CN102181311B - Process for producing lignin diesel - Google Patents
Process for producing lignin diesel Download PDFInfo
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- CN102181311B CN102181311B CN201110067823.2A CN201110067823A CN102181311B CN 102181311 B CN102181311 B CN 102181311B CN 201110067823 A CN201110067823 A CN 201110067823A CN 102181311 B CN102181311 B CN 102181311B
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Abstract
The invention discloses a process for producing lignin diesel. The method is characterized by comprising the following steps of: uniformly mixing the components of an emulsifier in a ratio, forcibly dispersing the uniformly mixed emulsifier and diesel by a physical means to obtain a stable dispersing system, then adding assistant emulsifier and an oil modifier in a certain ratio, injecting decolored alkali lignin aqueous solution from which impurities are removed into the system at a constant speed, continuously dispersing cyclically for certain times, taking out and naturally settling for 1 to 2 days, and filtering to obtain supernate, namely the lignin diesel. In the process, the lignin diesel is prepared from the waste lignin used as raw materials instead of partial diesel. The process has the advantages of simplicity, easiness in amplification, and industrialization and the like.
Description
Technical field
The present invention relates to a kind of biomass as the fuel production technique of fuel dope, particularly a kind of diesel oil emulsification production technique that contains xylogen with energy-conserving and environment-protective, long preservative period, the advantage such as easy to use.
Technical background
Xylogen is the class material that the aromatic alcohol by polymerization forms, and is respectively: a kind of complicated phenol polymer that tonquinol, lubanol, 5-hydroxyl lubanol, four kinds of alcohol monomers of sinapyl alcohol are formed is a kind of many rings macromolecule organic containing many negative electricity group.It is one of composition forming plant cell wall, and mainly, between cellulosic fibre, it forms and character more complicated, has the effect that strengthens cell walls and binder fibre in plant tissue.In xylophyta, xylogen accounts for 25%, is the abundantest organism of second in the world.
In theory, xylogen is the highest natural high moleculer eompound of occurring in nature unit volume energy density, the xylogen combustion heat is 26.6kJ/g, inexpensive (1500～2000 yuan/ton) containing the macromolecular compound of natural carbon containing that can be the highest, hydrogen, oxygen, suitable with the ethanol combustion heat 30kJ/g of same carbon containing, hydrogen, oxygen, but because xylogen is than great, its volume combustion heat is approximately 1.5 times of ethanol, close with diesel oil, and spontaneous ignition temperature and the diesel oil of xylogen are close, in diesel engine cylinder inter-sync, light acting after making it be suitable for mixing with diesel oil.The genetic prerequisite therefore, with diesel oil substitute.
In fact, from the nineteen thirty mankind, just start xylogen to study, within 1980, American advises xylogen and diesel oil mixing diesel oil substitute, but stable dispersion and the transportation problem of xylogen in diesel oil while all not solving technically xylogen as Alternative Diesel Fuel.Also owing to never searching out suitable dispersion agent or emulsifying agent, fine granular xylogen is as can not be used as the power fuel of Modern Engine in the past containing the inflammable high energy fuels of oxygen always.
Patent CN 101735871 A (quasi-liquid fuel for internal combustion engines and conveying thereof and injection method), CN 101724475 A (biomass base liquid fuels, utilize method and engine structure), CN 101792684 A (oil engine or gas-engine quasi-liquid fuel) and CN 101798534 A (oil engine or internal combustion turbine quasi-liquid fuel) disclose one group of feature of utilizing xylogen polymolecularity and mobility, by dispersion medium or emulsifying technology, xylogen subparticle and diesel oil are evenly mixed as a kind of quasi-liquid fuel between liquid and solid, diesel oil substitute partly.This method is complex process not only, and in the fuel making, to obtain particle diameter large, extremely unstable for xylogen particle, and the oil feeding system of oil engine must be carried out corresponding transformation and could be used, and is difficult to realize industrialization.
And alkali lignin is soluble in water, be insoluble to diesel oil.The present invention proposes that the aqueous solution that is dissolved with alkali lignin and diesel oil are formed to even one and stablizes and to obtain diesel oil emulsification based on changing thinking, with this solve that the xylogen addition of lignin diesel is low, poor stability, defect that cost is high.
Summary of the invention
The present invention relates to a kind of biomass as the fuel production technique of fuel dope, particularly a kind of diesel oil emulsification production technique that contains xylogen with energy-conserving and environment-protective, long preservative period, the advantage such as easy to use.
First each prescription of emulsifying agent is mixed in proportion, after the emulsifying agent mixing and diesel oil are adopted to physical means is powerful disperses to obtain stable dispersion system, then add a certain proportion of assistant for emulsifying agent and oil product modifying agent, finally the alkali lignin aqueous solution after decolouring removal of impurities is at the uniform velocity injected to above-mentioned system, continue circulation and disperse certain number of times, take out natural subsidence 1～2 day, filtering gained supernatant liquid is lignin diesel.
Advantage of the present invention:
1 technical process of the present invention is simple, easy and simple to handle, and favorable reproducibility is with low cost, is easy to be amplified to industrialization and produces.
2 gained lignin diesel content of lignin of the present invention are high, stable system, good fluidity.
The applied xylogen of 3 the present invention is trade waste, measures inexpensively greatly, turn waste into wealth for a kind of energy and material, and be a kind of circular economy industrial pattern.
4 the present invention can provide new approaches for national strategic reserves of energy plan.
Specific embodiments
Below embodiments of the invention are described in further detail: first each prescription of emulsifying agent is mixed in proportion, after the emulsifying agent mixing and diesel oil are adopted to physical means is powerful disperses to obtain stable dispersion system, then add a certain proportion of assistant for emulsifying agent and oil product modifying agent, finally the alkali lignin aqueous solution after decolouring removal of impurities is at the uniform velocity injected to above-mentioned system, continue circulation and disperse certain number of times, take out natural subsidence 1～2 day, filtering gained supernatant liquid is lignin diesel.
The prescription of described emulsifying agent can be the combination of any two or three tensio-active agent that contains hydrophilic radical or lipophilic group and to meet mixed HLB value scope be 6～11, and preferable range is 7～9.5.
The preferred sorbitol anhydride oleate of prescription (Span-80) of described emulsifying agent and the combination of cetyl trimethylammonium bromide (CTAB), its mass percent example is 1%～10%.
Described diesel oil can be the diesel oil of any model on the market, and the mass percent example of diesel oil in lignin diesel finished product is 60%～95%, and preferable range is 65%～85%.
Choosing of described assistant for emulsifying agent should be short chain alcohol or nonionic surface active agent, preferred propyl carbinol, and the mass percent example of assistant for emulsifying agent in lignin diesel finished product is 0.5%～8%.
Described alkali lignin used can be waste liquid that in any related production technique, the alkali lignin that is able to is main component or the dry product of by product, the dry products of the alkali lignin waste black liquor of preferred alkaline process paper technology gained, wherein the quality percentage composition of xylogen must not be lower than 20%.
After described removal of impurities, alkali lignin aqueous solution mass percentage concentration scope is 0.5%～50%, and removal of impurities mode can be filtration, centrifugal, natural subsidence.
It is discoloring agent that hydrogen peroxide is selected in the decolouring of the described alkali lignin aqueous solution, and discoloring agent usage quantity is 5%～20% of alkali lignin aqueous solution quality, and bleaching temperature is 60～90 ℃, and bleaching time is 20～40 minutes.
Described oil product modifying agent is the mixture of pyrogallol, hexadecanol and isooctyl ester nitrate, and usage quantity is respectively 0.003%～0.02%, 0.01%～0.08% and 0.05%～0.4% of lignin diesel final product quality.
The mass percent example of the described alkali lignin aqueous solution adding in lignin diesel finished product is 3%～30%, and preferable range is 5%～15%.
The powerful dispersion means of described emulsifying agent and diesel oil can be any physical techniques with dispersed function.
The dispersion means of described alkali lignin and emulsifying agent and diesel oil dispersion system can be any physical techniques with dispersed function.
It is 2～10 times that the circulation of described alkali lignin and emulsifying agent and diesel oil dispersion system disperses number of times.
Example 1:
First emulsifying agent Span-80 and CTAB are mixed in proportion under the effect of colloidal mill, wherein Span-80 is 1.945kg, CTAB is 1.055kg, after will in the emulsifying agent having prepared, with colloidal mill strong shear, be dispersed in 38.389kg diesel oil, obtain stable dispersion system, then add the assistant for emulsifying agent propyl carbinol of 1.111kg and contain 0.01kg pyrogallol, the oil product modifying agent of 0.04kg hexadecanol and 0.05kg isooctyl ester nitrate, finally 1.875kg alkali lignin being dissolved in 5.625kg water adds 10% hydrogen peroxide at the uniform velocity to inject above-mentioned dispersion system after 60 ℃ of decolourings 40 minutes filtering and impurity removing, with colloidal mill, continuing circulation disperses 3 times, take out natural subsidence 2 days, filtering gained supernatant liquid is lignin diesel.
Example 2:
First emulsifying agent Span-80 and CTAB are mixed in proportion under the effect of emulsification pump, wherein Span-80 is 3.469kg, CTAB is 0.531kg, after the emulsifying agent having prepared is dispersed in 39.519kg diesel oil with emulsification pump strong shear, obtain stable dispersion system, then add the assistant for emulsifying agent propyl carbinol of 1.481kg and contain 0.005kg pyrogallol, the oil product modifying agent of 0.005kg hexadecanol and 0.025kg isooctyl ester nitrate, finally 1.25kg alkali lignin being dissolved in 3.75kg water adds 5% hydrogen peroxide at the uniform velocity to inject above-mentioned dispersion system after 70 ℃ of decolourings 20 minutes filtering and impurity removing, with emulsification pump, continuing circulation disperses 5 times, take out natural subsidence 2 days, filtering gained supernatant liquid is lignin diesel.
Claims (9)
1. the production technique of a lignin diesel, comprise the following steps: first each prescription of emulsifying agent is mixed in proportion, after the emulsifying agent mixing and diesel oil are adopted to physical means is powerful disperses to obtain stable dispersion system, then add a certain proportion of assistant for emulsifying agent and oil product modifying agent, finally the alkali lignin aqueous solution after decolouring removal of impurities is at the uniform velocity injected to above-mentioned system, continue circulation and disperse certain number of times, take out natural subsidence 1～2 day, filtering gained supernatant liquid is lignin diesel; The preferred sorbitol anhydride oleate of prescription (Span-80) of emulsifying agent and the combination of cetyl trimethylammonium bromide (CTAB), its mass percent example is 1%～10%; Assistant for emulsifying agent is propyl carbinol, and the mass percent example of assistant for emulsifying agent in lignin diesel finished product is 0.5%～8%; Oil product modifying agent is the mixture of pyrogallol, hexadecanol and isooctyl ester nitrate, and usage quantity is respectively 0.003%～0.02%, 0.01%～0.08% and 0.05%～0.4% of lignin diesel final product quality.
2. according to the production technique of a kind of lignin diesel claimed in claim 1, it is characterized in that, diesel oil can be the diesel oil of any model on the market, and the mass percent example of diesel oil in lignin diesel finished product is 60%～95%.
3. according to the production technique of a kind of lignin diesel claimed in claim 1, it is characterized in that, alkali lignin used can be waste liquid that in any related production technique, the alkali lignin that is able to is main component or the dry product of by product, and wherein the quality percentage composition of xylogen must not be lower than 20%.
4. according to the production technique of a kind of lignin diesel claimed in claim 1, it is characterized in that, after decolouring removal of impurities, alkali lignin aqueous solution mass percentage concentration scope is 0.5%～50%, and removal of impurities mode can be filtration, centrifugal, natural subsidence.
5. according to the production technique of a kind of lignin diesel claimed in claim 1, it is characterized in that, it is discoloring agent that hydrogen peroxide is selected in the decolouring of the alkali lignin aqueous solution, discoloring agent usage quantity is 5%～20% of alkali lignin aqueous solution quality, bleaching temperature is 60～90 ℃, and bleaching time is 20～40 minutes.
6. according to the production technique of a kind of lignin diesel claimed in claim 1, it is characterized in that, the mass percent example of the alkali lignin aqueous solution adding in lignin diesel finished product is 3%～30%.
7. according to the production technique of a kind of lignin diesel claimed in claim 1, it is characterized in that, the powerful dispersion means of emulsifying agent and diesel oil can be any physical techniques with dispersed function.
8. according to the production technique of a kind of lignin diesel claimed in claim 1, it is characterized in that, the dispersion means of alkali lignin and emulsifying agent and diesel oil dispersion system can be any physical techniques with dispersed function.
9. according to the production technique of a kind of lignin diesel claimed in claim 1, it is characterized in that, it is 2～10 times that the circulation of alkali lignin and emulsifying agent and diesel oil dispersion system disperses number of times.
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| CN201110067823.2A CN102181311B (en) | 2011-03-21 | 2011-03-21 | Process for producing lignin diesel |
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| CN201110067823.2A CN102181311B (en) | 2011-03-21 | 2011-03-21 | Process for producing lignin diesel |
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| CN102181311B true CN102181311B (en) | 2014-04-23 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732344A (en) * | 2012-07-05 | 2012-10-17 | 东北林业大学 | Production technology of water-soluble cellulose gasoline |
| CN102719283A (en) * | 2012-07-05 | 2012-10-10 | 东北林业大学 | Production process of hemicellulose heavy oil |
| CN102732343A (en) * | 2012-07-05 | 2012-10-17 | 东北林业大学 | Production technology of amino-lignin diesel |
| CN106244251A (en) * | 2016-08-04 | 2016-12-21 | 陈永林 | A kind of method utilizing abandoned biomass to prepare biofuel oil |
| CN108559556B (en) * | 2018-05-16 | 2020-08-04 | 本溪怀特石油化工有限责任公司 | Environment-friendly boiler fuel oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040111955A1 (en) * | 2002-12-13 | 2004-06-17 | Mullay John J. | Emulsified water blended fuels produced by using a low energy process and novel surfuctant |
| CN101225319A (en) * | 2007-01-15 | 2008-07-23 | 北京大学 | Method for preparing hydrocarbon fuel and methanol |
| CN101792684A (en) * | 2009-01-29 | 2010-08-04 | 秦才东 | Quasi liquid fuel for internal-combustion engine or gas turbine engine |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040111955A1 (en) * | 2002-12-13 | 2004-06-17 | Mullay John J. | Emulsified water blended fuels produced by using a low energy process and novel surfuctant |
| CN101225319A (en) * | 2007-01-15 | 2008-07-23 | 北京大学 | Method for preparing hydrocarbon fuel and methanol |
| CN101792684A (en) * | 2009-01-29 | 2010-08-04 | 秦才东 | Quasi liquid fuel for internal-combustion engine or gas turbine engine |
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