CN102559252B - Non-hydrodenitrogeneration method for catalytically cracked gasoline - Google Patents
Non-hydrodenitrogeneration method for catalytically cracked gasoline Download PDFInfo
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Abstract
The invention discloses a non-hydrodenitrogeneration method for catalytically cracked gasoline. The non-hydrodenitrogeneration method for the catalytically cracked gasoline comprises the following steps: first, mixing a liquid denitrifying agent with the catalytically cracked gasoline by using a static mixer, standing, depositing, and pre-removing alkali nitrides; and then, performing contact reaction with a solid denitrifying agent through a fixed bed for finely removing the alkali nitrides. Through matching of the liquid denitrifying agent and the solid denitrifying agent, the alkali nitrides such as aliphatic amines, pyridines, quinolines and anilines and the like can be removed by pre-removing and finely removing steps; after the treatment of the liquid denitrifying agent, 80-90 percent of the alkali nitrides can be removed, and after the catalytically cracked gasoline passes through the solid denitrifying agent filled in a form of the fixed bed, the alkali nitrides can be removedcompletely, so that the negative effect of the alkali nitrides on a subsequent hydrodesulfurization catalyst can be completely eliminated. Therefore, the deep hydrodesulfurization of the catalytically cracked gasoline can be realized.
Description
One, technical field
The present invention relates to a kind of non-hydrodenitrification method of catalytically cracked gasoline, specifically is to adopt non-hydrodenitrification method to remove the basic nitrogen compound in the catalytically cracked gasoline, is conducive to realize further deep hydrodesulfurizationof.
Two, background technology
Since national unleaded gasolines such as the USA and Europe days eighties in 20th century, the development of world economy developed country clean fuel such as American-European-Japanese so far moves to maturity.Increasing developing country is also immediately following advanced country's developing steps.The quality of world's clean fuel improves constantly, and the ratio of clean fuel is progressively increasing.
The clean fuel of part Asia-Pacific nations such as the most of country in Europe, North America and Japan, Korea S, New Zealand has all reached the low-sulfur clean fuel standards at present, the wherein most of country in Europe, regional, Canadian, Japanese, the Korea S of California, USA, cleaning petrol and diesel oil standard has all reached the super low sulfur fuel standard, and the clean fuel sulphur content all is lower than 10 μ g/g.The regulation sulphur content is not more than 150 μ g/g in the China national compulsory standard " GB17930-2011 motor spirit ", and in Beijing, Shanghai, Guangzhou all carries out the standard that content of sulfur in gasoline is not more than 50 μ g/g.In a foreseeable future in several years, the super low-sulfur oil standard will generally be carried out in the whole nation.
At present, catalytically cracked gasoline ingredients constitute 70%～80% in the total amount of Chinese commodity gasoline, and sulphur in the catalytic gasoline, olefin(e) centent are higher, account for total sulfur content in the commercial gasoline 90%, more than 80% of total olefin content, become the main source of sulfur in gasoline and alkene.Therefore, the production of China's clean gasoline finally is summed up as the cleaning upgrading problem of catalytically cracked gasoline.
At present, the hydroprocessing technique of catalytically cracked gasoline can be divided into two big classes by reaction mechanism: the one, and olefin process falls in selective hydrodesulfurization; The 2nd, hydrogenating desulfurization recovers octane value technology.These two kinds of technologies have mature technology, and have realized industrial application, but also exist certain restricted condition.
Basic nitrogen compound nitrogen in the catalytically cracked gasoline has remarkable influence to activity of hydrocatalyst and the selectivity of downstream unit, is unfavorable for long-term operation and the safety in production of device.The acid sites of the alkaline substance mass-energy catalyst neutralisation that contains in the gasoline, thus activity of such catalysts reduced.Alkaline matter also can cause catalyst deactivation in the accumulation of catalyst surface.In order to prolong the work-ing life of catalyzer, before entering hydrogenator, the catalytic cracking petroleum naphtha basic nitrogen compound must be removed.And along with once the adding of crude oil poor qualityization and mining depth, the nitrogen content of crude oil has trend of rising, causes the catalytically cracked gasoline nitrogen content of catalytic cracking unit to exceed standard.Be the major issue that domestic and international oil refining enterprise faces for the following process device provides the raw material that meets quality index how.
The method that removes nitrogenous compound from oil and products thereof mainly contains: hydrofining, acid treating, solvent treatment, companion 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 unit, 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, active aluminum, silica gel, modified adsorbent etc. are denitrfying agent, but there are problems such as poor selectivity, loading capacity are little in these methods.
At present, the scientific worker to study maximum denitride technologies be solvent extration, absorption method, complexometry and microwave treatment method.Solvent extration exists when exquisite gasoline that yield of gasoline is low, easily produce emulsion in the extraction process, extraction liquid is difficult for problems such as processing.The activated carbon that absorption method mostly adopts, active aluminum, silica gel, modified adsorbent etc. are denitrfying agent, but there are problems such as poor selectivity, loading capacity are little in these methods.
Chinese patent application number is 201010543689.4 to disclose a kind of sorbent material and this preparation of adsorbent method that removes nitrogenous compound from petroleum naphtha.Adopt phosphoric acid, sulfuric acid or aqueous nitric acid dipping porous absorption carrier by activated alumina, activated carbon, diatomite, silica gel, 13X molecular sieve or neusilin.Although this kind denitrification adsorbent loading capacity is big, when amount of nitrides is high in the petroleum naphtha, needs the denitrification adsorbent in the frequent replacing fixed bed or carry out the repeated regeneration operation, in actual production process, still there is operational difficulty.
Three, summary of the invention
The non-hydrodenitrification method that the purpose of this invention is to provide a kind of catalytically cracked gasoline adopts this can reach the many deficiencies that overcome existing denitrogenation method effectively, thereby realizes the deep hydrodesulfurizationof of catalytically cracked gasoline.
For achieving the above object, the technical solution used in the present invention is: this method comprises the steps: that at first the liquid denitrfying agent being mixed the back standing sedimentation by static mixer with catalytically cracked gasoline removes basic nitrogen compound in advance, removes basic nitrogen compound by fixed bed and solid denitrfying agent contact reacts essence again.
Above-mentioned liquid denitrfying agent is that the water that the ortho-phosphoric acid of 70%-80%, cupric pyrophosphate that mass percent is 3%-10% and mass percent are 10%-25% is formed by mass percent.
Above-mentioned liquid denitrfying agent addition is 0.01%-0.02% for the catalytically cracked gasoline weight percentage.
Aforesaid liquid denitrfying agent and catalytically cracked gasoline are 1-4 h through the mixed settling time of static mixer, and temperature is 5-35 ℃, and pressure is 0.1-0.5 MPa.
The preparation of above-mentioned solid denitrfying agent is to be the aqueous solution dipping porous absorption carrier of the liquid denitrfying agent of 20%-30% with mass concentration, liquid-solid mass ratio is 1.5:1-3.0:1, dipping temperature is 15-25 ℃, and dipping time is 12-24 h, filters back 105 ℃ and dries to constant weight.
Above-mentioned porous absorption carrier is one or more in activated alumina, activated carbon, diatomite, silica gel, 13X molecular sieve or the neusilin.
The catalytically cracked gasoline that above-mentioned warp removes basic nitrogen compound in advance is 1-6 h by the volume space velocity of the solid denitrfying agent in the fixed bed
-1, temperature is 5-35 ℃, pressure is 0.1-0.5 MPa.
The present invention is the mating reaction by liquid denitrfying agent and solid denitrfying agent, goes on foot the basic nitrogen compounds such as aliphatics amine, pyridines, quinoline and phenyl amines in the catalytically cracked gasoline are removed by pre-, essence two.Wherein after handling, the liquid denitrfying agent can remove the basic nitrogen compound of 80%-90%, process is with the solid denitrfying agent of the form filling of fixed bed again, basic nitrogen compound all can be removed, thoroughly eliminate the negative impact that basic nitrogen compound causes the follow-up hydrogenation desulfurization catalyst, thereby realized the purpose of catalytically cracked gasoline deep hydrodesulfurizationof.Simultaneously, this invention side fails also effectively to have prolonged work-ing life of solid denitrfying agent, and its life-span can reach 8000-10000 h, has reduced the loss of material, has improved economic benefit.
Four, embodiment
Stock oil adopts typical catalytically cracked gasoline, and main physical and chemical sees the following form
| Project | Numerical value | Project | Numerical value |
| Boiling range/℃ (IBP) | 29.3 | Density (20 ℃) (kg/m3) | 711.7 |
| Boiling range/℃ (30%) | 62.3 | Total sulfur content (μ g/g) | 498 |
| Boiling range/℃ (50%) | 86.0 | Mercaptan sulfur content (μ g/g) | 26.4 |
| Boiling range/℃ (95%) | 168.9 | Total nitrogen content (μ g/g) | 67.7 |
| Boiling range/℃ (FBP) | 173.8 | Basic n content (μ g/g) | 59.8 |
Among the present invention, owing to when the lab scale of laboratory, can't realize with static mixer the liquid denitrfying agent being mixed with catalytically cracked gasoline, only be 0.01%-0.02% because the addition of liquid denitrfying agent accounts for the massfraction of catalytically cracked gasoline simultaneously, can't realize adding continuously with volume pump.Therefore, adopt the mode of magnetic agitation to carry out periodical operation, rotating speed mixes the liquid denitrfying agent for per minute 800-1000 changes with catalytically cracked gasoline, and churning time is 10 min.Facts have proved, adopt the mode of above-mentioned magnetic agitation can reach the effect of static mixer fully.
Among the present invention, total sulfur content is measured by LC-2 type coulomb meter, and instrument is to be produced by the Ao Pute of Jiangyan City Analytical Instrument Co., Ltd.
Among the present invention, the mensuration of catalytically cracked gasoline neutral and alkali nitrogen adopts SH/T 0162-92(2000 to confirm) standard, this standard adopts perchloric acid one Glacial acetic acid nonaqueous titrations.Sample is dissolved in an amount of benzene one glacial acetic acid solution, with perchloric acid one Glacial acetic acid standard solution titration sample.
Embodiment 1:
The preparation of liquid denitrfying agent: weighing 100 g 85% phosphoric acid, add 5 g water stirring and evenly mixings, 5 g cupric pyrophosphates are dissolved in the above-mentioned phosphoric acid solution.Wherein ortho-phosphoric mass percent is 77.3%, and the mass percent of cupric pyrophosphate is 4.5%, and the mass percent of water is 18.2%.
The preparation of solid denitrfying agent: weighing 25 g liquid denitrfying agents add 75 g water and are mixed with 25% aqueous solution, (Ф 1.5 ' 3-10), and mixing is in the above-mentioned aqueous solution, and dipping temperature is 20 ℃ to add the coal-based activated carbon of 50 g, flood 14 h, filter back 105 ℃ and dry to constant weight.
The pre-denitrogenation of liquid denitrfying agent: get 1 L catalytically cracked gasoline, its weight is 711.7g, place 2 L stainless steel reactors, add 0.107 g liquid denitrfying agent, it is 0.015% that liquid denitrfying agent addition accounts for the catalytically cracked gasoline weight percentage, under 0.1MPa and 25 ℃ of conditions, stirred 10 minutes, under 0.1MPa and 25 ℃ of conditions behind sedimentation 2 h, the nitrogen slag that is deposited in the Erlenmeyer flask bottom is separated with gasoline, the alkali nitrogen content of gasoline drops to 7.6 μ g/g after this pre-denitrogenation, and dealkalize nitrogen decreasing ratio is 87.3%.
The smart denitrogenation of solid denitrfying agent: solid denitrfying agent 8.2 g (10 mL) are placed fixed bed, Glass tubing interior diameter 25.4 mm, length 580mm uses fixedly TD solid denitrfying agent of 20mm Stainless Steel Cloth up and down respectively.Squeeze in the fixed bed with the gasoline of plunger type metering pump after with above-mentioned pre-denitrogenation, the flow velocity of volume pump is 0.5 mL/min, and volume space velocity is 3 h
-1, temperature is 25 ℃, and pressure is 0.2 MPa, is 0 through the gasoline alkali nitrogen content after the smart denitrogenation of solid denitrfying agent, and dealkalize nitrogen decreasing ratio is 100%.Removed the basic nitrogen compound more than 80% owing to adopt the liquid denitrfying agent to carry out pre-denitrogenation, the life-span of calculating solid denitrfying agent in the fixed bed according to liquid denitrfying agent charge capacity can reach 8000-10000 h.
The hydrogenating desulfurization by the following method of above-mentioned catalytically cracked gasoline after denitrogenation: the catalytically cracked gasoline after the denitrogenation removes mercaptan with conventional catalytic oxidation, is lighting end and last running with its prefractionation then, and the temperature cut point is 70 ℃.Heavy fractioning hydrogenation activity of such catalysts component is that MoO3 and CoO total mass mark are 10%, and carrier is γ-Al2O3, vulcanizes laggard reaction raw materials, hydrogen dividing potential drop 1.6 MPa, 270 ℃ of temperature, volume space velocity 3.0 h down at 270 ℃
-1The heavy fractioning hydrogenation desulfurization product mixes with lighting end that to obtain total sulfur content be 42 μ g/g again, and the research octane number (RON) loss is 1.8.
Comparative Examples 1:
Catalytically cracked gasoline is without denitrogenation processing, with embodiment 1 the same terms under carry out hydrogenating desulfurization, obtaining total sulfur content is 124 μ g/g, the research octane number (RON) loss is 1.6.Therefrom find out the negative impact that basic nitrogen causes hydrogenating desulfurization.
Embodiment 2:
The preparation of liquid denitrfying agent: weighing 90 g 85% phosphoric acid, add 10 g water stirring and evenly mixings, 7 g cupric pyrophosphates are dissolved in the above-mentioned phosphoric acid solution.Wherein ortho-phosphoric mass percent is 71.5%, and the mass percent of cupric pyrophosphate is 6.5%, and the mass percent of water is 22%.
The preparation of solid denitrfying agent: weighing 30 g liquid denitrfying agents add 70 g water and are mixed with 30% aqueous solution, add 66 g 13X molecular sieves, and mixing is in the above-mentioned aqueous solution, and dipping temperature is 25 ℃, floods 24 h, filter back 105 ℃ and dry to constant weight.
The pre-denitrogenation of liquid denitrfying agent: get 1 L catalytically cracked gasoline, its weight is 711.7g, place 2 L stainless steel reactors, add 0.07 g liquid denitrfying agent, it is 0.01% that liquid denitrfying agent addition accounts for the catalytically cracked gasoline weight percentage, under 0.2MPa and 10 ℃ of conditions, stirred 10 minutes, keeping under 0.2MPa and the 10 ℃ of conditions behind sedimentation 2 h, the nitrogen slag that is deposited in the Erlenmeyer flask bottom is separated with gasoline, the alkali nitrogen content of gasoline drops to 8.6 ppm after this pre-denitrogenation, and dealkalize nitrogen decreasing ratio is 85.6%.
The smart denitrogenation of solid denitrfying agent: solid denitrfying agent 8.7 g (10 mL) are placed fixed bed, Glass tubing interior diameter 25.4 mm, length 580mm uses fixedly TD solid denitrfying agent of 20mm Stainless Steel Cloth up and down respectively.Squeeze in the fixed bed with the gasoline of plunger type metering pump after with above-mentioned pre-denitrogenation, the flow velocity of volume pump is 0.5 mL/min, and volume space velocity is 3 h
-1, temperature is 25 ℃, and pressure is 0.2 MPa, is 0 through the gasoline alkali nitrogen content after the smart denitrogenation of solid denitrfying agent, and dealkalize nitrogen decreasing ratio is 100%.
The hydrogenating desulfurization by the following method of above-mentioned catalytically cracked gasoline after denitrogenation: the catalytically cracked gasoline after the denitrogenation removes mercaptan with conventional catalytic oxidation, is lighting end and last running with its prefractionation then, and the temperature cut point is 80 ℃.Heavy fractioning hydrogenation activity of such catalysts component is that MoO3 and CoO total mass mark are 10%, and carrier is γ-Al2O3, vulcanizes laggard reaction raw materials, hydrogen dividing potential drop 1.6 MPa, 270 ℃ of temperature, volume space velocity 4.0 h down at 270 ℃
-1The heavy fractioning hydrogenation desulfurization product mixes with lighting end that to obtain total sulfur content be 45 μ g/g again, and the research octane number (RON) loss is 1.9.
Embodiment 3:
The preparation of liquid denitrfying agent: weighing 110 g 85% phosphoric acid, add 5 g water stirring and evenly mixings, 10 g cupric pyrophosphates are dissolved in the above-mentioned phosphoric acid solution.Wherein ortho-phosphoric mass percent is 74.8%, and the mass percent of cupric pyrophosphate is 8.0%, and the mass percent of water is 17.2%.
The preparation of solid denitrfying agent: weighing 20 g liquid denitrfying agents add 80 g water and are mixed with 20% aqueous solution, add 33 g activated aluminas, and mixing is in the above-mentioned aqueous solution, and dipping temperature is 15 ℃, floods 20 h, filter back 105 ℃ and dry to constant weight.
The pre-denitrogenation of liquid denitrfying agent: get 1 L catalytically cracked gasoline, its weight is 711.7g, place 2 L stainless steel reactors, add 0.14 g liquid denitrfying agent, it is 0.02% that liquid denitrfying agent addition accounts for the catalytically cracked gasoline weight percentage, stirs 10 minutes under 0.3MPa and 30 ℃ of conditions, keeping 25 ℃ of normal pressures behind sedimentation 2 h, the nitrogen slag that is deposited in the Erlenmeyer flask bottom is separated with gasoline, and the alkali nitrogen content of gasoline drops to 5.5 ppm after this pre-denitrogenation, and dealkalize nitrogen decreasing ratio is 90.8%.
The smart denitrogenation of solid denitrfying agent: solid denitrfying agent 9.7 g (10 mL) are placed fixed bed, Glass tubing interior diameter 25.4 mm, length 580mm uses fixedly TD solid denitrfying agent of 20mm Stainless Steel Cloth up and down respectively.Squeeze in the fixed bed with the gasoline of plunger type metering pump after with above-mentioned pre-denitrogenation, the flow velocity of volume pump is 1.0 mL/min, and volume space velocity is 6 h
-1, temperature is 25 ℃, and pressure is 0.2 MPa, is 0 through the gasoline alkali nitrogen content after the smart denitrogenation of solid denitrfying agent, and dealkalize nitrogen decreasing ratio is 100%.
The hydrogenating desulfurization by the following method of above-mentioned catalytically cracked gasoline after denitrogenation: the catalytically cracked gasoline after the denitrogenation removes mercaptan with conventional catalytic oxidation, is lighting end and last running with its prefractionation then, and the temperature cut point is 60 ℃.Heavy fractioning hydrogenation activity of such catalysts component is that MoO3 and CoO total mass mark are 10%, and carrier is γ-Al2O3, vulcanizes laggard reaction raw materials, hydrogen dividing potential drop 1.2 MPa, 240 ℃ of temperature, volume space velocity 1.0 h down at 240 ℃
-1The heavy fractioning hydrogenation desulfurization product mixes with lighting end that to obtain total sulfur content be 44 μ g/g again, and the research octane number (RON) loss is 1.9.
Embodiment 4:
The preparation of liquid denitrfying agent: weighing 100 g 85% phosphoric acid, add 5 g water stirring and evenly mixings, 5 g cupric pyrophosphates are dissolved in the above-mentioned phosphoric acid solution.Wherein ortho-phosphoric mass percent is 77.3%, and the mass percent of cupric pyrophosphate is 4.5%, and the mass percent of water is 18.2%.
The preparation of solid denitrfying agent: weighing 25 g liquid denitrfying agents add 75 g water and are mixed with 25% aqueous solution, add the mixture of 50 g diatomite and silica gel, and mixing is in the above-mentioned aqueous solution, and dipping temperature is 20 ℃, floods 24 h, filter back 105 ℃ and dry to constant weight.
The pre-denitrogenation of liquid denitrfying agent: get 1 L catalytically cracked gasoline, its weight is 711.7g, place 2 L stainless steel reactors, add 0.107 g liquid denitrfying agent, it is 0.015% that liquid denitrfying agent addition accounts for the catalytically cracked gasoline weight percentage, under 0.4MPa and 35 ℃ of conditions, stirred 10 minutes, keeping under 0.4MPa and the 35 ℃ of conditions behind sedimentation 2 h, the nitrogen slag that is deposited in the Erlenmeyer flask bottom is separated with gasoline, the alkali nitrogen content of gasoline drops to 6.3 μ g/g after this pre-denitrogenation, and dealkalize nitrogen decreasing ratio is 89.5%.
The smart denitrogenation of solid denitrfying agent: solid denitrfying agent 7.2 g (10 mL) are placed fixed bed, Glass tubing interior diameter 25.4 mm, length 580mm uses fixedly TD solid denitrfying agent of 20mm Stainless Steel Cloth up and down respectively.Squeeze in the fixed bed with the gasoline of plunger type metering pump after with above-mentioned pre-denitrogenation, the flow velocity of volume pump is 0.5 mL/min, and volume space velocity is 3 h
-1, temperature is 25 ℃, and pressure is 0.2 MPa, is 0 through the gasoline alkali nitrogen content after the smart denitrogenation of solid denitrfying agent, and dealkalize nitrogen decreasing ratio is 100%.
The hydrogenating desulfurization by the following method of above-mentioned catalytically cracked gasoline after denitrogenation: the catalytically cracked gasoline after the denitrogenation removes mercaptan with conventional catalytic oxidation, is lighting end and last running with its prefractionation then, and the temperature cut point is 70 ℃.Heavy fractioning hydrogenation activity of such catalysts component is that MoO3 and CoO total mass mark are 10%, and carrier is γ-Al2O3, vulcanizes laggard reaction raw materials, hydrogen dividing potential drop 1.6 MPa, 270 ℃ of temperature, volume space velocity 3.0 h down at 270 ℃
-1The heavy fractioning hydrogenation desulfurization product mixes with lighting end that to obtain total sulfur content be 40 μ g/g again, and the research octane number (RON) loss is 1.8.
Embodiment
5:
The preparation of liquid denitrfying agent: weighing 110 g 85% phosphoric acid, add 5 g water stirring and evenly mixings, 10 g cupric pyrophosphates are dissolved in the above-mentioned phosphoric acid solution.Wherein ortho-phosphoric mass percent is 74.8%, and the mass percent of cupric pyrophosphate is 8.0%, and the mass percent of water is 17.2%.
The preparation of solid denitrfying agent: weighing 30 g liquid denitrfying agents add 70 g water and are mixed with 30% aqueous solution, add 50 g neusilins, and mixing is in the above-mentioned aqueous solution, and dipping temperature is 25 ℃, floods 20 h, filter back 105 ℃ and dry to constant weight.
The pre-denitrogenation of liquid denitrfying agent: get 1 L catalytically cracked gasoline, its weight is 711.7g, place 2 L stainless steel reactors, add 0.14 g liquid denitrfying agent, it is 0.02% that liquid denitrfying agent addition accounts for the catalytically cracked gasoline weight percentage, under 0.5MPa and 5 ℃ of conditions, stirred 10 minutes, keeping under 0.5MPa and the 5 ℃ of conditions behind sedimentation 2 h, the nitrogen slag that is deposited in the Erlenmeyer flask bottom is separated with gasoline, the alkali nitrogen content of gasoline drops to 7.7 ppm after this pre-denitrogenation, and dealkalize nitrogen decreasing ratio is 90.8%.
The smart denitrogenation of solid denitrfying agent: solid denitrfying agent 9.7 g (10 mL) are placed fixed bed, Glass tubing interior diameter 25.4 mm, length 580mm uses fixedly TD solid denitrfying agent of 20mm Stainless Steel Cloth up and down respectively.Squeeze in the fixed bed with the gasoline of plunger type metering pump after with above-mentioned pre-denitrogenation, the flow velocity of volume pump is 1.0 mL/min, and volume space velocity is 6 h
-1, temperature is 25 ℃, and pressure is 0.2 MPa, is 0 through the gasoline alkali nitrogen content after the smart denitrogenation of solid denitrfying agent, and dealkalize nitrogen decreasing ratio is 100%.
State through the hydrogenating desulfurization by the following method of the catalytically cracked gasoline after the denitrogenation: the catalytically cracked gasoline after the denitrogenation removes mercaptan with conventional catalytic oxidation, is lighting end and last running with its prefractionation then, and the temperature cut point is 70 ℃.Heavy fractioning hydrogenation activity of such catalysts component is that MoO3 and CoO total mass mark are 10%, and carrier is γ-Al2O3, vulcanizes laggard reaction raw materials, hydrogen dividing potential drop 1.6 MPa, 260 ℃ of temperature, volume space velocity 2.0 h down at 240 ℃
-1The heavy fractioning hydrogenation desulfurization product mixes with lighting end that to obtain total sulfur content be 41 μ g/g again, and the research octane number (RON) loss is 1.7.
Claims (6)
1. the non-hydrodenitrification method of a catalytically cracked gasoline, comprise the steps: that at first the liquid denitrfying agent being mixed the back standing sedimentation by static mixer with catalytically cracked gasoline removes basic nitrogen compound in advance, removes basic nitrogen compound by fixed bed and solid denitrfying agent contact reacts essence again; Described liquid denitrfying agent is that the water that the ortho-phosphoric acid of 70%-80%, cupric pyrophosphate that mass percent is 3%-10% and mass percent are 10%-25% is formed by mass percent.
2. the non-hydrodenitrification method of a kind of catalytically cracked gasoline according to claim 1, it is characterized in that: described liquid denitrfying agent addition is the 0.01%-0.02% of catalytically cracked gasoline weight.
3. the non-hydrodenitrification method of a kind of catalytically cracked gasoline according to claim 1 and 2, it is characterized in that: described liquid denitrfying agent and catalytically cracked gasoline are 1-4 h through the mixed settling time of static mixer, temperature is 5-35 ℃, and pressure is 0.1-0.5 MPa.
4. the non-hydrodenitrification method of a kind of catalytically cracked gasoline according to claim 1 and 2, it is characterized in that: the preparation of described solid denitrfying agent is to be the aqueous solution dipping porous absorption carrier of the liquid denitrfying agent of 20%-30% with mass concentration, liquid-solid mass ratio is 1.5:1-3.0:1, dipping temperature is 15-25 ℃, dipping time is 12-24 h, filters back 105 ℃ and dries to constant weight.
5. the non-hydrodenitrification method of a kind of catalytically cracked gasoline according to claim 4, it is characterized in that: described porous absorption carrier is one or more in activated alumina, activated carbon, diatomite, silica gel, 13X molecular sieve or the neusilin.
6. the non-hydrodenitrification method of a kind of catalytically cracked gasoline according to claim 1 and 2 is characterized in that: the catalytically cracked gasoline that described warp removes basic nitrogen compound in advance is 1-6 h by the volume space velocity of the solid denitrfying agent in the fixed bed
-1, temperature is 5-35 ℃, pressure is 0.1-0.5 MPa.
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| CN103184065B (en) * | 2013-04-01 | 2014-12-03 | 唐建云 | Method for removing nitrogen-containing compound from diesel oil by adsorbing |
| JP6393235B2 (en) * | 2014-05-20 | 2018-09-19 | Ｊｘｔｇエネルギー株式会社 | Adsorption removal of anilines from catalytic cracking gasoline |
| CN106645533B (en) * | 2015-10-29 | 2019-10-25 | 中国石油化工股份有限公司 | The extraction and separation and measuring method of organic nitrogen-containing and/or oxygen-containing additive in a kind of gasoline |
| CN105457600A (en) * | 2015-11-26 | 2016-04-06 | 王金明 | Method for preparing denitrifying adsorbent |
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| US4426280A (en) * | 1982-02-09 | 1984-01-17 | Occidental Petroleum Corporation | Process for removing nitrogen from shale oil |
| CN1199082A (en) * | 1997-05-13 | 1998-11-18 | 中国石油化工总公司 | Combined denitrification process for base oil of lubricant oil |
| CN1353167A (en) * | 2000-11-03 | 2002-06-12 | 石油大学(北京) | Modified argil as denitrifying agent and its preparing process |
| CN101121900A (en) * | 2006-08-10 | 2008-02-13 | 中国石化集团武汉石油化工厂 | Denitrogenation hydrogenation combination technique for secondary processing diesel oil |
| CN101972638A (en) * | 2010-11-12 | 2011-02-16 | 南开大学 | Deep denitrification method for fuel oil |
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