CN1146971A - Method for continuous production of carbon molecular sieve - Google Patents
Method for continuous production of carbon molecular sieve Download PDFInfo
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- CN1146971A CN1146971A CN 95111821 CN95111821A CN1146971A CN 1146971 A CN1146971 A CN 1146971A CN 95111821 CN95111821 CN 95111821 CN 95111821 A CN95111821 A CN 95111821A CN 1146971 A CN1146971 A CN 1146971A
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Abstract
A continuous process for producing carbon molecular sieve used to prepare nitrogen by air separation comprises breaking carbon-contained raw material, addition of adhesive, kneading, shaping, drying and 3-6 stages of serial reactions for removing volatile components, gas-phase chemical deposition and cooling. Obtained carbon molecular sieve features high air separation performace and strength. The volatile substance separated from solid material is used as pore regulator in gas-phase carbon deposition. Its advantages are high efficiency and low consumption.
Description
The invention belongs to a kind of continous way and prepare the method for transformation absorption nitrogen production by air separation with carbon molecular sieve.
Existing carbon molecular sieve preparation technology generally has three steps: carbonaceous material pulverizing, pre-treatment, adding additives moulding; Forming composition charing under inert atmosphere; The carbide partial gasification is or/and carbon laydown is transferred the hole.For example, the processing method of German BF company (Bergbau-Forschung GmbH) is: bituminous coal is pulverized, oxidation in fluidized-bed, add the binding agent moulding, forming composition is charing in converter under inert atmosphere, feeds hydro carbons then, makes its carbon laydown in the carbon molecular sieve hole transfer the hole, obtain nitrogen production by air separation carbon molecular sieve (H.J ü tgen at last, K.Kuoblauch, and H.Harder, Fuel, 60,817 (1981)).It is that thermal treatment in converter under the noble gas protection obtains carbon molecular sieve (USP4528281) after the cooling then with liquefied hydrocarbon or macromolecular compound dipping carbide that carbon laydown is transferred the another kind of method in hole.The contriver at two step charring technologies of high volatile nutshell (nuclear) class carbon raw material exploitation is: obtain carbon molecular sieve (Xu Shaoping, Guo Shucai after a charing of nutshell (nuclear), pulverizing, adding additives moulding, the charing of forming composition secondary, the cooling, Chinese patent application 92113349.9,94112601.3).In the above-mentioned the whole bag of tricks, charing or the converter of thermal treatment main equipment all are batch productions, be every production one stove carbonized material or carbon molecular sieve, converter and wherein material all experienced intensification, constant temperature and temperature-fall period, throughput is little, energy consumption is big, operational condition is harsh, the volatile matter that material is deviate from must adopt complex apparatus to be handled, otherwise causes environmental pollution.To adopting the gaseous hydrocarbon pyrolysis carbon laydown to transfer the technology in hole, need add hydrocarbon gas and transfer the hole agent; To adopting the pickling process carbon laydown to transfer the technology in hole, also can bring mass consumption steeping fluid, contaminate environment and problem such as inflammable and explosive.The problem of ubiquitous unstable product quality is also relevant with batch production technology in the industrial production.
The objective of the invention is to propose to adopt the continous way method to prepare the method for high-performance nitrogen production by air separation, to overcome the deficiencies in the prior art with carbon molecular sieve.
Technical scheme of the present invention is: carbon raw material is through pulverizing, adding additives kneading, extruded moulding or make ball forming, the forming composition standing and drying, successively by 3～6 sections placed in-line reactors that atmosphere is different, go through devolatilization, in the stage such as chemical vapour deposition, cooling, obtain to steady and continuous the high-performance carbon zeolite product.Described carbon raw material comprises the mixture etc. of oxidation products, timber, straw and nutshell (nuclear) semicoke, lignite semi-coke and above-mentioned partial material of oxidation products, the pulverized anthracite of non-caking coal, long-flame coal, the caking coal of low ash, its butt volatile matter is less than 50wt%, dry basis ash content is less than 20wt%, and its grinding particle size is less than 160 orders; Described binding agent can be following material or their mixture: coal tar, coal-tar pitch, petroleum pitch, pitch, naphtalene oil, carbolineum, resol, urea-formaldehyde resin, polyvinyl alcohol, polyoxyethylene glycol, starch, cellulose acetate, sulfonic acid xylogen, humic acids, cellulose lye, carboxymethyl cellulose, molasses, water, the weight proportion of binding agent are 20-60%; Described technology realizes in placed in-line 3-6 section reactor, the temperature distribution that is equipped with the section reactor immobilizes, can regulate separately, wherein first section temperature of reactor is 100～300 ℃, second section is 300～800 ℃, the 3rd section is 700～900 ℃, and the 4th～six section is that the atmosphere of 800～100 ℃ of reactors can be regulated normal pressure or micro-pressure operation separately.Reactor adopts the indirect heating mode, can adopt electrothermic type, also available fire coal, timber heating or stack gas heating, and temperature is the highest to be no more than 1000 ℃.Reactor is made with metallic substance, and its form can be that converter also can be fixed stove.Realize at the certain inclination angle that reactor is set that flows through of the former solid materials, is provided with fin in the converter, to guarantee the mass transfer of solid materials when the revolution reach, to conduct heat evenly.The latter is provided with screw compulsory and advances solid materials in reactor.The gaseous state material comprises the volatile matter that inert carrier gas and solid materials are deviate from, and advances with the solid materials adverse current, and except that cooling section, other sections also can adopt the following current form.
Implementing concrete grammar of the present invention is: carbon raw material is crushed to less than 160 orders, adds that binding agent is kneaded, extruded moulding or adding additives roller forming, forming composition is sent into continuous preparation device behind 60-100 ℃ of following standing and drying 1-24h.Continuous apparatus is formed by 3-6 section reactors in series, and molding mass is successively by each section reactor, and processes such as experience devolatilization, chemical gas phase carbon laydown and cooling obtain the carbon molecular sieve product.Feed nitrogen at the cooling section tail end, nitrogen with the solid materials volatile matter as shown in Figure 1 adverse current by each section reactor.Each section reactor keeps pressure-fired.
Basic design of the present invention is: the carbon raw material that is adopted should have suitable volatile content, to guarantee forming the required enough big micropore volume that possesses of carbon molecular sieve, be unlikely simultaneously because of excessively weightless contraction causes carbon molecular sieve intensity to reduce and do not meet application requiring by devolatilization; The binding agent that is adopted is except that guaranteeing that carbon molecular sieve has the sufficient intensity, and the chemical vapour deposition effect of its pyrolysis devolatilization product in charcoal matrix should be able to be regulated charcoal matrix micropores pore size distribution effectively; The continuous preparation technology who is adopted is one another in series by several sections continuously by molding mass, has separately that the different reactor of relatively-stationary temperature distribution, atmosphere, effect realizes.The volatile matter Returning reacting system that the adjusting that the carbon molecular sieve micropore size distributes is deviate from by being controlled to moulding mixture self is realized at charcoal stromal surface chemical gas phase carbon laydown, need not the external carbon deposition and transfers hole reagent.Each section reactor operating condition (temperature distribution, atmosphere, pressure, residence time of material etc.) does not become in time, thereby guarantees that quality product is relatively stable.
Owing to adopt continuous processing, make the production of carbon molecular sieve realize efficient (unit time, the unit reactor volume production improves), low consumption (less energy-consumption, need not to add transfer hole agent) and clean (effluxing volatile matter reduces also and can burn).
Fig. 1 is a continous way carbon molecular sieve preparation technology schema.
Embodiments of the invention are as follows:
1. non-caking coal (butt volatile matter 35wt%) is crushed to less than 160 orders, add 25wt% coal-tar heavy oil and less water, knead, extruded moulding, forming composition is dry 4h under 90 ℃, then, send into the continuously carbonizing device by screw feeder, the continuously carbonizing device is made of 5 sections placed in-line converters, and its temperature distribution is followed successively by 60-200 ℃, 200-700 ℃, 700-850 ℃, 850-500 ℃, 500-150 ℃.The converter rotating speed is 1rpm.Nitrogen is sent into by the end of the 5th section reaction, by shown in Figure 1, passes through each section reactor with the solid materials adverse current.The residence time of solid materials in each section reactor is followed successively by 20min, 40min, 20min, 20min, 30min.The sky branch performance of gained carbon molecular sieve product is N
299.0wt% (factor of created gase is 100l/hkgCMS).Empty divide test be on the twin columns pressure-swing absorption apparatus, carry out, adsorption column internal diameter 40mm, long 600mm, adsorptive pressure 0.4Mpa, desorption pressure 8kPa, adsorption time 60s all presses time 2s.
2. the continuously carbonizing device is in series by 5 sections horizontally disposed fixed stoves.Establish screw drive in solid materials the flowing through in stove.Other conditions embodiment 1.The sky branch performance of products obtained therefrom carbon molecular sieve is N
298.8vol% (product gas productive rate 100l/hkgCMS).
3. raw material is nut-shell semicoke (volatile matter 10wt%), and other conditions are with embodiment 1, and the empty branch performance of product carbon molecular sieve is N
299.2vol% (factor of created gase 100l/hkgCMS).
4. raw material is with example 3, and binding agent is the mixture of 15wt% coal-tar heavy oil, 10wt% resol and 20wt% water.Other conditions are with example 1.The sky branch performance of product carbon molecular sieve is N
299.1vol% (factor of created gase 100l/hkgCMS).
Claims (8)
1. one kind is raw material with the contenting carbon material, continous way prepares the production method of nitrogen production by air separation with carbon molecular sieve, it is characterized in that carbonaceous material pulverizing, adding additives moulding, forming composition standing and drying, send into then by 3-6 section reactors in series form continuously, solid materials is through continuous, go through devolatilization, chemical gas phase carbon laydown, cool off each stage, obtain to steady and continuous the carbon molecular sieve product.Feed nitrogen in the cooling section terminal, the volatile matter that this each section of gas-entrained solid materials is deviate from effluxes after by each section reactor continuously by certain flow direction.
2. the production method of carbon molecular sieve according to claim 1, it is characterized in that one or more mixtures of carbonaceous material comprise: the oxide compound of non-caking coal, long-flame coal, caking coal, the oxide compound of pulverized anthracite, timber, straw and nutshell (nuclear) semicoke, lignite semi-coke, its butt volatilization is divided into less than 50wt%, butt divides less than 20wt%, and its grinding particle size is less than 160 orders.
3. the production method of carbon molecular sieve according to claim 1, it is characterized in that binding agent is one or more a mixture of following material: coal tar, coal-tar pitch, petroleum pitch, pitch, naphtalene oil, carbolineum, resol, urea-formaldehyde resin, polyvinyl alcohol, polyoxyethylene glycol, starch, cellulose acetate, sulfonic acid xylogen, humic acids, cellulose lye, molasses, carboxymethyl cellulose, water, weight of binder proportioning are 20-60wt%.
4. the production method of carbon molecular sieve according to claim 1 is characterized in that molding mode comprises roller forming and extruded moulding.
5. the production method of carbon molecular sieve according to claim 1 is characterized in that drying conditions is temperature 60-100 ℃, time 1-24h.
6. the production method of carbon molecular sieve according to claim 1 is characterized in that reactor can be converter, and also fixed stove is provided with fin in the converter, and is even to guarantee the mass-and heat-transfer of solid materials when revolution moves forward; Be provided with screw rod in the stationary furnace, promote material and move ahead, and guarantee that the material mass-and heat-transfer is even, the temperature distribution of each section reactor, atmosphere, pressure, residence time of material relative fixed do not change in time; Reactor is made by metallic substance, external-heat, and electrically heated or stack gas heating, top temperature is no more than 1000 ℃.
7. the production method of carbon molecular sieve according to claim 1, the atmosphere that it is characterized in that each section reactor is determined by the nitrogen of latter end reactor tail end feeding and the gas material that is made of the volatilization branch that the solid materials that it carries is deviate from, gas material is continuously by each section reactor, can with the solid materials adverse current, also can be with it and stream.
8. the production method of carbon molecular sieve according to claim 1 is characterized in that the chemical gas phase carbon laydown is to transfer the hole behavior by the cracking carbon distribution of volatile matter on charcoal matrix that the solid materials that nitrogen carries is deviate from, and need not to add accent hole agent.
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| CN 95111821 CN1146971A (en) | 1995-06-23 | 1995-06-23 | Method for continuous production of carbon molecular sieve |
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| CN 95111821 CN1146971A (en) | 1995-06-23 | 1995-06-23 | Method for continuous production of carbon molecular sieve |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN102328924A (en) * | 2010-10-19 | 2012-01-25 | 胡耀明 | Method for manufacturing carbon molecular sieve with plant nutshell |
| CN102489236A (en) * | 2011-11-17 | 2012-06-13 | 四川嘉宝莉涂料有限公司 | Liquid granite paint production device |
| CN102502579A (en) * | 2011-10-28 | 2012-06-20 | 湖州强马分子筛有限公司 | Production method for shell-based carbon molecular sieve |
| CN101486885B (en) * | 2007-05-16 | 2012-07-18 | 周惠兴 | Binder for magnesium carbonaceous fire-resistant material |
| CN103072967A (en) * | 2013-01-10 | 2013-05-01 | 大连理工大学 | Continuously carbonizing device and method for preparing intermediate product carbonized material of carbon molecular sieve |
| CN104045083A (en) * | 2014-07-04 | 2014-09-17 | 湖南湘格新材料有限公司 | Preparation method of coconut shell carbon molecular sieve |
| CN105111468A (en) * | 2015-09-14 | 2015-12-02 | 大连理工大学 | Solidifying and powdering method for liquid thermoset high-molecular polymers |
| KR20160058818A (en) * | 2013-09-18 | 2016-05-25 | 후타무라 가가쿠 가부시키가이샤 | Synthetic resin binder-molded solid acid, and method for producing same |
| CN106010705A (en) * | 2016-05-31 | 2016-10-12 | 北京神雾环境能源科技集团股份有限公司 | Composite binder used for formed coke forming, formed coke, and production method of formed coke |
| CN106082220A (en) * | 2016-05-31 | 2016-11-09 | 神雾环保技术股份有限公司 | Compound binding agent, the mixture pelletizing comprising it and preparation method thereof |
| CN107321307A (en) * | 2017-07-12 | 2017-11-07 | 贵州益寿农业科技有限公司 | A kind of method that use oil tea shell makes carbon molecular sieve |
| CN111204730A (en) * | 2019-12-31 | 2020-05-29 | 太尔化工（南京）有限公司 | Preparation process for preparing carbon molecular sieve binder from PF waste resin |
| CN112142047A (en) * | 2020-09-23 | 2020-12-29 | 山东奥淼科技发展有限公司 | Method for preparing carbon molecular sieve by using biological semicoke |
| CN114700039A (en) * | 2022-04-12 | 2022-07-05 | 广州碳加科技有限公司 | System and process method for continuously producing carbon molecular sieve |
-
1995
- 1995-06-23 CN CN 95111821 patent/CN1146971A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486885B (en) * | 2007-05-16 | 2012-07-18 | 周惠兴 | Binder for magnesium carbonaceous fire-resistant material |
| CN101804979B (en) * | 2010-04-07 | 2012-04-18 | 煤炭科学研究总院 | Coal-based carbon molecular sieve and preparation method thereof |
| 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 |
| CN102328924A (en) * | 2010-10-19 | 2012-01-25 | 胡耀明 | Method for manufacturing carbon molecular sieve with plant nutshell |
| CN102502579A (en) * | 2011-10-28 | 2012-06-20 | 湖州强马分子筛有限公司 | Production method for shell-based carbon molecular sieve |
| CN102502579B (en) * | 2011-10-28 | 2013-06-12 | 湖州强马分子筛有限公司 | Production method for shell-based carbon molecular sieve |
| CN102489236A (en) * | 2011-11-17 | 2012-06-13 | 四川嘉宝莉涂料有限公司 | Liquid granite paint production device |
| CN102489236B (en) * | 2011-11-17 | 2013-11-27 | 四川嘉宝莉涂料有限公司 | Liquid granite paint production device |
| CN103072967A (en) * | 2013-01-10 | 2013-05-01 | 大连理工大学 | Continuously carbonizing device and method for preparing intermediate product carbonized material of carbon molecular sieve |
| CN103072967B (en) * | 2013-01-10 | 2014-06-25 | 大连理工大学 | Continuously carbonizing device and method for preparing intermediate product carbonized material of carbon molecular sieve |
| KR20160058818A (en) * | 2013-09-18 | 2016-05-25 | 후타무라 가가쿠 가부시키가이샤 | Synthetic resin binder-molded solid acid, and method for producing same |
| KR102201533B1 (en) * | 2013-09-18 | 2021-01-12 | 후타무라 가가쿠 가부시키가이샤 | Synthetic resin binder-molded solid acid, and method for producing same |
| CN104045083A (en) * | 2014-07-04 | 2014-09-17 | 湖南湘格新材料有限公司 | Preparation method of coconut shell carbon molecular sieve |
| CN105111468B (en) * | 2015-09-14 | 2018-04-10 | 大连理工大学 | A kind of liquid thermosetting high molecular polymer solidifies pulverization methods |
| CN105111468A (en) * | 2015-09-14 | 2015-12-02 | 大连理工大学 | Solidifying and powdering method for liquid thermoset high-molecular polymers |
| CN106010705A (en) * | 2016-05-31 | 2016-10-12 | 北京神雾环境能源科技集团股份有限公司 | Composite binder used for formed coke forming, formed coke, and production method of formed coke |
| CN106082220A (en) * | 2016-05-31 | 2016-11-09 | 神雾环保技术股份有限公司 | Compound binding agent, the mixture pelletizing comprising it and preparation method thereof |
| CN107321307A (en) * | 2017-07-12 | 2017-11-07 | 贵州益寿农业科技有限公司 | A kind of method that use oil tea shell makes carbon molecular sieve |
| CN111204730A (en) * | 2019-12-31 | 2020-05-29 | 太尔化工（南京）有限公司 | Preparation process for preparing carbon molecular sieve binder from PF waste resin |
| CN112142047A (en) * | 2020-09-23 | 2020-12-29 | 山东奥淼科技发展有限公司 | Method for preparing carbon molecular sieve by using biological semicoke |
| CN114700039A (en) * | 2022-04-12 | 2022-07-05 | 广州碳加科技有限公司 | System and process method for continuously producing carbon molecular sieve |
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