CN109179415A - Preparation method of coal-based carbon molecular sieve - Google Patents
Preparation method of coal-based carbon molecular sieve Download PDFInfo
- Publication number
- CN109179415A CN109179415A CN201811061435.1A CN201811061435A CN109179415A CN 109179415 A CN109179415 A CN 109179415A CN 201811061435 A CN201811061435 A CN 201811061435A CN 109179415 A CN109179415 A CN 109179415A
- Authority
- CN
- China
- Prior art keywords
- methane
- coal
- molecular sieve
- carbon molecular
- nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/372—Coating; Grafting; Microencapsulation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/306—Active carbon with molecular sieve properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a coal-based carbon molecular sieve, which mainly comprises the following steps: (1) screening coal-based activated carbon with a proper pore diameter; (2) depositing by using methane deposition agents with different concentrations, and adjusting the pore diameter of the coal-based activated carbon to prepare a carbon molecular sieve sample; (3) the prepared carbon molecular sieve sample has large nitrogen adsorption capacity and small methane adsorption capacity, and is favorable for kinetic separation. The invention has wider requirement on the aperture range of the coal-based activated carbon, wide source and low cost. The adopted deposition gas is a mixed gas of inert gas and methane, and the deposition gas has no pollution to the environment; the prepared product has large nitrogen adsorption capacity and small equilibrium separation coefficient, and is beneficial to the dynamic separation of nitrogen and methane.
Description
Technical field
The invention patent relates to a kind of preparation methods of coal-based carbon molecular sieve, wider using pore size distribution range, at low cost
Honest and clean coal activity charcoal, prepares the coal-based carbon molecular sieve with sieve effect, belongs to field of inorganic materials.
Background technique
PSA Gas separation is realized using balancing effect and kinetic effect and two ways.Methane and nitrogen molecule
Kinetic diameter is respectively 0.380nm and 0.364nm, and the pore-size distribution of active carbon is wider, absorption when and methane active force
Greater than the active force of nitrogen, but due to both nonpolar molecules and kinetic diameter differs smaller, adsorbing separation coefficient
Less, when carrying out separation of methane and nitrogen using balancing effect, separation is difficult, and energy consumption is larger.Separation of methane and nitrogen at present
Carbon molecular sieve mainly uses phenolic resin as raw material, and phenolic resin can prepare micropore without overactivation after charing
The matrix more flourishing, mesoporous and macropore are less, when adjusting hole under shorter sedimentation time, so that it may prepare high performance carbon point
Son sieve.But phenolic resin charing yield is lower, when charing, generates gas chromatography, pollutes environment.Coal resources in China resource
Abundant, coal utilizaton rate is low, and cost is relatively low, by selecting the coal active carbon in suitable aperture, can prepare by deposition excellent
Good carbon molecular sieve sample.The carbon molecular sieve producer well-known with Germany of Japan at present, mainly using coal as raw material, the carbon prepared divides
Son sieve sample has higher nitrogen adsorption capacity than phenolic resin, and methane separates preferably with nitrogen dynamics.
A kind of carbon molecular sieve of Chinese patent CN101935032A and preparation method thereof, using conventional carbon molecular sieve, using benzene
Deposition agent carries out deposition at 700~900 DEG C and adjusts hole, recycles activator KOH or CO2Nitrogen adsorption is increased to its second reaming
Amount, prepares the carbon molecular sieve of methane and nitrogen separation.Activating process is complex, and activating agent highly basic can corrode equipment, and
The nitrogen and methane adsorption amount that suitably adsorb aperture and sample are not pointed out.
Chinese patent CN103086354A discloses a kind of phenolic resin based carbon molecular sieve and preparation method thereof, mainly with
Phenolic resin waste is raw material, and used tune hole agent is mainly one kind of benzene,toluene,xylene, ethylene and methanol, 600
~1000 DEG C carry out deposition and adjust hole, and the volume content of methane can reach 90% or more after three-level is concentrated.Coal based activated carbon matrix
More complex than phenolic resin as matrix resin aperture, mesoporous is more with macropore, deposits complex.
Chinese patent CN103086354A, which is disclosed, a kind of utilizes brown coal base active carbon separation of methane, nitrogen and carbon dioxide
Method, active carbon from coal not by deposition, after five step single column single cycles, volume percent methane is increased to from 31%
51%, methane concentration improves 20%.The sample minimum-value aperture is 0.5nm, and average pore size is larger, and can from Dynamic Separation figure
Know, adsorbing separation is partial to activated carbon property after 7min.
Chinese patent CN101804979A discloses a kind of coal-based carbon molecular sieve and preparation method thereof, mainly uses benzene, first
The organic matters such as benzene are to adjust hole agent, and the sample nitrogen highest adsorbance of preparation is 5.95ml, methane highest adsorbance 17.1ml, balance
Separation is about 3, and nitrogen adsorption capacity is lower, and methane adsorption amount is big, is mainly partial to equilibrium adsorption, dynamic in pressure-variable adsorption
Energy consumption is increased in state adsorptive separation engineering, is unfavorable for methane and is separated with the dynamics of nitrogen mixture.
Chinese patent 105692613A discloses methane purification carbon molecular sieve preparation method, mainly using aromatic hydrocarbons such as benzene
Substance, molecular sieve bore diameter are adjusted to 0.36~0.40nm, do not carry out to the adsorbance tune hole of the nitrogen of carbon molecular sieve and methane
Detailed description, does not point out the selection mode of presoma.
Existing invention prepares coal-based carbon molecular sieve, and the process is more complicated, does not point out the suitable of coal-based carbon molecular sieve presoma
Pore diameter range, and nitrogen adsorption capacity is lower, and methane adsorption amount is relatively large, and dynamics separating effect is poor.Present invention preparation
Nitrogen adsorption capacity it is relatively large, deposited using methane, process conditions are simple, and dynamics separation is preferable.
Summary of the invention
The present invention provides a kind of preparation method of coal-based carbon molecular sieve, requires active carbon from coal pore diameter range wider, next
Source is extensive, cheap.The deposition gases used is indifferent gas and methane mixed gas, deposition gases no pollution to the environment；Preparation
Reconciliation of inventory separation is smaller, can promote the dynamics separating property of nitrogen and methane.
A kind of coal-based carbon molecular sieve preparation method provided by the invention comprising the steps of:
A. suitable coal-based carbon molecular sieve presoma is selected, it is 0.25~0.30cm that the hole 0.3~1nm of active carbon from coal, which holds,3/ g, 1
It is 0.05~0.10cm that the hole~2nmm, which holds,3It is 0.08~0.12cm that/g, mesoporous and macropore hole, which hold,3/g。
B. by a certain amount of sample, after being put into high temperature furnace, it is first passed through 10~20min of nitrogen, net air is driven, in indifferent gas flow
Under conditions of 100~200ml/min, when heating rate is 5~20 DEG C/min, preferably 10~15/min is warming up to high temperature furnace
Depositing temperature.
C. 800~1000 DEG C of depositing temperature, preferred deposition temperature be 850~950 DEG C, deposition gases be high concentration methane with
Inertia gas mixture (methane volumetric score is 20~40%).Sedimentation time is 60~150min, preferably 90~120min.
D. pore-size distribution is carried out to the carbon molecular sieve of preparation and gas absorption amount detects.
E. after stopping heating, using inert nitrogen gas, flow is that 100~200ml/min is cooled to 150 in high temperature furnace
After~200 DEG C, sample is moved on in hermetically drying device after being cooled to room temperature, vacuum sealed package.
The methane and inertia gas mixture that step c is used, indifferent gas can be the gases such as nitrogen, argon gas, deposition gases
It can be the gases such as the treated low concentration coal-bed gas only containing nitrogen and methane, natural gas and biogas.
Compared with prior art, nitrogen adsorption capacity prepared by the present invention is relatively large, after being deposited using methane, process conditions
Simply, dynamics separation is preferable.
Detailed description of the invention:
Fig. 1 is that 2 sample differential hole of embodiment holds with the wide variation tendency in hole.
Fig. 2 is that 4 sample differential hole of embodiment holds with the wide variation tendency in hole.
Specific embodiment
Below with reference to example, the present invention will be further described, but not as the foundation limited the present invention.In 298k,
Under the conditions of 760torr, using the methane adsorption amount and nitrogen adsorption capacity of Autosorb-IQ adsorption instrument measurement carbon molecular sieve.Using
The pore-size distribution and specific surface area of specific surface aperture tester ASAP2460 measurement carbon molecular sieve.
Embodiment 1:
By the Yilan quality about 30g active carbon from coal presoma (aperture in 0.3~1nm, 0.25~0.30cm3/g of Kong Rongwei；?
When 1~2nm, 0.05~0.10cm3/g of Kong Rongwei；It is 0.08~0.12cm3/g that mesoporous and macropore hole, which hold,.), it is put into high temperature furnace
Afterwards, it is first passed through nitrogen 15min, drives net air, under conditions of nitrogen flow is 200ml/min, by high temperature furnace in heating rate
Under adjusting for 20 DEG C/min, 850 DEG C of depositing temperature are warming up to, deposition gases are high concentration methane and nitrogen mixture (methane body
Fraction is 30%, methane flow 150ml/min), sedimentation time 90min, after stopping heating, using inert nitrogen gas,
Flow is after 200ml/min is cooled to 200 DEG C in high temperature furnace, sample to be moved on in hermetically drying device, after being cooled to room temperature, very
Empty sealed package.1nm or less the micropore size distribution of coal-based carbon molecular sieve is shown in Table 1(using HK method calculated hole diameters point after deposition
Cloth), the coal-based carbon molecular sieve atmosphere of static nitrogen adsorbance and methane adsorption amount of preparation are shown in Table 1.
Embodiment 2:
Sedimentation time becomes 120min, remaining experimental condition is the same as embodiment 1.1nm or less the micropore of coal-based carbon molecular sieve after deposition
Pore-size distribution is shown in Table 1(and is distributed using HK method calculated hole diameters), see Fig. 1, the coal-based carbon molecular sieve atmosphere of static nitrogen adsorbance of preparation with
Methane adsorption amount is shown in Table 1.
Embodiment 3:
Sedimentation time becomes 180min, remaining experimental condition is the same as embodiment 1.1nm or less the micropore of coal-based carbon molecular sieve after deposition
Pore-size distribution is shown in Table 1(and is distributed using HK method calculated hole diameters), the coal-based carbon molecular sieve atmosphere of static nitrogen adsorbance and methane of preparation are inhaled
Attached amount is shown in Table 1.
Embodiment 4:
Depositing temperature be 900 DEG C, sedimentation time 90min, methane volumetric score be 30%, methane flow 250ml/min,
Remaining experimental condition is the same as embodiment 1.1nm or less the micropore size distribution of coal-based carbon molecular sieve is shown in Table 1(and is calculated using HK method after deposition
Pore-size distribution), see Fig. 2, the coal-based carbon molecular sieve atmosphere of static nitrogen adsorbance and methane adsorption amount of preparation are shown in Table 1.
Embodiment 5:
Depositing temperature be 950 DEG C, sedimentation time 90min, methane volumetric score be 30%, methane flow 150ml/min,
Remaining experimental condition is the same as embodiment 1.1nm or less the micropore size distribution of coal-based carbon molecular sieve is shown in Table 1(and is calculated using HK method after deposition
Pore-size distribution), the coal-based carbon molecular sieve atmosphere of static nitrogen adsorbance and methane adsorption amount of preparation are shown in Table 1.
1 coal-based carbon molecular sieve pore structure parameter of table and gas absorption amount
| The hole 0.3-0.6nm holds (cm3/ g) | The hole 0.6-0.8nm holds (cm3/ g) | The hole 0.8-1nm holds (cm3/ g) | Methane adsorption amount (ml/g) | Nitrogen adsorption capacity (ml/g) | CH4/N2Equilibrium segregation coefficient α | |
| Embodiment 1 | 0.185 | 0.065 | 0.035 | 27.0 | 9.5 | 2.84 |
| Embodiment 2 | 0.145 | 0.055 | 0.035 | 18.0 | 7.8 | 2.31 |
| Embodiment 3 | 0.090 | 0.040 | 0.025 | 16.0 | 6.0 | 2.67 |
| Embodiment 4 | 0.160 | 0.070 | 0.035 | 18.6 | 7.8 | 2.38 |
| Embodiment 5 | 0.140 | 0.065 | 0.034 | 16.0 | 7.0 | 2.29 |
What has been described above is only a preferred embodiment of the present invention, it is noted that for those skilled in the art, not
It is detached under the premise of general idea of the present invention, several changes and improvements can also be made, these also should be considered as protection of the invention
Range, these all will not influence the effect and patent practicability that the present invention is implemented.
Claims (4)
1. a kind of preparation method of coal-based carbon molecular sieve, it is characterized in that: wider using pore size distribution range, low-cost coal is living
Property charcoal, deposited at high temperature using methane deposition agent, prepare that nitrogen adsorption capacity is big, separation of methane/nitrogen coal-based carbon
Molecular sieve.
2. according to preparation method required by right 1, it is characterised in that: 0.3~1nm of active carbon from coal as described in step (1)
0.25~0.30cm of Kong Rongwei3It is 0.05~0.10cm that the hole /g, 1~2nmm, which holds,3/ g, mesoporous and macropore hole hold for 0.08~
0.12cm3/g。
3. according to methane deposition agent required by right 1, it is characterised in that: deposition gases as described in step (1) are indifferent gas
With methane mixed gas, volume percent methane is 20~40%；Temperature as described in step (1) is 800~1000 DEG C, in step (1)
The sedimentation time is 90~120min.
4. can may be by processing for the gases such as nitrogen, argon gas, deposition gases according to indifferent gas required by right 1 and 3
The gases such as the low concentration coal-bed gas only containing nitrogen and methane, natural gas and biogas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811061435.1A CN109179415A (en) | 2018-09-12 | 2018-09-12 | Preparation method of coal-based carbon molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811061435.1A CN109179415A (en) | 2018-09-12 | 2018-09-12 | Preparation method of coal-based carbon molecular sieve |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109179415A true CN109179415A (en) | 2019-01-11 |
Family
ID=64910278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811061435.1A Pending CN109179415A (en) | 2018-09-12 | 2018-09-12 | Preparation method of coal-based carbon molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109179415A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110773120A (en) * | 2019-11-08 | 2020-02-11 | 四川大学 | Metal salt modified molecular sieve and preparation method and application thereof |
| CN110773121A (en) * | 2019-11-08 | 2020-02-11 | 四川大学 | Boric acid modified molecular sieve and preparation method and application thereof |
| CN110773125A (en) * | 2019-11-08 | 2020-02-11 | 四川大学 | Organic modified molecular sieve and preparation method and application thereof |
| CN113120903A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Activated carbon and preparation method and application thereof |
| CN117163955A (en) * | 2023-09-07 | 2023-12-05 | 煜爚(东海)新材料有限公司 | Coal-based porous carbon molecular sieve and processing technology thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101218174A (en) * | 2005-09-29 | 2008-07-09 | 昭和电工株式会社 | Activated carbon and process of making the same |
| CN101804979A (en) * | 2010-04-07 | 2010-08-18 | 煤炭科学研究总院 | Coal-based carbon molecular sieve and preparation method thereof |
| CN107324307A (en) * | 2017-06-06 | 2017-11-07 | 中国地质科学院郑州矿产综合利用研究所 | Preparation method of carbon molecular sieve for separating methane and nitrogen |
-
2018
- 2018-09-12 CN CN201811061435.1A patent/CN109179415A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101218174A (en) * | 2005-09-29 | 2008-07-09 | 昭和电工株式会社 | Activated carbon and process of making the same |
| CN101804979A (en) * | 2010-04-07 | 2010-08-18 | 煤炭科学研究总院 | Coal-based carbon molecular sieve and preparation method thereof |
| CN107324307A (en) * | 2017-06-06 | 2017-11-07 | 中国地质科学院郑州矿产综合利用研究所 | Preparation method of carbon molecular sieve for separating methane and nitrogen |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110773120A (en) * | 2019-11-08 | 2020-02-11 | 四川大学 | Metal salt modified molecular sieve and preparation method and application thereof |
| CN110773121A (en) * | 2019-11-08 | 2020-02-11 | 四川大学 | Boric acid modified molecular sieve and preparation method and application thereof |
| CN110773125A (en) * | 2019-11-08 | 2020-02-11 | 四川大学 | Organic modified molecular sieve and preparation method and application thereof |
| CN110773120B (en) * | 2019-11-08 | 2021-05-07 | 四川大学 | Metal salt modified molecular sieve and preparation method and application thereof |
| CN110773125B (en) * | 2019-11-08 | 2021-06-04 | 四川大学 | Organic modified molecular sieve and preparation method and application thereof |
| CN113120903A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Activated carbon and preparation method and application thereof |
| CN113120903B (en) * | 2019-12-31 | 2023-01-10 | 中国石油化工股份有限公司 | Activated carbon and preparation method and application thereof |
| CN117163955A (en) * | 2023-09-07 | 2023-12-05 | 煜爚(东海)新材料有限公司 | Coal-based porous carbon molecular sieve and processing technology thereof |
| CN117163955B (en) * | 2023-09-07 | 2024-04-30 | 煜爚(东海)新材料有限公司 | Coal-based porous carbon molecular sieve and processing technology thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109179415A (en) | Preparation method of coal-based carbon molecular sieve | |
| Zhang et al. | Micro-mesoporous activated carbon simultaneously possessing large surface area and ultra-high pore volume for efficiently adsorbing various VOCs | |
| Zhang et al. | Biochar for volatile organic compound (VOC) removal: Sorption performance and governing mechanisms | |
| Yang et al. | Surface modified and activated waste bone char for rapid and efficient VOCs adsorption | |
| Wang et al. | Chemical liquid deposition modified 4A zeolite as a size-selective adsorbent for methane upgrading, CO2 capture and air separation | |
| Chen et al. | Polyethylenimine-incorporated zeolite 13X with mesoporosity for post-combustion CO2 capture | |
| CN106006636A (en) | Biomass-based nitrogen-doped porous carbon material, and preparation method and application thereof | |
| CN110773125B (en) | Organic modified molecular sieve and preparation method and application thereof | |
| Yuan et al. | Effects of pore structure of prepared coal-based activated carbons on CH4 enrichment from low concentration gas by IAST method | |
| Wang et al. | Pith based spherical activated carbon for CO2 removal from flue gases | |
| Yang et al. | Advances in metal-organic frameworks for efficient separation and purification of natural gas | |
| Tiwari et al. | Epoxy based oxygen enriched porous carbons for CO2 capture | |
| Liu et al. | Role of molecular size of volatile organic compounds on their adsorption by KOH-activated micro-mesoporous carbon | |
| Yang et al. | Surface modification on semi-coke-based activated carbon for enhanced separation of CH4/N2 | |
| Wu et al. | A novel bio-cellulose membrane and modified adsorption approach in CO2/H2 separation technique for PEM fuel cell applications | |
| Wang et al. | Gaseous adsorption of hexamethyldisiloxane on carbons: Isotherms, isosteric heats and kinetics | |
| Zhou et al. | Adsorption/desorption of toluene on a hypercrosslinked polymeric resin in a highly humid gas stream | |
| CN110773121A (en) | Boric acid modified molecular sieve and preparation method and application thereof | |
| Liu et al. | Different CO2 absorbents-modified SBA-15 sorbent for highly selective CO2 capture | |
| Majchrzak-Kucęba et al. | The potential of biocarbon as CO2 adsorbent in VPSA unit | |
| Qiu et al. | Size‐Controllable Synthesis of ZIF‐8 and Derived Nitrogen‐Rich Porous Carbon for CO2 and VOCs Adsorption | |
| CN108993400A (en) | A kind of preparation method of the high-efficiency adsorbent of separation of nitrogen-methane | |
| Yang et al. | Molecular sieve supported ionic liquids as efficient adsorbent for CO2 capture | |
| CN107324307A (en) | Preparation method of carbon molecular sieve for separating methane and nitrogen | |
| WO2008072215A2 (en) | Separation column and pressure swing adsorption process for gas purification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190111 |
|
| WD01 | Invention patent application deemed withdrawn after publication |