CN105060244A - Continuous hydrogenation reaction system for liquid organic hydrogen storage carrier and hydrogenation reaction method - Google Patents
Continuous hydrogenation reaction system for liquid organic hydrogen storage carrier and hydrogenation reaction method Download PDFInfo
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Abstract
The invention discloses a continuous hydrogenation reaction system for a liquid organic hydrogen storage carrier and a hydrogenation reaction method. The system comprises a feeding system, preheaters, static bed reaction stills and separation devices. The feeding system is communicated with inlets of the preheaters through pipelines. Outlets of the preheaters are communicated with inlets of the static bed reaction stills through pipelines. Outlets of the static bed reaction stills are communicated with inlets of the separation devices through pipelines. The static bed reaction stills are filled with hydrogenation catalysts and inert materials. The interiors of the reaction stills are kept at the constant temperature through circulation heat conduction media in interlayers of the surfaces of the static bed reaction stills. According to the continuous hydrogenation reaction system, the single-tube type static bed reaction stills are mainly adopted, the single-tube type static bed reaction stills are filled with the hydrogenation catalysts and the inert materials, heat tracing and heating control systems are arranged in all the pipelines in the liquid feeding system to be used for conducting temperature-control heating on liquid flowing through the system, a plurality of sets of gas quality and flow controller systems are designed in the system, the preheaters in the system are designed to be gas-liquid blending type preheaters, and the hydrogenation effect of the liquid hydrogen storage carrier is improved beneficially.
Description
Technical field
The invention belongs to hydrogen storage technology field, particularly a kind of liquid state is stored up the continous way hydrogenation reaction system of hydrogen carrier and adopts this system liquid towards organic hydrogen storage carrier to carry out the method for continous way hydrogenation.
Background technology
Hydrogen Energy as a kind of rich reserves, wide material sources, green energy resource that energy density is high, at fuel cell and replace presenting good application prospect in fossil oil etc.In actual application, it stores and transport is crucial.Find high efficiency, low cost and can mass-producing utilize hydrogen storage method crucial especially.
Existing hydrogen storage method roughly can be divided into two kinds, i.e. Physical and chemical method.Low temperature liquid hydrogen storing method, high-pressure gaseous hydrogen storing method etc. is typically had in Physical.Although wherein low temperature liquid hydrogen storing method has higher volume energy density, because the critical temperature of hydrogen is lower, liquefaction of hydrogen will consume very large cooling energy, also inevitably there is vaporization losses in storage, and storage cost is higher.High-pressure gaseous hydrogen storing method is easy to use, but energy density is lower, and there is potential safety hazard.
In recent years, the hydrogen storage technology based on chemical reaction method is large with its hydrogen-storage amount, and the advantages such as energy density is high, convenient transportation cause the concern of Many researchers.Desirable hydrogen storage system should have good reversible hydrogenation/dehydrogenation performance.But, the general following existing defects of the existing hydrogen storage system based on chemical reaction method: self zero pour (fusing point) of hydrogen storage system is too high, at room temperature presents solid-state.This hydrogen storage system be in a liquid state after making hydrogenation is in certain embodiments, and the hydrogen storage system recovered after preferential dehydrogenation is easily condensed into solid.These coagulums easily cover dehydrogenation catalyst surface, thus cause dehydrogenation reaction to be interrupted.
Sustainable energy laboratory study team of China Geological Univ. Wuhan, under the leading of Organization Department of the CPC Central Committee's second batch " thousand people's plans " Cheng Hansong professor, on former U.S. working foundation, by long-term exploration and research, find a fluid-like state organic conjugated molecule hydrogen storage material, this type of material has fusing point low (technology of exploitation is at present low to moderate-20 DEG C), flash-point high (more than 150 DEG C), and under the effect of self-control effective catalyst, release gas purity high (99.99%), the features such as desorption temperature low (about 150 DEG C), and cycle life high (more than 2000 times), reversibility is strong, and do not produce the gas that carbon monoxide etc. poisons fuel cell.As the carrier of hydrogen, this kind of material in use exists all the time in a liquid-like manner, equally can store at normal temperatures and pressures and transports by image-stone oil, can utilize existing gasoline mode of movement and service station's framework completely.
Summary of the invention
An object of the present invention is to provide the continous way hydrogenation reaction system of above-mentioned liquid state storage hydrogen carrier in order to hydrogenation.
Two of object is to provide the method adopting said system liquid towards organic hydrogen storage carrier to carry out continous way hydrogenation.
To achieve these goals, the present invention by the following technical solutions: a kind of continous way hydrogenation reaction system of liquid organic hydrogen storage carrier, comprising: feed system, preheater, fixed bed reaction tower reactor and tripping device;
Described feed system is communicated with pre-heater inlet by pipeline, and preheater outlet is communicated with fixed bed reaction tower reactor entrance by pipeline, and the outlet of fixed bed reaction tower reactor is communicated with tripping device entrance by pipeline;
Described preheater is the blended formula preheater of gas-liquid, liquid organic hydrogen storage carrier and the mixed heating of hydrogen;
Described fixed bed reaction tower reactor is single hose fixed-bed reactor, and inside is filled with hydrogenation catalyst and inert material, and single hose fixed-bed reactor outer setting responds device heating control system, carries out temperature control heating to reactor.
Described inert material is filled in the upper and lower of single hose fixed-bed reactor, the mixture of central filler hydrogenation catalyst and inert material, and inert material accounts for 0% ~ 60% of mixture total mass.
Described hydrogenation catalyst is the bimetal that forms of precious metal and precious metal inclusive NAND precious metal or three metal load type catalysts, adopt polyol process to prepare many metal load type catalysts method and prepare hydrogenation catalyst nano particle, again obtained nano core-shell particulate load is deposited to porous support to be prepared from the surface, precious metal is Pd, Pt, Ru, Rh, base metal is Ni, Co, Fe, and porous support is porous SiO
2, Al
2o
3or activated carbon, the particle diameter of catalyzer is 0.6 ~ 1.0mm.
Described inert material is at least one in silicon-dioxide, aluminum oxide, gac, and the particle diameter of inert material is 0.25 ~ 0.5mm.
Described feed system comprises the hydrogen container of storage of hydrogen or adopts the mode of pipeline hydrogen supply, and the container for storing liquid of storing liquid storage hydrogen carrier, and described container for storing liquid outer setting has temperature control unit, makes container for storing liquid keep steady temperature.
Pipeline between described hydrogen container and preheater is provided with the gas mass flow controller system of stop valve, strainer, pressure maintaining valve, moisture eliminator and two cover more parallels.Described gas mass flow controller system of often overlapping comprises the mass flow controller that 1 has different flow span of control.
All pipelines between described container for storing liquid and preheater are outside equipped with pipeline heating control system, carry out temperature control heating to the liquid flowed through.
Described reactor heating control system is one-part form or Segmented heating temperature regulating device, carries out heated for controlling temperature by circulating heat conduction medium to reactor.Multi-stage type heating can be two-part, syllogic, four-part form or five-part form, and from top to bottom temperature successively increases.For two-part heat time, the temperature on top controls at 90 ~ 130 DEG C, and the temperature of bottom controls at 110 ~ 160 DEG C.During for Three-section type heating, upper temp controls at 90 ~ 130 DEG C, and middle portion temperature controls at 110 ~ 160 DEG C, and temperature of lower controls at 130 ~ 190 DEG C.For four-part form heat time, from top to bottom first paragraph temperature controls at 90 ~ 130 DEG C, and second segment temperature controls at 110 ~ 160 DEG C, and the 3rd section of temperature controls at 130 ~ 190 DEG C, and the 4th section of temperature controls at 150 ~ 210 DEG C.For five-part form heat time, from top to bottom first paragraph temperature controls at 90 ~ 130 DEG C, and second segment temperature controls at 110 ~ 160 DEG C, and the 3rd section of temperature controls at 130 ~ 190 DEG C, and the 4th section of temperature controls at 150 ~ 210 DEG C, and the 5th section of temperature controls at 170 ~ 230 DEG C.
Described tripping device comprises the condenser and gas-liquid separator that connect successively.
The liquid outlet of described gas-liquid separator is provided with sampler, and air outlet is provided with a kind of method adopting continous way hydrogenation reaction system liquid towards organic hydrogen storage carrier to carry out continous way hydrogenation of wet test meter, comprises the following steps:
(1) inert material is filled in the upper and lower of single hose fixed-bed reactor, the mixture of central filler hydrogenation catalyst and inert material, and deactivated catalyst;
(2) pass into the hydrogen of constant rate and liquid organic hydrogen storage carrier, mixture material is preheated rear feeding single hose fixed-bed reactor and carries out hydrogenation reaction;
(3) reaction product flows through condenser to gas-liquid separator, isolated liquid and hydrogenation products.
The process of described deactivated catalyst first leads to rare gas element to single hose fixed-bed reactor, and then pass into the mixed gas of hydrogen and rare gas element, wherein the mass content of hydrogen is 5% ~ 30%, is warming up to 300 DEG C, keeps 2 hours.
Described liquid organic hydrogen storage carrier comprises at least two kinds of different storage hydrogen components, and storage hydrogen component is unsaturated aromatic hydrocarbon or heterocycle unsaturated compound, and at least one storage hydrogen component is low melting component, and the fusing point of low melting component is lower than 80 DEG C.
Described mixture material is preheating to 120 ~ 250 DEG C.
The condition of described hydrogenation reaction is pressure 5 ~ 10MPa, and import and export hydrogen flowing quantity is balanced, and temperature of reactor is 120 ~ 250 DEG C, and the liquid starting material entering single hose fixed-bed reactor is 1000 ~ 2500:1 with hydrogen volume ratio.
Beneficial effect of the present invention:
(1) the present invention adopts continous way hydrogenation reaction system mainly to adopt single hose fixed-bed reactor, hydrogenation catalyst and inert material are filled in single hose fixed-bed reactor inside, inert material is filled in single hose fixed-bed reactor top and the bottom, the mixture of hydrogenation catalyst and inert material is filled at middle part, and the hydrogenation reaction being conducive to absorbing heat keeps steady temperature.
(2) in liquid feed line, all pipelines all devise the hot heating control system of companion, can carry out temperature control heating to the liquid flowing through system, and then change the viscosity of liquid storage hydrogen carrier, improve reaction effect.
(3) devise many cover gas mass flow controller systems in system, select the controller system of different range for different hydroconversion conditions.
(4) preheater design in system is the blended formula preheater of gas-liquid, i.e. gas and liquid mixing before preheating, then enters preheater, can realize limit heating edge blended, make hydrogen store up hydrogen carrier abundant premix before entering fixed bed tower reactor with liquid, improve reaction effect.
(5) adopt continous way hydrogenation reaction system, and adopt multi-stage type heating and temperature controlling device, effectively improve hydrogenation efficiency, and hydrogenation ratio is more than 90%.
Accompanying drawing explanation
Fig. 1 is the structural representation of specific embodiment of the invention continous way hydrogenation reaction system.
Embodiment
Below in conjunction with specific embodiments and the drawings, the present invention is further illustrated.
Liquid storage hydrogen carrier is a kind of hydrogen storage system that can present liquid state at normal temperatures and pressures, comprise at least two kinds of different storage hydrogen components, storage hydrogen component is unsaturated aromatic hydrocarbon or heterocycle unsaturated compound, and at least one storage hydrogen component is low melting component, the fusing point of low melting component is lower than 80 DEG C.
Further, storage hydrogen component is selected from heterocycle unsaturated compound, and the heteroatoms in heterocycle unsaturated compound is one or more in N, S, O and P.
Further, in heterocycle unsaturated compound heterocycle and aromatic ring add up to 1 ~ 20, heteroatomicly add up to 1 ~ 20.
Further, for the total mass of liquid hydrogen storage system, the massfraction of low melting component is 5% ~ 95%.
Liquid storage hydrogen carrier carries out hydrogenation chemistry reaction solution state hydrogen source material under the effect of hydrogenation catalyst, and liquid hydrogen source material carries out dehydrogenation chemical reaction and is reduced to liquid storage hydrogen carrier under the effect of dehydrogenation catalyst.
As shown in Figure 1, the continous way hydrogenation reaction system of liquid storage hydrogen carrier, comprising: feed system, preheater 1, fixed bed reaction tower reactor 2 and tripping device.Feed system is communicated with pre-heater inlet by pipeline, and preheater outlet is communicated with fixed bed reaction tower reactor entrance by pipeline, and the outlet of fixed bed reaction tower reactor is communicated with tripping device entrance by pipeline.
Feed system comprises the hydrogen container 3 of storage of hydrogen, and the container for storing liquid 4 of storing liquid storage hydrogen carrier.Container for storing liquid outer setting has temperature control unit, and temperature control unit comprises temperature controller TIC01, heating element TY01 and thermopair TE01.Temperature control unit makes container for storing liquid keep steady temperature.All pipelines between container for storing liquid and preheater are outside equipped with pipeline heating control system, and pipeline heating control system comprises temperature controller TIC03, heating element TY03 and thermopair TE03.Heating control system carries out temperature control heating to the pipeline entering infusion pump P and the pipeline of liquid stream warp carried by infusion pump, and then changes the viscosity of liquid storage hydrogen carrier, improves reaction effect.
Pipeline between hydrogen container and preheater is provided with stop valve GV1, filter F 1, pressure maintaining valve PSV1, moisture eliminator AC1 and two cover more parallels gas mass flow controller system.Be illustrated in figure 1 the gas mass flow controller system of 2 cover parallel connections, a set of gas mass flow controller system connects stop valve GV2, filter F 2, mass flow controller FT/FV1 and stop valve GV3 respectively successively, another set of gas mass flow controller system connects stop valve GV4, filter F 3, mass flow controller FT/FV2 and stop valve GV5 respectively successively, mass flow controller FT/FV1 and FT/FV2 has different flow control scopes, and reflection specifically needs to change hydrogen flowing quantity can switch different mass flow controllers.
Preheater Y is the blended formula preheater of gas-liquid, namely hydrogen stores up hydrogen carrier mix with liquid state before preheating, then enters preheater, can realize limit heating edge blended, make hydrogen store up hydrogen carrier abundant premix before entering fixed bed tower reactor with liquid, improve reaction effect.
Fixed bed reaction tower reactor is single hose fixed-bed reactor, and inside is filled with hydrogenation catalyst and inert material, and single hose fixed-bed reactor outer setting has one-part form heating and temperature controlling device, makes tower reactor inside keep steady temperature by circulating heat conduction oil.Inert material is filled in the upper and lower of single hose fixed-bed reactor, the mixture of central filler hydrogenation catalyst and inert material, and inert material accounts for 0% ~ 60% of mixture total mass.Hydrogenation catalyst is the load type metal catalyst containing Ru, Ni, and the particle diameter of catalyzer is 0.6 ~ 1.0mm.Inert material be in silicon-dioxide, aluminum oxide, gac one or both or more mixture, the particle diameter of inert material is 0.25 ~ 0.5mm.Catalyzer and inert material are all spherical.
In fixed bed reaction tower reactor, state storage hydrogen carrier carries out hydrogenation chemistry reaction solution state hydrogen source material under the effect of hydrogenation catalyst, and reaction product enters tripping device and is separated.
Tripping device comprises the condenser 5 and gas-liquid separator 6 that connect successively, and the liquid outlet of gas-liquid separator is provided with sampler 7, for measuring the hydrogenation ratio of product at any time.The air outlet of gas-liquid separator is provided with wet test meter 8, and for measuring unreacted hydrogen, unreacted hydrogen can recycle.
Liquid organic hydrogen storage carrier carries out the method for continous way hydrogenation:
(1) packed catalyst: the inert material Al of 43.3mL is filled in single hose fixed-bed reactor upper end
2o
3(Φ 0.25 ~ 0.5mm), 25cm is high; Central filler catalyzer 50%Ru/Al
2o
3(Φ 0.6 ~ 1.0mm) and 50% inert material Al
2o
3mixture, 80cm is high; 25mL inert material Al is filled in lower end
2o
3(Φ 3mm), 15cm is high.
(2) deactivated catalyst: driven out of by the air in reactor with nitrogen, passes into pure hydrogen to 4 ~ 5MPa, is warming up to 200 DEG C, keeps 2h.
(3) temperature setting gas-liquid preheater is 200 DEG C, and setting temperature of reaction kettle is 120 DEG C.
(4) tower reactor passes into hydrogen, arranges still pressure 7MPa, and makes import and export hydrogen balance.
(5) mixture of liquid organic hydrogen storage carrier carbazole and ethyl carbazole and hydrogen mixed and heat through preheater and be mixed into fixed bed reaction still with gas-liquid volume ratio 2000:1 and carry out hydrogenation reaction.
(6) from the liquid stream of reactor through condenser to gas-liquid separator, isolated liquid and hydrogenation products.
Detected result is: (A and B is respectively two kinds of moiety carbazoles and the ethyl carbazole of liquid organic hydrogen storage carrier, and add-on is that mol ratio 1:1, A12 and B12 represent product perhydro-carbazole and perhydro-ethyl carbazole).
Embodiment 1: when filling 140mL catalyzer in single hose fixed-bed reactor, air speed 0.3, gas-liquid volume ratio is 2000, infusion pump flow 0.7mL/min, hydrogen flowing quantity 1.4L/min, still pressure 7MPa.Reacted product is in table 1 (molar percentage).
Table 1
| A12/％ | B12/％ | A/％ | B/％ | Perhydro-/% |
| 47.320 | 49.655 | 1.010 | 2.015 | 96.975 |
Embodiment 2: when filling 70mL catalyzer in single hose fixed-bed reactor, air speed 0.5, gas-liquid volume ratio is 2000, infusion pump flow 0.58mL/min, hydrogen flowing quantity 1.16L/min, still pressure 7MPa.Reacted product is in table 2 (molar percentage).
Table 2
| A12/％ | B12/％ | A/％ | B/％ | Perhydro-/% |
| 46.183 | 48.986 | 1.410 | 3.421 | 95.169 |
Although the present invention with preferred embodiment openly as above; but embodiment is not for limiting the present invention, being anyly familiar with this those skilled in the art, without departing from the spirit and scope of the invention; can make various changes or retouch from working as, but same within protection scope of the present invention.What therefore protection scope of the present invention should define with the claims of the application is as the criterion.
Claims (15)
1. a continous way hydrogenation reaction system for liquid organic hydrogen storage carrier, is characterized in that comprising: feed system, preheater, fixed bed reaction tower reactor and tripping device;
Described feed system is communicated with pre-heater inlet by pipeline, and preheater outlet is communicated with fixed bed reaction tower reactor entrance by pipeline, and the outlet of fixed bed reaction tower reactor is communicated with tripping device entrance by pipeline;
Described preheater is the blended formula preheater of gas-liquid, liquid organic hydrogen storage carrier and the mixed heating of hydrogen;
Described fixed bed reaction tower reactor is single hose fixed-bed reactor, and inside is filled with hydrogenation catalyst and inert material, and single hose fixed-bed reactor outer setting responds device heating control system, carries out temperature control heating to reactor.
2. continous way hydrogenation reaction system according to claim 1, it is characterized in that: described inert material is filled in the upper and lower of single hose fixed-bed reactor, the mixture of central filler hydrogenation catalyst and inert material, inert material accounts for 0% ~ 60% of mixture total mass.
3. continous way hydrogenation reaction system according to claim 2, it is characterized in that: described hydrogenation catalyst is the bimetal that forms of precious metal and precious metal inclusive NAND precious metal or three metal load type catalysts, adopt polyol process to prepare many metal load type catalysts method and prepare hydrogenation catalyst nano particle, again obtained nano core-shell particulate load is deposited to porous support to be prepared from the surface, precious metal is Pd, Pt, Ru, Rh, base metal is Ni, Co, Fe, and porous support is porous SiO
2, Al
2o
3or activated carbon, the particle diameter of catalyzer is 0.6 ~ 1.0mm.
4. conventional load shaped metal catalyzer according to claim 3, is characterized in that: described inert material is at least one in silicon-dioxide, aluminum oxide, gac, the particle diameter of inert material is 0.25 ~ 0.5mm.
5. continous way hydrogenation reaction system according to claim 4, it is characterized in that: described feed system comprises the hydrogen container of storage of hydrogen and the container for storing liquid of storing liquid storage hydrogen carrier, described container for storing liquid outer setting has temperature control unit, makes container for storing liquid keep steady temperature.
6. continous way hydrogenation reaction system according to claim 5, is characterized in that: the gas mass flow controller system pipeline between described hydrogen container and preheater being provided with stop valve, strainer, pressure maintaining valve, moisture eliminator and two cover more parallels; Described gas mass flow controller system of often overlapping comprises the mass flow controller that 1 has different flow span of control.
7. continous way hydrogenation reaction system according to claim 6, is characterized in that: all pipelines between described container for storing liquid and preheater are outside equipped with pipeline heating control system, carry out temperature control heating to the liquid flowed through.
8. continous way hydrogenation reaction system according to claim 7, is characterized in that: described reactor heating control system is one-part form or Segmented heating temperature regulating device, carries out heated for controlling temperature by circulating heat conduction medium to reactor.
9. continous way hydrogenation reaction system according to claim 8, is characterized in that: described tripping device comprises the condenser and gas-liquid separator that connect successively.
10. continous way hydrogenation reaction system according to claim 9, is characterized in that: the liquid outlet of described gas-liquid separator is provided with sampler, and air outlet is provided with wet test meter.
11. 1 kinds adopt reactive system liquid towards organic hydrogen storage carrier described in claim 10 to carry out the method for continous way hydrogenation, it is characterized in that comprising the following steps:
(1) inert material is filled in the upper and lower of single hose fixed-bed reactor, the mixture of central filler hydrogenation catalyst and inert material, and deactivated catalyst;
(2) pass into the hydrogen of constant rate and liquid organic hydrogen storage carrier, mixture material is preheated rear feeding single hose fixed-bed reactor and carries out hydrogenation reaction;
(3) reaction product flows through condenser to gas-liquid separator, isolated liquid and hydrogenation products.
12. methods according to claim 11, it is characterized in that: the process of described deactivated catalyst first leads to rare gas element to single hose fixed-bed reactor, then the mixed gas of hydrogen and rare gas element is passed into, wherein the mass content of hydrogen is 5% ~ 30%, be warming up to 300 DEG C, keep 2 hours.
13. methods according to claim 11, it is characterized in that: described liquid organic hydrogen storage carrier comprises at least two kinds of different storage hydrogen components, storage hydrogen component is unsaturated aromatic hydrocarbon or heterocycle unsaturated compound, and at least one storage hydrogen component is low melting component, the fusing point of low melting component is lower than 80 DEG C.
14. methods according to claim 11, is characterized in that: described mixture material is preheating to 120 ~ 250 DEG C.
15. methods according to claim 11, it is characterized in that: the condition of described hydrogenation reaction is pressure 5 ~ 10MPa, and import and export hydrogen flowing quantity is balanced, temperature of reactor is 120 ~ 250 DEG C, and the liquid starting material entering single hose fixed-bed reactor is 1000 ~ 2500:1 with hydrogen volume ratio.
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Address after: 430040, Wuhan, Hubei, East and West Lake Road, general street street, North and South Silver pond, green road south, Wuhan Wu Jian Machinery Construction Company, the office building on the third floor Patentee after: Wuhan hydrogen energy Co., Ltd. Address before: 215634 room 807, ChangJiang Building, Zhangjiagang Free Trade Zone, Jiangsu, Suzhou Patentee before: JIANGSU QINGYANG ENERGY CO., LTD. |