CN102139200A - Preparation method of modified attapulgite adsorbent for recovering low-concentration methane in coal mine gas - Google Patents
Preparation method of modified attapulgite adsorbent for recovering low-concentration methane in coal mine gas Download PDFInfo
- Publication number
- CN102139200A CN102139200A CN 201110002435 CN201110002435A CN102139200A CN 102139200 A CN102139200 A CN 102139200A CN 201110002435 CN201110002435 CN 201110002435 CN 201110002435 A CN201110002435 A CN 201110002435A CN 102139200 A CN102139200 A CN 102139200A
- Authority
- CN
- China
- Prior art keywords
- coal mine
- modified attapulgite
- preparation
- methane
- silane coupler
- 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
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a modified attapulgite adsorbent for recovering low-concentration methane in coal mine gas, which comprises the following steps of: (1) activating attapulgite for 1 hour by using 1mol/L hydrochloric acid, wherein the ratio of the volume (mL) of hydrochloric acid to the mass (g) of attapulgite is 1:1; (2) repeatedly washing acidified attapulgite with water the volume of which is ten times as much as that of acid, and then filtering twice; (3) adding a filter cake obtained through filtration to water with equivalent volume, dispersing for 20 minutes under the action of ultrasonic waves; (4) refluxing the ultrasonically-dispersed acidified attapulgite and silane coupling agent hydrolyzate for 2 hours by means of microwave chemical reaction; (5) filtering after organic modification, washing the filter cake to be neutral with distilled water; and (6) drying the filter cake in a drying oven at 120 DEG C to obtain the modified attapulgite adsorbent. The modified attapulgite adsorbent obtained by using the method provided by the invention can selectively adsorb and recover methane in coal mine gas.
Description
Technical field
The present invention relates to the modified attapulgite adsorbent preparation method, be specifically related to reclaim the modified attapulgite adsorbent preparation method of low-concentration methane in the coal mine mash gas.
Background technology
Coal bed gas is commonly called as coal mine gas, mainly with methane (CH
4) be main, also have a spot of ethane (C
2H
6) and propane (C
3H
8) wait lighter hydrocarbons and AIR MIXTURES, be valuable energy resources.China's highly gassy mine is many, and coal mine gas is the major hidden danger of Safety of Coal Mine Production always.In recent years, the particularly serious gas explosion accident in colliery happens occasionally, and has caused heavy losses for people's lives and properties.Methane explosion ratio interval is 4.5% – 15%, and the outstanding direct effective method of prevention gas is to extract gas before mining earlier out, and every year is discharged a large amount of CH because of coal mining in the whole world in atmosphere
4, expect CH in 2010
4Discharge capacity will increase to 28Mt, and wherein 70% is from CH
4Concentration is lower than 1% mine.The main component CH of gas
4Having the effect that destroys earth's ozone layer, is CO to the greenhouse effects of weather
2More than 20 times, the direct discharging of coal mine mash gas will cause serious environmental to pollute and the wasting of resources.
For further strengthening coal bed gas methane drainage and utilization project dynamics; strengthen control of coalmine gas; alleviate the coal mine gas disaster; the General Office of the State Council is just dispatch as far back as 2006: " about accelerating some suggestions of coal bed gas (coal mine gas) methane drainage and utilization project " (Office of the State Council is sent out [2006] No. 47); clear and definite administer and utilize the policy that develops simultaneously; make full use of energy resources, effectively preserve the ecological environment.CH in coal mine gas
4Be enriched to more than 80%, can be used as industrial chemicals or highly effective fuel, and the coal bed gas that the down-hole extraction goes out is low because of the content of methane, impurity is many, presses for the purification separation problem that solves the extraction coal bed gas.
Traditional purification and separation method all has some defectives, and cryogenic rectification method only is applicable to the gaseous mixture that methane concentration is higher, and when methane concentration was low, cryogenic rectification existed energy consumption big, the shortcoming that cost is high.Country is 0.5% – 1.5% to the discharge standard of methane emptying concentration, and the methane of low concentration is too high with the method processing energy consumption of cryogenic rectification like this.Remove H through the preliminary clearning processing
2O, CO
2Deng the mash gas extraction of impurity, can regard CH as
4With Air mixing gas, the O in the mist
2Kinetics radius is little, molecular diffusion rate is fast, is easier to remove, so can be with mist with CH
4/ N
2Represent; N
2With CH
4Critical-temperature all very low, the two physical property is close, so the core technology that coal mine gas gas separates is CH
4With N
2Between separation.Molecular diameter of methane is 0.382nm, and nitrogen is 0.368nm, and both dynamics difference is not remarkable yet, and is therefore unsatisfactory by dynamics differential separation effect.Bibliographical information XPS film (expanded polystyrene) is to CH
4/ N
2The separation factor of system only is 1.39.And transformation absorption (Pressure Swing Adsorption, PSA) technology is an effective gas separation method of purification the most, since the eighties in 20th century, has been widely used in industrial gasses separation processes such as oil, natural gas, chemical industry.Abroad separate and concentrate CH
4Research be primarily aimed at natural gas or casing-head gas, CH in these gases
4Be main component.Because CH in the gas that the colliery extraction goes out
4Concentration be lower than 1% as the methane volume content that the coalmine ventilation well array goes out, thereby separating difficulty is bigger far below the concentration of methane in natural gas or the oil gas field.Both at home and abroad to CH
4/ N
2Low concentration CH in the system
4PSA reclaim research all extremely thin always a little less than.
Abroad to CH
4/ N
2The PSA of system research, major part are to adopt active carbon or carbon molecular sieve (Carbon Molecular Sieve CMS) is adsorbent.Active carbon is used for CH
4/ N
2The separation of system, majority are at CH
4Volume fraction is higher than 50% mixture, studies show that, the methane volume fraction is lower than 15%, separating with active carbon or carbon molecular sieve is the comparison difficulty, economic effect is not obvious, and the modified activated carbon complicated process of preparation, cost is higher relatively, and the recovery that is not suitable for low-concentration methane in the coal mine mash gas is used.Also have research and utilization zeolite molecules and metallic organic framework (MOF) to come adsorbed methane, but major part is to be used for high concentration methane to store research, mainly investigates adsorption capacity, and to CH
4/ N
2Selectivity is less demanding, also is not suitable for the absorption of methane transformation.Also have bibliographical information to utilize silica gel to come adsorbing separation CH
4/ N
2, but separation factor is not high, does not have using value equally.
Domestic correlative study is mainly learned good fortune academician research group from aquatic foods, and they are with active carbon (CH
4/ N
2Separation be 2.90) or the active carbon of modification is an adsorbent, adopts balancing effect to concentrate CH
4, can be with CH
4/ N
2The concentration of middle methane improves about 18% – 27%.But under the few situation of cycle-index, realize gas CH with the colliery extraction
4Concentration is brought up to 80% and also is difficult to, and charcoal absorption is based on the equilibrium separation principle, because CH
4/ N
2Equilibrium segregation coefficient is not high, can improve CH though improve cycle-index
4Concentration, but consumed a large amount of power costs, engineering is used uneconomical.Therefore, need to strengthen other adsorbents and be used for CH
4/ N
2The concentrating and separating research of system.
The excellent clay of recessed soil (Attapulgite is called for short recessed soil) is the zeopan clay mineral of a kind of layer of chain structure.The recessed soil resource in Jiangsu Province is abundant, by the end of the year 2006, reconnoitre once fairly large statistics and the prediction of resource potential distant view that the clay ore resources reserves of degree carry out by each mining area difference, the recessed native ore resources amount in area, Xuyi, Huai, Jiangsu Province is about 8.9 hundred million tons, accounts for 74% of the recessed native prospective reserves in the whole world.Recessed soil is given its very big specific surface and unique absorption property because of its special fiber rod crystalline form attitude with a layer chain crystal structure, is mainly used in industrial circles such as grease-decolor, water absorbing agent, catalysis, water treatment at present.
Summary of the invention
The objective of the invention is to: the modified attapulgite adsorbent preparation method who reclaims low-concentration methane in the coal mine mash gas is provided, and the modified attapulgite adsorbent that adopts this preparation method to obtain can optionally adsorb methane in the recovery coal mine gas gas.
Technical solution of the present invention is that this preparation method may further comprise the steps: (1) activates one hour with the hydrochloric acid of 1mol/L to recessed soil, and hydrochloric acid volume (mL) is 1:1 with recessed soil property amount (g) ratio; (2) recessed native water cyclic washing and filtration 2 times of acidifying with 10 times of sour volumes; (3) will filter in the filter cake adding and sour isopyknic water of gained, under the ultrasonic wave effect, disperse 20 min; (4) recessed soil of the acidifying of ultrasonic dispersion and silane coupler hydrolyzate use microwave chemical reaction backflow 2h; (5) organically-modified end back filtration is extremely neutral with the filter cake washing with distilled water; (6) filter cake in 120 ℃ of oven dry, gets modified attapulgite adsorbent in drying box.
Wherein, silane coupler is KH550, and chemical name is a gamma-aminopropyl-triethoxy-silane; Or silane coupler is KH570, and chemical name is γ-(methacryloxypropyl) propyl trimethoxy silicane.
Wherein, silane coupler volumetric usage (mL) is 1:100～1:10 with initial recessed soil property amount (g) ratio.
Wherein, the silane coupler hydrolyzate is by adding with sour isopyknic water stirring hydrolysis 30min in the silane coupler and getting.
Wherein, the reaction mechanism on silane coupler and recessed soil surface realizes by following process:
RSi (OR
/)
3+ 3H
2O → RSi (OH)
3+ 3R
/OH (hydrolysis)
(condensation)
The present invention has the following advantages: 1, recessed soil is after peracid treatment, and impurity such as calcium carbonate are removed, and inner duct enlarges, and specific area increases, the part metals Al in the recessed soil
3+, Mg
2+The ion stripping, the crystal structure part is changed into amorphous Si O
2, there is a large amount of Si – OH, utilize the recessed native surface hydroxyl isoreactivity of different base group modifications position to change recessed native surface polarity, and then influence its adsorption/desorption performance, improve recessed soil to CH
4/ N
2The separation of system, methane in the coal mine gas gas is reclaimed in selective absorption; 2, utilize the abundant hydroxyl in activation recessed soil surface, adopt organo silane coupling agent to carry out modification, improve the selection absorption to organic gas methane, silane coupler modified recessed soil is used for the adsorbing separation that molar concentration is lower than 5% coalmine ventilation mouth low concentration gas gas.
The specific embodiment
Further specify technical solution of the present invention below in conjunction with specific embodiment, these embodiment can not be interpreted as it is restriction to technical solution.
Embodiment 1: prepare modified attapulgite adsorbent according to following steps:
Take by weighing the recessed soil of 100g, add hydrochloric acid 100 mL of 1mol/L, stir 1 h, the recessed soil of acidifying adds the filter cake that filters gained at last in the 100mL water with 1L water cyclic washing and filtration 2 times, disperses 20 min under the ultrasonic wave effect; Get 1ml silane coupler KH550, add 100mL water, stir hydrolysis 30min, obtain the hydrolyzate of silane coupler; In the 500 mL there-necked flasks that stirring and condensing unit are arranged, add through recessed soil of the acidifying of ultrasonic dispersion and silane coupler hydrolyzate, under Temperature Control Type microwave chemical reaction system, power 0.2kV back flow reaction 2 hours; Suction filtration is washed with distilled water to neutrality, and 120 ℃ of oven dry in drying box must be used for the modified attapulgite adsorbent of adsorption of Low Concentration methane; The adsorbent of preparation is measured its absorption property to methane and nitrogen with the IGA intelligent gravimetric instrument that Britain HIDEN company produces, and its adsorbing separation coefficient to methane and nitrogen is that the adsorption capacity of 2.32,20 ℃ of methane under 1MPa is 8.1ml/g.
Embodiment 2: the consumption of modification coupling agent KH550 is 2ml, and all the other are with embodiment 1, and the adsorbing separation coefficient of the modified adsorbent of preparation is that the adsorption capacity of 2.86,20 ℃ of methane under 1MPa is 9.3ml/g.
Embodiment 3: the consumption of modification coupling agent KH550 is 5 ml, and all the other are with embodiment 1, and the adsorbing separation coefficient of the modified adsorbent of preparation is that the adsorption capacity of 4.12,20 ℃ of methane under 1MPa is 11.6ml/g.
Embodiment 4: the consumption of modification coupling agent KH550 is 10 ml, and all the other are with embodiment 1, and the adsorbing separation coefficient of the modified adsorbent of preparation is that the adsorption capacity of 3.57,20 ℃ of methane under 1MPa is 14.8ml/g.
Embodiment 5: the consumption of modification coupling agent KH570 is 1 ml, and all the other are with embodiment 1, and the adsorbing separation coefficient of the modified adsorbent of preparation is that the adsorption capacity of 2.19,20 ℃ of methane under 1MPa is 8.4ml/g.
Embodiment 6: the consumption of modification coupling agent KH570 is 5 ml, and all the other are with embodiment 1, and the adsorbing separation coefficient of the modified adsorbent of preparation is that the adsorption capacity of 3.75,20 ℃ of methane under 1MPa is 12.7ml/g.
Embodiment 7: the consumption of modification coupling agent KH570 is 10 ml, and all the other are with embodiment 1, and the adsorbing separation coefficient of the modified adsorbent of preparation is that the adsorption capacity of 3.02,20 ℃ of methane under 1MPa is about 16.2ml/g.
Comparative example: do not add any coupling agent, all the other are with embodiment 1, and its adsorbing separation coefficient to methane and nitrogen only is that the adsorption capacity of 1.56,20 ℃ of methane under 1MPa is 5.7ml/g.
The concrete numerical value of each composition that adopts only is to represent mutual proportionate relationship in the operating process of the present invention, it is not limited to the use of this numerical value in actual applications, can realize purpose of the present invention as long as meet mutual proportionate relationship, so all should be in protection scope of the present invention; Simultaneously; because the existence of permissible error is arranged in preparation process; the numerical value that the present invention mentioned also just has the meaning of directiveness, so as long as used the preparation and the modified condition of process of the present invention in actual applications, promptly should be in protection scope of the present invention.
Claims (4)
1. the modified attapulgite adsorbent preparation method of low-concentration methane in the recovery coal mine mash gas, it is characterized in that this preparation method may further comprise the steps: (1) activates one hour with the hydrochloric acid of 1mol/L to recessed soil, and hydrochloric acid volume (mL) is 1:1 with recessed soil property amount (g) ratio; (2) recessed native water cyclic washing and filtration 2 times of acidifying with 10 times of sour volumes; (3) will filter in the filter cake adding and sour isopyknic water of gained, under the ultrasonic wave effect, disperse 20 min; (4) recessed soil of the acidifying of ultrasonic dispersion and silane coupler hydrolyzate use microwave chemical reaction backflow 2h; (5) organically-modified end back filtration is extremely neutral with the filter cake washing with distilled water; (6) filter cake in 120 ℃ of oven dry, gets modified attapulgite adsorbent in drying box.
2. the modified attapulgite adsorbent preparation method of low-concentration methane in the recovery coal mine mash gas according to claim 1 is characterized in that: silane coupler is KH550, and chemical name is a gamma-aminopropyl-triethoxy-silane; Or silane coupler is KH570, and chemical name is γ-(methacryloxypropyl) propyl trimethoxy silicane.
3. the modified attapulgite adsorbent preparation method of low-concentration methane in the recovery coal mine mash gas according to claim 1 is characterized in that: silane coupler volumetric usage (mL) is 1:100～1:10 with initial recessed soil property amount (g) ratio.
4. the modified attapulgite adsorbent preparation method of low-concentration methane in the recovery coal mine mash gas according to claim 1 is characterized in that: the silane coupler hydrolyzate is by adding in the silane coupler and activating with sour isopyknic water stirring 30min and get.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110002435 CN102139200A (en) | 2011-01-07 | 2011-01-07 | Preparation method of modified attapulgite adsorbent for recovering low-concentration methane in coal mine gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110002435 CN102139200A (en) | 2011-01-07 | 2011-01-07 | Preparation method of modified attapulgite adsorbent for recovering low-concentration methane in coal mine gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102139200A true CN102139200A (en) | 2011-08-03 |
Family
ID=44407132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110002435 Pending CN102139200A (en) | 2011-01-07 | 2011-01-07 | Preparation method of modified attapulgite adsorbent for recovering low-concentration methane in coal mine gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102139200A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179249A (en) * | 2016-08-22 | 2016-12-07 | 中国科学院广州能源研究所 | A kind of preparation method of attapulgite cellulose composite adsorption microsphere |
| CN107126928A (en) * | 2017-07-06 | 2017-09-05 | 淮阴工学院 | A kind of adsorbent that two-dimensional metallic organic backbone separating low concentration methane is combined based on recessed native nano stick crystal and preparation method thereof |
-
2011
- 2011-01-07 CN CN 201110002435 patent/CN102139200A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 《江南大学博士学位论文》 20100430 黄健花 "凹凸棒土的有机改性及其应用" 第22页 , * |
| 《非金属矿》 20070531 钱运华 等， "凹凸棒石黏土超细粉制备与表面改性及其应用研究" 第9-11页 第30卷, 第3期 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179249A (en) * | 2016-08-22 | 2016-12-07 | 中国科学院广州能源研究所 | A kind of preparation method of attapulgite cellulose composite adsorption microsphere |
| CN106179249B (en) * | 2016-08-22 | 2018-10-02 | 中国科学院广州能源研究所 | A kind of preparation method of concave convex rod cellulose composite adsorption microballoon |
| CN107126928A (en) * | 2017-07-06 | 2017-09-05 | 淮阴工学院 | A kind of adsorbent that two-dimensional metallic organic backbone separating low concentration methane is combined based on recessed native nano stick crystal and preparation method thereof |
| CN107126928B (en) * | 2017-07-06 | 2019-08-06 | 淮阴工学院 | A kind of adsorbent and preparation method thereof based on the compound two-dimensional metallic organic backbone separating low concentration methane of recessed native nano stick crystal |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102439123B (en) | There is the application of zeolite character crystalline microporous material in natural gas processing process of RHO structure | |
| CN104087354B (en) | A kind of technique utilizing yellow phosphoric tail gas synthetic natural gas | |
| CN103801171B (en) | A kind of two-stage series connection swing adsorption oxygen generating system and method for operating thereof improving oxygen recovery rate | |
| CN102321494B (en) | Coal bed gas separating system and process | |
| US10882742B2 (en) | Process for separation of hydrogen and oxygen | |
| CN101628198A (en) | Pressure-swing adsorption method of directly enriching methane from coal bed gas | |
| CN103861422B (en) | A kind of concentrate is containing the new process of methane in oxygen coal-bed gas gas | |
| CN102502498A (en) | Method for separating and recovering chlorine and oxygen of hydrogen chloride oxidation gas mixture by use of PSA (Pressure Swing Adsorption) technology | |
| CN106824071A (en) | C@SiO of the one kind for Cr (VI) Adsorption2The preparation method of hollow ball | |
| CN114835142B (en) | Method for recovering carbon dioxide from industrial kiln tail gas and producing lithium carbonate | |
| CN103768891B (en) | A kind of two-stage series connection swing adsorption oxygen generating system and method for operating thereof that can improve oxygen recovery rate | |
| Krishnaiah et al. | Carbon dioxide removal by adsorption | |
| CN201924909U (en) | Coalbed gas separation device | |
| CN108126660A (en) | A kind of CO based on Immesion active carbon2Solid absorbent, preparation method and its usage | |
| CN102139200A (en) | Preparation method of modified attapulgite adsorbent for recovering low-concentration methane in coal mine gas | |
| CN101480559B (en) | Method for recycling sulfureous in flue gas using film | |
| CN108993400A (en) | A kind of preparation method of the high-efficiency adsorbent of separation of nitrogen-methane | |
| CN101485970A (en) | Method for developing high-efficient arsenic-removing sorbent Fe-Zr composite oxide | |
| CN105289508A (en) | Dedicated adsorbent for pressure swing adsorption of concentrated methane and preparation method thereof | |
| CN102321493B (en) | Coal bed gas separating system and process utilizing catalyst to deoxidize | |
| CN107126928B (en) | A kind of adsorbent and preparation method thereof based on the compound two-dimensional metallic organic backbone separating low concentration methane of recessed native nano stick crystal | |
| CN106866985B (en) | A kind of metal-organic framework materials and preparation method thereof separated for acetylene and methane adsorption | |
| CN202620982U (en) | Pressure swing adsorption system for separation of mixed gas including hydrogen and chlorosilane and/or chlorine hydride | |
| CN213037540U (en) | Geothermal deep well water-collecting purifying device | |
| CN106799210A (en) | A kind of preparation method and application of sepiolite base adsorbent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110803 |