CN103055882A - Preparation method for multi-metal monolithic tar cracking catalyst - Google Patents
Preparation method for multi-metal monolithic tar cracking catalyst Download PDFInfo
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- CN103055882A CN103055882A CN2012105756942A CN201210575694A CN103055882A CN 103055882 A CN103055882 A CN 103055882A CN 2012105756942 A CN2012105756942 A CN 2012105756942A CN 201210575694 A CN201210575694 A CN 201210575694A CN 103055882 A CN103055882 A CN 103055882A
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Abstract
The invention provides a preparation method for a multi-metal monolithic tar cracking catalyst. Iolite is used as a carrier in the method. The method comprises the following steps: (1) pretreatment of the iolite carrier with acid; (2) loading of nickel and cobalt; (3) loading of molybdenum; and (4) catalyst reduction. The method provided by the invention is simple to operate and can easily realize continuous preparation; the prepared monolithic tar cracking catalyst has the advantages of a small pressure drop in the process of reaction and easy separation and regeneration after reaction compared to a granular catalyst; after the catalyst is reduced, metal molybdenum and metal nickel can form Mo-Ni alloy, good activity and selectivity are showed in the process of reaction, nonpolar macro-molecular benzenes difficult to decompose in tar are substantially reduced, and even the content of some of the benzenes approaches zero; the catalyst provided by the invention has good anti-carbon formation capability, and catalytic activity of the catalyst in the process of reaction almost maintains stable.
Description
Technical field
The present invention relates to biomass energy utilization technologies, relate in particular to the preparation method of tar cracking catalyst in biomass high temperature pyrolysis/gasification aerogenesis.
Technical background
Along with a large amount of exploitations and the utilization of fossil energy, energy shortage, price skyrocket day by day serious with the problem such as environmental pollution, have that the source is wide, low pollutes and the biomass energy of renewable characteristics has become the topic that people show great attention to.And biomass coke tar is inevitable accessory substance in the biomass pyrogenation gasification process, and its existence causes easily that not only equipment pipe stops up and the waste of self-energy, has also reduced the utilization rate of biomass energy simultaneously.Therefore, tar content is very necessary in the reduction biomass pyrogenation gasification aerogenesis.
The focus of the at present relevant tar removal of Chinese scholars research is catalystic pyrolysis, namely transforms the low temperature conversion (700 ~ 900 ℃) that activation energy is realized tar by reducing tar.The catalyst of most study is ore class catalyst (dolomite, olivine, clay ore etc.), alkali metal class catalyst (generally being its carbonate, oxide and chloride) and nickel-base catalyst at present.Wherein the catalytic effect of nickel-base catalyst is best, still along with the exposure of pellet type catalyst shortcoming, namely causes easily the obstruction of beds in the long playing situation.Some scholar begins research direction is transferred to integral catalyzer in recent years, reduces because it has the lamination of biography; Mass-transfer efficiency is high; Enlarge-effect is little; Catalyst separation, the regeneration plurality of advantages such as easy.Therefore the research of efficient and eco-friendly monoblock type tar cracking catalyst will be conducive to promote the application level of biomass high temperature pyrolysis/gasification.
Summary of the invention
The purpose of this invention is to provide the preferably preparation method of biomass tar cracking catalyst of a kind of high-performance and stability.
The present invention adopts cordierite carrier, and preparation method's step is as follows:
(1) cordierite carrier acid preliminary treatment
Place the 30wt% oxalic acid solution to process 5h cordierite carrier, then 100 ℃ of dry 2h or microwave drying 30min, again 500 ℃ of calcining 2h.
(2) load of nickel, cobalt
Ni (the NO of preparation 1.2 ~ 2mol/L
3)
2And Co (NO
3)
2Mixed solution, wherein nickel/cobalt mol ratio is 3:1.Step 1) is processed cordierite carrier later place this mixed solution vacuum impregnation 1-2h, microwave drying 10-20min after taking out, then 550 ℃ of calcining 2-4h in Muffle furnace.Second step can repeat that the total load rate of nickel oxide and cobalt oxide is 18 ~ 25wt% to the catalyst.
(3) load of molybdenum
(the NH of preparation 0.04 ~ 0.07mol/L
4)
6Mo
7O
24Complex solution, adopt equally vacuum impregnation technology will be the cordierite carrier of nickel-loaded and cobalt in this solution, flood 1-2h, microwave drying 10-20min after taking out, then 550 ℃ of calcining 2-4h in Muffle furnace.Also can repeat that the load factor of molybdenum trioxide is 8 ~ 12wt% to the catalyst the 3rd step.
(4) catalyst reduction
The catalyst of preparing is placed H
2/ N
2Atmosphere (H
2: N
2=1: 8 ~ 10vol%, mixed gas flow: 0.45m
3/ h) in the reduction 5-7h, reduction temperature is 650 ℃.
Preparation method of the present invention is simple to operate, is easy to realize continuous production.Prepared monoblock type tar cracking catalyst is compared with pellet type catalyst, has the advantages such as the course of reaction pressure drop is little, the rear separation regeneration of reaction is easy; After this catalyst reduction, can form the Mo-Ni alloy between metal molybdenum and the nickel, show good activity and selectivity in the course of reaction, the difficult nonpolar large molecule benzene homologues that decomposes all has obvious minimizing in the tar, even some levels off to zero; Catalyst of the present invention has preferably carbon accumulation resisting ability, and its catalytic activity has certain stability in the course of reaction.
Description of drawings
Fig. 1 is the XRD collection of illustrative plates of Mo-Ni-Co/ cordierite catalyst of the present invention
Fig. 2 is the reacted Raman spectrogram of Mo-Ni-Co/ cordierite catalyst of the present invention (making comparisons with the Sm-Ni-Co/ cordierite catalyst)
The specific embodiment
Catalyst prepares commercial cordierite carrier (Φ 40 * 60mm, 31 orders/cm that required cordierite adopts Pingxiang pottery Co., Ltd of high section to produce
2, delthyrium).
Embodiment 1
(1) cordierite carrier acid preliminary treatment: take by weighing 181g oxalic acid (H
2C
2O
42H
2O) heating for dissolving can get the 30wt% oxalic acid solution in the 250g deionized water, after the oxalic acid solution boiling, off-the-shelf three peplolites are placed this solution acid corrosion 5h, taking-up is placed on the remaining oxalic acid solution of flush away in the boiling deionized water, 100 ℃ of dry 2h after repeatedly cleaning, again 500 ℃ of calcining 2h.
(2) load of nickel, cobalt: with 0.45molNi (NO
3)
26H
2O and 0.15molCo (NO
3)
26H
2After mixing, O adds the mixed solution 0.5L that appropriate amount of deionized water is mixed with 1.2mol/L.Acid treatment cordierite carrier is later placed this mixed solution vacuum impregnation 1h, microwave drying 10min after taking out, then 550 ℃ of calcining 2h in Muffle furnace.Repeat this step for several times so that in the catalyst nickel oxide and cobalt oxide total load rate reach 18wt%.
(3) load of molybdenum: in 0.02mol (NH
4)
6Mo
7O
244H
2Add appropriate amount of deionized water and stirring among the O, then take by weighing 13g ammoniacal liquor and pour into wherein, after ammonium molybdate dissolves fully, can obtain (the NH of 0.04mol/L
4)
6Mo
7O
24Complex solution 0.5L.Same adopt vacuum impregnation technology the catalyst of nickel-loaded and cobalt in this solution, flood 1h, microwave drying 10min after taking out, then 550 ℃ of calcining 2h in Muffle furnace.Repeat this step for several times so that in the catalyst molybdenum trioxide load factor reach 8wt%.
(4) catalyst reduction: the catalyst of preparing is placed H
2/ N
2Reduce 5h (H in the atmosphere
2: N
2=1: 10vol%, mixed gas flow: 0.45m
3/ h), reduction temperature is 650 ℃.
Embodiment 2
(1) cordierite carrier acid preliminary treatment: take by weighing 181g oxalic acid (H
2C
2O
42H
2O) heating for dissolving can get the 30wt% oxalic acid solution in the 250g deionized water, after the oxalic acid solution boiling, off-the-shelf three peplolites are placed this solution acid corrosion 5h, taking-up is placed on the remaining oxalic acid solution of flush away in the boiling deionized water, microwave drying 30min after repeatedly cleaning is again at 500 ℃ of calcining 2h.
(2) load of nickel, cobalt: with 0.75molNi (NO
3)
26H
2O and 0.25molCo (NO
3)
26H
2After mixing, O adds the mixed solution 0.5L that appropriate amount of deionized water is mixed with 2mol/L.Acid treatment cordierite carrier is later placed this mixed solution vacuum impregnation 2h, microwave drying 20min after taking out, then 550 ℃ of calcining 4h in Muffle furnace.Repeat this step for several times so that in the catalyst nickel oxide and cobalt oxide total load rate reach 25wt%.
(3) load of molybdenum: in 0.035mol (NH
4)
6Mo
7O
244H
2Add appropriate amount of deionized water among the O and stir, and then take by weighing 23g ammoniacal liquor and pour into wherein, after ammonium molybdate dissolves fully, can obtain (the NH of 0.07mol/L
4)
6Mo
7O
24Complex solution 0.5L.Same adopt vacuum impregnation technology the catalyst of nickel-loaded and cobalt in this solution, flood 2h, microwave drying 20min after taking out, then 550 ℃ of calcining 4h in Muffle furnace.Repeat this step for several times so that in the catalyst molybdenum trioxide load factor reach 12wt%.
(4) catalyst reduction: the catalyst of preparing is placed H
2/ N
2Reduce 7h (H in the atmosphere
2: N
2=1: 8vol%, mixed gas flow: 0.45m
3/ h), reduction temperature is 650 ℃.
Adopt biomass high temperature pyrolysis (800 ℃) aerogenesis as the thick combustion gas of this catalyst activity property testing.Consisting of of this thick combustion gas: V (H
2): V (CH
4): V (CO): V (CO
2): V (C
2H
4): V (C
2H
2): V (N
2)=10.2: 6.22: 19.31: 5.14: 1.74: 0.14: 57.25; The concentration of tar is 41.3g/Nm
3, thick gas flow is 0.27Nm
3/ h.Adopt the GC-20B-1 gas chromatograph that the reformation aerogenesis is carried out off-line analysis, adopt GC-MS that tar is carried out off-line analysis.
Embodiment 1 evaluating catalyst result is as shown in table 1:
Table 1 embodiment 1 evaluating catalyst result
Embodiment 2 evaluating catalyst results are as shown in table 2:
Table 2 embodiment 2 evaluating catalyst results
The tar component of tar behind embodiment 1 and embodiment 2 catalyst actions is as shown in table 3 in the thick combustion gas:
The tar component that table 3 embodiment 1 and embodiment 2 are corresponding
XRD before the above-mentioned catalyst reaction characterizes and reacted Raman sign can be referring to Fig. 1 and Fig. 2.XRD analysis show reduction in the rear catalyst metal molybdenum and nickel between stronger interaction has occured, and form the Mo-Ni alloy, the characteristic diffraction peak position of this alloy is 40.9 °, 43.2 °, 43.9 °, 44.4 °, 45.4 °.And by Raman analysis as can be known the Mo-Ni-Co/ cordierite catalyst be 1400cm in wave number
-1And 1581cm
-1The place is two obvious carbon distribution peaks shown in the Sm-Ni-Co/ cordierite catalyst not, and this explanation Mo-Ni-Co/ cordierite catalyst has preferably carbon accumulation resisting ability, thereby is conducive to slow down the deactivation rate of catalyst, improves the activity stability of catalyst.
Claims (1)
1. the preparation method of the tar cracking catalyst of metal integral formula more than a kind adopts cordierite carrier, and step is as follows:
(1) cordierite carrier acid preliminary treatment
Place the 30wt% oxalic acid solution to process 5h cordierite carrier, then 100 ℃ of dry 2h or microwave drying 30min, again 500 ℃ of calcining 2h;
(2) load of nickel, cobalt
Ni (the NO of preparation 1.2 ~ 2mol/L
3)
2And Co (NO
3)
2Mixed solution, wherein nickel/cobalt mol ratio is 3:1; Step 1) is processed cordierite carrier later place this mixed solution vacuum impregnation 1 ~ 2h, microwave drying 10 ~ 20min after taking out, then 550 ℃ of calcining 2-4h in Muffle furnace; Second step can repeat that the total load rate of nickel oxide and cobalt oxide is 18 ~ 25wt% to the catalyst;
(3) load of molybdenum
(the NH of preparation 0.04 ~ 0.07mol/L
4)
6Mo
7O
24Complex solution, adopt equally vacuum impregnation technology will be the cordierite carrier of nickel-loaded and cobalt in this solution, flood 1 ~ 2h, microwave drying 10 ~ 20min after taking out, then 550 ℃ of calcining 2 ~ 4h in Muffle furnace; Can repeat that the load factor of molybdenum trioxide is 8 ~ 12wt% to the catalyst the 3rd step;
(4) catalyst reduction
The catalyst of preparing is placed H
2/ N
2Reduce 5 ~ 7h in the atmosphere, reduction temperature is 650 ℃.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008491A (en) * | 2017-04-10 | 2017-08-04 | 东北农业大学 | A kind of preparation method and applications of biological tar catalytic modification catalyst |
| CN107233888A (en) * | 2017-07-06 | 2017-10-10 | 山东省科学院能源研究所 | Biomass prepares gas combustion multifunction catalyst and preparation method |
| CN107715884A (en) * | 2017-11-14 | 2018-02-23 | 太原理工大学 | A kind of metal load type biomass half char catalyst and preparation method thereof |
| CN109294219A (en) * | 2018-09-20 | 2019-02-01 | 黄勇 | A kind of impact resistance composite nylon material |
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| US4855037A (en) * | 1984-09-12 | 1989-08-08 | Nippon Kokan Kabushiki Kaisha | Hydrogenation catalyst for coal tar, a method of hydrogenation of coal tar with use of such catalyst, and a method of producing super needle coke from the hydrogenation product of coal tar |
| CN1935380A (en) * | 2006-09-30 | 2007-03-28 | 中国科学院广州能源研究所 | Method for preparing integral biomass gasified tarcracking catalyst |
| CN101444740A (en) * | 2008-12-16 | 2009-06-03 | 中国科学院广州能源研究所 | Catalyst for hydrogen production by bio-oil steam reforming and preparation method thereof |
| CN102218324A (en) * | 2011-04-19 | 2011-10-19 | 安徽理工大学 | Catalyst for removing oxygen and improving quality of bio-oil and preparation method thereof |
| CN102600846A (en) * | 2012-03-23 | 2012-07-25 | 中国科学院广州能源研究所 | Preparation method of bimetallic integral type tar cracking and gas reforming catalyst |
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2012
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Patent Citations (5)
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| US4855037A (en) * | 1984-09-12 | 1989-08-08 | Nippon Kokan Kabushiki Kaisha | Hydrogenation catalyst for coal tar, a method of hydrogenation of coal tar with use of such catalyst, and a method of producing super needle coke from the hydrogenation product of coal tar |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008491A (en) * | 2017-04-10 | 2017-08-04 | 东北农业大学 | A kind of preparation method and applications of biological tar catalytic modification catalyst |
| CN107008491B (en) * | 2017-04-10 | 2019-06-07 | 东北农业大学 | A kind of preparation method and application of biomass coke tar catalytic modification catalyst |
| CN107233888A (en) * | 2017-07-06 | 2017-10-10 | 山东省科学院能源研究所 | Biomass prepares gas combustion multifunction catalyst and preparation method |
| CN107233888B (en) * | 2017-07-06 | 2020-05-19 | 山东省科学院能源研究所 | Multifunctional catalyst for preparing fuel gas from biomass and preparation method thereof |
| CN107715884A (en) * | 2017-11-14 | 2018-02-23 | 太原理工大学 | A kind of metal load type biomass half char catalyst and preparation method thereof |
| CN107715884B (en) * | 2017-11-14 | 2019-08-09 | 太原理工大学 | A kind of metal load type biomass half char catalyst and preparation method thereof |
| CN109294219A (en) * | 2018-09-20 | 2019-02-01 | 黄勇 | A kind of impact resistance composite nylon material |
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Application publication date: 20130424 |