CN114604828A - Hydrogen concentration device and process by hydrate method - Google Patents
Hydrogen concentration device and process by hydrate method Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000001257 hydrogen Substances 0.000 title claims abstract description 90
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 56
- 230000008569 process Effects 0.000 title claims abstract description 29
- 238000003795 desorption Methods 0.000 claims abstract description 73
- 239000007789 gas Substances 0.000 claims abstract description 46
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 13
- 239000012224 working solution Substances 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 150000004677 hydrates Chemical class 0.000 claims abstract description 5
- 238000005057 refrigeration Methods 0.000 claims abstract description 4
- 239000012530 fluid Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 230000002195 synergetic effect Effects 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000006703 hydration reaction Methods 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000012267 brine Substances 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 26
- 239000012528 membrane Substances 0.000 description 19
- 238000001179 sorption measurement Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003384 small molecules Chemical group 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
-
- 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
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/002—Component parts of these vessels not mentioned in B01J3/004, B01J3/006, B01J3/02 - B01J3/08; Measures taken in conjunction with the process to be carried out, e.g. safety measures
-
- 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
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0064—Hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0068—Organic compounds
- C01B2210/007—Hydrocarbons
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- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
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- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention provides a hydrate method hydrogen concentration device and a process, wherein the device comprises a hydrate generation part consisting of a hydrogen heat exchanger, a Venturi jet mixer, a time delay reactor, a hydrate separator and a low-temperature circulating pump, and a hydrate decomposition part consisting of a desorption heat exchanger, a desorption heater and a high-pressure circulating pump; an outlet at the top of the hydrate separator is communicated to a shell pass inlet of the hydrogen heat exchanger, and the shell pass outlet of the hydrogen heat exchanger is used for discharging purified hydrogen; the hydrate separator is internally provided with a hydrate collecting device for collecting hydrates, the hydrate collecting device is communicated to the desorption heat exchanger, the desorption heat exchanger is communicated to the desorption heater, and an outlet at the top of the shell side of the desorption heater is used for discharging desorbed light hydrocarbon gas. The process comprises four steps of working solution preparation, refrigeration system operation, hydrate generation and hydrate decomposition. The technical scheme provided by the invention has the advantages that the hydrogen pressure is reduced, and the technical and economic indexes for low-concentration hydrogen concentration are better.
Description
Technical Field
The invention relates to the technical field of energy and chemical engineering, in particular to a device and a process for concentrating hydrogen by a hydrate method.
Background
Hydrogen is an important chemical raw material and energy, is widely applied to various fields of chemical industry, synthetic ammonia, new energy and the like, and is considered as an ideal clean and high-energy fuel. As a high-energy fuel, liquid hydrogen has been applied to the fields of aerospace and the like; as a chemical power source, a hydrogen-oxygen fuel cell has been used, for example, as a driving power source of an automobile or the like.
The technology for separating hydrogen-containing gas mainly comprises PSA pressure swing adsorption, membrane separation and the like, and the purification of hydrogen by a hydrate method is a new technology, and various technical descriptions are compared as follows.
Pressure Swing Adsorption (PSA) is widely used in various gas separation applications, and is based on the adsorption of impurity gases under high pressure, the concentration of unadsorbed gases, and then the desorption regeneration of the adsorbent under low pressure by depressurization. Hydrogen is not easy to be adsorbed and can directly pass through, but impurity gas molecules such as alkane and the like are easy to be adsorbed, so that the purity of the hydrogen is improved, and the pressure swing adsorption technology is mainly adopted for purifying the hydrogen in the industries such as petroleum refining, chemical fertilizers and the like.
The pressure swing adsorption process has the advantages that the separation effect and the concentration effect are excellent, and the purity of the hydrogen after the PSA separation can reach 99 to 99.99 percent. And the process system is mature, the adsorbent can be recycled, the gas to be separated with different impurity contents has better adaptability, and pretreatment is not needed unless the impurity gas content influencing the adsorption process is particularly high. The adsorptive separation effect of PSA is more pronounced when the hydrogen content is lower. Meanwhile, the operation cost of the PSA process is far lower than that of other hydrogen separation and concentration methods, and the PSA process is suitable for large and medium petrochemical enterprises.
The pressure swing adsorption has the disadvantages that the first point equipment has overhigh one-time investment cost, a plurality of towers are required for jointly completing the separation process in the pressure swing adsorption process, and the economic efficiency is lower when the treatment scale of the raw material gas is smaller; the overall recovery of hydrogen at the second point is low, typically only 60% to 80%. The third point is that the pressure swing adsorption adsorbent is easy to deactivate, raw gas needs to be pretreated, components harmful to the adsorbent are removed, and once the adsorbent is deactivated, the replacement is time-consuming. The fourth point is that the valve group is frequently opened and closed in the pressure swing adsorption process, the failure rate of the valve is high, and the product quality and the production safety are influenced.
The membrane separation method utilizes the selective semipermeable membrane to have the characteristics of selective permeation and diffusion for specific gas components. The driving force of the separation is the pressure difference existing at the two sides of the membrane, and the components at the raw material side selectively permeate the semipermeable membrane to achieve the purpose of separating and purifying certain key components. Due to the particularity of the structure of the semi-permeable membrane, the transfer rates of different components are different, the gas component with the high transfer rate passes through the separation membrane, and the gas component with the low transfer rate can only be retained on the other side of the separation membrane. Wherein hydrogen gas is separated from the gas mixture by preferentially passing through the semipermeable membrane due to its small molecular size and having a faster transport rate.
The membrane separation technology has the advantages of simple and feasible process operation, low process complexity and easy control of device investment and energy consumption cost, thereby becoming a hotspot in research field and application. However, the membrane separation method itself has inevitable disadvantages:
(1) the separation membrane has high requirement on raw material gas and is easy to be destroyed and deactivated by impurity gas. Therefore, the feed gas needs to be pretreated before membrane separation to remove impurity gases damaging the membrane, and the separation membrane needs to be cleaned, inspected and replaced regularly, which results in higher later operation cost.
(2) The separation membrane has low processing capacity, and the separation membrane per se has contradictory contradiction between permeation flux and permeation selectivity, which directly results in contradiction between hydrogen yield and hydrogen concentration, namely, the permeation flux of the porous membrane is increased, and the permeation selectivity is inevitably reduced, so that the concentration of H2 after separation is reduced. The amount of gas to be treated can be increased by increasing the area of the separation membrane to add additional investment without lowering the recovery concentration of H2.
The hydrate method is that gas small molecules and water form cage-shaped hydrate crystal lattice under certain pressure and temperature condition, and the gasThe small molecules are absorbed into the cage-shaped hydrated crystal lattice as object molecules, and the object gas small molecules tend to be stable after filling the crystal lattice. Different gas molecules can form cage-shaped lattices with different structures with water due to different structures and sizes, so that different gases have different hydrate forming difficulty. The gas which is easy to generate hydrate is preferentially generated to enter the hydrate phase, thereby realizing the separation of the gas mixture. Due to H2The molecule is too small to form stable hydrate under general conditions, and the gas molecules such as alkane and alkene and the impurity gas such as hydrogen sulfide can be enveloped by the cage structure to form stable hydrate, so the hydrate separation method is particularly suitable for separating hydrogen from other impurity gases.
Compared with the traditional mixed gas separation method, the method for separating the gas from the hydrate has the advantages of low process complexity, relatively mild operation conditions, wide application range and the like. The hydrate separation technology does not need to pretreat the raw materials, and heavy components in the tail gas have a promoting effect on the generation of the hydrate. In particular, the hydrogen sulfide component is an excellent thermodynamic accelerator for hydrates. In addition, the working fluid in the separation process is mainly water, and the common substances have no toxic action on the water, so that the working fluid does not have the problem of failure. Finally, because the hydration reaction is concentrated by reaction under high pressure, the pressure drop of the concentrated hydrogen is small and can be almost ignored.
Hydrogen occupies an increasingly important position in a new energy structure in the future, and a hydrate method is inevitably applied more and more as a new hydrogen purification technology.
Disclosure of Invention
According to the problems of high investment, large occupied area, complex process flow and the like of the hydrogen concentration device, the hydrate method hydrogen concentration device and the process are provided.
The technical means adopted by the invention are as follows:
a hydrate method hydrogen concentration device comprises a hydrate generation part consisting of a hydrogen heat exchanger, a Venturi jet mixer, a time delay reactor, a hydrate separator and a low-temperature circulating pump, and a hydrate decomposition part consisting of a desorption heat exchanger, a desorption heater and a high-pressure circulating pump;
the time delay reactor is a multi-tube pass heat exchanger, the tube pass of the time delay reactor is used for circulating a hydrogen-water mixture, and the shell pass of the time delay reactor is used for circulating refrigerating fluid; a synergistic spray head is arranged in the hydrate separator; the tube pass of the hydrogen heat exchanger is communicated with a bypass inlet of the Venturi jet mixer, a straight-through inlet of the Venturi jet mixer is communicated to an outlet of the low-temperature circulating pump, a straight-through outlet of the Venturi jet mixer is communicated to a tube pass inlet of the delay reactor, and a tube pass outlet of the delay reactor is communicated to the synergistic sprayer; an outlet at the top of the hydrate separator is communicated to a shell pass inlet of the hydrogen heat exchanger, and a shell pass outlet of the hydrogen heat exchanger is used for discharging purified hydrogen; an outlet at the bottom of the hydrate separator is communicated to an inlet of the low-temperature circulating pump;
the hydrate separator is internally provided with a hydrate collecting device used for collecting hydrates, the hydrate collecting device is communicated to an inlet at the bottom of a shell pass of the desorption heat exchanger, two outlets at the top of the shell pass of the desorption heat exchanger are communicated to a shell pass of the desorption heater, an outlet at the top of the shell pass of the desorption heater is used for discharging desorbed light hydrocarbon gas, an outlet at the bottom of the shell pass of the desorption heater is communicated to an inlet of a tube pass of the desorption heat exchanger, an outlet of the tube pass of the desorption heat exchanger is connected to an inlet of the high-pressure circulating pump through a filter, and an outlet of the high-pressure circulating pump is communicated to a straight-through inlet of the venturi jet mixer.
Further, the venturi jet mixer is a liquid-carrying-gas mixer; the time delay reactor is a U-shaped tube heat exchanger with 4-6 tube passes.
Further, the hydrate collection device includes a toothed weir structure.
Further, the desorption heat exchanger is a U-shaped tube heat exchanger with a liquid bag; the desorption heater is a kettle type U-shaped tube heat exchanger with a partition plate arranged inside, an air bag is arranged at the top of the desorption heater, and a defoaming net is arranged in the air bag.
The invention also provides a hydrate method hydrogen concentration process, which adopts the hydrate method hydrogen concentration device and specifically comprises the following steps:
step 1): preparing a working solution: adding a solvent T and an active agent S into the factory softened water, wherein the concentration of the solvent T is 20-30 wt%, the concentration of the active agent S is 100-1000mg/L, and introducing the prepared working solution into a Venturi jet mixer;
step 2): operation of a refrigeration system: starting a refrigerating machine set to refrigerate and cool the shell pass of the time-delay reactor, and removing reaction heat when hydration reaction occurs in the time-delay reactor, wherein refrigerating fluid is ammonia cold or frozen brine;
step 3): hydrate generation: hydrogen containing impurities such as light hydrocarbon and the like passes through a venturi jet mixer on the tube side of a hydrogen heat exchanger, is mixed with working liquid and then is introduced into the tube side of a delay reactor for hydration reaction, and then is introduced into a hydrate separator through a synergistic nozzle, the light hydrocarbon and the working liquid are combined in the hydrate separator to generate hydrate, the hydrate is slightly lighter than the working liquid, the hydrate floating on the water surface is collected through a hydrate collector and then enters the shell side of a desorption heat exchanger of a hydrate decomposition part, the working liquid is introduced into a low-temperature circulating pump through an outlet at the bottom of the hydrate separator and returns to the venturi jet mixer to enter the next cycle, the hydrogen enters the hydrogen heat exchanger through an outlet at the top of the hydrate separator, and the hydrogen is discharged out of a device through a shell side outlet of the hydrogen heat exchanger;
step 4): decomposition of hydrate: the hydrate enters the shell side of the desorption heater through the shell side of the desorption heat exchanger, is heated and decomposed under the condition of low pressure, releases light hydrocarbon gas, the light hydrocarbon is discharged from an outlet at the top of the shell side of the desorption heater, the working fluid returns to the tube side of the desorption heat exchanger through an outlet at the bottom of the shell side of the desorption heater, flows out from an outlet at the tube side of the desorption heat exchanger, and then sequentially passes through a filter and a high-pressure circulating pump to return to a Venturi jet mixer to enter the next round of circulation.
Further, in the step 1), the temperature of the working fluid is maintained at 40-60 ℃, and the suspended substance is less than 20 mg/L.
Furthermore, the Venturi jet mixer pressurizes the hydrogen by 0.5kPa to 5kPa, so that the pressure of the hydrogen reaches 2.0MPaG to 20.0 MPaG.
Further, the reaction time of the time delay reactor is 20-300 s, the reaction temperature is 3-10 ℃, and the temperature of refrigerating fluid is 0-5 ℃; the low-temperature circulating pump has a lift of 15-50 m and a circulating liquid-gas ratio of 1: 50-200; the tube pass of the desorption heater is heated by circulating hot water at 35-40 ℃; the shell side pressure of the desorption heater is controlled to be 0.3 MPag-2.2 MPag, and the temperature is controlled to be 15-22 ℃; the lift of the high-pressure circulating pump is 150-2000 m, and the circulating liquid-gas ratio is 1: 50-200.
Compared with the prior art, the invention has the following advantages:
the hydrogen concentration device and the process which adopt the hydrate formation from the light hydrocarbon and the water under the conditions of low temperature and high pressure and the hydrate decomposition under the conditions of high temperature and low pressure have the following beneficial effects:
(1) the investment is low, the occupied area is small, and the hydrogen pressure is reduced;
(2) the capability of removing multiple impurities such as light hydrocarbon, hydrogen sulfide and the like is realized;
(3) is suitable for various raw materials and does not need raw material pretreatment.
Based on the reasons, the invention can be widely popularized in the field of energy and chemical engineering.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of a hydrate hydrogen concentration device.
In the figure: 1. a hydrogen gas heat exchanger; 2. a venturi jet mixer; 3. a time delay reactor; 4. a hydrate separator; 5. a synergistic sprayer; 6. a hydrate collecting device; 7. a low temperature circulation pump; 8. a desorption heat exchanger; 9. a desorption heater; 11. a shell-side top outlet; 12. a filter; 13. a high pressure circulation pump.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise. Meanwhile, it should be understood that the sizes of the respective portions shown in the drawings are not drawn in an actual proportional relationship for the convenience of description. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. Any specific values in all examples shown and discussed herein are to be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
In the description of the present invention, it is to be understood that the directions or positional relationships indicated by the directional terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal" and "top, bottom", etc., are generally based on the directions or positional relationships shown in the drawings for the convenience of description and simplicity of description, and that these directional terms, unless otherwise specified, do not indicate and imply that the device or element so referred to must have a particular orientation or be constructed and operated in a particular orientation, and therefore should not be considered as limiting the scope of the invention: the terms "inner and outer" refer to the inner and outer relative to the profile of the respective component itself.
Spatially relative terms, such as "above … …," "above … …," "above … … surface," "above," and the like, may be used herein for ease of description to describe one device or feature's spatial relationship to another device or feature as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in the figures is turned over, devices described as "above" or "on" other devices or configurations would then be oriented "below" or "under" the other devices or configurations. Thus, the exemplary term "above … …" can include both an orientation of "above … …" and "below … …". The device may be otherwise variously oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
It should be noted that the terms "first", "second", and the like are used to define the components, and are only used for convenience of distinguishing the corresponding components, and the terms have no special meanings unless otherwise stated, and therefore, the scope of the present invention should not be construed as being limited.
Example 1
As shown in fig. 1, the invention provides a hydrate method hydrogen concentration device, which comprises a hydrate generation part consisting of a hydrogen heat exchanger 1, a venturi jet mixer 2, a time delay reactor 3, a hydrate separator 4 and a low-temperature circulating pump 7, and a hydrate decomposition part consisting of a desorption heat exchanger 8, a desorption heater 9 and a high-pressure circulating pump 13;
the time delay reactor 3 is a multi-tube pass heat exchanger, the tube pass of the time delay reactor 3 is used for circulating a hydrogen-water mixture, and the shell pass of the time delay reactor 3 is used for circulating refrigerating fluid; a synergistic spray head 5 is arranged in the hydrate separator 4; the tube side of the hydrogen heat exchanger 1 is communicated with a bypass inlet of the Venturi jet mixer 2, a straight-through inlet of the Venturi jet mixer 2 is communicated to an outlet of the low-temperature circulating pump 7, a straight-through outlet of the Venturi jet mixer 2 is communicated to a tube side inlet of the delay reactor 3, and a tube side outlet of the delay reactor 3 is communicated to the synergistic nozzle 5; an outlet at the top of the hydrate separator 4 is communicated to a shell pass inlet of the hydrogen heat exchanger 1, and a shell pass outlet of the hydrogen heat exchanger 1 is used for discharging purified hydrogen; an outlet at the bottom of the hydrate separator 4 is communicated to an inlet of the low-temperature circulating pump 7;
the hydrate separator 4 is internally provided with a hydrate collecting device 6 for collecting hydrates, the hydrate collecting device 6 is communicated to a shell pass bottom inlet of the desorption heat exchanger 8, two outlets at the top of the shell pass of the desorption heat exchanger 8 are communicated to a shell pass of the desorption heater 9, an outlet at the top of the shell pass of the desorption heater 9 is used for discharging desorption light hydrocarbon gas, an outlet at the bottom of the shell pass of the desorption heater 9 is communicated to a tube pass inlet of the desorption heat exchanger 8, a tube pass outlet of the desorption heat exchanger 8 is connected to an inlet of the high-pressure circulating pump 13 through a filter 12, and an outlet of the high-pressure circulating pump 13 is communicated to a straight-through inlet of the venturi jet mixer 2.
Further, the venturi jet mixer 2 is a liquid-gas mixer; the time delay reactor 3 is a U-shaped tube heat exchanger with 4-6 tube passes.
Further, the hydrate collecting device 6 comprises a toothed weir structure.
Further, the desorption heat exchanger 8 is a U-shaped tube heat exchanger with a liquid bag; the desorption heater 9 is a kettle type U-shaped tube heat exchanger with a partition plate arranged inside, an air bag is arranged at the top of the desorption heater 9, and a defoaming net is arranged in the air bag.
The invention also provides a hydrate method hydrogen concentration process, which adopts the principle that light hydrocarbon and water are hydrated into hydrate under the conditions of low temperature and high pressure and hydrate is decomposed under the conditions of high temperature and low pressure to realize the separation of the light hydrocarbon and the hydrogen, and adopts the hydrate method hydrogen concentration device, and the process specifically comprises the following steps:
step 1): preparing a working solution: adding a solvent T and an active agent S into factory softened water, wherein the concentration of the solvent T is 20-30 wt%, the concentration of the active agent S is 100-1000mg/L, and introducing the prepared working solution into a Venturi jet mixer 2;
step 2): the operation of a refrigeration system: starting a refrigerating machine set to refrigerate and cool the shell pass of the delay reactor 3 and remove reaction heat when hydration reaction occurs in the delay reactor 3, wherein the refrigerating fluid CWS is ammonia cold or frozen brine;
step 3): hydrate generation: hydrogen containing impurities such as light hydrocarbon and the like passes through a venturi jet mixer 2 on the tube side of a hydrogen heat exchanger 1, is mixed with working fluid and then is introduced into the tube side of a delay reactor 3 for hydration reaction, and then is introduced into a hydrate separator 4 through a synergistic nozzle 5, the light hydrocarbon and the working fluid are combined to generate hydrate in the hydrate separator 4, the hydrate is slightly lighter than the working fluid, the hydrate floating on the water surface is collected through a hydrate collector 6 and then enters the shell side of a desorption heat exchanger 8 of a hydrate decomposition part, the working fluid is introduced into a low-temperature circulating pump 7 through an outlet at the bottom of the hydrate separator and returns to the venturi jet mixer 2 to enter the next cycle, the hydrogen enters the hydrogen heat exchanger 1 through an outlet at the top of the hydrate separator 4, and is discharged from a device through a shell side outlet of the hydrogen heat exchanger 1;
step 4): decomposition of hydrate: the hydrate enters the shell pass of the desorption heater 9 through the shell pass of the desorption heat exchanger 8, is heated and decomposed under the low-pressure condition, releases light hydrocarbon gas, the light hydrocarbon is discharged from an outlet at the top of the shell pass of the desorption heater 9, the working solution returns to the tube pass of the desorption heat exchanger 8 through an outlet at the bottom of the shell pass of the desorption heater 9, flows out from an outlet at the tube pass of the desorption heat exchanger 8, then returns to the Venturi jet mixer 2 through a filter 12 and a high-pressure circulating pump 13 in sequence, and enters the next round of circulation.
Further, in the step 1), the temperature of the working fluid is maintained at 40-60 ℃, and the suspended substance is less than 20 mg/L.
Further, the venturi jet mixer 2 is used for uniformly mixing the hydrogen and the working fluid, and pressurizing the hydrogen by 0.5 kPa-5 kPa to enable the pressure of the hydrogen to reach 2.0 MPaG-20.0 MPaG.
Further, the reaction time of the time delay reactor 3 is 20-300 s, the reaction temperature is 3-10 ℃, and the temperature of the refrigerating fluid is 0-5 ℃; the low-temperature circulating pump 7 has a lift of 15-50 m and a circulating liquid-gas ratio of 1: 50-200; the tube pass of the desorption heater 9 is heated by circulating hot water at 35-40 ℃; the shell side pressure of the desorption heater 9 is controlled to be 0.3 MPag-2.2 MPag, and the temperature is controlled to be 15-22 ℃; the lift of the high-pressure circulating pump 13 is 150-2000 m, and the circulating liquid-gas ratio is 1: 50-200.
At 5000Nm3The hydrogen purification is carried out by respectively adopting the device and the process of the invention and PSA technology, and the technical and economic indexes of the two processes are shown in Table 1.
TABLE 1 comparison of the economic index of the invention with that of PSA technology
As can be seen from Table 1, the device and the process provided by the invention have the advantages of low investment, small occupied area, reduced hydrogen pressure and better technical and economic indexes for low-concentration hydrogen concentration.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A hydrate method hydrogen concentration device is characterized by comprising a hydrate generation part and a hydrate decomposition part, wherein the hydrate generation part consists of a hydrogen heat exchanger, a Venturi jet mixer, a time delay reactor, a hydrate separator and a low-temperature circulating pump, and the hydrate decomposition part consists of a desorption heat exchanger, a desorption heater and a high-pressure circulating pump;
the time delay reactor is a multi-tube pass heat exchanger, the tube pass of the time delay reactor is used for circulating a hydrogen-water mixture, and the shell pass of the time delay reactor is used for circulating refrigerating fluid; a synergistic spray head is arranged in the hydrate separator; the tube side of the hydrogen heat exchanger is communicated with a bypass inlet of the Venturi jet mixer, a straight-through inlet of the Venturi jet mixer is communicated to an outlet of the low-temperature circulating pump, a straight-through outlet of the Venturi jet mixer is communicated to a tube side inlet of the delay reactor, and a tube side outlet of the delay reactor is communicated to the synergistic sprayer; an outlet at the top of the hydrate separator is communicated to a shell pass inlet of the hydrogen heat exchanger, and a shell pass outlet of the hydrogen heat exchanger is used for discharging purified hydrogen; an outlet at the bottom of the hydrate separator is communicated to an inlet of the low-temperature circulating pump;
the hydrate separator is internally provided with a hydrate collecting device used for collecting hydrates, the hydrate collecting device is communicated to an inlet at the bottom of a shell pass of the desorption heat exchanger, two outlets at the top of the shell pass of the desorption heat exchanger are communicated to a shell pass of the desorption heater, an outlet at the top of the shell pass of the desorption heater is used for discharging desorbed light hydrocarbon gas, an outlet at the bottom of the shell pass of the desorption heater is communicated to an inlet of a tube pass of the desorption heat exchanger, an outlet of the tube pass of the desorption heat exchanger is connected to an inlet of the high-pressure circulating pump through a filter, and an outlet of the high-pressure circulating pump is communicated to a straight-through inlet of the venturi jet mixer.
2. The hydrate method hydrogen concentration device according to claim 1, wherein the venturi jet mixer is a liquid-gas mixer; the time delay reactor is a U-shaped tube heat exchanger with 4-6 tube passes.
3. The hydrate process hydrogen concentration apparatus according to claim 1, wherein the hydrate collecting device comprises a toothed weir structure.
4. The hydrate method hydrogen concentration device according to claim 1, wherein the desorption heat exchanger is a U-shaped tube heat exchanger with a liquid bag; the desorption heater is a kettle type U-shaped tube heat exchanger with a partition plate arranged inside, an air bag is arranged at the top of the desorption heater, and a defoaming net is arranged in the air bag.
5. A hydrate method hydrogen concentration process is characterized in that the hydrate method hydrogen concentration device in claim 1 is adopted, and the hydrate method hydrogen concentration process specifically comprises the following steps:
step 1): preparing a working solution: adding a solvent T and an active agent S into factory softened water, wherein the concentration of the solvent T is 20-30 wt%, the concentration of the active agent S is 100-1000mg/L, and introducing the prepared working solution into a Venturi jet mixer;
step 2): the operation of a refrigeration system: starting a refrigerating machine set to refrigerate and cool the shell pass of the time-delay reactor, and removing reaction heat when hydration reaction occurs in the time-delay reactor, wherein refrigerating fluid is ammonia cold or frozen brine;
step 3): hydrate generation: hydrogen containing impurities such as light hydrocarbon and the like passes through a tube pass Venturi jet mixer of a hydrogen heat exchanger, is mixed with working liquid and then is introduced into a tube pass of a time delay reactor for hydration reaction, and then is introduced into a hydrate separator through a synergistic nozzle, the light hydrocarbon and the working liquid are combined to generate hydrate in the hydrate separator, the hydrate is slightly lighter than the working liquid, the hydrate floating on the water surface is collected by a hydrate collector and then enters a shell pass of a desorption heat exchanger of a hydrate decomposition part, the working liquid is introduced into a low-temperature circulating pump through an outlet at the bottom of the hydrate separator and returns to the Venturi jet mixer to enter the next round of circulation, the hydrogen enters the hydrogen heat exchanger through an outlet at the top of the hydrate separator, and is discharged out of a device through a shell pass outlet of the hydrogen heat exchanger;
step 4): decomposition of hydrate: the hydrate enters the shell side of the desorption heater through the shell side of the desorption heat exchanger, is heated and decomposed under the condition of low pressure, releases light hydrocarbon gas, the light hydrocarbon is discharged from an outlet at the top of the shell side of the desorption heater, the working fluid returns to the tube side of the desorption heat exchanger through an outlet at the bottom of the shell side of the desorption heater, flows out from an outlet at the tube side of the desorption heat exchanger, and then sequentially passes through a filter and a high-pressure circulating pump to return to a Venturi jet mixer to enter the next round of circulation.
6. The hydrate method hydrogen concentration process according to claim 5, wherein in the step 1), the temperature of the working solution is maintained at 40-60 ℃, and the suspended matter is less than 20 mg/L.
7. The hydrate method hydrogen concentration process according to claim 5, wherein the Venturi jet mixer pressurizes the hydrogen by 0.5kPa to 5kPa, so that the pressure of the hydrogen reaches 2.0MPaG to 20.0 MPaG.
8. The hydrate method hydrogen concentration process according to claim 5, wherein the reaction time of the time delay reactor is 20-300 s, the reaction temperature is 3-10 ℃, and the temperature of the refrigerating fluid is 0-5 ℃; the low-temperature circulating pump has a lift of 15-50 m and a circulating liquid-gas ratio of 1: 50-200; the tube pass of the desorption heater is heated by circulating hot water at 35-40 ℃; the shell side pressure of the desorption heater is controlled to be 0.3 MPag-2.2 MPag, and the temperature is controlled to be 15-22 ℃; the lift of the high-pressure circulating pump is 150-2000 m, and the circulating liquid-gas ratio is 1: 50-200.
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