CN100344592C - Process for refining benzene raw materials containing basic nitrogen and olefin impurity - Google Patents
Process for refining benzene raw materials containing basic nitrogen and olefin impurity Download PDFInfo
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- CN100344592C CN100344592C CNB2005100597704A CN200510059770A CN100344592C CN 100344592 C CN100344592 C CN 100344592C CN B2005100597704 A CNB2005100597704 A CN B2005100597704A CN 200510059770 A CN200510059770 A CN 200510059770A CN 100344592 C CN100344592 C CN 100344592C
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Abstract
The present invention relates to a method for refining benzene raw materials containing alkali nitrogen and alkene impurities, which comprises that benzene raw materials pass through a cation exchange resin layer and an acidic white soil layer in turn under the conditions of a temperature from 15 DEG C to 80 DEG C and a linear velocity from 2.0 m /h to 20.0m/h, and the volume ratio of the cation exchange resin layer and the acidic white soil layer is 1-5: 7-1. The method can effectively eliminate alkali nitrogen compounds and alkene in the benzene raw materials, and the present invention having the advantage of simple operation can prolong the service life of white soil and reduce environmental pollution.
Description
Technical field
The present invention is a kind of process for purification that contains the benzene raw materials of basic nitrogen compound and olefin impurity, specifically, is the method that removes basic nitrogen compound and olefin impurity from benzene raw materials.
Background technology
In adopting the arene extracting process of organic nitrogen compound as extraction solvent such as morpholine, formyl morpholine and methylmorpholine, often contain the extraction solvent and the olefin impurity of trace in the benzene product of gained.The nitrogen compound that this benzene product contains slightly is alkalescence, and its accumulation can make an acidic catalyst poisoning and deactivation of downstream process.For example make the catalyst deactivation of alkylation to prepare ethylbenzene.Therefore it must be removed from the benzene product that extraction process obtains.
In addition, also contain small amounts of olefins impurity in the benzene of employing aromatic hydrocarbons method for extracting gained, its content is generally 10～40 μ gg
-1, even higher.The existence accumulation meeting of these alkene produces byproduct in downstream process, and makes the high temperature service fouling.Therefore also it must be removed from benzene.
At present, industrially be used for removing in the benzene raw materials process for purification of nitrogenous compound and alkene generally to adopt carclazyte be sorbent material, by basic nitrogen compound in the adsorbing and removing benzene raw materials and alkene.But the used carclazyte of clay-filtered method is changed once every year at least, and carclazyte can not regeneration behind the inactivation.This has not only increased running cost, has also caused the serious environmental pollution.
CN1338450A discloses a kind of process for purification of nitrogenous impurity toluene, and this method uses Zeo-karb to remove nitrogenous compound in the toluene, has obtained effect preferably, but the alkene of this method in can not effective elimination toluene.
Summary of the invention
The purpose of this invention is to provide the method for basic nitrogen compound and olefin impurity in a kind of effective elimination benzene raw materials, this method refining effect is good, easy and simple to handle, cost is low, and has caused of reduced contamination.
The process for purification that contains the benzene raw materials of basic nitrogen compound and olefin impurity provided by the invention, comprise with described benzene raw materials at 15～90 ℃, linear velocity be under 2.0～20.0 meters/hour the condition successively by cation exchange resin layer and acidic white earth layer, the volume ratio of described cation exchange resin layer and acidic white earth layer is 1～5: 7～1.
The inventive method employing Zeo-karb removes the basic nitrogen compound in the benzene raw materials, use acidic white earth adsorbing and removing alkene wherein again, thereby effectively reduce basic nitrogen compound and alkene in the benzene raw materials, make benzene after refining satisfy the purity requirement of the benzene raw materials that ethylbenzene uses in producing.Described method is simple, convenient, and used Zeo-karb iterative regenerable repeatedly uses.Because Zeo-karb can be removed most basic nitrogen compound in the raw material, can make the acidic white earth that uses thereafter only be used for adsorbing the small amounts of olefins impurity that raw material exists, prolong the work-ing life of carclazyte effectively, reduce its consumption, thereby reduce discarded carclazyte and unload outdegree and quantity, reduce labour intensity, reduce environmental pollution, reduce the refining cost of benzene raw materials.
Embodiment
In the inventive method, the benzene raw materials that will contain basic nitrogen compound and olefin impurity is earlier by the resin cation (R.C.) layer, make wherein nitrogenous compound adsorbed and separate with benzene by Zeo-karb, again by the acidic white earth layer, small amounts of olefins impurity is adsorbed by acidic white earth and from benzene raw materials, remove, thereby reach the purpose that removes basic nitrogen compound and alkene in the benzene raw materials.Preferred 20～60 ℃ of described benzene raw materials by the temperature of cation exchange resin layer and acidic white earth layer, preferred 2.0～15.0 meters/hour of linear velocity, more preferably 2.0～10.0 meters/hour.
The benzene raw materials that the inventive method will contain impurity contacts with cation exchange resin layer earlier, and basic nitrogen compound wherein is adsorbed by Zeo-karb, thereby separates with benzene, but the olefin impurity in the benzene can not be adsorbed by Zeo-karb.Therefore through behind the Zeo-karb, the basic nitrogen compound content in the benzene reduces greatly, but olefin(e) centent do not change, and also need use benzene after the denitrogenation again by the acidic white earth layer, and absorption alkene wherein further removes the olefin impurity in the benzene.
Described Zeo-karb optimization styrene cation exchange resin, more preferably polystyrene-sulfonic acid ion exchange resin.Acidic white earth preferred acidic wilkinite.The acid amount of described acidic white earth is 0.1～0.5 quality %, preferred 0.1～0.3 quality %.
Should determine the Zeo-karb of use and the ratio of acidic white earth according to the amount of the basic nitrogen compound that contains in the raw material in the described method.The basic nitrogen compound that contains in raw material should use more Zeo-karb more for a long time, and the volume ratio of itself and acidic white earth increases.Otherwise the basic nitrogen compound that contains in the raw material is seldom the time, and the amount of the Zeo-karb of use is also few, and the volume ratio of itself and carclazyte promptly reduces.The volume ratio of Zeo-karb and acidic white earth preferred 1～4 in present method: 4～1.
Described Zeo-karb should be hydrogen type cation exchange resin in use.Commercially available Zeo-karb is generally the storage type, need to be converted into hydrogen type cation exchange resin through pre-treatment, conversion method is: storage type Zeo-karb was soaked 0.5～3 day with deionized water at 20～30 ℃, be that 2～4% hydrochloric acid soln soaked 0.2～1.0 hour with concentration again, the volume of used salt acid solution is 3～4 times of the ion exchange resin volume, and then makes this hydrochloric acid soln pass through resin layer with 1～10 meter/hour linear velocity.Afterwards with deionized water drip washing resin to the pH of elutant be 6～7.
After described Zeo-karb in use lost activity, the ability that promptly removes basic nitrogen compound obviously reduced, and in the time of can not satisfying the requiring of technology, can continue after the inactivation resin regeneration to use.Inactivation regeneration of resin method is identical with the pretreatment process of above-mentioned resin.
Basic nitrogen compound in the described benzene raw materials mainly comes from the extraction solvent that contains nitrogen that uses in the aromatics extraction process; as morpholine, methylmorpholine, formyl morpholine etc.; this compounds still has trace to exist in the benzaldehyde product of aromatic hydrocarbons extracting gained, and its content is counted 1～10 μ gg with nitrogen
-1, be 1～5 μ gg generally speaking
-1It is the alkylation catalyst poisoning and deactivation of raw material production ethylbenzene with benzene that these basic nitrogen compounds can make follow-up, so should it be removed as far as possible, uses the nitrogen content in the benzene raw materials to reduce to 0.5 μ gg
-1Below.In addition, also contain small amounts of olefins in the aromatic hydrocarbons extracting benzaldehyde product, its content is 10～30 μ gg
-1The alkene that exists can polymerization produce colloid in reaction process, thereby influences quality product, and olefin(e) centent should be reduced to 3 μ gg behind the feed purification
-1Below.
Below by example in detail the present invention, but the present invention is not limited to this.
In the example, nitrogen content adopts trace N2 method mensuration in the petroleum chemical industry standard SH/T0657-1998 of the People's Republic of China (PRC) Naphtha solvent in the benzene raw materials, and the nitrogen content scope that this method is measured is 0.3～100 μ gg
-1, olefin(e) centent adopts the industry standard SH/T0236 of People's Republic of China (PRC) petroleum products bromine number assay method to measure.
Example 1
Handle the benzene raw materials that contains morpholine and alkene with the inventive method.
(1) preparation h type resin: get polystyrene-sulfonic acid ion exchange resin 11 grams, soaked 24 hours with deionized water, be loaded in the glass column, be that 3.0% hydrochloric acid soln soaked 30 minutes with the concentration of 3 times of column volumes then, make hydrochloric acid soln pass through resin again, resin is converted into Hydrogen with 3 meters/hour linear velocity.Be 6～7 with deionized water drip washing resin to elutant pH value afterwards, with nitrogen purging the free-water in the resin removed again.
(2) commercial benzene raw material: will contain the benzene of morpholine and alkene, under different condition, pass through the ion exchange column of the above-mentioned h type resin of filling, and then by being filled with the adsorption column of acidic white earth.Nitrogen in the described benzene (in the morpholine) content is 30 μ gg
-1, olefin(e) centent is 10 μ gg
-1, described acidic white earth is that acid content is the Acidic Bentonite of 0.2 quality %.Benzene raw materials carries out purified by resin and albic horizon and the results are shown in Table 1 under differing temps and linear velocity.
Example 2
Method by 1 (1) step of example changes into Hydrogen with polystyrene-sulfonic acid ion exchange resin.And then by (2) step method benzene raw materials is made with extra care, olefin(e) centent is 20 μ gg in the different benzene raw materials that is to use
-1Benzene raw materials carries out purified by resin and albic horizon and the results are shown in Table 2 under differing temps and linear velocity.
Example 3
Handle the benzene raw materials that contains N-formyl morpholine, N-methylmorpholine impurity and trace amounts of olefin with the inventive method.
Method by 1 (1) step of example changes into Hydrogen with polystyrene-sulfonic acid ion exchange resin.And then the method for pressing (2) step is made with extra care benzene raw materials.Different is to contain 15 μ gg in the benzene raw materials
-1N-formyl morpholine and 15 μ gg
-1N-methylmorpholine (all in nitrogen content), olefin(e) centent is 10 μ gg
-1Benzene raw materials carries out purified by resin and albic horizon and the results are shown in Table 3 under differing temps and linear velocity.
Example 4
Handle the benzene raw materials that contains morpholine, N-formyl morpholine and N-methylmorpholine and trace amounts of olefin with the inventive method.
Method by 1 (1) step of example changes into Hydrogen with polystyrene-sulfonic acid ion exchange resin.And then the method for pressing (2) step is made with extra care benzene raw materials.Different is to contain 25 μ gg in the benzene raw materials
-1Morpholine, 2 μ gg
-1N-formyl morpholine and 3 μ gg
-1N-methylmorpholine (all in nitrogen content), olefin(e) centent are 10 μ gg
-1Benzene raw materials carries out purified by resin and albic horizon and the results are shown in Table 4 under differing temps and linear velocity.
Example 5
Method by 1 (1) step of example changes into Hydrogen with polystyrene-sulfonic acid ion exchange resin.And then by (2) step method benzene raw materials is made with extra care, olefin(e) centent is 20 μ gg in the different benzene raw materials that is to use
-1Change the volume ratio of benzene raw materials extraction temperature, linear velocity and resin and albic horizon, make with extra care and the results are shown in Table 5.
Table 1
| The benzene feedstock purification condition | Foreign matter content in the benzene of refining back, μ gg -1 | |||
| Temperature, ℃ | Linear velocity, mhr -1 | Resin/carclazyte volume ratio | Nitrogen | Alkene |
| 25 | 2 | 1∶3 | ＜0.50 | ＜3 |
| 25 | 4 | 1∶3 | ＜0.50 | ＜3 |
| 25 | 6 | 1∶3 | ＜0.50 | ＜3 |
| 40 | 6 | 1∶3 | ＜0.50 | ＜3 |
Table 2
| The benzene feedstock purification condition | Foreign matter content in the benzene of refining back, μ gg -1 | |||
| Temperature, ℃ | Linear velocity, mhr -1 | Resin/carclazyte volume ratio | Nitrogen | Alkene |
| 20 | 2 | 1∶3 | ＜0.50 | ＜3 |
| 20 | 4 | 1∶3 | ＜0.50 | ＜3 |
| 20 | 6 | 1∶3 | ＜0.50 | ＜3 |
| 40 | 6 | 1∶3 | ＜0.50 | ＜3 |
Table 3
| The benzene feedstock purification condition | Foreign matter content in the benzene of refining back, μ gg -1 | |||
| Temperature, ℃ | Linear velocity, mhr -1 | Resin/carclazyte volume ratio | Nitrogen | Alkene |
| 20 | 2 | 1∶3 | ＜0.50 | ＜3 |
| 20 | 4 | 1∶3 | ＜0.50 | ＜3 |
| 20 | 6 | 1∶3 | ＜0.50 | ＜3 |
| 40 | 6 | 1∶3 | ＜0.50 | ＜3 |
Table 4
| The benzene feedstock purification condition | Foreign matter content in the benzene of refining back, μ gg -1 | |||
| Temperature, ℃ | Linear velocity, mhr -1 | Resin/carclazyte volume ratio | Nitrogen | Alkene |
| 25 | 2 | 1∶3 | ＜0.50 | ＜3 |
| 25 | 4 | 1∶3 | ＜0.50 | ＜3 |
| 25 | 6 | 1∶3 | ＜0.50 | ＜3 |
| 40 | 6 | 1∶3 | ＜0.50 | ＜3 |
| 60 | 10 | 1∶3 | ＜0.50 | ＜3 |
| 60 | 15 | 1∶3 | ＜0.50 | ＜3 |
Table 5
| The benzene feedstock purification condition | Foreign matter content in the benzene of refining back, μ gg -1 | |||
| Temperature, ℃ | Linear velocity, mhr -1 | Resin/carclazyte volume ratio | Nitrogen | Alkene |
| 25 | 2 | 1∶3 | ＜0.50 | ＜3 |
| 25 | 4 | 1∶1 | ＜0.50 | ＜3 |
| 25 | 6 | 2∶1 | ＜0.50 | ＜3 |
| 40 | 6 | 3∶1 | ＜0.50 | ＜3 |
| 50 | 10 | 4∶1 | ＜0.50 | ＜3 |
Claims (8)
1, a kind of process for purification that contains the benzene raw materials of basic nitrogen compound and olefin impurity, comprise with described benzene raw materials at 15～90 ℃, linear velocity be under 2.0～20.0 meters/hour the condition successively by cation exchange resin layer and acidic white earth layer, the volume ratio of described cation exchange resin layer and acidic white earth layer is 1～5: 7～1.
2, in accordance with the method for claim 1, it is characterized in that benzene raw materials is 20～60 ℃ by the temperature of cation exchange resin layer and acidic white earth layer, linear velocity is 2.0～15.0 meters/hour.
3,, it is characterized in that benzene raw materials is 2.0～10.0 meters/hour by the linear velocity of cation exchange resin layer and acidic white earth layer according to claim 1 or 2 described methods.
4, in accordance with the method for claim 1, it is characterized in that described Zeo-karb is a styrene type cation exchange resin, acidic white earth is an Acidic Bentonite.
5, in accordance with the method for claim 4, it is characterized in that described Zeo-karb is polystyrene-sulfonic acid ion exchange resin, the acid content of acidic white earth is 0.1～0.5 quality %.
6, according to the method for claim 1, the volume ratio that it is characterized in that described Zeo-karb and acidic white earth is 1～4: 4～1.
7, in accordance with the method for claim 1, it is characterized in that described Zeo-karb is a hydrogen type cation exchange resin.
8, in accordance with the method for claim 1, it is characterized in that olefin(e) centent is 10～30 μ gg in the described benzene raw materials
-1, nitrogen content is 1～10 μ gg
-1
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| 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 |
| CN101591212B (en) * | 2009-06-25 | 2012-11-07 | 中国石油化工集团公司 | Process for refining and removing olefin from aromatic hydrocarbon |
| CN102850175B (en) * | 2012-09-29 | 2015-06-03 | 北京旭阳化工技术研究院有限公司 | Method for purifying coked benzene |
| 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 |
| 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 |
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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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 |
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