CN104862023B - A kind of method of chemical catalysis production biological fuel gas - Google Patents
A kind of method of chemical catalysis production biological fuel gas Download PDFInfo
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- CN104862023B CN104862023B CN201510260157.2A CN201510260157A CN104862023B CN 104862023 B CN104862023 B CN 104862023B CN 201510260157 A CN201510260157 A CN 201510260157A CN 104862023 B CN104862023 B CN 104862023B
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Abstract
The present invention relates to a kind of method of chemical catalysis production biological fuel gas, use the biomass material rich in cellulose, hemicellulose, sugar or starch, through hydrolysis process containing aqueous acid, after neutralizing filtering, filtrate hydrogenated deoxidation cracking reaction under catalyst action produces biological fuel gas.The catalyst is loaded catalyst, and active component is selected from least one of Ni or Ru, and load capacity is 1~6wt%, and catalyst carrier is selected from activated carbon, ZrO2、TiO2、SiO2One or both of.The biological fuel gas of production is C1~C4 alkane, and the selectivity of wherein methane is up to 73%, and the selectivity of ethane, propane and butane is up to 12%, 7% and 4% respectively, and gas phase alkane gross production rate is up to 90%, and the biological fuel gas of high quality is can obtain after separating-purifying.The new method of combustion gas is produced using biomass as raw material this technology provides one, promotes the sustainability and recyclability of biological fuel gas production.
Description
Technical field
The present invention relates to a kind of chemical catalysis production biological fuel gas method, specifically, the present invention relates to one kind with
The method that agricultural-forestry biomass rich in cellulose, hemicellulose, sugar or starch in nature produces gas alkane for raw material.The party
Method for one kind by biomass through hydrolysis process containing aqueous acid after, it is neutralized and the carbohydrate aqueous solution that is formed passes through after filtering
The technology of hydrogenation deoxidation-cracking production gas alkane.
Technical background
Biomass is a kind of huge carbon containing renewable resource, including the discarded object of agricultural production and residue, forest and
The plants such as forestry processing waste, careless class, it is renewable resource most abundant on the earth, its main carbonaceous component includes fiber
Element, hemicellulose and lignin three parts, some also contain carbohydrate.In order to improve its energy density, people exist always
Abundant, to effectively utilize biomass new technology, new method are found, a variety of biomass energy utilization technologies are also studied exploitation successively
Out.At present, the Land use systems of biomass resource generally have physical transformations, three sides of chemical conversion and bioconversion
Face, can be specifically the technologies such as direct burning, gasification, pyrolysis liquefaction, solidification, fermentation very much.
The energy density of biomass economy is improved, the oxygen for removing the inside is a kind of one of best mode.Cellulose, half fibre
Dimension element and starch component can obtain sugar (mainly glucose and xylose) or sugar alcohol (mainly mountain by hydrolyzing and being hydrogenated with means
Pears alcohol and xylitol).These sugar/sugar alcohols are considered as biomass energy platform chemicals of new generation, pass through catalytic hydrodeoxygenation
Or aqueous phase reforming technology can synthesize hydrogen, alkane and chemicals.In the world, Huber et al. is as pioneer (Angew Chem
Int Ed,2004,43:1549), it is proposed that the new method of C5/C6 alkane is prepared by sugar alcohol deoxidation or reformation, is prepared for one kind
Pt/SiO2-Al2O3 catalyst, sugar alcohol effectively can be converted into C5/C6 alkane, so as to rise a kind of bio liquid
The development of alkane technology.On this basis, the country has carried out research and development in biomass C5/C6 alkane technology.Wherein, it is Chinese
Patent CN101550350A discloses the preparation method and catalyst of a kind of biogasoline, and its feature is with sorbitol aqueous solution
For raw material, using carried noble metal Pt/HZM-5 catalyst, high-pressure hydrogenation deoxygenation is carried out in paste state bed reactor, can
To obtain C5/C6 alkane more with high selectivity.
And smaller molecule alkane is prepared for biomass deoxidation, such as methane, ethane, report is mainly anaerobism hair at present
The conversion technology of fermenting process.Anaerobic fermentation refer to organic matter carried out in the presence of anaerobic bacteria metabolism produce using methane as
The process of main fuel gas (biogas).Whole conversion process can be divided into three steps, first turn insoluble compound organic matter
It is melted into soluble compounds；Then soluble compounds are then converted into short chain acids and ethanol；Biogas most is changed into through various anaerobic bacterias afterwards,
50-80% methane is typically contained, calorific value may be up to 20MJ/m3, it is a kind of excellent gaseous fuel.
In addition, catalytic hydrodeoxygenation or cracking are one of most common deoxidation means of chemical industry.For from biomass
Carbohydrate, in their molecular structure the presence of oxygen contribute to the reactivity of compound.Water soluble carbohydrates exist
Reacted on catalyst so as to produce polyalcohol, sugar alcohol and hydrocarbon compound by hydrogenation, hydrogenolysis, cracking or with hydrogen.
Cortright et al. United States Patent (USP) (publication number US20080216391 and US20100076233) describes a kind of chemical catalysis
Means can make the carbohydrate-modifying method into higher hydrocarbon.
The content of the invention
It is that agricultural-forestry biomass raw material turns it is an object of the present invention to provide a kind of method of new production biological fuel gas
Turn to hydrocarbon fuel route and provide a stronger technology of application.In order to achieve the above object, the present invention uses following technology
Scheme：
A kind of method of chemical catalysis production biological fuel gas, comprises the following steps：
(1) biomass material of hydrolysis process containing aqueous acid is used, obtained hydrolyzate is neutralized and filters；
(2) filtrate hydrogenated deoxidation-cracking reaction under catalyst action obtains mixed gas, and C1~C4 is obtained after separation
Alkane, as described biological fuel gas；The catalyst is loaded catalyst, active component in Ni or Ru at least one
Kind, preferably Ru or Ru-Ni composition metals component, load capacity are 1~6wt%, preferably 2~4wt%；Catalyst carrier is selected from
Activated carbon, ZrO2、TiO2And SiO2One or both of, preferably activated carbon, ZrO2Or SiO2-ZrO2Composite oxides.
Further, above-mentioned biomass material is rich in the agricultural of cellulose, hemicellulose, sugar and starch in nature
Discarded object or domestic waste；The agriculture and forestry organic waste material be selected from maize straw, corncob, sorghum stalk, duckweed, jerusalem artichoke, cassava,
Straw stalk, straw or bagasse；Domestic waste is preferably the mud of rubbish from cooking and sewer.
Further, the above-mentioned acid containing used in aqueous acid is selected from H2SO4、H3PO4, one or both of HCl, preferably
For H2SO4Or H2SO4-H3PO4；Concentration is 1.0~10.0wt%, preferably 3.0~7.0wt%.Hydrolysis process containing aqueous acid
The treatment temperature of step is 130~180 DEG C, and processing time is 1~4h, and biomass material is 1 with the mass ratio containing aqueous acid:
4~1:8.
Further, above-mentioned hydrogenation deoxidation-cracking reaction can be under hydrogenation reaction or the nitrogen atmosphere for facing hydrogen
Hydro-thermal reforming reaction, preferably face the hydrogenation reaction of hydrogen.Hydrogenation reaction for facing hydrogen, reaction temperature are 200~300 DEG C,
Hydrogen Vapor Pressure is 3.0~6.0MPa, and mass space velocity is 0.5~3.0h-1.Preferably, reaction temperature is 240~280 DEG C, hydrogen pressure
Power is 3.5~4.5MPa, mass space velocity 1.0-2.0h-1。
Further, hydrogenation deoxidation-cracking reaction reactor used trickle bed reactor or batch (-type) selected from continous way
Autoclave, preferred trickle bed reactor.
The principle of the present invention is to obtain hydrolyzate with the biomass material of hydrolysis process containing aqueous acid, hydrolyzate is through entering one
Step is neutralized, the aqueous solution of the carbohydrate aqueous solution and other carbon compounds is formed after Purification by filtration processing.Carbohydrate
Refer to oligosaccharides and monose (such as pentose and hexose, can be specifically xylose, glucose and arabinose), other carbon compounds
Refer to the alcohol such as poor furfural, levulic acid, aldehyde, acid compound.According to the difference of biomass material, the water in the aqueous solution
The total concentration of dissolubility carbon compound can be between 3~20wt% scopes.
The solution of above-mentioned acquisition under catalyst action, at a temperature of 200~300 DEG C carry out hydrogenation deoxidation-cracking reaction.
Used reactor can be the trickle bed reactor of continous way or the autoclave of batch (-type), preferably react
Device is the trickle bed reactor of continous way.The alkane containing C1~C4 can be obtained after reaction, in addition to the hydrogen (hydro-thermal reforming process hydrogen
Amount is less than methane) methane is main component, combustion gas use can be made.
Biological fuel gas refers to C1~C4 alkane as caused by biomass material, wherein methane, ethane, propane and fourth
The total content of alkane is up to 96%, and pentane, hexane and their content of isomer are 4% or so.For facing the hydrogenation reaction under hydrogen, just
Alkane total content is up to 11.3% in the tail gas of secondary acquisition, after circular response, in tail gas the content of alkane up to 51.2%, its
Remaining component is mainly hydrogen, and a small amount of carbon dioxide；On the basis of the total organic carbon in the aqueous solution, the carbon mole production of alkane
Rate reaches as high as 90%, the wherein selectivity of methane up to 73%, the selectivity of ethane, propane and butane respectively up to 12%,
7% and 4%, more than catalyst energy stable operation 500h.It is first to obtain in tail gas for the hydro-thermal reforming reaction under nitrogen atmosphere
Determination of Alkane Content is up to 32.1%, and remaining is carbon monoxide, carbon dioxide, nitrogen, but poor catalyst stability, and catalyst stabilization is transported
Row is less than 240h..
Compared with prior art, the method for chemical catalysis production biological fuel gas of the present invention, has advantages below：
(1) use hydrogenation deoxidation-cracking technology and corresponding catalyst come conversion of biomass hydrolyzate for gas alkane, institute
There is reaction to carry out in aqueous, realize the use of organic solvent-free.Biomass hydrolysate for acquisition is reaction solution, this
A variety of carbon water carbohydrate (xylose, grapes in the hydrogenation deoxidation-catalyst for cracking energy provided while catalyzing hydrolysis liquid are provided
Sugar, arabinose, furfural, levulic acid etc.) gas alkane is converted into, and C1~C4 alkane of high yield can be obtained, highest can
Up to 90%, methane accounts for 73%, and ethane, propane and butane account for 12%, 7% and 4% respectively, while catalyst is in hydrolyzate
Inorganic matter, organic impurities have good tolerance so as to keep catalyst activity, the most long stable fortune of catalyst for a long time
The row time is up to more than 500h.
(2) utilization of hydrocarbon fuel is converted for agricultural-forestry biomass hydrolyzate, the characteristics of existing hydrogenation deoxidation technology is main is
C5, C6 sugar in hydrolyzate or sugar alcohol are converted into C5, C6 alkane, such as Chinese patent CN101550350A and document (Angew
Chem Int Ed,2004,43:1549) loaded Pt catalyst disclosed in can preferably realize this process.Due to obtain
C5, C6 alkane of higher yields, catalyst carrier need to use acid stronger silicoaluminate, such as SiO2-Al2O3, HZM-5
Deng, but the hydrothermal stability of these oxide carriers is poor, the hydrogenation deoxidation stability in aqueous environment is poor, often
Catalyst structure change and silicon, aluminium can be caused to be lost in.The characteristics of catalysis technique and catalyst provided by the invention is to utilize acid
Weaker and good hydrothermal stability the carrier of property, such as activated carbon, TiO2, ZrO2 even load metal Ru or Ni catalyst, Ke Yi
Thermal and hydric environment long-time stable keeps catalytic activity, while the carbohydrate high productivity in hydrolyzate can be converted into
C1-C4 gas alkanes.In this reaction, compared to noble metals such as Pt metal, Rh and Pd, less expensive metal Ru or Ni have more preferable
Catalytic effect.
(3) technology path is simple to operate, and course of reaction is chemical catalysis, relative to traditional fermentation and enzymatic,
Chemical catalysis has the characteristics of high efficiency, high intensity production, while process conditions controllability is strong and is not influenceed by seasonal climate,
Raw material can be diversified, and fund cost and process operation cost are saved so as to realize.
(4) technology of the present invention can promote the sustainability and recyclability and biomass that biomass fuel produces
The variation of fuel production, the environmental pollution during biomass trans-utilization and problem of resource waste are advantageously accounted for, is met
The requirement of recycling economy.
Embodiment：
The present invention is described in more detail below by instantiation, the embodiment provided is given for example only the present invention, but
It is not in any way limit the scope of the present invention.
The preparation of hydrogenation deoxidation-catalyst for cracking：
Embodiment 1-24 and the 4.0Ru/C catalyst of embodiment 34 use equi-volume impregnating, take 50g activated carbons (20-40
Mesh) in beaker, 0.25mol/L chlorination ruthenium solution 80mL is then added, it is stirring while adding, stand after 12h 120 in baking oven
DEG C dry 12h, then in muffle furnace 300 DEG C roasting 6h.
The 3.0Ru3.0Ni/C catalyst of embodiment 25 and embodiment 32 uses equi-volume impregnating, takes 50g activated carbons
Then (20-40 mesh) adds mixed solution 80mL (ruthenic chloride 0.19mol/L, the nitric acid of chloride containing ruthenium and nickel nitrate in beaker
Nickel 0.32mol/L), it is stirring while adding, stand 120 DEG C of dry 12h, then 300 DEG C of roastings in muffle furnace in baking oven after 12h
6h.
The 4.0Ru/ZrO of embodiment 262The preparation method of catalyst and embodiment 1 are basically identical, and carrier is zirconium dioxide,
The temperature being finally calcined in muffle furnace is 500 DEG C.
The 3.0Ru3.0Ni/TiO of embodiment 272The preparation method of catalyst and embodiment 25 are basically identical, carrier two
Titanium oxide, the temperature being finally calcined in muffle furnace are 500 DEG C.
The 4.0Ru/SiO of embodiment 282-ZrO2The preparation method of catalyst and embodiment 1 are basically identical, carrier SiO2-
ZrO2Composite oxides, the temperature being finally calcined in muffle furnace are 500 DEG C.
The 3.0Ru3.0Ni/SiO of embodiment 292-ZrO2The preparation method of catalyst and embodiment 25 are basically identical, carrier
For SiO2-ZrO2Composite oxides, the temperature being finally calcined in muffle furnace are 500 DEG C.
The preparation method and embodiment 1 of the 1.0Ru/C catalyst of embodiment 30 are basically identical, and the chlorination ruthenium solution of addition is dense
Spend for 0.0625mol/L, volume 80mL.
The preparation method and embodiment 1 of the 6.0Ru/C catalyst of embodiment 31 are basically identical, and the chlorination ruthenium solution of addition is dense
Spend for 0.375mol/L, volume 80mL.
The 2.0Ru4.0Ni/C catalyst of embodiment 33 uses equi-volume impregnating, takes 50g activated carbons (20-40 mesh) in burning
In cup, mixed solution 80mL (ruthenic chloride 0.125mol/L, the nickel nitrate 0.43mol/ of chloride containing ruthenium and nickel nitrate are then added
L), it is stirring while adding, stand 12h after in baking oven 120 DEG C of drys 12h, then in muffle furnace 300 DEG C be calcined 6h.
Embodiment 35-37 method for preparing catalyst and embodiment 1 are basically identical, precursor solution be respectively chloroplatinic acid,
Palladium nitrate, rhodium nitrate, concentration are respectively 0.13mol/L, 0.24mol/L, 0.24mol/L.
Implementation process example of the present invention：
Embodiment 1：
Granule corn stalk (500 grams of butts) and 5% phosphoric acid solution 4L are added in 5L hydrolysis kettles, 2h is handled at 180 DEG C.
The solution of acquisition is neutralized, after filtering (carbon compound total concentration is 3.0wt%) through trickle bed reactor (in 316L reaction tubes
Footpath 10mm, long 1000mm) hydrogenation deoxidation-cracking reaction, catalyst is Ru/C (10g), catalyst in normal pressure, 300 DEG C of original positions also
Reaction is proceeded by after former 6h, reaction condition is 260 DEG C of temperature, pressure 4.0MPa, 1.0h-1Mass space velocity.After reaction, gas alkane
Methane selectively is 71% in hydrocarbon, and gas alkane yield is 45% (the carbon molar yield based on total organic carbon in reaction solution).
Embodiment 2~37
Embodiment 2~34 is with reference to embodiment 1, raw material in each embodiment, containing aqueous acid, hydrogenation deoxidation-cracking reaction bar
Part is shown in Table 1.In each embodiment the biomass material of hydrolysis process containing aqueous acid formed hydrolyzate in carbon compound concentration with
And the catalyst used in hydrogenation deoxidation reaction is shown in Table 2 with reaction result.Embodiment 35-37 is comparative example, hydrolysis used
For liquid as embodiment 20, the active component of hydrogenation deoxidation catalyst used is Pt metal, Pd, Rh.
The present invention is screened to the active component of catalyst, from data as can be seen that Pt, Rh and Pd are compared, with Ni
With active components of the Ru as catalyst, C1~C4 alkane tool is obtained to catalysis biomass hydrolyzate hydrogenation deoxidation-cracking reaction
There is a higher catalytic activity, gap is obvious.
Table 1. contains acids media processes condition and hydrogenation deoxidation-crack reacting condition
Remarks：*Hydrogenation deoxidation-cracking reactor of embodiment 34 is the autoclave reactor of batch (-type), and the reaction time is
4h, hydrogenation deoxidation-cracking reactor of remaining embodiment are the trickle bed reactor of continous way.
Table 2. contains acids media processes result and hydrogenation deoxidation catalyst and reaction result
Remarks：
a3.0Ru3.0Ni/C represents that activated carbon is carrier, and the load capacity of Ru, Ni metal is respectively 3.0wt.%.
b4.0Ru/SiO2-ZrO2Represent SiO2And ZrO2The complex carrier of composition, the load capacity of Ru metals is 4.0wt.%.
cHydrogenation deoxidation-cracking reactor of embodiment 34 be batch (-type) autoclave reactor, reaction time 4h, its
Hydrogenation deoxidation-cracking reactor of remaining embodiment is the trickle bed reactor of continous way.
Claims (4)
- A kind of 1. method of chemical catalysis production biological fuel gas, it is characterised in that comprise the following steps：(1) biomass material of hydrolysis process containing aqueous acid is used, obtained hydrolyzate is neutralized and filters；It is described to contain aqueous acid Acid used is selected from H2SO4、H3PO4, one or both of HCl, concentration is 1.0~10.0wt%；(2) filtrate hydrogenated deoxidation-cracking reaction under catalyst action obtains mixed gas, and C1~C4 alkane is obtained after separation Hydrocarbon, as described biological fuel gas；The catalyst is loaded catalyst, active component in Ni or Ru at least one Kind, load capacity is 1~6wt%, and catalyst carrier is selected from activated carbon, ZrO2、TiO2、SiO2One or both of；The hydrogenation The reaction temperature of deoxidation-cracking reaction is 200~300 DEG C, and Hydrogen Vapor Pressure be 3.0~6.0MPa, mass space velocity for 0.5~ 3.0h-1。
- 2. the method for chemical catalysis production biological fuel gas as claimed in claim 1, it is characterised in that the biomass is former Material be selected from agriculture and forestry organic waste material or domestic waste, the agriculture and forestry organic waste material selected from maize straw, corncob, sorghum stalk, duckweed, Jerusalem artichoke, cassava, straw stalk, straw or bagasse, the domestic waste are selected from rubbish from cooking or mud.
- 3. the method for chemical catalysis production biological fuel gas as claimed in claim 1 or 2, it is characterised in that molten containing sour water The temperature of liquid hydrolysis process step is 130~180 DEG C, and processing time is 1~4h, biomass material and the quality containing aqueous acid Than for 1:4~1:8.
- 4. the method for chemical catalysis production biological fuel gas as claimed in claim 1 or 2, it is characterised in that the hydrogenation The autoclave of deoxidation-cracking reaction reactor used trickle bed reactor or batch (-type) selected from continous way.
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| CN108993495B (en) * | 2018-08-01 | 2020-12-25 | 中国科学技术大学 | Method for preparing alkane compound by catalytic deoxidation of carbonyl or hydroxyl-containing compound |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995285A (en) * | 2006-12-21 | 2007-07-11 | 周开根 | Method and technology of low temperature electrocatalytic gasification and liquification for garbage and biomass |
| WO2010148348A2 (en) * | 2009-06-19 | 2010-12-23 | The Texas A&M University System | Integrated biofuel processing system |
| CN104245899A (en) * | 2011-10-05 | 2014-12-24 | Sea6能源有限公司 | Process of production of renewable chemicals and biofuels from seaweeds |
| CN104226358A (en) * | 2014-07-22 | 2014-12-24 | 中国科学院广州能源研究所 | Method for preparing alkane by catalyzing phenol compounds through hydrodeoxygenation and catalytic reaction system |
| CN104478647A (en) * | 2014-12-08 | 2015-04-01 | 中国科学院广州能源研究所 | Method for preparing hexane by catalyzing biomass in water phase |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995285A (en) * | 2006-12-21 | 2007-07-11 | 周开根 | Method and technology of low temperature electrocatalytic gasification and liquification for garbage and biomass |
| WO2010148348A2 (en) * | 2009-06-19 | 2010-12-23 | The Texas A&M University System | Integrated biofuel processing system |
| CN104245899A (en) * | 2011-10-05 | 2014-12-24 | Sea6能源有限公司 | Process of production of renewable chemicals and biofuels from seaweeds |
| CN104226358A (en) * | 2014-07-22 | 2014-12-24 | 中国科学院广州能源研究所 | Method for preparing alkane by catalyzing phenol compounds through hydrodeoxygenation and catalytic reaction system |
| CN104478647A (en) * | 2014-12-08 | 2015-04-01 | 中国科学院广州能源研究所 | Method for preparing hexane by catalyzing biomass in water phase |
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