CN1155682C - Modified argil as denitrifying agent and its preparing process - Google Patents
Modified argil as denitrifying agent and its preparing process Download PDFInfo
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- CN1155682C CN1155682C CNB001302833A CN00130283A CN1155682C CN 1155682 C CN1155682 C CN 1155682C CN B001302833 A CNB001302833 A CN B001302833A CN 00130283 A CN00130283 A CN 00130283A CN 1155682 C CN1155682 C CN 1155682C
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Abstract
The present invention relates to a modified argil denitrifier for denitrifying refinement of petroleum refinement and a preparation method thereof. The modified argil denitrifier is made from 5 to 55 wt% of acidizer A, 0 to 30 wt% of complex builder B, 20 to 95 wt% of argil and 1 to 15 wt% of water. The acidizer A and the complex builder B are carried on the argil to form the solid denitrifier. The modified argil denitrifier has high denitrification efficiency. The lubricating oil basic oil can be deeply denitrified by using the same process equipment and similar technological conditions with the argil refining process of normal lubricating oil so as to greatly improve the antioxidation stability of the lubricating oil basic oil and overcome the defect of difficulty in mixing and separating liquid denitrifiers; the use amount of the argil can be reduced by 20 to 80%. The acidizer is carried on the solid argil without entering the refined oil so as to prevent the acid value of oil from increasing and prevent equipment from being corroded; the modified argil denitrifier can be used for eliminating alkaline nitrogen for high viscosity oil, such as HVGO, crude oil, etc.
Description
Relate to the field
The invention belongs to the refining of petroleum field, relate to a kind of modified argil as denitrifying agent and preparation method thereof that the refining of petroleum product comprises the denitrification refining of gasoline, kerosene, diesel oil, lubricating oil, wax tailings and shale wet goods oil product that can be used for.
Background technology
The crude oil in China nitrogen content is generally higher, in wherein about 80% distillate that concentrates on more than 400 ℃, promptly concentrates in the lube cut.Generally believe that at present the sulfide in the lubricant base has certain positive interaction to the oxidation stability of lubricant base, promptly can suppress the oxidation of oil product to a certain extent, and nitride, especially basic nitrogen compound, the oxidation of lubricating oil stability there is certain negative interaction, can quickens the oxidation of lubricant base.For this reason, develop various method and be used for removing of oil product nitrogenous compound.
It is to improve the most effective means of petroleum oxidation stability that high-pressure hydrogenation is handled, but investment in fixed assets and running cost are very high, also are difficult to generally adopt at many refinerys.Conventional low pressure hydrofining process desulfurization degree height, and denitrification percent is very low, not obvious to the oxidation stability effect that improves lubricant base.Can be in the removing Process of Lube Solvent Refining residual various polar solvents of existing carclazyte refining with adsorbents process simultaneously, remove quite a few nitrogenous compound, but if need obtain the higher denitrogenation degree of depth, the add-on of carclazyte be must improve, the reduction of oil product yield and the increase of useless carclazyte quantity discharged caused.In recent years along with in the world wide to the increasingly stringent of improving constantly of requiring of oil quality and legislations of environmental protection, be the oxidation stability that improves lubricant base, people have extensively carried out the research of various non-hydrogenation lubricating oil denitrification process.U.S. Pat 4,426,280 utilize acidizers such as hydrochloric acid, phosphoric acid, formic acid to remove basic nitrogen in the leaf rock oil; U.S. Pat 4,846,962 employing furfurals, phenol and the solvent extraction of N-N-methyl-2-2-pyrrolidone N-isopolarity remove the basic nitrogen in the lubricant base; U.S. Pat 4,960,508 utilize aliphatics organic acid or halogenated aliphatic organic acid to remove basic nitrogen in the oil product for extraction agent; The denitrfying agent that Chinese patent CN1103106A then utilizes phosphoric acid, phosphorous oxides and polar solvent to form removes the basic nitrogen in the lubricant base; U.S. Pat 4,137,154 have reported that the complexing of employing iron trichloride removes the method for nitrogenous compound in the oil product, Choi (Choi, H.W.and Dinest, M.B., " Selective removal of nitrogen compounds from shale oil ", Fuel, 64,4-8 (1985)) etc. developed a kind of method that adopts the complexing of dichloride copper to remove nitrogenous compound.Above patent all is to utilize acidity or polar liquid solvent to extract the basic nitrogen that removes in the oil product, because the viscosity of lubricant base is higher, two contact is difficult to fully acidity and polar solvent be removed from refined oil fully afterwards, cause denitrfying agent residual in oil product, the character of the refining back of influence oil product, acidizer also can produce serious corrosion to equipment simultaneously.Given this, both at home and abroad some software engineering researchers invent utilize solid adsorbent except that carclazyte to be lubricated the method for oily complexing denitrification refining, as Yuan Xuezhi (Yuan Xuezhi, " utilize the FCC spent catalyst to sneak into clay-filtered lubricating oil for machining base oil ", lubricating oil, 10,9 (1995)) adopt useless catalytic cracking catalyst to sneak into carclazyte and remove nitrogenous compound in the lubricating oil, but because the deamidization of spent catalyst is limited in one's ability, the denitrogenation degree of depth is not enough, is difficult to satisfy new oil quality requirement; U.S. Pat 4,846,962 have introduced the method that on qualitative or non-type molecular sieve load acidizer is used for petroleum product denitrification, but because the sorbent material manufacturing cost is higher, are difficult to generally apply industrial.
Summary of the invention
The object of the present invention is to provide a kind of nitric efficiency height, refining effect is good and cost is low solid supported type oil denitrification agent, i.e. modified argil as denitrifying agent and preparation method thereof.
The present invention is achieved in that
Modified argil as denitrifying agent consists of: modified argil as denitrifying agent consists of: acidizer A 5～55% (wt), complexing agent B 0.7～34% (wt), carclazyte 20～88.5% (wt), water 1～15% (wt).
Above-mentioned acidizer A is one or more a mixture of sulfuric acid, nitric acid, hydrochloric acid, the agent of phosphoric acid mineral acid, said complexing agent B is one or more the mixture in copper sulfate, ferric sulfate, titanium sulfate, iron trichloride, dichloride copper, titanium tetrachloride, cupric phosphate, cupric nitrate, Titanium Nitrate, iron nitrate, tertiary iron phosphate, the titanium phosphate, and carclazyte is natural clay or atlapulgite.
A kind of preparation method of modified argil as denitrifying agent, it is characterized in that: acidizer A and complexing agent B load on the carclazyte, form a solid denitrfying agent, wherein acidizer A is one or more a mixture of sulfuric acid, nitric acid, hydrochloric acid, the agent of phosphoric acid mineral acid, said complexing agent B is one or more the mixture in copper sulfate, ferric sulfate, titanium sulfate, iron trichloride, dichloride copper, titanium tetrachloride, cupric phosphate, cupric nitrate, Titanium Nitrate, iron nitrate, tertiary iron phosphate, the titanium phosphate, and carclazyte is natural clay or atlapulgite; Concrete step is:
A. complexing agent B is dissolved in the aqueous solution of pure A of acidizer or A, produces and contain A 1～52.5%, the solution of B 0.1～50%;
B. the solution that step a is made mixes stirring after 2～30 minutes with carclazyte at 10～100 ℃, depend on liquid-solid ratio, be higher than 2V/V as liquid-solid ratio, need after solid-liquid separation dry down at 50～350 ℃, it is then directly dry down at 50～350 ℃ to be lower than 2V/V as liquid-solid ratio, be 1-5 hour time of drying, evaporates moisture in the solution, obtains powdery or blocky solid product;
C. be 50～300 purpose coccoids with the prepared powdery of step b or blocky solid product through the granularity of pulverizing, obtain after the screening, modified argil as denitrifying agent.
The invention has the advantages that: this denitrfying agent nitric efficiency height, can adopt process device identical and close processing condition to be lubricated the advanced nitrogen of oily base oil with traditional lubrication oil white soil treating process, improve the anti-oxidative stability of lubricant base greatly, the carclazyte consumption can reduce 20-80%.And because acidizer loads on the solid carclazyte, do not enter in the refined oil, avoided the increase of oil product acid number and the corrosion of equipment, can use and subtract removing of four lines and frivolous wet goods high viscosity oil product neutral and alkali nitrogen.Adopt suitable process conditions, this denitrfying agent also can be used for other light-end products, as the denitrification refining of gasoline, kerosene, diesel oil, wax tailings and shale oil.Can significantly improve the oxidation stability of oil product, overcome the shortcoming of liquid denitrfying agent mixing with separation difficulty.
Concrete enforcement
Embodiment 1
30g atlapulgite and 5g ferric sulfate are pulverized and are mixed, 10g sulfuric acid and 10g water mix, aqueous sulfuric acid is joined in carclazyte and the ferric sulfate, mixed 30 minutes at 50 ℃, reach evenly, 120 ℃ of dryings 2 hours, be crushed to 80～100 orders, this modified argil as denitrifying agent contains the sulfuric acid of 20.1% (wt), the ferric sulfate of 10% (wt), the carclazyte of the moisture of 9.5% (wt) and 60.4% (wt).
1% this modified argil joins in certain factory's second line of distillation base oil, and basic nitrogen is taken off to 39ppm by 135ppm, and rotary oxygen bomb value (ROBT) is increased to 192min by 114min.
2% this modified argil joins certain factory and subtracts in the three-way base oil, and basic nitrogen is taken off to 29ppm by 160ppm, and rotary oxygen bomb value (ROBT) is increased to 197min by 89min.
2% this modified argil joins certain factory and subtracts in the four line base oils, and basic nitrogen is taken off to 74ppm by 456ppm, and rotary oxygen bomb value (ROBT) is increased to 144min by 80min
4% this modified argil joins in the frivolous oil of certain factory, and basic nitrogen is taken off to 143ppm by 531ppm, and rotary oxygen bomb value (ROBT) is increased to 180min by 67min
1% this modified argil joins in certain factory's catalytic cracking diesel oil, and basic nitrogen is taken off to 25.6 μ g/g by 330 μ g/g, and colourity reaches 4.5 behind the oil oxidation of refining back
Embodiment 2
25g carclazyte and 5g cupric chloride are pulverized and are mixed, 10g phosphoric acid and 5g water mix, phosphate aqueous solution is joined in carclazyte and the cupric chloride, mixed 20 minutes at 80 ℃, reach evenly, 200 ℃ of dryings 1 hour, be crushed to the 100-120 order, this modified argil as denitrifying agent contains the phosphoric acid of 23.75 (wt), the cupric chloride of 11.9% (wt), the carclazyte of the moisture of 5% (wt) and 59.4% (wt).
2% this modified argil joins in the frivolous oil of certain factory, and basic nitrogen is taken off to 443ppm by 531ppm, and rotary oxygen bomb value (ROBT) is increased to 118min by 67min.
Embodiment 3
25g carclazyte and 5g titanium chloride are pulverized and are mixed, 10g hydrochloric acid and 5g water mix, aqueous hydrochloric acid is joined in carclazyte and the titanium chloride, mixed 30 minutes at 50 ℃, it was even to reach uniform mixing, 100 ℃ of dryings 1 hour, be crushed to 100～120 orders, this modified argil as denitrifying agent contains the phosphoric acid of 23% (wt), the titanium chloride of 11.5% (wt), the carclazyte of the moisture of 8% (wt) and 57.5% (wt).
2% this modified argil joins certain factory and subtracts in the four line base oils, and basic nitrogen is taken off to 95ppm by 456ppm, and rotary oxygen bomb value (ROBT) is increased to 148min by 80min
4% this modified argil joins in the frivolous oil of certain factory, and basic nitrogen is taken off to 164ppm by 531ppm, and rotary oxygen bomb value (ROBT) is increased to 167min by 67min
Embodiment 4
27g atlapulgite and 20g Titanium Nitrate are pulverized and are mixed, 2g nitric acid and 15g water mix, aqueous nitric acid is joined in carclazyte and the Titanium Nitrate, mixed 30 minutes at 50 ℃, reach and mix, 50 ℃ of dryings 1 hour, be crushed to 50～80 orders, this modified argil as denitrifying agent contains the nitric acid of 5.1% (wt), the Titanium Nitrate of 34.2% (wt), the carclazyte of the moisture of 14.5% (wt) and 46.1% (wt).
4% this modified argil joins in certain factory's second line of distillation base oil, and basic nitrogen is taken off to 65ppm by 135ppm, and rotary oxygen bomb value (ROBT) is increased to 178min by 114min
4% this modified argil joins in certain factory's catalytic cracking diesel oil, and basic nitrogen is taken off to 95.6 μ g/g by 330 μ g/g, and colourity reaches 5.5 behind the oil oxidation of refining back
Embodiment 5
30g atlapulgite and 0.5g ferric sulfate mix, 35g sulfuric acid and 5g water mix, aqueous sulfuric acid is joined in carclazyte and the ferric sulfate, mixed 30 minutes at 100 ℃, reach and mix, 350 ℃ of dryings 1 hour, be crushed to 200～300 orders, this modified argil as denitrifying agent contains the sulfuric acid of 52.5% (wt), the ferric sulfate of 0.7% (wt), the carclazyte of the moisture of 1.7% (wt) and 44.9% (wt).
1% this modified argil joins in certain factory's second line of distillation base oil, and basic nitrogen is taken off to 16ppm by 135ppm, and rotary oxygen bomb value (ROBT) is increased to 210min by 114min
2% this modified argil joins certain factory and subtracts in the four line base oils, and basic nitrogen is taken off to 54ppm by 456ppm, and rotary oxygen bomb value (ROBT) is increased to 174min by 80min
3% this modified argil joins in the frivolous oil of certain factory, and basic nitrogen is taken off to 97ppm by 531ppm, and rotary oxygen bomb value (ROBT) is increased to 190min by 67min
1% this modified argil joins in certain factory's catalytic cracking diesel oil, and basic nitrogen is taken off to 16 μ g/g by 330 μ g/g, and colourity reaches 4 behind the oil oxidation of refining back
Embodiment 6
20g atlapulgite and 5g ferric sulfate mix, 15g sulfuric acid and 40g water mix, aqueous sulfuric acid is joined in carclazyte and the ferric sulfate, mixed 30 minutes at 80 ℃, filter then, 150 ℃ of dryings 1 hour, be crushed to 50～80 orders, this modified argil as denitrifying agent contains the sulfuric acid of 5.8% (wt), the ferric sulfate of 1.5% (wt), the carclazyte of the moisture of 4.2% (wt) and 88.5% (wt).
2% this modified argil joins certain factory and subtracts in the four line base oils, and basic nitrogen is taken off to 104ppm by 456ppm, and rotary oxygen bomb value (ROBT) is increased to 156min by 80min
4% this modified argil joins in the frivolous oil of certain factory, and basic nitrogen is taken off to 132ppm by 531ppm, and rotary oxygen bomb value (ROBT) is increased to 168min by 67min
1% this modified argil joins in certain factory's catalytic cracking diesel oil, and basic nitrogen is taken off to 56 μ g/g by 330 μ g/g, and colourity reaches 4.5 behind the oil oxidation of refining back.
Claims (2)
1. the preparation method of a modified argil as denitrifying agent, it is characterized in that: acidizer A and complexing agent B load on the carclazyte, form a solid denitrfying agent, wherein acidizer A is one or more a mixture of sulfuric acid, nitric acid, hydrochloric acid, the agent of phosphoric acid mineral acid, said complexing agent B is one or more the mixture in copper sulfate, ferric sulfate, titanium sulfate, iron trichloride, dichloride copper, titanium tetrachloride, cupric phosphate, cupric nitrate, Titanium Nitrate, iron nitrate, tertiary iron phosphate, the titanium phosphate, and carclazyte is natural clay or atlapulgite; Concrete step is:
A. complexing agent B is dissolved in the aqueous solution of pure A of acidizer or A, produces and contain A 1～52.5%, the solution of B 0.1～50%;
B. the solution that step a is made mixes stirring after 2～30 minutes with carclazyte at 10～100 ℃, depend on liquid-solid ratio, be higher than 2V/V as liquid-solid ratio, need after solid-liquid separation dry down at 50～350 ℃, it is then directly dry down at 50～350 ℃ to be lower than 2V/V as liquid-solid ratio, be 1-5 hour time of drying, evaporates moisture in the solution, obtains powdery or blocky solid product;
C. be 50～300 purpose coccoids with the prepared powdery of step b or blocky solid product through the granularity of pulverizing, obtain after the screening, its component is acidizer A 5～55%wt, complexing agent B 0.7～34%wt, carclazyte 20～88.5%wt, the modified argil as denitrifying agent of water 1～15%wt.
2. modified argil as denitrifying agent, it is characterized in that: modified argil as denitrifying agent consists of: acidizer A 5～55%wt, complexing agent B 0.7～34%wt, carclazyte 20～88.5%wt, water 1～15%wt, described acidizer A is a sulfuric acid, nitric acid, hydrochloric acid, the mixture of one or more of phosphoric acid mineral acid agent, said complexing agent B is a copper sulfate, ferric sulfate, titanium sulfate, iron trichloride, dichloride copper, titanium tetrachloride, cupric phosphate, cupric nitrate, Titanium Nitrate, iron nitrate, tertiary iron phosphate, the mixture of one or more in the titanium phosphate, carclazyte are natural clay or atlapulgite.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB001302833A CN1155682C (en) | 2000-11-03 | 2000-11-03 | Modified argil as denitrifying agent and its preparing process |
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| CNB001302833A CN1155682C (en) | 2000-11-03 | 2000-11-03 | Modified argil as denitrifying agent and its preparing process |
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| CN1155682C true CN1155682C (en) | 2004-06-30 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967389A (en) * | 2010-10-27 | 2011-02-09 | 大庆油田有限责任公司 | Denitrifying agent for directly removing basic nitrogen compound from shale oil |
| CN102021014A (en) * | 2009-09-15 | 2011-04-20 | 中国石油天然气股份有限公司 | Method for removing alkali nitrogen from inferior diesel oil |
| CN104560124A (en) * | 2014-11-04 | 2015-04-29 | 华文蔚 | Fuel deep denitrification method for automobile industry |
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| CN102041034B (en) * | 2009-10-23 | 2013-08-21 | 中国石油化工股份有限公司 | Method for reducing neutralization value of base oil |
| CN102559252B (en) * | 2012-03-07 | 2013-10-09 | 抚顺石化北天集团众兴公司鸿远达精细化工厂 | Non-hydrodenitrogeneration method for catalytically cracked gasoline |
| CN103540339B (en) * | 2013-10-21 | 2015-10-28 | 中国石油化工股份有限公司 | A kind of lube stock process for purification that effectively can reduce base oil acid number |
| CN104694161A (en) * | 2015-03-10 | 2015-06-10 | 辽宁石油化工大学 | Method for improving oxidation stability of shale diesel oil |
| CN108641744B (en) * | 2018-05-11 | 2021-07-06 | 金浦新材料股份有限公司 | Denitrifying agent for denitrifying petroleum products, and preparation method and application thereof |
| CN114471451A (en) * | 2020-10-23 | 2022-05-13 | 华东理工大学 | Preparation method and application of adsorbent for removing basic nitride from lubricating oil base oil |
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2000
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021014A (en) * | 2009-09-15 | 2011-04-20 | 中国石油天然气股份有限公司 | Method for removing alkali nitrogen from inferior diesel oil |
| CN101967389A (en) * | 2010-10-27 | 2011-02-09 | 大庆油田有限责任公司 | Denitrifying agent for directly removing basic nitrogen compound from shale oil |
| CN104560124A (en) * | 2014-11-04 | 2015-04-29 | 华文蔚 | Fuel deep denitrification method for automobile industry |
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| Publication number | Publication date |
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| CN1353167A (en) | 2002-06-12 |
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