CN106861596B - A kind of preparation method and applications of grapheme foam rectifying tower packing - Google Patents
A kind of preparation method and applications of grapheme foam rectifying tower packing Download PDFInfo
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- CN106861596B CN106861596B CN201710286134.8A CN201710286134A CN106861596B CN 106861596 B CN106861596 B CN 106861596B CN 201710286134 A CN201710286134 A CN 201710286134A CN 106861596 B CN106861596 B CN 106861596B
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/30—Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/30—Details relating to random packing elements
- B01J2219/304—Composition or microstructure of the elements
- B01J2219/30491—Foam like materials
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/30—Details relating to random packing elements
- B01J2219/31—Size details
- B01J2219/312—Sizes
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/30—Details relating to random packing elements
- B01J2219/318—Manufacturing aspects
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Abstract
The present invention relates to a kind of preparation method and applications of novel grapheme foam rectifying tower packing, at high temperature, by way of solvent heat, graphene oxide solution is subjected to moulding, embedded metal frame structure in the process, to constitute a rectifying column filler unit, porous structure can be used as the microreactor of catalytic distillation.As a comparison by novel three-dimensional graphene filler and HY-Pac and Pall ring filler, rectifying column is filled, graphene filler largely keeps structured packing characteristic, and mass transfer ability is strong；Graphene filler liquid holdup can be used as greatly novel catalytic micro-reactor；The pressure drop of graphene filler can drop to the 1/3 of conventional filler.
Description
Technical field
The invention belongs to technical field of chemical separation, and in particular to a kind of system of novel grapheme foam rectifying tower packing
Preparation Method and its application.
Background technique
Chemical industry is the pillar industries of the national economy, and isolation technics is then purification of raw materials in chemical production process, produces
Product purification and waste processing etc. provide technology guarantee.With the development of technology of chemical engineering, isolation technics is gradually towards polynary
Change development.Conventional chemical separation technology includes rectifying, absorption, extraction, crystallization, absorption, UF membrane etc..Rectifying is still using most
Extensively, most mature one of the separation method of technology, occupies comparable specific gravity in the industrial production.
Rectifying is most widely used key common technology in chemical industry, is mainly used in petroleum, chemical industry, medicine, ring
The industries such as border protection.Rectifying has many advantages, such as to be widely used, technology maturation, but that there are equipment investments is big, separating energy consumption is high etc. asks
Topic, therefore the new and effective mass transfer component researched and developed, can be improved the separative efficiency of rectifiying plate, reduce the investment of tower at
This, has important social effect and economic value for entire rectifying industry.
Catalytic reaction rectification technology is will to react to be coupled together with separating, and reaction is separated with product to be carried out simultaneously, instead of
The process flow that the reaction of routine, separation the two separately carry out.However reversible reaction system most of for chemical industry, it needs
Timely product is wanted to separate, reaction balance is carried out to product direction is conducive to, and could be improved yield, be substantially reduced process energy consumption, reach
To energy-saving and emission-reduction purpose.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of novel grapheme foam rectifying tower packing, preparation is filled out
Material can effectively reduce pressure drop, improve mass-transfer efficiency, and effective liquid holdup enables three-dimensional graphene foam filler as rectifying
Novel catalytic micro-reactor in the process.
The technical solution adopted by the present invention to solve the technical problems is: a kind of novel grapheme foam rectifying tower packing
Preparation method, comprising the following steps:
1) magnetic agitation is carried out after 50mL graphene oxide slurry ultrasonic vibration being handled 30min, pipettes 7mL with liquid-transfering gun
Tween-80/alcohol mixed solution is added drop-wise in graphene oxide solution, after mixing to solution, continues to stir 10min；
2) mixed solution is transferred in the polytetrafluoro stainless steel cauldron of 100mL, while will be as used in fractional distillation filling-material
Metal frame structure be put into reaction kettle, incubating solvent thermal response 6h at 180 DEG C, the gel for taking out embedded metal frame structure is blocky
Object obtains the rectifying tower packing of three-dimensional outsourcing grapheme foam, embedded metal frame structure after vacuum freeze drying.
Specifically, the concentration of graphene oxide slurry is 8mg/mL, the lamellar spacing of graphene oxide in the step 1)
It is single layer, bilayer or few layer graphene oxide in 2-5nm, piece diameter size is small flake diameter graphene oxide in 2-10 μ m.
Specifically, Tween-80/ethanol solution concentration is 100-200mg/mL in the step 1).
Specifically, three-dimensional grapheme aperture size is 200-800nm, the graphite with this pore structure in the step 2)
Alkene foam shows very high absorption and desorption ability to organic solvent, has excellent mass-transfer performance, to alcohols and lipid
Organic solution adsorbance can reach 100-200g/g, and desorption rate can reach 80-170g/g.
Specifically, the condition of vacuum freeze drying is -55 DEG C, vacuum degree 5pa in the step 2), is freeze-dried 72h.
It is another object of the present invention to provide application of the grapheme foam rectifying tower packing in rectifying column.Stone
Black alkene foam has big liquid holdup 0.2-0.4m3/m3, each hole of three-dimensional grapheme can be used as the micro- anti-of catalytic distillation
Answer device.Rectifying column mass transfer ability using grapheme foam as filler promotes 2 times compared to common fillers, with traditional market
On fractional distillation filling-material comparison, pressure drop can drop to the 1/3 of conventional filler.
Grapheme foam of the invention uses support frame of the embedded metal frame structure as fractional distillation filling-material, can guarantee to fill out
The mechanical strength of material enhances crushing resistance, facilitates the stability of liquid phase mass transfer, moreover it is possible to reduce connecing for organic solvent and metal
Touching, effectively reduces extent of corrosion.The catalyst of catalytic rectification packing is first mixed with graphene oxide, be can be improved catalyst and is existed
The degree that is uniformly dispersed of three-dimensional grapheme inner surface helps to promote catalytic effect.
The three-dimensional grapheme metal frame structured packing of this invention design breathes out angstrom Parker (HY- compared to traditional fractional distillation filling-material
Pac), Pall ring (Pall ring) has following advantage:
1) three-dimensional grapheme metal frame structured packing mass-transfer performance is passed considerably beyond conventional filler HY-Pac, Pall ring
Mass-energy power promotes 2 times compared to common fillers, substantially increases rectification efficiency.
2) operating pressure needed for the structured packing of three-dimensional grapheme metal frame is smaller than conventional filler HY-Pac, Pall ring
Much, it can be reduced to the 1/3 of common fillers, reduce energy requirement, reach energy-efficient effect.
3) three-dimensional grapheme has excellent adsorption/desorption performance, and graphene filler compares conventional filler HY-Pac, Pall
Ring liquid holdup is able to ascend 3 times, and effective liquid holdup can reach 0.24m3/m3, as novel microreactor, can give and urge
The certain liquid phase reactor environment of agent, provides the sufficient reaction time, and three-dimensional grapheme have good mass transfer ability and
Capacity of heat transmission, can fast transfer product, discharge reaction heat, be conducive to product generation, thus greatly improve catalysis reaction effect
Rate.
Detailed description of the invention
Fig. 1 is the picture in kind of the grapheme foam rectifying tower packing of preparation of the embodiment of the present invention.
Fig. 2 is the SEM figure of the grapheme foam rectifying tower packing of preparation of the embodiment of the present invention.
Fig. 3 is novel graphene foam fractionation tower packing Δ P/Z-F prepared by the present inventionvFigure.
Fig. 4 is novel graphene foam fractionation tower packing liquid holdup-F prepared by the present inventionvFigure.
Fig. 5 is the Δ P/Z-F of three kinds of fillersvComparison diagram.
Fig. 6 is the liquid holdup-F of three kinds of fillersvComparison diagram.
Fig. 7 is the mass-transfer efficiency comparison diagram of three kinds of fillers.
Specific embodiment
The following is specific embodiments of the present invention, is described further to technical solution of the present invention, but of the invention
Protection scope is not limited to these examples.It is all to be included in the present invention without departing substantially from the change of present inventive concept or equivalent substitute
Protection scope within.
A kind of preparation method of novel grapheme foam rectifying tower packing, comprising the following steps:
1) magnetic agitation is carried out after the graphene oxide slurry ultrasonic vibration that 50mL concentration is 8mg/mL being handled 30min,
Tween-80/alcohol mixed solution that 7mL concentration is 100-200mg/mL, which is pipetted, with liquid-transfering gun is added drop-wise to graphene oxide solution
In, after mixing to solution, continue to stir 10min；The lamellar spacing of graphene oxide is single layer, bilayer or few in 2-5nm
Layer graphene oxide, piece diameter size are small flake diameter graphene oxide in 2-10 μ m.
2) mixed solution is transferred in the polytetrafluoro stainless steel cauldron of 100mL, while will be as used in fractional distillation filling-material
Metal frame structure be put into reaction kettle, incubating solvent thermal response 6h at 180 DEG C, the gel for taking out embedded metal frame structure is blocky
Object, -55 DEG C, three-dimensional outsourcing grapheme foam, embedded metal frame structure are obtained after vacuum degree 5pa vacuum freeze drying 72h
Rectifying tower packing.Three-dimensional grapheme aperture size is 200-800nm, and the grapheme foam with this pore structure is to organic solvent
Very high absorption and desorption ability are shown, there is excellent mass-transfer performance, to alcohols and lipid organic solution adsorbance energy
Reach 100-200g/g, desorption rate can reach 80-170g/g.
The dynamic performance of novel three-dimensional grapheme foam rectifying tower packing passes through hydrodynamics reality using air/water system
Experiment device carries out analog detection.Three-dimensional grapheme filler and market conventional filler carry out rectifying filling in an identical manner, tradition
Fillers selection typically breathes out an angstrom Parker (HY-Pac), Pall ring (Pallring) rectifying tower packing.
Laboratory apparatus is University Of Tianjin's Hydromechanics experimental device, and specific experiment is simulated using air/water system, adopted
It is experiment tower with the organic glass tower of Φ 380mm, the high 1m of tower internals test section is made of the filler of upper and lower two sections high 0.5m.
Using tubular liquid distributor, tower internals respectively has the corrugated plate regular packing of certain altitude up and down, plays even point and stablizes vapour-liquid
The effect of two-phase fluid.0~30m of sprinkle density3/m2H, 0.31~2.2m/s of empty tower gas velocity.First make tower liquid flooding, it is ensured that element
Surface all soaks, and tests pressure drop, liquid holdup and mass-transfer efficiency analysis of the graphene filler under different sprinkle densities respectively, it
Afterwards the sprinkle density selected to reselection test to graphene filler and HY-Pac and Pallring filler traditional on the market into
Row control.
Preflooding is carried out to packing layer, the measurement of wet filler pressure drop is carried out after soaking filler sufficiently.Fig. 3 is that graphene is filled out
Expect the pass of pressure drop and gas phase loading factor under the different sprinkle densities that Hydromechanics experimental device simulated air/water system obtains
The wet filler falloff curve trend of system's figure, this catalytic distillation structured packing and common fillers is essentially the same.According to graphite in Fig. 5
HY-Pac the and Pallring filler of alkene filler and tradition on the market compares, and the pressure drop of graphene filler can drop to conventional filler
1/3。
Fig. 4 is liquid holdup of the graphene filler under different sprinkle densities and gas phase loading factor relational graph, with spray
Density, which increases liquid holdup, increased and tend towards stability, and liquid holdup is in 0.24m3/m3, pass through the liquid holdup pair of three kinds of fillers in Fig. 6
Than it is found that graphene filler liquid holdup is higher than HY-Pac and Pallring filler 2 times or more.As novel microreactor,
It can give catalyst certain liquid phase reactor environment, the sufficient reaction time is provided, help to promote catalytic efficiency.
In the mass-transfer efficiency reflection to design parameter of filler, generally indicated with every meter of number of theoretical plate or the height equivalent to one theoretical plate (HETP).
By experiment, we have measured increases with gas phase load, the situation of change of every meter of number of theoretical plate of graphene filler.By in Fig. 7
Graphene filler and conventional filler HY-Pac and Pallring curve comparison, the variation tendency of three kinds of fillers is close, illustrates graphite
Alkene filler largely keeps structured packing characteristic, and number of theoretical plate is higher by twice, illustrates graphene filler good separating effect, mass transfer
Ability is strong.
Claims (6)
1. a kind of preparation method of grapheme foam rectifying tower packing, which comprises the following steps:
1) magnetic agitation is carried out after 50mL graphene oxide slurry ultrasonic vibration being handled 30min, 7mL is pipetted with liquid-transfering gun and spits
Warm -80/ alcohol mixed solution is added drop-wise in graphene oxide solution, after mixing to solution, continues to stir 10min；
2) mixed solution is transferred in the polytetrafluoro stainless steel cauldron of 100mL, while will be as gold used in fractional distillation filling-material
Belonging to frame structure to be put into reaction kettle, incubating solvent thermal response 6h at 180 DEG C takes out the gel block of embedded metal frame structure,
The rectifying tower packing of three-dimensional outsourcing grapheme foam, embedded metal frame structure is obtained after vacuum freeze drying.
2. the preparation method of grapheme foam rectifying tower packing as described in claim 1, which is characterized in that in the step 1)
The concentration of graphene oxide slurry is 8mg/mL, and the lamellar spacing of graphene oxide is single layer, bilayer or few layer oxygen in 2-5nm
Graphite alkene, piece diameter size are small flake diameter graphene oxide in 2-10 μ m.
3. the preparation method of grapheme foam rectifying tower packing as described in claim 1, which is characterized in that in the step 1)
Tween-80/ethanol solution concentration is 100-200mg/mL.
4. the preparation method of grapheme foam rectifying tower packing as described in claim 1, which is characterized in that in the step 2)
Grapheme foam aperture size is 200~800nm.
5. the preparation method of grapheme foam rectifying tower packing as described in claim 1, which is characterized in that in the step 2)
The condition of vacuum freeze drying is -55 DEG C, vacuum degree 5pa, is freeze-dried 72h.
6. application of the grapheme foam rectifying tower packing of method preparation a method as claimed in any one of claims 1 to 5 in rectifying column.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220911A (en) * | 1997-12-24 | 1999-06-30 | 淄博浩洋化工科技有限公司 | Carbon and/or graphite board corrugated regular filler for packed column |
| CN102674321A (en) * | 2011-03-10 | 2012-09-19 | 中国科学院金属研究所 | Graphene foam with three dimensional fully connected network and macroscopic quantity preparation method thereof |
| CN105779804A (en) * | 2016-03-21 | 2016-07-20 | 中南大学 | Foam skeleton structure reinforced metal-matrix composite material and preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006028407B3 (en) * | 2006-06-19 | 2008-03-27 | Sgl Carbon Ag | Support grate for packed packing |
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- 2017-04-27 CN CN201710286134.8A patent/CN106861596B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220911A (en) * | 1997-12-24 | 1999-06-30 | 淄博浩洋化工科技有限公司 | Carbon and/or graphite board corrugated regular filler for packed column |
| CN102674321A (en) * | 2011-03-10 | 2012-09-19 | 中国科学院金属研究所 | Graphene foam with three dimensional fully connected network and macroscopic quantity preparation method thereof |
| CN105779804A (en) * | 2016-03-21 | 2016-07-20 | 中南大学 | Foam skeleton structure reinforced metal-matrix composite material and preparation method |
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