CN105618131A - Compound dual-carrier catalyst as well as preparation method and application thereof - Google Patents
Compound dual-carrier catalyst as well as preparation method and application thereof Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
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- 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
Abstract
The invention belongs to the technical field of preparation of catalysts and discloses a compound dual-carrier catalyst as well as a preparation method and application thereof. According to the compound dual-carrier catalyst, a microporous molecular sieve or a solid acid catalyst is mixed with a mesoporous molecular sieve and then is loaded with metal nickel and metal tin; the microporous molecular sieve is HBeta or HZSM-5, the solid acid catalyst is Al2O3, and the mesoporous molecular sieve is MCM-41. By carrying out catalytic hydrogen production by reforming on wood vinegar liquid in the presence of the compound dual-carrier catalyst, the production efficiency of hydrogen-rich gas produced through catalytic hydrogen production by reforming of wood vinegar liquid can be improved, carbon deposit in the reaction process can be further reduced, and the service life of the catalyst can be prolonged; the content of each gas component is slightly decreased within 2 hours. Meanwhile, the optimal hydrogen content and yield are increased to 60.32% and 22.47mg/g sample, respectively.
Description
Technical field
The present invention relates to catalyst preparation technical field, more particularly, to a kind of Composite Double carried catalyst and preparation method thereof and application.
Background technology
Wood vinegar water vapour catalytic reforming prepares the basic course of hydrogen rich gas: first wood vinegar is cracked into Primary product (CO, CO2, CH4, C2) and carbon deposit, Primary product, under the effect of catalyst, carries out steam reforming with the moisture in wood vinegar and generates hydrogen-rich gas, and in solid acid catalyst, molecular sieve catalyst is cheap because of it, and activity is high and enjoys favor. But easily blocked by carbon deposit owing to its duct of microporous molecular sieve catalyst is less, cause that the service life of catalyst is shorter.
Summary of the invention
The technical problem to be solved is the defect overcoming in prior art the catalyst used by wood vinegar water vapour catalytic reforming preparing hydrogen-rich gas easily to deposit carbon deposit and causing catalyst service life short, it is provided that a kind of Composite Double carried catalyst.
The preparation method that second purpose of the present invention is to provide above-mentioned catalyst.
3rd purpose of the present invention is to provide the application of above-mentioned catalyst.
4th purpose of the present invention is to provide a kind of method of wood vinegar water vapour catalytic reforming preparing hydrogen-rich gas.
It is an object of the invention to be achieved by the following technical programs:
A kind of Composite Double carried catalyst, is after micro porous molecular sieve or solid acid catalyst being mixed with mesopore molecular sieve and carried metal nickel and metallic tin; Described micro porous molecular sieve is HBeta or HZSM-5, and described solid acid catalyst is Al2O3, described mesopore molecular sieve is MCM-41.
Single carrier is a lot of for the research of reformation hydrogen production, but the carbon deposit of single carrier is serious, affect the life-span of catalyst, the technological requirement of catalyst regeneration is high simultaneously, cost is high, molecular sieve catalyst presents good shape selectivity due to it in aromatic compound converts, and is therefore widely used in Industrial Catalysis. Owing to the catalysis activity of molecular sieve catalyst is main by the characteristic of acidic site, the structure of molecular sieve, molecular sieve pore passage geometry three dimensional structure determines. So the effect of same reaction is differed greatly by different molecular sieves, cause that the path of reaction and the product of generation differ greatly.
The present invention is by after mixing micro porous molecular sieve or solid acid catalyst with mesopore molecular sieve, screen the active substance of load again, acquisition can be greatly improved the Composite Double carried catalyst in catalyst ability and service life, the catalytic capability of this Composite Double carried catalyst is strong, and anti-carbon deposition ability is strong.
Preferably, the mass ratio of described micro porous molecular sieve or solid acid catalyst and mesopore molecular sieve is 1��5:1.
It is highly preferred that the mass ratio of described micro porous molecular sieve or solid acid catalyst and mesopore molecular sieve is 3��4:1.
Preferably, the mol ratio of described metallic nickel and metallic tin is 1��5:1.
The preparation method that the present invention also provides for described Composite Double carried catalyst, comprises the following steps:
(1) pre-treatment of molecular sieve: molecular sieve is warming up to 200��300 DEG C and keeps 0.5��1h, is continuously heating to 300��400 DEG C and keeps 0.5��1h, then be warming up to 500��700 DEG C of maintenance 3��8h, be finally down to room temperature;
(2) dipping: the molecular sieve after processing is placed in containing Sn2+And Ni2+Predecessor in, carry out supersound process, stirring is dried, roasting and get final product.
As a kind of specific embodiment, the preparation method of Composite Double carried catalyst of the present invention, comprises the following steps: the calcining (Fig. 6) of (1) carrier: raw molecule first sieves the mode heated up according to following substep in carrier placement Muffle furnace and carries out calcining to remove impurity under air atmosphere.
(2) dipping: by SnCl2With Ni (NO3)2Being dissolved in hydrochloric acid solution, according to water absorption rate result of calculation, the carrier impregnation after being calcined by certain mass is at certain density SnCl2With Ni (NO3)2In the predecessor of active substance, controlling Ni and Sn mol ratio in solution is 3:1. The ultrasonic cleaning equipment that frequency is 27KW carries out ultrasonic Treatment 0.5h, is followed by stirring for 2h, be subsequently placed with under room temperature impregnation drying 4h.
(3) dry: the carrier that step (2) processed moves to the Constant Temp. Oven forced air drying 24h of 70 DEG C.
(4) roasting: put in Muffle furnace by the carrier that step (3) processed, in air atmosphere, rises to 500 DEG C with the heating rate of 20 DEG C/min, and constant temperature 3h, is naturally down to room temperature afterwards, prepares required catalyst.
The present invention also provides for the application in wood vinegar catalytically reforming hydrogen producing of the described Composite Double carried catalyst.
The present invention also provides for a kind of method of wood vinegar water vapour catalytic reforming preparing hydrogen-rich gas, is gasified by wood vinegar, under the catalysis of described Composite Double carried catalyst under normal pressure, reacts 2��4h.
Compared with prior art, the method have the advantages that
The invention provides a kind of Composite Double carried catalyst, be after micro porous molecular sieve or solid acid catalyst are mixed with mesopore molecular sieve and carried metal nickel and metallic tin; Described micro porous molecular sieve is HBeta or HZSM-5, and described solid acid catalyst is Al2O3, described mesopore molecular sieve is MCM-41; Adopt this Composite Double carried catalyst to carry out wood vinegar catalytically reforming hydrogen producing, be possible not only to improve wood vinegar catalytic reforming and prepare the efficiency of hydrogen-rich gas, moreover it is possible to reduce the carbon deposit in course of reaction, extend the life-span of catalyst. In 2h the content of each gas component slightly under. Meanwhile, the content of best hydrogen and productivity have also risen to 60.32% and 22.47mg/gsample respectively.
Accompanying drawing explanation
Fig. 1 is wood vinegar water vapour catalytically reforming hydrogen producing apparatus figure.
Fig. 2 is that each component of wood vinegar list carrier catalysis reformation changes over trendgram, and in figure, C2 is C2H4And C2H6General designation, use C2Indicate that both content sums.
Fig. 3 is that the Composite Double carrier catalysis each component of reformation wood vinegar changes over trendgram, and in figure, C2 is C2H4And C2H6General designation, use C2Indicate that both content sums.
Fig. 4 is that the Composite Double carrier catalysis each component of reformation wood vinegar changes over trendgram.
Fig. 5 is the SEM collection of illustrative plates of catalyst before and after reaction.
Fig. 6 is the flow chart of carrier calcining.
Detailed description of the invention
Below in conjunction with specification drawings and specific embodiments, patent of the present invention is further described. Wherein, being merely cited for property of accompanying drawing illustrates, expression is only schematic diagram, but not pictorial diagram, it is impossible to it is interpreted as the restriction to this patent; In order to the embodiment of of the present invention patent is better described, some parts of accompanying drawing have omission, zoom in or out, and do not represent the size of actual product; It will be understood by those skilled in the art that some known features and explanation thereof are likely to omission and will be understood by accompanying drawing.
Fig. 1 is the Experimental equipment of wood vinegar water vapour catalytic reforming reaction. Wood vinegar water vapour catalytic reforming reaction carries out in atmospheric fixed bed quartz tube reactor, and quartz ampoule internal diameter is 26mm, long 700mm. In experiment, each catalyst amount is 10g. Catalyst lower end wire gauze is fixed, and about 50mm Gao Zhu is filled with silica wool in upper end, in order to volatile matter is uniformly through beds. In the performance test of catalyst, first catalyst is placed among quartz reactor, and pass into high pure nitrogen wherein to drive air, now tube type resistance furnace is heated up, by K type thermocouple measurement bed temperature, temperature controller temperature control, heating rate is about 30 DEG C/min, when rising to 750 DEG C, pass into reducing gases (90%H2/ 10%He) react 1h, reducing gases is 500ml/min by glass rotameter coutroi velocity, after reduction, closes reducing gases, regulates temperature to reaction temperature, and blow with nitrogen and be cooled to reaction temperature.
In an experiment the conical flask of dress wood vinegar is positioned on magnetic stirring apparatus, heats while stirring. The rotating speed 200r/min of magnetic stir bar, heating panel temperature is adjusted to 100 DEG C. Wood vinegar pumps into the flow velocity of 0.3g/min through peristaltic pump in reactor. Being carrier gas with nitrogen in course of reaction, flow velocity is 100ml/min. The gas of reaction generation and unreacted biomass pyrolytic volatile matter outflow reactor in the lump, at condensing tube place, condensable bio oil and water are collected by liquid header, and product gas measures after flow velocity through soap film flowmeter, Storage Time in Gas Collecting Bag collect. Collected liquid carries out GS-MS detection after extraction of weighing, and collected gaseous product is also by gas chromatogram offline inspection. Reaction unit is dropped to room temperature after terminating by reaction under nitrogen atmosphere, and collection catalyst remains late detection indices.
The preparation of embodiment 1 catalyst
Molecular sieve carrier (catalyst) characteristic such as table 1 used by the present embodiment, the present embodiment adopts equi-volume impregnating to prepare various catalyst.
The correlation properties of each molecular sieve carrier of table 1
(single carrier is HBeta, HZSM-5, Al to prepare two molecular sieve analog carriers, single carrier and complex carries altogether2O3Carrying active substance Ni and Sn. Complex carries is by list carrier HBeta, HZSM-5, Al2O3Mix according to the ratio of quality 1:1 with mesopore molecular sieve carrier MCM-41 respectively, stirring 2h is until mix homogeneously back loading active substance Ni and Sn), comprise the following steps: the calcining (Fig. 6) of (1) carrier: first raw molecule is sieved carrier and places the mode heated up according to following substep in Muffle furnace and carry out calcining to remove impurity under air atmosphere.
(2) mensuration of carrier water absorption rate: by certain mass through calcining after molecular sieve carrier be placed among container, it is gradually added into deionized water, until carrier reaches just wet condition, calculate the quality adding deionized water, by this numerical value quality divided by carrier, the water absorption rate of unit mass carrier can be obtained.
(3) dipping: by SnCl2With Ni (NO3)2Being dissolved in hydrochloric acid solution, according to water absorption rate result of calculation, the carrier impregnation after being calcined by certain mass is at certain density SnCl2With Ni (NO3)2In the predecessor of active substance, controlling Ni and Sn mol ratio in solution is 3:1. The ultrasonic cleaning equipment that frequency is 27KW carries out ultrasonic Treatment 0.5h, is followed by stirring for 2h, be subsequently placed with under room temperature impregnation drying 4h.
(4) dry: the carrier that step (3) processed moves to the Constant Temp. Oven forced air drying 24h of 70 DEG C.
(5) roasting: put in Muffle furnace by the carrier that step (4) processed, in air atmosphere, rises to 500 DEG C with the heating rate of 20 DEG C/min, and constant temperature 3h, is naturally down to room temperature afterwards, prepares required catalyst.
The single carrier Ni/Sn catalyst wood vinegar water vapour catalytic reforming characteristic research of embodiment 3
Experiment condition: reaction temperature 600 DEG C; Wood vinegar sample size 0.25g/min; Carrier gas N2Flow velocity 100mL/min; Catalyst amount 10g. Single carried catalyst respectively Ni/Sn/HBeta, Ni/Sn/HZSM-5, Ni/Sn/Al used2O3��
Utilizing described single carried catalyst to carry out wood vinegar water vapour catalytic reforming reaction, in gas, the situation of change of each component is as shown in Figure 2. When using Ni/Sn/HBeta catalyst, in 1h originally, the volumn concentration of hydrogen is always held at about 65%. When reaction proceeds, the content of hydrogen is remarkably decreased, and drops to about 30% from 65%. The content of CO but rises to 35% from 5%, CH4Content also rise to 16% from 5%.
When using catalyst n i/Sn/HZSM-5, the content of hydrogen gradually drop to 40% from 65% originally, and CO, CH4, C2H4Content have a degree of rising, most notable of which is that the content of CO about 10% rises to 25% from what start.
Compare first two catalyst, Ni/Sn/Al2O3Catalysis activity more lasting. Along with the carrying out of reaction, the changes of contents of hydrogen is comparatively inconspicuous, only drops to 45% from beginning 65%. The difference is that the content of CO first has slight decline then to present again the trend of rising, just with CO2Variation tendency contrary. And CH4And C2H4There is the trend of constantly rising.
Table 2 shows the productivity of each gas component. From Table 2, it can be seen that when using Ni/Sn/HBeta catalyst, in the mixing gas after wood vinegar water vapour catalytic reforming, the content of hydrogen is not the highest, but gas yield is the highest, reaches 114.75ml/min. Final within the response time of 2h, the productivity utilizing the obtained each gas component of Ni/Sn/HBeta catalyst is all higher, and especially the productivity of hydrogen has reached 21.58mg/gsample. Because the Lewis acidic site content of HBeta molecular sieve surface is the highest in three kinds of catalyst carriers.
The table 2 wood vinegar list carrier catalysis each constituent content of reformation and productivity thereof
Many researcheres find Ni catalyst based can the acids in conversion of biomass tar effectively, aldehydes, the small molecule organic compound such as ketone produces hydrogen. Adding Ni, Sn isoreactivity material and catalyst surface acidity has the impact of two aspects, active substance can cover the acidic site (including Bronsted acid and Lewis acid) of molecular sieve surface on the one hand, causes that the total acid content of catalyst surface declines. On the other hand, catalyst surface plays the cation of synergistic undersaturated Ni, will form new lewis acid site, makes up original capped lewis acidic site. From the results, it was seen that the covering effect of Ni, Sn isoreactivity material, higher make up effect in Ni is cationic.
The steam reforming reaction of tar is also played an important role by the character of carrier, and as can be seen from Table 2, the selective impact of hydrogen is followed successively by by different carriers: Al2O3>HBeta>HZSM-5��
Embodiment 4 Composite Double carrier catalysis reformation wood vinegar wood vinegar water vapour catalytic reforming characteristic research
Composite Double carrier catalysis reformation wood vinegar experiment condition: reaction temperature 600 DEG C; Wood vinegar sample size 0.25g/min; Carrier gas N2Flow velocity 100mL/min; Catalyst amount 10g (gross mass of complex carries).
Used catalyst is Ni/Sn/HBeta+MCM-41 respectively; Ni/Sn/HZSM-5+MCM-41; Ni/Sn/Al2O3+MCM-41��
Under the effect of Composite Double carried catalyst, in gas, the situation of change of each component is as shown in Figure 3. When using Ni/Sn/HBeta+MCM-41 complex carries catalyst, after going through 2h reaction, the content of hydrogen is dropped to 53% by original 60%, and compared with using single carried catalyst, the down ratio of hydrogen content substantially reduces. As can be seen here, mesoporous molecular sieve catalyst MCM-41 is added, it will be apparent that extend the service life of catalyst.
Ni/Sn/HZSM-5+MCM-41 catalyst is also by same effect. Significantly reduce the speed of catalysqt deactivation. Wherein extending catalysis activity, effect is Ni/Sn/Al most preferably2O3+ MCM-41 mixed catalyst, in the stage of reaction of 2h, the content of hydrogen only have dropped 4% from original 65%, and is always maintained at efficient conversion ratio. In the course of reaction of 2h, other each gas component content is also without the trend significantly raised or reduce.
Comparison sheet 2 and table 3 are it can be seen that after utilizing complex carries catalyst n i/Sn/HBeta+MCM-41 and Ni/Sn/HZSM-5+MCM-41, the flow of gas is decreased obviously. Respectively by original 114.75ml/min and 90.78ml/min, drop to 79.97ml/min and 53.55ml/min, have dropped close to 1/3rd, and then cause that the productivity of hydrogen is remarkably decreased. But this effect is not present in complex carries catalyst n i/Sn/Al2O3On+MCM-41, the contrary flow velocity mixing gas rises slightly to 104.29ml/min from original 96.68ml/min.
The table 3 Composite Double carrier catalysis each constituent content of reformation wood vinegar and productivity thereof
Analyze the changes of contents situation of each gas component further it can be seen that work as and use Ni/Sn/HZSM-5+MCM-41 and Ni/Sn/Al2O3After+MCM-41 catalyst, H2And CO2Content be all improved to some extent, but CH4, CO and C2H4Content have dropped. This is after the catalytic organism cracking in wood vinegar, there occurs steam reformation effect between the micro-molecular gas of generation. Such as CH4Steam reforming reaction (CH4+2H2O=CO2+4H2), the Water-gas shift reaction (CO+H of CO2O=CO2+H2) and C2H4Steam reforming reaction (C2H4+H2O=1.5CH4+0.5CO2), ultimately result in H2And CO2Content rise.
Embodiment 5 Composite Double carrier catalysis reformation wood vinegar life experiment
If the life experiment of Fig. 4 catalyst is it is shown that in 0.5h originally, H2And CO2Content be decreased obviously, CH4To a certain degree rise with the content of CO. This is because the reaction starting stage, whole course of reaction is but without reaching steady statue. Afterwards in 4.5h course of reaction, the content of each gaseous product is held essentially constant. To 5h, H2And CO2Content obvious decline occurs again, this shows that the activity of this stage catalyst begins to decline, and the life-span of catalyst is probably at about 4h.
Selecting the catalyst before and after different carriers reaction to carry out electron-microscope scanning sign, result is Fig. 5 such as. Contrast reaction procatalyst surface topography, and post catalyst reaction area carbon pattern can be seen that, before reaction, fresh complex carries catalyst n i/Sn/HBeta+MCM-41 surface, at random is dispersed with micropore, uneven, use rear catalyst Ni/Sn/HBeta+MCM-41 surface, gathered a thick layer of carbon distribution.
And some short grained materials of distribution that fresh Ni/Sn/HZSM-5+MCM-41 catalyst surface is scattered, this is because in dipping process, it is adsorbed on the active substance of catalyst surface or short grained ZSM or MCM-41 granule. Catalyst surface after using is spherical carbon granule, and diameter 1��2um is piled into tufted.
For fresh Ni/Sn/Al2O3+ MCM-41 catalyst, its surface is uneven, but surface exists apparent duct, and diameter is at about 0.4um. And the catalyst after using, surface define one layer loose, irregular carbon deposit, although quantity is more, but still leave the space of part, duct, reactant still can enter catalytic inner; This also explains Ni/Sn/HBeta+MCM-41 after 2h is reacted, the productivity of hydrogen declines relatively Ni/Sn/Al2O3+ MCM-41 catalyst becomes apparent from.
After table 4 describes different carriers catalyst reforming reaction, its heat differential thermogravimetric analysis situation under hot-air. Single carried catalyst surface carbon deposit accounts between the 3.28��3.53% of catalyst total amount, and carrier three kinds different, its surface area carbon content is without obvious difference. HBeta catalyst surface carbon deposit, slightly lower than other two kinds of carriers, this is because the pore passage structure of HBeta molecular sieve (its shape selectivity), is more suitable for the catalytic reforming of wood vinegar organic molecule. The total amount of catalyst surface carbon deposit is between 2.4��3.53%. The total amount of complex carries catalyst surface carbon deposit is significantly lower than correspondence list carried catalyst. This also keeps consistent with the active duration of above complex carries catalyst apparently higher than single carried catalyst. Can also speculate that the reason that single supported catalyst activity declines should be catalyst surface carbon deposit blocking molecular sieve pore passage, or caused by the avtive spot on covering catalyst surface. And in complex carries catalyst, mesostructured material, first the Organic substance that catalytic reforming segment space structure is bigger, thus reduce the Organic substance of this type due to not easily pass through or enter microporous molecular sieve catalyst pore passage structure and at catalyst surface or the internal content producing carbon deposit.
The mass losses corresponding to peak different in table 4 carbon deposit
Once had been reported that and utilize TPO technology for detection at four different temperature sections, weightless peak to occur to catalyst surface carbon deposit. The carbon deposit (table 4, Bayraktar, 2002) that the different peak of these four is corresponding 4 kinds different types of. First peak is the produced weightless peak of Hydrocarbon decomposition of carbon deposit absorption; Second peak is with carbon deposit produced by metal active catalytic reaction, and the 3rd peak is carbon deposit produced by acid catalyzed reaction. Cause different carbon deposits, mainly due to different Organic substances, their reactions vary sample with oxygen, such as aromatic compound, organic polymer, or graphitic carbon, the speed that they and oxygen react, temperature needed for burning is significantly different, and then causes different carbon deposit weightlessness peaks. As can be seen from Table 4, the corresponding complex carries catalyst of single carried catalyst is respectively first, second and the 3rd weightless peak place mass change amount substantially close to, the temperature section that simply the weightless peak of complex carries catalyst is corresponding significantly shifts to low-temperature space, the temperature at the maximum weightless peak place that such as second weightless peak of single carrier HBeta is corresponding is 368 DEG C, and temperature corresponding to this peak of complex carries catalyst has transferred to 292.8 DEG C, it will be apparent that have dropped. This is more beneficial for later stage catalyst and regenerates by calcining in atmosphere.
As can be seen here, complex carries catalyst can reduce catalyst carbon deposit content on the one hand, on the other hand the effective generation suppressing to be unfavorable for the carbon deposit type of catalyst regeneration. In addition, after utilizing complex carries catalyst, fourth stage weightless peak of carbon deposit produced by acidic catalyst disappears, this is because MCM-41 surface acidity is very weak, reduces total surface acidity (just for molecular sieve catalyst) after mixing. ��-Al2O3Carrier adds after MCM-41, however it remains fourth stage weightlessness peak, but with MCM-41 catalyst mix after, fourth stage weightlessness peak substantially weakens (dropping to 0.33% from original 0.53%).
Relatively each carrier surface carbon deposit distribution situation, it can be seen that ��-Al2O3In catalyst, the carbon deposit content in the phase III is maximum. Relatively Ni/Sn/Al2O3Carbon deposit content results after+MCM-41 complex carries catalyst reaction 2h and after reaction 5h it can be seen that after reaction 5h the content of carbon deposit be not 2.5 times of 2h. As can be seen here, the carbon deposit content of catalyst is not linear with the response time, it is affected by a lot of other factors, this is the incipient stage that reaction carries out, catalyst can be easier to produce carbon deposit, after reaction carries out a period of time, catalyst creates the patience to carbon deposit, and then the content of newly-generated carbon deposit slows down gradually.
Claims (6)
1. a Composite Double carried catalyst, it is characterised in that be after micro porous molecular sieve or solid acid catalyst are mixed with mesopore molecular sieve and carried metal nickel and metallic tin; Described micro porous molecular sieve is HBeta or HZSM-5, and described solid acid catalyst is Al2O3, described mesopore molecular sieve is MCM-41.
2. Composite Double carried catalyst according to claim 1, it is characterised in that the mass ratio of described micro porous molecular sieve or solid acid catalyst and mesopore molecular sieve is 1��5:1.
3. Composite Double carried catalyst according to claim 1, it is characterised in that the mol ratio of described metallic nickel and metallic tin is 1��5:1.
4. the preparation method of Composite Double carried catalyst described in any one of claims 1 to 3, it is characterised in that comprise the following steps:
(1) pre-treatment of molecular sieve: molecular sieve is warming up to 200��300 DEG C and keeps 0.5��1h, is continuously heating to 300��400 DEG C and keeps 0.5��1h, then be warming up to 500��700 DEG C of maintenance 3��8h, be finally down to room temperature;
(2) dipping: the molecular sieve after processing is placed in containing Sn2+And Ni2+Predecessor in, carry out supersound process, stirring is dried, roasting and get final product.
5. Composite Double carried catalyst application in wood vinegar catalytically reforming hydrogen producing described in any one of claims 1 to 3.
6. the method for a wood vinegar water vapour catalytic reforming preparing hydrogen-rich gas, it is characterised in that gasified by wood vinegar, under the catalysis of the Composite Double carried catalyst described in any one of claims 1 to 3 under normal pressure, reacts 2��4h.
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| CN113996293A (en) * | 2021-11-23 | 2022-02-01 | 有研工程技术研究院有限公司 | Cerium-lanthanum solid solution supported iridium catalyst, and preparation method and application thereof |
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