CN104962325B - Environmentally-friebiofuel biofuel and preparation method thereof - Google Patents
Environmentally-friebiofuel biofuel and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002551 biofuel Substances 0.000 title claims abstract description 13
- 241000192700 Cyanobacteria Species 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000284 extract Substances 0.000 claims abstract description 18
- 239000002283 diesel fuel Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- NSFKBZXCXCJZDQ-UHFFFAOYSA-N cumene;sodium Chemical compound [Na].CC(C)C1=CC=CC=C1 NSFKBZXCXCJZDQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 5
- 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
- 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 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
- 239000000203 mixture Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 229960004756 ethanol Drugs 0.000 claims description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 208000035126 Facies Diseases 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 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 5
- 238000006243 chemical reaction Methods 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
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000013517 stratification Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 22
- 239000000295 fuel oil Substances 0.000 abstract description 11
- 239000000446 fuel Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 5
- 238000002485 combustion reaction 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- KVCWSJZUKMSPLM-UHFFFAOYSA-N O.O[PH2]=O Chemical class O.O[PH2]=O KVCWSJZUKMSPLM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 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
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Abstract
The invention discloses a kind of Environmentally-friebiofuel biofuel and preparation method thereof, described Environmentally-friebiofuel biofuel includes following component by weight: cyanophyceae extracts oil 50～70 parts, cumene sodium sulfonate 2～4 parts, water 5～10 parts；Diesel oil 15～25 parts, oleic acid 2～6 parts, ethanol 2～6 parts, modifying agent 1～8 parts, cyclopentadiene tricarbonyl manganese 0.1～2 parts.The bio-fuel-oil of the present invention can be with diesel oil substitute, and calorific value is high, energy-conserving and environment-protective, and preparation method is simple, low cost, easily realizes engineering industry.
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 thereof
Method.
Background technology
Diesel oil, as a kind of important petroleum refining product, occupies the highest in various countries' fuel structure
Share, be the major impetus of many oversize vehicles (such as truck, internal combustion engine and electromotor etc.)
The advantages such as fuel, has power big, low price.Along with in world wide, diesel oil of vehicle becomes
The quickening of gesture, the demand of future diesel can be increasing, and petroleum resources day by day exhausted and
The raising of people's environmental consciousness, is greatly facilitated countries in the world and accelerates the exploitation of Alternative Diesel Fuel
Paces.
It is low, dirty to air that diesel oil there is also many problem, such as efficiency of combustion in application process
Dye is serious, produces substantial amounts of granule dust, CO2 emissions high.
Bio-fuel-oil refers to that the alcohol fuel, bio-fuel-oil and the aviation that are produced by living resources are raw
Thing fuel, can substitute the gasoline and diesel oil produced by oil, is that regenerative resource develops
Important directions.So-called living resources refer to utilize big gas and water, soil etc. by light cooperation
With and the various organisms that produce, i.e. all lived organic substances that can grow.Its bag
Include plant, animal and microorganism, be different from the traditional fuels such as oil, coal, nuclear energy, these
Emerging fuel is recyclable fuel.
Bio-fuel-oil is studied more as the fuel of a kind of alternative diesel oil at present.Biological combustion
Oil i.e. fatty acid methyl ester is a kind of oxygen-containing cleaning fuel, and owing to it has, combustion rate is high, it is few to pollute,
The advantage such as renewable, concerned.Bio-fuel-oil mainly produces with chemical method at present,
I.e. use animal and plant oils and fats and the low-carbon alcohols such as methanol or ethanol at sour or base catalyst and height
Carry out transesterification under temperature (230～250 DEG C), generate corresponding fatty acid methyl ester or ethyl ester.
Bio-fuel-oil is primarily present production cost height, the problems such as conversion ratio is low at present.
Summary of the invention
It is an object of the invention in view of the foregoing defects the prior art has, technology to be solved
One of problem is to provide a kind of Environmentally-friebiofuel biofuel.
The two of the technical problem to be solved are to provide the system of above-mentioned Environmentally-friebiofuel biofuel
Preparation Method.
A kind of Environmentally-friebiofuel biofuel that the present invention provides, includes following component by weight:
Wherein, described cyanophyceae extracts oil is to prepare in accordance with the following steps:
(1) it is that the ethanol of 60%～90% is by solid-to-liquid ratio (g/ml) by cyanophyceae and mass fraction
1:5～1:20 mixing is placed in reactor, adds catalyst, and the addition of catalyst is cyanophyceae
The 0.1～2% of weight, reacting by heating, reaction condition is: temperature is 260～360 DEG C, and pressure is
7～22MPa, the response time is 15～45min；Obtain reactant liquor；
(2) adding dehydrated alcohol extractive reaction liquid, sucking filtration isolates solid residue, liquid phase
Stratification is organic facies and ethanol water phase；
(3) by organic facies decompression distillation, the oily liquids obtained is that cyanophyceae extracts oil；Decompression
Distillation condition is: 0.085～0.1MPa, and temperature is 20～40 DEG C.
Preferably, the catalyst of step (1) by the three hypophosphite monohydrate ammoniums of 40-60wt% and
The six hydrated sulfuric acid ammonium manganese compositions of 40-60wt%.
Preferably, described modifying agent is selected from methyl tertiary butyl ether(MTBE), propandiol butyl ether, expoxy propane
In the mixture of one or more.
In the present invention,
Methyl tertiary butyl ether(MTBE), No. CAS: 1634-04-4.
Propandiol butyl ether, has another name called: 1,2-PD-1-monobutyl ether, and No. CAS: 15821-83-7.
Expoxy propane, 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 includes following step
Rapid:
(1) weigh cyanophyceae by weight and extract oil, cumene sodium sulfonate and water, mix homogeneously system
Obtain component A；
(2) diesel oil, oleic acid, ethanol, modifying agent and cyclopentadiene three carbonyl are weighed by weight
Base manganese, mix homogeneously, prepare B component；
(3) B component is added into component A, mix homogeneously, i.e. obtains life of the present invention
Thing fuel oil.
The bio-fuel-oil of the present invention can be with diesel oil substitute, energy-conserving and environment-protective, and preparation method is simple,
Low cost, easily realizes engineering industry.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, it is necessary to it is pointed out here that be
Following example are served only for being further described the present invention, it is impossible to be interpreted as protecting the present invention
Protect the restriction of scope.The person skilled in the art in this field can according to the content of the invention described above,
The present invention is made some nonessential improvement and adjustment.
Embodiment 1 cyanophyceae extracts the preparation of oil
It is to prepare in accordance with the following steps that cyanophyceae extracts oil:
(1) ethanol that cyanophyceae and mass fraction are 75% is mixed by solid-to-liquid ratio (g/ml) 1:10
Conjunction is placed in reactor, adds three hypophosphite monohydrate ammoniums, and the addition of described three hypophosphite monohydrate ammoniums is
The 0.5% of cyanophyceae weight, reacting by heating, reaction condition is: temperature is 320 DEG C, and pressure is
12MPa, the response time is 30min；Obtain reactant liquor；
Wherein, described solid-to-liquid ratio (g/ml) 1:10 refers to according to 1g cyanophyceae with 10ml's
Mass fraction is that the ratio of the ethanol of 75% mixes；
(2) adding dehydrated alcohol extractive reaction liquid, sucking filtration isolates solid residue, liquid phase
Stratification is organic facies and ethanol water phase；
(3) by organic facies decompression distillation, decompression distillation condition is: 0.09MPa, temperature is
25 DEG C, the oily liquids obtained is that cyanophyceae extracts oil, and it is 26.2% that cyanophyceae extracts the oil productivity of oil,
Calorific value is 26.3MJ/kg.
Cyanophyceae is extracted oil productivity (%)=cyanophyceae of oil and extracts oily weight/cyanophyceae weight × 100%.
Embodiment 2 cyanophyceae extracts the preparation of oil
According to method described in embodiment 1, three hypophosphite monohydrate ammoniums are replaced with six hydrated sulfuric acid ammoniums
Manganese, it is 27.3% that cyanophyceae extracts the oil productivity of oil, and calorific value is 26.0MJ/kg.
Embodiment 3 cyanophyceae extracts the preparation of oil
According to method described in embodiment 1, three hypophosphite monohydrate ammoniums are replaced with three hypophosphite monohydrate ammoniums with
The mixture of six hydrated sulfuric acid ammonium manganese weight ratios 1:1；I.e. three hypophosphite monohydrates described in embodiment 3
The addition of ammonium is the 0.25% of cyanophyceae weight, and the addition of six hydrated sulfuric acid ammoniums is cyanophyceae weight
0.25%.It is 30.1% that cyanophyceae extracts the oil productivity of oil, and calorific value is 27.5MJ/kg.
The preparation of embodiment 4 Environmentally-friebiofuel biofuel
Bio-fuel-oil is to prepare as follows:
(1) cyanophyceae that Example 3 prepares extracts oily 60 kilograms, cumene sodium sulfonate 3 kilograms,
7 kilograms of water, mix homogeneously, prepare component A；
(2) 0# diesel oil 20 kilograms, oleic acid 3.8 kilograms, ethanol 3.8 kilograms, methyl are taken
Tertbutyl ether 2 kilograms, cyclopentadiene tricarbonyl manganese 0.4 kilogram, mix homogeneously, prepare component
B；
(3) B component is added into component A, mix homogeneously, i.e. obtains the life of embodiment 4
Thing fuel oil, calorific value is 37.5MJ/kg.
By embodiment it can be seen that the bio-fuel-oil for preparing of the present invention, substantially can with diesel oil substitute,
Energy-conserving and environment-protective, and preparation method is simple, low cost, easily realizes engineering industry.
It addition, in the water body that some are nutritious, some cyanophyceae often in amount reproduction in summer,
And form one layer of aeruginous at the water surface and have the offscum of bad smell, it is referred to as " wawter bloom ", on a large scale
Blue algae bloom, be referred to as " green tide ".Green tide causes water quality deterioration, exhausts in water time serious
Oxygen and cause the death of Fish.More seriously, in cyanophyceae, some kind also can produce micro-
Capsule Algae toxins, outside producing murder by poisoning to Fish, people and animals.
The present invention is also the effective utilization to cyanophyceae, and especially embodiment 3 employs three hydration phosphorus
The catalyst that acid ammonium and six hydrated sulfuric acid ammonium manganese compound carries out cyanophyceae and extracts the extraction of oil so that produce
Oil rate, than single use catalyst time be significantly improved.
Claims (3)
1. an Environmentally-friebiofuel biofuel, includes following component by weight:
It is to prepare in accordance with the following steps that described cyanophyceae extracts oil:
(1) it is that the ethanol of 60%～90% is by solid-to-liquid ratio (g/ml) 1:5～1:20 by cyanophyceae and mass fraction
Mixing is placed in reactor, adds catalyst, and the addition of catalyst is the 0.1～2% of cyanophyceae weight, adds
Thermal response, reaction condition is: temperature is 260～360 DEG C, and pressure is 7～22MPa, and the response time is
15～45min；Obtain reactant liquor；
(2) adding dehydrated alcohol extractive reaction liquid, sucking filtration isolates solid residue, liquid phase stratification
For organic facies and ethanol water phase；
(3) by organic facies decompression distillation, the oily liquids obtained is that cyanophyceae extracts oil；Decompression distillation condition
For: 0.085～0.1MPa, temperature is 20～40 DEG C；
One or more in methyl tertiary butyl ether(MTBE), propandiol butyl ether, expoxy propane of described modifying agent
Mixture.
2. Environmentally-friebiofuel biofuel as claimed in claim 1, it is characterised in that: described in step (1)
Catalyst is made up of the three hypophosphite monohydrate ammoniums of 40～60wt% and the six hydrated sulfuric acid ammonium manganese of 40～60wt%.
3. the preparation method of the Environmentally-friebiofuel biofuel described in claim 1 or 2, it is characterised in that include
Following steps:
(1) weighing cyanophyceae by weight and extract oil, cumene sodium sulfonate and water, mix homogeneously prepares A group
Point；
(2) diesel oil, oleic acid, ethanol, modifying agent and cyclopentadiene tricarbonyl manganese are weighed by weight, mixed
Close uniformly, prepare B component；
(3) B component is added into component A, mix homogeneously.
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|---|---|---|---|---|
| CN101506336A (en) * | 2006-04-27 | 2009-08-12 | 新型生物燃料公司 | Biofuel composition and method of producing a biofuel |
| CN101580857A (en) * | 2009-07-01 | 2009-11-18 | 新奥科技发展有限公司 | Biomass energy prepared by one-step method of microalgae |
| CN103275813A (en) * | 2013-05-31 | 2013-09-04 | 江苏大学 | Biodiesel modification method |
| CN103320185A (en) * | 2013-07-05 | 2013-09-25 | 西北民族大学 | Knock preventing and air resistance lowering agent for bio-based methanol gasoline and preparation method of knock preventing and air resistance lowering agent |
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| US8273248B1 (en) * | 2010-04-06 | 2012-09-25 | Heliae Development, Llc | Extraction of neutral lipids by a two solvent method |
| US20130118058A1 (en) * | 2011-05-10 | 2013-05-16 | Thu Thi Le Nguyen | Diesel microemulsion biofuels |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101506336A (en) * | 2006-04-27 | 2009-08-12 | 新型生物燃料公司 | Biofuel composition and method of producing a biofuel |
| CN101580857A (en) * | 2009-07-01 | 2009-11-18 | 新奥科技发展有限公司 | Biomass energy prepared by one-step method of microalgae |
| CN103275813A (en) * | 2013-05-31 | 2013-09-04 | 江苏大学 | Biodiesel modification method |
| CN103320185A (en) * | 2013-07-05 | 2013-09-25 | 西北民族大学 | Knock preventing and air resistance lowering agent for bio-based methanol gasoline and preparation method of knock preventing and air resistance lowering agent |
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| Title |
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