CN1338450A - Process for refining toluene containing nitrogen impuritier - Google Patents
Process for refining toluene containing nitrogen impuritier Download PDFInfo
- Publication number
- CN1338450A CN1338450A CN 00121552 CN00121552A CN1338450A CN 1338450 A CN1338450 A CN 1338450A CN 00121552 CN00121552 CN 00121552 CN 00121552 A CN00121552 A CN 00121552A CN 1338450 A CN1338450 A CN 1338450A
- Authority
- CN
- China
- Prior art keywords
- exchange resin
- hour
- ion exchange
- meters
- toluene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000007670 refining Methods 0.000 title abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title description 38
- 229910052757 nitrogen Inorganic materials 0.000 title description 19
- 239000012535 impurity Substances 0.000 claims abstract description 20
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 15
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910001423 beryllium ion Inorganic materials 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 10
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种含有含氮杂质的甲苯的精制方法,该方法是将含有含氮杂质的甲苯在室温至80℃,线速低于10.0米/小时的条件下与磺酸型阳离子交换树脂层接触以除去其中的含氮杂质。该方法具有效果好,操作简单,成本低的优点。The invention discloses a method for refining toluene containing nitrogen-containing impurities. The method is to mix the toluene containing nitrogen-containing impurities with a sulfonic acid type cation exchange resin under the condition of room temperature to 80°C and a line speed of less than 10.0 m/hour. layer contact to remove nitrogen-containing impurities therein. The method has the advantages of good effect, simple operation and low cost.
Description
The invention relates to a kind of process for purification that contains the toluene of nitrogenous impurity.
At present; adopt in the arene extracting process of formyl morpholine as solvent; contain organic nitrogen impurity such as morpholine, formyl morpholine in the toluene products of gained; they are in nitrogen content; greater than 10 μ g/g; high like this nitrogen class foreign matter content can make the poisoning of catalyst of downstream process, therefore must they be removed from toluene by process for purification, the nitrogen content made from extra care back toluene is reduced to be lower than 1 μ g/g.
At present, wash and clay-filtered two kinds of methods for refining generally employing of the toluene that contains nitrogenous impurity.
Washing 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 heats operation stage by stage by the time, and carclazyte just must be changed in per 3～6 months, and this has not only increased operator's Operating Complexity and labour intensity, and also there is the handling problem of the three wastes in a large amount of useless carclazyte that changes.
The purpose of this invention is to provide one easy and simple to handle, pollute few, the refining novel method that contains the toluene of nitrogenous impurity that cost is low.
Process for purification provided by the invention is the toluene that will contain nitrogenous impurity in room temperature to 80 ℃, and linear speed is lower than under 10.0 meters/hour the condition and contacts with cation exchange resin layer.
The preferred temperature of said purification condition is 40～60 ℃ among the present invention, and linear speed is 4～6 meters/hour.
Said in the present invention Zeo-karb is for containing sulfonic group (SO
3H) sulfonic acid ion exchange resin, optimization styrene system-sulfonic acid ion exchange resin, the wherein more preferably polystyrene-sulfonic acid ion exchange resin of macropore.
Commercially available Zeo-karb is generally the storage type, and they need pass through pre-treatment before use, make it become Hydrogen by the storage type, and its pre-treatment step is as follows:
At room temperature soak more than 24 hours storage type resin cation (R.C.) with deionized water, again with volume be ion exchange resin volume 4-5 doubly, concentration is that the hydrochloric acid soln of 3-4 (weight) % was flowed through ion exchange resin 1-2 hour, is 6～7 with deionized water drip washing resin to the pH value of elutant then.
Described Zeo-karb can continue to use after losing activity through use through regeneration, and its renovation process is identical with the pretreatment process of resin.
Method of the present invention has following advantage:
(1) effective, organonitrogen content is reduced to from 50 μ g/g be lower than 1 μ g/g.
(2) simple, convenient.
(3) Zeo-karb iterative regenerable repeatedly uses, thereby has reduced refining cost.
Below will the present invention is further illustrated with example, but content of the present invention is not subjected to the restriction of these examples.
In example, the impurity 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 sample.
Example 1-7
The process of the toluene sample that contains morpholine impurity is handled in following example explanation with the inventive method.
Get macropore 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, be converted into Hydrogen with the hydrochloric acid soln of 4 (weight) % of 4 times of volumes, then with deionized water drip washing resin when elutant pH is 6.0-7.0, stop drip washing, with nitrogen with the water Ex-all.
To contain the toluene of counting 53 μ g/g morpholine impurity with nitrogen content and under different condition, pass through ion exchange column.Treatment condition and the nitrogen content of handling in the toluene of back see Table 1.
Example 8-14
The process of the toluene sample that contains formyl morpholine impurity is handled in following example explanation with the inventive method.
Get macropore sulfonic acid ion exchange resin (Chemical Plant of Nankai Univ.'s product, model is D001) 30 grams, soaked 25 hours with deionized water, be loaded in the glass column, by resin 1 hour, be converted into Hydrogen with the hydrochloric acid soln of 4 (weight) % of 4 times of volumes, then with deionized water drip washing resin when elutant pH is 6.0-7.0, stop drip washing, with nitrogen with the water Ex-all.
To contain the toluene of counting 37 μ g/g formyl morpholine impurity with nitrogen content and under different condition, pass through ion exchange column.Treatment condition and the nitrogen content of handling in the toluene of back see Table 2.Table 1
Table 2
| Example | Treatment condition | Nitrogen content (μ g/g) |
| ??1 | Room temperature, 2 meters/hour | ????0.33 |
| ??2 | 40 ℃, 4 meters/hour | ????0.43 |
| ??3 | 40 ℃, 6 meters/hour | ????0.62 |
| ??4 | 40 ℃, 8 meters/hour | ????0.82 |
| ??5 | 50 ℃, 6 meters/hour | ????0.52 |
| ??6 | 60 ℃, 6 meters/hour | ????0.34 |
| ??7 | 80 ℃, 6 meters/hour | ????0.31 |
| Example | Treatment condition | Nitrogen content |
| ??8 | Room temperature, 2 meters/hour | ????0.24 |
| ??9 | 40 ℃, 4 meters/hour | ????0.33 |
| ??10 | 40 ℃, 6 meters/hour | ????0.48 |
| ??11 | 40 ℃, 8 meters/hour | ????0.64 |
| ??12 | 50 ℃, 6 meters/hour | ????0.38 |
| ??13 | 60 ℃, 6 meters/hour | ????0.35 |
| ??14 | 80 ℃, 6 meters/hour | ????0.30 |
Example 15-21
The process of the toluene sample that contains morpholine and formyl morpholine impurity is handled in following example explanation with the inventive method.
Get macropore 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, be converted into Hydrogen with the hydrochloric acid soln of 4 (weight) % of 4 times of volumes, then with deionized water drip washing resin when elutant pH is 6.0-7.0, stop drip washing, with nitrogen with the water Ex-all.
Will be in nitrogen content, the toluene that contains 26 μ g/g morpholines and 19 μ g/g formyl morpholine impurity passes through exchange column under different condition.Treatment condition and the nitrogen content of handling in the toluene of back see Table 3.Table 3
| Example | Treatment condition | Nitrogen content |
| ??15 | Room temperature, 2 meters/hour | ????0.29 |
| ??16 | 40 ℃, 4 meters/hour | ????0.38 |
| ??17 | 40 ℃, 6 meters/hour | ????0.55 |
| ??18 | 40 ℃, 8 meters/hour | ????0.73 |
| ??19 | 50 ℃, 6 meters/hour | ????0.45 |
| ??20 | 60 ℃, 6 meters/hour | ????0.34 |
| ??21 | 80 ℃, 6 meters/hour | ????0.31 |
Example 22-28
The refining effect of gel-type polystyrene sulfonic group resin is adopted in these example explanations.
After adopting the method for example 1 to handle Zeo-karb (Chemical Plant of Nankai Univ.'s product, model 001 * 7) 30 grams, will contain the toluene of counting 53 μ g/g morpholine impurity with nitrogen content and under different condition, pass through exchange column.Treatment condition and the nitrogen content of handling in the toluene of back see Table 4.
Table 4
| Example | Treatment condition | Nitrogen content μ g/g |
| ????22 | Room temperature, 2 meters/hour | ????0.37 |
| ????23 | 40 ℃, 4 meters/hour | ????0.48 |
| ????24 | 40 ℃, 6 meters/hour | ????0.67 |
| ????25 | 40 ℃, 8 meters/hour | ????0.90 |
| ????26 | 50 ℃, 6 meters/hour | ????0.61 |
| ????27 | 60 ℃, 6 meters/hour | ????0.52 |
| ????28 | 80 ℃, 6 meters/hour | ????0.42 |
Claims (6)
1, a kind of process for purification that contains the toluene of nitrogenous impurity, the toluene that it is characterized in that containing nitrogenous impurity be in room temperature to 80 ℃, and linear speed is lower than under 10.0 meters/hour the condition and contacts with cation exchange resin layer.
2, in accordance with the method for claim 1, the toluene that it is characterized in that containing nitrogenous impurity is 40～60 ℃ of temperature, and linear speed is 4～6 meters and contacts with cation exchange resin layer down.
3, in accordance with the method for claim 1, it is characterized in that described Zeo-karb is a sulfonic acid ion exchange resin.
4, in accordance with the method for claim 3, it is characterized in that described sulfonic acid ion exchange resin is a styrene ion exchange resin.
5, in accordance with the method for claim 4, it is characterized in that described styrene ion exchange resin is a macroreticular ion exchange resin.
6, in accordance with the method for claim 1, it is characterized in that described Zeo-karb needs the storage type is converted to Hydrogen before use, its treatment step is: at room temperature soak more than 24 hours with deionized water storage type Zeo-karb, again with volume be ion exchange resin volume 4-5 doubly, concentration is flow through ion exchange resin 1～2 hour of the hydrochloric acid soln of 3-4 (weight) %, is 6～7 with deionized water drip washing resin to the pH value of elutant then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001215523A CN1142127C (en) | 2000-08-11 | 2000-08-11 | Process for refining toluene containing nitrogen impuritier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001215523A CN1142127C (en) | 2000-08-11 | 2000-08-11 | Process for refining toluene containing nitrogen impuritier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1338450A true CN1338450A (en) | 2002-03-06 |
| CN1142127C CN1142127C (en) | 2004-03-17 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001215523A Expired - Lifetime CN1142127C (en) | 2000-08-11 | 2000-08-11 | Process for refining toluene containing nitrogen impuritier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1142127C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317245C (en) * | 2004-09-28 | 2007-05-23 | 中国石油化工股份有限公司 | Refining method for toluene containing nitrogen and olefin |
| CN100344592C (en) * | 2005-03-31 | 2007-10-24 | 中国石油化工股份有限公司 | Process for refining benzene raw materials containing basic nitrogen and olefin impurity |
| US7473351B2 (en) | 2002-04-17 | 2009-01-06 | Bp Corporation North America Inc. | Removal of nitrogen, sulfur, and alkylating agents from hydrocarbon streams |
| 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 |
| CN105368481A (en) * | 2014-08-26 | 2016-03-02 | 中国石油化工股份有限公司 | Denitrification method for aromatics raffinate oil |
| CN105367376A (en) * | 2014-08-26 | 2016-03-02 | 中国石油化工股份有限公司 | Methylbenzene denitrification method |
| CN105461506A (en) * | 2014-08-26 | 2016-04-06 | 中国石油化工股份有限公司 | Method for removal of nitrogen from benzene |
| CN106478421A (en) * | 2015-08-31 | 2017-03-08 | 亚申科技研发中心（上海）有限公司 | DMC Processes |
-
2000
- 2000-08-11 CN CNB001215523A patent/CN1142127C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7473351B2 (en) | 2002-04-17 | 2009-01-06 | Bp Corporation North America Inc. | Removal of nitrogen, sulfur, and alkylating agents from hydrocarbon streams |
| CN1317245C (en) * | 2004-09-28 | 2007-05-23 | 中国石油化工股份有限公司 | Refining method for toluene containing nitrogen and olefin |
| CN100344592C (en) * | 2005-03-31 | 2007-10-24 | 中国石油化工股份有限公司 | Process for refining benzene raw materials containing basic nitrogen and olefin impurity |
| 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 |
| CN105368481A (en) * | 2014-08-26 | 2016-03-02 | 中国石油化工股份有限公司 | Denitrification method for aromatics raffinate oil |
| CN105367376A (en) * | 2014-08-26 | 2016-03-02 | 中国石油化工股份有限公司 | Methylbenzene denitrification method |
| CN105461506A (en) * | 2014-08-26 | 2016-04-06 | 中国石油化工股份有限公司 | Method for removal of nitrogen from benzene |
| CN106478421A (en) * | 2015-08-31 | 2017-03-08 | 亚申科技研发中心（上海）有限公司 | DMC Processes |
| CN106478421B (en) * | 2015-08-31 | 2019-09-13 | 亚申科技(浙江)有限公司 | DMC Processes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1142127C (en) | 2004-03-17 |
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Granted publication date: 20040317 |