CN109482145A - A kind of micro/nano level removes the preparation method of carbon adsorbent - Google Patents
A kind of micro/nano level removes the preparation method of carbon adsorbent Download PDFInfo
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- CN109482145A CN109482145A CN201811653249.7A CN201811653249A CN109482145A CN 109482145 A CN109482145 A CN 109482145A CN 201811653249 A CN201811653249 A CN 201811653249A CN 109482145 A CN109482145 A CN 109482145A
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel
Abstract
The invention belongs to pulping and paper-making industry methane purification fields, and in particular to a kind of micro/nano level removes the preparation method of carbon adsorbent, is mainly used for pulping and papermaking effluent biological fuel gas except carbon.The present invention is using aluminium isopropoxide, ethyl orthosilicate as raw material, by the proportion for adjusting ethyl orthosilicate, aluminium isopropoxide, cetyl trimethylammonium bromide is added as surfactant, the easy decomposed substances of macromolecules such as nano micro crystal cellulose, polyethylene glycol are added as pore-foaming agent, tight pore structure is generated in high-temperature activation, to improve its porosity.Adhesive etc. is added simultaneously, molding squeezes out, it is roasted in 500~700 DEG C, 2~4h is impregnated in sodium hydroxide solution, deionized water is washed to neutrality, and drying obtains the Si-Al molecular sieve of tight pore structure, is had by Si-Al molecular sieve prepared by this method highly selective, it is big to adsorb carbon dioxide capacity, and regenerates the features such as being easy.
Description
Technical field
The invention belongs to pulping and paper-making industry methane purification fields, and in particular to a kind of micro/nano level removes the system of carbon adsorbent
Preparation Method is mainly used for pulping and papermaking effluent biological fuel gas except carbon.
Background technique
Pulping and paper-making industry includes pulp-making waste-water in paper waste, also includes paper making waste water.China becomes the whole world most
Big paper and production state, paper industry waste water cause huge pressure to environment, and wastewater emission amount and COD discharge amount occupy
First of each industrial trade.Due to slurry kind and paper grades difference, manufacture paper with pulp the water quality and dirt of waste water from different slurry lines and paper kind
It is larger to contaminate property difference.Pulping and papermaking effluent pollutant concentration is high simultaneously, hardly degraded organic substance ingredient is more, biodegradability
Difference.So establishing paper-making effluent gasification system is to solve the effective means of paper-making effluent, economy is being solved
While development, minimizing, the innoxious, recycling, stabilisation of paper waste are realized.
It cannot directly be applied by the higher limitation of carbon dioxide content, biogas in biogas ingredient.Currently, biogas removes the side of carbon
Method mainly has: chemical absorption method, WATER-WASHING METHOD, low temperature processing, membrane separation process, carbon rejection processes and pressure swing adsorption method etc. in situ.Become
Press absorption method because reaction condition require it is low, high degree of automation and be widely applied, but the molecular sieve in pressure-variable adsorption holds very much
Easily poisoning, loses activity, and whole equipment is caused to stop working.Therefore need to have highly selective, circulation absorption, capacity
Greatly, regeneration is readily except carbon adsorbent handles it.But meaning that adsorption capacity is strong due to highly selective, elution is tired
Difficulty causes highly selective and easy regeneration to be difficult to coexist in same adsorbent material.
102423620 A of CN discloses a kind of Compositional type decarbonization solvent for removing carbon dioxide in methane, decarburization absorption
The main component of agent is that the ingredient of following mass percents is constituted: soft water is, potassium carbonate, corrosion inhibiter are, activator, defoaming agent,
Wherein corrosion inhibiter is potassium metavanadate or vanadic anhydride, and defoaming agent is that defoaming agent is selected from silicone, polyethers or higher alcohol.This is de-
The effective component of carbon agent has certain corrosivity, and additional component, the high requirements on the equipment need to be added.Adsorption process produces simultaneously
The absorption of the influence carbon dioxide such as raw solid particle of by-product, suspension.
108404883 A of CN discloses a kind of preparation method applied to Methane decarbonization pure solid adsorbent material, system
Standby step are as follows: (1) pretreatment of NKA-9 resin: NKA-9 is loaded in resin column, and it is organic that deionized water rinses dry (2)
Amine is loaded to NKA-9 anhydrous methanol and makees solvent, and BPEI, magnetic agitation, solvent volatile dry is added.The solid of this method preparation is inhaled
Attached dose uses methanol for solvent, volatilizees naturally, and technique not environmentally, is not suitable for the application that extensive biogas removes carbon.
107697924 A of CN discloses a kind of adsorbent and preparation method thereof of decarburization from admixture of gas, the absorption
Agent DD3R molecular sieve, by by previously prepared ZSM-58 sieve particle wet ball grinding and stewing process obtains crystal seed, and by its
It is mixed in the Synthesis liquid containing low template, and two sections of crystallization process is cooperated to prepare DD3R molecular sieve.It is prepared by the method
Journey needs higher to partial size uniformity, and stray crystal is also easy to produce in mechanical milling process, so requiring preparation process stringent, reduces suction
Attached dose of production efficiency and remove carbon effect.
Therefore develop it is a kind of prepare it is environmentally protective, it is low for equipment requirements, low in cost and efficient decarburization remove carbon adsorbent
It is extremely important.
Summary of the invention
The present invention is directed to paper-making effluent biological fuel gas feature, provides the system that a kind of micro/nano level removes carbon adsorbent
Preparation Method has highly selective, circulation absorption using desulfuration adsorbent prepared by the present invention, and absorption carbon dioxide capacity is big,
And regenerate the features such as being easy.
The present invention uniformly mixes ethyl orthosilicate, aluminium isopropoxide, surfactant, sodium hydroxide, a pore-foaming agent and water
It closes, adjusts Si/Al, generate gel；The Si-Al molecular sieve after crystallization is obtained after gel crystallization and ageing；To the silicoaluminophosphate molecular after crystallization
Adhesive and secondary pore-foaming agent, extrusion molding are added in sieve, high temperature bakes, and cooling, NaOH solution dipping, washing and drying obtains
Micro/nano level removes carbon adsorbent.
Further, the specific steps are that:
(1) using ethyl orthosilicate, aluminium isopropoxide as raw material, be added surfactant, sodium hydroxide, a pore-foaming agent and
Water adjusts Si/Al=1~4, generates gel；
(2) by the gel thermostatic crystallization prepared in (1) and ageing, washing, freeze-drying, the silicoaluminophosphate molecular after obtaining crystallization
Sieve；
(3) adhesive, secondary pore-foaming agent is added in the Si-Al molecular sieve after crystallization, molding squeezes out；
(4) carbon adsorbent that removes by extrusion molding in (3) is put in kiln roasting, after cooling down, impregnates in sodium hydroxide solution,
Deionized water is washed to neutrality, and drying obtains the molecular sieve of tight pore structure.
Step (1) mainly prepares Si-Al molecular sieve gel, and wherein the silica alumina ratio of Si-Al molecular sieve is an important parameter, this
Application preparation Si-Al molecular sieve be used for paper-making effluent methane purification, so select molecular sieve Si/Al ratio 1~4 it
Between, determine the important parameter of the efficiency except carbon adsorbent.In the range, molecular sieve can be used for biogas except carbon sublimated, sial point
Son sieves the absorption property highest to carbon dioxide, while reducing the absorption to methane gas, and silica alumina ratio is too large or too small, all will
The purifying for influencing biogas leads to carbon dioxide adsorption low efficiency, or even increases the absorption to methane gas, makes biogas purification efficiency
It is not high.
In step (1), the surfactant is cetyl trimethylammonium bromide, and effect is template, is formed with
The molecular sieve structure of sequence.The mass ratio of quality and ethyl orthosilicate that CTAB is added is 0.4~0.5:1.Disposably pore-foaming agent is
It is 0.05~0.08:1 that the quality of nano-cellulose and the mass ratio of ethyl orthosilicate, which is added, in nano micro crystal cellulose.It is added just
Silester, aluminium isopropoxide, sodium hydroxide, cetyl trimethylammonium bromide, nano micro crystal cellulose and water mass ratio be
1:0.5~0.8:1~1.5:0.25~0.3:0.01~0.05:4~5.
Gel obtained is mainly aged and crystallization by step (2), the growth of molecular sieve crystal.The ageing of gel, crystallization
Time and temperature are important parameter.Different crystallization temperatures and time will lead to going out for different crystal form difference and stray crystal
It is existing, while the constituent content of crystal phase is also different.
In step (2), the temperature of the thermostatic crystallization is 50~60 DEG C, when crystallization a length of 72~80h.The adhesive of addition
For clay, water, tar.The clay of Si-Al molecular sieve and addition after crystallization, water, tar quality proportioning be 1:1.5~2:0.7
~1:0.05~0.15.Secondary pore-foaming agent is nano micro crystal cellulose and polyethylene glycol, it is preferable that the nano microcrystalline of addition is added
The mass ratio of cellulose and polyethylene glycol is 1:1, and the quality proportioning with the Si-Al molecular sieve after crystallization of polyethylene glycol is added
For 0.05~0.1:1.
Step (3) removes carbon adsorbent pore for after molding.By roasting the dipping with sodium hydroxide solution, except removal carbon
Nano micro crystal cellulose and polyethylene glycol in agent achieve the purpose that pore.The time of roasting and temperature, sodium hydroxide dipping
Time, can all influence the pore-creating character of decarbonizer and the connectivity in duct.The temperature that step (3) high temperature bakes is 500~700
DEG C, calcining time is 6~7h, and a length of 2~4h, the concentration of the sodium hydroxide of dipping are when impregnating in sodium hydroxide solution
3mol/L。
In the present invention, by pore of nano micro crystal cellulose, the molecular sieve good dispersion of synthesis will not be assembled.It is poly-
Ethylene glycol is uniformly mixed as pore-foaming agent with molecular sieve, basis material.Pore and roasting are dissolved by the way that water is added, by nanometer
Microcrystalline cellulose and polyethylene glycol breakdown further reach the porous structure of the inside of decarbonizer.
Compared with prior art, the present invention by selecting ethyl orthosilicate and aluminium isopropoxide respectively as silicon source and silicon source,
Compared with other silicon sources and silicon source, the content of activated silica is increased, while also meeting the content of the framework of molecular sieve aluminium of preparation, is led to
Control molecular sieve silica alumina ratio is crossed, high selection is carried out to carbon dioxide impurities gas.It is micro- by the nanometer for adding natural degradable
For crystalline cellulose as pore-foaming agent, the molecular sieve of preparation has microcellular structure, while making the silicoaluminophosphate molecular of preparation to a certain extent
Sieve is uniformly dispersed.By secondary pore-foaming agent pore, increase the porosity of the internal structure of basis material, the decarbonizer of preparation has
The internal structure of multi-stage porous comes into full contact with the carbon adsorbent that removes of preparation with carbon dioxide, and then achievees the effect that improve except carbon,
And regeneration is easy, and is prolonged its service life.
Specific embodiment
Embodiment 1
The preparation and crystallization of Si-Al molecular sieve gel
10g ethyl orthosilicate is added to containing 2.5g cetyl trimethylammonium bromide, 0.1g nano micro crystal cellulose
30g aqueous solution in, be stirred at room temperature uniformly.3g aluminium isopropoxide and 10g sodium hydroxide are dissolved in 10g water, the mixing that will be obtained
Liquid drops evenly in above-mentioned teos solution, stirs evenly, and obtains gel.Gained gel is placed in sealing device, 50
DEG C thermostatic crystallization 72h takes out washing freeze-drying, the Si-Al molecular sieve after obtaining crystallization.
Micro/nano level removes the preparation of carbon adsorbent
Si-Al molecular sieve after taking 10g crystallization, is added 15g clay, 7g water, 0.8g tar, and total binder mass is
22.8g adds secondary pore-foaming agent polyethylene glycol 1g, stirs evenly, and molding squeezes out.By extrusion molding except carbon adsorbent is put in
500 DEG C of roastings in furnace roast duration 6h and are impregnated in 2h in the sodium hydroxide solution of 3mol/L after cooling, are washed with deionized water
It washs to neutrality, drying is obtained by the standby micro/nano level of the system with molecular sieve for preparing of tight pore structure except carbon adsorbent.
Embodiment 2
The preparation and crystallization of Si-Al molecular sieve gel
10g ethyl orthosilicate is added to containing 2.6g cetyl trimethylammonium bromide, 0.2g nano micro crystal cellulose
30g aqueous solution in, be stirred at room temperature uniformly.4g aluminium isopropoxide and 10g sodium hydroxide are dissolved in 10g water, the mixing that will be obtained
Liquid drops evenly in above-mentioned teos solution, stirs evenly, and obtains gel.Gained gel is placed in sealing device, 51
DEG C thermostatic crystallization 73h takes out washing freeze-drying, the Si-Al molecular sieve after obtaining crystallization.
Micro/nano level removes the preparation of carbon adsorbent
Si-Al molecular sieve after taking 10g crystallization, is added 16g clay, 8g water, 0.8g tar, and total binder mass is
24.8g adds secondary pore-foaming agent polyethylene glycol 1.4g, stirs evenly, and molding squeezes out.By extrusion molding except carbon adsorbent is put
520 DEG C of roastings in furnace roast duration 6.2h and are impregnated in 2h in the sodium hydroxide solution of 3mol/L after cooling, use deionization
Water washing to neutrality, drying is obtained by the standby micro/nano level of the system with molecular sieve for preparing of tight pore structure except carbon adsorbent.
Embodiment 3
The preparation and crystallization of Si-Al molecular sieve gel
10g ethyl orthosilicate is added to containing 2.5g cetyl trimethylammonium bromide, 0.1g nano micro crystal cellulose
30g aqueous solution in, be stirred at room temperature uniformly.5g aluminium isopropoxide and 12g sodium hydroxide are dissolved in 10g water, the mixing that will be obtained
Liquid drops evenly in above-mentioned teos solution, stirs evenly, and obtains gel.Gained gel is placed in sealing device, 52
DEG C thermostatic crystallization 75h takes out washing freeze-drying, the Si-Al molecular sieve after obtaining crystallization.
Micro/nano level removes the preparation of carbon adsorbent
Si-Al molecular sieve after taking 10g crystallization, is added 16g clay, 9g water, 0.9g tar, and total binder mass is
25.9g adds secondary pore-foaming agent polyethylene glycol 1.6g, stirs evenly, and molding squeezes out.By extrusion molding except carbon adsorbent is put
550 DEG C of roastings in furnace roast duration 6.5h and are impregnated in 2.4h in the sodium hydroxide solution of 3mol/L after cooling, spend from
Sub- water washing to neutrality, drying is obtained by the standby micro/nano level of the system with molecular sieve for preparing of tight pore structure except carbon adsorbent.
Embodiment 4
The preparation and crystallization of Si-Al molecular sieve gel
10g ethyl orthosilicate is added to containing 2.6g cetyl trimethylammonium bromide, 0.3g nano micro crystal cellulose
30g aqueous solution in, be stirred at room temperature uniformly.6g aluminium isopropoxide and 13g sodium hydroxide are dissolved in 10g water, the mixing that will be obtained
Liquid drops evenly in above-mentioned teos solution, stirs evenly, and obtains gel.Gained gel is placed in sealing device, 54
DEG C thermostatic crystallization 78h takes out washing freeze-drying, the Si-Al molecular sieve after obtaining crystallization.
Micro/nano level removes the preparation of carbon adsorbent
Si-Al molecular sieve after taking 10g crystallization, is added 17g clay, 9g water, 0.9g tar, and total binder mass is
26.9g adds secondary pore-foaming agent polyethylene glycol 2g, stirs evenly, and molding squeezes out.By extrusion molding except carbon adsorbent is put in
560 DEG C of roastings in furnace roast duration 6h and are impregnated in 2.8h in the sodium hydroxide solution of 3mol/L after cooling, use deionized water
Washing to neutrality, drying is obtained by the standby micro/nano level of the system with molecular sieve for preparing of tight pore structure except carbon adsorbent.
Embodiment 5
The preparation and crystallization of Si-Al molecular sieve gel
10g ethyl orthosilicate is added to containing 2.7g cetyl trimethylammonium bromide, 0.3g nano micro crystal cellulose
30g aqueous solution in, be stirred at room temperature uniformly.7g aluminium isopropoxide and 13g sodium hydroxide are dissolved in 10g water, the mixing that will be obtained
Liquid drops evenly in above-mentioned teos solution, stirs evenly, and obtains gel.Gained gel is placed in sealing device, 55
DEG C thermostatic crystallization 80h takes out washing freeze-drying, the Si-Al molecular sieve after obtaining crystallization.
Micro/nano level removes the preparation of carbon adsorbent
Si-Al molecular sieve after taking 10g crystallization, addition 18g clay, 8g water, 1g tar, total binder mass 27g, then
Secondary pore-foaming agent polyethylene glycol 2.2g is added, stirs evenly, molding squeezes out.The carbon adsorbent that removes of extrusion molding is put in furnace
600 DEG C of roastings roast duration 6.8h and are impregnated in 3h in the sodium hydroxide solution of 3mol/L after cooling, are washed with deionized
To neutrality, drying is obtained by the standby micro/nano level of the system with molecular sieve for preparing of tight pore structure except carbon adsorbent.
Embodiment 6
The preparation and crystallization of Si-Al molecular sieve gel
10g ethyl orthosilicate is added to containing 2.8g cetyl trimethylammonium bromide, 0.4g nano micro crystal cellulose
30g aqueous solution in, be stirred at room temperature uniformly.7g aluminium isopropoxide and 14g sodium hydroxide are dissolved in 10g water, the mixing that will be obtained
Liquid drops evenly in above-mentioned teos solution, stirs evenly, and obtains gel.Gained gel is placed in sealing device, 55
DEG C thermostatic crystallization 76h takes out washing freeze-drying, the Si-Al molecular sieve after obtaining crystallization.
Micro/nano level removes the preparation of carbon adsorbent
Si-Al molecular sieve after taking 10g crystallization, addition 20g clay, 10g water, 1g tar, total binder mass 31g, then
Secondary pore-foaming agent polyethylene glycol 2.4g is added, stirs evenly, molding squeezes out.The carbon adsorbent that removes of extrusion molding is put in furnace
620 DEG C of roastings roast duration 6.6h and are impregnated in 3.2h in the sodium hydroxide solution of 3mol/L after cooling, are washed with deionized water
It washs to neutrality, drying is obtained by the standby micro/nano level of the system with molecular sieve for preparing of tight pore structure except carbon adsorbent.
Embodiment 7
The preparation and crystallization of Si-Al molecular sieve gel
10g ethyl orthosilicate is added to containing 2.5g cetyl trimethylammonium bromide, 0.3g nano micro crystal cellulose
30g aqueous solution in, be stirred at room temperature uniformly.8g aluminium isopropoxide and 14g sodium hydroxide are dissolved in 10g water, the mixing that will be obtained
Liquid drops evenly in above-mentioned teos solution, stirs evenly, and obtains gel.Gained gel is placed in sealing device, 56
DEG C thermostatic crystallization 75h takes out washing freeze-drying, the Si-Al molecular sieve after obtaining crystallization.
Micro/nano level removes the preparation of carbon adsorbent
Si-Al molecular sieve after taking 10g crystallization, is added 18g clay, 10g water, 0.9g tar, and total binder mass is
28.9g adds secondary pore-foaming agent polyethylene glycol 2.6g, stirs evenly, and molding squeezes out.By extrusion molding except carbon adsorbent is put
650 DEG C of roastings in furnace roast duration 6h and are impregnated in 3.5h in the sodium hydroxide solution of 3mol/L after cooling, use deionization
Water washing to neutrality, drying is obtained by the standby micro/nano level of the system with molecular sieve for preparing of tight pore structure except carbon adsorbent.
Embodiment 8
The preparation and crystallization of Si-Al molecular sieve gel
10g ethyl orthosilicate is added to containing 2.9g cetyl trimethylammonium bromide, 0.4g nano micro crystal cellulose
30g aqueous solution in, be stirred at room temperature uniformly.5g aluminium isopropoxide and 15g sodium hydroxide are dissolved in 10g water, the mixing that will be obtained
Liquid drops evenly in above-mentioned teos solution, stirs evenly, and obtains gel.Gained gel is placed in sealing device, 52
DEG C thermostatic crystallization 72h takes out washing freeze-drying, the Si-Al molecular sieve after obtaining crystallization.
Micro/nano level removes the preparation of carbon adsorbent
Si-Al molecular sieve after taking 10g crystallization, is added 19g clay, 7g water, 0.8g tar, and total binder mass is
26.8g adds secondary pore-foaming agent polyethylene glycol 2.8g, stirs evenly, and molding squeezes out.By extrusion molding except carbon adsorbent is put
680 DEG C of roastings in furnace roast duration 6.8h and are impregnated in 3.8h in the sodium hydroxide solution of 3mol/L after cooling, spend from
Sub- water washing to neutrality, drying is obtained by the standby micro/nano level of the system with molecular sieve for preparing of tight pore structure except carbon adsorbent.
Embodiment 9
The preparation and crystallization of Si-Al molecular sieve gel
10g ethyl orthosilicate is added to containing 3g cetyl trimethylammonium bromide, 0.5g nano micro crystal cellulose
In 30g aqueous solution, it is stirred at room temperature uniformly.5g aluminium isopropoxide and 15g sodium hydroxide are dissolved in 10g water, the mixed liquor that will be obtained
It drops evenly in above-mentioned teos solution, stirs evenly, obtain gel.Gained gel is placed in sealing device, 60 DEG C
Thermostatic crystallization 80h takes out washing freeze-drying, the Si-Al molecular sieve after obtaining crystallization.
Micro/nano level removes the preparation of carbon adsorbent
Si-Al molecular sieve after taking 10g crystallization, is added 19g clay, 8g water, 0.9g tar, and total binder mass is
27.9g adds secondary pore-foaming agent polyethylene glycol 3g, stirs evenly, and molding squeezes out.By extrusion molding except carbon adsorbent is put in
700 DEG C of roastings in furnace roast duration 7h and are impregnated in 4h in the sodium hydroxide solution of 3mol/L after cooling, are washed with deionized water
It washs to neutrality, drying is obtained by the standby micro/nano level of the system with molecular sieve for preparing of tight pore structure except carbon adsorbent.
The preparation of molecular sieve of the embodiment 10 without nano micro crystal cellulose
The preparation and crystallization of Si-Al molecular sieve gel
By 10g ethyl orthosilicate, it is added in the 30g aqueous solution containing 3g cetyl trimethylammonium bromide, room temperature is stirred
It mixes uniformly.5g aluminium isopropoxide and 15g sodium hydroxide are dissolved in 10g water, obtained mixed liquor is dropped evenly into above-mentioned positive silicon
It in acetate solution, stirs evenly, obtains gel.Gained gel is placed in sealing device, 60 DEG C of thermostatic crystallization 80h, taking-up is washed
Wash freeze-drying, the Si-Al molecular sieve after obtaining crystallization.
Micro/nano level removes the preparation of carbon adsorbent
Si-Al molecular sieve after taking 10g crystallization, is added 19g clay, 7g water, 0.8g tar, and total binder mass is
26.8g adds secondary pore-foaming agent polyethylene glycol 1.4g, stirs evenly, and molding squeezes out.By extrusion molding except carbon adsorbent is put
680 DEG C of roastings in furnace roast duration 6.8h and are impregnated in 3.8h in the sodium hydroxide solution of 3mol/L after cooling, spend from
Sub- water washing to neutrality, drying is obtained by the standby micro/nano level of the system with molecular sieve for preparing of tight pore structure except carbon adsorbent.
Application example 1
Si-Al molecular sieve gel is prepared, ethyl orthosilicate, aluminium isopropoxide, sodium hydroxide, cetyl trimethyl bromine is added
Change the mass ratio of ammonium, nano micro crystal cellulose and water as 1:0.3:1:0.25:0.01:4 addition；Micro/nano level is prepared except carbon adsorption
The quality proportioning of agent, Si-Al molecular sieve, clay, water, tar, polyethylene glycol and nano micro crystal cellulose after the crystallization of addition is
1:1.5:0.7:0.08:0.05:0.05 the content of secondary pore-foaming agent is 2.9%.The Si-Al molecular sieve Si/Al=3.3 of preparation,
The aperture of prepared Si-Al molecular sieve about 65-70nm, partial size reach 85.8mg/g in 2-4mm, carbon dioxide adsorption.
Application example 2
Si-Al molecular sieve gel is prepared, ethyl orthosilicate, aluminium isopropoxide, sodium hydroxide, cetyl trimethyl bromine is added
Change the mass ratio of ammonium, nano micro crystal cellulose and water as 1:0.4:1.1:0.26:0.02:4.1 addition；Micro/nano level is prepared except carbon
The quality of adsorbent, Si-Al molecular sieve, clay, water, tar, polyethylene glycol and nano micro crystal cellulose after the crystallization of addition is matched
Than being 2.8% for the content of 1:1.6:0.8:0.08:0.035:0.035, secondary pore-foaming agent.The Si-Al molecular sieve Si/Al of preparation
=2.5, the aperture of prepared Si-Al molecular sieve about 50-60nm, partial size is reached in 3-4mm, carbon dioxide adsorption
114.6mg/g。
Application example 3
Si-Al molecular sieve gel is prepared, ethyl orthosilicate, aluminium isopropoxide, sodium hydroxide, cetyl trimethyl bromine is added
Change the mass ratio of ammonium, nano micro crystal cellulose and water as 1:0.5:1.2:0.25:0.01:4.2 addition；Micro/nano level is prepared except carbon
The quality of adsorbent, Si-Al molecular sieve, clay, water, tar, polyethylene glycol and nano micro crystal cellulose after the crystallization of addition is matched
Than being 3.1% for the content of 1:1.6:0.9:0.09:0.04:0.04, secondary pore-foaming agent.The Si-Al molecular sieve Si/Al=of preparation
2, the aperture of prepared Si-Al molecular sieve about 55-65nm, partial size reach 95.2mg/g in 2-3mm, carbon dioxide adsorption.
Application example 4
Si-Al molecular sieve gel is prepared, ethyl orthosilicate, aluminium isopropoxide, sodium hydroxide, cetyl trimethyl bromine is added
Change the mass ratio of ammonium, nano micro crystal cellulose and water as 1:0.6:1.3:0.26:0.03:4.2 addition；Micro/nano level is prepared except carbon
The quality of adsorbent, Si-Al molecular sieve, clay, water, tar, polyethylene glycol and nano micro crystal cellulose after the crystallization of addition is matched
Than being 3.7% for the content of 1:1.7:0.9:0.09:0.05:0.05, secondary pore-foaming agent.The Si-Al molecular sieve Si/Al=of preparation
1.7, the aperture of prepared Si-Al molecular sieve about 70-75nm, partial size reach 90.2mg/g in 2-3mm, carbon dioxide adsorption.
Application example 5
Si-Al molecular sieve gel is prepared, ethyl orthosilicate, aluminium isopropoxide, sodium hydroxide, cetyl trimethyl bromine is added
Change the mass ratio of ammonium, nano micro crystal cellulose and water as 1:0.7:1.3:0.27:0.03:4.3 addition；Micro/nano level is prepared except carbon
The quality of adsorbent, Si-Al molecular sieve, clay, water, tar, polyethylene glycol and nano micro crystal cellulose after the crystallization of addition is matched
Than being 4.1% for the content of 1:1.8:0.8:0.1:0.05:0.05, secondary pore-foaming agent.The Si-Al molecular sieve Si/Al=of preparation
1.5, the aperture of prepared Si-Al molecular sieve about 70-75nm, partial size reach 84.6mg/g in 2-4mm, carbon dioxide adsorption.
Application example 6
Si-Al molecular sieve gel is prepared, ethyl orthosilicate, aluminium isopropoxide, sodium hydroxide, cetyl trimethyl bromine is added
Change the mass ratio of ammonium, nano micro crystal cellulose and water as 1:0.7:1.4:0.28:0.04:4.3 addition；Micro/nano level is prepared except carbon
The quality of adsorbent, Si-Al molecular sieve, clay, water, tar, polyethylene glycol and nano micro crystal cellulose after the crystallization of addition is matched
Than being 3.9% for the content of 1:2:1:0.1:0.06:0.06, secondary pore-foaming agent.The Si-Al molecular sieve Si/Al=1.4 of preparation, institute
The aperture of the Si-Al molecular sieve of preparation about 50-60nm, partial size reach 82.5mg/g in 3-4mm, carbon dioxide adsorption.
Application example 7
Si-Al molecular sieve gel is prepared, ethyl orthosilicate, aluminium isopropoxide, sodium hydroxide, cetyl trimethyl bromine is added
Change the mass ratio of ammonium, nano micro crystal cellulose and water as 1:0.8:1.4:0.25:0.03:4.4 addition；Micro/nano level is prepared except carbon
The quality of adsorbent, Si-Al molecular sieve, clay, water, tar, polyethylene glycol and nano micro crystal cellulose after the crystallization of addition is matched
Than being 4.5% for the content of 1:1.8:1:0.09:0.065:0.065, secondary pore-foaming agent.The Si-Al molecular sieve Si/Al=of preparation
1.2, the aperture of prepared Si-Al molecular sieve about 50-55nm, partial size reach 80.3mg/g in 3-4mm, carbon dioxide adsorption.
Application example 8
Si-Al molecular sieve gel is prepared, ethyl orthosilicate, aluminium isopropoxide, sodium hydroxide, cetyl trimethyl bromine is added
Change the mass ratio of ammonium, nano micro crystal cellulose and water as 1:0.5:1.5:0.29:0.04:4.4 addition；Micro/nano level is prepared except carbon
The quality of adsorbent, Si-Al molecular sieve, clay, water, tar, polyethylene glycol and nano micro crystal cellulose after the crystallization of addition is matched
Than being 5.2% for the content of 1:1.9:0.7:0.08:0.07:0.07, secondary pore-foaming agent.The Si-Al molecular sieve Si/Al=of preparation
2, the aperture of prepared Si-Al molecular sieve about 40-50nm, partial size reach 112.6mg/g in 2-3mm, carbon dioxide adsorption.
Application example 9
Si-Al molecular sieve gel is prepared, ethyl orthosilicate, aluminium isopropoxide, sodium hydroxide, cetyl trimethyl bromine is added
Change the mass ratio of ammonium, nano micro crystal cellulose and water as 1:0.5:1.5:0.3:0.05:4.5 addition；Micro/nano level is prepared except carbon
The quality of adsorbent, Si-Al molecular sieve, clay, water, tar, polyethylene glycol and nano micro crystal cellulose after the crystallization of addition is matched
Than being 5.4% for the content of 1:1.9:0.8:0.09:0.075:0.075, secondary pore-foaming agent.The Si-Al molecular sieve Si/Al of preparation
=2, the aperture of prepared Si-Al molecular sieve about 40-50nm, partial size reach 110.3mg/ in 3-4mm, carbon dioxide adsorption
g。
Application example 10
Si-Al molecular sieve gel is prepared, ethyl orthosilicate, aluminium isopropoxide, sodium hydroxide, cetyl trimethyl bromine is added
Change the mass ratio of ammonium and water as 1:0.5:1.5:0.3:4.5 addition；Micro/nano level is prepared except carbon adsorbent, after the crystallization of addition
Si-Al molecular sieve, clay, water, tar, polyethylene glycol quality proportioning be 1:1.9:0.8:0.09:0.15, secondary pore-foaming agent
Content be 2.7%.The Si-Al molecular sieve Si/Al=2 of preparation, the aperture of prepared Si-Al molecular sieve about 80-120nm,
Partial size reaches 43.1mg/g in 3-4mm, carbon dioxide adsorption.
Claims (10)
1. the preparation method that a kind of micro/nano level removes carbon adsorbent, which is characterized in that by ethyl orthosilicate, aluminium isopropoxide, surface
Activating agent, sodium hydroxide, a pore-foaming agent and water uniformly mix, and adjust Si/Al, generate gel；After gel crystallization and ageing
Si-Al molecular sieve after crystallization；Adhesive and secondary pore-foaming agent, extrusion molding, high temperature are added into the Si-Al molecular sieve after crystallization
It bakes, cooling, NaOH solution dipping, washing and drying obtains micro/nano level except carbon adsorbent.
2. the preparation method that a kind of micro/nano level according to claim 1 removes carbon adsorbent, which is characterized in that the surface
Activating agent is cetyl trimethylammonium bromide, and the quality of cetyl trimethylammonium bromide and the quality of ethyl orthosilicate is added
Than for 0.4~0.5:1.
3. the preparation method that a kind of micro/nano level according to claim 1 removes carbon adsorbent, which is characterized in that described primary
Property pore-foaming agent be nano micro crystal cellulose, be added nano micro crystal cellulose quality and ethyl orthosilicate mass ratio be 0.05~
0.08:1。
4. the preparation method that a kind of micro/nano level according to claim 1 removes carbon adsorbent, which is characterized in that with mass ratio
Meter, ethyl orthosilicate: aluminium isopropoxide: sodium hydroxide: cetyl trimethylammonium bromide: nano micro crystal cellulose: water=1:0.5
~0.8:1~1.5:0.25~0.3:0.01~0.05:4~5.
5. the preparation method that a kind of micro/nano level according to claim 1 removes carbon adsorbent, which is characterized in that the Si/
Al=1~4.
6. the preparation method that a kind of micro/nano level according to claim 1 removes carbon adsorbent, which is characterized in that the crystallization
Temperature is 50~60 DEG C, when crystallization a length of 72~80h.
7. the preparation method that a kind of micro/nano level according to claim 1 removes carbon adsorbent, which is characterized in that described is viscous
Mixture is the mixture of clay, water and tar, by quality ratio, the Si-Al molecular sieve after crystallization: clay: water: tar=1:1.5
~2:0.7~1:0.05~0.15.
8. the preparation method that a kind of micro/nano level according to claim 1 removes carbon adsorbent, which is characterized in that described secondary
Pore-foaming agent is polyethylene glycol and nano micro crystal cellulose, and the nano micro crystal cellulose of addition and the mass ratio of polyethylene glycol are 1:
1, the polyethylene glycol of addition and the quality proportioning of the Si-Al molecular sieve after crystallization are 0.05~0.1:1.
9. the preparation method that a kind of micro/nano level according to claim 1 removes carbon adsorbent, which is characterized in that the high temperature
The temperature of baking is 500~700 DEG C, and calcining time is 6~7h.
10. the preparation method that a kind of micro/nano level according to claim 1 removes carbon adsorbent, which is characterized in that in hydrogen-oxygen
Change a length of 2~4h when impregnating in sodium solution, the concentration of sodium hydroxide solution is 3mol/L.
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