CN102125868A - Method for preparing microporous-mesoporous composite Fe-ZSM-5 zeolite molecular sieve catalyst - Google Patents
Method for preparing microporous-mesoporous composite Fe-ZSM-5 zeolite molecular sieve catalyst Download PDFInfo
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- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 72
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000010457 zeolite Substances 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 47
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title abstract description 6
- 238000000034 method Methods 0.000 title description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 36
- 239000003513 alkali Substances 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 32
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 78
- 238000006243 chemical reaction Methods 0.000 abstract description 53
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000001914 filtration Methods 0.000 abstract 2
- 238000005406 washing Methods 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 239000011148 porous material Substances 0.000 description 18
- 239000000523 sample Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013461 intermediate chemical Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明是一种微孔-介孔复合分子筛Fe-ZSM-5催化剂的制备方法。本发明的制备方法包括以下步骤：(1)将模板剂四丙基溴化铵溶解在去离子水中，在搅拌下，加入硫酸铝、硫酸、硝酸铁和水玻璃，所得到的透明溶液放入反应釜中进行晶化，得到固体样品；(2)将固体样品经焙烧除去模板剂、用硝酸铵溶液进行离子交换、过滤、用去离子水洗涤、干燥、焙烧后得到微孔Fe-ZSM-5沸石；(3)对微孔Fe-ZSM-5沸石进行碱处理后，经冷却、过滤、用去离子水洗涤、用硝酸铵溶液进行离子交换、过滤、用去离子水洗涤、干燥、焙烧后得到一种微孔-介孔复合Fe-ZSM-5沸石分子筛催化剂。本发明具有反应温度低、苯转化率高、在BTOP反应中催化性能高的特点。
The invention relates to a preparation method of a microporous-mesoporous composite molecular sieve Fe-ZSM-5 catalyst. The preparation method of the present invention comprises the following steps: (1) dissolving template agent tetrapropylammonium bromide in deionized water, adding aluminum sulfate, sulfuric acid, ferric nitrate and water glass under stirring, and putting the transparent solution obtained Carry out crystallization in a reaction kettle to obtain a solid sample; (2) remove the template agent by roasting the solid sample, carry out ion exchange with ammonium nitrate solution, filter, wash with deionized water, dry, and roast to obtain a microporous Fe-ZSM- 5 zeolite; (3) After alkali treatment of microporous Fe-ZSM-5 zeolite, cooling, filtering, washing with deionized water, ion exchange with ammonium nitrate solution, filtering, washing with deionized water, drying, roasting Finally, a microporous-mesoporous composite Fe-ZSM-5 zeolite molecular sieve catalyst is obtained. The invention has the characteristics of low reaction temperature, high benzene conversion rate and high catalytic performance in BTOP reaction.
Description
Technical field
The present invention relates to a kind of microporous-mesoporous composite molecular sieve Preparation of catalysts method, relate in particular to a kind of microporous-mesoporous composite molecular sieve Fe-ZSM-5 Preparation of catalysts method.
Background technology
Phenol is important organic chemical industry's intermediate and industrial chemicals, is mainly used in manufacturing phenolic resins, bisphenol-A and caprolactam.The topmost method of industrial production phenol is a cumene method at present, and it not only consumes national strategy resource propylene, and has the investment cost height, the reaction process complexity, environmental pollution is big, and many shortcomings such as by-product acetone do not meet the modern environmental requirement and the strategy of sustainable development.
Compare with the traditional mode of production phenol processes, more the attention that phenol (BTOP) catalysis new technology is subjected to academia and industrial quarters is gradually produced in the benzene direct oxidation of economy, environmental protection.Wherein U.S. Solutia company and the joint research exploitation of Russian Boreskov catalyticing research institute with N
2O is an oxidant, and the AlphOx technology that the Fe-ZSM-5 molecular sieve is produced phenol for the catalyst benzene hydroxylation is the most attractive.This technology not only can be utilized the useless N in the adipic acid industrial production
2O also can effectively integrate phenol production device and adipic acid process units, and gained phenol selectivity height is environmentally friendly chemical process.Yet Fe-ZSM-5 catalyst cycle of oparation is relatively poor, still has with a certain distance from industrialization.This mainly is that reactant benzene and the transmission of product phenol in molecular sieve pore passage are restricted because Fe-ZSM-5 is a kind of poromerics, and the easy deep oxidation of product phenol causes due to the catalyst carbon deposit inactivation.
Zeolite is carried out post processing improve the attention that its mass-transfer performance is subjected to the researcher always, the general method that adopts is that hydrothermal treatment consists or acid treatment remove framework of molecular sieve Al and produce mesoporous, yet the Al species that remove may stop up molecular sieve pore passage, the actual mass-transfer performance that can not obviously improve zeolite.Alkali treatment is another modification mode, and Lv Renqing etc. (Lv Renqing etc., the catalysis journal, 2002,23 (5), 421-424) investigated under the different temperatures with containing 10wt.%NH
3The Changing Pattern of steam treatment HZSM-5 zeolite (n (Si)/n (Al)=25) pore structure.Discovery is along with the raising of treatment temperature, and obvious variation does not take place the structure of HZSM-5, but the specific area of sample and micro pore volume reduce, and secondary pore volume and external surface area have the trend of increase.(Xiao Qiang etc. such as Xiao Qiang, the catalysis journal, 2005,26 (3), 243-247) studied the influence of alkali treatment to modenite thing phase, acid matter and catalytic performance, find that alkali treatment contains the relative crystallinity of the modenite of template agent, sour amount, specific area and pore volume and all increases, alkali treatment relative crystallinity, sour amount, specific area and the pore volume of the modenite of removed template method all reduces, and the modenite catalytic performance after the alkali treatment obviously improves.
Up-to-date studies show that, alkali treatment is taken off Si by Selective Control makes the molecular sieve generation mesoporous, and produce mesoporous also keeps communicating with micropore, thereby shorten the diffusion length of molecule in the zeolite micropore duct, improved mass-transfer performance (Groen J C, the et al of zeolite, J.Am.Chem.Soc., 2007,129 (2), 355-360; P é rez-Ram í rez J, et al, Chem.Soc.Rev.2008,37,2530-2542).Behind the alkali treatment modifying, the microcellular structure and the acidity of material crystals do not change substantially, and mesoporous generation helps the transmission of material, and micropore is as a kind of microreactor, chain carrier or adsorption potential not only are provided, and the shape and the size of molecule had selectivity.Although alkali treatment is a kind of effective means that obtains the mesoporous zeolite molecular sieve, yet whether this method is effective to the micropore Fe-ZSM-5 zeolite molecular sieve of iron content, whether the alkali treatment condition needs to optimize, whether the content of Fe species, existence form change after the modification, what the alkali treatment rear catalyst essential reason that catalytic performance improves in the BTOP reaction is, do not see open report as yet about these problems.
Nineteen eighty-three, and people such as Iwamoto (Iwamoto M, et al, J.Phys.Chem., 1983,87 (6), 903-905) adopt N first
2O is an oxidant, has finished the atmospheric gas phase reaction of one step of benzene synthesizing phenol.
U.S. Pat 5001280 (1991) provides a kind of N of being used for
2The O Oxybenzene prepares the ZSM-5 catalyst of phenol, is 120 at the zeolite silica alumina ratio, and reaction temperature is 400 ℃, benzene: inert gas: N
2O=2: under 5: 8 the condition, the conversion ratio of benzene can reach 16%, and the selectivity of phenol is 95%.
People such as Panov are to N
2O is an oxidant, with metal-modified ZSM-5 zeolite is catalyst, deep research has been carried out in the reaction of the direct synthesizing phenol of benzene, a series of patents have been applied for, as U.S. Pat 5110995 (1992), US5672777 (1997), US5756861 (1998), Chinese patent CN1071729C (2001); World patent WO9527691 (1998) etc.In Chinese patent CN1071729C, be catalyst at the ZSM-5 with iron content wherein, when reaction temperature was 430 ℃, the yield of phenol was still lower, has only about 5%.
In sum, the BTOP catalytic reaction based on the ZSM-5 zeolite catalyst of open report, reaction temperature higher (＞400 ℃), oxidant N
2O is generally excessive, utilization rate is not high.Benzene conversion ratio and phenol yield are generally still lower though so.Existing studies show that, when having a small amount of active Fe species in the ZSM-5 zeolite catalyst, just can significantly improve BTOP catalytic perfomance (Panov G.I, et al, Appl.Catal.A:Gen., 1992,82 (1): 31-36), catalytic performance is low to be because reactant benzene and product phenol due to mass transfer is restricted in the zeolite catalyst micropore canals.
Summary of the invention
The present invention is directed to the existing reaction temperature height of existing BTOP catalytic reaction, low, the oxidant N of benzene conversion ratio based on the ZSM-5 zeolite catalyst
2Weak points such as O is excessive provide that a kind of reaction temperature is low, benzene conversion ratio height, have the compound Fe-ZSM-5 zeolite molecular sieve catalyst of the micropore-mesopore preparation method of high catalytic performance in the BTOP reaction.
The present invention finishes by following technical scheme, the preparation method of the compound Fe-ZSM-5 zeolite molecular sieve catalyst of a kind of micropore-mesopore, and its preparation method may further comprise the steps:
(1) taking by weighing template agent 4-propyl bromide is dissolved in the deionized water, add aluminum sulfate again, stir 0.5～2h, dropwise add sulfuric acid and ferric nitrate, stir 1～3h, dropwise add waterglass (26.5wt.%SiO2 and 10.6wt.%Na2O) at last and continue to stir 2～5h and obtain clear solution, subsequently above-mentioned solution is put in the reactor, obtain solid sample at 140～180 ℃ of following crystallization 1～5d;
(2) solid sample that obtains is removed the template agent at 500～600 ℃ of following roasting 6～12h, in 50～60 ℃ of water-baths, carry out ion-exchange 3～4 times subsequently with ammonium nitrate solution, and filter, spend deionised water near neutral, dry down at 90～120 ℃, again at 400～700 ℃ of following roasting 4～8h, obtaining crystallite dimension at last is the micropore Fe-ZSM-5 zeolite of 1～5 μ m, and the Si/Al mol ratio is 10～50 in the micropore Fe-ZSM-5 zeolite, and the Fe/Si mol ratio is 0.001～0.007;
(3) micropore Fe-ZSM-5 zeolite is carried out alkali treatment, ratio in solid-liquid weight ratio 1: 3～8 mixes micropore Fe-ZSM-5 zeolite and concentration at the NaOH of 0.05～1mol/L aqueous slkali, under 60～80 ℃ of temperature, stir 0.5～3h, cooling then, filter, the deionised water system of spending is closely neutral, be that the ammonium nitrate solution of 0.1～1mol/L carries out ion-exchange 3～4 times with concentration again, and filter, spend deionised water near neutral, dry down at 90～120 ℃, at 500～600 ℃ of following roasting 4～8h, obtain the compound Fe-ZSM-5 zeolite molecular sieve catalyst of a kind of micropore-mesopore.
In the preparation method of the compound Fe-ZSM-5 zeolite molecular sieve catalyst of above-mentioned a kind of micropore-mesopore, the preferred 2～3d of crystallization time in preparation method's step (1).
In the preparation method of the compound Fe-ZSM-5 zeolite molecular sieve catalyst of above-mentioned a kind of micropore-mesopore, the Si/Al mol ratio is preferred 20～300 in the micropore Fe-ZSM-5 zeolite in preparation method's step (2), and the Fe/Si mol ratio is than preferred 0.003～0.005.
In the preparation method of the compound Fe-ZSM-5 zeolite molecular sieve catalyst of above-mentioned a kind of micropore-mesopore, micropore Fe-ZSM-5 zeolite crystal size is about 1～2 μ m in preparation method's step (2).
In the preparation method of the compound Fe-ZSM-5 zeolite molecular sieve catalyst of above-mentioned a kind of micropore-mesopore, solid-to-liquid ratio preferred 1: 4～6 in preparation method's step (3); Preferred 0.2～the 0.3mol/L of concentration of lye, preferred 60～80 ℃ of whipping temp, the preferred 1～2h of mixing time.
On fixed-bed micro-reactor, with N
2It is that probe reaction is estimated above-mentioned catalyst catalytic performance that the O Oxybenzene is produced phenol.By internal diameter is quartz ampoule filling 0.2g catalyst and 0.5g 40～60 purpose quartz sands of 6mm.The reaction procatalyst activates 1h under He atmosphere, reduce to the experiment desired reaction temperature again.320 ℃ of the main reaction temperatures that adopts of experiment, N is pressed in the reaction air inlet
2O: benzene: He=1: (mol ratio) was mixed into reactor in 1: 28, and its overall flow rate is 60ml/min (NTP), and air speed is 18000ml.g
Catal -1.h
-1
Characteristics of the present invention are: by changing the alkali treatment condition, as NaOH concentration, temperature and time etc., can change micropore and mesoporous ratio in the Fe-ZSM-5 microporous-mesoporous composite molecular sieve catalyst, thus the catalytic performance of catalyst in BTOP before and after the modulation alkali treatment.Sign and reaction evaluating result from sample, the mode of the present invention by alkali treatment is with in the mesoporous introducing micropore Fe-ZSM-5 molecular sieve crystal, the gained sample topography is complete, crystal structure is constant, and the molecular sieve mass-transfer performance significantly improves, and its catalytic activity and stability in the BTOP catalytic reaction also are significantly improved.Under the alkali treatment condition of optimizing, the catalyst after the modification reacts 3h under 320 ℃ of reaction temperatures, and the conversion ratio of benzene still maintains 20%, and apparently higher than the catalytic activity without the alkali treatment sample, and the selectivity of phenol reaches 100% under reaction condition.Compared with prior art, the present invention is to provide a kind of simply, effectively, in the BTOP reaction, have the compound Fe-ZSM-5 zeolite molecular sieve catalyst of the micropore-mesopore preparation method of high catalytic performance.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the compound Fe-ZSM-5 zeolite molecular sieve of micropore-mesopore of the present invention.
Fig. 2 is the transmission electron microscope picture of the compound Fe-ZSM-5 zeolite molecular sieve of micropore-mesopore of the present invention.
Fig. 3 is the compound Fe-ZSM-5 zeolite molecular sieve of micropore-mesopore of the present invention and the parent Fe-ZSM-5 uptake curve to benzene.
The specific embodiment
Below by embodiment the present invention is made further and to specify.
Embodiment 1
The preparation of the compound Fe-ZSM-5 zeolite molecular sieve of micropore-mesopore: will adopt the directly synthetic grain size of hydro-thermal method is that 2 μ m, Fe/Si carry out alkali treatment modifying than the Fe-ZSM-5 micro-pore zeolite that is 0.005, the NaOH concentration of using is 0.2mol/L, its alkali purification temp is 60 ℃, and the time is 2h.The gained catalyst sample is designated as Fe-ZSM-5-AT (0.2,2), its N
2The absorption test result sees Table 1.On this catalyst, behind the BTOP reaction 180min, the conversion ratio of benzene is 17.0%, phenol selectivity 100%.
The preparation of the compound Fe-ZSM-5 zeolite molecular sieve of micropore-mesopore: will adopt the directly synthetic grain size of hydro-thermal method is that 2 μ m, Fe/Si carry out alkali treatment modifying than the Fe-ZSM-5 micro-pore zeolite that is 0.005, the NaOH concentration of using is 0.3mol/L, its alkali purification temp is 80 ℃, and the time is 2h.The gained catalyst sample is designated as Fe-ZSM-5-AT (0.3,2), its N
2The absorption test result sees Table 1.On this catalyst, behind the BTOP reaction 180min, the conversion ratio of benzene is 14.5%, phenol selectivity 100%.
Embodiment 3
The preparation of the compound Fe-ZSM-5 zeolite molecular sieve of micropore-mesopore: will adopt the directly synthetic grain size of hydro-thermal method is that 2 μ m, Fe/Si carry out alkali treatment modifying than the Fe-ZSM-5 micro-pore zeolite that is 0.005, the NaOH concentration of using is 0.2mol/L, its alkali purification temp is 80 ℃, and the time is 1h.The gained catalyst sample is designated as Fe-ZSM-5-AT (0.2,1), its N
2The absorption test result sees Table 1.On this catalyst, behind the BTOP reaction 180min, the conversion ratio of benzene is 13.0%, phenol selectivity 100%.
Embodiment 4
The preparation of the compound Fe-ZSM-5 zeolite molecular sieve of micropore-mesopore: will adopt the directly synthetic grain size of hydro-thermal method is that 2 μ m, Fe/Si carry out alkali treatment modifying than the Fe-ZSM-5 micro-pore zeolite that is 0.005, the NaOH concentration of using is 0mol/L, its alkali purification temp is 60 ℃, time is 2h, and its N2 absorption test result sees Table 1.On this catalyst, behind the BTOP reaction 180min, the conversion ratio of benzene is 13.0%, phenol selectivity 100%.
The preparation of the compound Fe-ZSM-5 zeolite molecular sieve of micropore-mesopore: will adopt the directly synthetic grain size of hydro-thermal method is that 2 μ m, Fe/Si carry out alkali treatment modifying than the Fe-ZSM-5 micro-pore zeolite that is 0.005, the NaOH concentration of using is 0.2mol/L, its alkali purification temp is 60 ℃, time is 2h, and its N2 absorption test result sees Table 1.On this catalyst, behind the BTOP reaction 180min, the conversion ratio of benzene is 16.7%, phenol selectivity 100%.
Embodiment 6
The preparation of the compound Fe-ZSM-5 zeolite molecular sieve of micropore-mesopore: will adopt the directly synthetic grain size of hydro-thermal method is that 2 μ m, Fe/Si carry out alkali treatment modifying than the Fe-ZSM-5 micro-pore zeolite that is 0.005, the NaOH concentration of using is 0.3mol/L, its alkali purification temp is 60 ℃, time is 2h, and its N2 absorption test result sees Table 1.On this catalyst, behind the BTOP reaction 180min, the conversion ratio of benzene is 19.9%, phenol selectivity 100%.
Embodiment 7
The preparation of the compound Fe-ZSM-5 zeolite molecular sieve of micropore-mesopore: will adopt the directly synthetic grain size of hydro-thermal method is that 2 μ m, Fe/Si carry out alkali treatment modifying than the Fe-ZSM-5 micro-pore zeolite that is 0.005, the NaOH concentration of using is 0.5mol/L, its alkali purification temp is 60 ℃, and the time is 2h, its N
2The absorption test result sees Table 1.On this catalyst, behind the BTOP reaction 180min, the conversion ratio of benzene is 18.4%, phenol selectivity 100%.
Comparative Examples 1
With adopting the directly synthetic grain size of brilliant method of substitution is that 2 μ m, Fe/Si are directly used in the BTOP reaction than the Fe-ZSM-5 micro-pore zeolite that is 0.001, and behind the reaction 180min, the conversion ratio of benzene is 10.3%, phenol selectivity 100%.
Comparative Examples 2
With adopting the directly synthetic grain size of brilliant method of substitution is that 2 μ m, Fe/Si are directly used in the BTOP reaction than the Fe-ZSM-5 micro-pore zeolite that is 0.003, and behind the reaction 180min, the conversion ratio of benzene is 12%, phenol selectivity 100%.
Comparative Examples 3
With adopting the directly synthetic grain size of brilliant method of substitution is that 2 μ m, Fe/Si are directly used in the BTOP reaction than the Fe-ZSM-5 micro-pore zeolite that is 0.003, and behind the reaction 180min, the conversion ratio of benzene is 12.2%, phenol selectivity 100%.
Comparative Examples 4
With adopting the directly synthetic grain size of brilliant method of substitution is that 2 μ m, Fe/Si are directly used in the BTOP reaction than the Fe-ZSM-5 micro-pore zeolite that is 0.003, and behind the reaction 180min, the conversion ratio of benzene is 11.3%, phenol selectivity 100%.
N before and after the table 1Fe-ZSM-5 alkali treatment
2The adsorption desorption analysis result
Claims (6)
1. the compound Fe-ZSM-5 zeolite molecular sieve catalyst of micropore-mesopore preparation method is characterized in that the compound Fe-ZSM-5 zeolite molecular sieve catalyst of described micropore-mesopore preparation method may further comprise the steps:
(1) taking by weighing template agent 4-propyl bromide is dissolved in the deionized water, add aluminum sulfate again, stir 0.5～2h, dropwise add sulfuric acid and ferric nitrate, stir 1～3h, dropwise add waterglass at last and continue to stir 2～5h and obtain clear solution, subsequently above-mentioned solution is put in the reactor, obtain solid sample at 140～180 ℃ of following crystallization 1～5d;
(2) solid sample that obtains is removed the template agent at 500～600 ℃ of following roasting 6～12h, in 50～60 ℃ of water-baths, carry out ion-exchange 3～4 times subsequently with ammonium nitrate solution, and filter, spend deionised water near neutral, dry down at 90～120 ℃, again at 400～700 ℃ of following roasting 4～8h, obtaining crystallite dimension at last is the micropore Fe-ZSM-5 zeolite of 1～5 μ m, and the Si/Al mol ratio is 10～50 in the micropore Fe-ZSM-5 zeolite, and the Fe/Si mol ratio is 0.001～0.007;
(3) micropore Fe-ZSM-5 zeolite is carried out alkali treatment, ratio in solid-liquid weight ratio 1: 3～8 mixes micropore Fe-ZSM-5 zeolite and concentration at the NaOH of 0.05～1mol/L aqueous slkali, under 60～80 ℃ of temperature, stir 0.5～3h, cooling then, filter, the deionised water system of spending is closely neutral, be that the ammonium nitrate solution of 0.1～1mol/L carries out ion-exchange 3～4 times with concentration again, and filter, spend deionised water near neutral, dry down at 90～120 ℃, at 500～600 ℃ of following roasting 4～8h, obtain the compound Fe-ZSM-5 zeolite molecular sieve catalyst of a kind of micropore-mesopore.
2. according to the compound Fe-ZSM-5 zeolite molecular sieve catalyst of the described a kind of micropore-mesopore of claim 1 preparation method, it is characterized in that in the compound Fe-ZSM-5 zeolite molecular sieve catalyst of described micropore-mesopore preparation method's the step (1) that waterglass adopts sodium silicate.
3. according to the compound Fe-ZSM-5 zeolite molecular sieve catalyst of the described a kind of micropore-mesopore of claim 1 preparation method, it is characterized in that in the compound Fe-ZSM-5 zeolite molecular sieve catalyst of described micropore-mesopore preparation method's the step (1) the preferred 2～3d of crystallization time.
4. according to the compound Fe-ZSM-5 zeolite molecular sieve catalyst of the described a kind of micropore-mesopore of claim 1 preparation method, it is characterized in that in the compound Fe-ZSM-5 zeolite molecular sieve catalyst of described micropore-mesopore preparation method's the step (2), the Si/Al mol ratio is preferred 20～300 in the micropore Fe-ZSM-5 zeolite, and the Fe/Si mol ratio is than preferred 0.003～0.005.
5. according to the compound Fe-ZSM-5 zeolite molecular sieve catalyst of the described a kind of micropore-mesopore of claim 1 preparation method, it is characterized in that in the compound Fe-ZSM-5 zeolite molecular sieve catalyst of described micropore-mesopore preparation method's the step (2), micropore Fe-ZSM-5 zeolite crystal size is about 1～2 μ m.
6. according to the compound Fe-ZSM-5 zeolite molecular sieve catalyst of the described a kind of micropore-mesopore of claim 1 preparation method, it is characterized in that in the compound Fe-ZSM-5 zeolite molecular sieve catalyst of described micropore-mesopore preparation method's the step (3) solid-to-liquid ratio preferred 1: 4～6; Preferred 0.2～the 0.3mol/L of concentration of lye, preferred 60～80 ℃ of whipping temp, the preferred 1～2h of mixing time.
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