CN101792153B - Synthesizing method of gallosilicate molecule sieve Ga-ZSM-12 - Google Patents
Synthesizing method of gallosilicate molecule sieve Ga-ZSM-12 Download PDFInfo
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Abstract
The invention relates to a synthesizing method of a gallosilicate molecule sieve Ga-ZSM-12, belonging to the field of preparation of zeolite molecule sieve catalysts and solving the problems of high cost and low catalytic activity of a Ga-ZSM-12 molecule sieve synthesized by adopting a methyltriethylammonium bromide (MTEABr) template agent at present. The synthesizing method of the gallosilicate molecule sieve Ga-ZSM-12 comprises the following steps of: preparing an alkali source, a gallium source, a silicon source, a template agent and deionized water into a uniform mixture; crystallizing at160-200 DEG C for 4-6 days; cooling to room temperature; and filtering, washing, drying and roasting a product to prepare a pure-phase Ga-ZSM-12 molecule sieve. The synthesizing method has low synthesizing cost of the Ga-ZSM-12 molecule sieve; and in addition, the Ga-ZSM-12 molecule sieve can be outstandingly enhanced in catalytic property because a molecule sieve crystal has a secondary mesoporous structure and can be used in the fields of a petrochemical industry, an organic chemical industry, a fine chemical industry, and the like as a catalyst.
Description
Technical field
The invention belongs to the preparation field of zeolite [molecular sieve; Be specifically related to the method for synthetic Ga-ZSM-12 molecular sieve.
Background technology
The ZSM-12 molecular sieve is to have the MTW topological framework, has the non-intersection of the one-dimensional linear duct that twelve-ring constitutes, and the aperture is 0.57 * 0.61nm, belongs to high silicon class zeolite.This duct size between mesopore and large pore zeolite can realize the shape selective catalysis of most of organic molecules is transformed effectively, in reactions such as alkylating aromatic hydrocarbon, isomerizing, shows excellent catalytic performance, and application prospect is very wide.But because the duct size of ZSM-12 molecular sieve is less relatively, the diffusional resistance of the larger-size molecule of kinetics in its duct increases, and limited its application in the bulky molecular catalysis reaction to a certain extent.The successful preparation that has the ZSM-12 of meso-hole structure in recent years and since can improve to a certain extent more macromolecular product in its duct diffusion, its Application Areas is expected to further widen.
At present, the compound method with ZSM-12 of meso-hole structure mainly contains two kinds, and a kind of is that synthetic ZSM-12 molecular sieve is being carried out modification; Adopt methods such as alkali desiliconization, sour dealuminzation or steam treatment can in the microporous molecular sieve duct, form mesoporous passage; Help macromolecular cpd and diffuse into out the duct, reduce its diffusional resistance, though possibly improve the diffusion of product to a certain extent through the ZSM-12 molecular sieve of aforesaid method modification; If also maybe the micropore canals of molecular sieve be damaged but modified condition control is improper; Even causing the duct to subside, the result not only will reduce the acid site number, and hinder the diffusion of product on the contrary.Another kind method is exactly directly synthetic ZSM-12 molecular sieve with mesopore orbit structure.When the preparation mixed gel, add gallium oxide and replace the aluminium source; Directly synthetic gallosilicate molecule sieve Ga-ZSM-12 with meso-hole structure is to have solved the problems referred to above from the source, gallium is introduced in the skeleton structure of molecular sieve and has not only been produced meso-hole structure, can improve the diffusion of product effectively; Strengthen macromolecular conversion capability; But also the acidity of modulation molecular sieve is effectively improved its catalytic perfomance, when improving reactive behavior, improves the selectivity to specific product.
(Micropor. Mesopor. Mater. such as M.Tamura; 2008; 112:202 – 210) adopt different titanium sources to synthesize silicotitanate molecular sieve (titanium-silicon molecular sieve TS-1); Discover that the reactive behavior of Ti species directly influences the process that the Ti atom gets into the TS-1 framework of molecular sieve in the initial gel.Though document (Zeolites; 1992, reported with methyl triethyl brometo de amonio (MTEABr) to be the method for the synthetic gallosilicate molecule sieve Ga-ZSM-12 of template in 12:138-141), but the template price that is to use is very expensive; And synthetic Ga-ZSM-12 mainly is a micropore canals; The ratio of mesopore orbit is very little, and this influences its catalytic performance with the diffusion of the larger-size product molecule of restricted power.
Summary of the invention
The objective of the invention is to solve present employing MTEABr template synthetic Ga-ZSM-12 molecular sieve mainly is micropore canals, and the problem that cost is high, catalytic activity is low, and a kind of new synthetic method of gallosilicate molecule sieve Ga-ZSM-12 is provided.Adopt method synthetic Ga-ZSM-12 of the present invention to have a large amount of meso-hole structures; Therefore improve the problem of duct obstruction the causing catalyst deactivation that causes because of reactant and reaction product turnover molecular sieve pore passage difficulty significantly; Can improve the alkylation Synthetic 2 of Ga-ZSM-12 molecular sieve simultaneously to naphthalene; The catalytic reaction activity of 6-DMN and title product 2, the selectivity of 6-DMN.
Above-mentioned purpose realizes through following technical scheme:
Scheme one: the compound method of gallosilicate molecule sieve Ga-ZSM-12; With tetraethyl ammonium hydroxide as template; The compound method of said gallosilicate molecule sieve Ga-ZSM-12 realizes through following step: one, mark score another name is got 1 part of gallium oxide, 100～150 parts of TEAOH aqueous solution, 60～120 parts of silicon sol and 5～10 parts of SODIUM SULPHATE ANHYDROUS 99PCTs by weight; Weight percentage>=35% of TEAOH in the TEAOH aqueous solution wherein, SiO in the silicon sol
2Weight percentage is 39.1%; Two, the gallium oxide that step 1 is taken by weighing adds the TEAOH aqueous solution that step 1 takes by weighing; Stir and process mixing solutions; Then mixing solutions is placed the stainless closed reactor that has the polytetrafluoroethyllining lining pad; Under 160～200 ℃ temperature, handle 6～24h postcooling to room temperature shape, obtain A solution; Three, under the agitation condition of 200～400r/min rotating speed, join slowly in the A solution that (adding the used time of silicon sol is 10～20min), obtains B solution step 1 being taken by weighing silicon sol; Four, continue to stir, in B solution, add the SODIUM SULPHATE ANHYDROUS 99PCT that step 1 takes by weighing, the rotating speed stirring 5～10min with 500～1000r/min processes mixed gel C then; Five, step 4 is made mixed gel C and place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, 4～7 days postcooling of crystallization are to room temperature under 150～190 ℃ condition; Six, crystallization product is filtered, the water deionized water is washed till neutrality, under 100～120 ℃ of conditions, dries, and the speed with 5 ℃/min is warming up to 500～600 ℃ again, and insulation roasting 4～6h is cooled to room temperature subsequently, has promptly obtained gallosilicate molecule sieve Ga-ZSM-12.
Adopt the lower tetraethyl ammonium hydroxide (TEAOH) of price as template in the scheme one, reduced production cost, adopt in the TEAOH synthetic gallosilicate molecule sieve Ga-ZSM-12 crystal to have a large amount of secondary meso-hole structures; Acidity is improved the diffusion of product in this molecular sieve pore passage significantly than a little less than the ZSM-12 molecular sieve, improves the yield of product; Slow down the coke deposit rate of molecular sieve; Can improve the characteristics of its catalytic performance significantly, this molecular sieve can be used as naphthalene and one step of methanol alkylation catalyst for reaction highly selective Synthetic 2,6-dimethylnaphthalene (2; 6-DMN), in petrochemical complex and field of fine chemical, have broad application prospects.
Scheme two: the compound method of gallosilicate molecule sieve Ga-ZSM-12; With tetraethylammonium bromide as template; The compound method of said gallosilicate molecule sieve Ga-ZSM-12 realizes through following step: step a, the gallium oxide of 1g is added the sodium hydroxide of 2～4g and the deionized water and stirring of 20～40g is evenly processed mixing solutions; Then mixing solutions is placed the stainless closed reactor that has the polytetrafluoroethyllining lining pad; Under 160～200 ℃ of conditions, handle 6～24h postcooling, obtain A solution to room temperature; Step b, under the agitation condition of 200～400r/min rotating speed, the deionized water of the TEABr of 20～40g and 10～30g together slowly (is added TEABr and used time of deionized water and is 10～20min) and join in the A solution, make B solution; Step c, continuation are stirred; The deionized water of the silicon sol of 60～120g and 5～10g joined slowly together (adding silicon sol and used time of deionized water is 10～20min) in the B solution; Rotating speed stirring 10～20min with 500～1000r/min processes mixed gel C then, wherein SiO in the silicon sol
2Weight percentage is 39.1%; Steps d, the mixed gel C that step c is made place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, at 4～7 days postcooling of 150～190 ℃ of following crystallization to room temperature; Step e, crystallization product is filtered, the water deionized water is washed till neutrality, under 100～120 ℃ of conditions, dries, and is warming up to 500～600 ℃ with 5 ℃/min speed again, keeps 4～6h, is cooled to room temperature subsequently, has obtained gallosilicate molecule sieve Ga-ZSM-12 after promptly.
Adopt the lower tetraethylammonium bromide (TEABr) of price as template in the scheme two, reduced production cost, adopt in the TEABr synthetic gallosilicate molecule sieve Ga-ZSM-12 crystal to have more secondary meso-hole structure; Acid than a little less than the ZSM-12 molecular sieve; Improve the diffusion of product in this molecular sieve pore passage significantly, slow down the coke deposit rate of molecular sieve, can improve its catalytic performance significantly; This molecular sieve can be used as naphthalene and one step of methanol alkylation catalyst for reaction highly selective Synthetic 2; The 6-dimethylnaphthalene (2,6-DMN), in petrochemical complex and field of fine chemical, have broad application prospects.
Description of drawings
Fig. 1 is the XRD spectra of No. 1 sample in the embodiment six; Fig. 2 is the SEM spectrogram of No. 1 sample in the embodiment six; Fig. 3 is the XRD spectra of No. 2 samples in the embodiment seven; Fig. 4 is the SEM spectrogram of No. 2 samples in the embodiment seven; Fig. 5 is the XRD spectra of No. 3 samples in the embodiment 13; Fig. 6 is the SEM spectrogram of No. 3 samples in the embodiment 13; Fig. 7 is the XRD spectra of No. 4 samples in the embodiment 14, and Fig. 8 is the SEM spectrogram of No. 4 samples in the embodiment 14.
Embodiment
Embodiment one: in this embodiment the compound method of gallosilicate molecule sieve Ga-ZSM-12 with tetraethyl ammonium hydroxide (TEAOH) as template; Said compound method realizes through following step: one, mark score another name is got 1 part of gallium oxide, 100～150 parts of TEAOH aqueous solution, 60～120 parts of silicon sol and 5～10 parts of SODIUM SULPHATE ANHYDROUS 99PCTs by weight; Stir 15min; Weight percentage>=35% of TEAOH in the TEAOH aqueous solution wherein, SiO in the silicon sol
2Weight percentage is 39.1%; Two, the gallium oxide that step 1 is taken by weighing adds the TEAOH aqueous solution that step 1 takes by weighing; Stir and process mixing solutions; Then mixing solutions is placed the stainless closed reactor that has the polytetrafluoroethyllining lining pad; Under 160～200 ℃ temperature, handle 6～24h postcooling to room temperature, obtain A solution; Three, under the agitation condition of 200～400r/min rotating speed, step 1 is taken by weighing silicon sol at 10～20min and join slowly in the A solution that (adding the used time of silicon sol is 10～20min), obtains B solution; Four, continue to stir, in B solution, add the SODIUM SULPHATE ANHYDROUS 99PCT that step 1 takes by weighing, the rotating speed stirring 5～10min with 500～1000r/min processes mixed gel C then; Five, step 4 is made mixed gel C and place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, 4～7 days postcooling of crystallization are to room temperature under 150～190 ℃ condition; Six, crystallization product is filtered, the water deionized water is washed till neutrality, under 100～120 ℃ of conditions, dries; Be warming up to 500～600 ℃ with speed again with 5 ℃/min; Insulation roasting 4～6h is cooled to room temperature subsequently, has obtained gallosilicate molecule sieve Ga-ZSM-12 after promptly.
This embodiment adopts the lower tetraethyl ammonium hydroxide (TEAOH) of price as template, has reduced production cost, adopts in the TEABr synthetic gallosilicate molecule sieve Ga-ZSM-12 crystal to have the secondary meso-hole structure; Acidity is improved the diffusion of product in this molecular sieve pore passage significantly than a little less than the ZSM-12 molecular sieve, improves the yield of product; Slow down the coke deposit rate of molecular sieve; Can improve the characteristics of its catalytic performance significantly, this molecular sieve can be used as naphthalene and one step of methanol alkylation catalyst for reaction highly selective Synthetic 2,6-dimethylnaphthalene (2; 6-DMN), in petrochemical complex and field of fine chemical, have broad application prospects.
Embodiment two: what this embodiment and embodiment one were different is: in the step 1 by weight mark score another name get 1 part of gallium oxide, 103 parts of TEAOH aqueous solution, 82 parts of silicon sol and 7.6 parts of SODIUM SULPHATE ANHYDROUS 99PCTs.Other step is identical with embodiment one with parameter.
Embodiment three: what this embodiment was different with embodiment one or two is: under 180 ℃ temperature, handle 12h in the step 2.Other step is identical with embodiment one or two with parameter.
Embodiment four: what this embodiment and embodiment one to three were different is: crystallization temperature is 160 ℃ in the step 5, and crystallization time is 5 days.Other step is identical with embodiment one to three with parameter.
Embodiment five: what this embodiment and embodiment one to four were different is: maturing temperature is 550 ℃ in the step 6.Other step is identical with embodiment one to four with parameter.
Embodiment six: the compound method of this embodiment gallosilicate molecule sieve Ga-ZSM-12 realizes through following step: one, mark score another name is got 1 part of gallium oxide, 103 parts of TEAOH aqueous solution, 82 parts of silicon sol and 7.6 parts of SODIUM SULPHATE ANHYDROUS 99PCTs by weight; Stir 15min; Weight percentage>=35% of TEAOH in its TEAOH aqueous solution, SiO in the silicon sol
2Weight percentage is 39.1%; Two, the gallium oxide that step 1 is taken by weighing adds the TEAOH aqueous solution that step 1 takes by weighing; Stir and process mixing solutions; Then mixing solutions is placed the stainless closed reactor that has the polytetrafluoroethyllining lining pad; Under 160～200 ℃ temperature, handle 6～24h postcooling to room temperature shape, obtain A solution; Three, under 400r/min speed agitation condition, step 1 is taken by weighing silicon sol slowly join in the A solution, adding the used time of silicon sol is 15min, obtains B solution; Four, continue to stir, in B solution, add the SODIUM SULPHATE ANHYDROUS 99PCT that step 1 takes by weighing, the rotating speed stirring 8min with 650r/min processes mixed gel C then; Five, step 4 is made mixed gel C and place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, 5 days postcooling of crystallization are to room temperature under 180 ℃ condition; Six, crystallization product is filtered, the water deionized water is washed till neutrality, under 110 ℃ of conditions, dries, and the speed with 5 ℃/min is warming up to 550 ℃ again, and insulation roasting 5h is cooled to room temperature subsequently, has obtained gallosilicate molecule sieve Ga-ZSM-12 after promptly.
The XRD figure spectrum of the Ga-ZSM-12 molecular sieve (being designated as sample No. 1) of this embodiment preparation is as shown in Figure 1, and the SEM photo is as shown in Figure 2.Can be known by Fig. 1, be θ=8.8 ° at 2 θ, and 20.6 ° and 22.9 ° of characteristic diffraction peaks of locating all to have the MTW topological framework do not have other stray crystal.Can know that by Fig. 2 the Ga-ZSM-12 molecular sieve that this embodiment makes is the aggregate with regular spherical structure.
Embodiment seven: what this embodiment and embodiment six were different is: crystallization time is 7 days in the step 5.Other step and parameter and embodiment six phase are together.
The XRD figure spectrum of the Ga-ZSM-12 molecular sieve (being designated as sample No. 2) of this embodiment preparation is as shown in Figure 3, and the SEM photo is as shown in Figure 4.Can be known by Fig. 3, be θ=8.8 ° at 2 θ, and 20.6 ° and 22.9 ° of characteristic diffraction peaks of locating all to have the MTW topological framework a small amount of α-SiO occur but be 21.6 ° at 2 θ
2The diffraction peak of stray crystal, α-SiO appears in the visible long meeting of crystallization time
2Stray crystal.Can know that by Fig. 4 the Ga-ZSM-12 molecular sieve that this embodiment makes is the aggregate of globosity.
Embodiment eight: the compound method of this embodiment gallosilicate molecule sieve Ga-ZSM-12; With tetraethylammonium bromide (TEABr) as template; Said compound method realizes through following step: step a, the gallium oxide of 1g is added the sodium hydroxide of 2～4g and the deionized water and stirring of 20～40g is evenly processed mixing solutions; Then mixing solutions is placed the stainless closed reactor that has the polytetrafluoroethyllining lining pad; Under 160～200 ℃ of conditions, handle 6～24h postcooling, obtain A solution to room temperature; Step b, under the rotating speed agitation condition of 200～400r/min, the deionized water of the TEABr of 20～40g and 10～30g together slowly (is added TEABr and used time of deionized water and is 10～20min) and join in the A solution, make B solution; Step c, continuation are stirred; The deionized water of the silicon sol of 60～120g and 5～10g joined slowly together (adding silicon sol and used time of deionized water is 10～20min) in the B solution; Rotating speed stirring 10～20min with 500～1000r/min processes mixed gel C then, wherein SiO in the silicon sol
2Weight percentage is 39.1%; Steps d, the mixed gel C that step c is made place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, at 4～7 days postcooling of 150～190 ℃ of following crystallization to room temperature; Step e, crystallization product is filtered; The water deionized water is washed till neutrality; Under 100～120 ℃ of conditions, dry, be warming up to 500～600 ℃ with 5 ℃/min speed again, insulation 4～6h; Be cooled to room temperature subsequently, obtained gallosilicate molecule sieve Ga-ZSM-12 (Ga-ZSM-12/TEABr molecular sieve) after promptly.
Adopt the lower tetraethylammonium bromide (TEABr) of price as template, reduced production cost, adopt in the TEABr synthetic gallosilicate molecule sieve Ga-ZSM-12 crystal to have the secondary meso-hole structure; Acidity is improved the diffusion of product in this molecular sieve pore passage significantly than a little less than the ZSM-12 molecular sieve, improves the yield of product; Slow down the coke deposit rate of molecular sieve; Can improve the characteristics of its catalytic performance significantly, this molecular sieve can be used as naphthalene and one step of methanol alkylation catalyst for reaction highly selective Synthetic 2,6-dimethylnaphthalene (2; 6-DMN), in petrochemical complex and field of fine chemical, have broad application prospects.
Embodiment nine: what this embodiment and embodiment eight were different is: step a handles 12h under 180 ℃ of conditions.Other step is identical with embodiment eight with parameter.
Embodiment ten: what this embodiment was different with embodiment eight or nine is: the steps d crystallization temperature is 160 ℃.Other step is identical with embodiment eight or nine with parameter.
Embodiment 11: what this embodiment and embodiment eight to ten were different is: the steps d crystallization time is 5 days.Other step is identical with embodiment eight to ten with parameter.
Embodiment 12: what this embodiment and embodiment eight to 11 were different is: step e maturing temperature is 550 ℃.Other step is identical with embodiment eight to 11 with parameter.
Embodiment 13: the compound method of this embodiment gallosilicate molecule sieve Ga-ZSM-12 realizes through following step: step a, the gallium oxide of 1g is added the sodium hydroxide of 2.2g and the deionized water and stirring of 22g is evenly processed mixing solutions; Then mixing solutions is placed the stainless closed reactor that has the polytetrafluoroethyllining lining pad; Under 160 ℃ of conditions, handle the 12h postcooling to room temperature, obtain A solution; Step b, under the rotating speed agitation condition of 400r/min, the TEABr of 22.4g and the deionized water of 17.5g are together slowly joined in the A solution, adding TEABr and used time of deionized water is 10min, makes B solution; Step c, continuation are stirred; Together slowly join the silicon sol of 60～120g and the deionized water of 5～10g in the B solution; Adding silicon sol is 10～20min with the used time of deionized water, and processing with the rotating speed stirring 15min of 650r/min then is 1 mole of Ga in molar ratio
2O
3, 100 moles of SiO
2, 20 moles of TEABr, 10 moles of NaOH, 1000 moles of H
2The mixed gel C that O forms, wherein SiO in the silicon sol
2Weight percentage is 39.1%; Steps d, the mixed gel C that step c is made place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, at 4 days postcooling of 160 ℃ of following crystallization to room temperature; Step e, crystallization product is filtered, the water deionized water is washed till neutrality, under 110 ℃ of conditions, dries; Be warming up to 550 ℃ with 5 ℃/min speed again; Keep 5h, be cooled to room temperature subsequently, obtained gallosilicate molecule sieve Ga-ZSM-12 (Ga-ZSM-12/TEABr molecular sieve) after promptly.
The XRD figure spectrum of the Ga-ZSM-12 molecular sieve (being designated as sample No. 3) of this embodiment preparation is as shown in Figure 5, and the SEM photo is as shown in Figure 6.Can be known by Fig. 5, be 8.8 ° at 2 θ, locates all have the characteristic diffraction peak that the MTW topological framework is arranged, do not have other stray crystal for 20.6 ° and 22.9 °.Can know that by Fig. 6 the Ga-ZSM-12 molecular sieve that this embodiment makes is spherical accumulative crystal.
Embodiment 14: the catalytic performance of this embodiment checking product, concrete operations are following:
Comparative Examples is made the synthetic gallosilicate molecule sieve Ga-ZSM-12 of template with methyl triethyl brometo de amonio (MTEABr); Concrete compound method is as follows: a, the deionized water and stirring that by ratio of weight and the number of copies 1 part gallium oxide is added 2.2 parts sodium hydroxide and 22 parts are evenly processed all and behind the gel; Place the stainless closed reactor that has the polytetrafluoroethyllining lining pad; Make the gallium oxide dissolving behind the processing 12h down at 160 ℃, be cooled to room temperature and form A solution; B, the methyl triethyl brometo de amonio (MTEABr) and 17.5 parts by weight of de-ionized water of 20.9 parts by weight are slowly joined in the A solution under whipped state, make B solution; C, under agitation in B solution, add lentamente 82 parts by weight silicon sol (SiO
2Weight percentage is 39.1%) and 6.5 parts by weight of de-ionized water, the rotating speed stirring 15min with 650r/min processes mixed gel C then; D, above-mentioned mixed gel C is placed the stainless closed reactor that has the polytetrafluoroethyllining lining pad, at 5 days postcooling of 180 ℃ of following crystallization to room temperature; E, crystallization product is filtered, the water deionized water is washed till neutrality, obtains the Ga-ZSM-12 molecular sieve after 110 ℃ of dryings, 550 ℃ of following roastings; The XRD figure spectrum of the Ga-ZSM-12 molecular sieve (being designated as sample No. 4) of preparation is seen Fig. 7, and the SEM photo is as shown in Figure 8.Visible by Fig. 8, the Ga-ZSM-12 molecular sieve that this embodiment makes is to exist with aggregate form.
Make catalyzer with No. 1 sample, No. 3 samples and No. 4 samples respectively, in fixed-bed micro-reactor, carry out naphthalene (NAPH) and methyl alcohol (CH
3OH) alkylated reaction comes the catalytic performance of evaluate catalysts, with 1,2, the 4-trimethylbenzene (1,2,4-TMB) be solvent.Temperature of reaction is 350 ℃, and reaction pressure is 4 MPa, and WHSV is 3 h
-1(total air speed of material), the mol ratio of raw material is NAPH:CH
3OH:1,2,4-TMB=1:2:10, N
2Flow velocity be 10 mL/min, react sampling in two hours, form with the gas chromatographic analysis product, the result sees table 1 and table 2.
Table 1: the alkylated reaction result of capable naphthalene of Ga-ZSM-12 molecular sieve catalytic and methyl alcohol
MN representes methylnaphthalene in the table 1; DMN representes dimethylnaphthalene; TMN
+Expression trimethyl-naphthalene and multi-methylnaphthalene.
The specific surface area and the pore volume data of table 2:Ga-ZSM-12 molecular sieve
Can know by table 1; With tetraethyl ammonium hydroxide (TEAOH) and tetraethylammonium bromide (TEABr) is that template synthetic 1 and No. 3 Ga-ZSM-12 sieve samples obviously improve for the catalytic activity of No. 4 samples of template synthetic to the alkylated reaction of naphthalene than methyl triethyl brometo de amonio (MTEABr); The transformation efficiency of naphthalene doubles; 2,6-/2,7-DMN is than also being improved to some extent.Can know by table 2; Compare with No. 4 samples; The outer surface area of 1 and No. 3 sieve sample, mesoporous pore volume and total pore volume all are significantly improved, and explain to have produced the secondary meso-hole structure that more helps the product diffusion, therefore cause the catalytic activity of 1 and No. 3 sieve sample to significantly improve.
Claims (3)
1. the compound method of gallosilicate molecule sieve Ga-ZSM-12; It is characterized in that with tetraethyl ammonium hydroxide as template; The compound method of said gallosilicate molecule sieve Ga-ZSM-12 realizes through following step: one, mark score another name is got 1 part of gallium oxide, 103 parts of TEAOH aqueous solution, 82 parts of silicon sol and 7.6 parts of SODIUM SULPHATE ANHYDROUS 99PCTs by weight; Stir 15min, weight percentage>=35% of TEAOH in its TEAOH aqueous solution, SiO in the silicon sol
2Weight percentage is 39.1%; Two, the gallium oxide that step 1 is taken by weighing adds the TEAOH aqueous solution that step 1 takes by weighing; Stir and process mixing solutions; Then mixing solutions is placed the stainless closed reactor that has the polytetrafluoroethyllining lining pad; Under 160～200 ℃ temperature, handle 6～24h postcooling to room temperature, obtain A solution; Three, under 400r/min speed agitation condition, the silicon sol that step 1 is taken by weighing slowly joins in the A solution, and adding the used time of silicon sol is 15min, obtains B solution; Four, continue to stir, in B solution, add the SODIUM SULPHATE ANHYDROUS 99PCT that step 1 takes by weighing, the rotating speed stirring 8min with 650r/min processes mixed gel C then; Five, step 4 is made mixed gel C and place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, 5 days postcooling of crystallization are to room temperature under 180 ℃ condition; Six, crystallization product is filtered, the water deionized water is washed till neutrality, under 110 ℃ of conditions, dries, and the speed with 5 ℃/min is warming up to 550 ℃ again, and insulation roasting 5h is cooled to room temperature subsequently, has obtained gallosilicate molecule sieve Ga-ZSM-12 after promptly; Said gallosilicate molecule sieve Ga-ZSM-12 is the aggregate with regular spherical structure.
2. the compound method of gallosilicate molecule sieve Ga-ZSM-12; It is characterized in that with tetraethyl ammonium hydroxide as template; The compound method of said gallosilicate molecule sieve Ga-ZSM-12 realizes through following step: one, mark score another name is got 1 part of gallium oxide, 103 parts of TEAOH aqueous solution, 82 parts of silicon sol and 7.6 parts of SODIUM SULPHATE ANHYDROUS 99PCTs by weight; Stir 15min, weight percentage>=35% of TEAOH in its TEAOH aqueous solution, SiO in the silicon sol
2Weight percentage is 39.1%; Two, the gallium oxide that step 1 is taken by weighing adds the TEAOH aqueous solution that step 1 takes by weighing; Stir and process mixing solutions; Then mixing solutions is placed the stainless closed reactor that has the polytetrafluoroethyllining lining pad; Under 160～200 ℃ temperature, handle 6～24h postcooling to room temperature, obtain A solution; Three, under 400r/min speed agitation condition, the silicon sol that step 1 is taken by weighing slowly joins in the A solution, and adding the used time of silicon sol is 15min, obtains B solution; Four, continue to stir, in B solution, add the SODIUM SULPHATE ANHYDROUS 99PCT that step 1 takes by weighing, the rotating speed stirring 8min with 650r/min processes mixed gel C then; Five, step 4 is made mixed gel C and place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, 7 days postcooling of crystallization are to room temperature under 180 ℃ condition; Six, crystallization product is filtered, the water deionized water is washed till neutrality, under 110 ℃ of conditions, dries, and the speed with 5 ℃/min is warming up to 550 ℃ again, and insulation roasting 5h is cooled to room temperature subsequently, has obtained gallosilicate molecule sieve Ga-ZSM-12 after promptly; Said gallosilicate molecule sieve Ga-ZSM-12 is the aggregate of globosity.
3. the compound method of gallosilicate molecule sieve Ga-ZSM-12; It is characterized in that step a, the gallium oxide of 1g is added the sodium hydroxide of 2.2g and the deionized water and stirring of 22g is evenly processed mixing solutions; Then mixing solutions is placed the stainless closed reactor that has the polytetrafluoroethyllining lining pad; Under 160 ℃ of conditions, handle the 12h postcooling to room temperature, obtain A solution; Step b, under the rotating speed agitation condition of 400r/min, the TEABr of 22.4g and the deionized water of 17.5g are together slowly joined in the A solution, adding TEABr and used time of deionized water is 10min, makes B solution; Step c, continuation are stirred; Together slowly join the silicon sol of 60～120g and the deionized water of 5～10g in the B solution; Adding silicon sol is 10～20min with the used time of deionized water, and processing with the rotating speed stirring 15min of 650r/min then is 1 mole of Ga in molar ratio
2O
3, 100 moles of SiO
2, 20 moles of TEABr, 10 moles of NaOH, 1000 moles of H
2The mixed gel C that O forms, wherein SiO in the silicon sol
2Weight percentage is 39.1%; Steps d, the mixed gel C that step c is made place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, at 4 days postcooling of 160 ℃ of following crystallization to room temperature; Step e, crystallization product is filtered, the water deionized water is washed till neutrality, under 110 ℃ of conditions, dries, and is warming up to 550 ℃ with 5 ℃/min speed again, keeps 5h, is cooled to room temperature subsequently, has obtained gallosilicate molecule sieve Ga-ZSM-12 after promptly; Said gallosilicate molecule sieve Ga-ZSM-12 is spherical accumulative crystal.
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| CN106564909B (en) * | 2015-10-09 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of preparation method of ZSM-12 molecular sieve |
| CN106564910A (en) * | 2016-11-10 | 2017-04-19 | 徐州乐泰机电科技有限公司 | Modified Sc/ZSM-12 acoustic material |
| CN108423688B (en) * | 2018-05-22 | 2021-11-02 | 山西大同大学 | Method for synthesizing ZSM-12 molecular sieve |
| CN109437233B (en) * | 2019-01-17 | 2021-11-09 | 黑龙江大学 | Method for synthesizing nano GaZSM-5 silicon gallate molecular sieve by dry glue conversion method |
| CN115106123B (en) * | 2022-07-28 | 2023-03-24 | 黑龙江大学 | Method for preparing multi-branched isohexadecane by adopting Pd-supported HGaZSM-12 zeolite-based bifunctional catalyst |
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| CN1774398A (en) * | 2002-11-15 | 2006-05-17 | 埃克森美孚化学专利公司 | High activity small crystal zsm-12 |
| CN1830784A (en) * | 2000-10-20 | 2006-09-13 | Abb拉默斯环球有限公司 | Improved zeolites and molecular sieves and the use thereof |
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| CN1830784A (en) * | 2000-10-20 | 2006-09-13 | Abb拉默斯环球有限公司 | Improved zeolites and molecular sieves and the use thereof |
| CN1774398A (en) * | 2002-11-15 | 2006-05-17 | 埃克森美孚化学专利公司 | High activity small crystal zsm-12 |
Non-Patent Citations (3)
| Title |
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| Srikant Gopal et al..Synthesis of Al-rich ZSM-12 using TEAOH as template.《microporous and Mesoporous Materials》.2001,第49卷第149-156页. * |
| 吴伟 等.ZSM-12分子筛研究进展.《化工进展》.2007,第26卷(第7期),第921-926页. * |
| 吴维果.改性ZSM-12分子筛的制备及其催化烷基化反应研究.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2009,(第12期),第32-33页. * |
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