CN105947979A - Hydrogen production method by reforming methanol-glycerol in cooperation with water vapor, and catalyst applied to hydrogen production method - Google Patents
Hydrogen production method by reforming methanol-glycerol in cooperation with water vapor, and catalyst applied to hydrogen production method Download PDFInfo
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- 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
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
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- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
Abstract
The invention discloses a hydrogen production method by reforming methanol-glycerol in cooperation with water vapor. The method comprises the steps of (1) processing attapulgite, dipping the attapulgite into a soluble salt solution of nickel, calcium, cerium and iron, drying after active ingredients are adsorbed on the surface of the attapulgite to obtain a catalyst precursor, cooling and roasting to obtain an attapulgite-loaded nickel catalyst; (2) placing the catalyst in a constant-temperature environment, introducing H2 for activating the catalyst at 500 DEG C, cooling, mixing up a mixture of methanol and glycerin at the molar ratio of (1-6):1 with water, gasifying the mixture of methanol, glycerol and water through a preheater, feeding the gasified gas into a reactor to subject the gasified gas to the catalytic reforming reaction, cooling an obtained product to achieve the gas-liquid separation, and preparing a hydrogen-rich synthesis gas. The hydrogen production process through reforming methanol, glycerol and water vapor is conducted based on the inter-coupling and coordinating effect of glycerol and methanol, instead of the simple superposition of the gasification processes of methanol, glycerol and water vapor. Therefore, the hydrogen production speed and the hydrogen production depth through reforming glycerol and methanol are improved.
Description
Technical field
The present invention relates to belong to hydrogen preparation field, be specifically related to a kind of methanol-glycerol work in coordination with vapor reforming hydrogen production method and
Catalyst for this hydrogen production process.
Background technology
Along with the aggravation of energy crisis, the new forms of energy seeking alternative Fossil fuel have become as a study hotspot.Energy
Source problem has significant impact to national economy and national development, and therefore China also will tap a new source of energy as a strategy.
In numerous new forms of energy, Hydrogen Energy becomes one of 21 century optimal energy.This is because, identical heavy in burning
In the case of coal, gasoline and the hydrogen of amount, the energy that hydrogen produces is most, and the product of its burning is water, do not have lime-ash and
Waste gas, does not pollutes the environment；At present, the production of hydrogen mainly has two kinds: one, overwhelming majority hydrogen are from oil, coal and sky
So producing in gas, this method needs to consume fossil fuel the most in short supply；Two, produce by the method for electrolysis water, this
It is big that the method for kind consumes electric energy, does not calculates.Therefore energy scarcity, environmental pollution dual-pressure under, development utilization organic waste
The recycling of thing, it is achieved clean and process the new technique that combines with highly effective hydrogen yield and have important practical significance.
Biodiesel as a kind of regenerative resource, just by the attention of various countries and is developed energetically.The most industrial
Mainly use Production of Biodiesel Via Transesterification Method, during preparation biodiesel, often produce 10 tons of biodiesel and can produce about 1
The glycerin by-products of ton, additionally, be the carrying out promoting ester exchange reaction, is usually added into the methanol of excess to improve biodiesel
The glycerol that productivity, the methanol of these excess and reaction generate just constitutes the Main By product in preparation of biodiesel.Closely
Along with the increase of yield of biodiesel over Nian, the subsequent treatment of its a large amount of glycerol produced during generating and by-product methanol is asked
Topic is the most following, and the pair in production process is the most effectively disposed in greatly developing and increasing rapidly along with Global biodiesel
Product, reaches the double optimization of resource and environment, has been current biological diesel oil industry development problem demanding prompt solution.Present stage,
Crude glycerine is mainly sold for exquisite glycerol by refined purification, and not only cost is high, and market does not digests yet, it is therefore necessary to
New outlet is selected for biological diesel oil byproduct.
Summary of the invention
It is an object of the invention to provide a kind of methanol-glycerol and work in coordination with vapor reforming hydrogen production method, not only reduce hydrogen manufacturing
Cost of material, and be expected to solve and offer reference, to Hydrogen Energy and biodiesel for certainly biological diesel oil byproduct later use problem
The development of exploitation, the adjustment of energy resource structure, the protection of environment and industrial chain suffer from important realistic meaning.
The present invention is achieved by the following technical programs:
Vapor reforming hydrogen production method worked in coordination with by a kind of methanol-glycerol, comprises the following steps:
(1) preparation of attapulgite loaded Raney nickel: being activated by attapulgite, the total concentration that impregnated in soluble-salt is
In nickel, calcium, cerium and the ferrum soluble salt solutions of 1.0～1.5mol/L, treat that described nickel, calcium, cerium and ferrum active component are adsorbed in institute
State the attapulgite's surface after activation, drying, it is thus achieved that catalyst precursor, cool down roasting, i.e. prepare attapulgite loaded nickel
Catalyst；
(2) vapor reforming hydrogen production worked in coordination with by methanol-glycerol: put attapulgite loaded Raney nickel prepared by step (1)
In isoperibol, logical Hydrogen activation at 500 DEG C, cooling, be (1～6) by mol ratio: the methanol of 1 and the mixture of glycerol and
Water mixes, and is gasified by the preheated device of mixture of methanol, G & W, and the gas after gasification is entered by the pipeline of heating and thermal insulation
Catalytic reforming reaction, the cooled reality of reacted product is carried out in the reactor equipped with described attapulgite loaded Raney nickel
Existing gas-liquid separation, prepares hydrogen-rich synthetic gas.
Glycerol, hydrogen production from methanol-steam reforming process are not the simple superposition of both respective gasifications, but methanol
And the coordinative role that intercouples produced between glycerol.Methanol first decomposition caused heat release, the pyrolysis for glycerol provides certain heat
Amount, plays facilitation for sweet oil gasification, thus causes both reformation hydrogen production speed and the raising of the degree of depth.
Attapulgite has intergranular nano-pore structure and the character such as high-specific surface area and high porosity, noble metal and how gold
Belong to ionic catalyst and may be homogenously dispersed in surface and the internal gutter of attapulgite, be conducive to improving catalyst at low temperatures
Activity and eliminate effect of intraparticle diffusion, the most also will produce concerted acid-base catalysis and have molecular sieve shape selective catalysis cracking make
With.
Preferably, described in step (1), the preparation of attapulgite loaded Raney nickel comprises the steps:
A () attapulgite activates: attapulgite, through extruding, shearing and pulverize, obtains the attapulgite powder that granularity is 200 mesh
Body, described attapulgite powder body mass concentration is that the dilute hydrochloric acid of 5-10% soaks 8-12h, makes described attapulgite powder body obtain
Activation, is then washed with deionized and is precipitated to neutrality, and activated attapulgite PG represents；
B () infusion process prepares attapulgite loaded Raney nickel: weigh respectively nickel, calcium, cerium and ferrum soluble salt solutions in
In beaker, adding deionized water, the total concentration making described soluble-salt is 1.0～1.5mol/L, and mixed liquor is added step (a)
In attapulgite powder body after the described activation obtained, stirring, impregnate 12～16 hours, remove the supernatant, remaining suspension
Through decompression sucking filtration, gained filtration cakes torrefaction pulverized 40～80 sieves after being cooled to room temperature, and the granule roasting after pulverizing is the most prepared
Ca-Ce-Fe-Ni/PG attapulgite loaded Raney nickel.
The preparation method of described nickel, calcium, cerium and ferrum soluble salt solutions is: by nickel oxide, calcium oxide, cerium oxide and oxidation
Ferrum is dissolved in salpeter solution respectively, prepares nickel nitrate, calcium nitrate, cerous nitrate and iron nitrate solution.
Preferably, being calculated in mass percent, nickel oxide is 10～15wt%, and calcium oxide is 5～10wt%, and cerium oxide is 5
～10wt%, ferrum oxide is 5～10wt%.
Preferably, methanol-glycerol described in step (2) is worked in coordination with the method for vapor reforming hydrogen production and is: use flowing continuously
The atmospheric fixed bed reactor of formula, controls reactor temperature by temperature controller, fills described claim 1 step in catalyst bed
(1) the attapulgite loaded Raney nickel of 0.5～1g prepared by, the upper and lower of described attapulgite loaded Raney nickel
Adding quartz sand, be first passed through in reactor by nitrogen, after being warming up to 500 DEG C, logical hydrogen carries out activation of catalyst 1h, closes hydrogen
Gas；It is cooled to reaction temperature 450-650 DEG C under nitrogen protection, closes nitrogen, mol ratio is (1～6): the methanol of 1 is with sweet
The mixture of oil and water mixing, enter the preheater gasification that temperature is 250 DEG C, and the gas after gasification enters into equipped with described recessed
The crystal reaction tube of convex rod soil supported nickel catalyst carries out catalytic reforming reaction, and the cooled gas-liquid that realizes of reacted product is divided
From, prepare hydrogen-rich synthetic gas.
Preferably, amount ratio between methanol and the mixture of glycerol and water described in step (2) according to water and methanol and
The mol ratio of the carbon contained in the mixture of glycerol is (5～8): 1.
Preferably, the mass space velocity of methanol described in step (2) and glycerol and water charging is 2.5～5.0h-1。
It is a further object to provide a kind of catalysis working in coordination with vapor reforming hydrogen production method for methanol-glycerol
Agent, this catalyst preparation process is simple, can show good synergism, thus improve catalysis in catalytic reaction process
The activity of agent, stability and H2Yield.
A kind of catalyst working in coordination with vapor reforming hydrogen production method for methanol-glycerol, including catalyst active component and
Catalyst carrier, described catalyst active component includes that nickel, calcium, cerium and ferrum, described catalyst carrier are attapulgite.
Preferably, the content range of described catalyst active component is to be calculated in mass percent: nickel oxide be 10～
15wt%, calcium oxide is 5～10wt%, and cerium oxide is 5～10wt%, and ferrum oxide is 5～10wt%, nickel oxide be 10～
15wt%, described calcium oxide is 5～10wt%, and described cerium oxide is 5～10wt%, and described ferrum oxide is 5～10wt%, concavo-convex
The mass fraction of rod soil is 55%～75%.
The invention has the beneficial effects as follows:
(1) attapulgite has intergranular nano-pore structure and the character such as high-specific surface area and high porosity, noble metal and
Many metal ion catalysts may be homogenously dispersed in surface and the internal gutter of attapulgite, is conducive to improving catalyst at low temperature
Under activity and eliminate effect of intraparticle diffusion, the most also will produce concerted acid-base catalysis and there is the shape selective catalysis of molecular sieve split
Solution effect；
(2) iron nickel oxide is in the easily raw interaction of attapulgite plane of crystal, forms the cube nickel crystalline substance of easily reduction altogether
The structure deposited, promotes active phase dispersion, enhances C C and the activity of C H key in the catalyst big organic molecule of fracture；CeO2Mix
Miscellaneous energy can suppress glycerol second dehydration to form unstable hydro carbons, strengthens the anti-sintering of Ni, the performance of anti-carbon deposit；CaO doping can with instead
Answer product CO2There is absorption or chemical reaction, thus break thermodynamical equilibrium and limit, make steam reforming chemistry balance towards being conducive to
The direction that hydrogen produces is moved, and the catalyst of preparation can show good synergism in catalytic reaction process, thus carries
The high activity of catalyst, stability and H2Yield；
(3) in glycerol, add appropriate methanol can reduce sweet oil viscosity, reduce the generation of carbon deposit in course of reaction,
Extend the life-span of catalyst, not only increase activity and the stability of catalyst, and improve hydrogen yield and convert with carbon
Rate；
(4) glycerol, hydrogen production from methanol-steam reforming process are not the simple superposition of both respective gasifications, but first
The coordinative role that intercouples produced between alcohol and glycerol.Methanol first decomposition caused heat release, the pyrolysis for glycerol provides certain
Heat, plays facilitation for sweet oil gasification, thus causes both reformation hydrogen production speed and the raising of the degree of depth；
(5) current, domestic and international researcher is mostly just for single methanol or glycerol liquor vapour reforming hydrogen producing system
Studying, and the preparing hydrogen by mixing reaction system research for methanol-glycerol is less, the present invention prepares from cleaning hydrogen energy source
Send out, in conjunction with the practical problem that the present age, biological diesel oil byproduct utilized, propose methanol-glycerol and work in coordination with the new think of of vapor reforming hydrogen production
Road, it is achieved glycerol and methanol common activation on a catalyst so that it is work in coordination with and efficiently prepare with steam generation reforming reaction
Hydrogen, not only reduces the cost of material of hydrogen manufacturing, and is expected to solve biological diesel oil byproduct later use problem, it is achieved that money
Recycling of the sustainability of the source-energy-environmental integration, can obtain good economy, society and environmental benefit, and have
There are higher novelty and researching value.To Hydrogen Energy and the exploitation of biodiesel, the adjustment of energy resource structure, the protection of environment, with
And the development of industrial chain suffers from important realistic meaning.This project not only technical feasibility, the achievement of project is that alcohols is with biological
The utilization of coordinating of biodiesel by-product provides new thinking.
Detailed description of the invention:
The following is and the present invention is further illustrated rather than limitation of the present invention.
Except special instruction, equipment and reagent that the present invention uses are the art routine commercial products.
Vapor reforming hydrogen production method worked in coordination with by a kind of methanol-glycerol, comprises the following steps:
(1) preparation of attapulgite loaded Raney nickel: after attapulgite is size-reduced, acid activation, dried, dipping
In the nickel that total concentration is 1.0～1.5mol/L, calcium, cerium and the ferrum soluble salt solutions of soluble-salt, treat described nickel, calcium, cerium
It is adsorbed in described attapulgite's surface, drying with ferrum active component, it is thus achieved that catalyst precursor, cools down roasting, i.e. prepare recessed
Convex rod soil supported nickel catalyst；
(2) vapor reforming hydrogen production worked in coordination with by methanol-glycerol: use the atmospheric fixed bed reactor of continuous flowing type, by temperature
Control instrument control reactor temperature, the attapulgite loaded nickel catalysis of 0.5～1g prepared at catalyst bed filling step (1)
Agent, quartz sand is added in the upper and lower of described attapulgite loaded Raney nickel, first by N2It is passed through in reactor, is warming up to
After 500 DEG C, logical hydrogen carries out activation of catalyst 1h, closes hydrogen；It is cooled to reaction temperature 450-650 DEG C under nitrogen protection,
Close nitrogen, mol ratio be (1～6): the methanol of 1 mixes with G & W, enter the preheater gasification that temperature is 250 DEG C,
Gas after gasification enters into the crystal reaction tube equipped with described attapulgite loaded Raney nickel and carries out catalytic reforming reaction,
Reacted product is cooled realizes gas-liquid separation, prepares hydrogen-rich synthetic gas.
In step (1), the preparation of attapulgite supported nickel catalyst comprises the steps:
A () attapulgite activates: attapulgite, through extruding, shearing and pulverize, obtains the attapulgite powder that granularity is 200 mesh
Body, described attapulgite powder body mass concentration is that the dilute hydrochloric acid of 5-10% soaks 8-12h, makes described attapulgite powder body obtain
Activation, is then washed with deionized and is precipitated to neutrality, and activated attapulgite PG represents；
B () infusion process prepares attapulgite loaded Raney nickel: weigh respectively nickel, calcium, cerium and ferrum soluble salt solutions in
In 150ml beaker, adding deionized water, the total concentration making described soluble-salt is 1.0～1.5mol/L, and mixed liquor is added step
Suddenly in the attapulgite powder body after the described activation that (a) obtains, stirring, impregnate 12～16 hours, remove the supernatant, remaining outstanding
Supernatant liquid is through decompression sucking filtration, and gained filtration cakes torrefaction pulverized 40～80 sieves after being cooled to room temperature, and the granule roasting after pulverizing i.e. is made
Obtain Ca-Ce-Fe-Ni/PG attapulgite loaded Raney nickel.
The preparation method of nickel, calcium, cerium and ferrum soluble salt solutions is: nickel oxide, calcium oxide, cerium oxide and ferrum oxide are divided
It is not dissolved in salpeter solution, prepares nickel nitrate, calcium nitrate, cerous nitrate and iron nitrate solution.
Embodiment 1
(1) preparation of attapulgite loaded Raney nickel
Attapulgite, through extruding, shear, pulverizing, obtains the attapulgite powder body that granularity is 200 mesh, and attapulgite powder body is used
Mass concentration is the dilute hydrochloric acid immersion 8h of 5%, makes attapulgite powder body obtain activating in fluffy similar colloidal sol form, then uses
Deionized water cyclic washing is precipitated to neutral standby, and the attapulgite PG of activation represents.
According to NiO:CaO:CeO2: Fe2O3: PG mass ratio is that 2:1:1:1:15 weighs Ni (NO3)2·6H2O、Fe(NO3)3·
9H2O、Ce(NO3)3·6H2O、Ca(NO3)2·4H2O, in 150ml beaker, adds deionized water dissolving, makes the total of soluble-salt
Concentration is 1.0mol/L, during then heated and stirred limit in limit adds PG powder body, stirs 20min, impregnates 12 hours under room temperature, removes upper strata
Clear liquid, remaining suspension is directly through decompression sucking filtration, and gained filter cake is put into baking oven and is dried 12 hours at 110 DEG C, is cooled to room temperature
After pulverized 40～80 sieve, by this granule in tube furnace in 600 DEG C of roastings 4 hours, i.e. prepare attapulgite loaded nickel catalysis
Agent 10%Ni-5%Fe-5%Ce-5%Ca/PG catalyst.
(2) vapor reforming hydrogen production worked in coordination with by methanol-glycerol
Using the atmospheric fixed bed reactor of continuous flowing type, heat with the electric heater being close to reactor outer wall, thermocouple leads to
Cross sleeve pipe and be placed in reactor bed lower end position, control reactor temperature by temperature controller, a size of
Catalyst bed floor height 60mm, adds quartz sand up and down, fills 0.5g attapulgite loaded Raney nickel in catalyst bed, first by N2
(flow is 50mL/min) is passed through 15min in reactor, removes the air in reactor, then temperature programming is to after 500 DEG C, logical hydrogen
Gas (flow is 100mL/min), carries out activation of catalyst 1h, to be restored complete after, close H2；At N2Protection borehole cooling is to reaction
Temperature 450 DEG C, after temperature stabilization, closes N2, controlled glycerol, methanol, water sample by peristaltic meatering pump respectively, wherein methanol with
Consumption mol ratio between glycerol is 1:1；Usage ratio between methanol and glycerol and water vapour is according to water vapour, raw material carbon containing
Molar ratio (S/C) be 5:1 sample introduction, enter preheater (design temperature 250 DEG C), gasify laggard people's crystal reaction tube, in matter
Amount air speed is 2.5h-1；Reaction temperature is catalytic reforming under the conditions of 450 DEG C, reaction generate hydrogen-rich synthetic gas, cooled after drying
Import a gas chromatogram and carry out on-line analysis.
The conversion ratio of material benzenemethanol and glycerol is 89.5%, and the selectivity of hydrogen is 93.05%, the selectivity of carbon monoxide
Being 2.7%, the selectivity of carbon dioxide is 97.3%.
Comparative example 1
Hydrogen production from methanol-steam reforming
Using the atmospheric fixed bed reactor of continuous flowing type, heat with the electric heater being close to reactor outer wall, thermocouple leads to
Cross sleeve pipe and be placed in reactor bed lower end position, control reactor temperature by temperature controller, a size of
Catalyst bed floor height 60mm, adds quartz sand up and down, fills the attapulgite loaded nickel of 0.5g embodiment 1 preparation in catalyst bed
Catalyst, first by N2(flow is 50mL/min) is passed through in reactor, removes the air in reactor, then temperature programming is to 500
After DEG C, logical hydrogen (flow is 100mL/min), carry out activation of catalyst 1h, to be restored complete after, close H2；At N2Protection declines
Temperature is to reaction temperature 450 DEG C, after temperature stabilization, closes N2, controlled methanol, water sample, Qi Zhongjia by peristaltic meatering pump respectively
Usage ratio between alcohol and water vapour is 5:1 sample introduction according to the molar ratio (S/C) of water vapour, raw material carbon containing, enters preheating
Device (design temperature 250 DEG C), gasify laggard people's crystal reaction tube, is 2.5h at mass space velocity-1；Reaction temperature is 450 DEG C of conditions
Lower catalytic reforming, the hydrogen-rich synthetic gas that reaction generates, cooled one gas chromatogram of dried importing carries out on-line analysis.
The conversion ratio of methanol is 85.1%, and the selectivity of hydrogen is 92.05%, and the selectivity of carbon monoxide is 3.1%, two
The selectivity of carbonoxide is 96.9%.
Comparative example 2
Glycerol liquor vapour reforming hydrogen producing
Using the atmospheric fixed bed reactor of continuous flowing type, heat with the electric heater being close to reactor outer wall, thermocouple leads to
Cross sleeve pipe and be placed in reactor bed lower end position, control reactor temperature by temperature controller, a size of
Catalyst bed floor height 60mm, adds quartz sand up and down, fills the attapulgite loaded nickel of 0.5g embodiment 1 preparation in catalyst bed
Catalyst, first by N2(flow is 50mL/min) is passed through in reactor, removes the air in reactor, then temperature programming is to 500
After DEG C, logical hydrogen (flow is 100mL/min), carry out activation of catalyst 1h, to be restored complete after, close H2；At N2Protection declines
Temperature is to reaction temperature 450 DEG C, after temperature stabilization, closes N2, controlled glycerol, water sample by peristaltic meatering pump respectively, the sweetest
Usage ratio between oil and water vapour is 5:1 sample introduction according to the molar ratio (S/C) of water vapour, raw material carbon containing, enters preheating
Device (design temperature 250 DEG C), gasify laggard people's crystal reaction tube, is 2.5h at mass space velocity-1；Reaction temperature is 450 DEG C of conditions
Lower catalytic reforming, the hydrogen-rich synthetic gas that reaction generates, cooled one gas chromatogram of dried importing carries out on-line analysis.
The conversion ratio of glycerol is 80.1%, and the selectivity of hydrogen is 90.05%, and the selectivity of carbon monoxide is 4.6%, two
The selectivity of carbonoxide is 95.4%.
Compared by embodiment 1, comparative example 1 and comparative example 2 and draw, there is coupling between methanol and glycerol, there is phase
The positive role promoted mutually, their mixing reforming hydrogen preparation can improve feed stock conversion, improves hydrogen selective.
Embodiment 2
(1) preparation of attapulgite loaded Raney nickel
Attapulgite, through extruding, shear, pulverizing, obtains the attapulgite powder body that granularity is 200 mesh, and attapulgite powder body is used
Mass concentration is the dilute hydrochloric acid immersion 12h of 10%, makes attapulgite powder body obtain activating in fluffy similar colloidal sol form, then
Be precipitated to neutral standby with deionized water cyclic washing, the attapulgite PG of activation represents.
It is that 3:2:2:2:11 weighs Ni (NO according to NiO:CaO:CeO2:Fe2O3:PG mass ratio3)2·6H2O、Fe
(NO3)3·9H2O、Ce(NO3)3·6H2O、Ca(NO3)2·4H2O, in 150ml beaker, adds deionized water dissolving, makes solvable
Property salt total concentration be 1.25mol/L, during then heated and stirred limit in limit adds PG powder body, stir 50min, impregnate 16 little under room temperature
Time, removing the supernatant, remaining suspension is directly through decompression sucking filtration, and gained filter cake is put into baking oven and is dried 12 hours at 110 DEG C,
40～80 sieves were pulverized after being cooled to room temperature.By this granule in tube furnace in 600 DEG C of roastings 4 hours, i.e. prepare attapulgite
Supported nickel catalyst 15%Ni-10%Fe-10%Ce-10%Ca/PG catalyst.
(2) vapor reforming hydrogen production worked in coordination with by methanol-glycerol
Using the atmospheric fixed bed reactor of continuous flowing type, heat with the electric heater being close to reactor outer wall, thermocouple leads to
Cross sleeve pipe and be placed in reactor bed lower end position, control reactor temperature by temperature controller, a size of
Catalyst bed floor height 60mm, adds quartz sand up and down, fills 1g attapulgite loaded Raney nickel in catalyst bed, first by N2
(flow is 50mL/min) is passed through 15min in reactor, removes the air in reactor, then temperature programming is to after 500 DEG C, logical hydrogen
Gas (flow is 100mL/min), carries out activation of catalyst 1h, to be restored complete after, close H2；At N2Protection borehole cooling is to reaction
Temperature 650 DEG C, after temperature stabilization, closes N2, controlled glycerol, methanol, water sample by peristaltic meatering pump respectively, wherein methanol with
Consumption mol ratio between glycerol is 6:1；Usage ratio between methanol and glycerol and water vapour is according to water vapour, raw material carbon containing
Molar ratio (S/C) be 8:1 sample introduction, enter preheater (design temperature 250 DEG C), gasify laggard people's crystal reaction tube, in matter
Amount air speed is 5h-1；Reaction temperature is catalytic reforming under the conditions of 650 DEG C, the hydrogen-rich synthetic gas that reaction generates, and cooled leads after drying
Enter a gas chromatogram and carry out on-line analysis.
The conversion ratio of material benzenemethanol and glycerol is 95.35%, and the selectivity of hydrogen is 98.27%, the selection of carbon monoxide
Property is 4.2%, and the selectivity of carbon dioxide is 95.8%.
Comparative example 3
Hydrogen production from methanol-steam reforming
Using the atmospheric fixed bed reactor of continuous flowing type, heat with the electric heater being close to reactor outer wall, thermocouple leads to
Cross sleeve pipe and be placed in reactor bed lower end position, control reactor temperature by temperature controller, a size of
Catalyst bed floor height 60mm, adds quartz sand up and down, and the attapulgite loaded nickel filling 1g embodiment 2 preparation in catalyst bed is urged
Agent, first by N2(flow is 50mL/min) is passed through in reactor, removes the air in reactor, then temperature programming is to 500 DEG C
After, logical hydrogen (flow is 100mL/min), carry out activation of catalyst 1h, to be restored complete after, close H2；At N2Protection borehole cooling
To reaction temperature 650 DEG C, after temperature stabilization, close N2, controlled methanol, water sample, wherein methanol by peristaltic meatering pump respectively
And the usage ratio between water vapour is 8:1 sample introduction according to the molar ratio (S/C) of water vapour, raw material carbon containing, enter preheater
(design temperature 250 DEG C), gasify laggard people's crystal reaction tube, is 5h at mass space velocity-1；Reaction temperature is urged under the conditions of being 650 DEG C
Changing and reform, the hydrogen-rich synthetic gas that reaction generates, cooled one gas chromatogram of dried importing carries out on-line analysis.
The conversion ratio of methanol is 92.7%, and the selectivity of hydrogen is 95.33%, and the selectivity of carbon monoxide is 5.6%, two
The selectivity of carbonoxide is 94.4%.
Comparative example 4
Glycerol liquor vapour reforming hydrogen producing
Using the atmospheric fixed bed reactor of continuous flowing type, heat with the electric heater being close to reactor outer wall, thermocouple leads to
Cross sleeve pipe and be placed in reactor bed lower end position, control reactor temperature by temperature controller, a size of
Catalyst bed floor height 60mm, adds quartz sand up and down, and the attapulgite loaded nickel filling 1g embodiment 2 preparation in catalyst bed is urged
Agent, first by N2(flow is 50mL/min) is passed through in reactor, removes the air in reactor, then temperature programming is to 500 DEG C
After, logical hydrogen (flow is 100mL/min), carry out activation of catalyst 1h, to be restored complete after, close H2；At N2Protection borehole cooling
To reaction temperature 650 DEG C, after temperature stabilization, close N2, controlled glycerol, water sample, wherein glycerol by peristaltic meatering pump respectively
And the usage ratio between water vapour is 8:1 sample introduction according to the molar ratio (S/C) of water vapour, raw material carbon containing, enter preheater
(design temperature 250 DEG C), gasify laggard people's crystal reaction tube, is 5h at mass space velocity-1；Reaction temperature is urged under the conditions of being 650 DEG C
Changing and reform, the hydrogen-rich synthetic gas that reaction generates, cooled one gas chromatogram of dried importing carries out on-line analysis.
The conversion ratio of glycerol is 90.7%, and the selectivity of hydrogen is 93.67%, and the selectivity of carbon monoxide is 4.1%, two
The selectivity of carbonoxide is 95.9%.
Compared by embodiment 2, comparative example 3 and comparative example 4 and draw, there is coupling between methanol and glycerol, there is phase
The positive role promoted mutually, their mixing reforming hydrogen preparation can improve feed stock conversion, improves hydrogen selective.
Embodiment 3
(1) preparation of attapulgite loaded Raney nickel
Attapulgite, through extruding, shear, pulverizing, obtains the attapulgite powder body that granularity is 200 mesh, and attapulgite powder body is used
Mass concentration is the dilute hydrochloric acid immersion 10h of 10%, makes attapulgite powder body obtain activating in fluffy similar colloidal sol form, then
Be precipitated to neutral standby with deionized water cyclic washing, the attapulgite PG of activation represents.
According to NiO:CaO:CeO2:Fe2O3: PG mass ratio is that 3:1:1:1:14 weighs Ni (NO3)2·6H2O、Fe(NO3)3·
9H2O、Ce(NO3)3·6H2O、Ca(NO3)2·4H2O, in 150ml beaker, adds deionized water dissolving, makes the total of soluble-salt
Concentration is 1.5mol/L, during then heated and stirred limit in limit adds PG powder body, stirs 30min, impregnates 14 hours under room temperature, removes upper strata
Clear liquid, remaining suspension is directly through decompression sucking filtration, and gained filter cake is put into baking oven and is dried 12 hours at 110 DEG C, is cooled to room temperature
After pulverized 40～80 sieve.By this granule in tube furnace in 600 DEG C of roastings 4 hours, i.e. prepare attapulgite loaded nickel catalysis
Agent 15%Ni-5%Fe-5%Ce-5%Ca/PG catalyst.
(2) vapor reforming hydrogen production worked in coordination with by methanol-glycerol
Using the atmospheric fixed bed reactor of continuous flowing type, heat with the electric heater being close to reactor outer wall, thermocouple leads to
Cross sleeve pipe and be placed in reactor bed lower end position, control reactor temperature by temperature controller, a size of
Catalyst bed floor height 60mm, adds quartz sand up and down, fills 1g attapulgite loaded Raney nickel in catalyst bed, first by N2
(flow is 50mL/min) is passed through 15min in reactor, removes the air in reactor, then temperature programming is to after 500 DEG C, logical hydrogen
Gas (flow is 100mL/min), carries out activation of catalyst 1h, to be restored complete after, close H2；At N2Protection borehole cooling is to reaction
Temperature 550 DEG C, after temperature stabilization, closes N2, controlled glycerol, methanol, water sample by peristaltic meatering pump respectively, wherein methanol with
Consumption mol ratio between glycerol is 3:1；Usage ratio between methanol and glycerol and water vapour is according to water vapour, raw material carbon containing
Molar ratio (S/C) be 7:1 sample introduction, enter preheater (design temperature 250 DEG C), gasify laggard people's crystal reaction tube, in matter
Amount air speed is 3h-1；Reaction temperature is catalytic reforming under the conditions of 550 DEG C, the hydrogen-rich synthetic gas that reaction generates, and cooled leads after drying
Enter a gas chromatogram and carry out on-line analysis.
The conversion ratio of material benzenemethanol and glycerol is 98.64%, and the selectivity of hydrogen is 98.56%, the selection of carbon monoxide
Property is 5.1%, and the selectivity of carbon dioxide is 94.9%.
Comparative example 5
Hydrogen production from methanol-steam reforming
Using the atmospheric fixed bed reactor of continuous flowing type, heat with the electric heater being close to reactor outer wall, thermocouple leads to
Cross sleeve pipe and be placed in reactor bed lower end position, control reactor temperature by temperature controller, a size of
Catalyst bed floor height 60mm, adds quartz sand up and down, and the attapulgite loaded nickel filling 1g embodiment 3 preparation in catalyst bed is urged
Agent, first by N2(flow is 50mL/min) is passed through in reactor, removes the air in reactor, then temperature programming is to 500 DEG C
After, logical hydrogen (flow is 100mL/min), carry out activation of catalyst 1h, to be restored complete after, close H2；At N2Protection borehole cooling
To reaction temperature 550 DEG C, after temperature stabilization, close N2, controlled methanol, water sample, wherein methanol by peristaltic meatering pump respectively
And the usage ratio between water vapour is 7:1 sample introduction according to the molar ratio (S/C) of water vapour, raw material carbon containing, enter preheater
(design temperature 250 DEG C), gasify laggard people's crystal reaction tube, is 3h at mass space velocity-1；Reaction temperature is urged under the conditions of being 550 DEG C
Changing and reform, the hydrogen-rich synthetic gas that reaction generates, cooled one gas chromatogram of dried importing carries out on-line analysis.
The conversion ratio of methanol is 94.85%, and the selectivity of hydrogen is 96.17%, and the selectivity of carbon monoxide is 3.4%,
The selectivity of carbon dioxide is 96.6%.
Comparative example 6
Glycerol liquor vapour reforming hydrogen producing
Using the atmospheric fixed bed reactor of continuous flowing type, heat with the electric heater being close to reactor outer wall, thermocouple leads to
Cross sleeve pipe and be placed in reactor bed lower end position, control reactor temperature by temperature controller, a size of
Catalyst bed floor height 60mm, adds quartz sand up and down, and the attapulgite loaded nickel filling 1g embodiment 3 preparation in catalyst bed is urged
Agent, first by N2(flow is 50mL/min) is passed through in reactor, removes the air in reactor, then temperature programming is to 500 DEG C
After, logical hydrogen (flow is 100mL/min), carry out activation of catalyst 1h, to be restored complete after, close H2；At N2Protection borehole cooling
To reaction temperature 550 DEG C, after temperature stabilization, close N2, controlled glycerol, water sample, wherein glycerol by peristaltic meatering pump respectively
And the usage ratio between water vapour is 7:1 sample introduction according to the molar ratio (S/C) of water vapour, raw material carbon containing, enter preheater
(design temperature 250 DEG C), gasify laggard people's crystal reaction tube, is 3h at mass space velocity-1；Reaction temperature is urged under the conditions of being 550 DEG C
Changing and reform, the hydrogen-rich synthetic gas that reaction generates, cooled one gas chromatogram of dried importing carries out on-line analysis.
The conversion ratio of glycerol is 93.3%, and the selectivity of hydrogen is 91.16%, and the selectivity of carbon monoxide is 2.96%,
The selectivity of carbon dioxide is 97.04%.
Compared by embodiment 3, comparative example 5 and comparative example 6 and draw, there is coupling between methanol and glycerol, there is phase
The positive role promoted mutually, their mixing reforming hydrogen preparation can improve feed stock conversion, improves hydrogen selective.
At present, domestic and international researcher is carried out just for single methanol or glycerol liquor vapour reforming hydrogen producing system mostly
Research, and the preparing hydrogen by mixing reaction system research for methanol-glycerol is less, the present invention from the preparation cleaning hydrogen energy source,
In conjunction with the practical problem that the present age, biological diesel oil byproduct utilized, propose methanol-glycerol and work in coordination with the new approaches of vapor reforming hydrogen production,
Realize glycerol and methanol common activation on a catalyst so that it is collaborative and steam generation reforming reaction efficiently prepares hydrogen
Gas, not only reduces the cost of material of hydrogen manufacturing, and is expected to solve biological diesel oil byproduct later use problem, it is achieved that money
Recycling of the sustainability of the source-energy-environmental integration, can obtain good economy, society and environmental benefit, and have
There are higher novelty and researching value.To Hydrogen Energy and the exploitation of biodiesel, the adjustment of energy resource structure, the protection of environment, with
And the development of industrial chain suffers from important realistic meaning.This project not only technical feasibility, the achievement of project is that alcohols is with biological
The utilization of coordinating of biodiesel by-product provides new thinking.
Above-listed detailed description is illustrating for possible embodiments of the present invention, and this embodiment also is not used to limit this
Bright the scope of the claims, all equivalences done without departing from the present invention are implemented or change, are intended to be limited solely by the scope of patent protection of this case
In.
Claims (8)
1. vapor reforming hydrogen production method worked in coordination with by methanol-glycerol, it is characterised in that comprise the following steps:
(1) preparation of attapulgite loaded Raney nickel: being activated by attapulgite, the total concentration that impregnated in soluble-salt is 1.0
～in the nickel of 1.5mol/L, calcium, cerium and ferrum soluble salt solutions, treat that described nickel, calcium, cerium and ferrum active component are adsorbed in described work
Attapulgite's surface after change, drying, it is thus achieved that catalyst precursor, cool down roasting, i.e. prepare the catalysis of attapulgite loaded nickel
Agent；
(2) vapor reforming hydrogen production worked in coordination with by methanol-glycerol: attapulgite loaded Raney nickel prepared by step (1) is placed in perseverance
Temperature environment, logical Hydrogen activation at 500 DEG C, cooling, is (1～6) by mol ratio: the methanol of 1 mixes with the mixture of glycerol and water
Closing, gasified by the preheated device of mixture of methanol, G & W, the gas after gasification is entered into dress by the pipeline of heating and thermal insulation
Having in the reactor of described attapulgite loaded Raney nickel and carry out catalytic reforming reaction, reacted product is cooled realizes gas
Liquid separates, and prepares hydrogen-rich synthetic gas.
The most according to claim 1, vapor reforming hydrogen production method worked in coordination with by methanol-glycerol, it is characterised in that institute in step (1)
The preparation stating attapulgite loaded Raney nickel comprises the steps:
A () attapulgite activates: attapulgite, through extruding, shearing and pulverize, obtains the attapulgite powder body that granularity is 200 mesh,
Described attapulgite powder body mass concentration is that the dilute hydrochloric acid of 5-10% soaks 8-12h, makes described attapulgite powder body be lived
Changing, be then washed with deionized and be precipitated to neutrality, activated attapulgite PG represents；
B () infusion process prepares attapulgite loaded Raney nickel: weigh nickel, calcium, cerium and ferrum soluble salt solutions respectively in beaker
In, adding deionized water, the total concentration making described soluble-salt is 1.0～1.5mol/L, mixed liquor is added step (a) and obtains
Described activation after attapulgite powder body in, stirring, impregnate 12～16 hours, remove the supernatant, remainder suspension through subtracting
Pressing sucking filtration, gained filtration cakes torrefaction pulverized 40～80 sieves after being cooled to room temperature, and the granule roasting after pulverizing i.e. prepares Ca-Ce-
Fe-Ni/PG attapulgite loaded Raney nickel.
Vapor reforming hydrogen production method worked in coordination with by methanol-glycerol the most according to claim 1 or claim 2, it is characterised in that with quality hundred
Mark meter, nickel oxide is 10～15wt%, and calcium oxide is 5～10wt%, and cerium oxide is 5～10wt%, ferrum oxide be 5～
10wt%.
The most according to claim 1, vapor reforming hydrogen production method worked in coordination with by methanol-glycerol, it is characterised in that institute in step (2)
State methanol-glycerol and work in coordination with the method for vapor reforming hydrogen production and be: use the atmospheric fixed bed reactor of continuous flowing type, pass through temperature control
Instrument control reactor temperature, at the attapulgite of 0.5～1g prepared by catalyst bed described claim 1 step (1) of filling
Soil supported nickel catalyst, the upper and lower of described attapulgite loaded Raney nickel is added quartz sand, is first passed through instead by nitrogen
Answering in device, after being warming up to 500 DEG C, logical hydrogen carries out activation of catalyst 1h, closes hydrogen；It is cooled to reaction temperature under nitrogen protection
Spend 450-650 DEG C, close nitrogen, mol ratio is (1～6): the methanol of 1 mixes with the mixture of glycerol and water, enter temperature
Being the preheater gasification of 250 DEG C, it is anti-that the gas after gasification enters into the quartz equipped with described attapulgite loaded Raney nickel
Should carry out catalytic reforming reaction by pipe, reacted product is cooled realizes gas-liquid separation, prepares hydrogen-rich synthetic gas.
5. work in coordination with vapor reforming hydrogen production method according to methanol-glycerol described in claim 1 or 4, it is characterised in that step (2)
Described in amount ratio between methanol and the mixture of glycerol and water according to the carbon contained in water and the mixture of methanol and glycerol
Mol ratio be (5～8): 1.
Vapor reforming hydrogen production method worked in coordination with by methanol-glycerol the most according to claim 1 or claim 2, it is characterised in that step (2)
Described in the mass space velocity of methanol and glycerol and water charging be 2.5～5.0h-1。
7. work in coordination with a catalyst for vapor reforming hydrogen production method for methanol-glycerol described in claim 1, its feature exists
In, including catalyst active component and catalyst carrier, described catalyst active component includes nickel, calcium, cerium and ferrum, described catalysis
Agent carrier is attapulgite.
The most according to claim 7, work in coordination with the catalyst of vapor reforming hydrogen production method for methanol-glycerol, its feature exists
In, the content range of described catalyst active component is to be calculated in mass percent: nickel oxide is 10～15wt%, and calcium oxide is 5
～10wt%, cerium oxide is 5～10wt%, and ferrum oxide is 5～10wt%, and the mass fraction of attapulgite is 55%～75%.
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