CN101113348A - Process for preparing bio-fuel by high-pressure fluid transformation technique - Google Patents
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Abstract
The invention relates to a process for producing biofuel with a high pressure fluid conversion technology, in particular to an industrial applying and providing technology for producing biological liquid fuel with subcritical/supercritical liquid, and the invention pertains to chemical technology and preparation field thereof. The invention takes forestry or agricultural combustible solid wastes (for example, forestry processing sawdust, crop straws, etc.), combustible matters from domestic waste (for example, waste tire, waste plastics, packing box and waste paper, etc.), plants oils, animals greases (lard, tallow, fish oil, etc.) and waste edible oils as raw materials, subcritical/supercritical liquid conversion treatment is done continuously in a high pressure reactor to realize hydrolysis and lipid gasification of biomass and get small molecular organic compounds-liquid biofuel, which is the process for producing biological liquid with high pressure liquid conversion technology. The process can shorten reaction time of the biofuel preparation, improve biofuel fuel yield and simplify post-treating process of biological liquid fuel.
Description
Technical field: the present invention relates to a kind of technology of preparing bio-fuel by high-pressure fluid transformation technique, particularly a kind of application is subcritical/and supercutical fluid prepares the biological liquid fuel Industrial Application of Technology provides technical matters.Belong to chemical industry technology and preparation field.
Background technology: liquid fuel is one of foundation stone of keeping modern society's normal operation, is most important power fuel.Along with the development of world economy, global fossil fuel resource is exhausted day by day, and the supply conditions of liquid fuel are severe day by day, and energy shortage has become one of important factor of restriction countries in the world Economic development.Therefore, under the multiple pressure exhausted day by day at petroleum resources, that the liquid fuel demand enlarges day by day, seek and develop the liquid fuel substitute energy to ensureing national energy security, promoting that the sustainable development of socio-economy has its own strategic significance.
After fossil man's energy was exhausted, the human energy can only rely on renewable energy source such as sun power, wind energy, water energy, but these all can not directly change into liquid fuel.Biomass energy is the human energy that utilize the earliest, is unique reproducible carbon source, and can change into conventional solid-state, liquid state and gaseous fuel, also be human can Source Type for what solve that the dual crisis of energy and environment gives priority to.Biofuel based on biomass comprises bio-ethanol and biofuel, and they are proved to be good fuel substitute.
Biomass liquefying is through a series of chiral processes the biomass of solid state, make it change into the clean utilization technology of liquid fuel (mainly be meant liquid hydrocarbon products such as gasoline, diesel oil, liquefied petroleum gas (LPG), also comprise Aalcohols fuels such as methyl alcohol, ethanol sometimes).According to the different technologies route of chiral process, liquefaction can be divided into direct liquefaction and indirect liquefaction.
The biomass Direct liquefaction technology be biomass under high pressure and certain temperature directly and solvent reaction be converted into the thermochemical reaction process of liquid fuel.General Direct liquefaction technology all needs catalyzer, and reaction process has higher hydrogen dividing potential drop, to improve speed of response, improves the stability of process, and the biomass Direct liquefaction technology that therefore needs to add catalyzer is called chemical catalysis again.Continuity according to biomass direct liquefaction production process can be divided into intermittent type or continous way.But the chemical catalysis method increases the production cost of production energy consumption and biological liquid fuel to ingredient requirement height, long reaction time, back sepn process complexity.
Summary of the invention: purpose of the present invention is overcoming the shortcoming of prior art, inventing a kind of is to utilize forestry or agriculture flammable solid waste (as: forestry processing wood chip, agricultural crop straw etc.), and the flammable matter (as: junked tire in the domestic refuse, plastic waste, packing box, waste paper etc.), vegetables oil, animal grease (lard, butter, fish oil etc.) and waste edible oil be raw material, in high-pressure reactor, carry out subcritical or supercutical fluid conversion processing continuously, realize the hydrolysis and the esterification reaction of biomass, obtain micromolecular organic compound---liquid biofuel, the i.e. technology of preparing bio-fuel by high-pressure fluid transformation technique.This technology can shorten reaction times, raising biological liquid fuel productive rate, the simplification biological liquid fuel aftertreatment technology of preparation biological liquid fuel.
The technology of preparing bio-fuel by high-pressure fluid transformation technique of the present invention is finished by following manner: biomass material is transported in the sliming treater (1) carries out pre-treatment, obtain the sliming biomass material, to be transported in the high-pressure reactor (3) after the pressurization of sliming biomass material, carry out subcritical or supercutical fluid conversion reaction continuously, finish the hydrolysis and the esterification reaction of biomass material, receive micromolecular organic compound one liquid biofuel, liquid biofuel through separator separate biofuel, the rate of rotation of biofuel reaches 75～96%.
Described biomass material is solid-state biomass raw material and liquid biomass material, the solid-state biomass raw material is the flammable matter in forestry flammable solid waste, agriculture flammable solid waste, the domestic refuse, and liquid biomass material is waste edible oil, vegetables oil, animal grease.Solid biomass waste and domestic refuse be letter sorting earlier, remove not flammable composition, with water purification or dilute acetic acid solution it is carried out purifying treatment, to remove dust and other impurity wherein, the dilute acetic acid solution concentration expressed in percentage by weight of purifying treatment is 5～20%, clarification time is 10～100min, add-on is 1～10: 1 with the raw material weight ratio, dry under 60～90 ℃ the temperature condition, be crushed to back below 60 orders and mix with turning oil, in the sliming treater, carry out pre-treatment, send into the storage of sliming raw material after the sliming and deposit.
Sliming biomass material reacting fluid is divided into two strands and sends into high-pressure reactor, and raw material is given birth in one sliming that accounts for total mass 15～30%, is delivered directly in the high-pressure reactor after being pressurized to 0.15～30Mpa; Another burst sliming is given birth to raw material by pressurization, be transported to the waste heat in the absorption reaction product in the interchanger earlier, be heated to 230～460 ℃ outward by preheater more afterwards, be pressurized to 0.15～45Mpa, in high-pressure reactor, two strands of sliming biomass materials mix mutually by pipe-line transportation.
Mixed sliming biomass material is in high-pressure reactor, through outside the heating continue to be heated to technological temperature and pressure condition after, carry out subcritical/supercutical fluid conversion reaction, finish the hydrolysis and the fatization of biomass material, receive liquid bio-fuel product, the mol ratio of biomass material and alcohols or water high pressure fluid is: 1: 10～80, and controlling precritical reaction pressure is 0.15～20MPa, temperature is 255～350 ℃, and the reaction times is 5～90min; The condition of supercritical reaction control is: pressure 8～40MPa, and 250～450 ℃ of temperature, the reaction times is 2～40min.
The liquid bio-fuel product that the high-pressure reactor reaction obtains is high pressure, high-temperature gas and liquid, by pipe-line transportation in interchanger, the waste heat amount is passed to the alcohols or the aqueous fluid of input, again liquid bio-fuel product is transported in the pressure reducing radiator subsequently, continue the cooling step-down, obtain light oil, water, critical fluids alcohols product liquid and incondensible gas, gas evolution is used for industrial chemicals or fuel.
Product liquid is transported to and isolates alcohols or water high pressure fluid in the separator, unreacted biomass solid particle and other impurity, bio-oil, bio-oil is transported to and is used for the turning oil use, other impurity are then as the biomass liquid fuel product, and the transformation efficiency of biofuel reaches 75～96%.Separator is finished dealcoholysis and mask work.All waste water or the alcohols that produce in the technological process recycle as raw water behind purification utensil, and the clarification time is 4～30h.The outer heating of reactant is to obtain heat by the hot oil boiler heating installation in the technological process.
Principle of work of the present invention is:
1) biomass (if solid waste and domestic refuse should at first sort and remove not flammable composition, is carried out purifying treatment with water purification or dilute acetic acid solution to it, to remove dust and other impurity wherein.The dilute acetic acid solution concentration expressed in percentage by weight of purifying treatment is 5～20%, clarification time is 10～100min, add-on is 1～10 with the raw material weight ratio: 1) dry under 60～90 ℃ the temperature condition, be crushed to back below 60 orders and mix with turning oil, in the sliming treater, carry out pre-treatment, high-pressure reactor is sent in charging feed storehouse after the sliming under the conveying of high pressure fluid.
Biomass material for after the sliming processing for the ease of carrying, is divided into two strands with reacting fluid and sends into high-pressure reactor.One (account for total mass flow rate 15～30%) is used for the slurry conveyed biomass through being pressurized to 0.15～30MPa; Another stock-traders' know-how is crossed pressurization, behind the waste heat of absorption reaction product, continues heating, when temperature reaches 230～460 ℃, sends into reaction tower behind pressure 0.15～45MPa and mixes with the sliming biomass.For the liquid state biological raw material then with reacting fluid through pressurization, behind the waste heat of absorption reaction product, continue heating, when temperature reaches 230～460 ℃, send into reaction tower behind pressure 0.15～45MPa and mix with the liquid state biological raw material.
After the heating installation of mixed raw material in high-pressure reactor continues to be heated to technological temperature and pressure condition, carry out subcritical/overcritical conversion reaction.The mol ratio of biomass and critical fluids is: 1: 10～80.Controlling precritical reaction pressure is 0.15～20MPa, and temperature is 255～350 ℃, and the reaction times is 5～90min.The condition of supercritical reaction control is: pressure 8～40MPa, and 250～450 ℃ of temperature, the reaction times is 2～40min.
The product of high-pressure reactor reaction is high pressure, high-temperature gas and liquid, utilizes interchanger that heat is passed to reactive material (alcohols or water), behind the absorption waste heat, continues the cooling step-down, obtains light oil, water, critical fluids alcohols and incondensible gas.Gas evolution is used for industrial chemicals or fuel.
Product liquid is isolated alcohols or water high pressure fluid in separator, unreacted biomass solid particle and other impurity, bio-oil.A bio-oil part is used for turning oil and uses, other are then as the biomass liquid fuel product, as: glucose, fructose, wood sugar, cellobiose, furfural, alkane, paraffinic hydrocarbons, alkene, ethanol, terephthalic acid, phenylformic acid, acetic acid, ethylene glycol, biofuel (fatty acid methyl ester).Tripping device can be realized dealcoholysis and isolating purpose.
All waste water or the alcohols that produce in the technological process recycle as raw material after purifying.Cleaner is the ceramic plate that purifying adsorbent is housed, and the clarification time is 4～30h.
The outer heating of reacting fluid is to obtain heat by the hot oil boiler heating installation.
Send into high-pressure reactor after the liquid state biological raw material then directly pressurizes in this way and carry out conversion reaction.
For liquid biomass material, reacting fluid behind the reaction product waste heat, continues heating through pressurization in the absorption interchanger, when temperature reaches 230～460 ℃, sends into high-pressure reactor behind pressure 0.15～45MPa and mixes with liquid state.
Advantage that the present invention has and positively effect:
1) for chemical catalysis, shortened the time that bio-oil is converted into biological liquid fuel.After reaching design point, different biomass only need 0.5～60min just Wood Adhesives from Biomass can be become biological liquid fuel.
2) the technology of the present invention has realized that continous-stable prepares biofuel, has simplified the complicacy of schedule of operation, is convenient to the industrialization continuous production.
3) the technology of the present invention biofuel productive rate height generally can reach 75～96%.
4) the technology of the present invention adaptability to raw material is wide, production process and product environmentally safe.
Description of drawings: below in conjunction with the accompanying drawing illustrated embodiment.
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 is a process flow diagram of the present invention.
Wherein: 1-sliming treater; The former feed bin of 2-sliming; The 3-high-pressure reactor; The 4-interchanger; The 5-pressure reducing radiator; The 6-separator; The 7-boosting pump; The 8-preheater; The 9-cleaner.
Embodiment:
Embodiment 1 (wood chip hydrolysis)
At first, wood chip is pulverized, granularity was controlled at 60 orders, was supercritical fluid media with water, be wood chip in molar ratio: the ratio of water=1: 70 is provided and delivered.25% water is pressurized to 23MPa and is used for the slurry conveyed biomass material, and remaining 75% water, enters reaction tower and mixes with biomass material after temperature reaches 400 ℃ by pressurization, waste heat heat exchange and outer heating.The heating region that enters high-pressure reactor heats once more, makes the biomass mixing raw material reach supercritical state (390 ℃ of temperature, pressure reaches 27MPa), and fully react at conversion zone that the reaction times is 20min.Product behind the supercritical reaction is through the UTILIZATION OF VESIDUAL HEAT IN interchanger with after cooling off step-down equipment, and temperature is reduced to 120 ℃, and pressure is reduced to 0.25MPa.Separate water outlet and biomass liquid light oil by separating device.Water is through purifying the back recycle.The bio oil productive rate is 86%.
Embodiment 2 (vegetables oil esterification)
Vegetables oil (rapeseed oil) is sent into high-pressure reactor through force (forcing) pump to 18Mpa be pressurised into the methyl alcohol generation esterification of supercritical state with heating up, generate biofuel (fatty acid methyl ester) and glycerine.Methyl alcohol, enters reaction tower and mixes with biomass material after temperature reaches 340 ℃ by pressurization, waste heat heat exchange and outer heating.The mol ratio of methyl alcohol and vegetables oil is 42: 1.The heating region that enters high-pressure reactor heats once more, makes the biomass mixing raw material reach supercritical state (350 ℃ of temperature, pressure reaches 19MPa), and fully react at conversion zone that the reaction times is 4min.Product behind the supercritical reaction is through the UTILIZATION OF VESIDUAL HEAT IN interchanger with after cooling off step-down equipment, and temperature is reduced to 120 ℃, and pressure is reduced to 0.25MPa.Isolate methyl alcohol, glycerine and biofuel by separating device.Methyl alcohol is through recycle behind the filtration, purification.The bio oil productive rate is 95%.
Claims (10)
1. the technology of a preparing bio-fuel by high-pressure fluid transformation technique, it is characterized in that biomass material is transported in the sliming treater (1) and carry out pre-treatment, obtain the sliming biomass material, to be transported in the high-pressure reactor (3) after the pressurization of sliming biomass material, carry out subcritical or supercutical fluid conversion reaction continuously, finish the hydrolysis and the esterification reaction of biomass material, receive micromolecular organic compound---liquid biofuel, liquid biofuel through separator separate biofuel, the rate of rotation of biofuel reaches 75～96%.
2. the technology of preparing bio-fuel by high-pressure fluid transformation technique according to claim 1, it is characterized in that described biomass material is solid-state biomass raw material and liquid biomass material, the solid-state biomass raw material is the flammable matter in forestry flammable solid waste, agriculture flammable solid waste, the domestic refuse, and liquid biomass material is waste edible oil, vegetables oil, animal grease.
3. according to the technology of claim 1 or 2 described preparing bio-fuel by high-pressure fluid transformation technique, it is characterized in that the letter sorting earlier of solid biomass waste and domestic refuse, remove not flammable composition, with water purification or dilute acetic acid solution it is carried out purifying treatment, to remove dust and other impurity wherein, the dilute acetic acid solution concentration expressed in percentage by weight of purifying treatment is 5～20%, clarification time is 10～100min, add-on is 1～10: 1 with the raw material weight ratio, dry under 60～90 ℃ temperature condition, being crushed to the following back of 60 orders mixes with turning oil, in the sliming treater, carry out pre-treatment, send into the storage of sliming raw material after the sliming and deposit.
4. according to the technology of claim 1 or 2 described preparing bio-fuel by high-pressure fluid transformation technique, it is characterized in that sliming biomass material reacting fluid is divided into two strands and sends into high-pressure reactor, raw material is given birth in one sliming that accounts for total mass 15～30%, is delivered directly in the high-pressure reactor after being pressurized to 0.15 ~ 30Mpa; Another burst sliming is given birth to raw material by pressurization, be transported to the waste heat in the absorption reaction product in the interchanger earlier, be heated to 230～460 ℃ outward by preheater more afterwards, be pressurized to 0.15～45Mpa, in high-pressure reactor, two strands of sliming biomass materials mix mutually by pipe-line transportation.
5. the technology of preparing bio-fuel by high-pressure fluid transformation technique according to claim 1, it is characterized in that mixed sliming biomass material is in high-pressure reactor, through outside the heating continue to be heated to technological temperature and pressure condition after, carry out subcritical/supercutical fluid conversion reaction, finish the hydrolysis and the fatization of biomass material, receive liquid bio-fuel product, the mol ratio of biomass material and alcohols or water high pressure fluid is: 1: 10 ~ 80, controlling precritical reaction pressure is 0.15 ~ 20MPa, temperature is 255 ~ 350 ℃, and the reaction times is 5 ~ 90min; The condition of supercritical reaction control is: pressure 8 ~ 40MPa, and 250 ~ 450 ℃ of temperature, the reaction times is 2 ~ 40min.
6. the technology of preparing bio-fuel by high-pressure fluid transformation technique according to claim 1 or 5, it is characterized in that the liquid bio-fuel product that the high-pressure reactor reaction obtains is high pressure, high-temperature gas and liquid, by pipe-line transportation in interchanger, the waste heat amount is passed to the alcohols or the aqueous fluid of input, again liquid bio-fuel product is transported in the pressure reducing radiator subsequently, continue the cooling step-down, obtain light oil, water, critical fluids alcohols product liquid and incondensible gas, gas evolution is used for industrial chemicals or fuel.
7. according to the technology of claim 6 or described preparing bio-fuel by high-pressure fluid transformation technique, it is characterized in that product liquid is transported to isolates alcohols or water high pressure fluid in the separator, unreacted biomass solid particle and other impurity, bio-oil, bio-oil is transported to and is used for the turning oil use, other impurity are then as the biomass liquid fuel product, and the transformation efficiency of biofuel reaches 75～96%.
8. according to the technology of claim 7 or described preparing bio-fuel by high-pressure fluid transformation technique, it is characterized in that separator finishes dealcoholysis and mask work.
9. according to the technology of claim 7 or described preparing bio-fuel by high-pressure fluid transformation technique, it is characterized in that all waste water or the alcohols that produce in the technological process recycle as raw water behind purification utensil, the clarification time is 4～30h.
10. according to the technology of claim 7 or described preparing bio-fuel by high-pressure fluid transformation technique, it is characterized in that the outer heating of reactant is to obtain heat by the hot oil boiler heating installation in the technological process.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735843A (en) * | 2010-01-19 | 2010-06-16 | 田原宇 | Biomass high-pressure continuous tower-type liquefying process with pretreatment step |
| CN101777281A (en) * | 2010-03-08 | 2010-07-14 | 南京化工职业技术学院 | Comprehensive training equipment for fluid transfer |
| CN101899316A (en) * | 2010-07-29 | 2010-12-01 | 聊城大学 | Method and device for improving yield and cooling rate of reaction kettle |
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