阅读说明：本技术 一种含磷酸的萃取液脱除燃料油中氮化物的方法 (Method for removing nitride in fuel oil by extraction liquid containing phosphoric acid ) 是由 蒋成祥 于 2019-10-08 设计创作，主要内容包括：本发明公开了一种含磷酸的萃取液脱除燃料油中氮化物的方法,包括以下步骤：取磷酸、硫酸、磺酸、的亚磺酸和硫羧酸放入玻璃容器中,在常温下缓慢搅拌3min得到萃取液；S2、取适量页岩油放于反应釜中,加入易混合的非极性稀释液,搅拌10min后静置30min,再调至反应釜温度为50～60℃,对页岩油进行加热直至页岩油呈流动态,来降低页岩油的黏度,所得的作为脱氮的原料油；S3、取适量原料油与萃取液按质量1：15混合,放在恒温水浴中,稳定在50℃,均匀的磁力搅拌30min,静置沉淀分层,待完全冷却后液液分离,得到脱氮燃油和萃取相,用微库伦仪测定脱氮燃油中剩余氮含量,萃取相减压蒸馏后得到再生的萃取液循环使用；本发明脱氮效果好、设备简单、精制油收率高。(the invention discloses a method for removing nitride in fuel oil by extraction liquid containing phosphoric acid, which comprises the following steps: putting phosphoric acid, sulfuric acid, sulfonic acid, sulfinic acid and thiocarboxylic acid into a glass container, and slowly stirring at normal temperature for 3min to obtain an extract liquid; s2, placing a proper amount of shale oil into a reaction kettle, adding easily-mixed nonpolar diluent, stirring for 10min, standing for 30min, adjusting the temperature of the reaction kettle to 50-60 ℃, heating the shale oil until the shale oil is in a flowing state to reduce the viscosity of the shale oil, and obtaining the raw material oil serving as denitrification; s3, taking a proper amount of raw oil and an extracting solution according to the mass ratio of 1: 15 mixing, placing in a constant-temperature water bath, stabilizing at 50 ℃, uniformly and magnetically stirring for 30min, standing, precipitating and layering, performing liquid-liquid separation after complete cooling to obtain denitrified fuel oil and an extract phase, measuring the residual nitrogen content in the denitrified fuel oil by using a micro coulometer, and performing reduced pressure distillation on the extract phase to obtain regenerated extract liquid for recycling; the invention has good denitrification effect, simple equipment and high refined oil yield.)

1. A method for removing nitride in fuel oil by extraction liquid containing phosphoric acid is characterized in that: the method comprises the following steps:

S1, taking phosphoric acid, sulfuric acid, sulfonic acid, sulfinic acid and thiocarboxylic acid, putting into a glass container, and slowly stirring at normal temperature for 3min to obtain an extract liquid;

S2, placing a proper amount of shale oil into a reaction kettle, adding easily-mixed nonpolar diluent, stirring for 10min, standing for 30min, adjusting the temperature of the reaction kettle to 50-60 ℃, heating the shale oil until the shale oil is in a flowing state to reduce the viscosity of the shale oil, and obtaining the raw material oil serving as denitrification;

S3, taking a proper amount of raw oil and an extracting solution according to the mass ratio of 1: 15, placing the mixture in a constant-temperature water bath, stabilizing the mixture at 50 ℃, uniformly and magnetically stirring the mixture for 30min, standing the mixture, settling the mixture for layering, performing liquid-liquid separation after complete cooling to obtain denitrified fuel oil and an extract phase, measuring the content of residual nitrogen in the denitrified fuel oil by using a micro coulometer, and performing reduced pressure distillation on the extract phase to obtain regenerated extract for recycling.

2. The method for removing the nitride in the fuel oil by the extract liquid containing the phosphoric acid as claimed in claim 1, which is characterized in that: the extract composition included 50% phosphoric acid, 20% sulfuric acid, 10% sulfonic acid, 10% sulfinic acid, and 10% thiocarboxylic acid.

3. The method for removing the nitride in the fuel oil by the extract liquid containing the phosphoric acid as claimed in claim 1, which is characterized in that: the nonpolar diluent is low molecular weight alkane, low molecular weight aromatic hydrocarbon, ether or halohydrocarbon.

4. the method for removing the nitride in the fuel oil by the extract liquid containing the phosphoric acid as claimed in claim 1, which is characterized in that: when the extract liquid is mixed with raw oil, the contact temperature of the raw oil is 50-60 ℃.

5. the method for removing the nitride in the fuel oil by the extract liquid containing the phosphoric acid as claimed in claim 1, which is characterized in that: the mixing ratio of the raw oil to the extract is 1: 15, the temperature of the thermostatic waterbath is stabilized at 50 ℃, and the mixture is magnetically stirred for 30 min.

6. The method for removing the nitride in the fuel oil by the extract liquid containing the phosphoric acid as claimed in claim 1, which is characterized in that: and in the step S3, the raw oil and the extract liquid are mixed and magnetically stirred, and then are kept stand for 2.5 hours.

7. The method for removing the nitride in the fuel oil by the extract liquid containing the phosphoric acid as claimed in claim 1, which is characterized in that: the regeneration temperature of the extraction phase reduced pressure distillation in the step S3 is 100-150 ℃, the vacuum degree is-0.1 to-0.2 MPa, and the regeneration time is 1 to 4 hours.

8. The method for removing the nitride in the fuel oil by the extract liquid containing the phosphoric acid as claimed in claim 1, which is characterized in that: the content of the nitride is measured by adopting a WK-3 micro coulometer.

Technical Field

The invention belongs to the technical field of oil product denitrification, and particularly relates to a method for removing nitrides in fuel oil by using phosphoric acid-containing extract liquor.

Background

shale oil is used as a supplement to conventional energy, is an important component of energy industry, has profound influence and important significance on the continuous and stable development of human society, and most shale oil is burnt as boiler fuel after rough processing, which causes extreme waste of resources. The main reason is that shale oil contains more nitrogen-containing heterocyclic non-hydrocarbon compounds than conventional petroleum, and colloid and sediment are easily formed, so that the color of the oil product is blackened and the stability of the oil product is deteriorated. The hydrogenation method has complex equipment, needs additional hydrogen production, has larger energy consumption, and is not suitable for small and medium enterprises due to too high investment. The non-hydrodenitrogenation method also has the disadvantages of high energy consumption, low refined oil yield and the like, so that a method with low energy consumption and high refined oil yield is needed for the denitrification of shale oil.

Disclosure of Invention

The invention mainly solves the technical problem of providing the method for removing the nitride in the fuel oil by the extraction liquid containing phosphoric acid, and has good denitrification effect, simple equipment and high refined oil yield.

in order to solve the technical problems, the invention adopts a technical scheme that a method for removing nitride in fuel oil by using phosphoric acid-containing extract liquor is provided, which comprises the following steps:

S1, taking phosphoric acid, sulfuric acid, sulfonic acid, sulfinic acid and thiocarboxylic acid, putting into a glass container, and slowly stirring at normal temperature for 3min to obtain an extract liquid;

S2, placing a proper amount of shale oil into a reaction kettle, adding easily-mixed nonpolar diluent, stirring for 10min, standing for 30min, adjusting the temperature of the reaction kettle to 50-60 ℃, heating the shale oil until the shale oil is in a flowing state to reduce the viscosity of the shale oil, and obtaining the raw material oil serving as denitrification;

S3, taking a proper amount of raw oil and an extracting solution according to the mass ratio of 1: 15, placing the mixture in a constant-temperature water bath, stabilizing the mixture at 50 ℃, uniformly and magnetically stirring the mixture for 30min, standing the mixture, settling the mixture for layering, performing liquid-liquid separation after complete cooling to obtain denitrified fuel oil and an extract phase, measuring the content of residual nitrogen in the denitrified fuel oil by using a micro coulometer, and performing reduced pressure distillation on the extract phase to obtain regenerated extract for recycling.

Further, the composition of the extract comprises 50% phosphoric acid, 20% sulfuric acid, 10% sulfonic acid, 10% sulfinic acid and 10% thiocarboxylic acid.

further, the nonpolar diluent is low molecular weight alkane, low molecular weight aromatic hydrocarbon, ether or halohydrocarbon.

Further, when the extract is mixed with a feedstock oil, the contact temperature of the feedstock oil is 50 to 60 ℃.

Further, the mixing ratio of the raw oil to the extract is 1: 15, the temperature of the thermostatic waterbath is stabilized at 50 ℃, and the mixture is magnetically stirred for 30 min.

In step S3, the raw oil and the extract are mixed and magnetically stirred, and then left to stand for 2.5 hours.

Further, the regeneration temperature of the vacuum distillation of the extract phase in the step S3 is 100-150 ℃, the vacuum degree is-0.1 to-0.2 MPa, and the regeneration time is 1-4 h.

Further, the content of the nitride is measured by a WK-3 micro coulometer.

the invention has the beneficial effects that: the method for removing the nitride in the fuel oil is simple, the denitrification industrial material is economical, the equipment is simple, the denitrification effect is good, the yield of the refined oil is high, and the industrial application prospect is very wide;

And the desulfurization cost is low, the stability is good, almost no residue exists in the oil product, and the repeated utilization rate is high.

Detailed Description

The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention, and to clearly and unequivocally define the scope of the present invention.