CN1317245C - Refining method for toluene containing nitrogen and olefin - Google Patents
Refining method for toluene containing nitrogen and olefin Download PDFInfo
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- CN1317245C CN1317245C CNB2004100802263A CN200410080226A CN1317245C CN 1317245 C CN1317245 C CN 1317245C CN B2004100802263 A CNB2004100802263 A CN B2004100802263A CN 200410080226 A CN200410080226 A CN 200410080226A CN 1317245 C CN1317245 C CN 1317245C
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Abstract
The present invention relates to a refining method for toluene containing nitrogen and olefin, which comprises the steps that toluene passes through a cation exchange resin layer under the conditions of the temperature of 10 DEG C to 60 DEG C and the line flow rate of 3 m/h to 18 m/h and then passes through an acidic white soil layer, and the volume ratio of cation exchange resin to acidic white soil is 2.0 to 30.0: 1. The present invention has the advantages of simple operation, little pollution and low cost and can be used for effectively removing nitrogen impurities and olefin in toluene.
Description
Technical field
The present invention is a kind of process for purification of nitrogenous impurity toluene, specifically, is a kind of process for purification that contains the toluene of nitrogen and olefin impurity.
Background technology
In adopting the arene extracting process of formyl morpholine as solvent, contain organic nitrogen impurity such as morpholine, formyl morpholine in the gained toluene, its content in nitrogen content greater than 10 μ g/g.High like this nitrogen impurity content can make the poisoning of catalyst of downstream process, therefore must they be removed from toluene by process for purification, makes the nitrogen content of refining back toluene be lower than 1 μ g/g.
At present, normal washing and the clay-treated method of adopting made with extra care the toluene that contains impurity such as formyl morpholine.WATER-WASHING METHOD need expend great amount of water resources, and not only energy waste is big, and the nitric wastewater that washing produces also needs further processing.Clay treatment process needs to heat operation stage by stage by the time, and the every two weeks of carclazyte just must be changed, and this has not only increased the complicacy and the labour intensity of operation, and a large amount of useless carclazyte that changes can not regeneration, and its existence can bring environmental pollution.
In addition, also contain a certain amount of alkene in the toluene that aromatics extraction process obtains, generally greater than 10 μ g/g, the existence of alkene can produce following influence to its content: (1) influences the pickling colorimetric of toluene, and quality product is affected; (2) make in the course of processing of downstream and produce byproduct; (3) make the high temperature service fouling.Therefore must remove the alkene in the toluene, make its content be lower than 3 μ g/g, just can obtain qualified toluene product.
Be to remove the nitrogenous impurity in the toluene, CN1142127C adopts sulfonic acid cation resin to be lower than in room temperature～80 ℃, linear flow speed to carry out under 10 meters/hour the condition toluene refining, though can obtain denitrification effect preferably, can not remove the alkene in the raw material.
Summary of the invention
The process for purification that the purpose of this invention is to provide a kind of toluene of nitrogenous and alkene, this method is easy and simple to handle, pollute less, cost is low, and effect is remarkable.
The process for purification that contains the toluene of nitrogen and alkene provided by the invention, comprise with described toluene being to pass through cation exchange resin layer under 3～18 meters/hour the condition at 10～60 ℃, linear flow speed, and then by the acidic white earth layer, the volume ratio of described Zeo-karb and acidic white earth is 2.0～30.0: 1.
The inventive method use sulfonic acid ion exchange resin removes the nitrogenous compound in the toluene, re-use a small amount of acidic white earth and remove wherein alkene, can effectively reduce nitrogen content and olefin(e) centent in the toluene, organonitrogen content is reduced to below the 1 μ g/g from 50 μ g/g, and olefin(e) centent is reduced to below the 3 μ g/g.Used Zeo-karb iterative regenerable repeatedly uses, thereby has reduced refining cost; Used carclazyte only is used for removing the alkene of toluene, so consumption significantly reduces, and its consumption only is 15～20% of a clay-filtered method, and prolongs relatively work-ing life, can reach more than 1 year.
Embodiment
The inventive method will contain the toluene of impurity by the hydrogen type cation exchange resin layer, and nitrogenous compound is wherein separated with methylbenzene raw material by cationic exchange resin adsorption, but the small amounts of olefins that wherein contains can not be adsorbed by ion exchange resin.Thereby nitrogen content is few from the effusive toluene of ion exchange resin, and olefin(e) centent is constant, by the acidic white earth layer, the alkene that contains is adsorbed by acidic white earth it, can remove the alkene in the toluene.
Preferred 20～40 ℃ of toluene described in the present invention by the temperature of cation exchange resin layer and acidic white earth layer, preferred 6～15 meters/hour of linear flow speed.
The preferred sulfonic acid ion exchange resin of described Zeo-karb, more preferably polystyrene-sulfonic acid ion exchange resin, the preferred macroporous type polystyrene-sulfonic acid ion exchange resin of described polystyrene-sulfonic acid ion exchange resin.
When using, described Zeo-karb is Hydrogen.Hydrogen type cation exchange resin is converted by commercially available storage type resin, its conversion method is: with deionized water soaking 24 hour or more under 15～40 ℃ storage type Zeo-karb, making volume again is that 4～5 times of ion exchange resin volumes, concentration are flow through ion exchange resin 1～2 hour of the hydrochloric acid soln of 3～4 quality %, is 6～7 with deionized water drip washing resin to elutant pH value then.After dewatering, drying can use.
Described carclazyte is selected from wilkinite or clay, preferred wilkinite.
How many consumptions of described acidic white earth is decided by olefin(e) centent in the raw material, in raw material olefin(e) centent more for a long time, used carclazyte is more with respect to the amount of Zeo-karb, otherwise, in the raw material olefin(e) centent more after a little while, used carclazyte is then less with respect to the amount of Zeo-karb.Olefin(e) centent is 10～30 μ g/g in the general toluene, and the volume ratio of preferred cation exchange resin and acidic white earth is 2.5～5.0: 1.
After described Zeo-karb in use loses activity, can continue to use by regeneration, its renovation process be identical with the pretreatment process of resin.Acidic white earth should in time be changed after losing efficacy, and changing with the olefin(e) centent in the toluene of refining back is that standard is carried out less than 3 μ g/g, when promptly the olefin(e) centent in making with extra care back toluene is greater than 3 μ g/g, will change used carclazyte.
Further describe the present invention below by example, but the present invention is not limited to this.
In the example, nitrogen content is measured by trace N2 method in the petroleum chemical industry standard SH/T0657-1998 of the People's Republic of China (PRC) Naphtha solvent in the toluene, and olefin(e) centent is measured with the industry standard SH/T0236 of People's Republic of China (PRC) petroleum products bromine number assay method.
Example 1～7
Following example carries out refinement treatment with the inventive method to the toluene that contains morpholine.
Get macropore polystyrene-sulfonic acid ion exchange resin (Chemical Plant of Nankai Univ.'s product, model is D001) 30 grams, soaked 30 hours with deionized water, be loaded in the glass column, by resin 1 hour, make it be converted to Hydrogen the hydrochloric acid soln of 4 quality % of 4 times of volumes, then with deionized water drip washing resin to elutant pH be 6.0～7.0 o'clock, stop drip washing, with the water Ex-all, carry out drying with nitrogen.
To contain with nitrogen content count 56 μ g/g morpholine impurity and olefin(e) centent be the toluene of 10 μ g/g under different condition by above-mentioned hydrogen type cation exchange resin post, and then by the acidic white earth post, the carclazyte that uses is wilkinite, and the volume ratio of described hydrogen type cation exchange resin and acidic white earth is 3: 1.Each instance processes condition and nitrogen and the olefin(e) centent handled in the toluene of back see Table 1.
Example 8～14
Following example carries out refinement treatment with the inventive method to the toluene that contains morpholine, formyl morpholine and alkene.
To contain that to count 31 μ g/g morpholines, 23 μ g/g formyl morpholines and olefin(e) centent with nitrogen content be the toluene of 10 μ g/g; give the hydrogen type cation exchange resin post that makes by example 1 in different condition; and then by the acidic white earth post; the carclazyte that uses is wilkinite, and the volume ratio of described hydrogen type cation exchange resin and acidic white earth is 3: 1.Treatment condition and nitrogen and the olefin(e) centent handled in the toluene of back see Table 2.
Example 15～19
Method by example 1 is carried out refinement treatment to the toluene that contains morpholine and alkene, and different is changes the volume ratio of hydrogen type cation exchange resin and acidic white earth in the treating processes, makes with extra care and the results are shown in Table 3.
Table 1
| Instance number | The O for toluene condition | Handle back toluene foreign matter content, μ g/g | ||
| Temperature, ℃ | Linear velocity, rice/hour | Nitrogen | Alkene | |
| 1 | 20 | 6 | 0.31 | ＜3 |
| 2 | 20 | 8 | 0.42 | ＜3 |
| 3 | 20 | 10 | 0.51 | ＜3 |
| 4 | 40 | 8 | 0.29 | ＜3 |
| 5 | 40 | 10 | 0.35 | ＜3 |
| 6 | 40 | 12 | 0.42 | ＜3 |
| 7 | 40 | 15 | 0.54 | ＜3 |
Table 2
| Instance number | The O for toluene condition | Handle back toluene foreign matter content, μ g/g | ||
| Temperature, ℃ | Linear velocity, rice/hour | Nitrogen | Alkene | |
| 8 | 20 | 6 | 0.29 | ＜3 |
| 9 | 20 | 8 | 0.35 | ＜3 |
| 10 | 20 | 10 | 0.48 | ＜3 |
| 11 | 40 | 8 | 0.53 | ＜3 |
| 12 | 40 | 10 | 0.57 | ＜3 |
| 13 | 40 | 12 | 0.64 | ＜3 |
| 14 | 40 | 15 | 0.71 | ＜3 |
Table 3
| Instance number | The O for toluene condition | Handle back toluene foreign matter content, μ g/g | |||
| Temperature, ℃ | Linear velocity, rice/hour | Resin/carclazyte volume ratio | Nitrogen | Alkene | |
| 15 | 20 | 6 | 3.0∶1 | 0.20 | ＜3 |
| 16 | 20 | 10 | 5.0∶1 | 0.40 | ＜3 |
| 17 | 40 | 8 | 15.0∶1 | 0.48 | ＜3 |
| 18 | 40 | 15 | 28.0∶1 | 0.68 | ＜3 |
Claims (9)
1, a kind of process for purification that contains the toluene of nitrogen and alkene, comprise with described toluene being to pass through cation exchange resin layer under 3～18 meters/hour the condition at 10～60 ℃, linear flow speed, and then by the acidic white earth layer, the volume ratio of described Zeo-karb and acidic white earth is 2.0～30.0: 1.
2, in accordance with the method for claim 1, it is characterized in that 20～40 ℃ of the temperature of described toluene by cation exchange resin layer and acidic white earth layer, linear flow speed is 6～15 meters/hour.
3, in accordance with the method for claim 1, it is characterized in that described Zeo-karb is a sulfonic acid ion exchange resin, the carclazyte in the described acidic white earth is a wilkinite.
4, in accordance with the method for claim 3, it is characterized in that described sulfonic acid ion exchange resin is polystyrene-sulfonic acid ion exchange resin.
5, in accordance with the method for claim 4, it is characterized in that described polystyrene-sulfonic acid ion exchange resin is macroporous type polystyrene-sulfonic acid ion exchange resin.
6, in accordance with the method for claim 1, the volume ratio that it is characterized in that described Zeo-karb and acidic white earth is 2.5～5.0: 1.
7, in accordance with the method for claim 1, it is characterized in that described Zeo-karb is a Hydrogen.
8, in accordance with the method for claim 7, it is characterized in that hydrogen type cation exchange resin is converted by storage type resin, its conversion method is: with deionized water soaking 24 hour or more under 15～40 ℃ storage type Zeo-karb, making volume again is that 4～5 times of ion exchange resin volumes, concentration are flow through ion exchange resin 1～2 hour of the hydrochloric acid soln of 3～4 quality %, is 6～7 with deionized water drip washing resin to elutant pH value then.
9, in accordance with the method for claim 1, it is characterized in that olefin(e) centent is 10～30 μ g/g in the described toluene.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100802263A CN1317245C (en) | 2004-09-28 | 2004-09-28 | Refining method for toluene containing nitrogen and olefin |
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| CNB2004100802263A CN1317245C (en) | 2004-09-28 | 2004-09-28 | Refining method for toluene containing nitrogen and olefin |
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| CN1317245C true CN1317245C (en) | 2007-05-23 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747130B (en) * | 2008-12-11 | 2013-05-08 | 上海宝钢化工有限公司 | Refining method of coking benzene product containing nitrogen impurities |
| CN104557420B (en) * | 2013-10-11 | 2018-03-06 | 中国石油化工股份有限公司 | A kind of method of toluene denitrogenation |
| CN105367376A (en) * | 2014-08-26 | 2016-03-02 | 中国石油化工股份有限公司 | Methylbenzene denitrification method |
| CN114797999B (en) * | 2022-04-08 | 2023-11-10 | 英颇瑞智能科技(上海)有限公司 | Method for prolonging service life of phenol refined resin in phenol-acetone synthesis |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6133497A (en) * | 1995-03-31 | 2000-10-17 | Sud-Chemie A.G. | Catalyst for removing olefins from aromatic compounds or mixtures thereof |
| CN1338450A (en) * | 2000-08-11 | 2002-03-06 | 中国石油化工股份有限公司 | Process for refining toluene containing nitrogen impuritier |
| CN1403426A (en) * | 2001-09-13 | 2003-03-19 | 中国石化上海石油化工股份有限公司 | Method of eliminating alkali matter in toluene |
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- 2004-09-28 CN CNB2004100802263A patent/CN1317245C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6133497A (en) * | 1995-03-31 | 2000-10-17 | Sud-Chemie A.G. | Catalyst for removing olefins from aromatic compounds or mixtures thereof |
| CN1338450A (en) * | 2000-08-11 | 2002-03-06 | 中国石油化工股份有限公司 | Process for refining toluene containing nitrogen impuritier |
| CN1403426A (en) * | 2001-09-13 | 2003-03-19 | 中国石化上海石油化工股份有限公司 | Method of eliminating alkali matter in toluene |
Non-Patent Citations (1)
| Title |
|---|
| 改性白土用于芳烃抽提装置甲苯的精制试验 张彩娟，金山油化纤，第21卷第4期 2002 * |
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