CN103641102B - Preparation method of coke oven gas debenzolization agent - Google Patents
Preparation method of coke oven gas debenzolization agent Download PDFInfo
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- CN103641102B CN103641102B CN201310716891.6A CN201310716891A CN103641102B CN 103641102 B CN103641102 B CN 103641102B CN 201310716891 A CN201310716891 A CN 201310716891A CN 103641102 B CN103641102 B CN 103641102B
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- coke
- agent
- molecular sieve
- oven coal
- benzene
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Abstract
The invention discloses a preparation method of a coke oven gas debenzolization agent. The preparation method comprises the following steps: (1) uniformly mixing a crushed coal sample and an adhesive; (2) carbonizing in a carbonizing furnace at a temperature of 600 to 950 DEG C; (3) charging CO2 with purity of being larger than 99% into an activating oven at 600 to 850 DEG C; (4) charging homogenizing agent vapor into a homogenizing furnace to homogenize pores at 700 to 900 DEG C, and thus obtaining a carbon molecular sieve with uniformly distributed aperture; (5) dipping the carbon molecular sieve into a Zn<2+>-containing solution to obtain a zinc-loaded carbon molecular sieve; and (6) inerting and drying in inert gas, and cooling to reach room temperature. The coke oven gas debenzolization agent prepared by the method can solve the problem that insufficient debenzolization of activated carbon to coke oven gas does not meet the requirements of the downstream process to the benzene content, and enables the benzene content in the coke oven gas to be reduced to 0.05mg/Nm<3> when the activated carbon is used for carrying out debenzolization on coke oven gas.
Description
Technical field
The present invention relates to gas separation technique field, further, relate to the agent of a kind of coke-oven coal qi exhaustion benzene, preparation method and using method.
Background technology
Coke-oven gas is rich in H
2, CH
4, CO industrial gasses, industrial application mainly proposes hydrogen, directly burning and CCPP generating etc., and lower procedure all has respective requirement to coke-oven gas quality.Have the benzene of a great deal of in coke-oven gas, because benzene is carinogenicity material, have certain toxic action to human body, and its molecular weight is comparatively large, has and comparatively has a strong impact on, so general technology all requires benzene to be removed under specific indexes to lower procedure.
Coke-oven coal qi exhaustion benzene generally uses gac, and gac is a kind of sorbent material of excellent property, better to the adsorption effect of benzene.If but when lower procedure is harsh to benzene index request, due to the impact of adsorption equilibrium, gac cannot carry out the degree of depth and take off benzene.
Exploitation can be necessary greatly by the degree of depth carbon molecular sieve that takes off benzene.
Patent CN101935032A discloses a kind of preparation method of carbon molecular sieve, and the method uses KOH or CO to conventional carbon molecular sieve
2for activator carries out re-activation, to obtain the carbon molecular sieve of property, main application is that methane-nitrogen pressure-variable adsorption is separated.
Patent CN101214433 discloses a kind of preparation method of active carbon supported with zinc oxide, and the method is carrying the waste active carbon of zinc acetate for raw material, by changing different heating rate, soaking time and synthesis atmosphere, realizing the generation of active carbon supported with zinc oxide.The method carries out modification to gac, and it is zinc oxide in load.
Summary of the invention
The invention provides the manufacture method of coke-oven coal qi exhaustion benzene agent, overcome the difficulty of prior art, when the coke-oven coal qi exhaustion benzene agent adopting the present invention to obtain can solve and use gac to carry out coke-oven coal qi exhaustion benzene, de-benzene depth as shallow, do not reach the problem of lower procedure to benzene content requirement, make that benzene content in coke-oven gas is minimum is down to 0.05mg/Nm
3.
Present invention employs following technical scheme:
The invention provides the manufacture method of coke-oven coal qi exhaustion benzene agent, at least comprise the following steps:
(1) mix with binding agent after coal sample being pulverized;
(2) carbonize in charring furnace, temperature 600 to 950 DEG C;
(3) in activation furnace, CO is passed into
2, CO
2purity >99%, temperature 600 to 850 DEG C;
(4) in the stove of tune hole, pass into tune hole agent steam, carry out hole homogenization process, temperature 700 to 900 DEG C, obtain the carbon molecular sieve of even aperture distribution, described tune hole agent is at least one in isovaleric acid diethyl ester, tert.-butylbenzene, trieline or pentyl acetate;
(5) this carbon molecular sieve is soaked in containing Zn
2+solution in, obtain the carbon molecular sieve of zinc supported, described containing Zn
2+solution be ZnCl
2, ZnSO
4, Zn (OH)
2, [Zn (NH
3)
4] (OH)
2in one; And
(6) in inerting gas, inerting is dried, and the temperature that inerting is dried is 100 to 200 DEG C, and soaking time is 2.5 to 5.5 hours, and keeps passing into N
2, be cooled to room temperature.
Preferably, in described step (2), the temperature rise rate of described charring furnace is 15 DEG C/min.
Preferably, in described step (2), the time carbonized in described charring furnace is 45 minutes.
Preferably, in described step (3), the time in described activation furnace is 4 to 6 hours.
Preferably, in described step (4), the time in the stove of described tune hole is 1.5 to 2 hours.
Present invention also offers the agent of a kind of coke-oven coal qi exhaustion benzene, obtained by the manufacture method of above-mentioned coke-oven coal qi exhaustion benzene agent.
Present invention also offers the purposes of zinc supported carbon molecular sieve in coke-oven coal qi exhaustion benzene obtained by aforesaid method.
Owing to employing above technology, when the obtained coke-oven coal qi exhaustion benzene agent of the manufacture method of coke-oven coal qi exhaustion benzene of the present invention agent can solve and use gac to carry out coke-oven coal qi exhaustion benzene, de-benzene depth as shallow, do not reach the problem of lower procedure to benzene content requirement, make that benzene content in coke-oven gas is minimum is down to 0.05mg/Nm
3.
The present invention is further illustrated below in conjunction with drawings and Examples.
Accompanying drawing explanation
Fig. 1 is the schema of the manufacture method of coke-oven coal qi exhaustion benzene of the present invention agent;
Fig. 2 is the scanning electron microscope (SEM) photograph of the carbon molecular sieve of not yet zinc supported;
Fig. 3 is the scanning electron microscope (SEM) photograph of the carbon molecular sieve after zinc supported; And
Fig. 4 is carbon molecular sieve and zinc supported carbon molecular sieve adsorptive capacity comparison diagram.
Embodiment
Specific embodiments of the invention are introduced below by Fig. 1 to 4.
As shown in Figure 1, the invention provides the manufacture method of coke-oven coal qi exhaustion benzene agent, at least comprise the following steps:
(1) mix with binding agent after coal sample being pulverized;
(2) carbonize in charring furnace, temperature 600 to 950 DEG C;
(3) in activation furnace, CO is passed into
2, CO
2purity >99%, temperature 600 to 850 DEG C;
(4) in the stove of tune hole, pass into tune hole agent steam, carry out hole homogenization process, temperature 700 to 900 DEG C, obtain the carbon molecular sieve of even aperture distribution;
(5) this carbon molecular sieve is soaked in containing Zn
2+solution in, obtain the carbon molecular sieve of zinc supported; And
(6) in inerting gas, inerting is dried, and is cooled to room temperature, obtains the carbon molecular sieve of zinc supported.
In described step (2), the temperature rise rate of described charring furnace is 15 DEG C/min.
In described step (2), the time carbonized in described charring furnace is 45 minutes.
In described step (3), the time in described activation furnace is 4 to 6 hours.
In described step (4), the time in the stove of described tune hole is 1.5 to 2 hours.
In described step (4), be at least one in isovaleric acid diethyl ester, tert.-butylbenzene, trieline or pentyl acetate in described tune hole agent.
In described step (4), the aperture of carbon molecular sieve is slightly larger than benzene.
In described step (4), not yet the carbon molecular sieve (Carbon Molecular Sieve, CMS) of zinc supported as shown in Figure 2.
In described step (5), containing Zn
2+solution be ZnCl
2, ZnSO
4, Zn (OH)
2, [Zn (NH
3)
4] (OH)
2in one.
In described step (6), the temperature that inerting is dried is 100 to 200 DEG C, and soaking time is 2.5 to 5.5 hours, and keeps passing into N
2.
In described step (6), as shown in Figure 3, in figure, white mass is zinc in coke-oven coal qi exhaustion benzene of the present invention agent (carbon molecular sieve of zinc supported, CMS with Zinc).
Present invention also offers the agent of a kind of coke-oven coal qi exhaustion benzene, obtained by the manufacture method of above-mentioned coke-oven coal qi exhaustion benzene agent.
Present invention also offers a kind of coke-oven coal qi exhaustion benzene method, use above-mentioned coke-oven coal qi exhaustion benzene agent.
As shown in Figure 4, can find out that when being used in coke-oven coal qi exhaustion benzene, the adsorptive capacity of zinc supported carbon molecular sieve (CMS with Zinc) is higher than the carbon molecular sieve (CMS) of not yet zinc supported.
Embodiment 1
Coal sample is pulverized bonding, and put into charring furnace, carbonization temperature 650 to 950 DEG C, carbonization time 45 minutes, puts into activation furnace after charing, uses CO
2activate, CO
2purity >99%, temperature 650 to 850 DEG C, the time is 4.5 to 6 hours, obtains gac, and inserted by gac and adjust in the stove of hole, pass into isovaleric acid diethyl ester steam, temperature 750 to 900 DEG C, the time is 1.5 to 2 hours, obtains carbon molecular sieve.
Carbon molecular sieve above-mentioned steps obtained is soaked in ZnCl
2in solution, soak time 2.5 hours, passes into N in process furnace
2, N
2purity >99.9%, puts into this carbon molecular sieve, is heated to 120 to 200 DEG C, is incubated 2.5 to 5.5 hours, keeps N
2pass into, remove thermal source, make molecular sieve at the uniform velocity be cooled to room temperature, obtain the carbon molecular sieve of zinc supported.
Be used for carrying out de-benzene process to coke-oven gas by the carbon molecular sieve that above-mentioned steps is obtained.Coke-oven gas index is as follows:
Benzene 1500mg/Nm
3temperature 40 DEG C of pressure 10KPa(gauge pressures) Temp .-changing adsorption lock out operation is carried out to coke-oven gas, use special tune hole agent to make and the carbon molecular sieve of zinc supported shows excellent benzene separation performance, after purification, benzene content is 0.03mg/Nm
3.
Embodiment 2
Coal sample pulverizes bonding, and put into charring furnace, carbonization temperature 700 to 950 DEG C, carbonization time 45 minutes, puts into activation furnace after charing, use CO
2activate, CO
2purity >99%, temperature 650 to 850 DEG C, the time is 4.5 to 5.5 hours, obtains gac, and inserted by gac and adjust in the stove of hole, pass into trichloroethylene steam, temperature 750 to 900 DEG C, the time is 1.5 to 2 hours, obtains carbon molecular sieve.
Carbon molecular sieve above-mentioned steps obtained is soaked in ZnSO
4in solution, soak time 2.5 hours, passes into N in process furnace
2, N
2purity >99.9%, puts into this carbon molecular sieve, is heated to 130 to 200 DEG C, is incubated 2.5 to 5 hours, keeps N
2pass into, remove thermal source, make molecular sieve at the uniform velocity be cooled to room temperature, obtain the carbon molecular sieve of zinc supported.
Be used for carrying out de-benzene process to coke-oven gas by the carbon molecular sieve that above-mentioned steps is obtained.Coke-oven gas index is as follows: benzene 2000mg/Nm
3temperature 45 DEG C of pressure 12KPa(gauge pressures) Temp .-changing adsorption lock out operation is carried out to coke-oven gas, use special tune hole agent to make and the carbon molecular sieve of zinc supported shows excellent benzene separation performance, after purification, benzene content is 0.035mg/Nm
3.
The above-mentioned description to embodiment can understand and apply the invention for the ease of those skilled in the art.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement made for the present invention and amendment all should within protection scope of the present invention.
In summary, when the obtained coke-oven coal qi exhaustion benzene agent of the manufacture method of coke-oven coal qi exhaustion benzene of the present invention agent can solve and use gac to carry out coke-oven coal qi exhaustion benzene, de-benzene depth as shallow, does not reach the problem of lower procedure to benzene content requirement, makes that benzene content in coke-oven gas is minimum is down to 0.05mg/Nm
3.
Above-described embodiment is only for illustration of technological thought and the feature of this patent, its object is to enable those skilled in the art understand the content of this patent and implement according to this, the scope of the claims of this patent only can not be limited with the present embodiment, namely the equal change done of all spirit disclosed according to this patent or modification, still drop in the scope of the claims of this patent.
Claims (7)
1. a manufacture method for coke-oven coal qi exhaustion benzene agent, is characterized in that, at least comprise the following steps:
(1) mix with binding agent after coal sample being pulverized;
(2) carbonize in charring furnace, temperature 600 to 950 DEG C;
(3) in activation furnace, CO is passed into
2, CO
2purity >99%, temperature 600 to 850 DEG C;
(4) in the stove of tune hole, pass into tune hole agent steam, carry out hole homogenization process, temperature 700 to 900 DEG C, obtain the carbon molecular sieve of even aperture distribution, described tune hole agent is at least one in isovaleric acid diethyl ester, tert.-butylbenzene, trieline or pentyl acetate;
(5) this carbon molecular sieve is soaked in containing Zn
2+solution in, obtain the carbon molecular sieve of zinc supported, described containing Zn
2+solution be ZnCl
2, ZnSO
4, Zn (OH)
2, [Zn (NH
3)
4] (OH)
2in one; And
(6) in inerting gas, inerting is dried, and the temperature that inerting is dried is 100 to 200 DEG C, and soaking time is 2.5 to 5.5 hours, and keeps passing into N
2, be cooled to room temperature.
2. the manufacture method of coke-oven coal qi exhaustion benzene agent as claimed in claim 1, it is characterized in that: in described step (2), the temperature rise rate of described charring furnace is 15 DEG C/min.
3. the manufacture method of coke-oven coal qi exhaustion benzene agent as claimed in claim 1, it is characterized in that: in described step (2), the time carbonized in described charring furnace is 45 minutes.
4. the manufacture method of coke-oven coal qi exhaustion benzene agent as claimed in claim 1, it is characterized in that: in described step (3), the time in described activation furnace is 4 to 6 hours.
5. the manufacture method of coke-oven coal qi exhaustion benzene agent as claimed in claim 1, it is characterized in that: in described step (4), the time in the stove of described tune hole is 1.5 to 2 hours.
6. a coke-oven coal qi exhaustion benzene agent, is characterized in that: obtained by the manufacture method of the coke-oven coal qi exhaustion benzene agent described in claim 1.
7. the purposes of coke-oven coal qi exhaustion benzene agent in coke-oven coal qi exhaustion benzene that in claim 1 to 5, arbitrary described method obtains.
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|---|---|---|---|
| CN201310716891.6A CN103641102B (en) | 2013-12-24 | 2013-12-24 | Preparation method of coke oven gas debenzolization agent |
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| CN103641102B true CN103641102B (en) | 2015-04-08 |
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| CN108165322A (en) * | 2017-07-19 | 2018-06-15 | 湖北申昙环保新材料有限公司 | The purification method of coke-stove gas |
| CN112547007A (en) * | 2020-11-08 | 2021-03-26 | 中贞(上海)环境能源科技有限公司 | Novel carbon molecular sieve waste gas deamination agent |
| CN113322105B (en) * | 2021-07-02 | 2024-07-26 | 上海电气集团国控环球工程有限公司 | Efficient debenzolization and purification process of coke oven gas |
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| EP0542625B1 (en) * | 1991-11-15 | 1995-06-28 | Institut Francais Du Petrole | Aluminosilicate type catalyst and its use for the aromatizing of hydrocarbons containing 2 to 12 carbon atoms |
| KR100708642B1 (en) * | 2003-11-21 | 2007-04-18 | 삼성에스디아이 주식회사 | Mesoporous carbon molecular sieve and supported catalyst employing the same |
| CN100363086C (en) * | 2004-11-22 | 2008-01-23 | 四川天一科技股份有限公司 | Pressure swing absorption method for preparing nitrogen from air |
| CN101391757A (en) * | 2008-10-30 | 2009-03-25 | 常州星海半导体器件有限公司 | Process for preparation of nitrogen gas |
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