CN102816044A - Method for basic nitrogen removal of benzene or methylbenzene serving as raw materials for alkylation reaction - Google Patents
Method for basic nitrogen removal of benzene or methylbenzene serving as raw materials for alkylation reaction Download PDFInfo
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- CN102816044A CN102816044A CN2012103125601A CN201210312560A CN102816044A CN 102816044 A CN102816044 A CN 102816044A CN 2012103125601 A CN2012103125601 A CN 2012103125601A CN 201210312560 A CN201210312560 A CN 201210312560A CN 102816044 A CN102816044 A CN 102816044A
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- benzene
- adsorption tower
- toluene
- sorbent material
- basic nitrogen
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Abstract
The invention relates to a method for basic nitrogen removal of benzene or methylbenzene serving as raw materials for alkylation reaction. The method includes: delivering the benzene or methylbenzene serving as the raw materials to enter an adsorption column filled with adsorbents from the top of the adsorption column, so that basic nitrogen in the raw materials reacts with the adsorbents and is removed; and discharging the benzene or methylbenzene subjected to nitrogen removal from the bottom of the adsorption column, and feeding the discharged benzene or methylbenzene subjected to nitrogen removal to an alkylation reactor. By the method, the nitrogen in the benzene or methylbenzene serving as the raw materials can be effectively removed, so that the nitrogen content in the benzene or methylbenzene serving as the raw materials is decreased to be less than 30ppb by means of removal.
Description
Technical field
The present invention relates to a kind of petrochemical materials pretreatment process, be specifically related to the method for a kind of alkylated reaction benzene feedstock or toluene denitrogenation.
Technical background
The alkylated reaction raw material is benzene (or toluene) and methyl alcohol.Usually all contain a spot of nitride in technical benzene or the toluene, content generally about 1ppm, can reach 10ppm, and wherein basic nitrogen accounts for major part.
Basic nitrogen has very adverse influence to alkylated reaction.Basic nitrogen compound is considered to the promotor of oxidation, in oil product, exists, and can quicken the oxidation unstability of other acidic components and non-basic nitrogen compound component in the oil product.Nitride is the gelatigenous one of the main reasons of oil product, and the basic nitrogen compound in the oil product can impel solubility gelationus turnout slightly to increase.
The used catalyzer of alkylated reaction is an an acidic catalyst.The center of catalyzer is a tart, and basic nitrogen compound is alkalescence, and the acidity of meeting catalyst neutralisation reduces catalyst active center, and then causes the inactivation of catalyzer.According to the requirement of alkylation reaction technique, the raw material amount of nitrides that gets into reactor drum can not surpass 30ppb.Therefore, in order to prolong the quality of catalyzer work-ing life and assurance generation oil product, benzene feedstock or toluene must carry out denitrogenation.
Both at home and abroad in the method for lightweight oil denitrogenation except that adopting unifining, also extensively adopt non-hydrogenation, like solvent extraction, acid treating etc.Unifining needs hydrogen source; Petroleum products is behind solvent extraction, and the part hydro carbons also can be deviate from extracting oil out, has the problem of utilizing again of extracting oil out; There are problems such as environmental pollution and equipment corrosion in acid treating.Because sorbent material has stronger adsorption to polar compound, in Chemical Manufacture, have widely and use, the application in oil purification is also many.
Summary of the invention
The objective of the invention is to overcome the prior art defective, the method that provides a kind of alkylated reaction benzene feedstock or toluene to take off basic nitrogen.The object of the invention is realized according to following proposal:
The method that a kind of alkylated reaction benzene feedstock or toluene take off basic nitrogen; Be by pump delivery with benzene feedstock or toluene; Get into the adsorption tower that sorbent material is housed from the top of adsorption tower; Basic nitrogen in the raw material and sorbent material react and are removed, and benzene after the denitrogenation or toluene are discharged by the adsorption tower bottom, send into alkylation reactor;
Said ADSORPTION IN A FIXED BED tower is as denitrification equipment, and bed height is 1/2～4/5 of an adsorption tower tower height;
The sorbent material that uses in the said adsorption tower is the solid acid sorbent material;
Said solid acid sorbent material is sieve catalyst, siallite, silica gel, macropore weakly acidic cation-exchange resin, gac or its combination;
Used adsorption tower blade diameter length ratio is 1: 1.5～10;
Said adsorption tower service temperature is 10～150 ℃;
Said adsorption tower working pressure is 0.1～2.5MPa;
Said benzene or toluene feed weight space velocity 0.1～10h
-1
Total nitrogen content in the said raw material can be reduced to below the 30ppb.
Absorption method denitrification adsorbent kind is many, and scope is wide, and it is not high that process conditions requires yet, should use more convenient flexibly, be simply a kind of and denitrogenation method efficiently.Because sorbent material (sieve catalyst, macropore weakly acidic cation-exchange resin, siallite etc.) has stronger adsorptive power to basic nitrogen compound, and ideal composition in the oil product is had extremely faint adsorption.Can utilize these sorbent materials to adsorb the nitride in benzene or the toluene.
The center of benzene alcohol catalyst for alkylation reaction all is a tart, can utilize the acid sites of catalyzer come in benzene or toluene in basic nitrogen.Can select cheap an acidic catalyst such as catalyst of deposed molecular sieve as the basic nitrogen sorbent material, reach the purpose that removes basic nitrogen with the acid sites of sacrificing catalyzer.
Sieve catalyst since have big, the active high and good shape selectivity of specific surface area can, and be widely used as the sorbent material of NOx and sulfide.Because sieve catalyst has relatively mild acidity, also can be used for the absorption of basic nitrogen.
Ion exchange resin inside has the duct of a lot of molecular levels, and polymeric adsorbent has advantages such as big, the easy regeneration of loading capacity.Polymeric adsorbent has been widely used in fields such as oil denitrification, WWT, extraction at present.
Above-described sorbent material all has good adsorption effect, and sorbent material is packed into adsorption tower, and the nitrogen in benzene or the toluene is adsorbed, and the nitrogen content in benzene or the toluene is dropped to below the 30ppb by 1ppm～10ppm.
Description of drawings
Fig. 1 is a process flow diagram of the present invention, and among the figure, the meaning of each label is following:
1 end fittings
2 Ceramic Balls
3 thick silica sands
4 fine quartz sands
5 sorbent materials
6 Ceramic Balls
7 liquid distributors
8 interchanger
Embodiment
1, as shown in Figure 1, adsorption tower by cat head be respectively downwards liquid distributor, inert packing (as the silica sand of different diameter, porcelain ball etc. one or more), sorbent material, inert packing and Stainless Steel Cloth.Sorbent material is loaded and highly is about 3/5～4/5 of absorption tower height.
2, with benzene feedstock or toluene at normal temperatures (or the back of heating up) go into adsorption tower by pump delivery, by the adsorption tower top fed, the gross weight air speed is 0.1～10h
-1Benzene or toluene are with after sorbent material contacts, and nitrogen and sorbent reactions also are attracted on the sorbent material, and benzene after the denitrogenation or toluene are discharged by the adsorption tower bottom, get into alkylation reactor.
Embodiment 1
Catalyst of deposed molecular sieve pack in the adsorption tower into as sorbent material.Benzene feedstock or toluene are at 80～150 ℃ of following entering adsorption towers, and the gross weight air speed is 0.1～5h
-1, working pressure 0.5～2MPa, benzene or toluene contact the back absorption reaction take place with sorbent material, after the absorption denitrogenation, discharge from the adsorption tower bottom, send into alkylation reactor, and its total nitrogen content is reduced to 20～30ppb.
Embodiment 2
Modified zeolite pack in the adsorption tower into as sorbent material.Benzene feedstock or toluene are at 50～120 ℃ of following entering adsorption towers, and the gross weight air speed is 0.1～10h
-1, working pressure 0.5～2MPa, benzene or toluene contact the back absorption reaction take place with sorbent material, after the absorption denitrogenation, discharge from the adsorption tower bottom, send into alkylation reactor, and total nitrogen content is reduced to 10～20ppb.
Embodiment 3
D113 macropore acidulous acrylic acid cation exchange resin pack in the adsorption tower into as sorbent material, and benzene feedstock or toluene are 20～60 ℃ of chargings, and the gross weight air speed is 0.5～5h
-1, under pressure 0.1～1MPa after the ion exchange resin adsorbing nitride, discharge at the bottom of the adsorption tower, send into alkylation reactor, total nitrogen content is reduced to 20～30ppb.
Embodiment 4
Layering is packed D113 macropore acidulous acrylic acid cation exchange resin and modified zeolite each half into as sorbent material in the adsorption tower, and benzene feedstock or toluene are 20～60 ℃ of chargings, and the gross weight air speed is 0.5～5h
-1, after adsorbing nitride under pressure 0.1～1MPa, at the bottom of adsorption tower, discharge, send into alkylation reactor, total nitrogen content is reduced to 20～30ppb.
Embodiment 5
In the adsorption tower layering be respectively charged into modified zeolite, D113 macropore acidulous acrylic acid cation exchange resin and modified zeolite each 1/3rd as sorbent material, benzene feedstock or toluene are 20～60 ℃ of chargings, the gross weight air speed is 0.5～5h
-1, after adsorbing nitride under pressure 0.1～1MPa, at the bottom of adsorption tower, discharge, send into alkylation reactor, total nitrogen content is reduced to 20～30ppb.
Embodiment 6
In the adsorption tower layering be respectively charged into catalyst of deposed molecular sieve, modified zeolite, D113 macropore acidulous acrylic acid cation exchange resin and modified zeolite each 1/4th as sorbent material, benzene feedstock or toluene are 20～60 ℃ of chargings, the gross weight air speed is 0.5～5h
-1, after adsorbing nitride under pressure 0.1～1MPa, at the bottom of adsorption tower, discharge, send into alkylation reactor, total nitrogen content is reduced to 20～30ppb.
Claims (9)
1. alkylated reaction benzene feedstock or the toluene method of taking off basic nitrogen; It is characterized in that benzene feedstock or toluene by pump delivery; Get into the adsorption tower that sorbent material is housed from the top of adsorption tower; Basic nitrogen in the raw material and sorbent material react and are removed, and benzene after the denitrogenation or toluene are discharged by the adsorption tower bottom, send into alkylation reactor.
2. the method for claim 1 is characterized in that with the ADSORPTION IN A FIXED BED tower as denitrification equipment, bed height is 1/2～4/5 of an adsorption tower tower height.
3. the method for claim 1 is characterized in that the sorbent material that uses in the adsorption tower is the solid acid sorbent material.
4. method as claimed in claim 3 is characterized in that said solid acid sorbent material is sieve catalyst, siallite, silica gel, macropore weakly acidic cation-exchange resin, gac or its combination.
5. the method for claim 1 is characterized in that used adsorption tower blade diameter length ratio is 1: 1.5～10.
6. the method for claim 1 is characterized in that the adsorption tower service temperature is 10～150 ℃.
7. the method for claim 1 is characterized in that the adsorption tower working pressure is 0.1～2.5MPa.
8. the method for claim 1 is characterized in that benzene or toluene feed weight space velocity 0.1～10h
-1
9. the method for claim 1 is characterized in that the total nitrogen content in the raw material can be reduced to below the 30ppb.
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| CN2012103125601A CN102816044A (en) | 2012-08-30 | 2012-08-30 | Method for basic nitrogen removal of benzene or methylbenzene serving as raw materials for alkylation reaction |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382674A (en) * | 2017-07-31 | 2017-11-24 | 黄河三角洲京博化工研究院有限公司 | A kind of denitrification process of phenol products |
| CN112755590A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for removing alkaline nitrogenous substances in organic solvent |
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| US6297417B1 (en) * | 1996-08-20 | 2001-10-02 | The Dow Chemical Company | Alkylation/transalkylation process with pretreatment of the alkylation/transalkylation feedstock |
| US6617482B1 (en) * | 2000-08-16 | 2003-09-09 | Exxonmobil Chemical Patents Inc. | Removable of polar contaminants from aromatic feedstocks |
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2012
- 2012-08-30 CN CN2012103125601A patent/CN102816044A/en active Pending
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| US6297417B1 (en) * | 1996-08-20 | 2001-10-02 | The Dow Chemical Company | Alkylation/transalkylation process with pretreatment of the alkylation/transalkylation feedstock |
| CN1256260A (en) * | 1998-11-19 | 2000-06-14 | 英特卫普有限公司 | Selective nitrile separating method |
| US6617482B1 (en) * | 2000-08-16 | 2003-09-09 | Exxonmobil Chemical Patents Inc. | Removable of polar contaminants from aromatic feedstocks |
| CN1632063A (en) * | 2004-11-17 | 2005-06-29 | 南京工业大学 | Method for solid phase coordination extraction and removal of basic nitrogen compound from diesel and gasoline |
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| 李超等: "高效吸附精制脱除石脑油中氮化物的研究", 《石油技术与应用》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382674A (en) * | 2017-07-31 | 2017-11-24 | 黄河三角洲京博化工研究院有限公司 | A kind of denitrification process of phenol products |
| CN107382674B (en) * | 2017-07-31 | 2020-12-01 | 黄河三角洲京博化工研究院有限公司 | Denitrification process of phenol products |
| CN112755590A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for removing alkaline nitrogenous substances in organic solvent |
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