CN109081308A - A method of by glycerol and methane co-producing hydrogen and synthesis gas - Google Patents
A method of by glycerol and methane co-producing hydrogen and synthesis gas Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—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 by reaction of hydrocarbons with gasifying agents
- C01B3/38—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 by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—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 by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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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
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- C01B2203/1241—Natural gas or methane
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a kind of methods by glycerol and methane co-producing hydrogen and synthesis gas.This method loads with catalysis in fixed bed reactors and absorbs CO2The Ni-Ca-Al catalyst of function, reaction carry out in two stages: glycerol absorption enhancing reforming reaction high purity hydrogen is carried out in the case where inert atmosphere is as carrier gas；Then absorbing CO2Catalyst on carry out methane reforming reaction producing synthesis gas.Ni-Ca-Al catalyst used in the present invention is Ni, CaO and Ca12Al14O33Mixed catalyst.The present invention can produce purity up to 97% hydrogen, CH in glycerol reforming phase4CH in reforming phase4Conversion ratio, H2Each self-stabilization of molar ratio with CO is in ~ 95% and < 2, CO2Concentration below 4.5%.Ni-Ca-Al catalyst has high activity and high stability in this process.
Description
Technical field
The invention belongs to energy environment technical fields, and in particular to a kind of by glycerol and methane co-producing hydrogen and synthesis gas
Method.
Background technique
Main production of the ester-interchange method as biodiesel, it is public that every one ton of biodiesel of production will generate about 100
Jin crude glycerine, as biodiesel is widely applied, there is serious surplus in glycerol.Demand of the hydrogen in chemical industry and petroleum industry
It is very huge.Using glycerol hydrogen manufacturing, the problem of can not only efficiently solving glycerol overstock, also can satisfy the demand to hydrogen,
Prospect is considerable.
At present in the technology using glycerol hydrogen manufacturing, glycerol absorption enhancing reformation hydrogen production causes the very big pass of researchers
Note.It is by CO2Separation in situ is coupled with glycerol reforming reaction, by by CO2From reaction system Central Plains, displacement is removed, and is changed flat
Weigh concentration, promotes H2Generation, to obtain high-purity H2.This technology enormously simplifies subsequent H2Isolate and purify process.Patent
CN107098311A reports glycerol absorption enhancing hydrogen producing technology, and obtained hydrogen purity is up to 95%.Also, patent
CN101559924, which also proposed, can be applied to biogas steam reforming process for the concept of absorption enhancing, the purity of hydrogen from
65% or so is promoted to 90% or more.
In general, glycerol absorption enhancing reformation hydrogen production process needs the CO of a high temperature2Desorption process carrys out regenerative adsorption
Agent enhances reforming reaction with the absorption for carrying out next round.Dou Binlin (Enery&Fuels, 2015,29:7408-7418) etc.
The regeneration condition that person selects is 900 DEG C of temperature and 500ml/min N2Lower desorption 60min.This high-temperature operation can greatly increase energy
Consumption, and in order to handle the CO that these are desorbed out2, it usually needs to CO2Stored on a large scale further to utilize,
This needs a large amount of equipment investment, this series of technical process is all unfavorable for CO2Emission reduction and processing.If can be to these captures
After be present in CaCO3In CO2Process flow can be shortened by directly carrying out conversion, reduce energy consumption, while also avoid reaction and desorption
The continuous alternating temperature bring operation of interprocedual and energy consumption problem.Directly to the CO after capture2Or the material formed after capture carries out
The research of conversion has been reported.Jagadeesan Dinesh (ChemSusChem, 2009,2:878-882) et al. is with Co/CoO/
CaO is catalyst in a hydrogen atmosphere by CaCO3Completion is converted to methane.Steinfeild A et al. (Enery&Fuels,
Hydrogen and CaCO 2009,23:6207-6212) are replaced with methane3It carries out reforming reaction and obtains synthesis gas, improve conversion CaCO3
Economy.Also, M ü ller Christoph et al. (ACS Catalysis, 2018,8:2815-2823) shows CO2Capture
Form CaCO3Then carry out CH4The process that reformation obtains synthesis gas can recycle progress.Therefore, quasi- explore of the present invention inhales glycerol
Attached enhancing reformation hydrogen production process and CH4Reform generate synthesis gas process coupled, with realize the glycerol under same device with
The technique of methane co-producing hydrogen and synthesis gas, to avoid traditional CO2Desorption-trans-utilization high energy consumption and complicated technology.
Summary of the invention
The purpose of the present invention is to provide a kind of methods by glycerol and methane co-producing hydrogen and synthesis gas, enhance in absorption
The de- CO reformed2Stage introduces methane, by CO2Removing is coupled with conversion process, direct producing synthesis gas.
The present invention solves its technical problem, and the following technical solution is employed.
A method of by glycerol and methane co-producing hydrogen and synthesis gas, comprising the following steps:
(1) it loads to have in fixed bed reactors and is catalyzed and absorbs CO2The Ni-Ca-Al catalyst of function；
(2) in the case where inert gas is as carrier gas, glycerine water solution is injected in the fixed bed reactors, is passed through
Absorption enhancing reforming reaction produces high-purity hydrogen, CO2Then absorbed by Ni-Ca-Al catalyst；The concentration of the glycerine water solution
For 0.222-0.951g/ml, weight (hourly) space velocity (WHSV) 0.266-1.141h-1, reaction temperature is 400~700 DEG C；
It (3) is 600-12000h with air speed after the completion of the absorption of step (2) enhances reforming reaction-1It is passed through methane gas
It carries out methane reforming reaction and produces synthesis gas, reaction temperature is 500~900 DEG C.
Preferably, the mass content of Ni is 5-20% in Ni-Ca-Al catalyst described in step (1).
Preferably, the molar ratio of Ca and Al is 2.3-3.3 in Ni-Ca-Al catalyst described in step (1).
Preferably, the concentration of glycerine water solution described in step (2) is 0.222-0.383g/ml.
Preferably, the weight (hourly) space velocity (WHSV) of glycerine water solution described in step (2) is 0.266-0.394g/ml.
Preferably, reaction temperature described in step (2) is 500~600 DEG C.
Preferably, air speed described in step (3) is 3000~4500h-1。
Preferably, the concentration of step (3) described methane gas is 5vol%-100vol%.
It is further preferred that the concentration of the methane gas is 10vol%-20vol%.
Preferably, reaction temperature described in step (3) is 650~700 DEG C.
Compared with prior art, the present invention has the advantage that
(1) present invention is reformed using glycerol absorption enhancing and obtains hydrogen of the purity 97% or more；
(2) CO captured from glycerol2With CH4Reaction generates synthesis gas, avoids traditional CO2Desorption-trans-utilization
High energy consumption and complicated technology.
Detailed description of the invention
Fig. 1 is the performance chart of the methane reforming process in embodiment 30.
Fig. 2 is the CO in the glycerol absorption enhancing reforming process of 10 circle loop test processes in embodiment 332And H2Curve
Figure.
Fig. 3 is the performance chart in the methane reforming process in embodiment 33 during 10 circle loop tests.
Specific embodiment
It is illustrated by the following examples the preparation of method and catalyst of the invention, but the present invention is not limited to following reality
Apply example.
The concentration of hydrogen is measured by gas-chromatography (GC) analysis in the following example, and the calculation method of GC detection uses
External standard method.
Embodiment 1-4:
Take 15.561gCa (NO3)2·4H2O、8.828gAl(NO3)3·9H2O (Ca and Al molar ratio be 2.8) and press table 1
Middle Ni is containing a certain amount of Ni (NO of measurement3)2·6H2O, which is dissolved in 50mL deionized water, is made into mixed solution A, takes 4.24gNaCO3With
2.4gNaOH, which is dissolved in 50mL deionized water, is made into mixed solution B, and under conditions of magnetic agitation, mixed solution A is added dropwise
Enter and carries out coprecipitation reaction into mixed solution B, then, with the sodium hydrate regulator solution pH=10.0 of 3mol/L, acquisition
It is deposited in aging 16h at 65 DEG C, and after being filtered, washed, drying, then roasts 4h at 800 DEG C and urged to get to Ni-Ca-Al
Agent.In glycerol absorption enhancing reforming reaction, the Ni-Ca-Al catalyst in table 1 is loaded in fixed bed reactors, nitrogen is made
Carrier gas, with 0.394h-1Weight (hourly) space velocity (WHSV) be passed through concentration be 0.328g/mL glycerol water mixed liquid, reaction temperature be 550 DEG C.Through
GC is detected, and the concentration of hydrogen see the table below 1 in product after reaction 4min.
Table 1
| Embodiment | 1 | 2 | 3 | 4 |
| The content (wt%) of Ni | 5 | 10 | 15 | 20 |
| The purity (%) of hydrogen | 98.1 | 98.5 | 98.3 | 98.6 |
Embodiment 5-7:
Holding Ni content is 10wt%, changes Ca (NO3)2·4H2O and Al (NO3)3·9H2In the amount allocation list 2 of O Ca with
The Ni-Ca-Al catalyst of the molar ratio of Al, other conditions are the same as embodiment 2.In glycerol absorption enhancing reforming reaction, in fixed bed
The Ni-Ca-Al catalyst of Ca and Al molar ratio in table 2 are loaded in reactor, nitrogen makees carrier gas, with 0.394h-1Weight (hourly) space velocity (WHSV)
It is passed through the glycerol water mixed liquid that concentration is 0.328g/mL, reaction temperature is 550 DEG C.It is detected through GC, hydrogen in product after reaction 4min
The concentration of gas see the table below 2.
Table 2
| Embodiment | 5 | 6 | 2 | 7 |
| Ca and Al molar ratio | 1 | 2.3 | 2.8 | 3.3 |
| The purity (%) of hydrogen | 70.1 | 97.2 | 98.5 | 98.9 |
Embodiment 8-10:
In glycerol absorption enhancing reforming reaction, it is 10wt% and Ca and Al moles that Ni content is loaded in fixed bed reactors
Than the Ni-Ca-Al catalyst for 2.8, nitrogen makees carrier gas, is passed through concentration with the weight (hourly) space velocity (WHSV) in table 3 as the glycerol of 0.328g/mL
Water mixed liquid, reaction temperature are 550 DEG C.It is detected through GC, the concentration of hydrogen see the table below 3 in product after reaction 4min.
Table 3
| Embodiment | 8 | 2 | 9 | 10 |
| Weight (hourly) space velocity (WHSV) (h-1) | 0.266 | 0.394 | 0.899 | 1.141 |
| The purity (%) of hydrogen | 97.3 | 98.5 | 94.0 | 91.2 |
Embodiment 11-13:
In glycerol absorption enhancing reforming reaction, it is 10wt% and Ca and Al moles that Ni content is loaded in fixed bed reactors
Than the Ni-Ca-Al catalyst for 2.8, nitrogen makees carrier gas, with 0.394h-1Weight (hourly) space velocity (WHSV) be passed through concentration be table 4 in glycerol liquor
Mixed liquor, reaction temperature are 550 DEG C.It is detected through GC, the concentration of hydrogen see the table below 4 in product after reaction 4min.
Table 3
| Embodiment | 11 | 2 | 12 | 13 |
| Glycerol concentration (g/mL) | 0.222 | 0.328 | 0.749 | 0.951 |
| The purity (%) of hydrogen | 97.9 | 98.5 | 94.7 | 90.3 |
Embodiment 14-18:
In glycerol absorption enhancing reforming reaction, it is 10wt% and Ca and Al moles that Ni content is loaded in fixed bed reactors
Than the Ni-Ca-Al catalyst for 2.8, nitrogen makees carrier gas, with 0.394h-1Weight (hourly) space velocity (WHSV) be passed through concentration be 0.328g/mL it is sweet
Oil-water mixture, reaction temperature are as shown in table 5.It is detected through GC, the concentration of hydrogen see the table below 5 in product after reaction 4min.
Table 5
| Embodiment | 14 | 15 | 16 | 2 | 17 | 18 |
| Reaction temperature (DEG C) | 400 | 450 | 500 | 550 | 600 | 700 |
| The purity (%) of hydrogen | 67.2 | 77.0 | 98.4 | 98.5 | 97.5 | 87.5 |
Embodiment 19-23:
In glycerol absorption enhancing reforming reaction, it is 10wt% and Ca and Al moles that Ni content is loaded in fixed bed reactors
Than the Ni-Ca-Al catalyst for 2.8, nitrogen makees carrier gas, with 0.394h-1Weight (hourly) space velocity (WHSV) be passed through concentration be 0.328g/mL it is sweet
Oil-water mixture, reaction temperature are 550 DEG C.After the completion of absorption enhances reforming reaction, being passed through concentration with the air speed in table 6 is
The methane gas of 20vol% carries out methane reforming reaction, and reaction temperature is 650 DEG C.It is detected through GC, reacts CH after 4min4Turn
Rate, CO2H in selectivity and product2It see the table below 6 with the molar ratio of CO.
Table 6
| Embodiment | 19 | 20 | 21 | 22 | 23 |
| Air speed (h-1) | 600 | 3000 | 4500 | 9000 | 12000 |
| CH4Conversion ratio (%) | 96.4 | 81.9 | 68.2 | 30.5 | 10.2 |
| CO2Concentration (%) | 25.8 | 3.6 | 2.4 | 1.4 | 0.7 |
| H2With the molar ratio of CO | 3.5 | 1.7 | 2.2 | 2.0 | 1.9 |
Embodiment 24-27:
In glycerol absorption enhancing reforming reaction, it is 10wt% and Ca and Al moles that Ni content is loaded in fixed bed reactors
Than the Ni-Ca-Al catalyst for 2.8, nitrogen makees carrier gas, with 0.394h-1Weight (hourly) space velocity (WHSV) be passed through concentration be 0.328g/mL it is sweet
Oil-water mixture, reaction temperature are 550 DEG C.After the completion of absorption enhances reforming reaction, with 3000h-1Air speed be passed through concentration and be
The methane gas of table 7 carries out methane reforming reaction, and reaction temperature is 650 DEG C.It is detected through GC, reacts CH after 4min4Conversion ratio,
CO2H in selectivity and product2It see the table below 7 with the molar ratio of CO.
Table 7
| Embodiment | 24 | 25 | 17 | 26 | 27 |
| Methane concentration (vol%) | 5 | 10 | 20 | 50 | 100 |
| CH4Conversion ratio (%) | 93.1 | 92.1 | 81.9 | 68.8 | 33.5 |
| CO2Concentration (%) | 7.4 | 4.5 | 3.6 | 2.9 | 2.4 |
| H2With the molar ratio of CO | 1.3 | 1.4 | 1.7 | 3.1 | 6.3 |
Embodiment 28-32:
In glycerol absorption enhancing reforming reaction, it is 10wt% and Ca and Al moles that Ni content is loaded in fixed bed reactors
Than the Ni-Ca-Al catalyst for 2.8, nitrogen makees carrier gas, with 0.394h-1Weight (hourly) space velocity (WHSV) be passed through concentration be 0.328g/mL it is sweet
Oil-water mixture, reaction temperature are 550 DEG C.After the completion of absorption enhances reforming reaction, with 3000h-1Air speed be passed through concentration and be
The methane gas of 20vol% carries out methane reforming reaction, and reaction temperature is as shown in table 8.It is detected through GC, reacts CH after 4min4's
Conversion ratio, CO2H in selectivity and product2It see the table below 8 with the molar ratio of CO.
Table 8
| Embodiment | 28 | 29 | 17 | 30 | 31 | 32 |
| Reaction temperature (DEG C) | 500 | 600 | 650 | 700 | 750 | 900 |
| CH4Conversion ratio (%) | 32.6 | 62.1 | 81.9 | 92.5 | 86.3 | 65.2 |
| CO2Concentration (%) | 2.3 | 2.8 | 3.6 | 4.1 | 7.3 | 9.4 |
| H2With the molar ratio of CO | 4.7 | 3.5 | 1.7 | 1.0 | 1.2 | 5.9 |
Embodiment 33:
Stability test: in glycerol absorption enhancing reforming reaction, it is 10wt% that Ni content is loaded in fixed bed reactors
The Ni-Ca-Al catalyst for being 2.8 with Ca and Al molar ratio, nitrogen makees carrier gas, with 0.394h-1Weight (hourly) space velocity (WHSV) be passed through concentration and be
The glycerol water mixed liquid of 0.328g/mL, reaction temperature are 550 DEG C.After the completion of absorption enhances reforming reaction, with 3000h-1Sky
Speed is passed through the methane gas that concentration is 20vol% and carries out methane reforming reaction, and reaction temperature is 700 DEG C, recycles 10 times.It is examined through GC
It surveys, the concentration of hydrogen during absorption enhances after reaction 4min, the CH in methane reforming process4Conversion ratio, CO2Selectivity with
And H in product2It see the table below 9 with the molar ratio of CO.
Table 9
It can see from the result of table 9 and Fig. 2 and Fig. 3, under the conditions of the embodiment, 10 circle loop tests show that glycerol is inhaled
Density of hydrogen during attached enhancing is stablized 97% or more, meanwhile, CH in methane reforming process4Conversion ratio, H2With mole of CO
Than and CO2Concentration also each self-stabilization~95%, < 2 and < 4.5%.
It is important to emphasize that above-described embodiment is used for the purpose of clearly demonstrating examples of the invention, and simultaneously
The non-complete restriction to embodiment.Those of ordinary skill in the art can also make other on the basis of the above description
Various forms of variations can not provide embodiment without to all embodiments here, but thus amplify out aobvious and
The variation being clear to is still in protection scope of the present invention.
Claims (10)
1. a kind of method by glycerol and methane co-producing hydrogen and synthesis gas, which comprises the following steps:
(1) Ni-Ca-Al catalyst is loaded in fixed bed reactors；
(2) in the case where inert gas is as carrier gas, glycerine water solution is injected in the fixed bed reactors, passes through absorption
Enhancing reforming reaction produces high-purity hydrogen, CO2Then absorbed by Ni-Ca-Al catalyst；The concentration of the glycerine water solution is
0.222-0.951g/ml, weight (hourly) space velocity (WHSV) 0.266-1.141h-1, reaction temperature is 400~700 DEG C；
It (3) is 600-12000h with air speed after the completion of the absorption of step (2) enhances reforming reaction-1It is passed through methane gas progress
Methane reforming reaction produces synthesis gas, and reaction temperature is 500~900 DEG C.
2. the method according to claim 1, wherein in Ni-Ca-Al catalyst described in step (1) Ni matter
Amount content is 5-20%.
3. the method according to claim 1, wherein Ca and Al in Ni-Ca-Al catalyst described in step (1)
Molar ratio be 2.3-3.3.
4. the method according to claim 1, wherein the concentration of glycerine water solution described in step (2) is
0.222-0.383g/ml。
5. the method according to claim 1, wherein the weight (hourly) space velocity (WHSV) of glycerine water solution described in step (2) is
0.266-0.394g/ml。
6. the method according to claim 1, wherein reaction temperature described in step (2) is 500~600 DEG C.
7. the method according to claim 1, wherein air speed described in step (3) is 3000~4500 h-1。
8. the method according to claim 1, wherein the concentration of step (3) described methane gas is 5vol%-100
vol%。
9. according to the method described in claim 8, it is characterized in that, the concentration of the methane gas is 10 vol%-20 vol%.
10. the method according to claim 1, wherein reaction temperature described in step (3) is 650~700 DEG C.
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Cited By (1)
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| CN112156783A (en) * | 2020-09-07 | 2021-01-01 | 广州大学 | Ni-CaO-Ca12Al14O33Preparation method and application of bifunctional catalyst |
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| CN112156783B (en) * | 2020-09-07 | 2023-02-28 | 广州大学 | Ni-CaO-Ca 12 Al 14 O 33 Preparation method and application of bifunctional catalyst |
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