CN105112096B - Method of applying insulin to coking diesel oil desulfurization - Google Patents

Abstract

The invention discloses a method for applying insulin to desulfurization of coking diesel oil, which comprises the following steps: (1) adding medicinal dried hawthorn powder or hawthorn water to coking diesel oil, heating and stirring in a magnetic stirrer, reacting for 60-100min, taking out and cooling to room temperature; (2) adding insulin to the coked diesel oil obtained in step (1) according to the mass volume ratio of 0.05-1:1, and then placing it in a constant temperature water bath environment and heating and stirring at a constant temperature for 1-24 hours; (3) mixing the catalyst and The oxidizing agent is added to the coked diesel successively, and the catalytic oxidation reaction is carried out in a magnetic stirrer for 50‑100 min; (4) after cooling to room temperature, the extraction agent is added in a volume ratio of 1:1, stirred with a magnetic stirrer for 5‑10 min, and then poured Put it into a separatory funnel, let it stand for 20min, and collect the diesel layer. The method of the invention has mild desulfurization and refining reaction conditions, environmental protection, high desulfurization rate, significant yield of coked diesel oil and light color and light taste.

Description

Method of Insulin Applied to Desulfurization of Coked Diesel Oil

technical field

The invention relates to desulfurization technology of coked diesel oil, in particular to a method for desulfurizing coked diesel oil with high desulfurization rate.

Background technique

With the enhancement of people's awareness of environmental protection, people have increasingly strict requirements on the sulfur content of fuel oil. All countries in the world have formulated stricter new regulations on the sulfur content in fuel oil. In 2006, the United States stipulated that the sulfur content of diesel oil should be reduced from 500 μg/g to 15 μg/g; while Europe has implemented the Euro V standard with a sulfur content of 10 μg/g in 2009; Japan is an advanced country that produces clean gasoline, and the JISK 2202 gasoline standard implemented According to regulations, in 2005, the sulfur content of gasoline in Japan was limited to 50ppm, and in 2009, the ultra-low sulfur gasoline standard with a sulfur content of 10ppm was uniformly implemented nationwide. In my country, diesel and gasoline for vehicles have fully implemented European quality standards since July 1, 2005, and have all reached the standards in 2010. It is stipulated that the sulfur content in gasoline is less than 150 μg/g, and the sulfur content in diesel oil is less than 350 μg/g. Some first-tier cities such as Beijing, Shanghai, and Guangzhou implement European Standard IV, which stipulates that the sulfur content in gasoline and diesel should be less than 50 μg/g. At present, the latest "National V" standard reduces the sulfur content index limit from 50ppm in the fourth stage to 10ppm, a reduction of 80%. It has been implemented in Beijing and Shanghai. Before the end of 2017, the national supply will meet the "National V" standard Gasoline and diesel for vehicles. Therefore, it can be said that domestic vehicle fuels will enter a low-sulfur era with a sulfur content of less than 50 μg/g. Faced with the increasingly stringent fuel oil sulfur content standards and the huge market demand for low-sulfur clean fuel oil, countries have devoted themselves to the research of various desulfurization technologies.

With the deepening of petroleum processing technology, an important deep processing method of residual oil is coking. At present, there are two main methods: kettle coking and delayed coking. Coked diesel oil is the product obtained through the coking process of residual oil. Coking diesel oil occupies a considerable proportion in my country's finished diesel output, accounting for about 10% of light diesel output. Unrefined coked diesel oil is of poor quality, containing a large amount of unsaturated hydrocarbons, more sulfur, nitrogen, oxygen and other non-hydrocarbon compounds, which is black and smelly, and the diesel oil has poor stability, high colloid content, chroma and insoluble content is higher. A large number of analysis studies have shown that the sulfur-containing compounds in coking diesel mainly include elemental sulfur, hydrogen sulfide, mercaptans, sulfides, thiophenes, benzothiophene (BT), dibenzothiophene (DBT) and so on. Among them, thiophene sulfur compounds account for more than 85% of the total sulfur in coked diesel, while BT and DBT account for more than 70% of thiophenes. Therefore, research on the removal of thiophene sulfides has become the focus of oil desulfurization. Among them, elemental sulfur, hydrogen sulfide, mercaptan and other active sulfur compounds have a strong corrosion and damage effect on oil refining equipment. Elemental sulfur is a solid with a melting point of 113°C, which is insoluble in water but soluble in organic solvents. It has good solubility in gasoline, but when the temperature is higher than 115°C, it can react with certain hydrocarbons to form new sulfides And hydrogen sulfide, hydrogen sulfide is a colorless gas with the smell of rotten eggs, highly toxic, slightly soluble in water, easily soluble in oil, has strong reducing ability and corrosion ability, and the hydrogen sulfuric acid formed in water is weak Elemental acid. Mercaptans include alkyl mercaptans, naphthenic mercaptans and aryl mercaptans. Their boiling point and water solubility are lower than those of alcohols with the same carbon number, and they are easily soluble in ethanol and ether. In addition to the disgusting stench, mercaptan is also an oxidation inducer, which accelerates the oxidation of unstable components in gasoline to form gums, thereby deteriorating the quality of gasoline. Although inactive sulfur compounds such as sulfide and thiophene are less corrosive to refinery equipment, they will generate highly corrosive substances during combustion. Disulfides and polysulfides are characterized by decreasing stability and increasing chemical activity as the number of sulfur atoms increases. When the number of sulfur atoms is more than 3, its properties are similar to those of elemental sulfur. When heated, it is easily decomposed into sulfides, elemental sulfur, mercaptans and olefins. The direct use of these diesel oils not only does not comply with my country's regulations on the sulfur content in fuel oil, but also seriously pollutes the environment and seriously threatens human health. Therefore, coked diesel must be refined before use.

At present, the desulfurization technologies of fuel oil at home and abroad are mainly divided into two categories: hydrodesulfurization technology and non-hydrogenation desulfurization technology. Hydrodesulfurization technology produces low-sulfur diesel oil, which can greatly reduce the content of sulfur, nitrogen and colloid in coked diesel oil. The desulfurization effect is good, and high-quality diesel oil that meets national standards can be obtained. However, due to large investment and high processing costs (180 yuan/t), it is generally only widely used in large-scale refineries, while small and medium-sized refineries not only have limited funds, but also hydrogen sources. Insufficient, which limits the application of this method in small and medium refineries. Diesel non-hydrogenation desulfurization technologies mainly include adsorption desulfurization, extraction desulfurization, complexation desulfurization, biological desulfurization, oxidation desulfurization, etc. The fuel oil treated by the traditional acid-alkali refining method is difficult to meet the new low-sulfur standard, and the process itself has problems such as pollution and serious corrosion; because the biological desulfurization technology has not been well resolved in terms of desulfurization speed and stability Therefore, biological desulfurization has not yet shown its obvious advantages; catalytic oxidation desulfurization technology is very popular with small and medium-sized refineries because of its mild operating conditions and low production costs. Therefore, it is imperative to conduct research on new technologies for desulfurization of coked diesel oil and develop a new method for refining coked diesel oil without hydrodesulfurization.

Among them, oxidative desulfurization (ODS) technology has mild reaction conditions, simple process, non-hydrogen operation, low operating cost, safety and environmental protection, low equipment investment, and high desulfurization efficiency for dibenzothiophene compounds that are difficult to remove by catalytic hydrogenation , can meet the requirements of ultra-deep desulfurization, so the oxidation method is called a green desulfurization process facing the 21st century, and has become a new research hotspot in recent years. Oxidative desulfurization means that under the action of a strong oxidant, the less polar sulfide and thiophene sulfur-containing compounds in the oil are oxidized into more polar sulfoxide and sulfone compounds, and these sulfides absorb oxygen atoms to increase the coupling capacity. polar moment, thereby increasing the solubility in polar solvents, and then removing it by solvent extraction to achieve the purpose of desulfurization. At present, selective oxidation desulfurization technology has attracted great attention from the oil refining industry due to its mild process conditions and obvious desulfurization effect.

The oxidants currently used in the catalytic oxidation process of coked diesel mainly include hydrogen peroxide, O ₃ , air, oil-soluble oxidants, etc.; use organic acids, inorganic heteropolyacids, light or metal oxides as catalysts; in order to improve desulfurization efficiency, also Combining some auxiliary means for oxidative desulfurization, such as ultrasonic oxidation, plasma oxidation, etc. The commonly used extractants in the process of extracting and removing the sulfone and sulfoxide generated by the oxidation of sulfide in diesel oil mainly include dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone (NMP), N,N-dimethyl Formamide (DMF), furfural, nitromethane, ethylenediamine, etc. Studies have shown that these organic solvents are similar in polarity to sulfones, and can be well extracted and separated from sulfones in oxidized diesel oil. At present, the oxidative desulfurization technologies widely studied at home and abroad mainly include _hydrogen peroxide oxidative desulfurization, oxygen catalytic oxidative desulfurization, ultrasonic oxidative desulfurization and photochemical oxidative desulfurization, among which _H2O2 has the advantages of strong oxidizing property and no harm to the environment due to oxidative decomposition products. It has attracted much attention and is widely used in oxidation desulfurization research.

In recent years, fuel oil non-hydrogenation desulfurization technology has developed rapidly. This method is to oxidize and remove sulfur compounds such as sulfides, mercaptans and thiophenes in coked diesel oil under the condition of catalysts, and produce excellent desulfurization effects, thereby achieving decolorization and deodorization. , Slag removal, thereby improving the stability of diesel oil, coupled with mild operating conditions, low production costs, and environmentally friendly production processes, have attracted more and more attention from researchers at home and abroad.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for desulfurization of coked diesel oil with mild desulfurization and refining reaction conditions, environmental protection, high desulfurization rate, significant yield of coked diesel oil, light color and light taste insulin.

The present invention adopts following technical scheme to solve the above-mentioned technical problems:

The method that insulin is applied to the desulfurization of coked diesel oil comprises the following steps:

(1) Add medicinal dried hawthorn powder or hawthorn water into coking diesel oil at 0.2-0.8g/ml, heat and stir with a magnetic stirrer, the temperature is 40°C-100°C, the stirring speed is 20rpm, and the reaction is 60- 100min, then take it out and cool to room temperature;

(2) Add insulin to the coked diesel oil obtained in step (1), and then place it in a constant temperature water bath environment to heat and stir at a constant temperature, the temperature is 36.5°C-38°C, heat reaction for 1-24 hours, and the stirring speed is 20-40rpm ; The insulin is insulin powder for injection or insulin for injection, the amount of insulin for injection powder is 0.01-0.10mg/ml; the volume ratio of insulin for injection and coker diesel is 2:100-5:100;

(3), catalyzer and oxidizing agent are successively added in the coked diesel oil after step (2) process, and catalyzer is trichloroacetic acid or formic acid, and oxidizing agent is the hydrogen peroxide solution that mass concentration is 30%; Coked diesel oil, catalyzer and oxidizing agent The volume ratio is 10:2:1-10:4:4, the catalytic oxidation reaction is carried out in a magnetic stirrer, the reaction time is 50-100min, the temperature is 50°C-80°C, and the stirring speed is 40rpm;

(4), after the coked diesel oil obtained in step (3) is cooled to room temperature, an extractant is added in a volume ratio of 1:1, and the extractant is N, N-dimethylformamide or furfural, stirred with a magnetic stirrer for 5-10min, Stirring speed is 40rpm, then pour into a separatory funnel, let it stand for 20min, and collect the diesel oil layer.

The hawthorn water in the step (1) is the hawthorn water obtained after adding 300ml/g of medicinal dried hawthorn to water and decocting it for 2 hours.

The magnetic stirrer in the step (1) and the step (3) all adopts DF-101S instantaneous heating type constant temperature heating magnetic stirrer.

The step (2) adopts a constant temperature water bath magnetic stirrer with a power of 40w.

Compared with the prior art, the present invention has the advantages of:

1. The process flow is simple, and the operation is simple and easy;

2. The method is applied to desulfurization and refining of coking diesel oil. The reaction conditions are mild, green and environmentally friendly, the desulfurization rate is high, and the yield of clear and transparent light yellow diesel oil is remarkable.

detailed description

The present invention will be described in detail below in conjunction with specific embodiments, but it is not intended to limit the protection scope of the claims of the present invention.

Example 1:

Hawthorn is a commonly used Chinese medicinal material, also known as Shanliguo and Shanlihong, a small deciduous tree in the Rosaceae family. Its fruit contains chemical components such as flavonoids, flavans, triterpenoids and organic acids, among which hyperin and ursolic acid are The main components of flavonoids and triterpenoids are the active components of hawthorn for lipid-lowering. Hawthorn contains a lot of fruit acid, maslinic acid, citric acid, lipase and lipase, which can promote fat decomposition and degrade cholesterol and triglyceride. In addition, it also contains organic amine chemical components such as choline and acetylcholine, which are also effective components for lowering fat.

Weigh 2g of medicinal dried hawthorn powder and add it to 10ml of coked diesel oil, put them together into a beaker, and use DF-101S instant heating constant temperature heating magnetic stirrer, the temperature is 40°C, the stirring speed is 20rpm, react for 60min, and then take it out Cool to room temperature. Add the injection-like insulin to the coked diesel oil at room temperature at a volume ratio of 2:100; then place it in a constant temperature water bath environment and heat and stir at a constant temperature. The heating temperature is 36.5°C, and the reaction is heated for 1 hour. The power of the constant temperature magnetic stirrer is 40w , rotating speed is 20rpm; Catalyst and oxidant are successively added in the coked diesel oil, and catalyzer is trichloroacetic acid, and oxidant is the hydrogen peroxide solution that mass concentration is 30%; Coked diesel oil, catalyzer and oxidant volume ratio are 10: 2: 1, Then use the DF-101S collector type constant temperature heating magnetic stirrer to carry out the catalytic oxidation reaction, the reaction time is 50min, the heating temperature is 50°C, and the stirring speed is 40rpm; then, take out the coked diesel oil and cool it to room temperature, and then add the extractant N, N-dimethylformamide, the volume ratio of extractant and coked diesel oil is 1: 1, stir with a magnetic stirrer for 5min, the stirring speed is 40rpm, then pour into a separatory funnel, let stand for 20min, collect the diesel oil layer, And measure its volume to obtain the yield of diesel oil; the sulfur content of the collected diesel oil is measured by Sinie7039XR single-wavelength X fluorescent sulfur analyzer to be 0.00634%, the extraction desulfurization rate is 97.70%, and the diesel yield is 80%.

Example 2:

Weigh 4g of medicinal dried hawthorn powder and add it to 10ml of coked diesel oil, put them together into a beaker, and use DF-101S instant heating constant temperature heating magnetic stirrer, the temperature is 60°C, the stirring speed is 20rpm, react for 80min, and then take it out Cool to room temperature. Add 0.05 mg/ml of insulin powder for injection at room temperature to the coked diesel oil; then place it in a constant temperature water bath environment, heat and stir at a constant temperature, the heating temperature is 37°C, and the reaction is heated for 15 hours, using a constant temperature magnetic stirrer The power is 40w, and the rotating speed is 30rpm; Catalyst and oxidant are successively added in the coked diesel oil, and catalyzer is formic acid, and oxidant is the hydrogen peroxide solution that mass concentration is 30%; Coked diesel oil, catalyzer and oxidant volume ratio are 10: 2.5: 2. Then use the DF-101S collector type constant temperature heating magnetic stirrer to carry out the stirring and catalytic oxidation reaction. The reaction time is 70min, the heating temperature is 60°C, and the stirring speed is 40rpm; take out the coked diesel oil and cool it to room temperature, and then add the extraction Furfural, the volume ratio of extractant and coked diesel oil is 1:1, and then stirred with a magnetic stirrer for 7min at a stirring speed of 40rpm, then poured into a separatory funnel, allowed to stand for 20min, collected diesel oil layer, and measured its volume, obtained Diesel yield: the collected diesel oil was measured with a Sinie7039XR single-wavelength X-fluorescence sulfur analyzer to have a sulfur content of 0.00585%, an extractive desulfurization rate of 98.19%, and a diesel yield of 82%.

Example 3:

Add water at 300ml/g to medicinal dried hawthorn and decoct for 2 hours to obtain hawthorn water. Add 6g of hawthorn water to 10ml of coked diesel oil, put them together in a beaker, and use DF-101S instant heating constant temperature magnetic stirrer, The temperature was 80°C, the stirring speed was 20 rpm, and the reaction was carried out for 90 minutes, and then it was taken out and cooled to room temperature. Add 0.08 mg/ml powdered insulin for injection at room temperature to the coked diesel oil; then place it in a constant temperature water bath and heat and stir at a constant temperature. The heating temperature is 37.5°C and the reaction is heated for 20 hours. The power is 40w, and the rotating speed is 35rpm; Catalyst and oxidant are successively added in the coked diesel oil, and catalyzer is trichloroacetic acid, and oxidant is the hydrogen peroxide solution that mass concentration is 30%; Coked diesel oil, catalyzer and oxidant volume ratio are 10: 3:3, and then use the DF-101S collector type constant temperature heating magnetic stirrer to carry out the stirring catalytic oxidation reaction, the reaction time is 90min, the heating temperature is 70°C, and the stirring speed is 40rpm; then, take out the coked diesel oil and cool it to room temperature , then add the extractant N, N-dimethylformamide, the volume ratio of the extractant to coking diesel oil is 1:1, then stir with a magnetic stirrer for 8min at a stirring speed of 40rpm, then pour into a separatory funnel, and statically Put 20min, collect diesel oil layer, and measure its volume, obtain diesel oil yield, measure its sulfur content with the Sinie7039XR single-wavelength X fluorescent sulfur analyzer of collecting diesel oil to be 0.00463%, extraction desulfurization rate is 98.68%, and diesel oil yield is 85% %.

Example 4:

Weigh 8g of medicinal dried hawthorn powder and add it to 10ml of coked diesel oil, put them together in a beaker, and use DF-101S instant heating constant temperature heating magnetic stirrer, the temperature is 100°C, the stirring speed is 20rpm, react for 100min, and then take it out Cool to room temperature. Add injection-like insulin to coked diesel oil at a volume ratio of 5:100 at room temperature; then place it in a constant temperature water bath environment and heat and stir at a constant temperature. The heating temperature is 38°C, and the reaction is heated for 24 hours. The power of the constant temperature magnetic stirrer is 40w , rotating speed is 40rpm; Catalyst and oxidizing agent are successively added in coking diesel oil, and catalyzer is formic acid, and oxidizing agent is the hydrogen peroxide solution that mass concentration is 30%; Coking diesel oil, catalyst and oxidizing agent volume ratio are 10:4:4,, oxidation The temperature is 80°C, the stirring speed is 40rpm, and then the catalytic oxidation reaction is carried out in the DF-101S collector type constant temperature heating magnetic stirrer. The reaction time is 100min, and the heating temperature is 80°C; take out the coked diesel oil and cool it to room temperature, and then add Extracting agent furfural, the volume ratio of extracting agent and coking diesel oil is 1:1, then stir with a magnetic stirrer for 10min at a stirring speed of 40rpm, then pour into a separatory funnel, let stand for 20min, collect the diesel oil layer, and measure its volume, to obtain the yield of diesel oil, the collected diesel oil is measured with a Sinie7039XR single-wavelength X fluorescent sulfur analyzer to have a sulfur content of 0.00402%, an extraction desulfurization rate of 99.29%, and a diesel yield of 87%.

Claims (3)

1. insulin is applied to the method for coker gas oil desulfurization it is characterised in that comprising the following steps:

(1), by 0.2 0.8g/ml, medicinal dry hawthorn fruit or Fructus Crataegi water are added in coker gas oil, with magnetic stirring apparatuss plus Heat simultaneously stirs, and temperature is 40 DEG C 100 DEG C, and speed of agitator is 20rpm, reacts 60 100min, then takes out and be cooled to room temperature；

(2), insulin is added in the coker gas oil of step (1) gained, is subsequently placed in heated at constant temperature in water bath with thermostatic control environment Stirring, temperature is 36.5 DEG C 38 DEG C, reacting by heating 1 24 hours, and speed of agitator is 20 40rpm；Described insulin is note Penetrate with injectable powder insulin or injection shape insulin, the addition of powder ampoule agent for injection insulin is 0.01 0.10mg/ml； Injection shape insulin is 2:100 5:100 with the volume ratio of coker gas oil；

(3), catalyst and oxidant priority are added in the coker gas oil after step (2) is processed, catalyst is trichloroacetic acid Or formic acid, the hydrogenperoxide steam generator that oxidant is 30% for mass concentration；The volume ratio of coker gas oil, catalyst and oxidant is 10: 2: 1 10: 4: 4, magnetic stirring apparatuss carry out catalytic oxidation, the response time is 50 100min, temperature is 50 DEG C 80 DEG C, mixing speed is 40rpm；

(4) after, step (3) gained coker gas oil is cooled to room temperature, 1: 1 addition extractant by volume, extractant is n, n- bis- Methylformamide or furfural, use magnetic stirrer 5-10min, and mixing speed is 40rpm, then pours separatory funnel into, standing 20min, collects diesel oil layer；

Fructus Crataegi water in described step (1) presses, for water, the Fructus Crataegi water that 300ml/g adds medicinal dry Fructus Crataegi to obtain after decocting 2 hours.

2. insulin according to claim 1 is applied to the method for coker gas oil desulfurization it is characterised in that described step (1) magnetic stirring apparatuss and in step (3) are all using df-101s heat collecting type constant-temperature heating magnetic stirring apparatus.

3. insulin according to claim 1 is applied to the method for coker gas oil desulfurization it is characterised in that described step (2) water bath with thermostatic control magnetic stirring apparatuss are adopted, power is 40w.