CN109987582A - A kind of full liquid phase hydrogenation technology - Google Patents
A kind of full liquid phase hydrogenation technology Download PDFInfo
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- CN109987582A CN109987582A CN201910300091.3A CN201910300091A CN109987582A CN 109987582 A CN109987582 A CN 109987582A CN 201910300091 A CN201910300091 A CN 201910300091A CN 109987582 A CN109987582 A CN 109987582A
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 full liquid phase hydrogenation technologies, belong to hydrogenation stations field.It is the new energy road an of low-carbon environment-friendly by obtaining hydrogen by aqueous phase reforming hydrogen producing technology using biomass derivatives as raw material in the present invention, is finding today of fossil energy substitute with development potential.Ethylene glycol is selected to carry out aqueous phase reforming hydrogen production reaction for the representative object of polyalcohol, the doping vario-property of Pd series catalysts is had studied for the high problem of noble metal cost, according to design the shortcomings that Ni series catalysts prepare multiple catalysts, and each catalyst series ethylene glycol aqueous phase reforming hydrogen manufacturing performance of detailed examination.
Description
Technical field
The present invention relates to hydrogenation stations field more particularly to a kind of full liquid phase hydrogenation technologies.
Background technique
The high heating value and spatter property of Hydrogen Energy become the ideal energy of substitution fossil energy.Existing industrialization hydrogen manufacturing skill
Art or due to using petroleum for raw material, does not have sustainability, or expend energy by electrolysis, and transformation efficiency is low,
Following Hydrogen Energy development aspect is not dominant.Carrying out aqueous phase reforming technology using biomass derivatives has conversion to obtain hydrogen
Rate is high, equipment is simple, raw material sources are extensive and gas-phase product is easy to the advantages that purifying, and is considered as most potential novel system
Hydrogen technology.Design is prepared for multiple catalysts herein, and is studied the aqueous phase reforming hydrogen production reaction of ethylene glycol, achieves
Certain effect, but still there are some problems needs, and further research is carried out in subsequent work.
Current hydrogenation stations use plus hydrogen mode is typically chosen transport hydrogen to be supplemented, and storing for hydrogen does not have
Very good method, it is slow so as to cause the construction of hydrogenation stations, and effect is poor, first by building ethanol water in hydrogenation stations
Phase reformer apparatus, it is possible to reduce transportation cost and storage cost.
Summary of the invention
The purpose of the present invention is to solve hydrogenation stations transport and the higher problem of storage cost, and propose a kind of full liquid
Phase hydrogen addition technology effectively solves the problems, such as that hydrogenation stations transport and storage cost are higher.
To achieve the goals above, present invention employs following technical solutions:
A kind of full liquid phase hydrogenation technology, includes the following steps；
Ethanol raw material is sent to the ethanol raw material storage tank set up inside hydrogenation stations by S1, ethanol raw material waggon, and by ethyl alcohol
Feedstock transportation to raw material buffers preheating can；
The catalyst through hydrogen reducing is added in S2, the autoclave set up into hydrogenation stations, and opens control valve, to
The ethanol raw material in raw material buffering preheating can is injected in autoclave, and opens gas circuit valve, and nitrogen is added into autoclave
Gas, and 2.5-3MPa is boosted to, and heat up by the collet heat riser that external circuit controls autoclave bottom, it rises
Temperature is persistently stirred to 200-250 DEG C；
2.5-3.5h is persistently stirred in S3, reaction process, by the gas phase in autoclave, at heat exchanger tentatively cooling
It after reason, is pipelined in knockout drum, and continued down processing is carried out to knockout drum, be cooled to 5-15 DEG C,
Continue disengaging time 15-25min, later by gas-phase transport therein to next unit；
S4, the gas phase that will be isolated in S3, are pipelined in paddle dryer tower, later by gas-phase transport to Pd film
Separator, to prepare high-purity purified hydrogen, supply hydrogenation stations are used；
S5, the liquid phase that will be isolated in S3 return to the autoclave unit in S2 by circulating pump, carry out at recycling
Reason；
S6, the infiltration residual air generated to Pd membrane separator in S4 return in autoclave by circulating pump, serve as high pressure
Reaction kettle boosting gas is recycled.
Preferably, the S2 mesohigh reaction kettle stirring rate is 350r/min.
Preferably, after the S1-S6 step terminates, catalyst can be taken out and is filtered through multiplex vavuum pump of circulating water type,
It is washed with deionized water, is reused after being placed in a vacuum drying oven low temperature drying 12-16h repeatedly.
Preferably, the paddle dryer tower bottom in the S4 is provided with recovery pond, and liquid passes through pipeline in the recovery pond
Return to circular response in autoclave.
Preferably, catalyst used in the S2 uses Ni/ γ-Al2O3。
Preferably, the Ni/ γ-Al2O3Use following steps to prepare: the load capacity of control Ni metal weighs for 3wt%
γ-the Al of certain mass2O3Carrier is placed in container, and the nickel nitrate solution of a certain amount of 0.05mol/L is added thereto later；It will
The container for installing drug is placed in and keeps 10-14h at room temperature, later the dry 12-14h at 110-130 DEG C, and at 400-500 DEG C
Lower roasting 2.5-3.5h, later grinds product of roasting, and is restored under hydrogen environment, and Ni/ γ-is prepared
Al2O3。
Preferably, the hydrogenation stations further include data sampling and processing and safety monitoring system, to collect and record in real time
The operating parameter of hydrogen container, compressor and dispenser in hydrogenation stations, so that the operation conditions to the autoclave in S2 carries out
Adjustment, makes hydrogenation stations be in the state of a dynamic equilibrium.
Preferably, the road S1-S6 Zhong Ge pipeline is both provided with solenoid valve.
Compared with prior art, the present invention provides a kind of full liquid phase hydrogenation technology, have it is following the utility model has the advantages that
It is one low 1. obtaining hydrogen by aqueous phase reforming hydrogen producing technology using biomass derivatives as raw material in the present invention
The new energy road that carbocyclic ring is protected is finding today of fossil energy substitute with development potential.Select ethylene glycol for polyalcohol
Representative object carry out aqueous phase reforming hydrogen production reaction, the doping for having studied Pd series catalysts for the high problem of noble metal cost changes
Property, multiple catalysts are prepared according to design the shortcomings that Ni series catalysts, and each catalyst series ethylene glycol water of detailed examination
Phase reformation hydrogen production performance.
2. the present invention is using equi-volume impregnating as preparation method, common γ-Al2O3Metal premier opinion is prepared for for carrier
Load capacity is the Pd/ γ-Al of 3wt%2O3、PdNi/γ-Al2O3With Ni/ γ-Al2O3Catalyst is 20wt%%'s to concentration
Ethylene glycol solution carries out aqueous phase reforming hydrogen production reaction, investigates the catalytic activity of monometallic and bimetallic catalyst.Experimental result table
It is bright, Pd/ γ-Al2O3Hydrogen selective and ethylene glycol reforming rate on catalyst are respectively 38.9% and 13.7%, alkane selection
Property is only 11.3%.Although Ni/ γ-Al2O3The load capacity of W metal is only 3% on catalyst, still obtains 37.7% hydrogen
Gas selectivity, maintains and Pd/ γ-Al2O3The comparable level of catalyst, but since the methanation activity of Ni series catalysts is higher,
Paraffin selectivity thereon is caused to reach 37.8%PdNi/ γ-Al2O3Highest hydrogen selective is shown on catalyst, is approached
50%, ethylene glycol reforming rate also reach 22% or so, H2-TPR and XPS the result shows that, PdNi/ γ-Al at this time2O3On catalyst
Pd and Ni form alloy, and have stronger interaction therebetween, promote intermediate product CO from the desorption on metal active position,
The dispersion degree of active component is also improved, and the metal partial size on catalyst is smaller, obtains bigger specific surface area and more
Metal active position, promote going on smoothly for aqueous phase reforming hydrogen production reaction.Post catalyst reaction carbon distribution content results show
PdNi/γ-Al2O3Cause carbon deposition quantity minimum since the carbon distribution of generation can not deposit on the surface Pd on catalyst, Ni/ γ-Al2O3
CO disproportionation and methane cracking reaction have occurred on catalyst and forms a large amount of carbon distribution, biggish specific surface area in catalyst surface
The dispersion degree of PdNi alloy is increased with lesser alloy partial size, it is suppressed that the sintering of Ni improves PdNi/ γ-Al2O3Catalysis
The carbon accumulation resisting ability of agent.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of full liquid phase hydrogenation technology proposed by the present invention；
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.
In the description of the present invention, it is to be understood that, term " on ", "lower", "front", "rear", "left", "right", "top",
The orientation or positional relationship of the instructions such as "bottom", "inner", "outside" is to be based on the orientation or positional relationship shown in the drawings, merely to just
In description the present invention and simplify description, rather than the device or element of indication or suggestion meaning must have a particular orientation, with
Specific orientation construction and operation, therefore be not considered as limiting the invention.
Embodiment 1:
A kind of full liquid phase hydrogenation technology, includes the following steps；
Ethanol raw material is sent to the ethanol raw material storage tank set up inside hydrogenation stations by S1, ethanol raw material waggon, and by ethyl alcohol
Feedstock transportation to raw material buffers preheating can；
The catalyst through hydrogen reducing is added in S2, the autoclave set up into hydrogenation stations, and opens control valve, to
The ethanol raw material in raw material buffering preheating can is injected in autoclave, and opens gas circuit valve, and nitrogen is added into autoclave
Gas, and 2.5-3MPa is boosted to, and heat up by the collet heat riser that external circuit controls autoclave bottom, it rises
Temperature is persistently stirred to 200-250 DEG C；
2.5-3.5h is persistently stirred in S3, reaction process, by the gas phase in autoclave, at heat exchanger tentatively cooling
It after reason, is pipelined in knockout drum, and continued down processing is carried out to knockout drum, be cooled to 5-15 DEG C,
Continue disengaging time 15-25min,
Later by gas-phase transport therein to next unit；
S4, the gas phase that will be isolated in S3, are pipelined in paddle dryer tower, later by gas-phase transport to Pd film
Separator, to prepare high-purity purified hydrogen, supply hydrogenation stations are used；
S5, the liquid phase that will be isolated in S3 return to the autoclave unit in S2 by circulating pump, carry out at recycling
Reason；
S6, the infiltration residual air generated to Pd membrane separator in S4 return in autoclave by circulating pump, serve as high pressure
Reaction kettle boosting gas is recycled.
Further, it is preferable that S2 mesohigh reaction kettle stirring rate is 350r/min.
Further, it is preferable that after S1-S6 step terminates, catalyst can be taken out and be taken out through multiplex vavuum pump of circulating water type
Filter, is washed repeatedly with deionized water, is reused after being placed in a vacuum drying oven low temperature drying 12-16h.
Further, it is preferable that the paddle dryer tower bottom in S4 is provided with recovery pond, and liquid is returned by pipeline in recovery pond
Return circular response in autoclave.
Further, it is preferable that catalyst used in S2 uses Ni/ γ-Al2O3。
Further, it is preferable that Ni/ γ-Al2O3Use following steps to prepare: the load capacity of control Ni metal claims for 3wt%
Take the γ-Al of certain mass2O3Carrier is placed in container, and the nickel nitrate solution of a certain amount of 0.05mol/L is added thereto later；
The container for installing drug is placed in and keeps 10-14h at room temperature, later the dry 12-14h at 110-130 DEG C, and in 400-500
2.5-3.5h is roasted at DEG C, product of roasting is ground later, and is restored under hydrogen environment, and Ni/ γ-is prepared
Al2O3。
Further, it is preferable that hydrogenation stations further include data sampling and processing and safety monitoring system,
To collect and record hydrogen container in hydrogenation stations, compressor and the operating parameter of dispenser in real time, thus in S2
The operation conditions of autoclave be adjusted, so that hydrogenation stations is in the state of a dynamic equilibrium.
Further, it is preferable that the road S1-S6 Zhong Ge pipeline is both provided with solenoid valve.
Embodiment 2: based on embodiment 1 but different it is；
Gaseous product after gas-liquid separation uses Agilent 7890A gas chromatograph for determination, chromatographic column 5A molecular sieve
(2m, φ 3mm) packed column and PorapakQ (3m) packed column, nitrogen is carrier gas, and hydrogen is measured by TCD detector, C02, CO, CH4
It is detected with after the inverted furnace conversion of other alkane by fid detector.50 DEG C of column temperature, 100 DEG C of sample injector temperature, convert furnace temperature
380 DEG C, 100 DEG C of detector temperature.
Liquid product after gas-liquid separation uses Agilent 7890A gas chromatograph for determination, chromatographic column DB-WAX
(60m, φ 0.53mm), carrier gas is helium.40 DEG C of initial column temperature, 240 DEG C are risen to 10 DEG C/min of heating rate, keeps 8min,
Using inner mark method ration, using ethylene glycol-ether as internal standard compound.Acetaldehyde, acetone, methanol, isopropanol, ethyl alcohol, acetic acid and ethylene glycol
Relative correction factor be respectively 1.37/3.97,8.42,4.49,4.44,4.69 and 0.706.
Embodiment 3: based on Examples 1 and 2 but different it is；
Pd/ γ-Al is provided in following table2O3、PdNi/γ-Al2O3With Ni/ γ-Al2O3The basic physics knot of three kinds of catalyst
Structure property, three kinds of catalyst are all made of equi-volume impregnating preparation, and theoretical metal load capacity is that 3wt% actual negative carrying capacity passes through
ICP-AES is measured.As shown in the table, γ-Al before loading2O3The specific surface area of carrier is up to 167.40m2/ g, Kong Rong and average hole
Diameter is respectively 0.41cm3/ g and 9.35nm.Find which kind of metal no matter loaded after Metal Supported, although surveying through ICP-AES
Its fixed practical load factor in 3wt% hereinafter,
But γ-Al2O3Apparent decline has occurred in carrier specific surface area, from initial
167.40m2/ g drops to 124-133m2/ g or so, Kong Rong are down to simple γ-Al2O3The half of carrier, average hole
Diameter also drops to 6nm or so from 9.35nm, and illustrating to load a small amount of metal can specific surface area, Kong Rong and average hole to carrier
Larger impact occurs for diameter, this is because a small amount of metal of load thereon enters γ-Al2O3The duct of carrier is filled with original
Pore structure, the reason for making channel diameter become smaller.From three kinds of γ-Al2O3The physical structure data for loading different metal catalyst comes
It sees, since the amount of carried metal is lower, although carried metal type is different, the physical structure of catalyst is influenced smaller.To
Pd/γ-Al2O3After W metal is added in catalyst, PdNi/ γ-Al2O3Specific surface area 124.64m2/ g increases to 133.28m2/ g,
PdNi/ γ-Al simultaneously2O3The Kong Rong and average pore size of catalyst have to be increased by a small margin, this may be the presence due to Ni element
It can promote the dispersion of Pd.In the presence of there is no Pd element in catalyst, Ni/ γ-Al2O3The specific surface area and PdNi/ of catalyst
γ-Al2O3Catalyst is also demonstrated when Pd and Ni is existed simultaneously, metal dispersity may be improved compared in a slight decrease.
The active metal crystallite dimension being calculated by Debye-Scherrer formula.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of full liquid phase hydrogenation technology, it is characterised in that: include the following steps；
Ethanol raw material is sent to the ethanol raw material storage tank set up inside hydrogenation stations by S1, ethanol raw material waggon, and by ethanol raw material
It is delivered to raw material buffering preheating can；
The catalyst through hydrogen reducing is added in S2, the autoclave set up into hydrogenation stations, and opens control valve, to high pressure
The ethanol raw material in raw material buffering preheating can is injected in reaction kettle, and opens gas circuit valve, and nitrogen is added into autoclave, and
2.5-3MPa is boosted to, and is heated up by the collet heat riser that external circuit controls autoclave bottom, is warming up to
It 200-250 DEG C, is persistently stirred；
2.5-3.5h is persistently stirred in S3, reaction process, the gas phase in autoclave is handled through heat exchanger tentatively cooling
Afterwards, it is pipelined in knockout drum, and continued down processing is carried out to knockout drum, be cooled to 5-15 DEG C, hold
Continuous disengaging time 15-25min, later by gas-phase transport therein to next unit；
S4, the gas phase that will be isolated in S3, are pipelined in paddle dryer tower, later by gas-phase transport to Pd UF membrane
Device, to prepare high-purity purified hydrogen, supply hydrogenation stations are used；
S5, the liquid phase that will be isolated in S3 return to the autoclave unit in S2 by circulating pump, carry out recycling processing；
S6, the infiltration residual air generated to Pd membrane separator in S4 return in autoclave by circulating pump, serve as reaction under high pressure
Kettle boosting gas is recycled.
2. a kind of full liquid phase hydrogenation technology according to claim 1, it is characterised in that: the S2 mesohigh reaction kettle stirring
Rate is 350r/min.
3. a kind of full liquid phase hydrogenation technology according to claim 1, it is characterised in that: after the S1-S6 step terminates,
Catalyst can be taken out and be filtered through multiplex vavuum pump of circulating water type, washed, be placed in a vacuum drying oven low repeatedly with deionized water
It is reused after the dry 12-16h of temperature.
4. a kind of full liquid phase hydrogenation technology according to claim 1, it is characterised in that: the paddle dryer tower bottom in the S4
Portion is provided with recovery pond, and liquid returns to circular response in autoclave by pipeline in the recovery pond.
5. a kind of full liquid phase hydrogenation technology according to claim 1, it is characterised in that: catalyst used in the S2 is adopted
With Ni/ γ-Al2O3。
6. a kind of full liquid phase hydrogenation technology according to claim 1, it is characterised in that: the Ni/ γ-Al2O3Using following
Step preparation: the load capacity of control Ni metal is 3wt%, weighs the γ-Al of certain mass2O3Carrier is placed in container, backward
The nickel nitrate solution of a certain amount of 0.05mol/L is wherein added；The container for installing drug is placed in and keeps 10-14h at room temperature, later
The dry 12-14h at 110-130 DEG C, and 2.5-3.5h is roasted at 400-500 DEG C, product of roasting is ground later, and
It is restored under hydrogen environment, Ni/ γ-Al is prepared2O3。
7. a kind of full liquid phase hydrogenation technology according to claim 1, it is characterised in that: the hydrogenation stations further include that data are adopted
Collection, processing and safety monitoring system, the operation to collect and record hydrogen container in hydrogenation stations, compressor and dispenser in real time are joined
Number, to be adjusted to the operation conditions of the autoclave in S2, makes hydrogenation stations be in the state of a dynamic equilibrium.
8. a kind of full liquid phase hydrogenation technology according to claim 1, it is characterised in that: the road S1-S6 Zhong Ge pipeline
It is both provided with solenoid valve.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112054222A (en) * | 2020-09-04 | 2020-12-08 | 西安交通大学 | Carbon-supported palladium-nickel-tantalum nitride nano electro-catalyst for direct methanol fuel cell and preparation method thereof |
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| CN112054222A (en) * | 2020-09-04 | 2020-12-08 | 西安交通大学 | Carbon-supported palladium-nickel-tantalum nitride nano electro-catalyst for direct methanol fuel cell and preparation method thereof |
| CN112054222B (en) * | 2020-09-04 | 2021-12-28 | 西安交通大学 | Carbon-supported palladium-nickel-tantalum nitride nano electro-catalyst for direct methanol fuel cell and preparation method thereof |
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