CN102502624B - Preparation method for acquiring spherical activated carbon of carbon dioxide - Google Patents
Preparation method for acquiring spherical activated carbon of carbon dioxide Download PDFInfo
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- CN102502624B CN102502624B CN2011103293922A CN201110329392A CN102502624B CN 102502624 B CN102502624 B CN 102502624B CN 2011103293922 A CN2011103293922 A CN 2011103293922A CN 201110329392 A CN201110329392 A CN 201110329392A CN 102502624 B CN102502624 B CN 102502624B
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Abstract
Provided is a preparation method for acquiring spherical activated carbon of carbon dioxide. Linetype phenolic resin, nitrogenous compounds and industrial alcohol are mixed to be prepared to pulp, and the pulp is directly added to a reaction kettle which contains a surface active agent and water. After being tightly closed, the reaction kettle is turned on for mixing, heating rate is increased to 100 to 170 DEG C, and then the temperature is constant for 0.5 to 3 hours. After natural cooling, resin spheres are obtained. The resin spheres are placed in a carbonization activation furnace, inert gases are led in, proportion by weight of gas flow rate to the resin spheres is 300 to 1,000 L/min: 1kg, then the temperature is increased to 700 to 1,000 DEG C with the heating rate of 0.1 to 4 DEG C/min, the gases are changed to active gases, proportion of the active gases to the resin spheres is 100 to 300 L/min: 1kg, after 0.5 to 2 hours of activation, the gases are changed to inert gases, the temperature is lowered to below 50 DEG C, and the final products are obtained. The preparation method for acquiring spherical activated carbon of carbon dioxide has the advantages of being low in cost and high in nitrogen content.
Description
Technical field
The present invention relates to a kind of preparation method of gac, relate in particular to a kind of preparation method of alkyd resin based spheric active carbon.
Background technology
Although organic amine CO
2Absorption process is the CO of present comparative maturity
2Catching isolation technique also uses at Sweet natural gas and petroleum industry for a long time, but because this technology high energy consumption, high maintenance cost and because the high safe secret worry of using the highly corrosive amine solvent to bring, increase huge economic operation cost for the extensive use of this technology in the coal-burning power plant and increase considerably the floor space of power plant.Solid adsorbent CO
2Catch isolation technique and be considered to substitute the most promising technology of organic amine absorption process.
Spheric active carbon has been given its stronger resistance to abrasion because its outward appearance is regular sphere, and higher bulk density and constant gas penetration, extremely is suitable as the CO in the circulating fluidized bed
2Trapping agent uses.
Patent 98115717.3 discloses a kind of method for preparing ball shape active carbon, is after lacquer resins and solidifying agent are mixed, to make block mixture by the decompression desolvation, emulsification balling-up after pulverizing.The subject matter of the method causes resin crosslinks to be solidified when being the decompression desolvation easily, and often is spongiform molecule, also is that circulation ratio is relatively poor, and cost is high.
Patent 200410012346.X has further improved the technique of patent 98115717.3, has saved the resin of remarkably influenced gained resin balls performance and the step that solidifying agent is mixed and made into block raw material, but the resin balls that obtains is less, is not suitable as and catches CO
2Sorbent material.
Patent 200810079389.8 is the Continual Improvements to patent 200410012346.X, adopt directly reinforced mode, the multistep techniques such as material dissolution and proportioning dispersion soln have been saved, although have easy to operate, technique is simple, energy consumption is low, low cost and other advantages, but because solidifying agent is water-soluble better, so that solidifying agent dissolves in dispersion liquid is more, cause the nitrogen content in the final gained resin balls on the low side.
Patent 200910200119 adopts the method identical with patent 200810079389.8, with the disposable autoclave that solvent is housed that places of resol ethanolic soln, solidifying agent and dispersion agent, carry out the emulsification balling-up, afterwards the gained resin balls has been carried out microwave curing, the phenolic resin balls that is about to obtain places microwave device, the control microwave power is 40-80W, radiation 10-30min, again microwave power is adjusted to 240-400W, radiation 10-30min, at last microwave power is adjusted to 640-800W, radiation 15-30min, the phenolic resin balls that obtains solidifying; At last the phenolic resin balls that solidifies is carried out high-temperature activation and process the acquisition spheric active carbon.The microwave curing method steps that can find out this patent employing is various, causes operational path complicated, and cost is high.
Patent 200810035853 discloses the preparation method who uses high softening point bitumen to prepare nitrogenous ball shape active carbon as raw material, by in pitch, adding nitrogenous compound, then emulsification balling-up, do not melt, prepare asphalt-base spherical activated carbon after charing and the activation treatment.The method can't avoid using oxidation not only consuming time but also power consumption not melt, and starting material are again the high high softening point bitumen of price, causes its cost very high.
Goal of the invention
The purpose of this invention is to provide a kind of low cost, the high nitrogenous CO that is used for catching
2The preparation method of spheric active carbon.
Summary of the invention
Preparation method of the present invention comprises the steps:
The preparation of 1 balling-up soup compound: lacquer resins, nitrogenous compound and industrial spirit are take weight ratio as 1: (0.01-0.3): (0.3-0.9) mix, after being made into soup compound, directly be added in the reactor that contains tensio-active agent and water, wherein the weight ratio of lacquer resins and tensio-active agent and water is 1: (0.02-0.5): (10-800);
2 emulsification balling-up: after reactor is airtight, opens and stir, rotating speed is 200-1000 rev/min, is raised to 100-170 ℃ with 1-10 ℃/minute temperature rise rate, and constant temperature 0.5-3h after the cooling, obtains resin balls naturally afterwards; 3 carbonization-activations: resin balls is put in the carbonization-activation stove, pass into rare gas element, the weight ratio of gas flow rate and resin balls is: 300-1000L/min: 1kg, temperature rise rate with 0.1-4 ℃/min is warming up to 700-1000 ℃ afterwards, switch to activated gas, the ratio of activated gas and resin balls is: 100-300L/min: 1kg switches to rare gas element behind the activation 0.5-2h, and be cooled to below 50 ℃, get the finished product.
Aforesaid lacquer resins is the line style novolac resin of softening temperature between 70-120 ℃.
Aforesaid nitrogenous compound is one or both mixtures in polyoxymethylene, trimeric cyanamide, triethylene tetramine, tetraethylene pentamine, urea, bicarbonate of ammonia or the polyetherimide.
Aforesaid tensio-active agent is one or both mixtures in sodium lauryl sulphate, polyvinyl alcohol, the tetrafluoroethylene.
Aforesaid rare gas element is nitrogen or argon gas.
Aforesaid activated gas is water vapor, CO
2, NH
3In one or both mixtures.
The present invention has following advantage:
1 need not adopt solidifying agent to be cured, and nitrogenous compound not only serves as solidifying agent but also can be used as the additive that improves nitrogen content in the finished product.
2 adopt soup compounies can reduce in the dispersion agent water to the meltage of solidifying agent or nitrogenous compound, thereby increase the nitrogen content in the finished product.
3 nitrogenous compounds are because disperse is in resol, and its curing reaction is very fast and thoroughly, can save like this step that adopts microwave curing, and after solidifying product performance especially intensity be significantly higher than the product of microwave curing.
Embodiment
Embodiment 1
Be that 70 ℃ lacquer resins 10Kg, nitrogenous compound polyoxymethylene 0.1Kg, industrial spirit 3Kg is formulated as soup compound with softening temperature, directly be added in the autoclave that contains Surfactant SDS 0.2Kg and water 100Kg, then with 500 turn/speed of min at the uniform velocity stirs, open heating schedule, temperature rise rate with 10 ℃/min is raised to 170 ℃, constant temperature 1h obtains phenolic resin balls.
The 1kg resin balls is put in the carbonization-activation integral stove, passes into the nitrogen of 1000L/min, the temperature rise rate with 4 ℃/min is warming up to 700 ℃ afterwards, switch to the 100L/min water vapor, activation switches to nitrogen behind the 2h, and cooling is taken out and namely got the finished product until drop to 35 ℃.Nitrogen content is 2.8wt% in the product.
At CO
2Content is 100%, when 30 ℃ of probe temperatures, gaseous tension 1atm, this product is to CO
2Quantity of the catch be 8wt%.
Embodiment 2
Be that 90 ℃ lacquer resins 10Kg, nitrogenous compound trimeric cyanamide 3Kg, industrial spirit 9Kg is formulated as soup compound with softening temperature, directly be added in the autoclave that contains surface active agent polyvinyl alcohol 3Kg and water 800Kg, then with 200 turn/speed of min at the uniform velocity stirs, open heating schedule, temperature rise rate with 1 ℃/min is raised to 100 ℃, constant temperature 0.5h obtains phenolic resin balls.
The 1kg resin balls is put in the carbonization-activation integral stove, passes into the argon gas of 300L/min, the temperature rise rate with 4 ℃/min is warming up to 1000 ℃ afterwards, switch to 200L/minCO2 gas, activation switches to argon gas behind the 1h, and cooling is taken out and namely got the finished product until drop to 45 ℃.Nitrogen content is 3.3wt% in the product.
At CO
2Content is 100%, when 30 ℃ of probe temperatures, gaseous tension 1atm, this product is to CO
2Quantity of the catch be 12.2wt%.
Embodiment 3
Be that 120 ℃ lacquer resins 10Kg, nitrogenous compound triethylene tetramine 2Kg, industrial spirit 6Kg is formulated as soup compound with softening temperature, directly be added in the autoclave that contains tensio-active agent tetrafluoroethylene 5Kg and water 400Kg, then with 1000 turn/speed of min at the uniform velocity stirs, open heating schedule, temperature rise rate with 3 ℃/min is raised to 100 ℃, constant temperature 3h obtains phenolic resin balls.
The 1kg resin balls is put in the carbonization-activation integral stove, passes into the argon gas of 500L/min, the temperature rise rate with 0.5 ℃/min is warming up to 800 ℃ afterwards, switch to the 100L/min ammonia, activation switches to argon gas behind the 2h, and cooling is taken out and namely got the finished product until drop to 50 ℃.Nitrogen content is 2.8wt% in the product.
At CO
2Content is 100%, when 30 ℃ of probe temperatures, gaseous tension 1atm, this product is to CO
2Quantity of the catch be 11.5wt%.
Embodiment 4
Be that 110 ℃ lacquer resins 10Kg, nitrogenous compound trimeric cyanamide and triethylene tetramine (weight ratio 1: 1) 1Kg, industrial spirit 3Kg is formulated as soup compound with softening temperature, directly be added in the autoclave that contains surface active agent polyvinyl alcohol and tetrafluoroethylene (weight ratio 1: 1) 2Kg and water 100Kg, then with 700 turn/speed of min at the uniform velocity stirs, open heating schedule, temperature rise rate with 5 ℃/min is raised to 150 ℃, constant temperature 1h obtains phenolic resin balls.
The 1kg resin balls is put in the carbonization-activation integral stove, pass into the argon gas of 800L/min, temperature rise rate with 1 ℃/min is warming up to 800 ℃ afterwards, switch to 1: 1 700L/min water vapor of volume ratio and CO2 gas, switch to argon gas behind the activation 2h, and cooling is taken out and is namely got the finished product until drop to 35 ℃.Nitrogen content is 5.4wt% in the product.
At CO
2Content is 100%, when 30 ℃ of probe temperatures, gaseous tension 1atm, this product is to CO
2Quantity of the catch be 14.8wt%.
Embodiment 5
Be that 80 ℃ lacquer resins 10Kg, nitrogenous compound polyetherimide and polyoxymethylene (weight ratio 1: 1) 2Kg, industrial spirit 6Kg is formulated as soup compound with softening temperature, directly be added in the autoclave that contains Surfactant SDS and polyvinyl alcohol (weight ratio 1: 1) 0.2Kg and water 500Kg, then with 400 turn/speed of min at the uniform velocity stirs, open heating schedule, temperature rise rate with 8 ℃/min is raised to 170 ℃, constant temperature 0.5h obtains phenolic resin balls.
The 1kg resin balls is put in the carbonization-activation integral stove, pass into the nitrogen of 400L/min, temperature rise rate with 3 ℃/min is warming up to 900 ℃ afterwards, switch to volume ratio 1: 1 1000L/minCO2 gas and ammonia, switch to nitrogen behind the activation 2h, and cooling is taken out and is namely got the finished product until drop to 50 ℃.Nitrogen content is 3.4wt% in the product.
At CO
2Content is 100%, when 30 ℃ of probe temperatures, gaseous tension 1atm, this product is to CO
2Quantity of the catch be 10.9wt%.
Embodiment 6
Be that 80 ℃ lacquer resins 10Kg, nitrogenous compound tetraethylene pentamine and urea (weight ratio 1: 1) 3Kg, industrial spirit 4Kg is formulated as soup compound with softening temperature, directly be added in the autoclave that contains surface active agent polyvinyl alcohol (weight ratio 1: 1) 0.2Kg and water 100Kg, then with 200 turn/speed of min at the uniform velocity stirs, open heating schedule, temperature rise rate with 2 ℃/min is raised to 100 ℃, constant temperature 3h obtains phenolic resin balls.
The 1kg resin balls is put in the carbonization-activation integral stove, passes into the argon gas of 900L/min, the temperature rise rate with 4 ℃/min is warming up to 1000 ℃ afterwards, the 1000L/min ammonia that switches to, activation switches to argon gas behind the 2h, and cooling is taken out and namely got the finished product until drop to 40 ℃.Nitrogen content is 4.6wt% in the product.
At CO
2Content is 100%, when 30 ℃ of probe temperatures, gaseous tension 1atm, this product is to CO
2Quantity of the catch be 14.1wt%.
Embodiment 7
Be that 100 ℃ lacquer resins 10Kg, nitrogenous compound bicarbonate of ammonia 1Kg, industrial spirit 3Kg is formulated as soup compound with softening temperature, directly be added in the autoclave that contains Surfactant SDS and tetrafluoroethylene (weight ratio 1: 1) 0.4Kg and water 600Kg, then with 500 turn/speed of min at the uniform velocity stirs, open heating schedule, temperature rise rate with 8 ℃/min is raised to 160 ℃, constant temperature 1h obtains phenolic resin balls.
The 1kg resin balls is put in the carbonization-activation integral stove, passes into the argon gas of 400L/min, the temperature rise rate with 2 ℃/min is warming up to 700 ℃ afterwards, the 1000L/min water vapor that switches to, activation switches to argon gas behind the 0.5h, and cooling is taken out and namely got the finished product until drop to 45 ℃.Nitrogen content is 1.8wt% in the product.
At CO
2Content is 100%, when 30 ℃ of probe temperatures, gaseous tension 1atm, this product is to CO
2Quantity of the catch be 7.4wt%.
Comparative Examples:
Be that 100 ℃ lacquer resins 10Kg, solidifying agent hexamethylenetetramine 2Kg, industrial spirit 4Kg is formulated as soup compound with softening temperature, directly be added in the autoclave that contains surface active agent polyvinyl alcohol 0.2Kg and water 500Kg, then with 300 turn/speed of min at the uniform velocity stirs, open heating schedule, temperature rise rate with 3 ℃/min is raised to 120 ℃, constant temperature 1h obtains phenolic resin balls.
The 1kg resin balls is put in the carbonization-activation integral stove, passes into the argon gas of 300L/min, the temperature rise rate with 1 ℃/min is warming up to 900 ℃ afterwards, the 500L/min water vapor that switches to, activation switches to argon gas behind the 2h, and cooling is taken out and namely got the finished product until drop to 50 ℃.Nitrogen content is 0.4wt% in the product.
At CO
2Content is 100%, when 30 ℃ of probe temperatures, gaseous tension 1atm, this product is to CO
2Quantity of the catch be 5.8wt%.
Claims (3)
1. one kind is used for catching CO
2The preparation method of spheric active carbon, it is characterized in that comprising the steps:
(1), balling-up soup compound preparation: lacquer resins, nitrogenous compound and industrial spirit mix take weight ratio as 1:0.01-0.3:0.3-0.9, after being made into soup compound, directly be added in the reactor that contains tensio-active agent and water, wherein the weight ratio of lacquer resins and tensio-active agent and water is 1:0.02-0.5:10-800;
(2), emulsification balling-up: after reactor is airtight, opens and stir, rotating speed is 200-1000 rev/min, is raised to 100-170 ℃ with 1-10 ℃/minute temperature rise rate, and constant temperature 0.5-3h after the cooling, obtains resin balls naturally afterwards;
(3), carbonization-activation: resin balls is put in the carbonization-activation stove, pass into rare gas element, the weight ratio of gas flow rate and resin balls is: 300-1000L/min:1kg, temperature rise rate with 0.1-4 ℃/min is warming up to 700-1000 ℃ afterwards, switch to activated gas, the ratio of activated gas and resin balls is: 100-300L/min:1kg switches to rare gas element behind the activation 0.5-2h, and be cooled to below 50 ℃, get the finished product;
Described nitrogenous compound is one or both mixtures of triethylene tetramine, tetraethylene pentamine;
Described tensio-active agent is one or both mixtures in sodium lauryl sulphate, polyvinyl alcohol, the tetrafluoroethylene;
Described activated gas is NH
3
2. as claimed in claim 1 a kind of be used to catching CO
2The preparation method of spheric active carbon, it is characterized in that described lacquer resins is the line style novolac resin of softening temperature between 70-120 ℃.
3. as claimed in claim 1 a kind of be used to catching CO
2The preparation method of spheric active carbon, it is characterized in that described rare gas element is nitrogen or argon gas.
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| CN102862983A (en) * | 2012-09-26 | 2013-01-09 | 中国科学院山西煤炭化学研究所 | Preparation method of spherical active carbon for capturing CO2 |
| JP6485999B2 (en) | 2013-09-20 | 2019-03-20 | アイオン株式会社 | Electrode of electric storage device and method of manufacturing the same |
| CN104310396B (en) * | 2014-10-21 | 2016-04-20 | 中国科学院山西煤炭化学研究所 | A kind of efficient adsorption CO 2the preparation method of gac |
| CN104843670B (en) * | 2015-04-28 | 2016-11-16 | 江苏省农业科学院 | A kind of method utilizing corn cob to prepare bulky grain Carbon foam |
| CN106348290B (en) * | 2016-08-30 | 2018-10-26 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of high-termal conductivity asphalt-base globular active carbon |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583837A (en) * | 2004-06-11 | 2005-02-23 | 中国科学院山西煤炭化学研究所 | Preparation of phenolic resin based micro-balls |
| CN101348573A (en) * | 2008-09-11 | 2009-01-21 | 中国科学院山西煤炭化学研究所 | Preparation of spherical phenolic resin |
| CN101721972A (en) * | 2009-12-08 | 2010-06-09 | 华东理工大学 | Method for preparing spherical activated carbon with large CO2absorption capacity |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583837A (en) * | 2004-06-11 | 2005-02-23 | 中国科学院山西煤炭化学研究所 | Preparation of phenolic resin based micro-balls |
| CN101348573A (en) * | 2008-09-11 | 2009-01-21 | 中国科学院山西煤炭化学研究所 | Preparation of spherical phenolic resin |
| CN101721972A (en) * | 2009-12-08 | 2010-06-09 | 华东理工大学 | Method for preparing spherical activated carbon with large CO2absorption capacity |
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