CN106362682B - A kind of biomass gas adsorbent and preparation method thereof based on dynamics separation - Google Patents
A kind of biomass gas adsorbent and preparation method thereof based on dynamics separation Download PDFInfo
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- CN106362682B CN106362682B CN201610946786.5A CN201610946786A CN106362682B CN 106362682 B CN106362682 B CN 106362682B CN 201610946786 A CN201610946786 A CN 201610946786A CN 106362682 B CN106362682 B CN 106362682B
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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
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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
- C10L3/105—Removal of contaminants of nitrogen
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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
- 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 discloses a kind of biomass gas adsorbents and preparation method thereof based on dynamics separation, and the adsorbent is faster than the rate of adsorption of nitrogen the rate of adsorption to methane；The present invention proposes methane/nitrogen separation technology that pressure-variable adsorption separation is carried out based on dynamic absorption rate difference, in the adsorption separation process, adsorbent is set to be faster than the rate of adsorption to methane to the rate of adsorption of nitrogen, so no matter adsorbent to the equilibrium adsorption capacity of nitrogen be compare methane equilibrium adsorption capacity it is big or small, as long as the rate of adsorption of nitrogen than methane the rate of adsorption after to a certain degree, preferable separating effect can be embodied and methane losses are also little.Biomass gas adsorbent proposed by the present invention based on dynamics separation can obtain with the high methane/nitrogen rate of adsorption than sorbing material, there is application prospect in the methane purification processes based on Kinetic differences.
Description
Technical field
The invention belongs to sorbing material technical field, more particularly to a kind of biomass gas absorption based on dynamics separation
Agent and preparation method thereof.
Background technology
In the biomass gas purification processes such as rubbish landfill gas, need to separate impurity component therein, to carry
The purity of high methane.Major impurity component includes carbon dioxide, oxygen, nitrogen, vapor and vulcanization in rubbish landfill gas
Hydrogen etc., it is maximum with the difficulty of denitrogenation processing in the removing purification of these impurity compositions, this is because nitrogen content and not bery high
（In 0.5~8.0% range）, according to technologies such as conventional low-temperature liquefaction, pressure-variable adsorptions, not only operating cost is high, but also is transporting
The methane losses amount that row generates in the process is very big, and economy is caused to be deteriorated.Therefore, for its nitrogen component content range feature,
Develop an emphasis research and development technology for being convenient for the denitrogenation technology of engineer application to be the field.
In rubbish landfill gas purification technique, wherein carbon dioxide, oxygen, vapor, sulphur can be removed relatively inexpensively
Change the components such as hydrogen, can thus obtain the main bicomponent system for including methane and nitrogen, and due to methane in this system
Content is very high（80~90% can be reached）, adsorbed according to conventional pressure swing adsorption, that is, based on thermodynamical equilibrium
The separation for measuring difference, is difficult to reach engineer application requirement, even be adsorbed by ADSORPTION STATE component of methane（It adsorbs at this time
Agent is higher than the adsorbance of methane the adsorbance to nitrogen）, it will cause the very big situations of methane losses, and if being absorption with nitrogen
State component is adsorbed（Adsorbent is higher than the adsorbance of nitrogen the adsorbance to methane at this time）, since the partial pressure of nitrogen is remote
Less than methane, it is attracted on adsorbent and is caused damages by regeneration so actually also having larger amount of methane.Therefore,
Pressure-variable adsorption is carried out based on thermodynamical equilibrium adsorbance difference, is difficult to meet application request.
According to above-mentioned analysis, the present invention proposes the first that pressure-variable adsorption separation is carried out based on dynamic absorption rate difference
Alkane/nitrogen separation technology makes adsorbent be faster than the absorption speed to methane to the rate of adsorption of nitrogen in the adsorption separation process
Rate, so no matter adsorbent to the equilibrium adsorption capacity of nitrogen be compare methane equilibrium adsorption capacity it is big or small, as long as nitrogen
The rate of adsorption than methane the rate of adsorption after to a certain degree, preferable separating effect and methane losses can be embodied
Less.In order to obtain with the high methane/nitrogen rate of adsorption than sorbing material have developed one kind by studying for a long period of time
Novel sorbing material has the application prospect in the methane purification processes based on Kinetic differences.
Invention content
In order to solve the problems in the prior art.The present invention provides a kind of biomass gas absorption detached based on dynamics
Agent and preparation method thereof, adsorbent prepared by the method are faster than the rate of adsorption of nitrogen the rate of adsorption to methane.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of the biomass gas adsorbent based on dynamics separation, includes the following steps：
（1）It is prepared by Molecular sieve raw material：First 10~20g sodium silicate solutions, 5~10g sodium metaaluminates be added to 30g go from
In sub- water, being stirred at 50 DEG C makes it be uniformly mixed；Then successively by 1~3g triethylene tetramines, 2~7g sodium chloride, 1~3g
Potassium chloride and 2~4g titanium tetrachlorides are added in above-mentioned solution, persistently stir 60min；It is anti-that gained suspension is transferred to high pressure
It answers in kettle, reacts 48h in 250 DEG C of static hydrothermals；It is cooled to room temperature, through being filtered, washed and in 70 DEG C of dry 10h, obtaining molecule
Sieve raw material；
（2）Ion exchange：Configuration contains MnCl2、ZrCl2、CeCl2In one kind, two or three substance aqueous solution make
It is 1 by Molecular sieve raw material and ion exchanged soln mass ratio for ion exchanged soln:20, it is added and divides into ion exchanged soln
Son sieve raw material, solution are heated to 65 DEG C and exchange for 24 hours, and filtering, the solid-liquid two-phase detached will using filtrate as liquid waste processing
Fresh ion exchanged soln is added again after 105 DEG C of drying of solid, repeats ion exchange；
（3）Drying：Filtering washing after the completion of exchanging, until being free of Cl-Ion is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material after to ion exchange；
（4）Activation process：By step（3）Obtained material is heated to 650 DEG C, keeps the temperature 5h, is down to room temperature taking-up, then send
Enter tube furnace and be warming up to 500 DEG C in pure methane atmosphere, keep the temperature 8h, is down to room temperature taking-up, obtains final target product.
Further, the content of sodium metasilicate is 35% in the sodium silicate solution.
Further, the step（2）In ion exchanged soln be contain MnCl2、ZrCl2、CeCl2In one kind, two
The aqueous solution of kind or three kinds of substances, wherein MnCl2A concentration of 0.3-2.0mol/L, ZrCl2A concentration of 0.2-1.2mol/L,
CeCl2A concentration of 0.5-1.0mol/L.
Further, the step（2）Intermediate ion exchanges in triplicate.
Further, the step（4）In, by step（3）Obtained material heats under Muffle furnace air atmosphere.
Further, the step（4）Methane content is more than 99% in middle pure methane atmosphere.
A kind of biomass gas adsorbent based on dynamics separation, the adsorbent are faster than pair the rate of adsorption of nitrogen
The rate of adsorption of methane.Compared with prior art, the present invention has the following advantages：
The present invention proposes methane/nitrogen separation skill that pressure-variable adsorption separation is carried out based on dynamic absorption rate difference
Art makes adsorbent be faster than the rate of adsorption to methane to the rate of adsorption of nitrogen in the adsorption separation process, no matter inhales in this way
Attached dose to the equilibrium adsorption capacity of nitrogen be compare methane equilibrium adsorption capacity it is big or small, as long as the rate of adsorption of nitrogen compares methane
The rate of adsorption after to a certain degree, preferable separating effect can be embodied and methane losses are also little.The present invention carries
The biomass gas adsorbent detached based on dynamics gone out can obtain with the high methane/nitrogen rate of adsorption than adsorption material
Material has the application prospect in the methane purification processes based on Kinetic differences.
Specific implementation mode
The present invention is further described with reference to embodiment.
Embodiment 1
A kind of preparation method of the biomass gas adsorbent based on dynamics separation, includes the following steps：
（1）It is prepared by Molecular sieve raw material：15g sodium silicate solutions, 8g sodium metaaluminates are added in 30g deionized waters first,
Stirring makes it be uniformly mixed at 50 DEG C；Then successively by 2g triethylene tetramines, tetra- chlorination of 5g sodium chloride, 2g potassium chloride and 3g
Titanium is added in above-mentioned solution, persistently stirs 60min；Gained suspension is transferred in autoclave, in 250 DEG C of Static Waters
Thermal response 48h；It is cooled to room temperature, through being filtered, washed and in 70 DEG C of dry 10h, obtaining Molecular sieve raw material；
（2）Ion exchange：Configuration contains MnCl2（A concentration of 1.0mol/L）、ZrCl2（A concentration of 0.8mol/L）、CeCl2
（A concentration of 0.8mol/L）Ion exchange aqueous solution, be 1 by Molecular sieve raw material and ion exchanged soln mass ratio:20, Xiang Rong
Molecular sieve raw material is added in liquid, solution is heated to 65 DEG C and exchanges for 24 hours, and filtering replaces fresh ion exchange after 105 DEG C of drying
Solution repeats step（2）In ion exchange three times.
（3）Drying：Filtering washing after the completion of exchanging, until being free of Cl-Ion is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material after to ion exchange；
（4）Activation process：By step（3）Obtained material is heated to 650 DEG C under Muffle furnace air atmosphere, keeps the temperature 5h,
It is down to room temperature taking-up, is then fed into tube furnace in pure methane atmosphere（Methane content is more than 99%）500 DEG C are warming up to, 8h, drop are kept the temperature
It is taken out to room temperature, obtains final target product.
Adsorbent made from the preparation method is faster than the rate of adsorption of nitrogen the rate of adsorption to methane.
Embodiment 2
A kind of preparation method of the biomass gas adsorbent based on dynamics separation, includes the following steps：
（1）It is prepared by Molecular sieve raw material：10g sodium silicate solutions, 10g sodium metaaluminates are added in 30g deionized waters first,
Stirring makes it be uniformly mixed at 50 DEG C；Then successively by 1g triethylene tetramines, tetra- chlorination of 7g sodium chloride, 1g potassium chloride and 4g
Titanium is added in above-mentioned solution, persistently stirs 60min；Gained suspension is transferred in autoclave, in 250 DEG C of Static Waters
Thermal response 48h；It is cooled to room temperature, through being filtered, washed and in 70 DEG C of dry 10h, obtaining Molecular sieve raw material；
（2）Ion exchange：Configuration contains MnCl2（A concentration of 0.3mol/L）、ZrCl2（A concentration of 1.2mol/L）、CeCl2
（A concentration of 0.5mol/L）Ion exchange aqueous solution, be 1 by Molecular sieve raw material and ion exchanged soln mass ratio:20, Xiang Rong
Molecular sieve raw material is added in liquid, solution is heated to 65 DEG C and exchanges for 24 hours, and filtering is replaced and fresh ion is added after 105 DEG C of drying
Solution is exchanged, step is repeated（2）Three times.
（3）Drying：Filtering washing after the completion of exchanging, until being free of Cl-Ion is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material after to ion exchange；
（4）Activation process：By step（3）Obtained material is heated to 650 DEG C under Muffle furnace air atmosphere, keeps the temperature 5h,
It is down to room temperature taking-up, is then fed into tube furnace in pure methane atmosphere（Methane content is more than 99%）500 DEG C are warming up to, 8h, drop are kept the temperature
It is taken out to room temperature, obtains final target product.
Adsorbent made from the preparation method is faster than the rate of adsorption of nitrogen the rate of adsorption to methane.
Embodiment 3
A kind of preparation method of the biomass gas adsorbent based on dynamics separation, includes the following steps：
（1）It is prepared by Molecular sieve raw material：20g sodium silicate solutions, 5g sodium metaaluminates are added in 30g deionized waters first,
Stirring makes it be uniformly mixed at 50 DEG C；Then successively by 3g triethylene tetramines, tetra- chlorination of 2g sodium chloride, 3g potassium chloride and 2g
Titanium is added in above-mentioned solution, persistently stirs 60min；Gained suspension is transferred in autoclave, in 250 DEG C of Static Waters
Thermal response 48h；It is cooled to room temperature, through being filtered, washed and in 70 DEG C of dry 10h, obtaining Molecular sieve raw material；
（2）Ion exchange：Configuration contains MnCl2（A concentration of 2.0mol/L）、ZrCl2（A concentration of 0.2mol/L）、CeCl2
（A concentration of 1.0mol/L）Ion exchange aqueous solution, be 1 by Molecular sieve raw material and ion exchanged soln mass ratio:20, Xiang Rong
Molecular sieve raw material is added in liquid, solution is heated to 65 DEG C and exchanges for 24 hours, and filtering is replaced and fresh ion is added after 105 DEG C of drying
Solution is exchanged, step is repeated（2）In ion exchange three times.
（3）Drying：Filtering washing after the completion of exchanging, until being free of Cl-Ion is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material after to ion exchange；
（4）Activation process：By step（3）Obtained material is heated to 650 DEG C under Muffle furnace air atmosphere, keeps the temperature 5h,
It is down to room temperature taking-up, is then fed into tube furnace in pure methane atmosphere（Methane content is more than 99%）500 DEG C are warming up to, 8h, drop are kept the temperature
It is taken out to room temperature, obtains final target product.
Adsorbent made from the preparation method is faster than the rate of adsorption of nitrogen the rate of adsorption to methane.
Embodiment 4
A kind of preparation method of the biomass gas adsorbent based on dynamics separation, includes the following steps：
（1）It is prepared by Molecular sieve raw material：20g sodium silicate solutions, 5g sodium metaaluminates are added in 30g deionized waters first,
Stirring makes it be uniformly mixed at 50 DEG C；Then successively by 3g triethylene tetramines, tetra- chlorination of 2g sodium chloride, 3g potassium chloride and 2g
Titanium is added in above-mentioned solution, persistently stirs 60min；Gained suspension is transferred in autoclave, in 250 DEG C of Static Waters
Thermal response 48h；It is cooled to room temperature, through being filtered, washed and in 70 DEG C of dry 10h, obtaining Molecular sieve raw material；
（2）Ion exchange：Configuration contains MnCl2（A concentration of 1.0mol/L）、ZrCl2（A concentration of 1.0mol/L）Ion
Aqueous solution is exchanged, is 1 by Molecular sieve raw material and ion exchanged soln mass ratio:20, Molecular sieve raw material, solution are added into solution
It is heated to 65 DEG C to exchange for 24 hours, filtering is replaced and fresh ion exchanged soln is added after 105 DEG C of drying, repeats step（2）In
Ion exchange is three times.
（3）Drying：Filtering washing after the completion of exchanging, until being free of Cl-Ion is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material after to ion exchange；
（4）Activation process：By step（3）Obtained material is heated to 650 DEG C under Muffle furnace air atmosphere, keeps the temperature 5h,
It is down to room temperature taking-up, is then fed into tube furnace in pure methane atmosphere（Methane content is more than 99%）500 DEG C are warming up to, 8h, drop are kept the temperature
It is taken out to room temperature, obtains final target product.
Adsorbent made from the preparation method is faster than the rate of adsorption of nitrogen the rate of adsorption to methane.
Embodiment 5
A kind of preparation method of the biomass gas adsorbent based on dynamics separation, includes the following steps：
（1）It is prepared by Molecular sieve raw material：20g sodium silicate solutions, 5g sodium metaaluminates are added in 30g deionized waters first,
Stirring makes it be uniformly mixed at 50 DEG C；Then successively by 3g triethylene tetramines, tetra- chlorination of 2g sodium chloride, 3g potassium chloride and 2g
Titanium is added in above-mentioned solution, persistently stirs 60min；Gained suspension is transferred in autoclave, in 250 DEG C of Static Waters
Thermal response 48h；It is cooled to room temperature, through being filtered, washed and in 70 DEG C of dry 10h, obtaining Molecular sieve raw material；
（2）Ion exchange：Configuration contains ZrCl2（A concentration of 0.8mol/L）、CeCl2（A concentration of 0.6mol/L）Ion
Aqueous solution is exchanged, is 1 by Molecular sieve raw material and ion exchanged soln mass ratio:20, Molecular sieve raw material, solution are added into solution
It is heated to 65 DEG C to exchange for 24 hours, filtering is replaced and fresh ion exchanged soln is added after 105 DEG C of drying, repeats step（2）In
Ion exchange is three times.
（3）Drying：Filtering washing after the completion of exchanging, until being free of Cl-Ion is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material after to ion exchange；
（4）Activation process：By step（3）Obtained material is heated to 650 DEG C under Muffle furnace air atmosphere, keeps the temperature 5h,
It is down to room temperature taking-up, is then fed into tube furnace in pure methane atmosphere（Methane content is more than 99%）500 DEG C are warming up to, 8h, drop are kept the temperature
It is taken out to room temperature, obtains final target product.
Adsorbent made from the preparation method is faster than the rate of adsorption of nitrogen the rate of adsorption to methane.
Embodiment 6
A kind of preparation method of the biomass gas adsorbent based on dynamics separation, includes the following steps：
（1）It is prepared by Molecular sieve raw material：20g sodium silicate solutions, 5g sodium metaaluminates are added in 30g deionized waters first,
Stirring makes it be uniformly mixed at 50 DEG C；Then successively by 3g triethylene tetramines, tetra- chlorination of 2g sodium chloride, 3g potassium chloride and 2g
Titanium is added in above-mentioned solution, persistently stirs 60min；Gained suspension is transferred in autoclave, in 250 DEG C of Static Waters
Thermal response 48h；It is cooled to room temperature, through being filtered, washed and in 70 DEG C of dry 10h, obtaining Molecular sieve raw material；
（2）Ion exchange：Configuration contains MnCl2（A concentration of 1.0mol/L）、CeCl2（A concentration of 1.0mol/L）Ion
Aqueous solution is exchanged, is 1 by Molecular sieve raw material and ion exchanged soln mass ratio:20, Molecular sieve raw material, solution are added into solution
It is heated to 65 DEG C to exchange for 24 hours, filtering is replaced and fresh ion exchanged soln is added after 105 DEG C of drying, repeats step（2）In
Ion exchange is three times.
（3）Drying：Filtering washing after the completion of exchanging, until being free of Cl-Ion is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material after to ion exchange；
（4）Activation process：By step（3）Obtained material is heated to 650 DEG C under Muffle furnace air atmosphere, keeps the temperature 5h,
It is down to room temperature taking-up, is then fed into tube furnace in pure methane atmosphere（Methane content is more than 99%）500 DEG C are warming up to, 8h, drop are kept the temperature
It is taken out to room temperature, obtains final target product.
Adsorbent made from the preparation method is faster than the rate of adsorption of nitrogen the rate of adsorption to methane.
Embodiment 7
A kind of preparation method of the biomass gas adsorbent based on dynamics separation, includes the following steps：
（1）It is prepared by Molecular sieve raw material：20g sodium silicate solutions, 5g sodium metaaluminates are added in 30g deionized waters first,
Stirring makes it be uniformly mixed at 50 DEG C；Then successively by 3g triethylene tetramines, tetra- chlorination of 2g sodium chloride, 3g potassium chloride and 2g
Titanium is added in above-mentioned solution, persistently stirs 60min；Gained suspension is transferred in autoclave, in 250 DEG C of Static Waters
Thermal response 48h；It is cooled to room temperature, through being filtered, washed and in 70 DEG C of dry 10h, obtaining Molecular sieve raw material；
（2）Ion exchange：Configuration contains MnCl2（A concentration of 2.0mol/L）Ion exchange aqueous solution, by molecular screen primary
Material is 1 with ion exchanged soln mass ratio:20, Molecular sieve raw material is added into solution, solution is heated to 65 DEG C and exchanges for 24 hours, mistake
Filter is replaced and fresh ion exchanged soln is added after 105 DEG C of drying, repeats step（2）In ion exchange three times.
（3）Drying：Filtering washing after the completion of exchanging, until being free of Cl-Ion is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material after to ion exchange；
（4）Activation process：By step（3）Obtained material is heated to 650 DEG C under Muffle furnace air atmosphere, keeps the temperature 5h,
It is down to room temperature taking-up, is then fed into tube furnace in pure methane atmosphere（Methane content is more than 99%）500 DEG C are warming up to, 8h, drop are kept the temperature
It is taken out to room temperature, obtains final target product.
Adsorbent made from the preparation method is faster than the rate of adsorption of nitrogen the rate of adsorption to methane.
Embodiment 8
A kind of preparation method of the biomass gas adsorbent based on dynamics separation, includes the following steps：
（1）It is prepared by Molecular sieve raw material：20g sodium silicate solutions, 5g sodium metaaluminates are added in 30g deionized waters first,
Stirring makes it be uniformly mixed at 50 DEG C；Then successively by 3g triethylene tetramines, tetra- chlorination of 2g sodium chloride, 3g potassium chloride and 2g
Titanium is added in above-mentioned solution, persistently stirs 60min；Gained suspension is transferred in autoclave, in 250 DEG C of Static Waters
Thermal response 48h；It is cooled to room temperature, through being filtered, washed and in 70 DEG C of dry 10h, obtaining Molecular sieve raw material；
（2）Ion exchange：Configuration contains ZrCl2（A concentration of 1.2mol/L）Ion exchange aqueous solution, by molecular screen primary
Material is 1 with ion exchanged soln mass ratio:20, Molecular sieve raw material is added into solution, solution is heated to 65 DEG C and exchanges for 24 hours, mistake
Filter is replaced and fresh ion exchanged soln is added after 105 DEG C of drying, repeats step（2）In ion exchange three times.
（3）Drying：Filtering washing after the completion of exchanging, until being free of Cl-Ion is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material after to ion exchange；
（4）Activation process：By step（3）Obtained material is heated to 650 DEG C under Muffle furnace air atmosphere, keeps the temperature 5h,
It is down to room temperature taking-up, is then fed into tube furnace in pure methane atmosphere（Methane content is more than 99%）500 DEG C are warming up to, 8h, drop are kept the temperature
It is taken out to room temperature, obtains final target product.
Adsorbent made from the preparation method is faster than the rate of adsorption of nitrogen the rate of adsorption to methane.
Embodiment 9
A kind of preparation method of the biomass gas adsorbent based on dynamics separation, includes the following steps：
（1）It is prepared by Molecular sieve raw material：20g sodium silicate solutions, 5g sodium metaaluminates are added in 30g deionized waters first,
Stirring makes it be uniformly mixed at 50 DEG C；Then successively by 3g triethylene tetramines, tetra- chlorination of 2g sodium chloride, 3g potassium chloride and 2g
Titanium is added in above-mentioned solution, persistently stirs 60min；Gained suspension is transferred in autoclave, in 250 DEG C of Static Waters
Thermal response 48h；It is cooled to room temperature, through being filtered, washed and in 70 DEG C of dry 10h, obtaining Molecular sieve raw material；
（2）Ion exchange：Configuration contains CeCl2（A concentration of 0.8mol/L）Ion exchange aqueous solution, by molecular screen primary
Material is 1 with ion exchanged soln mass ratio:20, Molecular sieve raw material is added into solution, solution is heated to 65 DEG C and exchanges for 24 hours, mistake
Filter is replaced and fresh ion exchanged soln is added after 105 DEG C of drying, repeats step（2）In ion exchange three times.
（3）Drying：Filtering washing after the completion of exchanging, until being free of Cl-Ion is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material after to ion exchange；
（4）Activation process：By step（3）Obtained material is heated to 650 DEG C under Muffle furnace air atmosphere, keeps the temperature 5h,
It is down to room temperature taking-up, is then fed into tube furnace in pure methane atmosphere（Methane content is more than 99%）500 DEG C are warming up to, 8h, drop are kept the temperature
It is taken out to room temperature, obtains final target product.
Adsorbent made from the preparation method is faster than the rate of adsorption of nitrogen the rate of adsorption to methane.
Diffusion coefficient of the sorbing material provided in embodiment 1 to nitrogen and methane（D.R-2）Measured value is as shown in table 1, from
In the diffusion coefficient of visible nitrogen to be significantly greater than the diffusion coefficient of methane, illustrate that there is good dynamics separating property.
Diffusion coefficient of the table 1 to nitrogen and methane adsorption
The above is only a preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of preparation method of the biomass gas adsorbent based on dynamics separation, which is characterized in that include the following steps：
（1）It is prepared by Molecular sieve raw material：10~20g sodium silicate solutions, 5~10g sodium metaaluminates are added to 30g deionized waters first
In, being stirred at 50 DEG C makes it be uniformly mixed；Then successively by 1~3g triethylene tetramines, 2~7g sodium chloride, 1~3g chlorinations
Potassium and 2~4g titanium tetrachlorides are added in above-mentioned solution, persistently stir 60min；Gained suspension is transferred to autoclave
In, react 48h in 250 DEG C of static hydrothermals；It is cooled to room temperature, through being filtered, washed and in 70 DEG C of dry 10h, obtaining molecular screen primary
Material；
（2）Ion exchange：Configuration contains MnCl2Aqueous solution as ion exchanged soln, it is molten with ion exchange by Molecular sieve raw material
Liquid mass ratio is 1:20, Molecular sieve raw material is added into ion exchanged soln, solution is heated to 65 DEG C and exchanges for 24 hours, and filtering obtains
The solid-liquid two-phase of separation, it is molten by fresh ion exchange is added again after 105 DEG C of drying of solid using filtrate as liquid waste processing
Liquid repeats ion exchange；
（3）Drying：Filtering washing after the completion of exchanging, until being free of Cl-Ion is subsequently placed in baking oven 105 DEG C of drying, obtain from
Material after son exchange；
（4）Activation process：By step（3）Obtained material is heated to 650 DEG C, keeps the temperature 5h, is down to room temperature taking-up, is then fed into pipe
Formula stove is warming up to 500 DEG C in pure methane atmosphere, keeps the temperature 8h, is down to room temperature taking-up, obtains final target product.
2. the preparation method of the biomass gas adsorbent according to claim 1 based on dynamics separation, feature exist
In：The content of sodium metasilicate is 35% in the sodium silicate solution.
3. the preparation method of the biomass gas adsorbent according to claim 1 based on dynamics separation, feature exist
In：The step（2）In ion exchanged soln be contain MnCl2Aqueous solution, wherein MnCl2A concentration of 0.3-2.0mol/
L。
4. the preparation method of the biomass gas adsorbent according to claim 1 based on dynamics separation, feature exist
In：The step（2）Intermediate ion exchanges in triplicate.
5. the preparation method of the biomass gas adsorbent according to claim 1 based on dynamics separation, feature exist
In：The step（4）In, by step（3）Obtained material heats under Muffle furnace air atmosphere.
6. the preparation method of the biomass gas adsorbent according to claim 1 based on dynamics separation, feature exist
In：The step（4）The content of methane is more than 99% in middle pure methane atmosphere.
7. according to adsorbent made from any preparation methods of claim 1-6, it is characterised in that：The adsorbent is to nitrogen
The rate of adsorption of gas is faster than the rate of adsorption to methane.
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