CN103447077B - In situ modification method of zeolite socony mobil-five (ZSM-5)/foam silicon carbide structured catalyst - Google Patents
In situ modification method of zeolite socony mobil-five (ZSM-5)/foam silicon carbide structured catalyst Download PDFInfo
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title abstract description 22
- 229910010271 silicon carbide Inorganic materials 0.000 title abstract description 22
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- 238000002715 modification method Methods 0.000 title abstract 3
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 21
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 47
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- 239000007864 aqueous solution Substances 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
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Classifications
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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)
Abstract
The invention belongs to the technical field of catalysts and applications thereof, and particularly discloses an in situ modification method of a zeolite socony mobile-five (ZSM-5)/foam silicon carbide structured catalyst. The modification method comprises the following steps: carrying out warming and pressurizing treatment on the ZSM-5/ foam silicon carbide structured catalyst or a foam silicon carbide carrier which is coated with a ZSM-5 precursor in advance in an organic/inorganic amine solution or steam, so as to play an effect of regulating the property of solid acid. Strong acid of the ZSM-5/foam silicon carbide structured catalyst is reduced; mediate strong acid and weak acid of the ZSM-5/foam silicon carbide structured catalyst are increased after modified treatment; meanwhile, the crystallinity of the modified catalyst is improved; ducts of the modified catalyst are open; the pore volume of the modified catalyst is increased; the molecular diffusion performance of the modified catalyst is also improved. The carbon deposition resistance of the modified ZSM-5/foam silicon carbide structured catalyst is greatly improved in a reaction of preparing propylene from methanol under the premise of keeping high propylene selectivity of the ZSM-5/foam silicon carbide structured catalyst; the one-way service life is prolonged; the renewability is also improved.
Description
Technical field
The invention belongs to catalyst and applied technical field thereof, specifically a kind of Method in situ modification of ZSM-5/ foam silicon carbon structural catalyst.
Background technology
Zeolite molecular sieve has unique pore passage structure and solid acid characteristic, is widely used in the field such as petrochemical industry, environmental protection as catalyst, catalyst carrier or adsorbent.Traditional zeolite molecular sieve catalyst is all add binding agent in the former powder of zeolite molecular sieve after, after granulation, is applied in the form of granules in fixed bed or fluid bed.Particulate molecular sieve catalyst application is when fixed bed, because beaded catalyst mass-and heat-transfer ability is poor, not only cause bed pressure drop to raise the waste causing industrial energy, and also produce larger concentration and thermograde in process of production, reduce the catalytic efficiency of catalyst.When particulate molecular sieve catalyst application is in fluid bed, although can solve heat transfer that fixed bed exists, mass transfer problem, in moving bed, particulate molecular sieve size is less, and catalyst abrasion is serious, and cause the separation of catalyst and recovery difficult large.
Zeolite molecular sieve is carried on structured supports surface with specific paint-on technique, makes structural catalyst.Relative to normal granular zeolite molecular sieve catalyst, structuring molecular sieve catalyst combines the advantage of fixed bed and moving bed and overcomes its shortcoming separately, shows that catalytic activity is high, diffusion length is short, carbon accumulation resisting ability is strong, stability advantages of higher.In the laboratory research of the reaction such as synthesis of the oligomerisation reaction of the alkylation of hydrocracking, fluid catalytic cracking, benzene, alkene, preparing gasoline by methanol, preparing propylene from methanol, methanol-to-olefins, methylamine, structuring molecular sieve catalyst all achieves the effect being significantly better than conventional zeolite molecular sieve, fully demonstrates structuring zeolite molecular sieve catalyst catalyst to the importance improving chemical industry resource utilization and added value of product, development high-efficiency cleaning production technology.
But its relative normal granular zeolite catalyst, structuring molecular sieve catalyst Middle molecule sieve is at carrier surface, and the active sites of exposure is too much.Nano molecular sieve is carried on this phenomenon in structured supports just more obvious.For some specific reactions, too high catalytic activity is disadvantageous, thus needs to carry out modification to structuring molecular sieve catalyst, its acidity is adjusted to and is suitable for specific reaction.The chemical erosion process such as usual steam treatment and acid treatment or by the two combine to remove framework aluminum, reduce acid amount and improve acid strength.But framework dealumination can partial destruction zeolite molecular sieve lattice, forms skeleton defect, makes catalyst easily coking in catalytic reaction, thus reduce its reaction stability, the heat endurance of skeleton structure and hydrothermal stability, reduction of service life.Metal cation exchanges and salt solution impregnation can make zeolite molecular sieve supported active metals oxide, and the solid acid character of catalyst is changed.But the active component of institute's load blocking zeolite cavity, affects reactant and product spreads in duct, thus reduces its kinetic property.In addition, in high-temperature reaction process, active component such as metal or the metal oxide of load easily move, assemble or run off, and catalyst activity and selectivity is deteriorated, sometimes also may pollutes reaction system.In addition, active component is to human body poisonous (as Cd, Cr, Hg, In etc.), and some is expensive (as Pt, Pt etc.) then, and catalyst application is restricted.
Summary of the invention
The object of the present invention is to provide a kind of Method in situ modification of ZSM-5/ foam silicon carbon structural catalyst, the solid acid character of regulation and control catalyst, improves the stability of ZSM-5/ foam silicon carbon structural catalyst in the alcohols dehydration reactions such as preparing propylene from methanol.
Technical scheme of the present invention is:
A kind of Method in situ modification of ZSM-5/ foam silicon carbon structural catalyst, the foam silicon carbon carrier of ZSM-5/ foam silicon carbon structural catalyst or precoating ZSM-5 precursor is heated in the solution or steam of organic or inorganic amine, pressurized treatments, play the effect of adjustment solid acid character.After modification, the strong acid of ZSM-5/ foam silicon carbon structural catalyst reduces, and middle strong acid, weak acid increase; Meanwhile, the degree of crystallinity of modified catalysts improves, and duct is open, and pore volume increases, and molecular diffusion performance is good.The present invention through modification ZSM-5/ foam silicon carbon structural catalyst preparing propylene from methanol reaction in, under the prerequisite keeping ZSM-5/ foam silicon carbon structural catalyst high olefin selectivity, significantly improve the stability of catalyst, single pass life and recyclability.
In the present invention, the foam silicon carbon carrier of ZSM-5/ foam silicon carbon structural catalyst or precoating ZSM-5 precursor is heated in organic/inorganic amine aqueous solution or steam, pressurized treatments, play the effect of adjustment solid acid character.
In the present invention, ZSM-5/ foam silicon carbon structural catalyst, be made up of foam silicon carbon carrier and the type ZSM 5 molecular sieve that is carried on its surface, the part by weight shared by type ZSM 5 molecular sieve is 1-60%, and the part by weight shared by foam silicon carbon is 40-99%.Part by weight shared by type ZSM 5 molecular sieve is preferably 5-50%, and the part by weight shared by foam silicon carbon is preferably 50-95%.
In the present invention, the foam silicon carbon carrier of precoating ZSM-5 precursor, the part by weight shared by type ZSM 5 molecular sieve presoma is 5-65%, and the part by weight shared by foam silicon carbon is 35-95%.Part by weight shared by type ZSM 5 molecular sieve presoma is preferably 5-55%, and the part by weight shared by foam silicon carbon is preferably 45-95%.
In the present invention, ZSM-5/ foam silicon carbon structural catalyst is mixed with organic/inorganic amine aqueous solution, is placed in reactor, carry out hydrothermal synthesis reaction; Heating-up temperature is 90-250 DEG C, and reaction pressure is solution self-generated pressure or pressurized treatments, and pressure is 0.1-5MPa, and the reaction time is 2-72h; Or, organic/inorganic amine aqueous solution is placed in reactor bottom, the foam silicon carbon carrier of ZSM-5/ foam silicon carbon structural catalyst or precoating ZSM-5 precursor is placed in upper strata, utilizes the foam silicon carbon carrier of steam and ZSM-5/ foam silicon carbon structural catalyst or the precoating ZSM-5 precursor produced during heating that gas/solid phase reaction occurs; Heating-up temperature is 90-250 DEG C, and reaction pressure is solution self-generated pressure or pressurized treatments, and pressure is 0.1-5MPa, and the reaction time is 2-72h; Or, the foam silicon carbon carrier of ZSM-5/ foam silicon carbon structural catalyst or precoating ZSM-5 precursor is placed in reactor, passes into ammonia and pressurize, heat; Heating-up temperature is 90-250 DEG C, and reaction pressure is 0.1-5MPa, and the reaction time is 2-72h.
In the present invention, described inorganic/organic amine is ammoniacal liquor, methylamine, dimethylamine, trimethylamine, ethamine, n-propylamine or positive tripropyl amine (TPA).
In the present invention, resulting materials is further through 400-600 DEG C of roasting 1-10 hour.
In the present invention, after modification, the strong acid of ZSM-5/ foam silicon carbon structural catalyst reduces, and middle strong acid, weak acid increase; Meanwhile, the degree of crystallinity of modified catalysts improves, and duct is open, and pore volume increases, and molecular diffusion performance is good.
In the present invention, through the ZSM-5/ foam silicon carbon structural catalyst of modification in MTP preparing propylene from methanol process, material liquid is the industrial crude methanol solution of 40-95wt%, and volume space velocity is 0.3-10h
-1, reaction temperature is 400-550 DEG C.
In the present invention, porous (foam) thyrite can use properties of SiC foam ceramics material of a kind of high strength dense mentioned in Chinese invention patent application (publication number: CN1600742A) and preparation method thereof.After foamed plastics is cut out, immerse in slip, after taking-up, remove unnecessary slip, semi-solid preparation, then high temperature, high-pressure curing; By the foams pyrolysis after solidification, obtain the equiform foam-like carbon skeleton be made up of carborundum and RESEARCH OF PYROCARBON with original foam; Carbon skeleton centre bore left by mill, will fill centre bore, then pyrolysis by pressure injection method in silicon carbide slurry pressure injection to carbon skeleton centre bore; Through siliconising process, the carbon in carbon skeleton and gas phase or liquid-phase silicone react Formed SiClx, and combine with the original silicon carbide silicon grain in foam framework, thus obtain the foam silicon carbide ceramics of high strength dense.The present invention's pottery muscle density is high, microscopic structure uniform strength is high.The preparation of honeycomb silicon carbide ceramics adopts powdered carbon and carborundum powder as raw material, epoxy resin as binding agent, by extruded.After shaping, through siliconising process, carbon and gas phase or liquid-phase silicone react Formed SiClx, and combine with the original silicon carbide silicon grain in foam framework, thus obtain the foam silicon carbide ceramics of high strength dense.
In the present invention, the preparation method of ZSM-5/ foam SiC structural catalyst can use porous silicon carbide carrier surface height intercrystalline pore rate ZSM-5 type zeolite coating material mentioned in Chinese invention patent application (application number: ZL201010199071.0) and preparation method thereof.The method of foam SiC carrier surface growth in situ ZSM-5 type zeolite can use the porous silicon carbide carrier surface individual layer, b axle orientation ZSM-5 type zeolite coating material and preparation method thereof mentioned in Chinese invention patent application (application number: ZL201010199076.3).The method of foam SiC carrier surface growth in situ ZSM-5 type zeolite can use porous zeolite molecular sieve coating material on surface of silicon carbide ceramics mentioned in Chinese invention patent application (application number: ZL200910013245.7) and preparation method thereof.The method by the preset crystal seed colloid in Carboround surface, and controls the basicity of diauxic growth solution, nutrient concentrations and alkali metal ion addition, realizes zeolite crystal at Carboround surface preferential growth and controls zeolite crystal pattern.
In the present invention, the preparation method of the foam SiC carrier of precoating non-complete crystallization molecular sieve precursor can use a kind of superfine molecular sieves structured catalyst material based on porous silicon carbide silicon carrier mentioned in Chinese invention patent application (application number: ZL201110156980.0) and preparation method thereof.This material for active primitive, has multi-stage artery structure and whole superfine molecular sieves coating all has catalytic activity with superfine molecular sieves crystal.Micelle is sieved precursor and is coated in foam silicon carbon carrier surface through modification by the method, by vapor phase process, molecular sieve precursor is converted into superfine molecular sieves crystal and realizes the strong bonded between coating and carrier.Control the synthesis condition of micelle sieve precursor and add the method for pore creating material, molecular sieve crystal size, sial when intercrystalline pore rate can be controlled; And can according to the pore structure of the Geometric configuration design catalyst of target product and molecular sieve type, while maintenance superfine molecular sieves high activity, high target product selectivity, improve the appearance carbon ability of superfine molecular sieves, the mass transfer ability of fortifying catalytic agent, the life-span of extending catalyst.
The Method in situ modification of the molecular sieve catalyst that the present invention is new, the method is particularly suitable for the modification of structuring molecular sieve catalyst.ZSM-5/ foam silicon carbon structural catalyst in ammoniacal liquor, methylamine, dimethylamine, trimethylamine, ethamine, n-propylamine or positive tripropyl amine (TPA) solution or in its steam, obtains through heating, pressurizeing by the method.Modified through the method, the solid acid character of ZSM-5/ foam silicon carbon structural catalyst changes.Strong acid amount reduces, and middle strong acid, weak acid amount increase.Meanwhile, in ZSM-5/ foam silicon carbon structural catalyst, the crystallinity of type ZSM 5 molecular sieve strengthens, pore volume increases.The higher stability of relatively unmodified ZSM-5/ foam silicon carbon structural catalyst and selective is shown in preparing propylene from methanol reaction.
The present invention has following beneficial effect:
1, after adopting modification of the present invention, the strong acid of ZSM-5/ foam silicon carbon structural catalyst reduces, and middle strong acid, weak acid increase;
2, after adopting modification of the present invention, the degree of crystallinity of catalyst improves, and duct is open, and pore volume increases, and molecular diffusion performance is good.
3, the ZSM-5/ foam silicon carbon structural catalyst after modification is in preparing propylene from methanol reaction, under the prerequisite keeping ZSM-5/ foam silicon carbon structural catalyst height Propylene Selectivity, significantly improve the stability of catalyst, single pass life and recyclability.
Accompanying drawing explanation
The surface of Fig. 1 ZSM-5/ foam silicon carbon structured catalyst material and fracture apperance.Wherein, Fig. 1 a, 1b is macro morphology; Fig. 1 c is surface microscopic topographic; Fig. 1 d is cross-section morphology.
Fig. 2 is the NH of rear ZSM-5/ foam silicon carbon structured catalyst material before modified
3-TPD curve.
Fig. 3 is nitrogen adsorption, the desorption curve of rear ZSM-5/ foam silicon carbon structured catalyst material before modified.Wherein, illustration is the pore-size distribution of rear ZSM-5/ foam silicon carbon structured catalyst material before modified.
Fig. 4 is the XRD curve of rear ZSM-5/ foam silicon carbon structured catalyst material before modified.
Fig. 5 be before modified after ZSM-5/ foam silicon carbon structured catalyst material preparing propylene from methanol reaction in catalytic performance.
Detailed description of the invention
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
In the present embodiment, ZSM-5/ foam silicon carbon structural catalyst is made up of foam silicon carbon carrier and the type ZSM 5 molecular sieve that is carried on its surface, and the part by weight shared by type ZSM 5 molecular sieve is 30%, and the part by weight shared by foam silicon carbon is 70%.The Method in situ modification of ZSM-5/ foam silicon carbon structural catalyst:
Ammoniacal liquor is placed in reactor bottom, ZSM-5/ foam silicon carbon structural catalyst is placed in upper strata, and centre porous Teflon support separates.Reactor is placed in 160 DEG C of baking ovens, reacts 24 hours under 0.3MPa pressure.The ZSM-5/ foam silicon carbon structural catalyst above-mentioned process obtained, 550 DEG C of roastings 4 hours, obtains modified ZSM-5/foam silicon carbon structural catalyst.
After modification, the strong acid of ZSM-5/ foam silicon carbon structural catalyst reduces, and middle strong acid, weak acid increase; Meanwhile, the degree of crystallinity of modified catalysts improves, and duct is open, and pore volume increases, and molecular diffusion performance is good.
The technical parameter of the present embodiment modified ZSM-5/ foam silicon carbon structural catalyst is as follows: zeolite crystal load capacity is 10wt%; The specific area of structural catalyst is 106.53m
2g
-1, weak acid, middle strong acid account for 60% of total acid content.
Through the ZSM-5/ foam silicon carbon structural catalyst of modification in MTP preparing propylene from methanol process, material liquid is the industrial crude methanol solution of 50wt%, and volume space velocity is 1h
-1, reaction temperature is 480 DEG C.
Embodiment 2
In the present embodiment, ZSM-5/ foam silicon carbon structural catalyst is made up of foam silicon carbon carrier and the type ZSM 5 molecular sieve that is carried on its surface, and the part by weight shared by type ZSM 5 molecular sieve is 20%, and the part by weight shared by foam silicon carbon is 80%.The Method in situ modification of ZSM-5/ foam silicon carbon structural catalyst:
Methylamine is placed in reactor bottom, ZSM-5/ foam silicon carbon structural catalyst is placed in upper strata, and centre porous Teflon support separates.Reactor is placed in 180 DEG C of baking ovens, reacts 18 hours under solution self-generated pressure.The ZSM-5/ foam silicon carbon structural catalyst above-mentioned process obtained, 500 DEG C of roastings 6 hours, obtains modified ZSM-5/foam silicon carbon structural catalyst.
After modification, the strong acid of ZSM-5/ foam silicon carbon structural catalyst reduces, and middle strong acid, weak acid increase; Meanwhile, the degree of crystallinity of modified catalysts improves, and duct is open, and pore volume increases, and molecular diffusion performance is good.
The technical parameter of the present embodiment modified ZSM-5/ foam silicon carbon structural catalyst is as follows: the specific area of structural catalyst is 76.53m
2g
-1, weak acid, middle strong acid account for 70% of total acid content.
Through the ZSM-5/ foam silicon carbon structural catalyst of modification in MTP preparing propylene from methanol process, material liquid is the industrial crude methanol solution of 40wt%, and volume space velocity is 2h
-1, reaction temperature is 470 DEG C.
Embodiment 3
In the present embodiment, ZSM-5/ foam silicon carbon structural catalyst is made up of foam silicon carbon carrier and the type ZSM 5 molecular sieve that is carried on its surface, and the part by weight shared by type ZSM 5 molecular sieve is 40%, and the part by weight shared by foam silicon carbon is 60%.The Method in situ modification of ZSM-5/ foam silicon carbon structural catalyst:
ZSM-5/ foam silicon carbon structural catalyst is placed in reactor bottom, passes into ammonia.Reactor is placed in 200 DEG C of baking ovens, reacts 48 hours under 3.0MPa pressure.The ZSM-5/ foam silicon carbon structural catalyst above-mentioned process obtained, 500 DEG C of roastings 6 hours, obtains modified ZSM-5/foam silicon carbon structural catalyst.
After modification, the strong acid of ZSM-5/ foam silicon carbon structural catalyst reduces, and middle strong acid, weak acid increase; Meanwhile, the degree of crystallinity of modified catalysts improves, and duct is open, and pore volume increases, and molecular diffusion performance is good.
The specific area of the following structural catalyst of technical parameter of the present embodiment modified ZSM-5/ foam silicon carbon structural catalyst is 156.42m
2g
-1, weak acid, middle strong acid account for 650% of total acid content.
Through the ZSM-5/ foam silicon carbon structural catalyst of modification in MTP preparing propylene from methanol process, material liquid is the industrial crude methanol solution of 50wt%, and volume space velocity is 3h
-1, reaction temperature is 490 DEG C.
Embodiment 4
In the present embodiment, in the foam silicon carbon carrier of precoating ZSM-5 precursor, the part by weight shared by type ZSM 5 molecular sieve presoma is 20%, and the part by weight shared by foam silicon carbon is 80%.The Method in situ modification of the foam silicon carbon carrier of precoating ZSM-5 molecular sieve presoma:
Methylamine is placed in reactor bottom, the foam silicon carbon carrier of precoating ZSM-5 molecular sieve presoma is placed in upper strata, and centre porous Teflon support separates.Reactor is placed in 180 DEG C of baking ovens, reacts 48 hours under 0.2MPa pressure.The ZSM-5/ foam silicon carbon structural catalyst above-mentioned process obtained, 550 DEG C of roastings 6 hours, obtains modified ZSM-5/foam silicon carbon structural catalyst.
After modification, the strong acid of ZSM-5/ foam silicon carbon structural catalyst reduces, and middle strong acid, weak acid increase; Meanwhile, the degree of crystallinity of modified catalysts improves, and duct is open, and pore volume increases, and molecular diffusion performance is good.
The specific area of the following structural catalyst of technical parameter of the present embodiment ZSM-5/ foam silicon carbon structural catalyst is 86.33m
2g
-1, weak acid, middle strong acid account for 80% of total acid content.
Through the ZSM-5/ foam silicon carbon structural catalyst of modification in MTP preparing propylene from methanol process, material liquid is the industrial crude methanol solution of 70wt%, and volume space velocity is 9h
-1, reaction temperature is 470 DEG C.
Embodiment 5
In the present embodiment, in the foam silicon carbon carrier of precoating ZSM-5 precursor, the part by weight shared by type ZSM 5 molecular sieve presoma is 30%, and the part by weight shared by foam silicon carbon is 70%.The Method in situ modification of precoating ZSM-5/ foam silicon carbon structural catalyst:
Ethylenediamine is placed in reactor bottom, ZSM-5/ foam silicon carbon structural catalyst is placed in ethylenediamine solution.Reactor is placed in 120 DEG C of baking ovens, reacts 10 hours under solution self-generated pressure.The ZSM-5/ foam silicon carbon structural catalyst above-mentioned process obtained, 500 DEG C of roastings 6 hours, obtains modified ZSM-5/foam silicon carbon structural catalyst.
After modification, the strong acid of ZSM-5/ foam silicon carbon structural catalyst reduces, and middle strong acid, weak acid increase; Meanwhile, the degree of crystallinity of modified catalysts improves, and duct is open, and pore volume increases, and molecular diffusion performance is good.
The technical parameter of the present embodiment modified ZSM-5/ foam silicon carbon structural catalyst is as follows: the specific area of structural catalyst is: 127.52m
2g
-1, weak acid, middle strong acid account for 85% of total acid content.
Through the ZSM-5/ foam silicon carbon structural catalyst of modification in MTP preparing propylene from methanol process, material liquid is the industrial crude methanol solution of 70wt%, and volume space velocity is 5h
-1, reaction temperature is 500 DEG C.
Embodiment 6
In the present embodiment, in the foam silicon carbon carrier of precoating ZSM-5 precursor, the part by weight shared by type ZSM 5 molecular sieve presoma is 40%, and the part by weight shared by foam silicon carbon is 50%.The Method in situ modification of precoating ZSM-5/ foam silicon carbon structural catalyst:
Ethamine is placed in reactor bottom, ZSM-5/ foam silicon carbon structural catalyst is placed in ethylenediamine solution.Reactor is placed in 150 DEG C of baking ovens, reacts 12 hours under solution self-generated pressure.The ZSM-5/ foam silicon carbon structural catalyst above-mentioned process obtained, 520 DEG C of roastings 6 hours, obtains modified ZSM-5/foam silicon carbon structural catalyst.
After modification, the strong acid of ZSM-5/ foam silicon carbon structural catalyst reduces, and middle strong acid, weak acid increase; Meanwhile, the degree of crystallinity of modified catalysts improves, and duct is open, and pore volume increases, and molecular diffusion performance is good.
The technical parameter of the present embodiment modified ZSM-5/ foam silicon carbon structural catalyst is as follows: the specific area of structural catalyst is: 165.22m
2g
-1, weak acid, middle strong acid account for 90% of total acid content.
Through the ZSM-5/ foam silicon carbon structural catalyst of modification in MTP preparing propylene from methanol process, material liquid is the industrial crude methanol solution of 80wt%, and volume space velocity is 8h
-1, reaction temperature is 480 DEG C.
As shown in Figure 1, from surface and the fracture apperance of ZSM-5/ foam silicon carbon structured catalyst material, can find out that zeolite molecular sieve coating is at foam silicon carbon carrier surface Load Balanced, does not occur the phenomenon that coating shedding, cracking, molecular sieve crystal lack.
As shown in Figure 2, from the NH of ZSM-5/ foam silicon carbon structured catalyst material after before modified
3-TPD curve, can find out the weak acid of modification rear catalyst, middle strong acid amount increases, strong acid amount reduces.
As shown in Figure 3, can find out that the pore volume of modified ZSM-5/ foam silicon carbon structured catalyst material increases, mesopore volume increases.
As shown in Figure 4, from the XRD curve of ZSM-5/ foam silicon carbon structured catalyst material after before modified, the characteristic peak intensity enhancing of molecular sieve after modification can be found out, show that modification is conducive to improving the crystallinity of molecular sieve.
As shown in Figure 5, from the catalytic performance of ZSM-5/ foam silicon carbon structured catalyst material after before modified preparing propylene from methanol reaction, can find out that the stability of modification rear catalyst improves, propylene can keep higher productive rate in a long time.
Embodiment result shows, after modification, the strong acid of ZSM-5/ foam silicon carbon structural catalyst reduces, and middle strong acid, weak acid increase; Meanwhile, the degree of crystallinity of modified catalysts improves, and duct is open, and pore volume increases, and molecular diffusion performance is good.The present invention through modification ZSM-5/ foam silicon carbon structural catalyst preparing propylene from methanol reaction in, under the prerequisite keeping ZSM-5/ foam silicon carbon structural catalyst height Propylene Selectivity, significantly improve the stability of catalyst, single pass life and recyclability.
Claims (6)
1. the Method in situ modification of a ZSM-5/ foam silicon carbon structural catalyst, it is characterized in that: the foam silicon carbon carrier of ZSM-5/ foam silicon carbon structural catalyst or precoating ZSM-5 precursor is heated by this method of modifying in organic/inorganic amine aqueous solution or steam, pressurized treatments, play the effect of adjustment solid acid character;
Described ZSM-5/ foam silicon carbon structural catalyst, be made up of foam silicon carbon carrier and the type ZSM 5 molecular sieve that is carried on its surface, the part by weight shared by type ZSM 5 molecular sieve is 1-60%, and the part by weight shared by foam silicon carbon is 40-99%;
In the foam silicon carbon carrier of described precoating ZSM-5 precursor, the part by weight shared by type ZSM 5 molecular sieve presoma is 5-65%, and the part by weight shared by foam silicon carbon is 35-95%;
Described organic/inorganic amine is ammoniacal liquor, methylamine, dimethylamine, trimethylamine, ethamine, n-propylamine or positive tripropyl amine (TPA);
ZSM-5/ foam silicon carbon structural catalyst is mixed with organic/inorganic amine aqueous solution, is placed in reactor, carries out hydrothermal synthesis reaction; Heating-up temperature is 90-250 DEG C, and reaction pressure is solution self-generated pressure or pressurized treatments, and pressure is 0.1-5MPa, and the reaction time is 2-72h; Or, organic/inorganic amine aqueous solution is placed in reactor bottom, the foam silicon carbon carrier of ZSM-5/ foam silicon carbon structural catalyst or precoating ZSM-5 precursor is placed in upper strata, utilizes the foam silicon carbon carrier of steam and ZSM-5/ foam silicon carbon structural catalyst or the precoating ZSM-5 precursor produced during heating that gas/solid phase reaction occurs; Heating-up temperature is 90-250 DEG C, and reaction pressure is solution self-generated pressure or pressurized treatments, and pressure is 0.1-5MPa, and the reaction time is 2-72h; Or, the foam silicon carbon carrier of ZSM-5/ foam silicon carbon structural catalyst or precoating ZSM-5 precursor is placed in reactor, passes into ammonia and pressurize, heat; Heating-up temperature is 90-250 DEG C, and reaction pressure is 0.1-5MPa, and the reaction time is 2-72h.
2. according to the Method in situ modification of ZSM-5/ foam silicon carbon structural catalyst according to claim 1, it is characterized in that, described ZSM-5/ foam silicon carbon structural catalyst, be made up of foam silicon carbon carrier and the type ZSM 5 molecular sieve that is carried on its surface, part by weight shared by type ZSM 5 molecular sieve is 5-50%, and the part by weight shared by foam silicon carbon is 50-95%.
3. according to the Method in situ modification of ZSM-5/ foam silicon carbon structural catalyst according to claim 1, it is characterized in that, in the foam silicon carbon carrier of described precoating ZSM-5 precursor, part by weight shared by type ZSM 5 molecular sieve presoma is 5-55%, and the part by weight shared by foam silicon carbon is 45-95%.
4. according to the Method in situ modification of ZSM-5/ foam silicon carbon structural catalyst according to claim 1, it is characterized in that, resulting materials is further through 400-600 DEG C of roasting 1-10 hour.
5. according to the Method in situ modification of ZSM-5/ foam silicon carbon structural catalyst according to claim 1, it is characterized in that, after modification, the strong acid of ZSM-5/ foam silicon carbon structural catalyst reduces, and middle strong acid, weak acid increase; Meanwhile, the degree of crystallinity of modified catalysts improves, and duct is open, and pore volume increases, and molecular diffusion performance is good.
6. according to the Method in situ modification of ZSM-5/ foam silicon carbon structural catalyst according to claim 1, it is characterized in that, through the ZSM-5/ foam silicon carbon structural catalyst of modification in MTP preparing propylene from methanol process, material liquid is the industrial crude methanol solution of 40-95wt%, and volume space velocity is 0.3-10 h
-1, reaction temperature is 400-550 DEG C.
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| CN101181692A (en) * | 2007-11-08 | 2008-05-21 | 复旦大学 | Framework modification acid-alkali bifunctional ZSM-5 zeolite catalyst and method for preparing the same |
| CN102531823A (en) * | 2010-12-23 | 2012-07-04 | 中国科学院金属研究所 | Propylene preparation method with high propylene production rate by using methanol |
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| CN102531823A (en) * | 2010-12-23 | 2012-07-04 | 中国科学院金属研究所 | Propylene preparation method with high propylene production rate by using methanol |
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