CN104962325A - Environment-friendly bio-oil and preparation method thereof - Google Patents
Environment-friendly bio-oil and preparation method thereof Download PDFInfo
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- CN104962325A CN104962325A CN201510408709.XA CN201510408709A CN104962325A CN 104962325 A CN104962325 A CN 104962325A CN 201510408709 A CN201510408709 A CN 201510408709A CN 104962325 A CN104962325 A CN 104962325A
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- green algae
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000012075 bio-oil Substances 0.000 title abstract 4
- 241000192700 Cyanobacteria Species 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000284 extract Substances 0.000 claims abstract description 19
- 239000002283 diesel fuel Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005642 Oleic acid Substances 0.000 claims abstract description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 4
- 239000002551 biofuel Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 229960004756 ethanol Drugs 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- XHAFPKVCDCRTLV-UHFFFAOYSA-L N.S(=O)(=O)([O-])[O-].[Mn+2] Chemical compound N.S(=O)(=O)([O-])[O-].[Mn+2] XHAFPKVCDCRTLV-UHFFFAOYSA-L 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- CLLSOFHOYCGNJP-UHFFFAOYSA-N carbon monoxide cyclopenta-1,3-diene manganese Chemical compound [Mn].[C]=O.[C]=O.[C]=O.C1C=CC=C1 CLLSOFHOYCGNJP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- NSFKBZXCXCJZDQ-UHFFFAOYSA-N cumene;sodium Chemical compound [Na].CC(C)C1=CC=CC=C1 NSFKBZXCXCJZDQ-UHFFFAOYSA-N 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical compound CCCCOC(O)CC IDQBJILTOGBZCR-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000013517 stratification Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000003921 oil Substances 0.000 abstract description 23
- DEIHRWXJCZMTHF-UHFFFAOYSA-N [Mn].[CH]1C=CC=C1 Chemical compound [Mn].[CH]1C=CC=C1 DEIHRWXJCZMTHF-UHFFFAOYSA-N 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 229940079842 sodium cumenesulfonate Drugs 0.000 abstract 1
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 abstract 1
- 239000000295 fuel oil Substances 0.000 description 11
- 239000000446 fuel Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- SRUWWOSWHXIIIA-UKPGNTDSSA-N Cyanoginosin Chemical compound N1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H](C)[C@H](C(O)=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)C(=C)N(C)C(=O)CC[C@H](C(O)=O)N(C)C(=O)[C@@H](C)[C@@H]1\C=C\C(\C)=C\[C@H](C)[C@@H](O)CC1=CC=CC=C1 SRUWWOSWHXIIIA-UKPGNTDSSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 108010067094 microcystin Proteins 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention discloses environment-friendly bio-oil and a preparation method thereof. The environment-friendly bio-oil comprises the following components in part by weight: 50 to 70 parts of cyanobacteria extract oil, 2 to 4 parts of sodium cumenesulfonate, 5 to 10 parts of water, 15 to 25 parts of diesel oil, 2 to 6 parts of oleic acid, 2 to 6 parts of ethyl alcohol, 1 to 8 parts of modifier and 0.1 to 2 parts of cyclopentadienyl manganese tricarbonyl. The bio-oil disclosed by the invention can replace diesel and is high in heat value, energy-saving, environment-friendly, simple in preparation method, low in cost and easy for realizing engineering industrialization.
Description
Technical field
The present invention relates to chemical industry environmental protection field, be specifically related to a kind of Environmentally-friebiofuel biofuel and preparation method thereof.
Background technology
Diesel oil, as a kind of important refining of petroleum product, occupies very high share in various countries' fuel structure, is the major impetus fuel of many oversize vehicles (as truck, oil engine and generator etc.), has power large, the advantages such as low price.Along with the quickening of diesel oil of vehicle trend in world wide, the demand of future diesel can be increasing, and the raising of day by day exhausted and people's environmental consciousness of petroleum resources, greatly facilitate the exploitation paces that Alternative Diesel Fuel is accelerated in countries in the world.
Also there is many problems in diesel oil, such as efficiency of combustion is low, serious to atmospheric pollution, produces a large amount of granule dusts, CO2 emissions is high in application process.
Bio-fuel-oil refers to alcohol fuel, bio-fuel-oil and the aviation biofuel produced by Biological resources, can substitute the gasoline and diesel oil produced by oil, is the important directions that renewable energy source develops.So-called Biological resources refer to the various organisms utilizing air, water, soil etc. to be produced by photosynthesis, i.e. all lived organic substances that can grow.It comprises plant, animal and microorganism, and be different from the traditional fuels such as oil, coal, nuclear energy, these emerging fuel are recyclable fuels.
Current bio-fuel-oil is studied more as a kind of fuel of alternative diesel oil.Bio-fuel-oil and fatty acid methyl ester are a kind of containing oxygen clean fuel, because it has the advantages such as rate of combustion is high, pollution is few, renewable, by people are paid close attention to.Current bio-fuel-oil is mainly produced with chemical method, namely uses animal and plant grease and the low-carbon alcohol such as methyl alcohol or ethanol to carry out transesterification under acid or basic catalyst and high temperature (230 ~ 250 DEG C), generates corresponding fatty acid methyl ester or ethyl ester.
It is high mainly to there is production cost in current bio-fuel-oil, the problems such as low conversion rate.
Summary of the invention
The object of the invention is in view of the foregoing defects the prior art has, one of technical problem to be solved is to provide a kind of Environmentally-friebiofuel biofuel.
Two of technical problem to be solved by this invention is to provide the preparation method of above-mentioned Environmentally-friebiofuel biofuel.
A kind of Environmentally-friebiofuel biofuel provided by the invention, comprises following component by weight:
Wherein, described blue-green algae extracts oil is prepare in accordance with the following steps:
(1) by blue-green algae and massfraction be 60% ~ 90% ethanol mix by solid-to-liquid ratio (g/ml) 1:5 ~ 1:20 and be placed in reactor, add catalyzer, the add-on of catalyzer is 0.1 ~ 2% of blue-green algae weight, reacting by heating, reaction conditions is: temperature is 260 ~ 360 DEG C, pressure is 7 ~ 22MPa, and the reaction times is 15 ~ 45min; Obtain reaction solution;
(2) add dehydrated alcohol extractive reaction liquid, suction filtration isolates solid residue, and liquid phase stratification is organic phase and aqueous ethanolic solution phase;
(3) by organic phase underpressure distillation, the oily liquids obtained is that blue-green algae extracts oil; Underpressure distillation condition is: 0.085 ~ 0.1MPa, and temperature is 20 ~ 40 DEG C.
Preferably, the catalyzer of step (1) is made up of the three hypophosphite monohydrate ammoniums of 40-60wt% and the six hydrated sulfuric acid ammonium manganese of 40-60wt%.
Preferably, described properties-correcting agent is selected from one or more the mixture in methyl tertiary butyl ether, propandiol butyl ether, propylene oxide.
In the present invention,
Methyl tertiary butyl ether, No. CAS: 1634-04-4.
Propandiol butyl ether, has another name called: 1,2-PD-1-monobutyl ether, No. CAS: 15821-83-7.
Propylene oxide, No. CAS: 75-569.
Cyclopentadiene tricarbonyl manganese, No. CAS: 12079-65-1.
Cumene sodium sulfonate, No. CAS: 28348-53-0.
Three hypophosphite monohydrate ammoniums, No. CAS: 25447-33-0.
Six hydrated sulfuric acid ammonium manganese, No. CAS: 7785-19-5.
Present invention also offers the preparation method of above-mentioned Environmentally-friebiofuel biofuel, it comprises the following steps:
(1) take blue-green algae by weight and extract oil, cumene sodium sulfonate and water, mix obtained component A;
(2) take diesel oil, oleic acid, ethanol, properties-correcting agent and cyclopentadiene tricarbonyl manganese by weight, mix, obtained B component;
(3) B component is added into component A, mixes, namely obtain bio-fuel-oil of the present invention.
Bio-fuel-oil of the present invention can diesel oil substitute, energy-conserving and environment-protective, and preparation method is simple, and cost is low, easily realizes engineering industry.
Embodiment
Be specifically described the present invention below by embodiment, what be necessary to herein means out is that following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the scope of the invention.The person skilled in the art in this field according to the content of the invention described above, can make some nonessential improvement and adjustment to the present invention.
Embodiment 1 blue-green algae extracts the preparation of oil
It is prepare in accordance with the following steps that blue-green algae extracts oil:
(1) by blue-green algae and massfraction be 75% ethanol mix by solid-to-liquid ratio (g/ml) 1:10 and be placed in reactor, add three hypophosphite monohydrate ammoniums, the add-on of described three hypophosphite monohydrate ammoniums is 0.5% of blue-green algae weight, reacting by heating, reaction conditions is: temperature is 320 DEG C, pressure is 12MPa, and the reaction times is 30min; Obtain reaction solution;
Wherein, the ratio that it is the ethanol of 75% that described solid-to-liquid ratio (g/ml) 1:10 refers to according to 1g blue-green algae and the massfraction of 10ml mixes;
(2) add dehydrated alcohol extractive reaction liquid, suction filtration isolates solid residue, and liquid phase stratification is organic phase and aqueous ethanolic solution phase;
(3) by organic phase underpressure distillation, underpressure distillation condition is: 0.09MPa, and temperature is 25 DEG C, and the oily liquids obtained is that blue-green algae extracts oil, and the oil yield rate that blue-green algae extracts oil is 26.2%, and calorific value is 26.3MJ/kg.
Oil yield rate (%)=blue-green algae that blue-green algae extracts oil extracts oily weight/blue-green algae weight × 100%.
Embodiment 2 blue-green algae extracts the preparation of oil
According to method described in embodiment 1, three hypophosphite monohydrate ammoniums are replaced with six hydrated sulfuric acid ammonium manganese, the oil yield rate that blue-green algae extracts oil is 27.3%, and calorific value is 26.0MJ/kg.
Embodiment 3 blue-green algae extracts the preparation of oil
According to method described in embodiment 1, three hypophosphite monohydrate ammoniums are replaced with the mixture of three hypophosphite monohydrate ammoniums and six hydrated sulfuric acid ammonium manganese weight ratio 1:1; Namely the add-on of three hypophosphite monohydrate ammoniums described in embodiment 3 is the add-on of 0.25%, six hydrated sulfuric acid ammoniums of blue-green algae weight is 0.25% of blue-green algae weight.The oil yield rate that blue-green algae extracts oil is 30.1%, and calorific value is 27.5MJ/kg.
The preparation of embodiment 4 Environmentally-friebiofuel biofuel
Bio-fuel-oil prepares as follows:
(1) blue-green algae that Example 3 is obtained extracts oil 60 kilograms, cumene sodium sulfonate 3 kilograms, and 7 kilograms, water, mixes, obtained component A;
(2) get 0# diesel oil 20 kilograms, oleic acid 3.8 kilograms, ethanol 3.8 kilograms, methyl tertiary butyl ether 2 kilograms, cyclopentadiene tricarbonyl manganese 0.4 kilogram, mixes, obtained B component;
(3) B component is added into component A, mixes, namely obtain the bio-fuel-oil of embodiment 4, calorific value is 37.5MJ/kg.
As can be seen from embodiment, the bio-fuel-oil that the present invention obtains, substantially can diesel oil substitute, energy-conserving and environment-protective, and preparation method is simple, and cost is low, easily realizes engineering industry.
In addition, in the water body that some are nutritious, some blue-green algae often in amount reproduction in summer, and forms one deck blue-greenish colour at the water surface and has the offscum of bad smell, is called " wawter bloom ", large-scale blue algae bloom, is called as " green tide ".Green tide causes water quality deterioration, exhausts water oxygen gas and cause the death of fish time serious.More seriously, in blue-green algae, some kind also can produce Microcystin, produces outside murder by poisoning fish, people and animals.
The present invention is also the effective utilization to blue-green algae, and especially embodiment 3 employs three hypophosphite monohydrate ammoniums and the composite catalyzer of six hydrated sulfuric acid ammonium manganese carries out the extraction that blue-green algae extracts oil, makes oil yield rate, is significantly improved than during single use catalyzer.
Claims (5)
1. an Environmentally-friebiofuel biofuel, comprises following component by weight:
2. Environmentally-friebiofuel biofuel as claimed in claim 1, is characterized in that: it is prepare in accordance with the following steps that described blue-green algae extracts oil:
(1) by blue-green algae and massfraction be 60% ~ 90% ethanol mix by solid-to-liquid ratio (g/ml) 1:5 ~ 1:20 and be placed in reactor, add catalyzer, the add-on of catalyzer is 0.1 ~ 2% of blue-green algae weight, reacting by heating, reaction conditions is: temperature is 260 ~ 360 DEG C, pressure is 7 ~ 22MPa, and the reaction times is 15 ~ 45min; Obtain reaction solution;
(2) add dehydrated alcohol extractive reaction liquid, suction filtration isolates solid residue, and liquid phase stratification is organic phase and aqueous ethanolic solution phase;
(3) by organic phase underpressure distillation, the oily liquids obtained is that blue-green algae extracts oil; Underpressure distillation condition is: 0.085 ~ 0.1MPa, and temperature is 20 ~ 40 DEG C.
3. Environmentally-friebiofuel biofuel as claimed in claim 2, is characterized in that: the catalyzer described in step (1) is made up of the three hypophosphite monohydrate ammoniums of 40 ~ 60wt% and the six hydrated sulfuric acid ammonium manganese of 40 ~ 60wt%.
4. Environmentally-friebiofuel biofuel as claimed in claim 1 or 2, is characterized in that: described properties-correcting agent is selected from one or more the mixture in methyl tertiary butyl ether, propandiol butyl ether, propylene oxide.
5. the preparation method of the Environmentally-friebiofuel biofuel described in Claims 1 to 4, is characterized in that, comprises the following steps:
(1) take blue-green algae by weight and extract oil, cumene sodium sulfonate and water, mix obtained component A;
(2) take diesel oil, oleic acid, ethanol, properties-correcting agent and cyclopentadiene tricarbonyl manganese by weight, mix, obtained B component;
(3) B component is added into component A, mixes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105132043A (en) * | 2015-07-15 | 2015-12-09 | 广西南宁高斯特科贸有限公司 | Bio-fuel oil and preparation method thereof |
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Effective date of registration: 20210527 Address after: 100176 1306, 13th floor, building 41, yard 1, Disheng North Street, Beijing Economic and Technological Development Zone, Daxing District, Beijing Patentee after: Beijing youyou Environmental Protection Technology Co.,Ltd. Address before: No. 544, Hengtian Road, business operation center, north railway station, Jimei District, Xiamen City, Fujian Province, 361021 Patentee before: XIAMEN BOYA WONDERFUL ENVIRONMENTAL TECHNOLOGY Co.,Ltd. |
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Effective date of registration: 20211104 Address after: Room T6, Room 121, 1st Floor, Lane 11, 16299, Puwei Highway, Shanyang Town, Jinshan District, Shanghai, 201500 Patentee after: Shanghai Jiyou Environmental Protection Technology Co.,Ltd. Address before: 100176 1306, 13th floor, building 41, yard 1, Disheng North Street, Beijing Economic and Technological Development Zone, Daxing District, Beijing Patentee before: Beijing youyou Environmental Protection Technology Co.,Ltd. |