CN106362682A - Biomass gas adsorbent based on dynamic separation and preparation method thereof - Google Patents
Biomass gas adsorbent based on dynamic separation and preparation method thereof Download PDFInfo
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- CN106362682A CN106362682A CN201610946786.5A CN201610946786A CN106362682A CN 106362682 A CN106362682 A CN 106362682A CN 201610946786 A CN201610946786 A CN 201610946786A CN 106362682 A CN106362682 A CN 106362682A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000002028 Biomass Substances 0.000 title claims abstract description 25
- 238000000926 separation method Methods 0.000 title abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 140
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000001179 sorption measurement Methods 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims description 47
- 239000002808 molecular sieve Substances 0.000 claims description 42
- 239000002994 raw material Substances 0.000 claims description 42
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 42
- 238000005342 ion exchange Methods 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- 150000002500 ions Chemical group 0.000 claims description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 239000004115 Sodium Silicate Substances 0.000 claims description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 230000003068 static effect Effects 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 11
- 229960001124 trientine Drugs 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000010808 liquid waste Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 18
- 230000008859 change Effects 0.000 description 10
- 239000001103 potassium chloride Substances 0.000 description 9
- 235000011164 potassium chloride Nutrition 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- -1 vapor Chemical compound 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a biomass gas adsorbent based on dynamic separation and a preparation method thereof. The adsorption rate of the adsorbent on nitrogen gas is greater than the adsorption rate of the adsorbent on methane. A methane/nitrogen gas separation technology for performing variable pressure adsorption separation on the basis of dynamic adsorption rate differences is provided; in an adsorption separation process, the adsorption rate of the adsorbent on the nitrogen gas is greater than the adsorption rate of the adsorbent on the methane, so that no matter whether the balance adsorption quantity of the adsorbent on the nitrogen gas is greater or smaller than the balance adsorption quantity of the adsorbent on the methane, after the adsorption rate of the adsorbent on the nitrogen gas is greater than the adsorption rate of the adsorbent on th methane for a certain degree, a better separation effect can be shown; the methane loss is not high. The biomass gas adsorbent based on the dynamic separation provided by the invention has the advantages that an adsorption material with high nitrogen gas/methane adsorption rate ratio can be obtained; application prospects are realized in methane purification treatment on the basis of dynamic differences.
Description
Technical field
The invention belongs to adsorbing material technical field, particularly to a kind of based on the absorption of kinetics detached biomass gas
Agent and preparation method thereof.
Background technology
In the biomass gas purification processes such as rubbish landfill gas, need to fall impurity Component seperation therein, to carry
The purity of high methane.In rubbish landfill gas, major impurity component includes carbon dioxide, oxygen, nitrogen, vapor and sulfuration
Hydrogen etc., in the removing of these impurity compositions is purified, maximum with the difficulty of denitrogenation processing, this is because nitrogen content not bery high
(in 0.5～8.0% scope), according to technology such as conventional low-temperature liquefaction, pressure-variable adsorptions, not only operating cost is high, and in fortune
The methane losses amount producing during row is very big, leads to economy to be deteriorated.Therefore, for its nitrogen component content range feature,
Develop be easy to engineer applied denitrogenation technology be this field an emphasis research and development technology.
In rubbish landfill gas purification technique, wherein carbon dioxide, oxygen, vapor, sulfur can have been removed relatively inexpensively
Change the components such as hydrogen, thus can obtain the bicomponent system mainly comprising methane and nitrogen, and due to methane in this system
Content very high (can reach 80～90%), according to conventional pressure swing adsorption, that is, based on thermodynamical equilibrium absorption
The separation of amount difference, is difficult to reach engineer applied requirement, is even adsorbed for ADSORPTION STATE component with methane and (now adsorb
Agent is to the adsorbance that the adsorbance of methane is higher than to nitrogen), then can cause the very big situation of methane losses, and if with nitrogen for absorption
State component is adsorbed (now adsorbent is higher than the adsorbance to methane to the adsorbance of nitrogen), because the partial pressure of nitrogen is remote
Less than methane, so actually also have larger amount of methane to be adsorbed causing damage on the sorbent and by regeneration.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 is proposed and is carried out the detached first of pressure-variable adsorption based on dynamic absorption speed difference
Alkane/nitrogen separation technology, in this adsorption separation process, makes adsorbent that the rate of adsorption of nitrogen is faster than with the absorption speed to methane
Rate, so no matter adsorbent to the equilibrium adsorption capacity of nitrogen be compare methane equilibrium adsorption capacity big or little, as long as nitrogen
The rate of adsorption than methane the rate of adsorption after to a certain degree, just can embody preferable separating effect and methane losses
Less.In order to be able to obtain the adsorbing material with high methane/nitrogen rate of adsorption ratio, through studying for a long period of time, have developed one kind
New adsorbing material, has the application prospect in the methane purification processes based on Kinetic differences.
Content of the invention
In order to solve the problems of the prior art.The present invention provides a kind of detached biomass gas of kinetics that are based on to adsorb
Agent and preparation method thereof, the adsorbent of the method preparation is faster than the rate of adsorption to methane to the rate of adsorption of nitrogen.
For achieving the above object, the technical solution used in the present invention is:
A kind of preparation method based on kinetics detached biomass gas adsorbent, comprises the following steps:
(1) Molecular sieve raw material preparation: first 10～20g sodium silicate solution, 5～10g sodium metaaluminate are added to 30g deionized water
In, stirring at 50 DEG C makes its mix homogeneously；Then successively by 1～3g triethylene tetramine, 2～7g sodium chloride, 1～3g chlorination
Potassium and 2～4g titanium tetrachloride are added in above-mentioned solution, continuously stirred 60min；Gained suspension is transferred to autoclave
In, react 48h in 250 DEG C of static hydrothermal；It is cooled to room temperature, 10h is dried through filtering, washing and in 70 DEG C, obtains molecular screen primary
Material；
(2) ion exchange: configuration contains mncl2、zrcl2、cecl2One of, the aqueous solution of two or three material as from
Son exchanges solution, is 1:20 by Molecular sieve raw material and ion exchanged soln mass ratio, adds molecular sieve in ion exchanged soln
Raw material, solution is heated to 65 DEG C of exchange 24h, filters, obtains detached solid-liquid biphase, using filtrate as liquid waste processing, by solid
Add fresh ion exchanged soln again after 105 DEG C of drying, repeat ion exchange；
(3) dry: filter washing after the completion of exchange, until without cl-Ion, is subsequently placed in baking oven 105 DEG C of drying, obtain from
Material after son exchange；
(4) activation processing: the material that step (3) is obtained is heated to 650 DEG C, is incubated 5h, is down to room temperature and takes out, and is then fed into managing
Formula stove is warming up to 500 DEG C in pure methane atmosphere, is incubated 8h, is down to room temperature and takes out, obtains final target product.
Further, in described sodium silicate solution, the content of sodium silicate is 35%.
Further, the ion exchanged soln in described step (2) is containing mncl2、zrcl2、cecl2One of, two
Kind or the aqueous solution of three kinds of materials, wherein mncl2Concentration be 0.3-2.0mol/l, zrcl2Concentration be 0.2-1.2mol/l,
cecl2Concentration be 0.5-1.0mol/l.
Further, described step (2) intermediate ion exchanges in triplicate.
Further, in described step (4), the material that step (3) is obtained heats under Muffle furnace air atmosphere.
Further, in pure methane atmosphere in described step (4), methane content is more than 99%.
One kind is based on kinetics detached biomass gas adsorbent, and it is right that described adsorbent is faster than to the rate of adsorption of nitrogen
The rate of adsorption of methane.Compared with prior art, the invention has the advantages that
The present invention is proposed and is carried out the detached methane of pressure-variable adsorption/nitrogen separation technology based on dynamic absorption speed difference,
In this adsorption separation process, make adsorbent be faster than the rate of adsorption to methane to the rate of adsorption of nitrogen, so no matter adsorb
Agent is that the equilibrium adsorption capacity of comparison methane is big or little, as long as the rate of adsorption of nitrogen is than methane to the equilibrium adsorption capacity of nitrogen
The rate of adsorption after to a certain degree, just can embody preferable separating effect and methane losses are also little.The present invention proposes
The adsorbing material with high methane/nitrogen rate of adsorption ratio can be obtained based on kinetics detached biomass gas adsorbent,
There is the application prospect in the methane purification processes based on Kinetic differences.
Specific embodiment
With reference to embodiment, the present invention is further described.
Embodiment 1
A kind of preparation method based on kinetics detached biomass gas adsorbent, comprises the following steps:
(1) Molecular sieve raw material preparation: first 15g sodium silicate solution, 8g sodium metaaluminate are added in 30g deionized water, 50
At DEG C, stirring makes its mix homogeneously；Then successively 2g triethylene tetramine, 5g sodium chloride, 2g potassium chloride and 3g titanium tetrachloride are added
Enter in above-mentioned solution, continuously stirred 60min；Gained suspension is transferred in autoclave, anti-in 250 DEG C of static hydrothermal
Answer 48h；It is cooled to room temperature, 10h is dried through filtering, washing and in 70 DEG C, obtains Molecular sieve raw material；
(2) ion exchange: configuration contains mncl2(concentration is 1.0mol/l), zrcl2(concentration is 0.8mol/l), cecl2(concentration
For 0.8mol/l) ion exchange aqueous solution, be 1:20 by Molecular sieve raw material and ion exchanged soln mass ratio, in solution plus
Enter Molecular sieve raw material, solution is heated to 65 DEG C of exchange 24h, filters, after 105 DEG C dry, change fresh ion exchanged soln, weight
Ion exchange in multiple step (2) three times.
(3) dry: filter washing after the completion of exchange, until without cl-Ion, is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material to after ion exchange；
(4) activation processing: the material that step (3) is obtained is heated to 650 DEG C under Muffle furnace air atmosphere, is incubated 5h, is down to
Room temperature is taken out, and is then fed into tube furnace and is warming up to 500 DEG C in pure methane atmosphere (methane content is more than 99%), is incubated 8h, is down to room
Temperature is taken out, and obtains final target product.
The adsorbent that described preparation method is obtained is faster than the rate of adsorption to methane to the rate of adsorption of nitrogen.
Embodiment 2
A kind of preparation method based on kinetics detached biomass gas adsorbent, comprises the following steps:
(1) Molecular sieve raw material preparation: first 10g sodium silicate solution, 10g sodium metaaluminate are added in 30g deionized water, 50
At DEG C, stirring makes its mix homogeneously；Then successively 1g triethylene tetramine, 7g sodium chloride, 1g potassium chloride and 4g titanium tetrachloride are added
Enter in above-mentioned solution, continuously stirred 60min；Gained suspension is transferred in autoclave, anti-in 250 DEG C of static hydrothermal
Answer 48h；It is cooled to room temperature, 10h is dried through filtering, washing and in 70 DEG C, obtains Molecular sieve raw material；
(2) ion exchange: configuration contains mncl2(concentration is 0.3mol/l), zrcl2(concentration is 1.2mol/l), cecl2(concentration
For 0.5mol/l) ion exchange aqueous solution, be 1:20 by Molecular sieve raw material and ion exchanged soln mass ratio, in solution plus
Enter Molecular sieve raw material, solution is heated to 65 DEG C of exchange 24h, filters, after 105 DEG C dry, change and add fresh ion exchange molten
Liquid, repeat step (2) three times.
(3) dry: filter washing after the completion of exchange, until without cl-Ion, is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material to after ion exchange；
(4) activation processing: the material that step (3) is obtained is heated to 650 DEG C under Muffle furnace air atmosphere, is incubated 5h, is down to
Room temperature is taken out, and is then fed into tube furnace and is warming up to 500 DEG C in pure methane atmosphere (methane content is more than 99%), is incubated 8h, is down to room
Temperature is taken out, and obtains final target product.
The adsorbent that described preparation method is obtained is faster than the rate of adsorption to methane to the rate of adsorption of nitrogen.
Embodiment 3
A kind of preparation method based on kinetics detached biomass gas adsorbent, comprises the following steps:
(1) Molecular sieve raw material preparation: first 20g sodium silicate solution, 5g sodium metaaluminate are added in 30g deionized water, 50
At DEG C, stirring makes its mix homogeneously；Then successively 3g triethylene tetramine, 2g sodium chloride, 3g potassium chloride and 2g titanium tetrachloride are added
Enter in above-mentioned solution, continuously stirred 60min；Gained suspension is transferred in autoclave, anti-in 250 DEG C of static hydrothermal
Answer 48h；It is cooled to room temperature, 10h is dried through filtering, washing and in 70 DEG C, obtains Molecular sieve raw material；
(2) ion exchange: configuration contains mncl2(concentration is 2.0mol/l), zrcl2(concentration is 0.2mol/l), cecl2(concentration
For 1.0mol/l) ion exchange aqueous solution, be 1:20 by Molecular sieve raw material and ion exchanged soln mass ratio, in solution plus
Enter Molecular sieve raw material, solution is heated to 65 DEG C of exchange 24h, filters, after 105 DEG C dry, change and add fresh ion exchange molten
Liquid, the ion exchange in repeat step (2) three times.
(3) dry: filter washing after the completion of exchange, until without cl-Ion, is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material to after ion exchange；
(4) activation processing: the material that step (3) is obtained is heated to 650 DEG C under Muffle furnace air atmosphere, is incubated 5h, is down to
Room temperature is taken out, and is then fed into tube furnace and is warming up to 500 DEG C in pure methane atmosphere (methane content is more than 99%), is incubated 8h, is down to room
Temperature is taken out, and obtains final target product.
The adsorbent that described preparation method is obtained is faster than the rate of adsorption to methane to the rate of adsorption of nitrogen.
Embodiment 4
A kind of preparation method based on kinetics detached biomass gas adsorbent, comprises the following steps:
(1) Molecular sieve raw material preparation: first 20g sodium silicate solution, 5g sodium metaaluminate are added in 30g deionized water, 50
At DEG C, stirring makes its mix homogeneously；Then successively 3g triethylene tetramine, 2g sodium chloride, 3g potassium chloride and 2g titanium tetrachloride are added
Enter in above-mentioned solution, continuously stirred 60min；Gained suspension is transferred in autoclave, anti-in 250 DEG C of static hydrothermal
Answer 48h；It is cooled to room temperature, 10h is dried through filtering, washing and in 70 DEG C, obtains Molecular sieve raw material；
(2) ion exchange: configuration contains mncl2(concentration is 1.0mol/l), zrcl2The ion exchange of (concentration is 1.0mol/l)
Aqueous solution, is 1:20 by Molecular sieve raw material and ion exchanged soln mass ratio, adds Molecular sieve raw material in solution, and solution heats
To 65 DEG C of exchange 24h, filter, after 105 DEG C dry, change and add fresh ion exchanged soln, the ion in repeat step (2)
Exchange three times.
(3) dry: filter washing after the completion of exchange, until without cl-Ion, is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material to after ion exchange；
(4) activation processing: the material that step (3) is obtained is heated to 650 DEG C under Muffle furnace air atmosphere, is incubated 5h, is down to
Room temperature is taken out, and is then fed into tube furnace and is warming up to 500 DEG C in pure methane atmosphere (methane content is more than 99%), is incubated 8h, is down to room
Temperature is taken out, and obtains final target product.
The adsorbent that described preparation method is obtained is faster than the rate of adsorption to methane to the rate of adsorption of nitrogen.
Embodiment 5
A kind of preparation method based on kinetics detached biomass gas adsorbent, comprises the following steps:
(1) Molecular sieve raw material preparation: first 20g sodium silicate solution, 5g sodium metaaluminate are added in 30g deionized water, 50
At DEG C, stirring makes its mix homogeneously；Then successively 3g triethylene tetramine, 2g sodium chloride, 3g potassium chloride and 2g titanium tetrachloride are added
Enter in above-mentioned solution, continuously stirred 60min；Gained suspension is transferred in autoclave, anti-in 250 DEG C of static hydrothermal
Answer 48h；It is cooled to room temperature, 10h is dried through filtering, washing and in 70 DEG C, obtains Molecular sieve raw material；
(2) ion exchange: configuration contains zrcl2(concentration is 0.8mol/l), cecl2The ion exchange of (concentration is 0.6mol/l)
Aqueous solution, is 1:20 by Molecular sieve raw material and ion exchanged soln mass ratio, adds Molecular sieve raw material in solution, and solution heats
To 65 DEG C of exchange 24h, filter, after 105 DEG C dry, change and add fresh ion exchanged soln, the ion in repeat step (2)
Exchange three times.
(3) dry: filter washing after the completion of exchange, until without cl-Ion, is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material to after ion exchange；
(4) activation processing: the material that step (3) is obtained is heated to 650 DEG C under Muffle furnace air atmosphere, is incubated 5h, is down to
Room temperature is taken out, and is then fed into tube furnace and is warming up to 500 DEG C in pure methane atmosphere (methane content is more than 99%), is incubated 8h, is down to room
Temperature is taken out, and obtains final target product.
The adsorbent that described preparation method is obtained is faster than the rate of adsorption to methane to the rate of adsorption of nitrogen.
Embodiment 6
A kind of preparation method based on kinetics detached biomass gas adsorbent, comprises the following steps:
(1) Molecular sieve raw material preparation: first 20g sodium silicate solution, 5g sodium metaaluminate are added in 30g deionized water, 50
At DEG C, stirring makes its mix homogeneously；Then successively 3g triethylene tetramine, 2g sodium chloride, 3g potassium chloride and 2g titanium tetrachloride are added
Enter in above-mentioned solution, continuously stirred 60min；Gained suspension is transferred in autoclave, anti-in 250 DEG C of static hydrothermal
Answer 48h；It is cooled to room temperature, 10h is dried through filtering, washing and in 70 DEG C, obtains Molecular sieve raw material；
(2) ion exchange: configuration contains mncl2(concentration is 1.0mol/l), cecl2The ion exchange of (concentration is 1.0mol/l)
Aqueous solution, is 1:20 by Molecular sieve raw material and ion exchanged soln mass ratio, adds Molecular sieve raw material in solution, and solution heats
To 65 DEG C of exchange 24h, filter, after 105 DEG C dry, change and add fresh ion exchanged soln, the ion in repeat step (2)
Exchange three times.
(3) dry: filter washing after the completion of exchange, until without cl-Ion, is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material to after ion exchange；
(4) activation processing: the material that step (3) is obtained is heated to 650 DEG C under Muffle furnace air atmosphere, is incubated 5h, is down to
Room temperature is taken out, and is then fed into tube furnace and is warming up to 500 DEG C in pure methane atmosphere (methane content is more than 99%), is incubated 8h, is down to room
Temperature is taken out, and obtains final target product.
The adsorbent that described preparation method is obtained is faster than the rate of adsorption to methane to the rate of adsorption of nitrogen.
Embodiment 7
A kind of preparation method based on kinetics detached biomass gas adsorbent, comprises the following steps:
(1) Molecular sieve raw material preparation: first 20g sodium silicate solution, 5g sodium metaaluminate are added in 30g deionized water, 50
At DEG C, stirring makes its mix homogeneously；Then successively 3g triethylene tetramine, 2g sodium chloride, 3g potassium chloride and 2g titanium tetrachloride are added
Enter in above-mentioned solution, continuously stirred 60min；Gained suspension is transferred in autoclave, anti-in 250 DEG C of static hydrothermal
Answer 48h；It is cooled to room temperature, 10h is dried through filtering, washing and in 70 DEG C, obtains Molecular sieve raw material；
(2) ion exchange: configuration contains mncl2The ion exchange aqueous solution of (concentration be 2.0mol/l), by Molecular sieve raw material with
Ion exchanged soln mass ratio is 1:20, adds Molecular sieve raw material in solution, and solution is heated to 65 DEG C of exchange 24h, filters,
After 105 DEG C dry, change and add fresh ion exchanged soln, the ion exchange in repeat step (2) three times.
(3) dry: filter washing after the completion of exchange, until without cl-Ion, is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material to after ion exchange；
(4) activation processing: the material that step (3) is obtained is heated to 650 DEG C under Muffle furnace air atmosphere, is incubated 5h, is down to
Room temperature is taken out, and is then fed into tube furnace and is warming up to 500 DEG C in pure methane atmosphere (methane content is more than 99%), is incubated 8h, is down to room
Temperature is taken out, and obtains final target product.
The adsorbent that described preparation method is obtained is faster than the rate of adsorption to methane to the rate of adsorption of nitrogen.
Embodiment 8
A kind of preparation method based on kinetics detached biomass gas adsorbent, comprises the following steps:
(1) Molecular sieve raw material preparation: first 20g sodium silicate solution, 5g sodium metaaluminate are added in 30g deionized water, 50
At DEG C, stirring makes its mix homogeneously；Then successively 3g triethylene tetramine, 2g sodium chloride, 3g potassium chloride and 2g titanium tetrachloride are added
Enter in above-mentioned solution, continuously stirred 60min；Gained suspension is transferred in autoclave, anti-in 250 DEG C of static hydrothermal
Answer 48h；It is cooled to room temperature, 10h is dried through filtering, washing and in 70 DEG C, obtains Molecular sieve raw material；
(2) ion exchange: configuration contains zrcl2The ion exchange aqueous solution of (concentration be 1.2mol/l), by Molecular sieve raw material with
Ion exchanged soln mass ratio is 1:20, adds Molecular sieve raw material in solution, and solution is heated to 65 DEG C of exchange 24h, filters,
After 105 DEG C dry, change and add fresh ion exchanged soln, the ion exchange in repeat step (2) three times.
(3) dry: filter washing after the completion of exchange, until without cl-Ion, is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material to after ion exchange；
(4) activation processing: the material that step (3) is obtained is heated to 650 DEG C under Muffle furnace air atmosphere, is incubated 5h, is down to
Room temperature is taken out, and is then fed into tube furnace and is warming up to 500 DEG C in pure methane atmosphere (methane content is more than 99%), is incubated 8h, is down to room
Temperature is taken out, and obtains final target product.
The adsorbent that described preparation method is obtained is faster than the rate of adsorption to methane to the rate of adsorption of nitrogen.
Embodiment 9
A kind of preparation method based on kinetics detached biomass gas adsorbent, comprises the following steps:
(1) Molecular sieve raw material preparation: first 20g sodium silicate solution, 5g sodium metaaluminate are added in 30g deionized water, 50
At DEG C, stirring makes its mix homogeneously；Then successively 3g triethylene tetramine, 2g sodium chloride, 3g potassium chloride and 2g titanium tetrachloride are added
Enter in above-mentioned solution, continuously stirred 60min；Gained suspension is transferred in autoclave, anti-in 250 DEG C of static hydrothermal
Answer 48h；It is cooled to room temperature, 10h is dried through filtering, washing and in 70 DEG C, obtains Molecular sieve raw material；
(2) ion exchange: configuration contains cecl2The ion exchange aqueous solution of (concentration be 0.8mol/l), by Molecular sieve raw material with
Ion exchanged soln mass ratio is 1:20, adds Molecular sieve raw material in solution, and solution is heated to 65 DEG C of exchange 24h, filters,
After 105 DEG C dry, change and add fresh ion exchanged soln, the ion exchange in repeat step (2) three times.
(3) dry: filter washing after the completion of exchange, until without cl-Ion, is subsequently placed in 105 DEG C of drying in baking oven, obtains
Material to after ion exchange；
(4) activation processing: the material that step (3) is obtained is heated to 650 DEG C under Muffle furnace air atmosphere, is incubated 5h, is down to
Room temperature is taken out, and is then fed into tube furnace and is warming up to 500 DEG C in pure methane atmosphere (methane content is more than 99%), is incubated 8h, is down to room
Temperature is taken out, and obtains final target product.
The adsorbent that described preparation method is obtained is faster than the rate of adsorption to methane to the rate of adsorption of nitrogen.
Diffusion coefficient (the d.r to nitrogen and methane for the adsorbing material providing in embodiment 1-2) measured value 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 kinetics separating property.
The diffusion coefficient to nitrogen and methane adsorption for the table 1
The above be only the preferred embodiment of the present invention it should be pointed out that: those skilled in the art are come
Say, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (7)
1. a kind of preparation method based on kinetics detached biomass gas adsorbent is it is characterised in that comprise the following steps:
(1) Molecular sieve raw material preparation: first 10～20g sodium silicate solution, 5～10g sodium metaaluminate are added to 30g deionized water
In, stirring at 50 DEG C makes its mix homogeneously；Then successively by 1～3g triethylene tetramine, 2～7g sodium chloride, 1～3g chlorination
Potassium and 2～4g titanium tetrachloride are added in above-mentioned solution, continuously stirred 60min；Gained suspension is transferred to autoclave
In, react 48h in 250 DEG C of static hydrothermal；It is cooled to room temperature, 10h is dried through filtering, washing and in 70 DEG C, obtains molecular screen primary
Material；
(2) ion exchange: configuration contains mncl2、zrcl2、cecl2One of, the aqueous solution of two or three material as from
Son exchanges solution, is 1:20 by Molecular sieve raw material and ion exchanged soln mass ratio, adds molecular sieve in ion exchanged soln
Raw material, solution is heated to 65 DEG C of exchange 24h, filters, obtains detached solid-liquid biphase, using filtrate as liquid waste processing, by solid
Add fresh ion exchanged soln again after 105 DEG C of drying, repeat ion exchange；
(3) dry: filter washing after the completion of exchange, until without cl-Ion, is subsequently placed in baking oven 105 DEG C of drying, obtain from
Material after son exchange；
(4) activation processing: the material that step (3) is obtained is heated to 650 DEG C, is incubated 5h, is down to room temperature and takes out, and is then fed into managing
Formula stove is warming up to 500 DEG C in pure methane atmosphere, is incubated 8h, is down to room temperature and takes out, obtains final target product.
2. the preparation method based on kinetics detached biomass gas adsorbent according to claim 1, its feature exists
In: in described sodium silicate solution, the content of sodium silicate is 35%.
3. the preparation method based on kinetics detached biomass gas adsorbent according to claim 1, its feature exists
In: the ion exchanged soln in described step (2) is containing mncl2、zrcl2、cecl2One of, two or three material
Aqueous solution, wherein mncl2Concentration be 0.3-2.0mol/l, zrcl2Concentration be 0.2-1.2mol/l, cecl2Concentration be
0.5-1.0mol/l.
4. the preparation method based on kinetics detached biomass gas adsorbent according to claim 1, its feature exists
In: described step (2) intermediate ion exchanges in triplicate.
5. the preparation method based on kinetics detached biomass gas adsorbent according to claim 1, its feature exists
In: in described step (4), the material that step (3) is obtained heats under Muffle furnace air atmosphere.
6. the preparation method based on kinetics detached biomass gas adsorbent according to claim 1, its feature exists
In: in pure methane atmosphere in described step (4), methane content is more than 99%.
7. according to the arbitrary described preparation method of claim 1-6 be obtained adsorbent it is characterised in that: described adsorbent is to nitrogen
The rate of adsorption of gas is faster than the rate of adsorption to methane.
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