CN108217593A - A kind of lignin monomer phenols model compound aqueous phase reforming hydrogen production process - Google Patents
A kind of lignin monomer phenols model compound aqueous phase reforming hydrogen production process Download PDFInfo
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- CN108217593A CN108217593A CN201611155274.3A CN201611155274A CN108217593A CN 108217593 A CN108217593 A CN 108217593A CN 201611155274 A CN201611155274 A CN 201611155274A CN 108217593 A CN108217593 A CN 108217593A
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- autoclave
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
A kind of lignin monomer phenols model compound aqueous phase reforming hydrogen production process, the method that the invention mainly utilizes aqueous phase reforming hydrogen manufacturing, lignin monomer model compound is converted, obtain clean energy resource hydrogen, advantage is to can be applied to aqueous or water-soluble raw material, and with excellent water gas shift reaction performance, relatively low reaction temperature and higher pressure.In aqueous phase reforming reaction, by regulating and controlling reaction pressure（0.5‑5Mpa）And temperature so that reactant carries out water gas shift reaction, so as to obtain the product of low CO contents and high hydrogen yield.
Description
Technical field
The invention belongs to biomass resource recovery energy technical field more particularly to by a kind of wood after biomass pyrolytic
Lignin monomer phenols model compound aqueous phase reforming hydrogen production process.
Background technology
The energy is the important energy source of human social development, and with the development of human society, non-renewable energy resources are increasingly
Exhaustion, status of the regenerative resource in human social development is more and more important, and regenerative resource includes biomass energy, the sun
Energy, wind energy etc., wherein biomass can obtain human lives institute by being pyrolyzed obtained monomeric compound by further refining
Hydrogen Energy needed etc..
Hydrogen is a kind of cleaning, efficient, reproducible new energy, is known as 21 century most potential alternative energy source.It is existing
Some hydrogen preparing methods-fossil fuel method, consumption is that oil, coal, natural gas etc. can not regenerative resources.
In all biological oil components, phenolic compound is important one of composition, and the utilization of phenolic compound is to biology
Making full use of for oil has great importance.From H made from biological oil reforming2It can be used for biorefinery or integration with synthesis gas
Into traditional oil product refining process, such as hydrogenation, ammonification, methanol processed, F- T synthesis.
Reformation hydrogen production is a kind of more perfect technology.Mainly there is following several method：Steam reforming（SR）, confession
Thermal reforming（ATR）, dry gas reform（DR）, aqueous phase reforming（APR）And the partial oxidation of renewable carboxylate.
The phenolic compound reformation hydrogen production that document can be looked into mainly uses vapor reforming hydrogen production, needs to pass through in hydrogen production process
Heating will be water, which has the shortcomings that energy consumption is high, and mixes in product there are a large amount of CO with hydrogen.
Aqueous phase reforming is a kind of effective ways proposed by professor Dumesic, it can utilize under the conditions of water phase and come from
The reactant production hydrogen and alkane of biomass.
Invention content
In order to solve the problems, such as lignin monomer phenols model compound hydrogen manufacturing, present invention offer is a kind of to utilize aqueous phase reforming
The advantages of method of hydrogen manufacturing converts lignin monomer model compound, obtains clean energy resource hydrogen, the invention is can
Applied to aqueous or water-soluble raw material, and with excellent water gas shift reaction performance, relatively low reaction temperature and
Higher pressure.In aqueous phase reforming reaction, by regulating and controlling reaction pressure（0.5-5Mpa）And temperature so that reactant carries out water
Syngas conversion reactor, so as to obtain the product of low CO contents and high hydrogen yield.
A kind of lignin monomer phenols model compound aqueous phase reforming hydrogen production process of the present invention is as follows：
1st, quantitative Ni/ZSM-5 catalyst is weighed with assay balance, is put into the autoclave that volume is 100mL, Ran Hou
Quantitative lignin-base phenols solution is added in autoclave；
2nd, the stir speed (S.S.) of autoclave agitating shaft is adjusted to 130r/min, and be passed through the hydrogen needed for reaction toward autoclave
Gas simultaneously keeps reaction to carry out in the liquid phase；
3rd, the gas vent valve on autoclave is closed, autoclave is rapidly increased to reaction temperature using thermocouple and is stopped
Stay certain time；
4th, after reaction, autoclave is positioned in ice-water bath, it is made to be rapidly decreased to room temperature；
5th, the gas-phase product that gas collection bag is collected by gas vent valve in autoclave carries out constituent analysis, then opens
Autoclave takes out liquid product with Dispette and carries out component analysis；
6th, with reference to gas-phase product and liquid product, analysis obtains the conversion of lignin-base phenolic compound water phase hydrogenation deoxidation reaction
Rate and selectivity of product.
Description of the drawings
Fig. 1 is present invention experiment reaction unit schematic diagram.
In figure：1st, autoclave；2nd, thermocouple；3rd, liquid product；4th, agitating shaft；5th, gas vent valve；6th, gas phase is produced
Object；7th, hydrogen.
Specific embodiment
The invention will be further described in the following with reference to the drawings and specific embodiments, but invention which is intended to be protected is simultaneously
It is without being limited thereto.
Embodiment 1：A kind of lignin monomer model compound phenol aqueous phase reforming hydrogen production process.
1st, the Ni/ZSM-5 catalyst that 0.3g Ni contents are 16% is weighed with assay balance, the wherein silica alumina ratio of ZSM-5 is
25, be put into volume be 100mL autoclave 1 in, be then separately added into autoclave 1 a concentration of 0.1M of 50 mL,
The phenol solution of 0.2M, 0.4M and 0.5M, and glass bar is uniformly mixed with catalyst.
2nd, 2 stir speed (S.S.) of agitating shaft is adjusted to 130r/min, and hydrogen 7 is passed through into autoclave 1, make reaction pressure
For 4Mpa.
3rd, the gas vent valve 5 on autoclave 1 is closed, makes 1 temperature of autoclave fast by the effect of thermocouple 2
Speed rises to 240 DEG C, and reacts 3h at such a temperature.
4th, autoclave 1 is positioned in ice-water bath, it is made to be rapidly decreased to room temperature.
5th, the gas-phase product that gas collection bag is collected by gas vent valve 5 in autoclave 1 carries out constituent analysis, so
Autoclave 1 is opened afterwards, and taking out liquid product with Dispette carries out component analysis, obtained various concentration phenol water phase
Reformation hydrogen production performance.
With the increase of reactant concentration, when reactant concentration increases to 0.4mol/L from 0.1mol/L, hydrogen selection
Property variation be not the selective highest of hydrogen in the product it is obvious that when reactant concentration is 0.2mol/L, phenol at this time
Conversion ratio slightly reduces, and will be 92% from the conversion ratio close to 100%.The concentration of reactant is further improved to 0.5mol/L, hydrogen
The selectivity of gas in the product is substantially reduced, and only 43%.
Embodiment 2：A kind of lignin monomer model compound phenol aqueous phase reforming hydrogen production process.
1st, the Ni/ZSM-5 catalyst that 0.3g Ni contents are 16% is weighed with assay balance, the wherein silica alumina ratio of ZSM-5 is
25, it is put into the reaction under high pressure 1 that volume is 100mL, is then respectively adding the phenol solution of a concentration of 0.1M of 50 mL, and glass
Stick is uniformly mixed with catalyst.
2nd, 2 stir speed (S.S.) of agitating shaft is adjusted to 130r/min, and hydrogen 7 is passed through into autoclave 1, distinguish pressure
Reach 4Mpa, 4.9Mpa, 5.6Mpa and 7Mpa.
3rd, the gas vent valve 5 on autoclave 1 is closed, 1 temperature of autoclave is rapidly increased to 240 DEG C, and
3h is reacted at this temperature.
4th, autoclave 1 is positioned in ice-water bath, it is made to be rapidly decreased to room temperature.
5th, the gas-phase product that gas collection bag is collected by gas vent valve 5 in autoclave 1 carries out constituent analysis, so
Autoclave 1 is opened afterwards, and taking out liquid product with Dispette carries out component analysis, the conversion ratio of obtained phenol and production
The selectivity of object.
With the increase of reaction pressure, the conversion ratio of phenol declines apparent, and conversion ratio is 100 when from reaction pressure being 4Mpa
% has dropped to 55 % during 7 Mpa.And opposite variation tendency is presented in the selectivity of carbon dioxide in product, from initial 4 Mpa
When being increased to 7 Mpa close to the selectivity of 0 % in the product close to the selectivity of 20 %.When reaction pressure increases from 4 Mpa
When adding to 5.6 Mpa, the selectivity variation unobvious of hydrogen, the selectivity of hydrogen in the product is both greater than 65 %, works as reaction pressure
When power is 4.9 Mpa, the selective highest of hydrogen in the product is 77.9 %.
Embodiment 3：A kind of lignin monomer model compound phenol aqueous phase reforming hydrogen production process.
1st, the Ni/ZSM-5 catalyst that 0.3g Ni contents are 16% is weighed with assay balance, the wherein silica alumina ratio of ZSM-5 is
25, it is put into the reaction under high pressure 1 that volume is 100mL, then in the phenol solution for being separately added into a concentration of 0.1M of 50 mL, and glass
Glass stick is uniformly mixed with catalyst.
2nd, 4 stir speed (S.S.) of agitating shaft is adjusted to 130r/min, and hydrogen 7 is passed through into autoclave 1, reach pressure
4Mpa。
3rd, the gas vent valve 5 on autoclave 1 is closed, distinguishes the temperature of autoclave 1 by thermocouple 2 fast
Speed rises to 200 DEG C, 240 DEG C, 260 DEG C and 280 DEG C, and reacts 3h at such a temperature.
4th, autoclave 1 is positioned in ice-water bath, it is made to be rapidly decreased to room temperature.
5th, the gas-phase product 6 that gas collection bag is collected by gas vent valve 5 in autoclave 1 carries out constituent analysis,
Then autoclave 1 is opened, taking out liquid product 3 with Dispette carries out component analysis, obtained phenol aqueous phase reforming
Hydrogen production reaction performance.
When reaction temperature is 200oC, the conversion ratio of phenol and the selectivity of hydrogen are all very low, with the warm temperature of reaction
Raising, the conversion ratio of phenol increases, and last conversion ratio is more than 93 %.The selectivity presentation of hydrogen in the product first rises drops afterwards
Low trend, and the selectivity of hydro carbons in the product has opposite variation tendency.
Claims (1)
1. a kind of lignin monomer phenols model compound aqueous phase reforming hydrogen production process, it is characterised in that：Preparation method is as follows：
1) quantitative Ni/ZSM-5 catalyst, is weighed with assay balance, is put into the autoclave that volume is 100mL, then
Quantitative lignin-base phenols solution is added in autoclave；
2) stir speed (S.S.) of autoclave agitating shaft, is adjusted to 130r/min, and be passed through needed for reaction toward autoclave
Hydrogen simultaneously keeps reaction to carry out in the liquid phase；
3) the gas vent valve on autoclave, is closed, autoclave is rapidly increased to reaction temperature simultaneously using thermocouple
Stop certain time；
4), after reaction, autoclave is positioned in ice-water bath, it is made to be rapidly decreased to room temperature；
5), the gas-phase product that gas collection bag is collected by gas vent valve in autoclave carries out constituent analysis, then beats
Autoclave is opened, taking out liquid product with Dispette carries out component analysis；
6), with reference to gas-phase product and liquid product, analysis obtains turning for lignin-base phenolic compound water phase hydrogenation deoxidation reaction
Rate and selectivity of product.
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| CN201611155274.3A CN108217593A (en) | 2016-12-14 | 2016-12-14 | A kind of lignin monomer phenols model compound aqueous phase reforming hydrogen production process |
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| CN201611155274.3A CN108217593A (en) | 2016-12-14 | 2016-12-14 | A kind of lignin monomer phenols model compound aqueous phase reforming hydrogen production process |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508858A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method for preparing aromatic compounds employing catalytic cracking of industrial lignins |
| CN104311394A (en) * | 2014-10-14 | 2015-01-28 | 上海应用技术学院 | Phenol deoxidizing method |
-
2016
- 2016-12-14 CN CN201611155274.3A patent/CN108217593A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508858A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method for preparing aromatic compounds employing catalytic cracking of industrial lignins |
| CN104311394A (en) * | 2014-10-14 | 2015-01-28 | 上海应用技术学院 | Phenol deoxidizing method |
Non-Patent Citations (1)
| Title |
|---|
| 周铭昊: "水相生物油提质制备含氧燃料催化剂制备与研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
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