CN102363117A - Carbon adsorbent special for methane in pressure swing adsorption and preparation method for carbon adsorbent - Google Patents
Carbon adsorbent special for methane in pressure swing adsorption and preparation method for carbon adsorbent Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 title abstract description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 91
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 66
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 64
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 60
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 33
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 33
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 32
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001868 water Inorganic materials 0.000 claims abstract description 24
- 230000004913 activation Effects 0.000 claims abstract description 21
- 239000011280 coal tar Substances 0.000 claims abstract description 20
- 239000003245 coal Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 11
- 239000011630 iodine Substances 0.000 claims abstract description 11
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 10
- 239000002817 coal dust Substances 0.000 claims description 35
- 238000010521 absorption reaction Methods 0.000 claims description 33
- 230000009466 transformation Effects 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000001994 activation Methods 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 206010013786 Dry skin Diseases 0.000 claims description 11
- 230000004888 barrier function Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 13
- 238000003795 desorption Methods 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 239000011269 tar Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 235000013339 cereals Nutrition 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 235000013312 flour Nutrition 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000005539 carbonized material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000037452 priming Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a carbon adsorbent special for methane in pressure swing adsorption and a preparation method for the carbon adsorbent. The carbon adsorbent with the iodine value of 900-1,000mg/g and the methylene blue value of 100-150mg/g is prepared from the following raw materials in part by mass: 100 parts of pulverized coal, 35 to 45 parts of coal tar, 3 to 8 parts of potassium hydroxide, 2 to 6 parts of potassium nitrate, 3 to 8 parts of calcium carbonate, 2 to 6 parts of magnesium chloride and 10 to 20 parts of water through pressing, carbonization and activation. The carbon adsorbent special for methane in pressure swing adsorption has high strength of over 95 percent, concentrated micropores with large pore volume, quick adsorption and desorption, the CH4 adsorption capacity of 25.0mL/g, and the CO adsorption capacity of 2.0mL/g, and can completely meet the requirement of the current domestic industrial application.
Description
One, technical field
The present invention relates to a kind of adsorbent and preparation method thereof, special-purpose carbon adsorbent of methane and preparation method thereof in specifically a kind of transformation absorption.
Two, background technology
In modern times in the industry, N
2, methane (CH
4) CH
4With CO be important basic chemical industry raw material.N
2Obtained already to use widely in fields such as chemical industry, electronics, metallurgy, food, machineries, modern industry increases with the speed greater than 10% demand of nitrogen every year; CH
4Except that as the synthesis material; Current more is to use as the energy; And CO is the important source material of carbonyl synthetic organic chemistry article; Can also produce multiple organic chemicals, like formic acid, oxalic acid, acetic acid, propionic acid and acrylate, carboxylic esters, dimethyl formamide DMF, diisocyanate resin TDL etc.In industrial processes such as mining industry, coal tar chemical industry, petrochemical industry, often multiple gases composition such as CO, CO
2, N
2, CH
4, H
2With ethene etc. and deposit, transformation absorption (Pressure SwingAdsorption is called for short PSA) technology is the most cost-effective at present gas process for separation and purification, and the selection of the adsorbent key that to be PSA can realize separates.
The PSA technology is the gas separation that in industry, newly emerges in recent years; Its basic principle is to utilize difference and the adsorbance of gas component characterization of adsorption on the solid material characteristic with change in pressure, realizes the separation or the purification of gas through periodic pressure conversion process.
Nineteen fifty-nine, U.S. Esso company succeeds in developing the PSA technology first, is applied to air dry-set.This technology realized plant-scale hydrogen manufacturing in 1962.Get into the phase at the beginning of the eighties in last century, the transformation adsorption separation technology has obtained development rapidly.Current; Because this type of PSA separator operation energy consumption is low, performance good, technological process is simple, automaticity is high, easy to operate; The advantage of having established it at middle and small scale gas separation field, and just constantly to large scale development, its importance is day by day remarkable; Its research has been become a focus of present chemical field; And the core of PSA separator technology is the technical performance of carbon adsorbent, and the microcellular structure of carbon adsorbent, pore volume, loading density, intensity, adsorption capacity and separation are most important technical parameters, and adsorbent mass directly influences product yield, product purity, production efficiency and the life-span of separator.
For CO, N
2And CH
4The separation of gas, the research of external acticarbon mainly contains Germany, the U.S., Japan and Italian several developed country, and is wherein successful with the adsorbent of Germany, the U.S., Japanology, and obtained industrial applications.The product adsorbents adsorb amount that the U.S. released in nearly 2 years has reached CH
4Greater than 25.0mL/g, CO is less than the level of 2.0mL/g, and China CH
4The development of the separating adsorbent of gas is not achieved success as yet.
Three, summary of the invention
The present invention is for avoiding above-mentioned existing in prior technology weak point, a kind of CH being provided
4CH during high adsorption capacity, component separation transformation big, that can realize suitability for industrialized production are adsorbed
4Special-purpose carbon adsorbent and preparation method thereof.
1) selection of catalysts:
Active carbon is as the flourishing adsorbent of a kind of hole; Air cleaning, gas separation, liquid and aspects such as solution decolouring, catalyst and catalyst carrier have been widely used in; But the height of the absorption property of active carbon depends primarily on the pore structure characteristic; Different process object, distribution requires difference to structure of activated carbon, therefore will adjust active carbon pore structure according to adsorbed process object.And the simple dependence carbonization-activation process conditions scope of the regulation and control in active carbon hole is little, and this will lodge some additives is that catalytic activation is adjusted the active carbon hole.For containing CO, N
2And CH
4The separation of mist, adopt the Physical Separation Technology of transformation absorption PSA, because CO and N
2Molecular diameter all very little, be respectively 0.28nm and 0.3nm, and very approaching, therefore be difficult to separate, and CH
4Molecular diameter be 0.4nm, influence less relatively.CO is a polar gas, CH
4Be nonpolar molecule, active carbon is a polar substances, according to the principle of the easy absorption of the big molecule of adsorption theory, selects research and development PSA-CH
4Acticarbon.
According to absorption principle; The primary study direction is in the formation of different catalytic reaction mesopores and the controllability of pore size at active carbon; Promptly on the basis that conventional post shaped activated carbon Material Physics method is produced, add and transfer hole and intensity chemical material, make it to form advanced physical-chemical catalysis method production technology process; The hole of adsorbent is formed concentrate on the 0.7-1.4nm scope relatively, to produce suitable product.Methane molecule motion diameter is 0.38nm, and is approaching with oxygen, nitrogen, belongs to little minute subcategory.According to absorption principle of dynamics opinion; The molecular diameter of adsorbate should be 2-3 times that is adsorbed the matter molecular diameter; Be 0.76-1.14nm
and divide by the active carbon pore-size distribution and should be the micropore active carbon, that is to say that the micropore pore volume big active carbon of healing is just bigger to the adsorbance of methane.Micropore is the more more concentrated, and the micropore pore volume is just bigger.
Activating process is exactly the pore-creating process, be from micropore progressively activation become mesopore, macropore, 3 stages have been experienced in activation process pore structure development:
1, activator (H
2O) make the already present closed pore of carbon matrix (carbonized material) open (generation be micropore).
2, activator gets into the inner activation of carbonized material through opened hole, and weak point is that priming reaction mainly produces when soak time is micropore.
3, along with the prolongation of soak time, arrive to a certain degree, priming reaction mainly is reaming, and promptly a part of micropore burns to lose and produces mesopore, and macropore burns the increase of mistake rate this moment, and bulk density descends, and intensity reduces.
Pursuing activation deeply,, methane is being adsorbed adiaphorous mesopore and macropore also can increase though the micropore amount increases.How just can make the increase of micropore pore volume bigger, and invalid hole is less, approach has two: the control of activating process mainly refers to the control of steam vapour amount and temperature, soak time; Catalyzing and carbonizing and catalytic activation.
2) alkali metal, alkaline earth metal compound: potassium nitrate, potassium hydroxide, calcium carbonate, magnesium chloride
Alkali metal, at high temperature activity is stronger for its oxide of alkaline earth metal compound, adds the back simultaneously under hot conditions, when charing, can impel the aromatic ring fracture of coal molecule to be divided into non-hydrocarbon functional groups; Reduced the macromolecular ordering of coal, the macromolecular active site of coal is increased, it decomposes the strong oxidation of the nascent oxygen of back generation simultaneously; Oxygen-containing functional group is increased; Improved activating velocity, the while alkaline earth metal compound, activation energy can be reduced; Help the increase of micropore pore volume, burn the reduction of mistake rate, bulk density increase.With potassium nitrate, calcium carbonate is example:
KNO
3→K
2O+O
2+N
2
KNO
3+C→K
2CO
3+CO
2+N
2
Potassium nitrate and carbon reaction generate potash; Not only make the local mistake generation hole that burns also can influence the distribution of carbon atom electronics on every side; Form activated point, the oxygen that potassium nitrate decomposition simultaneously produces has been accelerated reaction speed (oxygen and carbon reaction speed are carbon and steam reaction speed 30 times).
Add calcium carbonate its activation energy is reduced, with C-H
2The activation energy of O reaction is reduced to 164kJ/mol from 185kJ/mol, and under the similarity condition, its reaction speed improves, and helps the cultivation of micropore, increases with bulk density.
Comprehensive above the analysis, technical solution problem of the present invention adopts following technical scheme:
CH in the transformation absorption of the present invention
4Special-purpose carbon adsorbent, the iodine number 900-1000mg/g that after press strip, charing, activation, obtains successively by the raw material of following mass fraction, the adsorbent of methylene blue number 100-150mg/g:
100 parts of coal dusts, coal tar 35-45 part, potassium hydroxide 3-8 part, potassium nitrate 2-6 part, calcium carbonate 3-8 part, magnesium chloride 2-6 part, water 10-20 part;
Quality percentage composition＜5% of ash content in the said coal dust;
Said coal tar is high temperature coal-tar, and high temperature coal-tar is higher than the bitumen content of coalite tar, thereby makes the intensity of active carbon of preparation better.
CH in the transformation absorption of the present invention
4The preparation method of special-purpose carbon adsorbent operates according to the following steps:
The preparation of presoma: coal dust is crushed to grain diameter gets the coal dust material greater than 200 orders; In said coal dust material, add coal tar, potassium hydroxide, potassium nitrate, calcium carbonate, magnesium chloride and water; The forcing press extrusion use in the back that stirs, and leaves standstill after 2-3 days charing and removes the impurity of water and tar, the intensity increase; Generate simultaneously and produce certain hole, promptly get presoma;
Preparation of adsorbent: the gained presoma placed in department Depew stove or the multi-functional converter in the presence of steam, be activated to iodine number 900-1000mg/g in 850-950 ℃; Steam is to feed in the activation furnace through boiler pressure; Presoma 800kg per ton and material get in the lump; Methylene blue number 100-150mg/g, the hydrochloric acid solution with mass concentration 3-10% soaked 8-24 hour then, washed to pH value 7-9 to get product in 1 hour in 120 ℃ of dryings.
Said charing is 500-700 ℃ of oxygen barrier charing 2-3 hour.
The feeding amount of steam is presoma 800kg per ton during said activation, and the feeding flow velocity is 20mL/min.
The mensuration of iodine number, methylenum careuleum bulk density is to measure according to the standard of GB GB7702-97 among the present invention, and the determining instrument of methane adsorbance is the U.S. ASAP2020M of a MICROMETRICS company type tester.The micropore pore volume is measured with the DFT method.
Compared with present technology, beneficial effect of the present invention is embodied in:
1, CH in the transformation absorption of the present invention
4Special-purpose carbon adsorbent intensity is high, micropore is concentrated, pore volume is big, absorption and desorption rate is fast, CH
4Adsorption capacity reaches 25.0mL/g, and less than 2.0mL/g, intensity is greater than 95% for the absorption of CO.Can satisfy the needs that current domestic industry is used fully.
2, the present invention shortens soak time through adding catalyst in the preparation process, and the micropore amount is increased, and reduce in invalid hole, thereby increases the adsorbance of active carbon to methane.
Four, description of drawings
The electromicroscopic photograph of the adsorbent that Fig. 1-the 4th, the present invention prepare.The as can be seen from the figure existence of the adsorbent hole of the present invention's preparation.
Five, the specific embodiment
Embodiment 1:
CH in the transformation absorption in the present embodiment
4The raw material of special-purpose carbon adsorbent constitutes by mass fraction:
100 parts of the coal dusts of ash content＜5%, 35 parts of high temperature coal-tars, 3 parts in potassium hydroxide, 2 parts in potassium nitrate, 3 parts in calcium carbonate, 2 parts in magnesium chloride, 10 parts in water.
CH in the transformation absorption in the present embodiment
4Special-purpose carbon adsorbent is to prepare according to the following steps:
The preparation of presoma: the coal dust of ash content＜5% is crushed to grain diameter with 4R Raymond mill flour mill gets the coal dust material greater than 200 orders; In the coal dust material, add high temperature coal-tar, potassium hydroxide, potassium nitrate, calcium carbonate, magnesium chloride and water; Stir the back with 315 tons of forcing press extrusions, leave standstill that 500 ℃ of oxygen barrier charings promptly got presoma in 3 hours after 2 days;
Preparation of adsorbent: the gained presoma placed in department's Depew stove in the presence of steam, be activated to iodine number 900mg/g in 850 ℃; Methylene blue number 105mg/g; The feeding amount of steam is presoma 800kg per ton; The flow velocity of steam is 20mL/min, and the hydrochloric acid solution with 3% mass concentration soaked 8 hours then, washes to pH value 7 backs to get product in 1 hour in 120 ℃ of dryings.
Embodiment 2:
CH in the transformation absorption in the present embodiment
4The raw material of special-purpose carbon adsorbent constitutes by mass fraction:
100 parts of the coal dusts of ash content＜5%, 45 parts of high temperature coal-tars, 8 parts in potassium hydroxide, 6 parts in potassium nitrate, 8 parts in calcium carbonate, 6 parts in magnesium chloride, 20 parts in water.
CH in the transformation absorption in the present embodiment
4Special-purpose carbon adsorbent is to prepare according to the following steps:
The preparation of presoma: the coal dust of ash content＜5% is crushed to grain diameter with 4R Raymond mill flour mill gets the coal dust material greater than 200 orders; In the coal dust material, add high temperature coal-tar, potassium hydroxide, potassium nitrate, calcium carbonate, magnesium chloride and water; Stir the back with 315 tons of forcing press extrusions, leave standstill that 700 ℃ of oxygen barrier charings promptly got presoma in 2 hours after 3 days;
Preparation of adsorbent: the gained presoma placed in the multi-functional converter in the presence of steam, be activated to iodine number 960mg/g in 880 ℃; Methylene blue number 130mg/g; The feeding amount of steam is presoma 800kg per ton; The flow velocity of steam is 20mL/min, and the hydrochloric acid solution with 10% mass concentration soaked 12 hours then, washes to pH value 8 backs to get product in 1 hour in 120 ℃ of dryings.
Embodiment 3:
CH in the transformation absorption in the present embodiment
4The raw material of special-purpose carbon adsorbent constitutes by mass fraction:
100 parts of the coal dusts of ash content＜5%, 40 parts of high temperature coal-tars, 5 parts in potassium hydroxide, 4 parts in potassium nitrate, 5 parts in calcium carbonate, 4 parts in magnesium chloride, 15 parts in water.
CH in the transformation absorption in the present embodiment
4Special-purpose carbon adsorbent is to prepare according to the following steps:
The preparation of presoma: the coal dust of ash content＜5% is crushed to grain diameter with 4R Raymond mill flour mill gets the coal dust material greater than 200 orders; In the coal dust material, add high temperature coal-tar, potassium hydroxide, potassium nitrate, calcium carbonate, magnesium chloride and water; Stir the back with 315 tons of forcing press extrusions, leave standstill that 600 ℃ of oxygen barrier charings promptly got presoma in 2 hours after 2 days;
Preparation of adsorbent: the gained presoma placed in the multi-functional converter in the presence of steam, be activated to iodine number 905mg/g in 880 ℃; Methylene blue number 110mg/g; The feeding amount of steam is presoma 800kg per ton; The flow velocity of steam is 20mL/min, and the hydrochloric acid solution with 5% mass concentration soaked 20 hours then, washes to pH value 7 backs to get product in 1 hour in 120 ℃ of dryings.
Embodiment 4:
CH in the transformation absorption in the present embodiment
4The raw material of special-purpose carbon adsorbent constitutes by mass fraction:
100 parts of the coal dusts of ash content＜5%, 40 parts of high temperature coal-tars, 6 parts in potassium hydroxide, 5 parts in potassium nitrate, 4 parts in calcium carbonate, 5 parts in magnesium chloride, 18 parts in water.
CH in the transformation absorption in the present embodiment
4Special-purpose carbon adsorbent is to prepare according to the following steps:
The preparation of presoma: the coal dust of ash content＜5% is crushed to grain diameter with 4R Raymond mill flour mill gets the coal dust material greater than 200 orders; In the coal dust material, add high temperature coal-tar, potassium hydroxide, potassium nitrate, calcium carbonate, magnesium chloride and water; Stir the back with 315 tons of forcing press extrusions, leave standstill that 500 ℃ of oxygen barrier charings promptly got presoma in 3 hours after 3 days;
Preparation of adsorbent: the gained presoma placed in department's Depew stove in the presence of steam, be activated to iodine number 950mg/g in 950 ℃; Methylene blue number 120mg/g; The feeding amount of steam is presoma 800kg per ton; The flow velocity of steam is 20mL/min, and the hydrochloric acid solution with 8% mass concentration soaked 24 hours then, washes to pH value 9 backs to get product in 1 hour in 120 ℃ of dryings.
Embodiment 5:
CH in the transformation absorption in the present embodiment
4The raw material of special-purpose carbon adsorbent constitutes by mass fraction:
100 parts of the coal dusts of ash content＜5%, 45 parts of high temperature coal-tars, 4 parts in potassium hydroxide, 4 parts in potassium nitrate, 6 parts in calcium carbonate, 3 parts in magnesium chloride, 16 parts in water.
CH in the transformation absorption in the present embodiment
4Special-purpose carbon adsorbent is to prepare according to the following steps:
The preparation of presoma: the coal dust of ash content＜5% is crushed to grain diameter with 4R Raymond mill flour mill gets the coal dust material greater than 200 orders; In the coal dust material, add high temperature coal-tar, potassium hydroxide, potassium nitrate, calcium carbonate, magnesium chloride and water; Stir the back with 315 tons of forcing press extrusions, leave standstill that 600 ℃ of oxygen barrier charings promptly got presoma in 3 hours after 3 days;
Preparation of adsorbent: the gained presoma placed in the multi-functional converter in the presence of steam, be activated to iodine number 1000mg/g in 950 ℃; Methylene blue number 150mg/g; The feeding amount of steam is presoma 800kg per ton; The flow velocity of steam is 20mL/min, and the hydrochloric acid solution with 10% mass concentration soaked 18 hours then, washes to pH value 7 backs to get product in 1 hour in 120 ℃ of dryings.
The active carbon test data
Be comparative analysis below to preparation method's of the present invention optimum condition:
Embodiment 6: soak time is to the influence of adsorbent mass
CH in the transformation absorption in the present embodiment
4The raw material of special-purpose carbon adsorbent constitutes by mass fraction:
100 parts of the coal dusts of ash content＜5%, 45 parts of high temperature coal-tars, 8 parts in potassium hydroxide, 6 parts in potassium nitrate, 8 parts in calcium carbonate, 6 parts in magnesium chloride, 20 parts in water.
CH in the transformation absorption in the present embodiment
4Special-purpose carbon adsorbent is to prepare according to the following steps:
The preparation of presoma: the coal dust of ash content＜5% is crushed to grain diameter with 4R Raymond mill flour mill gets the coal dust material greater than 200 orders; In the coal dust material, add high temperature coal-tar, potassium hydroxide, potassium nitrate, calcium carbonate, magnesium chloride and water; Stir the back with 315 tons of forcing press extrusions, leave standstill that 700 ℃ of oxygen barrier charings promptly got presoma in 2 hours after 3 days;
Preparation of adsorbent: the gained presoma is placed in the multi-functional converter in the presence of steam in 880 ℃ of activation 2,2.5,3.0,4.0 and 4.5 hours respectively; The feeding amount of steam is presoma 800kg per ton; The flow velocity of steam is 20mL/min; Hydrochloric acid solution with 10% mass concentration soaked 12 hours then, washed to pH value 8 backs to get product in 1 hour in 120 ℃ of dryings.Obtain following table after tested.Can find out that from table the methane adsorbance of the adsorbent of preparation was maximum when the identical soak time of other conditions was 3.0 hours.
Soak time is to the influence of adsorbent mass
Embodiment 7: activation temperature is to the influence of adsorbent mass
CH in the transformation absorption in the present embodiment
4The raw material of special-purpose carbon adsorbent constitutes by mass fraction:
100 parts of the coal dusts of ash content＜5%, 45 parts of high temperature coal-tars, 8 parts in potassium hydroxide, 6 parts in potassium nitrate, 8 parts in calcium carbonate, 6 parts in magnesium chloride, 20 parts in water.
CH in the transformation absorption in the present embodiment
4Special-purpose carbon adsorbent is to prepare according to the following steps:
The preparation of presoma: the coal dust of ash content＜5% is crushed to grain diameter with 4R Raymond mill flour mill gets the coal dust material greater than 200 orders; In the coal dust material, add high temperature coal-tar, potassium hydroxide, potassium nitrate, calcium carbonate, magnesium chloride and water; Stir the back with 315 tons of forcing press extrusions, leave standstill that 700 ℃ of oxygen barrier charings promptly got presoma in 2 hours after 3 days;
Preparation of adsorbent: the gained presoma is placed in the multi-functional converter in the presence of steam respectively at 800 ℃, 820 ℃, 850 ℃, 880 ℃, 900 ℃ and 950 ℃ of activation 3.0 hours; The feeding amount of steam is presoma 800kg per ton; The flow velocity of steam is 20mL/min; Hydrochloric acid solution with 10% mass concentration soaked 12 hours then, washed to pH value 8 backs to get product in 1 hour in 120 ℃ of dryings.Obtain following table after tested.Can find out that from table the methane adsorbance of the adsorbent of preparation was maximum when the identical activation temperature of other conditions was 880 ℃.
Activation temperature is to the influence of adsorbent mass
Embodiment 8: the ratio of catalyst is to the influence of product quality
CH in the transformation absorption in the present embodiment
4The raw material of special-purpose carbon adsorbent constitutes by mass fraction:
100 parts of the coal dusts of ash content＜5%, 40 parts of high temperature coal-tars, 20 parts in water and catalyst;
Wherein catalyst promptly refers to potassium hydroxide, potassium nitrate, calcium carbonate and magnesium chloride; Ratio between the catalyst makes an experiment according to following six groups respectively:
Group 1: 4 parts in 6 parts in potassium hydroxide, 4 parts in potassium nitrate, 6 parts in calcium carbonate and magnesium chloride;
Group 2: 6 parts in 8 parts in potassium hydroxide, 6 parts in potassium nitrate, 8 parts in calcium carbonate and magnesium chloride;
Group 3: 4 parts in 5 parts in potassium hydroxide, 4 parts in potassium nitrate, 5 parts in calcium carbonate and magnesium chloride;
Group 4: 5 parts in 6 parts in potassium hydroxide, 5 parts in potassium nitrate, 4 parts in calcium carbonate and magnesium chloride;
Group 5: 3 parts in 4 parts in potassium hydroxide, 4 parts in potassium nitrate, 6 parts in calcium carbonate and magnesium chloride;
Group 6: 5 parts in 4 parts in potassium hydroxide, 4 parts in potassium nitrate, 7 parts in calcium carbonate and magnesium chloride;
CH in the transformation absorption in the present embodiment
4Special-purpose carbon adsorbent is to prepare according to the following steps:
The preparation of presoma: the coal dust of ash content＜5% is crushed to grain diameter with 4R Raymond mill flour mill gets the coal dust material greater than 200 orders; In the coal dust material, add high temperature coal-tar, potassium hydroxide, potassium nitrate, calcium carbonate, magnesium chloride and water; Stir the back with 315 tons of forcing press extrusions, leave standstill that 700 ℃ of oxygen barrier charings promptly got presoma in 2 hours after 3 days;
Preparation of adsorbent: the gained presoma is placed in the multi-functional converter in the presence of steam in 880 ℃ of activation 3.0 hours; The feeding amount of steam is presoma 800kg per ton; The flow velocity of steam is 20mL/min; Hydrochloric acid solution with 10% mass concentration soaked 12 hours then, washed to pH value 8 backs to get product in 1 hour in 120 ℃ of dryings.Obtain following table after tested.From table, can find out, the Preparation of Catalyst of identical interpolation group of other conditions 4 and group 5 the methane adsorbance of adsorbent be maximum.
The ratio of catalyst is to the influence of adsorbent mass
Embodiment 9: the flow velocity of activator is to the influence of adsorbent mass
CH in the transformation absorption in the present embodiment
4The raw material of special-purpose carbon adsorbent constitutes by mass fraction:
100 parts of the coal dusts of ash content＜5%, 45 parts of high temperature coal-tars, 6 parts in potassium hydroxide, 5 parts in potassium nitrate, 4 parts in calcium carbonate, 5 parts in magnesium chloride, 20 parts in water.
CH in the transformation absorption in the present embodiment
4Special-purpose carbon adsorbent is to prepare according to the following steps:
The preparation of presoma: the coal dust of ash content＜5% is crushed to grain diameter with 4R Raymond mill flour mill gets the coal dust material greater than 200 orders; In the coal dust material, add high temperature coal-tar, potassium hydroxide, potassium nitrate, calcium carbonate, magnesium chloride and water; Stir the back with 315 tons of forcing press extrusions, leave standstill that 700 ℃ of oxygen barrier charings promptly got presoma in 2 hours after 3 days;
Preparation of adsorbent: the gained presoma is placed in the multi-functional converter in the presence of steam in 880 ℃ of activation 3.0 hours; The feeding amount of steam is presoma 800kg per ton; Hydrochloric acid solution with 10% mass concentration soaked 12 hours then, washed to pH value 8 backs to get product in 1 hour in 120 ℃ of dryings.Change the feeding flow velocity of steam respectively, obtain following table through test.Can find out that from table the methane adsorbance of the adsorbent that the flow velocity of the identical steam of other conditions prepares during for 20mL/min is maximum.
The flow velocity of activator steam is to the influence of adsorbent mass
Claims (4)
1. the special-purpose carbon adsorbent of methane in the transformation absorption is characterized in that the iodine number 900-1000mg/g that the raw material by following mass fraction obtains successively, the adsorbent of methylene blue number 100-150mg/g after press strip, charing, activation:
100 parts of coal dusts, coal tar 35-45 part, potassium hydroxide 3-8 part, potassium nitrate 2-6 part, calcium carbonate 3-8 part, magnesium chloride 2-6 part, water 10-20 part;
Quality percentage composition＜5% of ash content in the said coal dust;
Said coal tar is high temperature coal-tar.
2. the preparation method of the special-purpose carbon adsorbent of methane in the transformation absorption as claimed in claim 1 is characterized in that operating according to the following steps:
The preparation of presoma: coal dust is crushed to grain diameter gets the coal dust material greater than 200 orders; In said coal dust material, add coal tar, potassium hydroxide, potassium nitrate, calcium carbonate, magnesium chloride and water; The forcing press extrusion is used in the back that stirs, and leaves standstill that charing promptly gets presoma after 2-3 days;
Preparation of adsorbent: the gained presoma placed in department Depew stove or the multi-functional converter in the presence of steam, be activated to iodine number 900-1000mg/g in 850-950 ℃; Methylene blue number 100-150mg/g; Hydrochloric acid solution with mass concentration 3-10% soaked 8-24 hour then, washed to pH value 7-9 to get product in 1 hour in 120 ℃ of dryings.
3. preparation method according to claim 2 is characterized in that: said charing is 500-700 ℃ of oxygen barrier charing 2-3 hour.
4. preparation method according to claim 2 is characterized in that: the feeding amount of steam is presoma 800kg per ton during said activation, and the feeding flow velocity is 20mL/min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055812A (en) * | 2012-12-24 | 2013-04-24 | 淮北市森化碳吸附剂有限责任公司 | Preparation method for methane special-purpose carbon adsorbent in pressure swing adsorption |
| CN105502380A (en) * | 2016-01-12 | 2016-04-20 | 宁夏宝塔石化科技实业发展有限公司 | Preparation method of activated carbon for organic solvent recycling |
| CN106422663A (en) * | 2016-12-22 | 2017-02-22 | 华北科技学院 | Device and method for increasing gas concentration of coal mine ventilation air methane |
| CN110354803A (en) * | 2019-07-10 | 2019-10-22 | 大连理工大学 | A kind of separation of methane and the monoblock type composite porous charcoal adsorbent material of nitrogen and preparation method thereof |
| CN114191939A (en) * | 2020-09-02 | 2022-03-18 | 中国科学院理化技术研究所 | Methane and nitrogen mixture separation system and separation process |
| CN114682209A (en) * | 2020-12-25 | 2022-07-01 | 柳州柳晶环保科技有限公司 | Method for preparing adsorbing material by using coal dust-containing casting dust and adsorbing material |
| CN114772594A (en) * | 2022-04-25 | 2022-07-22 | 山西新华防化装备研究院有限公司 | Activated carbon with developed mesopores and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4696680A (en) * | 1985-10-03 | 1987-09-29 | The United States Of America As Represented By The United States Department Of Energy | Method and apparatus for the selective separation of gaseous coal gasification products by pressure swing adsorption |
| US20060278078A1 (en) * | 2005-05-25 | 2006-12-14 | Thorstein Holt | Methods and systems for generation of gases |
| CN1919448A (en) * | 2006-07-15 | 2007-02-28 | 中国矿业大学 | Process for preparing active carbon for pressure swing adsorption |
| CN101531365A (en) * | 2009-03-18 | 2009-09-16 | 重庆大学 | Preparation method of pressed active carbon for pressure swing adsorption/separation of methane/nitrogen |
| CN101628198A (en) * | 2009-08-26 | 2010-01-20 | 同济大学 | Pressure-swing adsorption method of directly enriching methane from coal bed gas |
-
2011
- 2011-11-18 CN CN2011103672219A patent/CN102363117A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4696680A (en) * | 1985-10-03 | 1987-09-29 | The United States Of America As Represented By The United States Department Of Energy | Method and apparatus for the selective separation of gaseous coal gasification products by pressure swing adsorption |
| US20060278078A1 (en) * | 2005-05-25 | 2006-12-14 | Thorstein Holt | Methods and systems for generation of gases |
| CN1919448A (en) * | 2006-07-15 | 2007-02-28 | 中国矿业大学 | Process for preparing active carbon for pressure swing adsorption |
| CN101531365A (en) * | 2009-03-18 | 2009-09-16 | 重庆大学 | Preparation method of pressed active carbon for pressure swing adsorption/separation of methane/nitrogen |
| CN101628198A (en) * | 2009-08-26 | 2010-01-20 | 同济大学 | Pressure-swing adsorption method of directly enriching methane from coal bed gas |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055812A (en) * | 2012-12-24 | 2013-04-24 | 淮北市森化碳吸附剂有限责任公司 | Preparation method for methane special-purpose carbon adsorbent in pressure swing adsorption |
| CN105502380A (en) * | 2016-01-12 | 2016-04-20 | 宁夏宝塔石化科技实业发展有限公司 | Preparation method of activated carbon for organic solvent recycling |
| CN106422663A (en) * | 2016-12-22 | 2017-02-22 | 华北科技学院 | Device and method for increasing gas concentration of coal mine ventilation air methane |
| CN106422663B (en) * | 2016-12-22 | 2022-10-25 | 华北科技学院 | A device and method for improving gas concentration in coal mine exhaust air |
| CN110354803A (en) * | 2019-07-10 | 2019-10-22 | 大连理工大学 | A kind of separation of methane and the monoblock type composite porous charcoal adsorbent material of nitrogen and preparation method thereof |
| CN114191939A (en) * | 2020-09-02 | 2022-03-18 | 中国科学院理化技术研究所 | Methane and nitrogen mixture separation system and separation process |
| CN114682209A (en) * | 2020-12-25 | 2022-07-01 | 柳州柳晶环保科技有限公司 | Method for preparing adsorbing material by using coal dust-containing casting dust and adsorbing material |
| CN114772594A (en) * | 2022-04-25 | 2022-07-22 | 山西新华防化装备研究院有限公司 | Activated carbon with developed mesopores and preparation method thereof |
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