CN101462740B - Method for preparing ZSM-5 zeolite by in situ crystallization - Google Patents
Method for preparing ZSM-5 zeolite by in situ crystallization Download PDFInfo
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- CN101462740B CN101462740B CN2007101799806A CN200710179980A CN101462740B CN 101462740 B CN101462740 B CN 101462740B CN 2007101799806 A CN2007101799806 A CN 2007101799806A CN 200710179980 A CN200710179980 A CN 200710179980A CN 101462740 B CN101462740 B CN 101462740B
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Abstract
The invention relates to a method for preparing ZSM-5 zeolite through in-situ crystallization, which comprises that: kaolin slurry containing kaolin, adhesive and water is prepared into kaolin microspheres through spray drying, and the prepared kaolin microspheres are baked; silicon-enriched clay slurry containing silicon-enriched clay, adhesive and water is prepared into silicon-enriched clay microspheres through spray drying, and the prepared silicon-enriched clay microspheres are baked; and the respectively baked kaolin microspheres and silicon-enriched clay microspheres are mixed with a water solution containing alkali, and the mixture is subjected to in-situ hydrothermal crystallization to obtain crystallization product, wherein the mol ratio of SiO2 to Al2O3 in the silicon-enriched clay is more than 2. The ZSM-5 zeolite prepared by the method has high content of zeolite and rich middle holes, so the ZSM-5 zeolite can be used as a catalyst in the field of petrochemical industry.
Description
Technical field
The present invention relates to a kind of method of preparing ZSM-5 zeolite by in situ crystallization.
Background technology
The ZSM-5 zeolite from 1972 by U.S. Mobil company reported first (USP3702886) since, because the three-dimensional open-framework and the shape selective catalysis effect of ZSM-5 zeolite uniqueness, therefore it has the characteristic of high silica alumina ratio and oleophilic drainage, have the high and high characteristics of catalytic activity of heat endurance simultaneously, be widely used as the catalyst of the whole bag of tricks.
Shown that the ZSM-5 zeolite is useful especially catalyst relating to aromatic compounds, particularly having in the reaction of aromatic compounds of single carbocyclic ring.Therefore, to the conversion reaction of aromatic compounds and in the reaction as isomerization, alkylation, dealkylation and the transalkylation of aromatic compounds, the ZSM-5 zeolite all demonstrates unique selectivity at alkene, naphthalene, alcohol, ether and alkane.The ZSM-5 zeolite also is widely used in catalytic cracking and catalytic dewaxing.The ZSM-5 zeolite being used for the catalytic cracking of oil, can making the octane number of gasoline obtain to improve, also is the important means of propylene enhancing simultaneously.
In the prior art of preparation ZSM-5 zeolite, by two kinds of technology the activated zeolite component is incorporated in the catalyst microballoon usually, a kind of technology is with the zeolite component crystallization, to be attached in the microballoon in independent step then; Another kind of technology, promptly the technology of in-situ crystallization at first forms microballoon, then in microballoon self crystalline zeolite component, so that the microballoon that contains zeolite component to be provided.
For many years, the commercial ZSM-5 zeolite of part synthesizes and prepares by containing kaolinic precursor microballoon original position, and wherein kaolin was calcined under different conditions before forming microballoon by spray-drying.
" kaolin microsphere synthetic ZSM-5 zeolite and catalytic cracking performance " thereof (people such as Sun Shuhong, " silicate journal ", 2006, Vol.34 discloses the method for the synthetic ZSM-5 zeolite of a kind of kaolin microsphere in No.6:757-761), and this method comprises, with kaolin 950-1000 ℃ of high-temperature roasting of process earlier, mix by 1: 0.4: 5 mass ratio with NaOH, water, 95 ℃ of reactions 2 hours, reactant mixture after filtration, washing, dry back be standby again.Then with kaolin, ZSM-5 crystal seed and Ludox by calcination after 70: 5: 25 ratio of quality mix, after stirring, the microballoon of 20-110 micron is made in spray-dried moulding, after 950-1000 ℃ of high-temperature roasting, mix with NaOH, sodium chloride, n-butylamine and water, each constituent content is 0.46Na in the mixture
2OSiO
20.09C
4H
11N28H
2O, mixture are transferred in the stainless cylinder of steel of being furnished with teflon lined, and 150 ℃ of crystallization 72 hours, separation, suction filtration, washing, drying obtained crystallization product.Crystallization product carries out ion-exchange through 600 ℃ of roastings and falls sodium and handle after 4 hours, drying obtains containing the microballoon of ZSM-5 zeolite.The method that adopts this method to prepare the ZSM-5 zeolite is comparatively complicated, and crystallization time reaches 72 hours, and after the crystallization in the microballoon content of ZSM-5 zeolite lower, and micropore area and micro pore volume are less.
USP 6,908,603 disclose the method for a kind of ZSM-5 of preparation, this method comprises the formation aqueous reaction mixture, this reactant mixture comprises burnt kaolin microsphere, is characterized as the seed-solution and the silicate that promote the zeolite Y crystal growth, the silica of described reactant mixture and the mol ratio of activated alumina are at least 20, and pH is less than 14; Described mixture is at high temperature reacted a period of time, and to form in-situ ZSM-5-5 crystal on described microballoon, wherein, described aqueous reaction mixture does not contain organic template and does not contain the ZSM-5 crystal seed.But adopt the ZSM-5 zeolite content of zeolite product of this method preparation lower, and micropore area and micro pore volume are less.
Summary of the invention
The ZSM-5 zeolite content that the objective of the invention is to overcome zeolite product prepared in the above-mentioned prior art is lower, and micropore area and micro pore volume smaller defect, provide a kind of ZSM-5 zeolite content of zeolite product higher, and the method for the bigger preparing ZSM-5 zeolite by in situ crystallization of micropore area and micro pore volume.
The invention provides a kind of method of preparing ZSM-5 zeolite by in situ crystallization, this method comprises: will contain the spray-dried kaolin microsphere of making of kaolin slurry of kaolin, bonding agent and water, and the kaolin microsphere of making is carried out roasting; Other will contain the spray-dried Silicon-rich clay microphere of making of Silicon-rich clay slurry of Silicon-rich clay, bonding agent and water, and the Silicon-rich clay microphere of making is carried out roasting; With kaolin microsphere after the roasting and the Silicon-rich clay microphere after the roasting and after containing the aqueous solution of alkali, the gained mixture is carried out the original position hydrothermal crystallizing, obtain crystallization product; The SiO of wherein said Silicon-rich clay
2/ Al
2O
3Mol ratio is greater than 2.
When preparation ZSM-5 zeolite, if adopt single kaolin microsphere, must be by high-temperature roasting, the system alumina content of making minimizes, and improves system SiO
2/ Al
2O
3Ratio.Because the system alumina content is low, causes final crystallization product mesolite content low.Because sintering temperature is too high, causes the bulk density of zeolite system big, micropore area and micro pore volume are little, and this zeolite then is difficult for fluidisation if be used for the FCC process.The inventor is through discovering, carries out crystallization after kaolin microsphere by roasting respectively and Silicon-rich clay mix, and can increase microsphere system SiO
2/ Al
2O
3Molar ratio effectively improves the zeolite content of crystallization product, improves the micropore area and the micro pore volume of crystallization product, and the hydrothermal stability of ZSM-5 zeolite is improved.
According to the method for preparing ZSM-5 zeolite by in situ crystallization provided by the invention, kaolin microsphere by roasting respectively and Silicon-rich clay microphere carry out crystallization after mixing, and can improve the active SiO of crystallization system
2/ Al
2O
3Molar ratio can improve the micropore area and the micro pore volume of product, effectively improves the zeolite content of crystallization product, and ZSM-5 zeolite product hydrothermal stability is improved.Therefore, therefore the ZSM-5 zeolite product that adopts method preparation of the present invention can be used in the petrochemical industry as catalyst owing to zeolite content height, mesopore are abundant.
Description of drawings
Fig. 1 is the XRD spectra of prepared ZSM-5 zeolite product in the embodiment of the invention 1;
Fig. 2 is the XRD spectra of prepared ZSM-5 zeolite product in the embodiment of the invention 7;
Fig. 3 is the SEM figure of prepared ZSM-5 zeolite product in the embodiment of the invention 6.
The specific embodiment
The method of preparing ZSM-5 zeolite by in situ crystallization provided by the invention comprises: will contain the spray-dried kaolin microsphere of making of kaolin slurry of kaolin, bonding agent and water, and the kaolin microsphere of making is carried out roasting; Other will contain the spray-dried Silicon-rich clay microphere of making of Silicon-rich clay slurry of Silicon-rich clay, bonding agent and water, and the Silicon-rich clay microphere of making is carried out roasting; With kaolin microsphere after the roasting and the Silicon-rich clay microphere after the roasting and after containing the aqueous solution of alkali, the gained mixture is carried out the original position hydrothermal crystallizing, obtain crystallization product; The SiO of wherein said Silicon-rich clay
2/ Al
2O
3Mol ratio is greater than 2.
According to method provided by the invention, in the preferred case, in described mixture, the weight ratio of kaolin microsphere after the described roasting and the Silicon-rich clay microphere after the roasting is 1: 0.1-10.
According to method provided by the invention, in the preferred case, in described kaolin slurry, be in the kaolin of butt and weight ratio in the bonding agent of butt, kaolin: bonding agent=1: 0.1-10, the solid content of described kaolin slurry are 30-60 weight %; In described Silicon-rich clay slurry, be the Silicon-rich clay in the Silicon-rich clay of butt and weight ratio in the bonding agent of butt: bonding agent=1: 0.1-10, the solid content of described Silicon-rich clay slurry are 30-60 weight %.
According to method provided by the invention, described Silicon-rich clay is defined as SiO
2/ Al
2O
3Mol ratio is greater than 2 clay, for example can be in diatomite, bentonite, imvite, attapulgite, pyrophillite and the perlite one or more.
According to method provided by the invention, described kaolin is defined as SiO
2/ Al
2O
3Mol ratio is the clay of 1.5-2, and for example described kaolin is one or more in hydrous kaolin, metakaolin and the kaolin that is higher than 950 ℃ of roastings.
According to method provided by the invention, described bonding agent can be the various bonding agents that are used to prepare microballoon that well known to a person skilled in the art, for example this bonding agent can be in silicon gel, Ludox and the waterglass one or more.
According to method provided by the invention, in the preferred case, described kaolin slurry and/or Silicon-rich clay slurry also contain zeolite seed crystal, add zeolite seed crystal and can shorten crystallization induction period.Described zeolite seed crystal is to be selected from ZSM-5 type, Y type, X type, A type, β type and the SAPO type zeolite one or more.In described kaolin slurry, be 1 in the kaolin and the described zeolite seed crystal weight ratio of butt: 0.01-0.05; In described Silicon-rich clay slurry, be 1 in the Silicon-rich clay of butt and the weight ratio of described zeolite seed crystal: 0.01-0.05.
According to method provided by the invention, in the preferred case, in order to improve SiO
2/ Al
2O
3Mol ratio can also be added the silicon source again in described slurries, described silicon source is silica gel and/or estersil, and with the butt calculating of the described slurries of 100 weight portions, the consumption in described silicon source is with SiO
2Count the 5-50 weight portion.
According to method provided by the invention, will obtain the microballoon that average particulate diameter is 20-110 μ m after this kaolin slurry and the Silicon-rich clay slurry spray-drying respectively.Usually adopt spray drying tower separately these two kinds of slurries to be carried out spray-drying, the nozzle bore of this drying tower is 3-3.5mm, and atomisation pressure is 8-12MPa, and inlet temperature of stabilizer is 600-650 ℃, and exhaust temperature is 220-300 ℃.
According to method provided by the invention, preferably made microballoon is washed with water to remove sodium ion.
According to method provided by the invention, the described temperature that the kaolin microsphere of making is carried out roasting is 700-1200 ℃, is preferably 850-1000 ℃ that the time is 0.1-10 hour, is preferably 0.5-6 hour; The described temperature that the Silicon-rich clay microphere of making is carried out roasting is 150-750 ℃, is preferably 300-650 ℃ that the time is 0.1-10 hour, is preferably 0.5-6 hour.
According to method provided by the invention, in the preferred case, describedly the kaolin microsphere of making is carried out roasting comprise kaolin microsphere with the alkali roasting; Describedly the Silicon-rich clay microphere of making is carried out roasting comprise the Silicon-rich clay microphere with the alkali roasting.Silicon in kaolin and the Silicon-rich clay can be activated like this, increase utilization, obtain the silica alumina ratio that needs silicon in kaolin and the Silicon-rich clay.The consumption of described alkali is that to make the weight ratio of butt microballoon and alkali be 1: 0.01-0.7, described alkali are one or more in NaOH, sodium carbonate and the sodium acid carbonate.
According to method provided by the invention, in the preferred case, kaolin microsphere after the roasting and/or the Silicon-rich clay microphere after the roasting are carried out sour extracting processing, and then carry out described original position hydrothermal crystallizing.Handle carrying out extracting, can reduce the content of aluminium oxide in this microballoon, be beneficial to improve silica alumina ratio with kaolin microsphere after the acid solution processing roasting and/or the Silicon-rich clay microphere after the roasting.Described acid-treated method comprises, under 50-140 ℃ temperature, kaolin microsphere after the described roasting and/or the Silicon-rich clay microphere after the roasting is contacted 0.5-4 hour with acid solution.Described acid can be adopted various acid, for example is in hydrochloric acid, sulfuric acid, nitric acid and the orthophosphoric acid one or more.The concentration of the acid solution that is adopted is at least 1M, preferably is at least 3M, most preferably is at least 5M.Acid solution and butt kaolin microsphere or respectively be preferably 2-10: 1 with the weight ratio of butt Silicon-rich clay microphere.
According to method provided by the invention, the method for carrying out the original position hydrothermal crystallizing comprises that with the kaolin microsphere after the roasting and Silicon-rich clay microphere after the roasting and the aqueous solution that contains alkali, the mixture to gained carries out the original position hydrothermal crystallizing then, obtains crystallization product.The consumption of described alkali is to make total active SiO in the described mixture
2With OH
-Mol ratio be 1: 0.04-0.4.Employed alkali adopts NaOH usually for well known to a person skilled in the art alkali.
" active SiO as herein described
2" expression implication be, in the microballoon high-temperature calcination process, the part Si O in the microballoon
2Meeting and Al
2O
3Reaction generates spinelle and/or mullite, this part SiO
2In hydrothermal crystallization process, can not be converted into zeolite, another part SiO
2The SiO that in roasting, still keeps amorphous state
2, and in hydrothermal crystallization process, can be converted into zeolite, this part SiO
2Be referred to as active SiO
2
Active SiO
2The Determination on content method is as follows:
Kaolin microsphere or the Silicon-rich clay microphere got after the 5g roasting add in the conical flask, add 15% sodium hydroxide solution 25mL, constant temperature 1h in 85 ℃ water-bath then, and intermittently shake, filter then, sodium hydroxide solution flushing solid product with 0.5mol/L, filtrate is moved in the volumetric flask of 250mL, the sodium hydroxide solution that adds 0.5mol/L is 250mL to volume, and the amount of the silica of employing stoechiometric process analysis and NaOH reaction and the percentage of microballoon weight are active silica content.
According to method provided by the invention, in the preferred case, in described mixture, also contain organic formwork agent A, the consumption of described organic formwork agent A is to make total active SiO in the described mixture
2With the mol ratio of A be 1: 0.04-0.4.Described organic formwork agent can adopt and well known to a person skilled in the art various organic formwork agents, and for example described organic formwork agent can be in tetramethyl-ammonium chloride, 4-propyl bromide, positive propyl bromo, tetrapropylammonium hydroxide, n-propylamine and the n-butylamine one or more.
According to method provided by the invention, the method of described crystallization can adopt and well known to a person skilled in the art the whole bag of tricks, for example can adopt thermostatic crystallization or multistage variable temperature crystallization, in adopting above-mentioned two kinds of crystallization methods, specifically can adopt static crystallization, dynamic crystallization or batch (-type) dynamic crystallization.
According to method provided by the invention, the step of the mixture of gained being carried out obtaining behind the original position hydrothermal crystallizing crystallization product comprises separating solids product, suction filtration, washing and dry.
According to method provided by the invention, the condition of described crystallization is known in those skilled in the art, is 110-200 ℃ at crystallization temperature for example, and crystallization time is 8-30 hour.Can also be under 0-100 ℃ temperature before the crystallization ageing a period of time, for example 0.5-24 hour.
According to method provided by the invention, in selectable embodiment, this method also comprises carries out roasting with described crystallization product, carries out the ammonium exchange then.The condition of described roasting is for well known to a person skilled in the art, for example 350-650 ℃ roasting temperature 0.5-4 hour.The method of described ammonium exchange is known in those skilled in the art, and purpose is the sodium ion exchange is made the ZSM-5 zeolite product of Hydrogen.Especially for the mixture that contains the template agent, need carry out roasting after the crystallization, the template agent is removed.
Adopt the mode of embodiment that the present invention is described in further detail below.
Embodiment 1
1, preparation kaolin microsphere
Kaolin, Ludox and water added in the glue jar mix homogeneous, obtaining solid content is 30 weight % kaolin slurries, and this kaolin slurry spray-drying is obtained the kaolin microsphere that average particulate diameter is 50 μ m.The ratio that with the decationized Y sieve water of pH=2-4 in the mass ratio with kaolin microsphere is 10: 1 is with twice of kaolin microsphere washing.Raw material properties sees Table 1, and each composition sees Table 2 with the composition content that butt calculates in the slurries.
Table 1
Table 2
2, preparation Silicon-rich clay microphere
The Silicon-rich clay adopts diatomite.In addition diatomite, Ludox and water are added other becoming in the glue jar and mix homogeneous, obtaining solid content is 60 weight % Silicon-rich clay slurries, and this Silicon-rich clay slurry spray-drying is obtained the Silicon-rich clay microphere that average particulate diameter is 50 μ m.The ratio that with the decationized Y sieve water of pH=2-4 in the mass ratio with the Silicon-rich clay microphere is 10: 1 is with twice of Silicon-rich clay microphere washing.Raw material properties sees Table 1, and each composition sees Table 2 with the composition content that butt calculates in the slurries.
3, difference roasting kaolin microballoon and Silicon-rich clay microphere and original position hydrothermal crystallizing
Kaolin microsphere after the washing 950 ℃ roasting temperature 2 hours, is obtained the kaolin microsphere after the roasting, active SiO in the kaolin microsphere after this roasting
2Content be 39 weight %.
Silicon-rich clay microphere after the washing 300 ℃ roasting temperature 2 hours, is obtained the Silicon-rich clay microphere after the roasting, active SiO in the Silicon-rich clay microphere after this roasting
2Content be 90 weight %.
Get kaolin microsphere after the 15g roasting and the Silicon-rich clay microphere after the 6g roasting, mix wherein active SiO with 1.8g NaOH, 3.5g n-butylamine and 76g water
2With OH
-Mol ratio be 1: 0.24, active SiO
2With the mol ratio of n-butylamine be 1: 0.25.Resulting mixture immigration is provided with in the stainless steel still of teflon lined, and dynamic crystallization is 17 hours under 150 ℃ temperature, and separating solids product, suction filtration, washing and dry obtain crystallization product then.With the crystallization product that obtains 550 ℃ roasting temperature 2 hours.
The water of the crystallization product after the above-mentioned roasting of 1 weight portion and 0.3 weight portion ammonium sulfate and 10 weight portions is mixed, stirred 0.5 hour down, repeat 3 times, so carry out the ammonium exchange to remove sodium ion at 80 ℃.Then drying obtains product under 120 ℃ temperature.
The XRD diffraction pattern of this product shows that this product is the product that contains the ZSM-5 zeolite as shown in Figure 1.
Embodiment 2
1, preparation kaolin microsphere
Kaolin, ZSM-5 zeolite seed crystal, Ludox added in the glue jar with water mix homogeneous, obtaining solid content is 40 weight % kaolin slurries, and this kaolin slurry spray-drying is obtained the kaolin microsphere that average particulate diameter is 60 μ m.The ratio that with the decationized Y sieve water of pH=2-4 in the mass ratio with kaolin microsphere is 10: 1 is with twice of kaolin microsphere washing.Raw material properties sees Table 1, and each composition sees Table 2 with the composition content that butt calculates in the slurries.
2, preparation Silicon-rich clay microphere
The Silicon-rich clay adopts diatomite and pyrophillite.In addition diatomite, pyrophillite, Ludox and water are added other becoming in the glue jar and mix homogeneous, obtaining solid content is 50 weight % Silicon-rich clay slurries, and this Silicon-rich clay slurry spray-drying is obtained the Silicon-rich clay microphere that average particulate diameter is 70 μ m.The ratio that with the decationized Y sieve water of pH=2-4 in the mass ratio with the Silicon-rich clay microphere is 10: 1 is with twice of Silicon-rich clay microphere washing.Raw material properties sees Table 1, and each composition sees Table 2 with the composition content that butt calculates in the slurries.
3, difference roasting kaolin microballoon and Silicon-rich clay microphere and original position hydrothermal crystallizing
Kaolin microsphere after the washing 850 ℃ roasting temperature 2.5 hours, is obtained the kaolin microsphere after the roasting, active SiO in the kaolin microsphere after this roasting
2Content be 62 weight %.
Silicon-rich clay microphere after the washing 500 ℃ roasting temperature 3 hours, is obtained the Silicon-rich clay microphere after the roasting, active SiO in the Silicon-rich clay microphere after this roasting
2Content be 55 weight %.
Get kaolin microsphere after the 21g roasting and the Silicon-rich clay microphere after the 3g roasting, mix wherein active SiO with 1.42g NaOH and 87g water
2With OH
-Mol ratio be 1: 0.14.Resulting mixture immigration is provided with in the stainless steel still of teflon lined, and static crystallization is 26 hours under 170 ℃ temperature, and separating solids product, suction filtration, washing and dry obtain crystallization product then.With the crystallization product that obtains 550 ℃ roasting temperature 2 hours.
The water of the crystallization product after the above-mentioned roasting of 1 weight portion and 0.3 weight portion ammonium sulfate and 10 weight portions is mixed, stirred 0.5 hour down, repeat 3 times, so carry out the ammonium exchange to remove sodium ion at 80 ℃.Then drying obtains product under 120 ℃ temperature.
The product that the XRD diffraction pattern of this product and embodiment 1 make is similar, shows that this product is the product that contains the ZSM-5 zeolite.
Embodiment 3
1, preparation kaolin microsphere
Kaolin, y-type zeolite crystal seed, Ludox added in the glue jar with water mix homogeneous, obtaining solid content is 30 weight % kaolin slurries, and this kaolin slurry spray-drying is obtained the kaolin microsphere that average particulate diameter is 80 μ m.The ratio that with the decationized Y sieve water of pH=2-4 in the mass ratio with kaolin microsphere is 10: 1 is with twice of kaolin microsphere washing.Raw material properties sees Table 1, and each composition sees Table 2 with the composition content that butt calculates in the slurries.
2, preparation Silicon-rich clay microphere
The Silicon-rich clay adopts bentonite.In addition bentonite, waterglass and water are added other becoming in the glue jar and mix homogeneous, obtaining solid content is 30 weight % Silicon-rich clay slurries, and this Silicon-rich clay slurry spray-drying is obtained the Silicon-rich clay microphere that average particulate diameter is 70 μ m.The ratio that with the decationized Y sieve water of pH=2-4 in the mass ratio with the Silicon-rich clay microphere is 10: 1 is with twice of Silicon-rich clay microphere washing.Raw material properties sees Table 1, and each composition sees Table 2 with the composition content that butt calculates in the slurries.
3, difference roasting kaolin microballoon and Silicon-rich clay microphere and original position hydrothermal crystallizing
Kaolin microsphere after the washing 1000 ℃ roasting temperature 1.5 hours, is obtained the kaolin microsphere after the roasting, active SiO in the kaolin microsphere after this roasting
2Content be 58 weight %.
Silicon-rich clay microphere after the washing 550 ℃ roasting temperature 2 hours, is obtained the Silicon-rich clay microphere after the roasting, active SiO in the Silicon-rich clay microphere after this roasting
2Content be 63 weight %.
Get kaolin microsphere after the 6g roasting and the Silicon-rich clay microphere after the 22.6g roasting, mix wherein active SiO with 0.6g NaOH, 0.9g n-butylamine and 70g water
2With OH
-Mol ratio be 1: 0.05, active SiO
2With the mol ratio of n-butylamine be 1: 0.04.Resulting mixture immigration is provided with in the stainless steel still of teflon lined, in 1 hour, be warming up to 110 ℃ from room temperature, 110 ℃ of dynamic crystallizations 12 hours, in 1 hour, be warming up to 175 ℃ again from 110 ℃, 175 ℃ of following static crystallizations 12 hours, separating solids product, suction filtration, washing and dry obtain crystallization product then.With the crystallization product that obtains 550 ℃ roasting temperature 2 hours.
The water of the crystallization product after the above-mentioned roasting of 1 weight portion and 0.3 weight portion ammonium sulfate and 10 weight portions is mixed, stirred 0.5 hour down, repeat 3 times, so carry out the ammonium exchange to remove sodium ion at 80 ℃.Then drying obtains product under 120 ℃ temperature.
The product that the XRD diffraction pattern of this product and embodiment 1 make is similar, shows that this product is the product that contains the ZSM-5 zeolite.
Embodiment 4
1, preparation kaolin microsphere
Prepare kaolin microsphere according to the method for describing among the embodiment 1 for preparing kaolin microsphere.
2, preparation Silicon-rich clay microphere
The Silicon-rich clay adopts diatomite.In addition diatomite, SAPO-11 type zeolite seed crystal, Ludox and water are added other becoming in the glue jar and mix homogeneous, obtaining solid content is 50 weight % Silicon-rich clay slurries, and this Silicon-rich clay slurry spray-drying is obtained the Silicon-rich clay microphere that average particulate diameter is 60 μ m.The ratio that with the decationized Y sieve water of pH=2-4 in the mass ratio with the Silicon-rich clay microphere is 10: 1 is with twice of Silicon-rich clay microphere washing.Raw material properties sees Table 1, and each composition sees Table 2 with the composition content that butt calculates in the slurries.
3, difference roasting kaolin microballoon and Silicon-rich clay microphere and original position hydrothermal crystallizing
Kaolin microsphere after the washing 980 ℃ roasting temperature 2 hours, is obtained the kaolin microsphere after the roasting, active SiO in the kaolin microsphere after this roasting
2Content be 37 weight %.
Silicon-rich clay microphere after the washing 600 ℃ roasting temperature 2 hours, is obtained the Silicon-rich clay microphere after the roasting, active SiO in the Silicon-rich clay microphere after this roasting
2Content be 88 weight %.
Get kaolin microsphere after the 5.6g roasting and the Silicon-rich clay microphere after the 44.5g roasting, mix wherein active SiO with 8.78g NaOH, 12g n-propylamine and 360g water
2With OH
-Mol ratio be 1: 0.32, active SiO
2With the mol ratio of n-propylamine be 1: 0.29.Resulting mixture immigration is provided with in the stainless steel still of teflon lined, and dynamic crystallization is 8 hours under 180 ℃ temperature, and separating solids product, suction filtration, washing and dry obtain crystallization product then.With the crystallization product that obtains 550 ℃ roasting temperature 2 hours.
The water of the crystallization product after the above-mentioned roasting of 1 weight portion and 0.3 weight portion ammonium sulfate and 10 weight portions is mixed, stirred 0.5 hour down, repeat 3 times, so carry out the ammonium exchange to remove sodium ion at 80 ℃.Then drying obtains product under 120 ℃ temperature.
The product that the XRD diffraction pattern of this product and embodiment 1 make is similar, shows that this product is the product that contains the ZSM-5 zeolite.
1, preparation kaolin microsphere
Prepare kaolin microsphere according to the method for describing among the embodiment 1 for preparing kaolin microsphere.
2, preparation Silicon-rich clay microphere
The Silicon-rich clay adopts bentonite.In addition bentonite, Beta zeolite seed crystal, waterglass and water are added other becoming in the glue jar and mix homogeneous, obtaining solid content is 30 weight % Silicon-rich clay slurries, and this Silicon-rich clay slurry spray-drying is obtained the Silicon-rich clay microphere that average particulate diameter is 70 μ m.The ratio that with the decationized Y sieve water of pH=2-4 in the mass ratio with the Silicon-rich clay microphere is 10: 1 is with twice of Silicon-rich clay microphere washing.Raw material properties sees Table 1, and each composition sees Table 2 with the composition content that butt calculates in the slurries.
3, difference roasting kaolin microballoon and Silicon-rich clay microphere and original position hydrothermal crystallizing
Kaolin microsphere after the washing 1000 ℃ roasting temperature 2 hours, is obtained the kaolin microsphere after the roasting, active SiO in the kaolin microsphere after this roasting
2Content be 36 weight %.
Silicon-rich clay microphere after the washing 300 ℃ roasting temperature 1.6 hours, is obtained the Silicon-rich clay microphere after the roasting, active SiO in the Silicon-rich clay microphere after this roasting
2Content be 78 weight %.
Get kaolin microsphere after the 8.8g roasting and the Silicon-rich clay microphere after the 13.1g roasting, mix wherein active SiO with 3.65g NaOH, 6.25g n-butylamine and 150g water
2With OH
-Mol ratio be 1: 0.40, active SiO
2With the mol ratio of n-butylamine be 1: 0.38.Resulting mixture immigration is provided with in the stainless steel still of teflon lined, and dynamic crystallization is 24 hours under 150 ℃ temperature, and separating solids product, suction filtration, washing and dry obtain crystallization product then.With the crystallization product that obtains 550 ℃ roasting temperature 2 hours.
The water of the crystallization product after the above-mentioned roasting of 1 weight portion and 0.3 weight portion ammonium sulfate and 10 weight portions is mixed, stirred 0.5 hour down, repeat 3 times, so carry out the ammonium exchange to remove sodium ion at 80 ℃.Then drying obtains product under 120 ℃ temperature.
The product that the XRD diffraction pattern of this product and embodiment 1 make is similar, shows that this product is the product that contains the ZSM-5 zeolite.
Embodiment 6
1, preparation kaolin microsphere
Prepare kaolin microsphere according to the method for describing among the embodiment 2 for preparing kaolin microsphere.
2, preparation Silicon-rich clay microphere
Prepare the Silicon-rich clay microphere according to the method for describing among the embodiment 2 for preparing the Silicon-rich clay microphere.
3, difference roasting kaolin microballoon and Silicon-rich clay microphere and original position hydrothermal crystallizing
Kaolin microsphere after the washing with after NaOH mixes with 1: 0.08 weight ratio, 800 ℃ roasting temperatures 2 hours, is obtained the kaolin microsphere after the roasting, active SiO in the kaolin microsphere after this roasting
2Content be 60 weight %.
Silicon-rich clay microphere after the washing 350 ℃ roasting temperature 3 hours, is obtained the Silicon-rich clay microphere after the roasting, active SiO in the Silicon-rich clay microphere after this roasting
2Content be 56 weight %.
Get kaolin microsphere after the 22.6g roasting and the Silicon-rich clay microphere after the 15.3g roasting, mix wherein active SiO with 2.78g NaOH, 3.56g n-butylamine and 146g water
2With OH
-Mol ratio be 1: 0.19, active SiO
2With the mol ratio of n-butylamine be 1: 0.13.Resulting mixture moved into be provided with in the stainless steel still of teflon lined, in the room temperature ageing after 6 hours, be warming up to 175 ℃ of intermittently dynamic crystallizations 11 hours, separating solids product, suction filtration, washing and dry obtain crystallization product then.With the crystallization product that obtains 550 ℃ roasting temperature 2 hours.
The water of the crystallization product after the above-mentioned roasting of 1 weight portion and 0.3 weight portion ammonium sulfate and 10 weight portions is mixed, stirred 0.5 hour down, repeat 3 times, so carry out the ammonium exchange to remove sodium ion at 80 ℃.Then drying obtains product under 120 ℃ temperature.
The product that the XRD diffraction pattern of this product and embodiment 1 make is similar, shows that this product is the product that contains the ZSM-5 zeolite.The SEM figure of this product under ESEM sees Fig. 3, and as can be seen from the figure, it is good that the micro-sphere structure after the crystallization keeps, and ZSM-5 zeolite growth in situ is in microsphere surface.
Embodiment 7
1, preparation kaolin microsphere
Prepare kaolin microsphere according to the method for describing among the embodiment 3 for preparing kaolin microsphere.
2, preparation Silicon-rich clay microphere
Prepare the Silicon-rich clay microphere according to the method for describing among the embodiment 3 for preparing the Silicon-rich clay microphere.
3, difference roasting kaolin microballoon and Silicon-rich clay microphere and original position hydrothermal crystallizing
Kaolin microsphere after the washing with after NaOH mixes with 1: 0.03 weight ratio, 918 ℃ roasting temperatures 2 hours, is obtained the kaolin microsphere after the roasting, active SiO in the kaolin microsphere after this roasting
2Content be 60 weight %.
Silicon-rich clay microphere after the washing with after NaOH mixes with 1: 0.05 weight ratio, 500 ℃ roasting temperatures 1 hour, is obtained the Silicon-rich clay microphere after the roasting, active SiO in the Silicon-rich clay microphere after this roasting
2Content be 65 weight %.
Get kaolin microsphere after the 3.5g roasting and the Silicon-rich clay microphere after the 32g roasting, mix wherein active SiO with 4.75g NaOH 203g water
2With OH
-Mol ratio be 1: 0.31.Resulting mixture immigration is provided with in the stainless steel still of teflon lined, and dynamic crystallization is 8 hours under 185 ℃ temperature, and separating solids product, suction filtration, washing and dry obtain crystallization product then.With the crystallization product that obtains 550 ℃ roasting temperature 2 hours.
The water of the crystallization product after the above-mentioned roasting of 1 weight portion and 0.3 weight portion ammonium sulfate and 10 weight portions is mixed, stirred 0.5 hour down, repeat 3 times, so carry out the ammonium exchange to remove sodium ion at 80 ℃.Then drying obtains product under 120 ℃ temperature.
The XRD diffraction pattern of this product shows that this product is the product that contains the ZSM-5 zeolite as shown in Figure 2.
Embodiment 8
1, preparation kaolin microsphere
Prepare kaolin microsphere according to the method for describing among the embodiment 1 for preparing kaolin microsphere.
2, preparation Silicon-rich clay microphere
Prepare the Silicon-rich clay microphere according to the method for describing among the embodiment 5 for preparing the Silicon-rich clay microphere.
3, difference roasting kaolin microballoon and Silicon-rich clay microphere and original position hydrothermal crystallizing
With the kaolin microsphere after the washing 750 ℃ roasting temperature 2 hours, obtain the kaolin microsphere after the roasting, the kaolin microsphere of getting after the 20g roasting adds in the there-necked flask, the hydrochloric acid that in there-necked flask, adds 176 gram 6M again, sour extracting processing was carried out in the water bath with thermostatic control stirring that there-necked flask is put into 85 ℃ in 2 hours, filter then and obtain solid product, follow the kaolin microsphere after washing and drying obtain sour extracting, active SiO in the kaolin microsphere after this roasting, acid are taken out
2Content be 43 weight %.
Silicon-rich clay microphere after the washing 540 ℃ roasting temperature 1 hour, is obtained the Silicon-rich clay microphere after the roasting, active SiO in the Silicon-rich clay microphere after this roasting
2Content be 77 weight %.
Get kaolin microsphere after the above-mentioned sour extracting of 18g and the Silicon-rich clay microphere after the 19g roasting, mix wherein active SiO with 1.21g NaOH, 1.89g n-butylamine and 75g water
2With OH
-Mol ratio be 1: 0.08, active SiO
2With the mol ratio of n-butylamine be 1: 0.07.Resulting mixture immigration is provided with in the stainless steel still of teflon lined, and dynamic crystallization is 20 hours under 150 ℃ temperature, and separating solids product, suction filtration, washing and dry obtain crystallization product then.With the crystallization product that obtains 550 ℃ roasting temperature 2 hours.
The water of the crystallization product after the above-mentioned roasting of 1 weight portion and 0.3 weight portion ammonium sulfate and 10 weight portions is mixed, stirred 0.5 hour down, repeat 3 times, so carry out the ammonium exchange to remove sodium ion at 80 ℃.Then drying obtains product under 120 ℃ temperature.
The product that the XRD diffraction pattern of this product and embodiment 1 make is similar, shows that this product is the product that contains the ZSM-5 zeolite.
Comparative Examples 1
Kaolin through 1000 ℃ high-temperature roasting, mixes by 1: 0.4: 5 mass ratio with NaOH, water earlier again, and reaction is 2 hours under 95 ℃ temperature, with reactant mixture after filtration, standby after the washing, drying.
With kaolin, ZSM-5 crystal seed and Ludox by calcination after 70: 5: 25 ratio of quality mix, obtaining solid content is 40 weight % kaolin slurries, after stirring, the microballoon of 60 μ m is made in spray-dried moulding, after 850 ℃ high-temperature roasting, mix with NaOH, sodium chloride, n-butylamine and water, each constituent content is 0.46Na in the mixture
2O: SiO
2: 0.09 n-butylamine: 28H
2O is provided with the mixture immigration in the stainless cylinder of steel of teflon lined, and crystallization is 72 hours under 170 ℃ temperature, and separating solids product, suction filtration, washing and dry obtain crystallization product then.The crystallization product that obtains is carried out the ammonium exchange to remove sodium ion at 550 ℃ roasting temperature after 2 hours, then drying obtains product.The product that the XRD diffraction pattern of this product and embodiment 1 make is similar, shows that this product is the product that contains the ZSM-5 zeolite.
Performance test
1, test microvia area, total specific area, micro pore volume and total pore volume
Use the U.S. ASAP2400 of Micromeritics company type to adsorb instrument automatically, adopt total specific area of low temperature static determination of nitrogen adsorption and micro pore volume.Total specific area adopts two B parameter ET equations to calculate, and the micropore area is calculated by the t-plot method.
The The pretreatment condition is: the degassing is 4 hours under 300 ℃ temperature, and vacuum is 1.33 * 10
-5Pa.
2, ZSM-5 zeolite content
The ZSM-5 zeolite content represents with relative crystallinity, and relative crystallinity is that the ratio of the peak area sum of five characteristic diffraction peaks of 2 θ between 22.5 °-25.00 ° in the XRD spectra of the peak area sum of five characteristic diffraction peaks of 2 θ between 22.5 °-25.00 ° in the XRD spectra of preparation-obtained product and ZSM-5 zeolite standard specimen is represented with percentage.The qualified ZSM-5 zeolite industrial products that standard specimen adopts commercially available Sinopec catalyst Co. Shandong branch company to produce are set at 100% with the degree of crystallinity of this product.
3, crystallization reservation degree
Crystallization reservation degree is: relative crystallinity * 100% of the relative crystallinity/aging preceding sample of aging back sample.
Aging condition is that hydrothermal aging is 17 hours under 800 ℃ temperature.
4, in heavy oil catalytic cracking process to the evaluation of ZSM-5 zeolite product
With the microballoon that contains the ZSM-5 zeolite for preparing under 800 ℃ temperature, in 100% water vapour aging 17 hours, as catalyst aid.Major catalyst adopts residual oil cracking agent DVR-3 poising agent (Sinopec Yanshan Petrochemical company).
In small fixed flowing bed heavy oil feedstock oil is carried out catalytic cracking, reaction temperature is 500 ℃, and the weight ratio of catalyst and heavy oil feedstock oil is 5.9.The heavy oil feedstock oil that is adopted is military three heavy oil (being that pipe defeated wax oil in Wuhan is mixed 30 weight % decompression residuum) that mix, and this raw material oil properties is as shown in table 3.
Table 3
According to above-mentioned 1,2 and 3 method of testing, embodiment 1-8 and Comparative Examples 1 prepared ZSM-5 zeolite product are carried out performance test, the results are shown in Table 4 for gained.
Table 4
As can be seen from Table 4, hydrothermal stability from specific area, pore volume, ZSM-5 zeolite content and ZSM-5 zeolite, the performance of the ZSM-5 zeolite product that embodiment of the invention 1-8 is prepared is all fine, all is better than the prepared ZSM-5 zeolite product of Comparative Examples 1.
Estimate according to 4 couples of embodiment 4 of above-mentioned method of testing and Comparative Examples 1 prepared ZSM-5 zeolite product, the results are shown in Table 5 for gained.
Table 5
(productive rate of conversion ratio=(dry gas+liquefied gas+gasoline+coke))
As can be seen from Table 5, adopt the prepared ZSM-5 zeolite product of the embodiment of the invention 4 as the comparing of FCC auxiliary agent and Comparative Examples 2, the productive rate of productivity of propylene and liquefied gas is higher.Therefore ZSM-5 zeolite product of the present invention can propylene enhancing in the FCC process, thereby can make the refinery obtain more economic benefit.
Claims (13)
1. the method for a preparing ZSM-5 zeolite by in situ crystallization, this method comprises: will contain the spray-dried kaolin microsphere of making of kaolin slurry of kaolin, bonding agent and water, and the kaolin microsphere of making is carried out roasting; Other will contain the spray-dried Silicon-rich clay microphere of making of Silicon-rich clay slurry of Silicon-rich clay, bonding agent and water, and the Silicon-rich clay microphere of making is carried out roasting; With kaolin microsphere after the roasting and the Silicon-rich clay microphere after the roasting and after containing the aqueous solution of alkali, the gained mixture is carried out the original position hydrothermal crystallizing, obtain crystallization product; The SiO of wherein said Silicon-rich clay
2/ Al
2O
3Mol ratio is greater than 2.
2. method according to claim 1, wherein, in described mixture, the weight ratio of kaolin microsphere after the described roasting and the Silicon-rich clay microphere after the roasting is 1: 0.1-10.
3. method according to claim 1, wherein, in described kaolin slurry, be kaolin in the kaolin of butt and weight ratio in the bonding agent of butt: bonding agent=1: 0.1-1, the solid content of described kaolin slurry are 30-60 weight %; In described Silicon-rich clay slurry, be the Silicon-rich clay in the Silicon-rich clay of butt and weight ratio in the bonding agent of butt: bonding agent=1: 0.1-1, the solid content of described Silicon-rich clay slurry are 30-60 weight %.
4. according to claim 1 or 3 described methods, wherein, described kaolin is one or more in hydrous kaolin, metakaolin and the kaolin that is higher than 950 ℃ of roastings; Described Silicon-rich clay is one or more in diatomite, bentonite, imvite, attapulgite, pyrophillite and the perlite; Described bonding agent is one or more in silicon gel, Ludox and the waterglass.
5. according to claim 1 or 3 described methods, wherein, described kaolin slurry and/or Silicon-rich clay slurry also contain zeolite seed crystal, and described zeolite seed crystal is to be selected from ZSM-5 type, Y type, X type, A type, β type and the SAPO type zeolite one or more; In the described kaolin slurry, be 1 in the kaolin of butt and the weight ratio of described zeolite seed crystal: 0.01-0.05; In the described Silicon-rich clay slurry, be 1 in the Silicon-rich clay of butt and the weight ratio of described zeolite seed crystal: 0.01-0.05.
6. method according to claim 1, wherein, the described temperature that the kaolin microsphere of making is carried out roasting is 700-1200 ℃, the time is 0.1-10 hour; The described temperature that the Silicon-rich clay microphere of making is carried out roasting is 150-750 ℃, and the time is 0.1-10 hour.
7. method according to claim 6, wherein, the described temperature that the kaolin microsphere of making is carried out roasting is 850-1000 ℃, the time is 0.5-6 hour; The described temperature that the Silicon-rich clay microphere of making is carried out roasting is 300-650 ℃, and the time is 0.5-6 hour.
8. according to claim 1,6 or 7 described methods, wherein, describedly the kaolin microsphere of making is carried out roasting comprise kaolin microsphere roasting after alkali mixes; Describedly the Silicon-rich clay microphere of making is carried out roasting comprise the roasting after alkali mixes of Silicon-rich clay microphere.
9. according to claim 1,6 or 7 described methods, wherein, described method also comprises, before carrying out described original position hydrothermal crystallizing, earlier kaolin microsphere after the roasting and/or the Silicon-rich clay microphere after the roasting are carried out sour extracting processing, the method that described sour extracting is handled is included under 50-140 ℃ the temperature, kaolin microsphere after the described roasting and/or the Silicon-rich clay microphere after the roasting are contacted 0.5-4 hour with acid solution, described acid solution with in the kaolin microsphere of butt and described acid solution and the 2-10 that respectively does for oneself in the weight ratio of the Silicon-rich clay microphere of butt: 1.
10. method according to claim 1, wherein, in described mixture, the consumption of described alkali is to make total active SiO in the described mixture
2With OH
-Mol ratio be 1: 0.04-0.4.
11. method according to claim 1 wherein, also contains organic formwork agent A in the described mixture, the consumption of described organic formwork agent A is to make total active SiO in the described mixture
2With the mol ratio of organic formwork agent A be 1: 0.04-0.4.
12. method according to claim 1, wherein, the condition of described crystallization is: crystallization temperature is 110-200 ℃, and crystallization time is 8-30 hour.
13. according to claim 1 or 11 described methods, this method also comprises carries out roasting with described crystallization product, carries out the ammonium exchange then.
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| CN102019196B (en) * | 2009-09-18 | 2012-12-12 | 中国石油天然气股份有限公司 | Method for improving pore structure of kaolin microsphere in-situ crystallization product |
| CN102372284B (en) * | 2010-08-23 | 2013-01-09 | 中国石油化工股份有限公司 | Method for preparing small crystal grain ZSM-5 zeolite |
| CN102886275B (en) * | 2011-07-18 | 2016-12-21 | 卓润生 | The preparation of a kind of in-situ crystallization is containing the method for bimolecular sieve Cracking catalyst |
| CN103848439B (en) * | 2012-11-29 | 2015-07-01 | 中国石油大学(北京) | Synthetic method of ZSM-5 type molecular sieve |
| CN104211086B (en) * | 2014-09-22 | 2016-04-13 | 湖南理工学院 | ZSM-5 zeolite molecular sieve and preparation method thereof |
| EP3280530B1 (en) * | 2015-04-09 | 2022-03-16 | BASF Corporation | Zsm-5 catalyst |
| CN106745054B (en) * | 2016-12-16 | 2019-04-12 | 西京学院 | A kind of preparation method of ZSM-5 molecular sieve |
| CN106745047B (en) * | 2016-12-16 | 2019-04-12 | 西京学院 | A kind of preparation method of modenite |
| CN116371456B (en) * | 2023-06-02 | 2023-09-15 | 潍坊正轩稀土催化材料有限公司 | Liquefied gas aromatization catalyst and preparation method thereof |
| CN116351460A (en) * | 2023-06-02 | 2023-06-30 | 潍坊正轩稀土催化材料有限公司 | Small-grain ZSM-5 catalytic cracking catalyst and preparation method thereof |
| CN116371457B (en) * | 2023-06-02 | 2023-09-15 | 潍坊正轩稀土催化材料有限公司 | Low-carbon alkane aromatization catalyst and preparation method thereof |
| CN116351462B (en) * | 2023-06-02 | 2023-09-15 | 潍坊正轩稀土催化材料有限公司 | Catalyst for preparing propylene from methanol and preparation method thereof |
| CN116351459B (en) * | 2023-06-02 | 2023-09-15 | 潍坊正轩稀土催化材料有限公司 | Methanol aromatization catalyst and preparation method thereof |
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