CN103769201A - Anti-coking modification method for biomass catalytic pyrolysis catalyst ZSM-5 molecular sieve - Google Patents
Anti-coking modification method for biomass catalytic pyrolysis catalyst ZSM-5 molecular sieve Download PDFInfo
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Abstract
The invention relates to an anti-coking modification method for a biomass catalytic pyrolysis catalyst ZSM-5 molecular sieve. The modification method comprises the following steps: (1) adding a ZSM-5 molecular sieve catalyst into an EDTA (Ethylene Diamine Tetraacetic Acid) disodium solution according to a liquid-solid ratio of 7-12ml/g; agitating the catalyst and a modified solution in a heating agitator in a 70-90 DEG C constant-temperature water bath at a low speed for 1.5-2.5 hours; (2) after the modification is finished, filtering a mixture of the catalyst and the modified solution in vacuum and repeatedly washing by using de-ionized water until the pH (Potential of Hydrogen) of a washing solution is neutral; (3) transferring the modified catalyst into an air blowing drying oven and setting the temperature to 105-120 DEG C; and drying for 3-5 hours to remove water adsorbed by the molecular sieve, thus finally obtaining the modified catalyst. The ZSM-5 molecular sieve modified by the method can guarantee that an acid site in the molecular sieve can be retained and the surface acid site is reduced, so as to relieve a coking process of the surface of the catalyst in a biomass catalytic pyrolysis process and prolong the service life of the catalyst.
Description
Technical field
The anti-coking method of modifying that the present invention relates to a kind of catalytic pyrolysis of biomass catalyst Z SM-5 molecular sieve, belongs to biomass energy utilization technologies field.
Background technology
Biomass energy is prevailing a kind of regenerative resource on the earth, and it is to be only second to coal, oil and natural gas and the energy that occupy the 4th of world energy sources total quantity consumed, in whole energy resource system, occupies critical role.Develop the Biomass Energy Resources of China's abundant, there is extremely important effect for aspects such as China's energy resource structure diversification, alleviation liquid for treating calculus fluid fuel supply pressure, guarantee energy security and environmental protection.China biomass energy develops the initial stage that is still in development, and wherein biomass liquid fuel industry development is not only limited by the difficult problems such as cost, and key is also in biomass efficient conversion process the research difficult problems such as how grade lifting.
Heat chemistry transformation technology is one of higher value application technology that living beings are the most general, and directly pyrolysis liquefaction, because fluid product has storage, convenient transportation and energy density advantages of higher, is considered to the most promising biomass liquefying technology.Pyrolytic reaction is the mode by Fast Heating, is not having completely under oxygen or anoxia condition, makes the high molecular polymer that forms living beings be cracked into low molecule organic matter steam, and is condensed into the bio oil of liquid.Fast pyrogenation is the technology of a kind of liquid producing take pyrolysis as target product, pyrogenous origin bio oil (Bio-oil) is a kind of complicated mixture being made up of multiple oxygen-bearing organic matter, comprises the oligomer of organic acid, alcohol, aldehyde, ester, carbohydrate, aromatic and lignin etc.The bio oil physicochemical property generating is poor, as high in oxygen content (35～40%), moisture high (15～30%), solid content high (0.2～1%), acid large (pH value 2～3), calorific value low (higher calorific value 16～19MJ/kg, far below diesel oil 40MJ/kg) and poor heat stability (80 ℃ are easy to polymerization above) etc.Catalytic pyrolysis of biomass refers under middle temperature, normal pressure and acidic catalyst effect, and the oxygen in bio oil is reacted with CO, CO by deoxidation, decarboxylation, decarbonylation base etc.
2and H
2the process that the form of O removes.
In catalytic pyrolysis of biomass, catalyst plays vital effect in pyrolysis oil upgrading process.ZSM-5 molecular sieve is as the one of zeolite catalyst, there is three-dimensional ten-ring structure, have and be of a size of " Z " pore passage structure of 0.54 × 0.56nm and the straight channel of 0.52 × 0.58nm, unique channel system, become important shape-selective catalyst, be widely used in the fields such as catalytic cracking alkylating aromatic hydrocarbon and methanol-to-olefins.In recent years, zeolites catalyst is prepared aspect high-quality liquid fuel and chemicals and has also been shown good application prospect at catalyzed conversion living beings and derivative thereof, wherein, ZSM-5 molecular sieve catalyst has higher aromatic hydrocarbon and olefins yield in the zeolite catalysis conversion process of living beings and derivative thereof, is the emphasis of studying at present.Although ZSM-5 molecular sieve catalyst has good catalytic effect, catalyst is easy to inactivation, and in catalytic pyrolysis of biomass, ZSM-5 molecular sieve catalysqt deactivation causes mainly due to surperficial coking.The regular pore passage structure of ZSM-5 molecular sieve catalyst tool, the acidic site in duct is main catalysis place.Large molecule Jiao, cannot be inner generation the in the less duct of ZSM-5 molecular sieve owing to having larger diameter.And catalyst surface or porch be owing to having larger extending space, and have certain acidic site, large molecule is burnt easily to be generated and develops, finally blocking catalyst duct.Although there is a large amount of acidic sites in duct, reactant, because duct is stopped up, cannot or be difficult to diffuse in duct react, and finally causes the deactivation phenomenom on apparent.
Summary of the invention
Technical problem: the present invention is to provide a kind of anti-coking method of modifying of catalytic pyrolysis of biomass catalyst Z SM-5 molecular sieve, guaranteeing under the prerequisite of the quality of bio-oil that catalyse pyrolysis produces, to solve the problem of catalyst easy coking in catalyse pyrolysis reaction, to reach the service life of extending catalyst, reduce the object of bio oil pyrolysis operating cost.
Technical scheme: for solving the problems of the technologies described above, technical scheme provided by the invention is: a kind of anti-coking method of modifying of catalytic pyrolysis of biomass catalyst Z SM-5 molecular sieve, this method of modifying comprises the following steps:
1), by catalyst Z SM-5 molecular sieve by liquid-solid ratio 7～12ml/g, join in large molecule chelating agent modified solution, described catalyst and modified solution stir in heating stirrer;
2), after modification completes, by the mixture vacuum filtration of catalyst and modified solution composition, adopt deionized water cyclic washing, until cleaning solution pH is neutrality;
3), catalyst that filtration is obtained moves in convection oven and dries, and obtains modification rear catalyst.
Described large molecule chelating agent modified solution is disodium ethylene diamine tetraacetate (EDETATE SODIUM) solution.
Described heating stirrer temperature is 70～90 ℃, and heating mixing time is 1.5～2.5h.
Described convection oven Temperature Setting is 105～120 ℃, and drying time is 3～5h.
Beneficial effect:
1, modification rear catalyst has kept the MFI topological structure of ZSM-5 molecular sieve catalyst, and the inner acid invariant position in ZSM-5 molecular sieve duct, but the minimizing of catalyst surface acidic site, in catalytic pyrolysis of biomass reaction, have the performance of anti-coking.
2, this method of modifying is simple to operate, can guarantee under the prerequisite of quality of bio-oil, extending catalyst service life, reduces biomass pyrolytic and produce the operating cost of high-quality biological oil, realizes the production of bio oil continous-stable.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of unmodified ZSM-5 molecular sieve;
Fig. 2 is the XRD spectra of the modified zsm-5 zeolite that obtains of embodiment 1;
Fig. 3 is unmodified ZSM-5 molecular sieve tube furnace catalyse pyrolysis oil GC/MS(gas chromatography mass spectrometry) spectrogram;
Fig. 4 is embodiment 1 modified zsm-5 zeolite tube furnace catalyse pyrolysis oil GC/MS(gas chromatography mass spectrometry) spectrogram;
Fig. 5 is flow chart of the present invention.
The specific embodiment
In order to solve in catalytic pyrolysis of biomass process, catalyst is easy to the problem of coking, the invention provides a kind of catalyst anti-coking method of modifying, the method comprises the following steps: ZSM-5 molecular sieve catalyst to join by liquid-solid ratio 7～12ml/g in the solution of EDETATE SODIUM, catalyst and modified solution stirring at low speed 1.5～2.5h under 70～90 ℃ of constant temperature water baths in heating stirrer, after modification completes, by the mixture vacuum filtration of catalyst and modified solution, adopt deionized water cyclic washing simultaneously, until cleaning solution pH is neutrality, the catalyst having washed is moved in convection oven, Temperature Setting is 105～120 ℃, dry 3～5h, finally obtain modified catalyst.
Below by concrete case study on implementation, ZSM-5 molecular sieve Zeolite modifying method of the present invention is given to detailed description, but be not limited to example.
The raw material ZSM-5 molecular sieve zeolite molecular sieve using in embodiment in the present invention is purchased from Catalyst Factory, Nankai Univ, and its silica alumina ratio is 30, and EDETATE SODIUM, purchased from Nanjing Chemistry Reagent Co., Ltd., is analyzed pure.
Embodiment 1
With deionized water preparation 0.333mol/LEDTA bis-sodium solutions, measure the solution of 50ml preparation and take 5.0gZSM-5 molecular sieve zeolites and join together in beaker, be placed in heat collecting type magnetic force heating stirrer heating water bath, temperature is 80 ℃, mixing speed is low speed, and the processing time is 2h.After modification completes, by the mixture vacuum filtration of catalyst and modified solution, use deionized water cyclic washing simultaneously, until cleaning solution pH is neutrality, the catalyst after washing is moved to convection oven, Temperature Setting is 110 ℃, dry 4h, obtain modification rear catalyst.For the crystal characteristic of modification rear catalyst and raw catalyst relatively, two kinds of catalyst are carried out to XRD sign, as depicted in figs. 1 and 2, it is good zeolite structured that the catalyst after modification still keeps.Compared with raw catalyst, modified catalyst relative crystallinity (with the ratio of 23.1 ° of intensity of the strongest diffraction maximum 2 θ ≈ of former state) approaches 1, show EDTA modification on crystal structure of molecular sieve almost without impact.
Embodiment 2
For the anti-coking characteristic of checking molecular sieve catalyst, adopt tube furnace Pyrolysis Experiment device.Pyrolysis temperature is set as 500 ℃, and testing raw materials used is maize straw, and raw material needs to carry out pretreatment before test: first raw material is selected through 40 mesh sieves, be then placed in baking oven, and stand-by after dry 24h at 105 ℃.High-purity N is selected in carrier gas
2, flow is 0.5L/min, and raw material sample size is 4g, and catalyst amount is 2g, selects respectively the catalyst after former state and embodiment 1 modification, and pyrolysis time is 35min.In order to characterize the coking amount of catalyst surface, with reference to " proximate analysis of coal " (GB/T212-2008), adopt the mode of Muffle furnace high-temperature calcination, according to the coking amount that can think catalyst surface of poor quality before and after calcining.Before Muffle furnace calcining, post catalyst reaction is placed at 120 ℃, baking oven and dries 2h, to remove the water of molecular sieve adsorption in course of reaction.Catalyst coking contrast is as shown in table 1, and the catalyst after modification is compared with unmodified, and coking quality reduces 32.9%, and effect is remarkable.Separately, be the relatively impact of modification rear catalyst on thermal decomposition product, pyrolysis gas is collected after rapid condensation, and the pyrolysis oil after collection is by GC/MS qualitative analysis, and result is as shown in table 2, and modification rear catalyst is negligible to pyrolysis oil product distribution influence.
Table 1 catalyst unmodified with modification coking contrast table
500 ℃ of catalyse pyrolysis product distribution tables of table 2 maize straw tube furnace
Embodiment 3
For the impact of better checking modification rear catalyst on thermal decomposition product, adopt Py-GC/MS(fast pyrolysis-gas chromatography mass spectrometry) impact of analysis of catalyst on thermal decomposition product.Will be respectively before test by maize straw and catalyst (unmodified and modification after) fragmentation, divide through 100 mesh sieves.When test, accurately take 0.5mg left and right raw material, it is that the assay balance of 0.01mg is with the accuracy of assurance weighing that raw material is selected precision in the time weighing.In quartz ampoule, raw material is placed on middle part, and a certain amount of silica wool is all inserted at two ends, prevents that dusty raw materials from blowing out, and while carrying out catalyse pyrolysis test, adds enough catalyst at raw material two ends.CDS5200 type cracking instrument is take high-purity helium (99.999%) as carrier gas, and it is 20 ℃/ms that heating rate is set in test.Use NIST database to detect product.Adopt area normalization method to carry out qualitative analysis to the GC-MS spectrogram of thermal cracking products.For with the continuity of embodiment 2, pyrolysis temperature adopts 500 ℃, but according to pertinent literature report, thermal cracking instrument apparent temperature and actual pyrolysis temperature differ 100 ℃ of left and right, therefore, thermal cracking instrument Temperature Setting is 600 ℃.Summarized results is as shown in table 3, and as can be found from Table 3: modification rear catalyst is little to the content influence of pyrolysis target product-hydro carbons, and modification rear catalyst has higher CO
2productive rate, has good deoxidation effect.
Quick catalysis thermal decomposition product distribution table at 600 ℃ of table 3 maize straws
Claims (4)
1. an anti-coking method of modifying for catalytic pyrolysis of biomass catalyst Z SM-5 molecular sieve, is characterized in that: this method of modifying comprises the steps:
1), by catalyst Z SM-5 molecular sieve by liquid-solid ratio 7～12ml/g, join in large molecule chelating agent modified solution, described catalyst and modified solution stir in heating stirrer;
2), after modification completes, by the mixture vacuum filtration of catalyst and modified solution composition, adopt deionized water cyclic washing, until cleaning solution pH is neutrality;
3), catalyst that filtration is obtained moves in convection oven and dries, and obtains modification rear catalyst.
2. the anti-coking method of modifying of catalyse pyrolysis catalyst Z SM-5 molecular sieve according to claim 1, is characterized in that described large molecule chelating agent modified solution is disodium ethylene diamine tetra-acetic acid solution.
3. the anti-coking method of modifying of catalyse pyrolysis catalyst Z SM-5 molecular sieve according to claim 1, is characterized in that described heating stirrer temperature is 70～90 ℃, and heating mixing time is 1.5～2.5h.
4. the anti-coking method of modifying of catalyse pyrolysis catalyst Z SM-5 molecular sieve according to claim 1, is characterized in that described convection oven Temperature Setting is 105～120 ℃, and drying time is 3～5h.
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Cited By (4)
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| CN109201106A (en) * | 2017-06-30 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of multi-stage porous HZSM-5 molecular sieve |
| CN109876850A (en) * | 2019-03-06 | 2019-06-14 | 东南大学 | A kind of preparation method of the composite molecular screen for bio oil deoxidation upgrading |
| CN111939980A (en) * | 2020-08-17 | 2020-11-17 | 杭州电子科技大学 | Preparation method of MOF framework catalyst for biomass catalytic pyrolysis |
| CN112275313A (en) * | 2020-09-18 | 2021-01-29 | 东南大学 | Preparation method of shell-core structure molecular sieve catalyst for biomass pyrolysis, reforming and upgrading |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109201106A (en) * | 2017-06-30 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of multi-stage porous HZSM-5 molecular sieve |
| CN109201106B (en) * | 2017-06-30 | 2021-08-31 | 中国石油化工股份有限公司 | Hierarchical pore HZSM-5 molecular sieve |
| CN109876850A (en) * | 2019-03-06 | 2019-06-14 | 东南大学 | A kind of preparation method of the composite molecular screen for bio oil deoxidation upgrading |
| CN111939980A (en) * | 2020-08-17 | 2020-11-17 | 杭州电子科技大学 | Preparation method of MOF framework catalyst for biomass catalytic pyrolysis |
| CN111939980B (en) * | 2020-08-17 | 2022-11-25 | 杭州电子科技大学 | Preparation method of MOF framework catalyst for biomass catalytic pyrolysis |
| CN112275313A (en) * | 2020-09-18 | 2021-01-29 | 东南大学 | Preparation method of shell-core structure molecular sieve catalyst for biomass pyrolysis, reforming and upgrading |
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Application publication date: 20140507 |