CN105947979B - A kind of methanol glycerol collaboration vapor reforming hydrogen production method and the catalyst for the hydrogen production process - Google Patents
A kind of methanol glycerol collaboration vapor reforming hydrogen production method and the catalyst for the hydrogen production process Download PDFInfo
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Abstract
Vapor reforming hydrogen production method is cooperateed with the invention discloses a kind of methanol glycerol, is comprised the following steps：(1) after attapulgite is handled, it is impregnated in nickel, calcium, cerium and iron soluble salt solutions, treats that active component is adsorbed in the attapulgite's surface, through drying, obtains catalyst precursor, cooling roasting is made attapulgite loaded Raney nickel；(2) catalyst is placed at isoperibol, 500 DEG C and leads to H2Activation, mol ratio is (1~6) by cooling:1 methanol is mixed with the mixture of glycerine and water, the preheated device of the mixture of methanol, G ＆ W is gasified, the gas after gasification enters and catalytic reforming reaction is carried out in reactor, product realizes gas-liquid separation through cooling, hydrogen-rich synthetic gas is made.Glycerine, hydrogen production from methanol-steam reforming process are not the simple superposition of both respective gasifications, but the coordinative role that intercouples produced between methanol and glycerine, promote the raising of both reformation hydrogen production speed and depth.
Description
Technical field
The present invention relates to belong to hydrogen preparation field, and in particular to a kind of methanol-glycerine collaboration vapor reforming hydrogen production method and
Catalyst for the hydrogen production process.
Background technology
With the aggravation of energy crisis, the new energy for seeking alternative fossil fuel has become a study hotspot.Energy
Source problem has significant impact to national economy and national development, therefore China will also tap a new source of energy as a strategy.
In numerous new energy, Hydrogen Energy turns into one of 21 century optimal energy.Because, it is identical heavy burning
In the case of coal, gasoline and the hydrogen of amount, at most, and the product that it burns is water to the energy that hydrogen is produced, without lime-ash and
Waste gas, does not pollute the environment；At present, the production of hydrogen mainly has two kinds：One, most hydrogen are from oil, coal and day
Produced in right gas, this method needs to consume natively very fossil fuel in short supply；Secondly, produced with the method for electrolysis water, this
The method of kind consumption electric energy is big, does not calculate very much.Therefore under energy scarcity, the dual-pressure of environmental pollution, development utilization organic waste
The recycling of thing, realization cleans processing and had important practical significance with the new technology that highly effective hydrogen yield is combined.
Biodiesel as a kind of regenerative resource, just by various countries attention and developed energetically.It is industrial at present
Production of Biodiesel Via Transesterification Method mainly is used, during biodiesel is prepared, about 1 can be produced by often producing 10 tons of biodiesel
The glycerin by-products of ton, in addition, the progress to promote ester exchange reaction, is usually added into excessive methanol to improve biodiesel
The glycerine of yield, these excessive methanol and reaction generation just constitutes the Main By product in preparation of biodiesel.Closely
With the increase of yield of biodiesel over year, a large amount of glycerine and the subsequent treatment of by-product methanol produced in its generating process are asked
How topic just following, greatly developing and increasing rapidly with Global biodiesel, effectively dispose the pair in production process
Product, reaches the double optimization of resource and environment, has been current biological diesel oil industry development urgent problem to be solved.At this stage,
Crude glycerine is mainly sold by refined purification for exquisite glycerine, and not only cost is high, and market does not digest yet, it is therefore necessary to
New outlet is selected for biological diesel oil byproduct.
The content of the invention
It is an object of the invention to provide a kind of methanol-glycerine collaboration vapor reforming hydrogen production method, hydrogen manufacturing is not only reduced
Cost of material, and be expected to solution and offered reference for certainly biological diesel oil byproduct later use problem, to Hydrogen Energy and biodiesel
Exploitation, the adjustment of energy resource structure, the protection of environment and the development of industrial chain suffer from important realistic meaning.
The present invention is achieved by the following technical programs：
A kind of methanol-glycerine collaboration vapor reforming hydrogen production method, comprises the following steps：
(1) preparation of attapulgite loaded Raney nickel：Attapulgite is activated, the total concentration for being impregnated in soluble-salt is
In 1.0~1.5mol/L nickel, calcium, cerium and iron soluble salt solutions, treat that the nickel, calcium, cerium and iron active component are adsorbed in institute
The attapulgite's surface after activation is stated, through drying, catalyst precursor is obtained, cooling roasting is made attapulgite loaded nickel
Catalyst；
(2) methanol-glycerine collaboration vapor reforming hydrogen production：Attapulgite loaded Raney nickel prepared by step (1) is put
In isoperibol, Hydrogen activation is led at 500 DEG C, mol ratio is (1~6) by cooling:1 methanol and the mixture of glycerine and
Water is mixed, and the preheated device of the mixture of methanol, G ＆ W is gasified, and the gas after gasification is entered by the pipeline of heating and thermal insulation
Catalytic reforming reaction is carried out into the reactor equipped with the attapulgite loaded Raney nickel, reacted product is real through cooling
Existing gas-liquid separation, is made hydrogen-rich synthetic gas.
Glycerine, hydrogen production from methanol-steam reforming process are not the simple superposition of both respective gasifications, but methanol
The coordinative role that intercouples produced between glycerine.Methanol decomposition caused heat release first, certain heat is provided for the pyrolysis of glycerine
Amount, is that facilitation is played in the gasification of glycerine, so as to cause the raising of both reformation hydrogen production speed and depth.
Attapulgite has the properties such as intergranular nano-pore structure and high-specific surface area and high porosity, more noble metal and gold
Category ionic catalyst may be homogenously dispersed in the surface and internal gutter of attapulgite, be conducive to improving catalyst at low temperature
Activity and elimination effect of intraparticle diffusion, while the shape selective catalysis also by generation concerted acid-base catalysis and with molecular sieve is cracked and made
With.
Preferably, the preparation of attapulgite loaded Raney nickel comprises the following steps described in step (1)：
(a) attapulgite is activated：Attapulgite is through extruding, shearing and crushes, and obtains the attapulgite powder that granularity is 200 mesh
Body, the watery hydrochloric acid immersion 8-12h that the attapulgite powder is 5-10% with mass concentration, obtains the attapulgite powder
Activation, is then washed with deionized and is precipitated to neutrality, activated attapulgite is represented with PG；
(b) infusion process prepares attapulgite loaded Raney nickel：Weigh respectively nickel, calcium, cerium and iron soluble salt solutions in
In beaker, deionized water is added, the total concentration for making the soluble-salt is 1.0~1.5mol/L, and mixed liquor is added into step (a)
In attapulgite powder after the obtained activation, stirring impregnates 12~16 hours, removes supernatant liquor, remaining suspension
Through depressurizing suction filtration, gained filtration cakes torrefaction, which is cooled to after room temperature, crushed 40~80 sieves, and the particle after crushing is calcined, that is, is made
Ca-Ce-Fe-Ni/PG attapulgite loaded Raney nickels.
The nickel, calcium, the preparation method of cerium and iron soluble salt solutions are：By nickel oxide, calcium oxide, cerium oxide and oxidation
Iron is dissolved in salpeter solution respectively, and nickel nitrate, calcium nitrate, cerous nitrate and iron nitrate solution is made.
Preferably, it is calculated in mass percent, nickel oxide is 10~15wt%, calcium oxide is 5~10wt%, and cerium oxide is 5
~10wt%, iron oxide is 5~10wt%.
Preferably, the method for methanol described in step (2)-glycerine collaboration vapor reforming hydrogen production is：Using continuous flowing
The atmospheric fixed bed reactor of formula, reactor temperature is controlled by temperature controller, and claim 1 step is filled in catalyst bed
(1) the attapulgite loaded Raney nickel of 0.5~1g prepared by, the upper and lower part of the attapulgite loaded Raney nickel
Quartz sand is added, first nitrogen is passed through in reactor, is warming up to after 500 DEG C, leads to hydrogen and carries out activation of catalyst 1h, close hydrogen
Gas；450-650 DEG C of reaction temperature is cooled under nitrogen protection, nitrogen is closed, and is (1~6) by mol ratio:1 methanol with it is sweet
Mixture and the water mixing of oil, gasify, the gas after gasification is entered equipped with described recessed into temperature for 250 DEG C of preheater
The crystal reaction tube of the native supported nickel catalyst of convex rod carries out catalytic reforming reaction, and reacted product realizes gas-liquid point through cooling
From obtained hydrogen-rich synthetic gas.
Preferably, the amount ratio described in step (2) between methanol and the mixture and water of glycerine according to water and methanol and
The mol ratio of the carbon contained in the mixture of glycerine is (5~8):1.
Preferably, the mass space velocity that methanol described in step (2) and glycerine are fed with water is 2.5~5.0h-1。
It is a further object to provide a kind of catalysis for methanol-glycerine collaboration vapor reforming hydrogen production method
Agent, the catalyst preparation process is simple, synergy well can be shown in catalytic reaction process, so as to improve catalysis
Activity, stability and the H of agent2Yield.
A kind of catalyst for cooperateing with vapor reforming hydrogen production method for methanol-glycerine, including catalyst active component and
Catalyst carrier, the catalyst active component includes nickel, calcium, cerium and iron, and the catalyst carrier is attapulgite.
Preferably, the content range of the catalyst active component is to be calculated in mass percent：Nickel oxide be 10~
15wt%, calcium oxide be 5~10wt%, cerium oxide be 5~10wt%, iron oxide be 5~10wt%, nickel oxide be 10~
15wt%, the calcium oxide is 5~10wt%, and the cerium oxide is 5~10wt%, and the iron oxide is 5~10wt%, concavo-convex
The mass fraction of rod soil is 55%~75%.
The beneficial effects of the invention are as follows：
(1) attapulgite has a properties such as intergranular nano-pore structure and high-specific surface area and high porosity, noble metal and
Many metal ion catalysts may be homogenously dispersed in the surface and internal gutter of attapulgite, be conducive to improving catalyst in low temperature
Under activity and eliminate effect of intraparticle diffusion, while will also produce concerted acid-base catalysis and shape selective catalysis with molecular sieve splits
Solution is acted on；
(2) iron nickel oxide forms the cube nickel crystalline substance easily reduced altogether in the easily raw interaction of attapulgite plane of crystal
The structure deposited, promotes active phase dispersion, enhances the activity that catalyst is broken C-C and C-H keys in big organic molecule；CeO2Mix
The miscellaneous glycerine second dehydration that be able to can suppress forms unstable hydro carbons, the anti-sintering of enhancing Ni, the performance of anti-carbon deposit；CaO doping can with it is anti-
Answer product CO2Generation is adsorbed or chemically reacted, so as to break thermodynamical equilibrium limitation, is conducive to steam reforming chemistry balance court
The direction movement that hydrogen is produced, the catalyst of preparation can show good synergy in catalytic reaction process, so as to carry
The high activity of catalyst, stability and H2Yield；
(3) appropriate methanol is added into glycerine can reduce the viscosity of glycerine, reduce the generation of carbon deposit in course of reaction,
The life-span of catalyst is extended, the activity and stability of catalyst is not only increased, and improves hydrogen yield and carbon conversion
Rate；
(4) glycerine, 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 glycerine.Methanol decomposition caused heat release first, is provided necessarily for the pyrolysis of glycerine
Heat, is that facilitation is played in the gasification of glycerine, so as to cause the raising of both reformation hydrogen production speed and depth；
(5) at present, domestic and international researcher is mostly just for single methanol or glycerine vapor reforming hydrogen production system
Studied, and the preparing hydrogen by mixing reaction system research for methanol-glycerine is less, the present invention is prepared from cleaning hydrogen energy source
Hair, the practical problem utilized with reference to contemporary biological diesel oil byproduct proposes that methanol-glycerine cooperates with the new think of of vapor reforming hydrogen production
Road, realizes the common activation of glycerine and methanol on a catalyst, makes its collaboration occur reforming reaction efficiently to prepare with vapor
Hydrogen, not only reduces the cost of material of hydrogen manufacturing, and is expected to solve the problems, such as biological diesel oil byproduct later use, realizes money
Recycling for the sustainability of the source-energy-environmental integration, can obtain good economy, society and environmental benefit, and tool
There are higher novelty and researching value.The adjustment of exploitation, energy resource structure to Hydrogen Energy and biodiesel, the protection of environment, with
And the development of industrial chain suffers from important realistic meaning.The project not only technical feasibility, the achievement of project for alcohols with it is biological
The coordination of biodiesel by-product is using there is provided new thinking.
Embodiment：
Further illustrated the following is to the present invention, rather than limitation of the present invention.
The equipment and reagent used except special instruction, the present invention is the conventional commercial products of the art.
A kind of methanol-glycerine collaboration vapor reforming hydrogen production method, comprises the following steps：
(1) preparation of attapulgite loaded Raney nickel：By attapulgite is size-reduced, acid activation, after drying process, dipping
In soluble-salt total concentration for 1.0~1.5mol/L nickel, calcium, cerium and iron soluble salt solutions in, treat the nickel, calcium, cerium
The attapulgite's surface is adsorbed in iron active component, through drying, catalyst precursor is obtained, cooling roasting is made recessed
The native supported nickel catalyst of convex rod；
(2) methanol-glycerine collaboration vapor reforming hydrogen production：Using the atmospheric fixed bed reactor of continuous flowing type, pass through temperature
Instrument control reactor temperature is controlled, the 0.5~1g prepared in catalyst bed filling step (1) attapulgite loaded nickel catalysis
Agent, the upper and lower part addition quartz sand of the attapulgite loaded Raney nickel, first by N2It is passed through in reactor, is warming up to
After 500 DEG C, lead to hydrogen and carry out activation of catalyst 1h, close hydrogen；450-650 DEG C of reaction temperature is cooled under nitrogen protection,
Nitrogen is closed, is (1~6) by mol ratio:1 methanol is mixed with G ＆ W, is gasified into temperature for 250 DEG C of preheater,
Gas after gasification enters the crystal reaction tube equipped with the attapulgite loaded Raney nickel and carries out catalytic reforming reaction,
Reacted product realizes gas-liquid separation through cooling, and hydrogen-rich synthetic gas is made.
The preparation of attapulgite supported nickel catalyst comprises the following steps in step (1)：
(a) attapulgite is activated：Attapulgite is through extruding, shearing and crushes, and obtains the attapulgite powder that granularity is 200 mesh
Body, the watery hydrochloric acid immersion 8-12h that the attapulgite powder is 5-10% with mass concentration, obtains the attapulgite powder
Activation, is then washed with deionized and is precipitated to neutrality, activated attapulgite is represented with PG；
(b) infusion process prepares attapulgite loaded Raney nickel：Weigh respectively nickel, calcium, cerium and iron soluble salt solutions in
In 150ml beakers, deionized water is added, the total concentration for making the soluble-salt is 1.0~1.5mol/L, and mixed liquor is added and walked
Suddenly in the attapulgite powder after the activation that (a) is obtained, stirring impregnates 12~16 hours, removes supernatant liquor, and remainder is outstanding
Supernatant liquid is through depressurizing suction filtration, and gained filtration cakes torrefaction, which is cooled to after room temperature, crushed 40~80 sieves, and the particle after crushing is calcined, that is, made
Obtain Ca-Ce-Fe-Ni/PG attapulgite loaded Raney nickels.
Nickel, calcium, the preparation method of cerium and iron soluble salt solutions are：By nickel oxide, calcium oxide, cerium oxide and iron oxide point
It is not dissolved in salpeter solution, nickel nitrate, calcium nitrate, cerous nitrate and iron nitrate solution is made.
Embodiment 1
(1) preparation of attapulgite loaded Raney nickel
Attapulgite obtains the attapulgite powder that granularity is 200 mesh through extruding, shearing, crushing, and attapulgite powder is used
Mass concentration is 5% watery hydrochloric acid immersion 8h, and it is in fluffy similar colloidal sol form, Ran Houyong attapulgite powder is obtained activation
Deionized water cyclic washing is precipitated to neutral standby, and the attapulgite of activation is represented with PG.
According to NiO：CaO：CeO2：Fe2O3：PG mass ratioes are 2:1:1:1:15 weigh Ni (NO3)2·6H2O、Fe(NO3)3·
9H2O、Ce(NO3)3·6H2O、Ca(NO3)2·4H2O adds deionized water dissolving, makes the total of soluble-salt in 150ml beakers
Concentration is 1.0mol/L, is then added in heating stirring in PG powders, stirs 20min, is impregnated 12 hours at room temperature, removes upper strata
Clear liquid, remaining suspension is directly through depressurizing suction filtration, and gained filter cake is put into baking oven in being dried 12 hours at 110 DEG C, is cooled to room temperature
After crushed 40~80 sieves, this particle is calcined 4 hours in tube furnace in 600 DEG C, that is, the catalysis of attapulgite loaded nickel is made
Agent 10%Ni-5%Fe-5%Ce-5%Ca/PG catalyst.
(2) methanol-glycerine collaboration vapor reforming hydrogen production
Using the atmospheric fixed bed reactor of continuous flowing type, heated with the electric heater for being close to reactor outer wall, thermocouple
Reactor bed lower end position is placed in by sleeve pipe, reactor temperature is controlled by temperature controller, size isCatalyst bed floor height 60mm, adds quartz sand up and down, and 0.5g attapulgite loadeds are filled in catalyst bed
Raney nickel, first by N2(flow is 50mL/min) is passed through 15min in reactor, removes the air in reactor, then program liter
Temperature leads to hydrogen (flow is 100mL/min) to after 500 DEG C, carries out activation of catalyst 1h, it is to be restored after the completion of, close H2；In N2
450 DEG C of reaction temperature is cooled under protection, after after temperature stabilization, N is closed2, respectively by peristaltic meatering pump control glycerine, methanol,
Consumption mol ratio between water sample, wherein methanol and glycerine is 1:1；Usage ratio between methanol and glycerine and water vapour is pressed
It is 5 according to the carbon containing molar ratio of water vapour, raw material (S/C):1 sample introduction, into preheater (250 DEG C of design temperature), gasifies laggard
People's crystal reaction tube, is 2.5h in mass space velocity-1；Reaction temperature is catalytic reforming under the conditions of 450 DEG C, and the hydrogen-rich of reaction generation is closed
Into gas, a gas-chromatography progress on-line analysis is imported after cool drying.
The conversion ratio of material benzenemethanol and glycerine is 89.5%, and the selectivity of hydrogen is 93.05%, the selectivity of carbon monoxide
For 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, heated with the electric heater for being close to reactor outer wall, thermocouple
Reactor bed lower end position is placed in by sleeve pipe, reactor temperature is controlled by temperature controller, size isCatalyst bed floor height 60mm, adds quartz sand up and down, fills prepared by 0.5g embodiments 1 in catalyst bed
Attapulgite loaded Raney nickel, first by N2(flow is 50mL/min) is passed through in reactor, removes the air in reactor, then
Temperature programming leads to hydrogen (flow is 100mL/min) to after 500 DEG C, carries out activation of catalyst 1h, it is to be restored after the completion of, close
H2；In N2450 DEG C of reaction temperature is cooled under protection, after after temperature stabilization, N is closed2, respectively by peristaltic meatering pump control methanol,
Usage ratio between water sample, wherein methanol and water vapour is 5 according to the carbon containing molar ratio of water vapour, raw material (S/C):1
Sample introduction, into preheater (250 DEG C of design temperature), gasify laggard people's crystal reaction tube, is 2.5h in mass space velocity-1；Reaction temperature
Spend for catalytic reforming under the conditions of 450 DEG C, the hydrogen-rich synthetic gas of reaction generation, one gas-chromatography progress of importing after cool drying
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
Glycerine vapor reforming hydrogen production
Using the atmospheric fixed bed reactor of continuous flowing type, heated with the electric heater for being close to reactor outer wall, thermocouple
Reactor bed lower end position is placed in by sleeve pipe, reactor temperature is controlled by temperature controller, size isCatalyst bed floor height 60mm, adds quartz sand up and down, fills prepared by 0.5g embodiments 1 in catalyst bed
Attapulgite loaded Raney nickel, first by N2(flow is 50mL/min) is passed through in reactor, removes the air in reactor, then
Temperature programming leads to hydrogen (flow is 100mL/min) to after 500 DEG C, carries out activation of catalyst 1h, it is to be restored after the completion of, close
H2；In N2450 DEG C of reaction temperature is cooled under protection, after after temperature stabilization, N is closed2, respectively by peristaltic meatering pump control glycerine,
Usage ratio between water sample, wherein glycerine and water vapour is 5 according to the carbon containing molar ratio of water vapour, raw material (S/C):1
Sample introduction, into preheater (250 DEG C of design temperature), gasify laggard people's crystal reaction tube, is 2.5h in mass space velocity-1；Reaction temperature
Spend for catalytic reforming under the conditions of 450 DEG C, the hydrogen-rich synthetic gas of reaction generation, one gas-chromatography progress of importing after cool drying
On-line analysis.
The conversion ratio of glycerine 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 glycerine, with phase
The positive role mutually promoted, their mixing reforming hydrogen preparation can improve feed stock conversion, improve hydrogen selective.
Embodiment 2
(1) preparation of attapulgite loaded Raney nickel
Attapulgite obtains the attapulgite powder that granularity is 200 mesh through extruding, shearing, crushing, and attapulgite powder is used
Mass concentration is 10% watery hydrochloric acid immersion 12h, and it is in fluffy similar colloidal sol form attapulgite powder is obtained activation, then
It is precipitated to deionized water cyclic washing neutral standby, the attapulgite of activation is represented with PG.
According to NiO:CaO:CeO2：Fe2O3：PG mass ratioes are 3:2:2:2:11 weigh Ni (NO3)2·6H2O、Fe
(NO3)3·9H2O、Ce(NO3)3·6H2O、Ca(NO3)2·4H2O adds deionized water dissolving, made solvable in 150ml beakers
Property salt total concentration be 1.25mol/L, then add in heating stirring in PG powders, stir 50min, impregnate 16 small at room temperature
When, supernatant liquor is removed, remaining suspension is directly through depressurizing suction filtration, and gained filter cake is put into baking oven in drying 12 hours at 110 DEG C,
It is cooled to after room temperature and crushed 40~80 sieves.This particle is calcined 4 hours in tube furnace in 600 DEG C, that is, attapulgite is made
Supported nickel catalyst 15%Ni-10%Fe-10%Ce-10%Ca/PG catalyst.
(2) methanol-glycerine collaboration vapor reforming hydrogen production
Using the atmospheric fixed bed reactor of continuous flowing type, heated with the electric heater for being close to reactor outer wall, thermocouple
Reactor bed lower end position is placed in by sleeve pipe, reactor temperature is controlled by temperature controller, size isCatalyst bed floor height 60mm, adds quartz sand up and down, and 1g attapulgite loaded nickel is filled in catalyst bed
Catalyst, first by N2(flow is 50mL/min) is passed through 15min in reactor, removes the air in reactor, then temperature programming
To after 500 DEG C, lead to hydrogen (flow is 100mL/min), carry out activation of catalyst 1h, it is to be restored after the completion of, close H2；In N2Protect
650 DEG C of reaction temperature is cooled under shield, after after temperature stabilization, N is closed2, glycerine, methanol, water are controlled by peristaltic meatering pump respectively
Consumption mol ratio between sample, wherein methanol and glycerine is 6:1；Usage ratio between methanol and glycerine and water vapour according to
The carbon containing molar ratio of water vapour, raw material (S/C) is 8:1 sample introduction, into preheater (250 DEG C of design temperature), laggard people of gasifying
Crystal reaction tube, is 5h in mass space velocity-1；Reaction temperature is catalytic reforming under the conditions of 650 DEG C, the hydrogen-rich synthesis of reaction generation
Gas, imports a gas-chromatography progress on-line analysis after cool drying.
The conversion ratio of material benzenemethanol and glycerine is 95.35%, and the selectivity of hydrogen is 98.27%, the selection of carbon monoxide
Property be 4.2%, 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, heated with the electric heater for being close to reactor outer wall, thermocouple
Reactor bed lower end position is placed in by sleeve pipe, reactor temperature is controlled by temperature controller, size isCatalyst bed floor height 60mm, adds quartz sand up and down, and the recessed of the preparation of 1g embodiments 2 is filled in catalyst bed
The native supported nickel catalyst of convex rod, first by N2(flow is 50mL/min) is passed through in reactor, removes the air in reactor, then journey
Sequence is warming up to after 500 DEG C, leads to hydrogen (flow is 100mL/min), carries out activation of catalyst 1h, it is to be restored after the completion of, close H2；
In N2650 DEG C of reaction temperature is cooled under protection, after after temperature stabilization, N is closed2, methanol, water are controlled by peristaltic meatering pump respectively
Usage ratio between sample, wherein methanol and water vapour is 8 according to the carbon containing molar ratio of water vapour, raw material (S/C):1 enters
Sample, into preheater (250 DEG C of design temperature), gasify laggard people's crystal reaction tube, is 5h in mass space velocity-1；Reaction temperature is
Catalytic reforming under the conditions of 650 DEG C, reacts the hydrogen-rich synthetic gas of generation, and a gas-chromatography is imported after cool drying and is carried out online
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
Glycerine vapor reforming hydrogen production
Using the atmospheric fixed bed reactor of continuous flowing type, heated with the electric heater for being close to reactor outer wall, thermocouple
Reactor bed lower end position is placed in by sleeve pipe, reactor temperature is controlled by temperature controller, size isCatalyst bed floor height 60mm, adds quartz sand up and down, fills prepared by 1g embodiments 2 in catalyst bed
Attapulgite loaded Raney nickel, first by N2(flow is 50mL/min) is passed through in reactor, removes the air in reactor, then
Temperature programming leads to hydrogen (flow is 100mL/min) to after 500 DEG C, carries out activation of catalyst 1h, it is to be restored after the completion of, close
H2；In N2650 DEG C of reaction temperature is cooled under protection, after after temperature stabilization, N is closed2, respectively by peristaltic meatering pump control glycerine,
Usage ratio between water sample, wherein glycerine and water vapour is 8 according to the carbon containing molar ratio of water vapour, raw material (S/C):1
Sample introduction, into preheater (250 DEG C of design temperature), gasify laggard people's crystal reaction tube, is 5h in mass space velocity-1；Reaction temperature
For catalytic reforming under the conditions of 650 DEG C, the hydrogen-rich synthetic gas of generation is reacted, a gas-chromatography is imported after cool drying and is carried out
Line analysis.
The conversion ratio of glycerine 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 glycerine, with phase
The positive role mutually promoted, their mixing reforming hydrogen preparation can improve feed stock conversion, improve hydrogen selective.
Embodiment 3
(1) preparation of attapulgite loaded Raney nickel
Attapulgite obtains the attapulgite powder that granularity is 200 mesh through extruding, shearing, crushing, and attapulgite powder is used
Mass concentration is 10% watery hydrochloric acid immersion 10h, and it is in fluffy similar colloidal sol form attapulgite powder is obtained activation, then
It is precipitated to deionized water cyclic washing neutral standby, the attapulgite of activation is represented with PG.
According to NiO:CaO:CeO2:Fe2O3:PG mass ratioes are 3：1：1：1：14 weigh Ni (NO3)2·6H2O、Fe(NO3)3·
9H2O、Ce(NO3)3·6H2O、Ca(NO3)2·4H2O adds deionized water dissolving, makes the total of soluble-salt in 150ml beakers
Concentration is 1.5mol/L, is then added in heating stirring in PG powders, stirs 30min, is impregnated 14 hours at room temperature, removes upper strata
Clear liquid, remaining suspension is directly through depressurizing suction filtration, and gained filter cake is put into baking oven in being dried 12 hours at 110 DEG C, is cooled to room temperature
After crushed 40~80 sieve.This particle is calcined 4 hours in tube furnace in 600 DEG C, that is, the catalysis of attapulgite loaded nickel is made
Agent 15%Ni-5%Fe-5%Ce-5%Ca/PG catalyst.
(2) methanol-glycerine collaboration vapor reforming hydrogen production
Using the atmospheric fixed bed reactor of continuous flowing type, heated with the electric heater for being close to reactor outer wall, thermocouple
Reactor bed lower end position is placed in by sleeve pipe, reactor temperature is controlled by temperature controller, size isCatalyst bed floor height 60mm, adds quartz sand up and down, and 1g attapulgite loaded nickel is filled in catalyst bed
Catalyst, first by N2(flow is 50mL/min) is passed through 15min in reactor, removes the air in reactor, then temperature programming
To after 500 DEG C, lead to hydrogen (flow is 100mL/min), carry out activation of catalyst 1h, it is to be restored after the completion of, close H2；In N2Protect
550 DEG C of reaction temperature is cooled under shield, after after temperature stabilization, N is closed2, glycerine, methanol, water are controlled by peristaltic meatering pump respectively
Consumption mol ratio between sample, wherein methanol and glycerine is 3:1；Usage ratio between methanol and glycerine and water vapour according to
The carbon containing molar ratio of water vapour, raw material (S/C) is 7:1 sample introduction, into preheater (250 DEG C of design temperature), laggard people of gasifying
Crystal reaction tube, is 3h in mass space velocity-1；Reaction temperature is catalytic reforming under the conditions of 550 DEG C, the hydrogen-rich synthesis of reaction generation
Gas, imports a gas-chromatography progress on-line analysis after cool drying.
The conversion ratio of material benzenemethanol and glycerine is 98.64%, and the selectivity of hydrogen is 98.56%, the selection of carbon monoxide
Property be 5.1%, 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, heated with the electric heater for being close to reactor outer wall, thermocouple
Reactor bed lower end position is placed in by sleeve pipe, reactor temperature is controlled by temperature controller, size isCatalyst bed floor height 60mm, adds quartz sand up and down, and the recessed of the preparation of 1g embodiments 3 is filled in catalyst bed
The native supported nickel catalyst of convex rod, first by N2(flow is 50mL/min) is passed through in reactor, removes the air in reactor, then journey
Sequence is warming up to after 500 DEG C, leads to hydrogen (flow is 100mL/min), carries out activation of catalyst 1h, it is to be restored after the completion of, close H2；
In N2550 DEG C of reaction temperature is cooled under protection, after after temperature stabilization, N is closed2, methanol, water are controlled by peristaltic meatering pump respectively
Usage ratio between sample, wherein methanol and water vapour is 7 according to the carbon containing molar ratio of water vapour, raw material (S/C):1 enters
Sample, into preheater (250 DEG C of design temperature), gasify laggard people's crystal reaction tube, is 3h in mass space velocity-1；Reaction temperature is
Catalytic reforming under the conditions of 550 DEG C, reacts the hydrogen-rich synthetic gas of generation, and a gas-chromatography is imported after cool drying and is carried out online
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
Glycerine vapor reforming hydrogen production
Using the atmospheric fixed bed reactor of continuous flowing type, heated with the electric heater for being close to reactor outer wall, thermocouple
Reactor bed lower end position is placed in by sleeve pipe, reactor temperature is controlled by temperature controller, size isCatalyst bed floor height 60mm, adds quartz sand up and down, and the recessed of the preparation of 1g embodiments 3 is filled in catalyst bed
The native supported nickel catalyst of convex rod, first by N2(flow is 50mL/min) is passed through in reactor, removes the air in reactor, then journey
Sequence is warming up to after 500 DEG C, leads to hydrogen (flow is 100mL/min), carries out activation of catalyst 1h, it is to be restored after the completion of, close H2；
In N2550 DEG C of reaction temperature is cooled under protection, after after temperature stabilization, N is closed2, glycerine, water are controlled by peristaltic meatering pump respectively
Usage ratio between sample, wherein glycerine and water vapour is 7 according to the carbon containing molar ratio of water vapour, raw material (S/C):1 enters
Sample, into preheater (250 DEG C of design temperature), gasify laggard people's crystal reaction tube, is 3h in mass space velocity-1；Reaction temperature is
Catalytic reforming under the conditions of 550 DEG C, reacts the hydrogen-rich synthetic gas of generation, and a gas-chromatography is imported after cool drying and is carried out online
Analysis.
The conversion ratio of glycerine 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 glycerine, with phase
The positive role mutually promoted, their mixing reforming hydrogen preparation can improve feed stock conversion, improve hydrogen selective.
At present, domestic and international researcher is carried out just for single methanol or glycerine vapor reforming hydrogen production system mostly
Research, and the preparing hydrogen by mixing reaction system research for methanol-glycerine is less, the preparation of the invention from cleaning hydrogen energy source,
The practical problem utilized with reference to contemporary biological diesel oil byproduct, proposes that methanol-glycerine cooperates with the new approaches of vapor reforming hydrogen production,
The common activation of glycerine and methanol on a catalyst is realized, makes its collaboration occur reforming reaction efficiently to prepare hydrogen with vapor
Gas, not only reduces the cost of material of hydrogen manufacturing, and is expected to solve the problems, such as biological diesel oil byproduct later use, realizes money
Recycling for the sustainability of the source-energy-environmental integration, can obtain good economy, society and environmental benefit, and tool
There are higher novelty and researching value.The adjustment of exploitation, energy resource structure to Hydrogen Energy and biodiesel, the protection of environment, with
And the development of industrial chain suffers from important realistic meaning.The project not only technical feasibility, the achievement of project for alcohols with it is biological
The coordination of biodiesel by-product is using there is provided new thinking.
Above-listed detailed description is illustrating for possible embodiments of the present invention, and the embodiment simultaneously is not used to limit this hair
Bright the scope of the claims, all equivalence enforcements or change without departing from carried out by the present invention are intended to be limited solely by the scope of patent protection of this case
In.
Claims (7)
1. a kind of methanol-glycerine collaboration vapor reforming hydrogen production method, it is characterised in that comprise the following steps：
(1) preparation of attapulgite loaded Raney nickel：Attapulgite is activated, the total concentration for being impregnated in soluble-salt is 1.0
In~1.5mol/L nickel, calcium, cerium and iron soluble salt solutions, treat that the nickel, calcium, cerium and iron active component are adsorbed in the work
Attapulgite's surface after change, through drying, obtains catalyst precursor, cooling roasting is made the catalysis of attapulgite loaded nickel
Agent；
(2) methanol-glycerine collaboration vapor reforming hydrogen production：Attapulgite loaded Raney nickel prepared by step (1) is placed in perseverance
Warm environment, leads to Hydrogen activation, mol ratio is (1~6) by cooling at 500 DEG C:1 methanol and the mixture of glycerine and water are mixed
Close, the preheated device of the mixture of methanol, G ＆ W is gasified, the gas after gasification enters dress by the pipeline of heating and thermal insulation
Catalytic reforming reaction is carried out in the reactor for having the attapulgite loaded Raney nickel, reacted product realizes gas through cooling
Liquid is separated, and hydrogen-rich synthetic gas is made.
2. methanol-glycerine cooperates with vapor reforming hydrogen production method according to claim 1, it is characterised in that institute in step (1)
The preparation for stating attapulgite loaded Raney nickel comprises the following steps：
(a) attapulgite is activated：Attapulgite is through extruding, shearing and crushes, and obtains the attapulgite powder that granularity is 200 mesh,
The watery hydrochloric acid immersion 8-12h that the attapulgite powder is 5-10% with mass concentration, makes the attapulgite powder be lived
Change, be then washed with deionized and be precipitated to neutrality, activated attapulgite is represented with PG；
(b) infusion process prepares attapulgite loaded Raney nickel：Nickel, calcium, cerium and iron soluble salt solutions are weighed respectively in beaker
In, deionized water is added, the total concentration for making the soluble-salt is 1.0~1.5mol/L, mixed liquor is added into step (a) obtains
The activation after attapulgite powder in, stirring, impregnate 12~16 hours, remove supernatant liquor, remaining suspension is through subtracting
Suction filtration is pressed, gained filtration cakes torrefaction, which is cooled to after room temperature, crushed 40~80 sieves, and the particle after crushing is calcined, that is, Ca-Ce- is made
Fe-Ni/PG attapulgite loaded Raney nickels.
3. methanol according to claim 1 or claim 2-glycerine collaboration vapor reforming hydrogen production method, it is characterised in that with quality hundred
Fraction meter, nickel oxide be 10~15wt%, calcium oxide be 5~10wt%, cerium oxide be 5~10wt%, iron oxide be 5~
10wt%.
4. methanol-glycerine cooperates with vapor reforming hydrogen production method according to claim 1, it is characterised in that institute in step (2)
Stating the method for methanol-glycerine collaboration vapor reforming hydrogen production is：Using the atmospheric fixed bed reactor of continuous flowing type, pass through temperature control
Instrument control reactor temperature, the concave convex rod of 0.5~1g prepared by claim 1 step (1) is filled in catalyst bed
Nitrogen, is first passed through instead by native supported nickel catalyst, the upper and lower part addition quartz sand of the attapulgite loaded Raney nickel
Answer in device, be warming up to after 500 DEG C, lead to hydrogen and carry out activation of catalyst 1h, close hydrogen；Reaction temperature is cooled under nitrogen protection
450-650 DEG C of degree, closes nitrogen, is (1~6) by mol ratio:1 methanol is mixed with the mixture of glycerine and water, into temperature
Gasify for 250 DEG C of preheaters, it is anti-that the gas after gasification enters the quartz equipped with the attapulgite loaded Raney nickel
Should pipe carry out catalytic reforming reaction, reacted product through cooling realize gas-liquid separation, be made hydrogen-rich synthetic gas.
5. methanol-glycerine collaboration vapor reforming hydrogen production method according to claim 1 or 4, it is characterised in that step (2)
Described in the carbon that contains in the mixture of amount ratio between methanol and the mixture and water of glycerine according to water and methanol and glycerine
Mol ratio be (5~8):1.
6. methanol according to claim 1 or claim 2-glycerine collaboration vapor reforming hydrogen production method, it is characterised in that step (2)
Described in methanol and glycerine and the mass space velocity that water is fed be 2.5~5.0h-1。
7. a kind of catalyst for methanol described in claim 1-glycerine collaboration vapor reforming hydrogen production method, its feature exists
In including catalyst active component and catalyst carrier, the catalyst active component include nickel, calcium, cerium and iron, the catalysis
Agent carrier is attapulgite；The content range of the 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 iron oxide is 5~10wt%, the quality point of attapulgite
Number is 55%~75%.
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