CN103773589B - The method of blue-green algae vacuum catalytic cracking preparing bio-oil - Google Patents
The method of blue-green algae vacuum catalytic cracking preparing bio-oil Download PDFInfo
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- CN103773589B CN103773589B CN201410017836.2A CN201410017836A CN103773589B CN 103773589 B CN103773589 B CN 103773589B CN 201410017836 A CN201410017836 A CN 201410017836A CN 103773589 B CN103773589 B CN 103773589B
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Abstract
The invention discloses a kind of method of blue-green algae vacuum catalytic cracking preparing bio-oil, with blue-green algae powder for raw material, hydrotalcite is the complex metal oxides of presoma is catalyzer, and catalytic pyrolysis produces bio oil under vacuo.The catalyzer that the present invention uses is complex metal oxides, and preparation is simple; By the catalyst application of preparation in blue-green algae cracking, the productive rate of bio oil effectively can be improved; And metal oxide can absorb the moisture in blue-green algae, promote the quality of bio oil.The inventive method is simple, to cause the arch-criminal-blue-green algae of body eutrophication for raw material, turns waste into wealth, and reduces environmental pollution.
Description
Technical field
The present invention relates to the treatment process of a kind of blue-green algae, particularly a kind of take complex metal oxides as the method for catalyzer vacuum catalytic cracking blue-green algae preparing bio-oil.
Background technology
Blue-green algae is domestic and most important one in the planktonic algae of the world's a lot of inland lake eutrophication generation, it is present in water body, bring infinite harm, such as, destroy the health and discharge odor pollution air etc. of the ecosystem, polluted source harm humans.Salvaging is the common measures taken that China takes for the pollution that lake wawter bloom causes, and is used by normalization in China Dian Chi, Taihu Lake, Chaohu etc.According to incompletely statistics, Jiangsu Province in 2011 adds up from Taihu Lake to salvage blue algae liquid 970,000 tons, increases nearly 300,000 tons than salvaging amount in 2010.And these salvage the blue algae liquid of disembarkation, how in time, harmless treatment fast and utilization, be the key that bloom blue algae is administered.If to the blue-green algae of salvaging can not in time, harmless treatment effectively, the environmental pollution of secondary can be produced because rotten smelly, nitrogen, the phosphorus nutrient of blue-green algae etc. discharges.
At present, domestic to salvaging blue-green algae mainly adopt the method for anaerobic digestion to process, as the patent No. Chinese patent that is 200810022548.0 reports a kind of method of anaerobic fermentation of bloom blue algae, improve processing efficiency by shortening digestion time, but can't resolve the key issue of reaction needed long period.Meanwhile, there is a large amount of moisture in the blue algae liquid salvaging disembarkation, can cause the problems such as anaerobic digester scale is bigger than normal, floor space is large.
In addition, also the useful blue algae liquid salvaging disembarkation is prepared fertilizer, is built the methods such as microbiological fuel cell, but the particular problem of all depositing on the implementation, as prepared fertilizer needs, the blue algae liquid salvaging disembarkation is carried out second dehydration, during high-moisture percentage, its processing rate is low.
In addition, also have patent report supercritical water treatment blue algae liquid, the patent No. is the Chinese patent of 201010520895.3, reports the reactive mode taking supercritical water oxidation and blue-green algae is converted into CO
2and H
2o.And this kind of method owing to adding oxygenant in reaction process, its main purpose is the harmless treatment realizing blue algae liquid, and cost is higher, and does not consider the transition problem of the energy; Again because need dehydration before blue-green algae reaction, technique is more complicated.
Domestic and international investigator is that bio oil prepared by raw material with blue-green algae, the main thermochemical study technology adopting rapidly pyrolysing and liquefying and direct liquefaction.At present, blue-green algae prepares bio oil very large difficulty, there is the series of problems such as the imperfection of technology, oily productive rate are not high, production cost is high, oil quality is low.
Summary of the invention
The object of this invention is to provide a kind of method of blue-green algae vacuum catalytic cracking preparing bio-oil, prepare the problems such as bio oil oil productive rate is not high, production cost is high, oil quality is low to solve existing blue-green algae.
For solving the problem, the present invention by the following technical solutions:
A method for blue-green algae vacuum catalytic cracking preparing bio-oil, with blue-green algae powder for raw material, hydrotalcite is the complex metal oxides of presoma is catalyzer, and catalytic pyrolysis produces bio oil under vacuo, comprises the steps:
Step one, hydrotalcite is calcined 1 ~ 5h at 300 ~ 600 DEG C after obtain complex metal oxides;
Step 2, the complex metal oxides step one prepared and blue-green algae powder in mass ratio 0.5 ~ 2:10 mix;
Step 3, mixture step 2 obtained put into tube furnace, and vacuum tightness is 50 ~ 100kPa, at 100 ~ 200 DEG C, stop 20 ~ 60min, afterwards temperature is increased to 400 ~ 600 DEG C, cracking 0.5 ~ 2h, passes through-20 ~ 0 DEG C of cold hydrazine condensation by the splitting gas of generation, collect and obtain bio oil.
Hydrotalcite described in step one is one or more in Mg-Al hydrotalcite, Ca-Mg-Al hydrotalcite, Zn-Mg-Al hydrotalcite.
Beneficial effect of the present invention:
1, the present invention is to cause the arch-criminal-blue-green algae of body eutrophication to be waste bio oil, turns waste into wealth, and reduces environmental pollution.Simple, the oily productive rate of the inventive method technique is high.
2, the catalyzer that the present invention uses is complex metal oxides, and preparation is simple; By the catalyst application of preparation in blue-green algae cracking, the productive rate of bio oil effectively can be improved; And metal oxide can absorb the moisture in blue-green algae, promote the quality of bio oil.
3, the main component of complex metal oxides is the oxide compound of MAGNESIUM METAL, aluminium, calcium, zinc, avoids the use of rare precious metals and toxic metal, not only environmental protection but also significantly reduce production cost; And this catalyzer has higher catalytic efficiency, bio oil yield can reach 65.7%.
4, adopt vacuum environment cracking, the cracking temperature of biomass can be reduced, quick collection splitting gas condensation obtains bio oil.
Embodiment
Below in conjunction with embodiment the present invention done and further explain.The following example only for illustration of the present invention, but is not used for limiting practical range of the present invention.
The preparation method of the Mg-Al hydrotalcite that following examples are used is as follows:
Step 1, get magnesium nitrate and aluminum nitrate in molar ratio 3:1 add in 1L beaker, it is even to add deionized water and stirring;
Step 2, get sodium hydroxide and sodium carbonate in molar ratio 1:1 add in 1L beaker, it is even to add deionized water and stirring;
Step 3, being transferred to constant pressure funnel respectively by processing the mixing solutions obtained in described step 1,2, being added drop-wise to simultaneously and adding in the 2L beaker of a certain amount of deionized water, in dropping process, constantly regulating flow velocity, guaranteeing that the pH value of mixed solution is between 9 ~ 11;
Step 4, dropwise rear continuation stir for some time, then thermostatic crystallization at 40 ~ 100 DEG C, in 400 ~ 600 DEG C calcining 2 ~ 5h, grind into powder after solid drying, particle diameter is less than 0.2mm.
The preparation method of Ca-Mg-Al hydrotalcite and Zn-Mg-Al hydrotalcite is the same, just raw material and material molar ratio difference, and the raw material that preparation Ca-Mg-Al hydrotalcite is used and material molar ratio are: Ca:Mg:Al=3:3:2, NaOH:Na
2cO
3=4:1, the raw material that preparation Zn-Mg-Al hydrotalcite is used and material molar ratio are: Zn:Mg:Al=3:2:2, NaOH:Na
2cO
3=3:1.
Embodiment blue-green algae powder used is that the blue-green algae salvaged by Taihu Lake pulverizes through Exposure to Sunlight, vacuum drying oven drying, Universalpulverizer, filters out through 40 ~ 100 object standard sieves the powder that particle diameter is 150 microns again, gained after 60 ~ 100 DEG C of drying 2 ~ 6h.
Embodiment 1
Mg-Al hydrotalcite is calcined 1h at 300 DEG C, getting after 0.5g product mixes with 10g blue-green algae powder adds in tube furnace, vacuum tightness is 100kPa, 60min is stopped at 100 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 400 DEG C afterwards, cracking 0.5h, splitting gas passes through the condensation of-20 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.23g, carbon residue 2.42g, splitting gas 1.35g.Bio oil yield is 62.3%.
Embodiment 2
Ca-Mg-Al hydrotalcite is calcined 3h at 450 DEG C, getting after 0.5g product mixes with 10g blue-green algae powder adds in tube furnace, vacuum tightness is 50kPa, 20min is stopped at 100 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 400 DEG C afterwards, cracking 1.0h, splitting gas passes through the condensation of-20 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.37g, carbon residue 2.34g, splitting gas 1.29g.Bio oil yield is 63.7%.
Embodiment 3
Mg-Al hydrotalcite is calcined 5h at 600 DEG C, getting after 0.5g product mixes with 10g blue-green algae powder adds in tube furnace, vacuum tightness is 100kPa, 20min is stopped at 100 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 400 DEG C afterwards, cracking 1.5h, splitting gas passes through the condensation of-20 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.42g, carbon residue 2.35g, splitting gas 1.23g.Bio oil yield is 64.2%.
Embodiment 4
Zn-Mg-Al hydrotalcite is calcined 3h at 450 DEG C, getting after 1g product mixes with 10g blue-green algae powder adds in tube furnace, vacuum tightness is 100kPa, 40min is stopped at 100 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 400 DEG C afterwards, cracking 1h, splitting gas passes through the condensation of-20 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.47g, carbon residue 2.30g, splitting gas 1.23g.Bio oil yield is 64.7%.
Embodiment 5
Product 0.2g is got after Mg-Al hydrotalcite is calcined 1h at 500 DEG C, product 0.3g is got after Ca-Mg-Al hydrotalcite is calcined 3h at 300 DEG C, add in tube furnace after mixing with 10g blue-green algae powder again, vacuum tightness is 100kPa, stop 40min at 100 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 400 DEG C afterwards, cracking 1.0h, splitting gas passes through the condensation of-20 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.26g, carbon residue 2.41g, splitting gas 1.33g.Bio oil yield is 62.6%.
Embodiment 6
Product 0.5g is got after Mg-Al hydrotalcite is calcined 1h at 300 DEG C, product 0.5g is got after Zn-Mg-Al hydrotalcite is calcined 3h at 450 DEG C, add in tube furnace after mixing with 10g blue-green algae powder again, vacuum tightness is 50kPa, stop 40min at 100 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 400 DEG C afterwards, cracking 1.5h, splitting gas passes through the condensation of-20 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.40g, carbon residue 2.28g, splitting gas 1.32g.Bio oil yield is 64.0%.
Embodiment 7
Product 1.0g is got after Ca-Mg-Al hydrotalcite is calcined 5h at 450 DEG C, product 0.5g is got after Zn-Mg-Al hydrotalcite is calcined 1h at 600 DEG C, add in tube furnace after mixing with 10g blue-green algae powder again, vacuum tightness is 50kPa, stop 40min at 100 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 500 DEG C afterwards, cracking 1.5h, splitting gas passes through the condensation of-20 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.50g, carbon residue 2.28g, splitting gas 1.22g.Bio oil yield is 65.0%.
Embodiment 8
Product 1.0g is got after Mg-Al hydrotalcite is calcined 5h at 450 DEG C, product 1.0g is got after Zn-Mg-Al hydrotalcite is calcined 1h at 450 DEG C, add in tube furnace after mixing with 10g blue-green algae powder again, vacuum tightness is 50kPa, stop 60min at 100 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 500 DEG C afterwards, cracking 1.5h, splitting gas passes through the condensation of-20 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.55g, carbon residue 2.28g, splitting gas 1.17g.Bio oil yield is 65.5%.
Embodiment 9
Product 1.0g is got after Ca-Mg-Al hydrotalcite is calcined 3h at 450 DEG C, product 0.5g is got after Zn-Mg-Al hydrotalcite is calcined 4h at 500 DEG C, add in tube furnace after mixing with 10g blue-green algae powder again, vacuum tightness is 100kPa, stop 40min at 100 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 450 DEG C afterwards, cracking 1.5h, splitting gas passes through the condensation of-20 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.57g, carbon residue 2.21g, splitting gas 1.22g.Bio oil yield is 65.7%.
Embodiment 10
Ca-Mg-Al hydrotalcite is calcined 2h at 600 DEG C, getting after product 1.5g mixes with 10g blue-green algae powder adds in tube furnace, vacuum tightness is 50kPa, 40min is stopped at 100 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 400 DEG C afterwards, cracking 1.0h, splitting gas passes through the condensation of-20 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.41g, carbon residue 2.49g, splitting gas 1.10g.Bio oil yield is 64.1%.
Embodiment 11
Zn-Mg-Al hydrotalcite is calcined 2h at 300 DEG C, getting after product 1.5g mixes with 10g blue-green algae powder adds in tube furnace, vacuum tightness is 100kPa, 40min is stopped at 100 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 500 DEG C afterwards, cracking 1h, splitting gas passes through the condensation of-20 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.37g, carbon residue 2.25g, splitting gas 1.38g.Bio oil yield is 63.7%.
Embodiment 12
Product 0.7g is got after Mg-Al hydrotalcite is calcined 4h at 500 DEG C, product 0.8g is got after Ca-Mg-Al hydrotalcite is calcined 3h at 400 DEG C, product 0.5g is got after Zn-Mg-Al hydrotalcite is calcined 2h at 300 DEG C, add in tube furnace after mixing with 10g blue-green algae powder, vacuum tightness is 100kPa again, stops 40min at 100 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 400 DEG C afterwards, cracking 1.0h, splitting gas passes through the condensation of-20 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.36g, carbon residue 2.35g, splitting gas 1.29g.Bio oil yield is 63.6%.
Embodiment 13
Mg-Al hydrotalcite is calcined 1h at 300 DEG C, getting after 0.5g product mixes with 10g blue-green algae powder adds in tube furnace, vacuum tightness is 100kPa, 60min is stopped at 150 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 600 DEG C afterwards, cracking 2.0h, splitting gas, by the condensation of 0 DEG C of glass cold hydrazine, carries out collecting biological oil.Obtain bio oil 6.18g, carbon residue 2.45g, splitting gas 1.37g.Bio oil yield is 61.8%.
Embodiment 14
Ca-Mg-Al hydrotalcite is calcined 3h at 450 DEG C, getting after 0.5g product mixes with 10g blue-green algae powder adds in tube furnace, vacuum tightness is 50kPa, 20min is stopped at 200 DEG C, with the heating rate of 10 DEG C/min, temperature is risen to 600 DEG C afterwards, cracking 2.0h, splitting gas passes through the condensation of-10 DEG C of glass cold hydrazines, carries out collecting biological oil.Obtain bio oil 6.23g, carbon residue 2.42g, splitting gas 1.35g.Bio oil yield is 62.3%.
In addition to the implementation, all employings are equal to the technical scheme of replacement or equivalent transformation formation, all at the protection domain of application claims.
Claims (1)
1. a method for blue-green algae vacuum catalytic cracking preparing bio-oil, is characterized in that, with blue-green algae powder for raw material, hydrotalcite is the complex metal oxides of presoma is catalyzer, and catalytic pyrolysis produces bio oil under vacuo, comprises the steps:
Step one, hydrotalcite is calcined 1 ~ 5h at 300 ~ 600 DEG C after obtain complex metal oxides; Wherein, described hydrotalcite is one or more in Mg-Al hydrotalcite, Ca-Mg-Al hydrotalcite, Zn-Mg-Al hydrotalcite;
Step 2, the complex metal oxides step one prepared and blue-green algae powder in mass ratio 0.5 ~ 2:10 mix;
Step 3, mixture step 2 obtained put into tube furnace, and vacuum tightness is 50 ~ 100kPa, at 100 ~ 200 DEG C, stop 20 ~ 60min, afterwards temperature is increased to 400 ~ 600 DEG C, cracking 0.5 ~ 2h, passes through-20 ~ 0 DEG C of cold hydrazine condensation by the splitting gas of generation, collect and obtain bio oil.
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| CN106367090A (en) * | 2016-11-03 | 2017-02-01 | 东南大学 | Method for preparing bio-oil by catalyzing thermal cracking of blue-green algae under methanol atmosphere |
| CN106753479B (en) * | 2016-12-26 | 2021-02-26 | 山东理工大学 | Method for treating lignocellulose by coupling biogas fermentation and rapid pyrolysis with poly-generation |
| CN108504377B (en) * | 2018-03-30 | 2020-10-16 | 东南大学 | Method for preparing organic nitrogen-containing compound by catalytic thermal cracking of blue algae |
| CN110129086B (en) * | 2019-03-13 | 2021-07-13 | 盐城工业职业技术学院 | Method for preparing biological aviation kerosene by catalytic cracking of plant asphalt |
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