CN102008938A - Naphtha denitrification adsorbent and preparation method thereof - Google Patents
Naphtha denitrification adsorbent and preparation method thereof Download PDFInfo
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- CN102008938A CN102008938A CN 201010543689 CN201010543689A CN102008938A CN 102008938 A CN102008938 A CN 102008938A CN 201010543689 CN201010543689 CN 201010543689 CN 201010543689 A CN201010543689 A CN 201010543689A CN 102008938 A CN102008938 A CN 102008938A
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Abstract
The invention relates to a naphtha denitrification adsorbent which is stable in absorption performance, large in absorption capacity, high in absorption efficiency, high in absorption selectively and renewable and a preparation method thereof. The adsorbent comprises a porous absorption carrier and acidic impregnation liquid loaded on the carrier. The absorbent can deeply remove organic nitride from naphtha by liquid-phase absorption and gas-phase absorption; the nitrogen content in the refined naphtha is less than or equal to 2.5ppm; and with the obvious reduction in the nitrogen content in the naphtha, the influences on the catalyst activity and equipment service life of downstream devices are reduced greatly, and the long-term operation and safe production of the devices are guaranteed.
Description
Technical field
The present invention relates to the refining of petroleum products field, be specifically related to a kind of adsorbent and this preparation of adsorbent method that from naphtha, removes nitrogen-containing compound.
Background technology
Naphtha need satisfy the raw material index request of reformer and ethylene unit as the primary raw material of catalytic reforming process and preparing ethylene by steam cracking technology.Nitrogen content in the naphtha is to the catalyst activity of downstream unit and remarkable influence is arranged equipment life, is unfavorable for the long-term operation and the safety in production of device.And along with the increase of crude oil poor qualityization and mining depth, the nitrogen content of crude oil has trend of rising, causes the naphtha product nitrogen content of atmospheric and vacuum distillation unit to exceed standard.Be the major issue that domestic and international oil refining enterprise faces how for the following process device provides the raw material that meets quality index.
The method that removes nitrogen-containing compound from oil and products thereof mainly contains: hydrofinishing, acid treating, solvent refining, matching method, absorption method (comprising clay-filtered) etc.The hydrofining technology advanced person, but hydrogen-consuming volume is big, and it is big to reach the investment of hydrogen manufacturing and hydrogenation plant, makes the production cost height of hydrogenation.Therefore, non-hydrogenation fine built in one period inherent China also have a large amount of market.The activated carbon that absorption method mostly adopts, activated aluminum, silica gel, modified adsorbent etc. are denitrifier, but there are problems such as poor selectivity, adsorption capacity are little in these methods.
Summary of the invention
In order rationally to solve above problems of the prior art, the invention provides that a kind of absorption property is stable, adsorption capacity is big, adsorption efficiency is high, adsorptive selectivity is high, renewable naphtha denitrification adsorbent, and this preparation of adsorbent method.
The present invention is achieved by the following technical solutions:
First scheme of the present invention provides a kind of naphtha denitrification adsorbent, and described adsorbent comprises the acid maceration extract of load on porous absorption carrier and the carrier.
Described porous absorption carrier is with the form filling of fixed bed.
Described porous absorption carrier is by any one or more constitutes in activated alumina, activated carbon, diatomite, silica gel, 13X molecular sieve or the aluminium-magnesium silicate.
Described acid maceration extract be in phosphoric acid, sulfuric acid or the nitric acid any one or more, mainly adopt the acid of low concentration.
The concentration of described acid maceration extract is 0.1~2mol/L.
Alternative plan of the present invention provides the preparation method of above-mentioned naphtha denitrification adsorbent, may further comprise the steps:
1) absorption carrier is dropped into flooded in the acid maceration extract 5~28 hours, wherein the mass ratio of absorption carrier and acid maceration extract is 1: 2~5, obtains the denitrification adsorbent head product;
2) with the denitrification adsorbent head product freeze-day with constant temperature that obtains in the step 1 1~5 hour;
3) dried denitrification adsorbent head product is advanced 200~400 ℃ carry out the high temperature roast and and activating and reducing 1~5 hour;
4) product of step 3 is cooled to room temperature and promptly obtains the denitrification adsorbent finished product.
For reaching more excellent invention effect, can adopt following prioritization scheme:
The mass ratio of absorption carrier and acid maceration extract is 1: 4 in the step 1.
Dip time is 24 hours in the described step 1.
Freeze-day with constant temperature is 3 hours in the described step 2.
300 ℃ of high-temperature roastings and activating and reducing are 3 hours in the described step 3.
Principle of the present invention is: nitride mainly comprises aliphatic amine, pyridines, quinolines and phenyl amines in the naphtha.Adsorbent is with the form filling of fixed bed, and oil product can remove the Semi-polarity material (comprising nitrogen-containing compound) that deoils by adsorbent bed.Because considerable part is a basic nitrogen compound in the nitride, therefore the certain acidic components of load can improve adsorptive selectivity to nitride on adsorbent, and the key of this technology is the selection of adsorbent, reinforcement and life cycle.The main purpose of strengthening is to improve the polarity and the acidity of adsorbent, thereby helps removing of nitrogen-containing compound.
Infusion process is one of method for preparing the load type adsorbing agent extensive use.Choose different carriers and active component, by the denitrification adsorbent of immersion process for preparing support type.The present invention with in activated alumina, activated carbon, diatomite, silica gel, 13X molecular sieve, the aluminium-magnesium silicate one or more as absorption carrier, in phosphoric acid, hydrochloric acid, sulfuric acid, the nitric acid one or more are as maceration extract, adopt the immersion process for preparing denitrification adsorbent, in order to the organic nitrogen compound in the adsorbing and removing naphtha.
Preparation process needs at first absorption carrier to be put in the liquid that contains active material to flood, fully diffuse into the solid endoporus Deng solution, after the dipping balance, remaining liquid is removed, carry out drying, roasting, activation, final chemical form when making the active component feedstock conversion for absorption, and form the certain activity structure.
Beneficial effect of the present invention is: naphtha denitrification adsorbent provided by the invention, can be by the organic nitrogen compound in liquid phase or the Gas Phase Adsorption deep removal naphtha, make nitrogen content≤2.5ppm in the naphtha after making with extra care, remarkable reduction along with nitrogen content in the naphtha, obviously reduce the catalyst activity of downstream unit and the influence of equipment life are helped the long-term operation and the safety in production of device.Simultaneously, adsorbent preparation method of the present invention is simple, and material is cheap and easy to get, and the adsorbent of making has stable, the advantages such as adsorption capacity is big, adsorptive selectivity is high, renewable use of absorption property.
Description of drawings
Fig. 1 is preparation flow figure of the present invention.
The specific embodiment
Below in conjunction with the drawings and specific embodiments the present invention is described in further details.
Embodiment 1
(1) compound concentration is that the phosphoric acid of 1mol/L is as maceration extract.
(2) press carrier: maceration extract=1: 4 (mass ratio), in the phosphate impregnation liquid of 13X molecular sieve with the filling of fixed bed form as absorption carrier adding respective volume, dipping 24h.
(3) the adsorbent head product is put into the dry 3h of thermostatic drier after, put into chamber type electric resistance furnace, in 300 ℃ of activation 3h, obtain denitrification adsorbent after being cooled to room temperature.
The graininess of preparation is carried sour 13X adsorbent of molecular sieve, removes the organic nitrogen in the piped oil straight-run naphtha, and denitrification percent can reach 71.6%, and adsorbent intensity is 30-80N, realizes that nitrogen content is less than 1.5ppm in the refined oil.Organic nitrogen in the first adsorbing and removing naphtha, finish can reach 190.3 than (quality), and adsorbent is reusable after hot nitrogen purges; Behind the phosphoric acid solvent washing, adsorption capacity can return to more than 95% of fresh adsorbent desorption ability.
Embodiment 2
(1) compound concentration is that the sulfuric acid of 1mol/L is as maceration extract.
(2) press carrier: maceration extract=1: 5 (mass ratio), in the sulfuric acid maceration extract of activated alumina with the filling of fixed bed form as absorption carrier adding respective volume, dipping 17h.
(3) the adsorbent head product is put into the dry 4h of thermostatic drier after, put into chamber type electric resistance furnace, in 200 ℃ of activation 4h, obtain denitrification adsorbent after being cooled to room temperature.
The gained adsorbent is through the complete preparation requirement according to the invention of check adsorption strength, and adsorbent is reusable after hot nitrogen purges; Behind the sulfuric acid solvent washing, adsorption capacity can return to more than 95% of fresh adsorbent desorption ability.
Embodiment 3
(1) compound concentration be 1.5mol/L nitric acid as maceration extract.
(2) press carrier: maceration extract=1: 2 (mass ratio), in the sulfuric acid maceration extract of activated carbon with the filling of fixed bed form as absorption carrier adding respective volume, dipping 10h.
(3) the adsorbent head product is put into the dry 2h of thermostatic drier after, put into chamber type electric resistance furnace, in 200 ℃ of activation 2h, obtain denitrification adsorbent after being cooled to room temperature.
The gained adsorbent is through the complete preparation requirement according to the invention of check adsorption strength, and adsorbent is reusable after hot nitrogen purges; Behind the nitric acid solvent washing, adsorption capacity can return to more than 95% of fresh adsorbent desorption ability.
Embodiment 4
(1) compound concentration is that the sulfuric acid of 1mol/L and nitric acid mixed liquor are as maceration extract.
(2) press carrier: maceration extract=1: 4 (mass ratio) adds in the sulfuric acid and nitric acid mixed liquor of respective volume dipping 5h with the diatomite of fixed bed form filling and the mixture of silica gel as absorption carrier.
(3) the adsorbent head product is put into the dry 1.5h of thermostatic drier after, put into chamber type electric resistance furnace, in 300 ℃ of activation 1.5h, obtain denitrification adsorbent after being cooled to room temperature.
The gained adsorbent is through the complete preparation requirement according to the invention of check adsorption strength, and adsorbent is reusable after hot nitrogen purges; After sulfuric acid and the flushing of nitric acid mixed liquor, adsorption capacity can return to more than 95% of fresh adsorbent desorption ability.
Embodiment 5
(1) compound concentration is that the phosphoric acid of 1.8mol/L and nitric acid mixed liquor are as maceration extract.
(2) press carrier: maceration extract=1: 3 (mass ratio) adds the aluminium-magnesium silicate of fixed bed form filling in the mixed liquor of the phosphoric acid of respective volume and nitric acid dipping 18h as absorption carrier.
(3) the adsorbent head product is put into the dry 3.5h of thermostatic drier after, put into chamber type electric resistance furnace, in 400 ℃ of activation 4.5h, obtain denitrification adsorbent after being cooled to room temperature.
The gained adsorbent is through the complete preparation requirement according to the invention of check adsorption strength, and adsorbent is reusable after hot nitrogen purges; Behind phosphoric acid and hydrochloric acid mixed solution solvent washing, adsorption capacity can return to more than 95% of fresh adsorbent desorption ability.
Above embodiment shows naphtha denitrification adsorbent provided by the invention, can be by the organic nitrogen compound in liquid phase or the Gas Phase Adsorption deep removal naphtha, make nitrogen content≤2.5ppm in the naphtha after making with extra care, remarkable reduction along with nitrogen content in the naphtha, can obviously reduce the catalyst activity of downstream unit and the influence of equipment life are helped the long-term operation and the safety in production of device.Simultaneously, adsorbent preparation method of the present invention is simple, and material is cheap and easy to get, and the adsorbent of making has stable, the advantages such as adsorption capacity is big, adsorptive selectivity is high, renewable use of absorption property.
Claims (10)
1. a naphtha denitrification adsorbent is characterized in that described adsorbent comprises the acid maceration extract of load on porous absorption carrier and the carrier.
2. denitrification adsorbent according to claim 1 is characterized in that the form filling of described porous absorption carrier with fixed bed.
3. denitrification adsorbent according to claim 1 and 2 is characterized in that described porous absorption carrier is by any one or more constitutes in activated alumina, activated carbon, diatomite, silica gel, 13X molecular sieve or the aluminium-magnesium silicate.
4. denitrification adsorbent according to claim 1, it is characterized in that described acid maceration extract be in phosphoric acid, sulfuric acid or the nitric acid any one or more.
5. denitrification adsorbent according to claim 4, the concentration that it is characterized in that described acid maceration extract is 0.1~2mol/L.
6. the preparation method of a naphtha denitrification adsorbent is characterized in that may further comprise the steps:
1) absorption carrier is dropped into flooded in the acid maceration extract 5~28 hours, wherein the mass ratio of absorption carrier and acid maceration extract is 1: 2~5, obtains the denitrification adsorbent head product;
2) with the denitrification adsorbent head product freeze-day with constant temperature that obtains in the step 1 1~5 hour;
3) dried denitrification adsorbent head product is advanced 200~400 ℃ carry out the high temperature roast and and activating and reducing 1~5 hour;
4) product of step 3 is cooled to room temperature and promptly obtains the denitrification adsorbent finished product.
7. preparation method according to claim 6 is characterized in that the mass ratio of absorption carrier and acid maceration extract is 1: 4 in the described step 1.
8. preparation method according to claim 6 is characterized in that dip time is 24 hours in the described step 1.
9. preparation method according to claim 6 is characterized in that in the described step 2 freeze-day with constant temperature 3 hours.
10. preparation method according to claim 6 is characterized in that in the described step 3 300 ℃ of high-temperature roastings and activating and reducing 3 hours.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104232149A (en) * | 2013-11-26 | 2014-12-24 | 苏州大学 | Material for efficiently removing alkaline nitride in oil product |
CN104560124A (en) * | 2014-11-04 | 2015-04-29 | 华文蔚 | Fuel deep denitrification method for automobile industry |
CN105112095A (en) * | 2015-09-10 | 2015-12-02 | 长沙理工大学 | Method for removing basic nitrogen compound and phospholipid of biological fuel oil |
CN105457600A (en) * | 2015-11-26 | 2016-04-06 | 王金明 | Method for preparing denitrifying adsorbent |
CN109731547A (en) * | 2019-01-29 | 2019-05-10 | 江南大学 | A kind of efficient absorption takes off the modified activated carbon and preparation method thereof of virtue |
CN109939662A (en) * | 2019-03-28 | 2019-06-28 | 广东石油化工学院 | Dealkalize nitrogen absorber for light fraction obtained by the rectifying of ethylene production sump oil |
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CN1386822A (en) * | 2001-05-18 | 2002-12-25 | 韩剑峰 | Efficient denitrifying agent for removing nitride from fraction oil of petroleum and its denitrifying process |
CN101555417A (en) * | 2008-09-04 | 2009-10-14 | 北京三聚环保新材料股份有限公司 | Denitrifier and preparation method thereof |
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2010
- 2010-11-15 CN CN 201010543689 patent/CN102008938A/en active Pending
Patent Citations (2)
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CN1386822A (en) * | 2001-05-18 | 2002-12-25 | 韩剑峰 | Efficient denitrifying agent for removing nitride from fraction oil of petroleum and its denitrifying process |
CN101555417A (en) * | 2008-09-04 | 2009-10-14 | 北京三聚环保新材料股份有限公司 | Denitrifier and preparation method thereof |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104232149A (en) * | 2013-11-26 | 2014-12-24 | 苏州大学 | Material for efficiently removing alkaline nitride in oil product |
CN104560124A (en) * | 2014-11-04 | 2015-04-29 | 华文蔚 | Fuel deep denitrification method for automobile industry |
CN105112095A (en) * | 2015-09-10 | 2015-12-02 | 长沙理工大学 | Method for removing basic nitrogen compound and phospholipid of biological fuel oil |
CN105457600A (en) * | 2015-11-26 | 2016-04-06 | 王金明 | Method for preparing denitrifying adsorbent |
CN109731547A (en) * | 2019-01-29 | 2019-05-10 | 江南大学 | A kind of efficient absorption takes off the modified activated carbon and preparation method thereof of virtue |
CN109939662A (en) * | 2019-03-28 | 2019-06-28 | 广东石油化工学院 | Dealkalize nitrogen absorber for light fraction obtained by the rectifying of ethylene production sump oil |
CN109939662B (en) * | 2019-03-28 | 2021-11-16 | 广东石油化工学院 | Dealkalized nitrogen adsorbent for light fraction obtained by sump oil rectification in ethylene production process |
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Application publication date: 20110413 |