CN103641102A - Preparation method of coke oven gas debenzolization agent - Google Patents
Preparation method of coke oven gas debenzolization agent Download PDFInfo
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- CN103641102A CN103641102A CN201310716891.6A CN201310716891A CN103641102A CN 103641102 A CN103641102 A CN 103641102A CN 201310716891 A CN201310716891 A CN 201310716891A CN 103641102 A CN103641102 A CN 103641102A
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- agent
- coke
- benzene
- molecular sieve
- oven coal
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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 to be rich in H
2, CH
4, CO industrial gasses, industrial application is mainly to propose hydrogen, directly burning and CCPP generating etc., lower procedure all has requirement separately to coke-oven gas quality.The benzene that has a great deal of in coke-oven gas, because benzene is carinogenicity material, human body is had to certain toxic action, and its molecular weight is larger, and lower procedure is had and had a strong impact on, so general technology all requires benzene to be removed under specific indexes.
Coke-oven coal qi exhaustion benzene is generally used 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 de-benzene of the degree of depth.
Exploitation can the degree of depth carbon molecular sieve of de-benzene be necessary greatly.
Patent CN101935032A discloses a kind of preparation method of carbon molecular sieve, and the method is that conventional carbon molecular sieve is used to KOH or CO
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 that to take the waste active carbon that carries zinc acetate be raw material, by changing different heating rate, soaking time and synthetic atmosphere, realizes the generation of active carbon supported with zinc oxide.The method is that gac is carried out to modification, and load on it is zinc oxide.
Summary of the invention
The invention provides the manufacture method of coke-oven coal qi exhaustion benzene agent, overcome the difficulty of prior art, the coke-oven coal qi exhaustion benzene agent that adopts the present invention to make can solve while using 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 the minimum 0.05mg/Nm of being down to of benzene content in coke-oven gas
3.
The present invention has adopted following technical scheme:
The manufacture method that the invention provides the agent of coke-oven coal qi exhaustion benzene, at least comprises the following steps:
(1) will after coal sample pulverizing, mix with binding agent;
(2) charing in charring furnace, 600 to 950 ℃ of temperature;
(3) in activation furnace, pass into CO
2, CO
2purity >99%, 600 to 850 ℃ of temperature;
(4) in adjusting hole stove, pass into and adjust hole agent steam, carry out hole homogenization processing, 700 to 900 ℃ of temperature, obtain the carbon molecular sieve of even aperture distribution, and the hole agent of described tune 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 a kind of; And
(6) in inerting gas, inerting is dried, and the temperature that inerting is dried is 100 to 200 ℃, 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 ℃/min.
Preferably, in described step (2), in described charring furnace, the time of charing 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.
The present invention also provides the agent of a kind of coke-oven coal qi exhaustion benzene, by the manufacture method of above-mentioned coke-oven coal qi exhaustion benzene agent, is made.
The present invention also provides the zinc supported carbon molecular sieve that makes by the aforesaid method purposes aspect coke-oven coal qi exhaustion benzene.
Owing to having used above technology, the coke-oven coal qi exhaustion benzene agent that the manufacture method of coke-oven coal qi exhaustion benzene of the present invention agent makes can solve while using 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 the minimum 0.05mg/Nm of being down to of benzene content in coke-oven gas
3.
Below in conjunction with drawings and Examples, further illustrate the present invention.
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 zinc supported not yet;
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
Below by Fig. 1 to 4, introduce specific embodiments of the invention.
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) will after coal sample pulverizing, mix with binding agent;
(2) charing in charring furnace, 600 to 950 ℃ of temperature;
(3) in activation furnace, pass into CO
2, CO
2purity >99%, 600 to 850 ℃ of temperature;
(4) in adjusting hole stove, pass into and adjust hole agent steam, carry out hole homogenization processing, 700 to 900 ℃ of temperature, 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 ℃/min.
In described step (2), in described charring furnace, the time of charing 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), in the hole agent of described tune, be at least one in isovaleric acid diethyl ester, tert.-butylbenzene, trieline or pentyl acetate.
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 of zinc supported (Carbon Molecular Sieve, CMS) 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 a kind of.
In described step (6), the temperature that inerting is dried is 100 to 200 ℃, 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).
The present invention also provides the agent of a kind of coke-oven coal qi exhaustion benzene, by the manufacture method of above-mentioned coke-oven coal qi exhaustion benzene agent, is made.
The present invention also provides a kind of coke-oven coal qi exhaustion benzene method, uses above-mentioned coke-oven coal qi exhaustion benzene agent.
As shown in Figure 4, can find out while being used in coke-oven coal qi exhaustion benzene, the adsorptive capacity of zinc supported carbon molecular sieve (CMS with Zinc) will be higher than the carbon molecular sieve of zinc supported (CMS) not yet.
Coal sample is pulverized to bonding, put into charring furnace, 650 to 950 ℃ of carbonization temperatures, carbonization time 45 minutes, puts into activation furnace after charing, use CO
2activate CO
2purity >99%, 650 to 850 ℃ of temperature, the time is 4.5 to 6 hours, obtains gac, and gac is inserted and adjusted in the stove of hole, passes into isovaleric acid diethyl ester steam, 750 to 900 ℃ of temperature, the time is 1.5 to 2 hours, obtains carbon molecular sieve.
The carbon molecular sieve that above-mentioned steps is 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 ℃, 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.
The carbon molecular sieve making by above-mentioned steps is processed for coke-oven gas is taken off to benzene.Coke-oven gas index is as follows:
Benzene 1500mg/Nm
340 ℃ of pressure 10KPa(gauge pressures of temperature) coke-oven gas is carried out to Temp .-changing adsorption lock out operation, use the hole agent of special tune to make and the carbon molecular sieve of zinc supported shows excellent benzene separation performance, after purifying, benzene content is 0.03mg/Nm
3.
Embodiment 2
Coal sample is pulverized bonding, puts into charring furnace, 700 to 950 ℃ of carbonization temperatures, and carbonization time 45 minutes, puts into activation furnace after charing, use CO
2activate CO
2purity >99%, 650 to 850 ℃ of temperature, the time is 4.5 to 5.5 hours, obtains gac, and gac is inserted and adjusted in the stove of hole, passes into trichloroethylene steam, 750 to 900 ℃ of temperature, the time is 1.5 to 2 hours, obtains carbon molecular sieve.
The carbon molecular sieve that above-mentioned steps is 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 ℃, 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.
The carbon molecular sieve making by above-mentioned steps is processed for coke-oven gas is taken off to benzene.Coke-oven gas index is as follows: benzene 2000mg/Nm
345 ℃ of pressure 12KPa(gauge pressures of temperature) coke-oven gas is carried out to Temp .-changing adsorption lock out operation, use the hole agent of special tune to make and the carbon molecular sieve of zinc supported shows excellent benzene separation performance, after purifying, benzene content is 0.035mg/Nm
3.
The above-mentioned description to embodiment is can understand and apply the invention for the ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement of making for the present invention and modification all should be within protection scope of the present invention.
In summary, the coke-oven coal qi exhaustion benzene agent that the manufacture method of coke-oven coal qi exhaustion benzene of the present invention agent makes can solve while using 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 the minimum 0.05mg/Nm of being down to of benzene content in coke-oven gas
3.
Above-described embodiment is only for illustrating technological thought and the feature of this patent, its object is the content that makes those skilled in the art can understand this patent and implements according to this, can not only with the present embodiment, limit the scope of the claims of this patent, be equal variation or the modification that all spirit disclosing according to this patent is done, 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 comprises the following steps:
(1) will after coal sample pulverizing, mix with binding agent;
(2) charing in charring furnace, 600 to 950 ℃ of temperature;
(3) in activation furnace, pass into CO
2, CO
2purity >99%, 600 to 850 ℃ of temperature;
(4) in adjusting hole stove, pass into and adjust hole agent steam, carry out hole homogenization processing, 700 to 900 ℃ of temperature, obtain the carbon molecular sieve of even aperture distribution, and the hole agent of described tune 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 a kind of; And
(6) in inerting gas, inerting is dried, and the temperature that inerting is dried is 100 to 200 ℃, 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 as claimed in claim 1 agent, is characterized in that: in described step (2), the temperature rise rate of described charring furnace is 15 ℃/min.
3. the manufacture method of coke-oven coal qi exhaustion benzene as claimed in claim 1 agent, is characterized in that: in described step (2), in described charring furnace, the time of charing is 45 minutes.
4. the manufacture method of coke-oven coal qi exhaustion benzene as claimed in claim 1 agent, 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 as claimed in claim 1 agent, 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: by making as the manufacture method of coke-oven coal qi exhaustion benzene agent as described in claim 1 to 5.
7. the purposes of the coke-oven coal qi exhaustion benzene agent that in claim 1 to 5, arbitrary described method makes aspect coke-oven coal qi exhaustion benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310716891.6A CN103641102B (en) | 2013-12-24 | 2013-12-24 | Preparation method of coke oven gas debenzolization agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310716891.6A CN103641102B (en) | 2013-12-24 | 2013-12-24 | Preparation method of coke oven gas debenzolization agent |
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| Publication Number | Publication Date |
|---|---|
| CN103641102A true CN103641102A (en) | 2014-03-19 |
| CN103641102B CN103641102B (en) | 2015-04-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310716891.6A Expired - Fee Related CN103641102B (en) | 2013-12-24 | 2013-12-24 | Preparation method of coke oven gas debenzolization agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113322105A (en) * | 2021-07-02 | 2021-08-31 | 上海电气集团国控环球工程有限公司 | High-efficiency debenzolization and purification process for coke oven gas |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0542625A1 (en) * | 1991-11-15 | 1993-05-19 | Institut Francais Du Petrole | Aluminosilicate type catalyst and its use for the aromatizing of hydrocarbons containing 2 to 12 carbon atoms |
| CN1631489A (en) * | 2004-11-22 | 2005-06-29 | 四川天一科技股份有限公司 | Pressure swing absorption method for preparing nitrogen from air |
| CN1636634A (en) * | 2003-11-21 | 2005-07-13 | 三星Sdi株式会社 | Mesoporous carbon molecular sieve and supported catalyst employing the same |
| 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 |
-
2013
- 2013-12-24 CN CN201310716891.6A patent/CN103641102B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0542625A1 (en) * | 1991-11-15 | 1993-05-19 | Institut Francais Du Petrole | Aluminosilicate type catalyst and its use for the aromatizing of hydrocarbons containing 2 to 12 carbon atoms |
| CN1636634A (en) * | 2003-11-21 | 2005-07-13 | 三星Sdi株式会社 | Mesoporous carbon molecular sieve and supported catalyst employing the same |
| CN1631489A (en) * | 2004-11-22 | 2005-06-29 | 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113322105A (en) * | 2021-07-02 | 2021-08-31 | 上海电气集团国控环球工程有限公司 | High-efficiency debenzolization and purification process for coke oven gas |
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| CN103641102B (en) | 2015-04-08 |
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