG C of temperature ranges, operate under air atmosphere or under inert gas atmosphere, such as, can, first under maturing temperature, carry out in nitrogen atmosphere in air atmosphere, carrying out 3 ~ 12 hours after 0.5 ~ 6 hour.
In method provided by the invention, said acid is one or more in organic acid and mineral acid.Wherein mineral acid can be one or more in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid etc., and organic acid can be one or more in formic acid, acetic acid, propionic acid, naphthenic acid and Peracetic Acid, Perpropionic Acid etc.The wherein mineral acid such as preferably sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, more preferably phosphoric acid.In method provided by the invention, the preferred pH<0 of said acid solution, acid solution volumetric molar concentration >0.1mol/L, in a preferred embodiment of the invention, acid solution volumetric molar concentration preferably >=1mol/L, its pore volume of the si molecular sieves prepared like this, specific surface area, benzene adsorptive capacity and more obvious in the feature of the pore distribution etc. of 0.9 ~ 1.5nm.
In method provided by the invention, with SiO
2meter MFI crystalline structure HTS with in the molar ratio of the acid of H+ for 100:(5 ~ 200), preferred 100:(20 ~ 50).
In method provided by the invention, said mixing making beating is preferably carried out at normal temperatures and pressures, and said mixing making beating also processes 0.5 ~ 36 hour treating processes at 10 ~ 200 DEG C, preferably at 100 ~ 180 DEG C, processes 1 ~ 24 hour.At one more preferably in embodiment of the present invention, said HTS mixes the process processed of pulling an oar with the acid solution of volumetric molar concentration >0.1mol/L be carry out under acid solution reflux conditions, and the si molecular sieves obtained with this understanding has more obvious physical chemical characteristics.
In method provided by the invention, the process of said recovery product is ordinary method, by those skilled in the art is familiar with, has no special requirements at this, generally refer to that product filters, washing, dry and roasting process.Wherein, said drying process can be carried out at the temperature between room temperature ~ 200 DEG C, and said roasting process first can carry out between 300 ~ 800 DEG C for after 0.5 ~ 6 hour 3 ~ 12 hours in air atmosphere in nitrogen atmosphere.
Below by embodiment, the invention will be further described, but therefore do not limit content of the present invention.
In comparative example and embodiment, agents useful for same is commercially available chemically pure reagent.
The oximes catalyst source of inactivation used in embodiment is in following process: get TS-1 molecular sieve and (prepare by the method described in " Zeolites, 1992, Vol.12:943 ~ 950 ", TiO
2mass percentage be 2.1%) be placed in 100mL and be with in continuously feeding and membrane separation unit slurry bed reactor, add the mixture (volume ratio of water and hydrogen peroxide is 10:9) of the hydrogen peroxide of water and 30wt% with the speed of 5.7mL/h under whipped state, the mixture (volume ratio of pimelinketone and the trimethyl carbinol is for 1:2.5) of pimelinketone and the trimethyl carbinol is added with the speed of 10.5mL/h, 36wt% ammoniacal liquor is added with the speed of 5.7mL/h, above-mentioned three bursts of streams are for add simultaneously, simultaneously with corresponding speed continuous discharge, temperature of reaction maintains 80 DEG C, every 1 hour, product sampling chromatogram is analyzed after stable reaction.The pimelinketone transformation efficiency that first time measures is its initial activity, and its value is 99.5%.Through about 168 hours after a while, after pimelinketone transformation efficiency drops to 50% by initial 99.5%, (at 570 DEG C in air atmosphere roasting 4 hours) are regenerated by roasting regeneration mode after isolating catalyzer, then continue on in cyclohexanone oxamidinating reaction, repeatedly carry out this step, until the activity after regeneration is lower than 50% of initial activity.At this moment the oximes catalyst sample of inactivation is designated as SH-1.The oximes catalyst S H-B of the inactivation after 550 DEG C of roasting temperatures obtain roasting in 3 hours.
In embodiments, X-ray diffraction (XRD) the crystalline phase figure of sample measures on SiemensD5005 type x-ray diffractometer, be that the ratio of diffracted intensity (peak height) sum at the five fingers diffractive features peak between 22.5 ° ~ 25.0 ° is to represent the degree of crystallinity of sample relative to authentic specimen at 2 θ with sample and authentic specimen, here with comparative example 1 sample for authentic specimen, its degree of crystallinity counts 100%, and the relative crystallinity data of each sample and the yield data of preparation process are in table 1.The benzene adsorptive capacity of sample, pore volume, pore size distribution, total specific surface area and external surface area measure on the static n2 absorption apparatus of Micromeritics company ASAP2405, and concrete data are in table 1.
Comparative example 1
This comparative example illustrates that conventional hydrothermal crystallization prepares the process of S-1 sieve sample.
Tetraethyl orthosilicate is mixed with TPAOH, and adds appropriate distilled water and be uniformly mixed, mole consist of tetraethyl orthosilicate among reaction system: TPAOH: water=100:10:200, wherein tetraethyl orthosilicate is with SiO
2meter; At normal pressure and 60 DEG C, be hydrolyzed 1.0 hours, then stir 3 hours at 75 DEG C, obtain clear colloid.This colloid is put into stainless steel sealed reactor, and at the temperature of 170 DEG C, constant temperature places 3 days, obtains the mixture of crystallization product; This mixture is filtered, washes with water, and in 110 DEG C of dryings 60 minutes, obtains the former powder of S-1.By former for this S-1 powder in 550 DEG C of roasting temperatures 3 hours, obtain S-1 molecular sieve, its XRD crystalline phase is MFI structure.The relative crystallinity data of later embodiment and comparative example are all 100% degree of crystallinity benchmark with it.
Embodiment 1
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first by the hydrochloric acid soln of inactivation pimelinketone oximate catalyst S H-B and the 1mol/L after roasting mixing making beating, then by mixed serum mix and blend reflow treatment 2 hours at 120 DEG C, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:20, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washes with water, and dries 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain molecular sieve.Its XRD crystalline phase figure is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 2
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first by the hydrochloric acid soln of inactivation pimelinketone oximate catalyst S H-B and the 5mol/L after roasting mixing making beating, then by mixed serum mix and blend reflow treatment 1 hour at 160 DEG C, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:10, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washes with water, and dries 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain molecular sieve.Its XRD crystalline phase figure is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 3
The present embodiment illustrates method provided by the invention and product.
Be at normal temperatures and pressures, first by the salpeter solution of inactivation pimelinketone oximate catalyst S H-B and the 8mol/L after roasting mixing making beating, then by mixed serum mix and blend reflow treatment 2 hours at 100 DEG C, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:5, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washes with water, and dries 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain molecular sieve.Its XRD crystalline phase figure is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 4
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first by the sulphuric acid soln of inactivation pimelinketone oximate catalyst S H-B and the 5mol/L after roasting mixing making beating, then by mixed serum mix and blend reflow treatment 1 hour at 120 DEG C, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:30, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washes with water, and dries 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain molecular sieve.Its XRD crystalline phase figure is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 5
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first by the sulphuric acid soln of pimelinketone oximate catalyst S H-B and the 2mol/L of the inactivation after roasting mixing making beating, then by mixed serum mix and blend reflow treatment 5 hours at 170 DEG C, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:2, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washes with water, and dries 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain molecular sieve.Its XRD crystalline phase figure is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 6
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first by the acetic acid solution of pimelinketone oximate catalyst S H-B and the 12mol/L of the inactivation after roasting mixing making beating, then by mixed serum mix and blend reflow treatment 6 hours at 160 DEG C, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:10, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washes with water, and dries 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain molecular sieve.Its XRD crystalline phase figure is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 7
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first by the sulphuric acid soln of pimelinketone oximate catalyst S H-B and the 0.5mol/L of the inactivation after roasting mixing making beating, then by mixed serum mix and blend reflow treatment 4 hours at 130 DEG C, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:45, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washes with water, and dries 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain molecular sieve.Its XRD crystalline phase figure is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 8
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first by the phosphoric acid solution of pimelinketone oximate catalyst S H-B and the 15mol/L of the inactivation after roasting mixing making beating, then by mixed serum mix and blend reflow treatment 3 hours at 180 DEG C, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:20, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washes with water, and dries 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain molecular sieve.Its XRD crystalline phase figure is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 9
The present embodiment illustrates method provided by the invention and product.
Prepare molecular sieve according to the method for embodiment 8, consist of the pimelinketone oximate catalyzer of inactivation unlike material mole: acid=100:5.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 10
The present embodiment illustrates method provided by the invention and product.
Prepare molecular sieve according to the method for embodiment 8, consist of the pimelinketone oximate catalyzer of inactivation unlike material mole: acid=100:100.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 11
The present embodiment illustrates method provided by the invention and product.
Prepare molecular sieve according to the method for embodiment 8, the concentration unlike raw material phosphoric acid is 0.2mol/L.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 12
The present embodiment illustrates method provided by the invention and product.
Preparing molecular sieve according to the method for embodiment 8, is the TS-1 molecular sieve after roasting unlike raw material.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 13
The present embodiment illustrates method provided by the invention and product.
Molecular sieve is prepared, unlike mixed serum airtight static process 3 hours at 180 DEG C according to the method for embodiment 8.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Embodiment 14
The present embodiment illustrates method provided by the invention and product.
Prepare molecular sieve according to the method for embodiment 2, substitute hydrochloric acid unlike with phosphoric acid.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Comparative example 2
The situation that this comparative example illustrates without the pimelinketone oximate catalyzer of the inactivation of roasting when being raw material.
Preparing molecular sieve according to the method for embodiment 8, is the pimelinketone oximate catalyst S H-1 of inactivation unlike raw material.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Comparative example 3
This comparative example illustrates prepares S-1 sieve sample according to the method for embodiment in CN1338427A 1.
The data such as relative crystallinity, pore volume, total specific surface area, external surface area, 0.9 ~ 1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield of sample are in table 1.
Table 1
As can be seen from Table 1: its relative crystallinity of si molecular sieves prepared by the preferred process of the present invention and yield are all better than comparative example.In addition, its pore volume of si molecular sieves that prepared by the preferred process of the present invention is greater than 0.3cm
3/ g, total specific surface area 200 ~ 400m
2/ g, wherein, outer surface area 30 ~ 150m
2/ g, and outer surface area accounts for the ratio of total specific surface area between 10% ~ 55%.
Claims (11)
1. a si molecular sieves, it is characterized in that this molecular sieve has MFI crystalline structure, its pore volume is greater than 0.3cm
3/ g, total specific surface area 200 ~ 400m
2/ g, outer surface area 30 ~ 150m
2/ g, and the ratio that outer surface area accounts for total specific surface area is 10% ~ 55%; This molecular sieve is at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity that records under the condition of 1 hour is at least 75mg/g molecular sieve, N
2under Static Adsorption test, there is the micropore size of 0.9 ~ 1.5nm scope and the said micropore size with 0.9 ~ 1.5nm scope accounts for ratio>=5% of total pore size distribution amount.
2. according to the si molecular sieves of claim 1, wherein, said pore volume is at 0.3 ~ 0.5cm
3/ g, the ratio that said outer surface area accounts for total specific surface area is 10% ~ 35%.
3. according to the si molecular sieves of claim 1, wherein, said at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity that records under the condition of 1 hour is at least 100mg/g molecular sieve.
4. according to the si molecular sieves of claim 1, wherein, the said micropore size with 0.9 ~ 1.5nm scope accounts for ratio >=10% of total pore size distribution amount.
5. according to the si molecular sieves of claim 1, wherein, the said micropore size with 0.9 ~ 1.5nm scope accounts for ratio >=15% of total pore size distribution amount.
6. according to the si molecular sieves of claim 1, wherein, the said micropore size with 0.9 ~ 1.5nm scope accounts for the ratio of total pore size distribution amount 15 ~ 30%.
7. the preparation method of the si molecular sieves of one of claim 1 ~ 6, it is characterized in that the HTS of the MFI crystalline structure of inactivation after roasting, mix with the acid solution of volumetric molar concentration >0.1mol/L again and pull an oar and process 0.5 ~ 36 hour at 10 ~ 200 DEG C, reclaim product and obtain si molecular sieves, wherein, with SiO
2meter inactivation MFI crystalline structure HTS with H
+the molar ratio of the acid of meter is 100:(5 ~ 200).
8., according to the method for claim 7, wherein the HTS of the MFI crystalline structure of said inactivation is the pimelinketone oximate catalyzer of inactivation.
9., according to the method for claim 8, the wherein pimelinketone oximate catalyzer of said inactivation, its activity is down to less than 50% of initial activity.
10. according to the method for claim 7, the volumetric molar concentration >=1mol/L of wherein acid in said acid solution.
11. according to the method for claim 7, wherein said process, is to reflux 1 ~ 24 hour at 100 ~ 180 DEG C.
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| CN106031882A (en) * | 2015-03-10 | 2016-10-19 | 中国石油化工股份有限公司 | Molecular sieve containing precious metals, preparation method and applications thereof, and alkene direct oxidation method |
| CN106032277B (en) * | 2015-03-10 | 2018-09-28 | 中国石油化工股份有限公司 | Titanium Si-Al molecular sieve and its preparation method and application and a kind of method of cyclic ketones oxidation |
| CN106032279B (en) * | 2015-03-10 | 2018-09-28 | 中国石油化工股份有限公司 | Si-Al molecular sieve and its preparation method and application and a kind of method of cyclic ketones conversion |
| CN106032283B (en) * | 2015-03-10 | 2018-09-28 | 中国石油化工股份有限公司 | Tin Titanium Sieve Molecular Sieve and its preparation method and application and a kind of method of cyclic ketones oxidation |
| CN106915753B (en) * | 2015-12-24 | 2019-07-23 | 中国石油化工股份有限公司 | Modified with noble metals Titanium Sieve Molecular Sieve and its preparation method and application and a kind of method of alkene direct oxidation |
| CN107400051B (en) * | 2016-05-20 | 2021-01-08 | 中国石油化工股份有限公司 | Method for preparing p-benzoquinone |
| CN107840346B (en) * | 2016-09-21 | 2019-07-19 | 中国石油化工股份有限公司 | A kind of application of the preparation method of silica zeolite, processing method and silica zeolite, catalyst and catalyst |
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