CN105582887B - A kind of alkali halide expanded graphite solidification mixed adsorbent - Google Patents
A kind of alkali halide expanded graphite solidification mixed adsorbent Download PDFInfo
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- CN105582887B CN105582887B CN201511031140.6A CN201511031140A CN105582887B CN 105582887 B CN105582887 B CN 105582887B CN 201511031140 A CN201511031140 A CN 201511031140A CN 105582887 B CN105582887 B CN 105582887B
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
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Abstract
The present invention provides a kind of alkali halide expanded graphite solidification mixed adsorbent, the mass ratio of alkali halide and expanded graphite is 1:1~8:1, pressed density is 300~900 kg/m3, the radial mass transfer and heat-transfer path of adsorbent are 10~100mm.Alkali halide is dissolved in solvent first, expanded graphite is then added and stirs evenly, then through drying, compacting, obtains solidification mixed adsorbent.Solidification mixed adsorbent in the present invention can solve mass transfer problem of alkali halide adsorbent during adsorption and desorption caused by expanding with caking, while can increase substantially heat conductivility, and can increase substantially storage ammonia efficiency.
Description
Technical field
The present invention relates to absorbent fields more particularly to a kind of alkali halide expanded graphite to cure mixed adsorbent.
Background technology
Oxynitrides (NOx) it is a kind of compound being made of two kinds of nitrogen, oxygen elements, it common are nitric oxide
(NO), nitrogen dioxide (NO2), nitrous oxide (N2O), dinitrogen pentoxide (N2O5) etc..In these compounds, in addition to dioxy
Change other than nitrogen, other oxynitrides are all extremely unstable, finally all become nitrogen dioxide.Nitrogen dioxide is to form photochemistry cigarette
In addition one major reason of mist and acid rain can cause bronchitis or pulmonary edema by human body sucking respiratory tract.As people give birth to
The flat increasingly raising of running water, per capita car owning amount increase year by year, especially in some big cities, vehicle exhaust has become shadow
Ring one of the major pollutants of air quality.
Currently, selective catalytic reduction (SCR) is that vehicle exhaust oxynitride discharge amount is maximally efficient, technology for control
On also more mature method.The operation principle of SCR is reducing agent (such as ammonia, liquefied ammonia, urea) choosing under the effect of the catalyst
Selecting property with the NO in tail gasxReact and generate the N of clean environment firendly2And H2O.And urea tank is the most commonly used reducing agent storage
Device provides reproducibility ammonia and NO by heating urea tankxReaction, to control NOxDischarge capacity.But urea tank is in reality
It is had the following disadvantages during use：One, urea usage amount is larger, general urea usage amount be fuel consumption 3%~
5%；Two, the place filled is mismatched with filling demand；Three, urea easily crystallizes, under the efficiency and stability that lead to urea tank body
Drop.
Therefore provide it is a kind of it is effective, storage is convenient, the ammonia storage method that can be recycled has become this field
The primary technical problem of technical staff's urgent need to resolve.It is found being retrieved to existing technical literature, it can using bulk metal chloride
To adsorb An Qi [The characterization of adsorption of Wang Liwei, Wang Ruzhu, Wu Jingyi, wangkai Fullerenes chlorides are studied and apply in refrigeration
E volumes of Chinese science technology：Technological sciences, 2004,34 (3)：268-279], but this single, pure alkali metal chloride exists
Apparent expansion and caking phenomenon can be deposited in adsorption process, can cause being greatly lowered for mass-transfer performance in this way, cause alkali golden
Belong to chloride after having carried out multiple desorption-absorption, larger decaying occurs in desorption-adsorption rate.
Invention content
The first object of the present invention is to provide a kind of alkali halide expanded graphite solidification mixed adsorbent, existing to solve
There is the drawbacks described above in technology.
The second object of the present invention is to provide the preparation of above-mentioned alkali halide expanded graphite solidification mixed adsorbent
Method, to solve drawbacks described above in the prior art.
The third object of the present invention is to provide the absorption of above-mentioned alkali halide expanded graphite solidification mixed adsorbent
Device, to solve drawbacks described above in the prior art.
Technical scheme is as follows：
A kind of alkali halide expanded graphite solidification mixed adsorbent, the mass ratio of alkali halide and expanded graphite
It is 1:1~8:1, pressed density is 300~900kg/m3, the radial mass transfer and heat-transfer path of adsorbent are 10~100mm.
Further preferably, above-mentioned alkali halide expanded graphite cures mixed adsorbent, the alkali halide
For strontium chloride, the mass ratio of strontium chloride and expanded graphite is 6:1, pressed density 700kg/m3, the radial mass transfer of adsorbent and
Heat-transfer path is 76mm.Can also be preferably that above-mentioned alkali halide expanded graphite cures mixed adsorbent, alkali gold
Category halide is calcium chloride, and the mass ratio of calcium chloride and expanded graphite is 6:1, pressed density 761kg/m3, the diameter of adsorbent
It is 76mm to mass transfer and heat-transfer path.
Further preferably, the expanded graphite is one of common expanded graphite or vulcanization expanded graphite.More
Preferably vulcanize expanded graphite.
The present invention also provides the preparation methods that above-mentioned alkali halide expanded graphite cures mixed adsorbent, including with
Lower step：
(1) adsorbent mixes：Alkali halide is dissolved in solvent, expanded graphite is then added and is sufficiently stirred；
(2) after adsorbent mixing, through drying, compacting, solidification mixed adsorbent is obtained.
Method made above is preferred, and the alkali halide is one of calcium chloride, strontium chloride or manganese chloride.
Method made above is preferred, and the solvent is the one or more of which of methanol, ethyl alcohol or water.
Method made above is preferred, and the pressing direction and heat and mass direction are perpendicular.
In some specific examples of the present invention, the solidification mixed adsorbent suppressed is cylinder, tetrahedroid, six
One of face bodily form.It is more preferably cylindrical.
The present invention also provides the adsorbent equipment that a kind of above-mentioned alkali halide expanded graphite cures mixed adsorbent, institutes
It includes tank body to state adsorbent equipment, and the tank body is internally provided with the alkali halide expanded graphite solidification mixing and absorption
Agent；The adsorbent equipment is additionally provided with mass transfer channel and end cap.
The above adsorbent equipment is preferred, and mass transfer channel is set to the internal or external of the adsorbent equipment.
Alkali halide expanded graphite provided by the invention cures mixed adsorbent, and alkali halide can realize and ammonia
The reversible process of gas absorption-desorption, while expanded graphite has higher thermal coefficient, can both enhance the biography of mixed adsorbent
Matter performance, but can solve mixed adsorbent absorption ammonia after expansion and agglomeration problems.Therefore the present invention can be effectively
It realizes that ammonia quickly fills, reaches the adsorption saturation state of solidification mixed adsorbent ammonia in a relatively short period of time.At tail gas
When reason system needs reproducibility ammonia, the solidification mixed adsorbent by heating adsorption saturation makes it desorb a certain amount of ammonia
Gas is reacted with oxynitrides.This method has many advantages, such as that preparation process is simple, storage efficiency is big, process costs point, and overcomes
The shortcomings of urea tank urea easily crystallizes.
In addition the adsorbent equipment of alkali halide expanded graphite of the invention solidification mixed adsorbent is in adsorption process,
The effective expansion for limiting system.Relative to the single alkali metal halide for not adding expanded graphite completely, in of the invention
Solidification mixed adsorbent improves 50 times perpendicular to the thermal coefficient of pressing direction, and solution ammonia rate improves 33%, inhales ammonia rate
Improve 30%.
Description of the drawings
Fig. 1 is the preparation process that alkali halide expanded graphite cures mixed adsorbent；
Fig. 2 is the mass transfer channel schematic diagram for the adsorbent equipment that alkali halide expanded graphite cures mixed adsorbent；
Fig. 3 is an embodiment of the adsorbent equipment that alkali halide expanded graphite cures mixed adsorbent.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit protection scope of the present invention.Those skilled in the art change according to what the present invention made in practical applications
Into and adjustment, still fall within protection scope of the present invention.
Herein, the range indicated by " numerical value to another numerical value ", is that one kind avoids enumerating in the description
The summary representation of all numerical value in the range.Therefore, the record of a certain special value range, covers the numberical range
Interior any number and the relatively fractional value range defined by any number in the numberical range, as bright in the description
Text writes out any number and is somebody's turn to do as compared with fractional value range.
Embodiment
Fig. 1 is the flow signal that the alkali halide expanded graphite of the present invention cures the preparation method of mixed adsorbent
Figure.Solubilizer dissolves alkali halide to obtain salting liquid first, is stirred after then mixing the salting liquid and expanded graphite
Mixed adsorbent uniformly is obtained, then the mixed adsorbent after dry mixed, finally compacting obtains solidification mixed adsorbent.
Fig. 2 is the installation position schematic diagram for the mass transfer channel that alkali halide expanded graphite cures mixing and absorption device,
Its adsorbent equipment shape can be cylinder, one of tetrahedroid or hexahedron.Wherein, (a)-(c) is alkali in Fig. 2
Metal halide expanded graphite cures the adsorbent equipment shape of mixed adsorbent and several embodiments of mass transfer channel installation position；
Wherein, (a) cylindrical adsorbent, inside are mass transfer channel；(b) cylindrical adsorbent, outside are mass transfer channel；(c) rectangular suction
Attached dose, inside is mass transfer channel.When mass transfer channel is when internal, (a), (c) are shown in Fig. 2, mixed by being heating and curing at this time
The outer surface for closing adsorbent, to desorb the ammonia of adsorbent；When mass transfer channel is when external, (b) is shown in Fig. 2, leads at this time
The inner surface for crossing the adsorbent that is heating and curing, to desorb the ammonia of adsorbent.
Fig. 3 is that a kind of alkali halide expanded graphite of the present embodiment cures the adsorbent equipment of mixed adsorbent, absorption
Device includes tank body, and tank body is internally provided with alkali halide expanded graphite solidification mixed adsorbent, in adsorbent equipment
It is internally provided with an ammonia channel, mass transfer channel is provided on the conduit wall of ammonia, and in at least one end in ammonia channel
It is provided with opening, adsorbent equipment end is additionally provided with end cap, and welding or flange may be used in end cap set-up mode.
For common expanded graphite compared to vulcanization expanded graphite, manufacturing process is simpler, and price is also more cheap；Simultaneously
It can solve the technical problems to be solved by the invention.But alkali halide and expanded graphite in identical mass ratio and
Under pressed density, the thermal conductivity ratio vulcanization expanded graphite solidification mixed adsorbent of common expanded graphite solidification mixed adsorbent
Thermal coefficient is low, if the mass ratio of alkali halide and graphite is 3:1, pressed density 400kg/m3, calcium chloride/vulcanization is swollen
The thermal coefficient of swollen graphite solidification mixed adsorbent is 15.2W/ (mK), calcium chloride/expanded graphite solidification mixed adsorbent
Thermal coefficient is 1.35W/ (mK).
The performance test of the alkali halide expanded graphite solidification mixed adsorbent prepared in the present embodiment includes following
Project：
1. heat conductivility detects：
The hot physical property of adsorbent is carried out using unidirectional Transient Heat Transfer method using the resistance to hot food texture measurements of speeding of LFA 447
Test.One of sample is that calcium chloride/vulcanization expanded graphite cures mixed adsorbent, pressed density 400kg/m3, calcium chloride with
The ratio for vulcanizing expanded graphite is 3:1.Specific detecting step is to make solid mixed adsorbent block first, and thickness is in 3mm
Left and right, a diameter of 12.6m obtain the thermal diffusion coefficient in laser impact direction.Utilize the pass between thermal coefficient and thermal diffusivity
System, is calculated, and can reach 15.2W/ (mK) with the thermal coefficient highest of compacting vertical direction, and alkali metal halogenation in bulk
The thermal coefficient of object is only 0.3W/ (mK), therefore relative to common alkali halide in bulk, cures mixed adsorbent
Nearly 50 times are improved with the thermal coefficient of compacting vertical direction.
2. absorption property and the rate of adsorption
Using establishing performance of the adsorbent experimental apparatus for testing.Cure mixed adsorbent using Rubotherm magnetic suspension balances
Absorption property tested.One of sample is that calcium chloride/vulcanization expanded graphite cures mixed adsorbent, and pressed density is
400kg/m3, the ratio of calcium chloride and vulcanization expanded graphite is 3:1.When heating temperature is 90 DEG C, and cooling temperature is 30 DEG C, obtain
Maximum adsorption ammonia rate to alkali halide in bulk is 0.0069kg/ (kgs), cures the maximum adsorption of mixed adsorbent
Rate is 0.009kg/ (kgs).Accordingly, with respect to alkali halide in bulk, solidification mixed adsorbent is inhaled ammonia rate and is improved
30%.
Several specific examples of the present embodiment are see following table one and table two.
Table one
Table two
From upper table, it can be seen that, the alkali halide expanded graphite that the present invention is prepared cures mixed adsorbent heat conduction
Coefficient significantly improves compared with pure alkali halide, and its rate of adsorption desorption rate is (according to common sense in the field, parsing speed
Rate is equal or higher with the rate of adsorption) also increase.
Under the introduction of the present invention and above-described embodiment, those skilled in the art are easy to it is envisioned that cited by the present invention
Or each raw material enumerated or its equivalent alterations, each processing method or its equivalent alterations can realize the present invention and each original
The parameter bound value of material and processing method, interval value can realize the present invention, embodiment numerous to list herein.
Claims (8)
1. a kind of alkali halide expanded graphite solidification mixed adsorbent alternatively in property catalytic reduction method ammonia absorption
The purposes of agent, which is characterized in that the alkali halide is strontium chloride, and the mass ratio of strontium chloride and expanded graphite is 6:
1, pressed density is 700 kg/m3, the radial mass transfer and heat-transfer path of adsorbent are 76mm.
2. alkali halide expanded graphite as described in claim 1 cures mixed adsorbent alternatively property catalytic reduction method
The purposes of the adsorbent of middle ammonia, which is characterized in that the expanded graphite is common expanded graphite or vulcanization expanded graphite
One of them.
3. alkali halide expanded graphite as described in claim 1 cures mixed adsorbent alternatively property catalytic reduction method
The purposes of the adsorbent of middle ammonia, which is characterized in that the system of the alkali halide expanded graphite solidification mixed adsorbent
Preparation Method includes the following steps：
（1）Adsorbent mixes：Alkali halide is dissolved in solvent, expanded graphite is then added and is sufficiently stirred；
（2）After adsorbent mixing, solidification mixed adsorbent is obtained through drying, compacting.
4. alkali halide expanded graphite as claimed in claim 3 cures mixed adsorbent alternatively property catalytic reduction method
The purposes of the adsorbent of middle ammonia, which is characterized in that the solvent is the one or more of which of water, methanol or ethyl alcohol.
5. alkali halide expanded graphite as claimed in claim 3 cures mixed adsorbent alternatively property catalytic reduction method
The purposes of the adsorbent of middle ammonia, which is characterized in that the pressing direction and heat and mass direction are perpendicular.
6. alkali halide expanded graphite as claimed in claim 3 cures mixed adsorbent alternatively property catalytic reduction method
The purposes of the adsorbent of middle ammonia, which is characterized in that the step（2）In, the solidification mixed adsorbent suppressed is cylinder
One of shape, tetrahedroid or hexahedron.
7. alkali halide expanded graphite as described in claim 1 cures mixed adsorbent alternatively property catalytic reduction method
The purposes of the adsorbent of middle ammonia, which is characterized in that a kind of to be inhaled using the alkali halide expanded graphite solidification mixing
Attached dose of adsorbent equipment, the adsorbent equipment include tank body, and the tank body is internally provided with the alkali halide expansion
Graphite cures mixed adsorbent；The adsorbent equipment is additionally provided with mass transfer channel and end cap.
8. alkali halide expanded graphite as claimed in claim 7 cures mixed adsorbent alternatively property catalytic reduction method
The purposes of the adsorbent of middle ammonia, which is characterized in that the mass transfer channel is set to the internal or external of the adsorbent equipment.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108554376A (en) * | 2018-04-11 | 2018-09-21 | 上海交通大学 | A kind of salty adsorbent of solid-state and the salty storage ammonia module of solid-state |
| CN109812692A (en) * | 2019-02-13 | 2019-05-28 | 上海交通大学 | It fills ammonia station and fills ammonia method |
| CN110559996A (en) * | 2019-09-18 | 2019-12-13 | 付华 | Solidified composite adsorbent |
| CN112915969B (en) * | 2021-02-04 | 2022-07-22 | 上海交通大学 | Metal organic framework/halide composite ammonia adsorbent and preparation method thereof |
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| CN103191704A (en) * | 2013-04-18 | 2013-07-10 | 中国科学技术大学 | Composite adsorbent and preparation method thereof |
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| CN101249420A (en) * | 2007-11-29 | 2008-08-27 | 上海交通大学 | Preparation of expanded graphite-chlorides composite adsorbing agent |
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