CN114292668A - Oxidation treatment method for fuel oil deep desulfurization process - Google Patents

Oxidation treatment method for fuel oil deep desulfurization process Download PDF

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CN114292668A
CN114292668A CN202111569071.XA CN202111569071A CN114292668A CN 114292668 A CN114292668 A CN 114292668A CN 202111569071 A CN202111569071 A CN 202111569071A CN 114292668 A CN114292668 A CN 114292668A
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fuel oil
oxidant
raw material
oxidation
catalyst
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刘福杰
刘福燕
张铭
王国喜
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Zhenjiang College
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Zhenjiang College
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Abstract

The invention discloses an oxidation treatment method for a fuel oil deep desulfurization process, which adopts the technical scheme that: comprises the following steps of; s1: adding a fuel oil raw material into a reaction kettle, heating the fuel oil raw material in the reaction kettle for a period of time at a certain temperature, then adding a catalyst and an oxidant into the reaction kettle, and stirring the fuel oil raw material while adding the catalyst and the oxidant until the fuel oil raw material and the oxidant are uniformly mixed; s2: continuing to heat the reaction kettle to a certain temperature, and carrying out oxidation reaction on the fuel oil raw material and the oxidant in the heating process; the oxidation treatment process for the deep desulfurization process of the fuel oil has the beneficial effects that: the speed of the deep desulfurization of the fuel is improved, the problems that the conventional deep oxidation desulfurization of the fuel generally needs to be oxidized by adding a large amount of catalyst, the desulfurization speed is low, the reduction of the operation cost is not facilitated, and the difficulty in separation and extraction is increased are solved.

Description

Oxidation treatment method for fuel oil deep desulfurization process
Technical Field
The invention relates to the technical field of fuel oil processing, in particular to an oxidation treatment method for a fuel oil deep desulfurization process.
Background
The fuel oil is generally prepared from crude oil atmospheric distillation residual oil, the heavy oil contains more sulfur, and the sulfur is large molecular cyclic sulfide. The desulfurization of fuel oil refers to the removal of sulfur content before the combustion process of fuel oil, and the difficulty of the desulfurization of heavy oil lies in thoroughly processing fuel, destroying the original organization and generating new solid, liquid and gaseous substances.
The conventional common method for deep desulfurization of fuel oil is oxidative desulfurization, under the action of a catalyst and under a mild condition of a certain temperature, the fuel oil can be easily combined with extraction, adsorption, distillation and other methods to remove oxidation products after catalytic oxidation, and sulfur contained in the fuel oil is separated from the oxidation products.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problem to be solved by the invention is to provide an oxidation treatment method for the deep desulfurization process of fuel oil, which can reduce the using amount of a catalyst, has high desulfurization rate and low treatment cost.
The oxidation treatment method for the deep desulfurization process of the fuel oil comprises the following operation steps;
s1: adding a fuel oil raw material into a reaction kettle, heating the fuel oil raw material in the reaction kettle for a period of time at a certain temperature, then adding a catalyst and an oxidant into the reaction kettle, and stirring the fuel oil raw material while adding the catalyst and the oxidant until the fuel oil raw material and the oxidant are uniformly mixed;
s2: continuing to heat the reaction kettle to a certain temperature, carrying out oxidation reaction on the fuel oil raw material and an oxidant in the heating process, and oxidizing the fuel oil raw material by the oxidant after reacting for a period of time to obtain a mixed solution of fuel oil, an oxidation product and a catalyst;
s3: continuously adding an oxidant into the mixed liquid obtained in the step S2, continuously heating to a certain temperature, continuously reacting sulfur in the fuel raw material which is not completely reacted by the mixed liquid of the step S2 with the oxidant, and further completely oxidizing the mixed liquid obtained in the step S2 to obtain a mixed liquid of the desulfurized fuel, an oxidation product and a catalyst;
s4: adding the mixed solution of the desulfurized fuel oil obtained in the step S3, the oxidation product and the catalyst into an extraction device for extraction, removing the catalyst after extraction, and then removing the extractant to obtain the mixed solution of the desulfurized fuel oil and the oxidation product;
s5: adding the mixed liquid of the desulfurized fuel oil and the oxidation products obtained in the step S4 into a distiller, and removing the oxidation products in the desulfurized fuel oil by a distillation method;
s6: and (4) standing and cooling the mixed solution distilled in the step S5 to obtain the desulfurized fuel oil.
The extraction is a unit operation for separating a mixture by utilizing different solubility of components in a solvent in a system, and the extraction is a method for transferring solute substances from one solvent to another solvent by utilizing the difference of solubility or partition coefficient of the substances in two solvents which are not mutually soluble.
The distillation is a unit operation process for evaporating low-boiling components and condensing to separate the whole components by utilizing different boiling points of the components in a mixed liquid or liquid-solid system, and is a combination of two unit operations of evaporation and condensation.
Preferably, the heating temperature of the fuel oil raw material in the reaction kettle in the S1 is 30-55 ℃, and the heating time is 0.8-3 h.
Preferably, the mass ratio of the catalyst to the oxidant added in S1 is 1: 5-1: 10, the material of the oxidizing agent comprises hydrogen peroxide.
Preferably, the temperature of the oxidation reaction between the fuel oil raw material and the oxidant in the S2 is 48-60 ℃, and the time of the oxidation reaction is 1.2-4 h.
Preferably, the mass ratio of the oxidant added for the second time to the oxidant added for the first time in S3 is 1: 3-1: 7.
preferably, the temperature for continuously carrying out the oxidation reaction of the sulfur in the incompletely reacted fuel oil raw material in the S3 and the oxidant is 40-54 ℃, and the time for the oxidation reaction is 0.8-2.4 h.
Preferably, the material of the catalyst comprises a titanium silicalite.
The embodiment of the invention has the following advantages:
the invention removes the sulfur element contained in the fuel oil raw material by carrying out catalytic oxidation on the fuel oil raw material, the fuel oil raw material is heated for a period of time to prevent the fuel oil raw material from being too viscous, then a catalyst and an oxidant with a certain mass ratio are added, then continuously heating for oxidation reaction, continuously adding oxidant after the first oxidation reaction, continuously carrying out oxidation reaction, completely removing sulfur element contained in the fuel oil raw material, then extracting the mixed solution generated after desulfurization, distilling the extracted mixed solution to obtain the desulfurized fuel oil, this an oxidation treatment process for fuel degree of depth desulfurization process is organized clearly, has promoted the speed of fuel degree of depth desulfurization, has avoided current fuel degree of depth oxidation desulfurization generally to need add a large amount of catalysts to carry out the oxidation, and the speed of desulfurization is slower, and is unfavorable for reducing operating cost, has increased the problem of separation and extraction difficulty again.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides an oxidation treatment process for a fuel oil deep desulfurization process, which comprises the following operation steps;
s1: adding a fuel oil raw material into a reaction kettle, heating the fuel oil raw material in the reaction kettle for 0.8h at the temperature of 30 ℃, then adding a catalyst and an oxidant into the reaction kettle, stirring the fuel oil raw material while adding the catalyst and the oxidant, wherein the mass ratio of the added catalyst to the added oxidant is 1: 5, until the fuel oil raw material and the oxidant are uniformly mixed;
s2: continuing to heat the reaction kettle to 48 ℃, wherein the fuel oil raw material and the oxidant undergo an oxidation reaction in the heating process, and after reacting for 1.2h, the fuel oil raw material is oxidized by the oxidant to obtain a mixed solution of fuel oil, an oxidation product and a catalyst;
s3: continuously adding an oxidant into the mixed solution obtained in the step S2, continuously heating to 40 ℃, continuously reacting sulfur in the fuel oil raw material which is not completely reacted by the mixed solution of the step S2 with the oxidant, wherein the time of the second oxidation reaction is 0.8h, and the mass ratio of the oxidant added for the second time to the oxidant added for the first time is 1: 3, further completely oxidizing the mixed solution obtained in the step S2 to obtain a mixed solution of desulfurized fuel oil, oxidation products and a catalyst;
s4: adding the mixed solution of the desulfurized fuel oil obtained in the step S3, the oxidation product and the catalyst into an extraction device for extraction, removing the catalyst after extraction, and then removing the extractant to obtain the mixed solution of the desulfurized fuel oil and the oxidation product;
s5: adding the mixed liquid of the desulfurized fuel oil and the oxidation products obtained in the step S4 into a distiller, and removing the oxidation products in the desulfurized fuel oil by a distillation method;
s6: and (4) standing and cooling the mixed solution distilled in the step S5 to obtain the desulfurized fuel oil.
In this example, the extraction is a unit operation that separates a mixture by utilizing the different solubilities of components in the system in solvents, and the extraction is a method that transfers solute species from one solvent to another by utilizing the difference in solubility or partition coefficient of the species in two immiscible solvents; the distillation is a unit operation process for evaporating low-boiling-point components and condensing to separate the whole components by utilizing different boiling points of the components in a mixed liquid or liquid-solid system, and is a combination of evaporation and condensation unit operations; the material of the catalyst comprises a titanium silicalite molecular sieve.
Example 2:
the invention provides an oxidation treatment process for a fuel oil deep desulfurization process, which comprises the following operation steps;
s1: adding a fuel oil raw material into a reaction kettle, heating the fuel oil raw material in the reaction kettle for 1.2 hours at the temperature of 35 ℃, then adding a catalyst and an oxidant into the reaction kettle, stirring the fuel oil raw material while adding the catalyst and the oxidant, wherein the mass ratio of the added catalyst to the added oxidant is 1: 6, until the fuel oil raw material and the oxidant are uniformly mixed;
s2: continuing to heat the reaction kettle to 52 ℃, wherein the fuel oil raw material and the oxidant are subjected to oxidation reaction in the heating process, and after the fuel oil raw material is reacted for 1.6 hours, the fuel oil raw material is oxidized by the oxidant to obtain a mixed solution of fuel oil, an oxidation product and a catalyst;
s3: continuously adding an oxidant into the mixed solution obtained in the step S2, continuously heating to 43 ℃, continuously reacting sulfur in the fuel oil raw material which is not completely reacted by the mixed solution of the step S2 with the oxidant, wherein the time of the second oxidation reaction is 1h, and the mass ratio of the oxidant added for the second time to the oxidant added for the first time is 1: 4, further completely oxidizing the mixed solution obtained in the step S2 to obtain a mixed solution of desulfurized fuel oil, oxidation products and a catalyst;
s4: adding the mixed solution of the desulfurized fuel oil obtained in the step S3, the oxidation product and the catalyst into an extraction device for extraction, removing the catalyst after extraction, and then removing the extractant to obtain the mixed solution of the desulfurized fuel oil and the oxidation product;
s5: adding the mixed liquid of the desulfurized fuel oil and the oxidation products obtained in the step S4 into a distiller, and removing the oxidation products in the desulfurized fuel oil by a distillation method;
s6: and (4) standing and cooling the mixed solution distilled in the step S5 to obtain the desulfurized fuel oil.
Example 3:
the invention provides an oxidation treatment process for a fuel oil deep desulfurization process, which comprises the following operation steps;
s1: adding a fuel oil raw material into a reaction kettle, heating the fuel oil raw material in the reaction kettle for 1.6 hours at the temperature of 40 ℃, then adding a catalyst and an oxidant into the reaction kettle, stirring the fuel oil raw material while adding the catalyst and the oxidant, wherein the mass ratio of the added catalyst to the added oxidant is 1: 7, until the fuel oil raw material and the oxidant are uniformly mixed;
s2: continuing to heat the reaction kettle to 54 ℃, wherein the fuel oil raw material and the oxidant are subjected to oxidation reaction in the heating process, and after the fuel oil raw material is reacted for 2 hours, the fuel oil raw material is oxidized by the oxidant to obtain a mixed solution of fuel oil, an oxidation product and a catalyst;
s3: continuously adding an oxidant into the mixed solution obtained in the step S2, continuously heating to 46 ℃, continuously reacting sulfur in the fuel oil raw material which is not completely reacted by the mixed solution of the step S2 with the oxidant, wherein the time of the second oxidation reaction is 1.2h, and the mass ratio of the oxidant added for the second time to the oxidant added for the first time is 1: 5, further completely oxidizing the mixed solution obtained in the step S2 to obtain a mixed solution of desulfurized fuel oil, oxidation products and a catalyst;
s4: adding the mixed solution of the desulfurized fuel oil obtained in the step S3, the oxidation product and the catalyst into an extraction device for extraction, removing the catalyst after extraction, and then removing the extractant to obtain the mixed solution of the desulfurized fuel oil and the oxidation product;
s5: adding the mixed liquid of the desulfurized fuel oil and the oxidation products obtained in the step S4 into a distiller, and removing the oxidation products in the desulfurized fuel oil by a distillation method;
s6: and (4) standing and cooling the mixed solution distilled in the step S5 to obtain the desulfurized fuel oil.
Example 4:
the invention provides an oxidation treatment process for a fuel oil deep desulfurization process, which comprises the following operation steps;
s1: adding a fuel oil raw material into a reaction kettle, heating the fuel oil raw material in the reaction kettle at the temperature of 45 ℃ for 2 hours, then adding a catalyst and an oxidant into the reaction kettle, stirring the fuel oil raw material while adding the catalyst and the oxidant, wherein the mass ratio of the added catalyst to the added oxidant is 1: 8, until the fuel oil raw material and the oxidant are uniformly mixed;
s2: continuing to heat the reaction kettle to a temperature of 58 ℃, carrying out oxidation reaction on the fuel oil raw material and an oxidant in the heating process, and after reacting for 3 hours, oxidizing the fuel oil raw material by the oxidant to obtain a mixed solution of fuel oil, an oxidation product and a catalyst;
s3: continuously adding an oxidant into the mixed solution obtained in the step S2, continuously heating to 50 ℃, continuously reacting sulfur in the fuel oil raw material which is not completely reacted by the mixed solution of the step S2 with the oxidant, wherein the time of the second oxidation reaction is 2 hours, and the mass ratio of the oxidant added in the second time to the oxidant added in the first time is 1: 6, further completely oxidizing the mixed solution obtained in the step S2 to obtain a mixed solution of desulfurized fuel oil, oxidation products and a catalyst;
s4: adding the mixed solution of the desulfurized fuel oil obtained in the step S3, the oxidation product and the catalyst into an extraction device for extraction, removing the catalyst after extraction, and then removing the extractant to obtain the mixed solution of the desulfurized fuel oil and the oxidation product;
s5: adding the mixed liquid of the desulfurized fuel oil and the oxidation products obtained in the step S4 into a distiller, and removing the oxidation products in the desulfurized fuel oil by a distillation method;
s6: and (4) standing and cooling the mixed solution distilled in the step S5 to obtain the desulfurized fuel oil.
Example 5:
the invention provides an oxidation treatment process for a fuel oil deep desulfurization process, which comprises the following operation steps;
s1: adding a fuel oil raw material into a reaction kettle, heating the fuel oil raw material in the reaction kettle at the temperature of 55 ℃ for 3 hours, then adding a catalyst and an oxidant into the reaction kettle, stirring the fuel oil raw material while adding the catalyst and the oxidant, wherein the mass ratio of the added catalyst to the added oxidant is 1: 10, until the fuel oil raw material and the oxidant are uniformly mixed;
s2: continuing to heat the reaction kettle to 60 ℃, wherein the fuel oil raw material and the oxidant are subjected to oxidation reaction in the heating process, and after the reaction is carried out for 4 hours, the fuel oil raw material is oxidized by the oxidant to obtain a mixed solution of fuel oil, an oxidation product and a catalyst;
s3: continuously adding an oxidant into the mixed solution obtained in the step S2, continuously heating to 54 ℃, continuously reacting sulfur in the fuel oil raw material which is not completely reacted by the mixed solution of the step S2 with the oxidant, wherein the time of the second oxidation reaction is 2.4 hours, and the mass ratio of the oxidant added for the second time to the oxidant added for the first time is 1: 7, further completely oxidizing the mixed solution obtained in the step S2 to obtain a mixed solution of desulfurized fuel oil, oxidation products and a catalyst;
s4: adding the mixed solution of the desulfurized fuel oil obtained in the step S3, the oxidation product and the catalyst into an extraction device for extraction, removing the catalyst after extraction, and then removing the extractant to obtain the mixed solution of the desulfurized fuel oil and the oxidation product;
s5: adding the mixed liquid of the desulfurized fuel oil and the oxidation products obtained in the step S4 into a distiller, and removing the oxidation products in the desulfurized fuel oil by a distillation method;
s6: and (4) standing and cooling the mixed solution distilled in the step S5 to obtain the desulfurized fuel oil.
From the above example the following table can be derived:
s1 heating temperature (DEG C) S1 heating time (h) Mass ratio of catalyst to oxidant Temperature (. degree.C.) of the first oxidation reaction Time of first oxidation reaction (h)
Example 1 30 0.8 1:5 48 1.2
Example 2 35 1.2 1:6 52 1.6
Example 3 40 1.6 1:7 54 2
Example 4 45 2 1:8 58 3
Example 5 55 3 1:10 60 4
Second oxidation reaction temperature (. degree. C.) Second oxidation reaction time (h) Mass ratio of the second oxidant to the first oxidant Time required for desulfurization (h)
Example 1 40 0.8 1:3 1.24
Example 2 43 1 1:4 1.18
Example 3 46 1.2 1:5 1.32
Example 4 50 2 1:6 1.36
Example 5 54 2.4 1:7 1.45
According to the two tables, the speed of deep desulfurization of the fuel is fastest and the required time is minimum under the condition of the embodiment 2, and the fuel can be deeply desulfurized through oxidation under a mild condition, so that a large amount of energy consumption is reduced, the cost of deep desulfurization through oxidation is reduced, and the problems of difficult separation and extraction after desulfurization are solved.
The above description is only a preferred embodiment of the present invention, and any person skilled in the art may modify the present invention or modify it into an equivalent technical solution by using the technical solution described above. Therefore, any simple modifications or equivalent substitutions made in accordance with the technical solution of the present invention are within the scope of the claims of the present invention.

Claims (9)

1. An oxidation treatment method for a fuel oil deep desulfurization process is characterized by comprising the following steps: comprises the following steps of;
s1: adding a fuel oil raw material into a reaction kettle, heating the fuel oil raw material in the reaction kettle for a period of time at a certain temperature, then adding a catalyst and an oxidant into the reaction kettle, and stirring the fuel oil raw material while adding the catalyst and the oxidant until the fuel oil raw material and the oxidant are uniformly mixed;
s2: continuing to heat the reaction kettle to a certain temperature, carrying out oxidation reaction on the fuel oil raw material and an oxidant in the heating process, and oxidizing the fuel oil raw material by the oxidant after reacting for a period of time to obtain a mixed solution of fuel oil, an oxidation product and a catalyst;
s3: continuously adding an oxidant into the mixed liquid obtained in the step S2, continuously heating to a certain temperature, continuously reacting sulfur in the fuel raw material which is not completely reacted by the mixed liquid of the step S2 with the oxidant, and further completely oxidizing the mixed liquid obtained in the step S2 to obtain a mixed liquid of the desulfurized fuel, an oxidation product and a catalyst;
s4: adding the mixed solution of the desulfurized fuel oil obtained in the step S3, the oxidation product and the catalyst into an extraction device for extraction, removing the catalyst after extraction, and then removing the extractant to obtain the mixed solution of the desulfurized fuel oil and the oxidation product;
s5: adding the mixed liquid of the desulfurized fuel oil and the oxidation products obtained in the step S4 into a distiller, and removing the oxidation products in the desulfurized fuel oil by a distillation method;
s6: and (4) standing and cooling the mixed solution distilled in the step S5 to obtain the desulfurized fuel oil.
2. The oxidation treatment method for the deep desulfurization process of fuel according to claim 1, characterized in that: the heating temperature of the fuel oil raw material in the reaction kettle in the S1 is 30-55 ℃, and the heating time is 0.8-3 h.
3. The oxidation treatment method for the deep desulfurization process of fuel according to claim 1, characterized in that: the mass ratio of the catalyst to the oxidant added in the S1 is 1: 5-1: 10, the material of the oxidizing agent comprises hydrogen peroxide.
4. The oxidation treatment method for the deep desulfurization process of fuel according to claim 1, characterized in that: the temperature of the oxidation reaction of the fuel oil raw material and the oxidant in the S2 is 48-60 ℃, and the time of the oxidation reaction is 1.2-4 h.
5. The oxidation treatment method for the deep desulfurization process of fuel according to claim 1, characterized in that: the mass ratio of the oxidant added for the second time to the oxidant added for the first time in the S3 is 1: 3-1: 7.
6. the oxidation treatment method for the deep desulfurization process of fuel according to claim 1, characterized in that: the temperature of the continuous oxidation reaction of the sulfur in the incompletely reacted fuel oil raw material in the S3 and the oxidant is 40-54 ℃, and the time of the oxidation reaction is 0.8-2.4 h.
7. The oxidation treatment method for the deep desulfurization process of fuel according to claim 1, characterized in that: the extraction is a unit operation for separating a mixture by utilizing different solubility of components in a solvent in a system, and the extraction is a method for transferring solute substances from one solvent to another solvent by utilizing the difference of solubility or partition coefficient of the substances in two solvents which are not mutually soluble.
8. The oxidation treatment method for the deep desulfurization process of fuel according to claim 1, characterized in that: the distillation is a unit operation process for evaporating low-boiling components and condensing to separate the whole components by utilizing different boiling points of the components in a mixed liquid or liquid-solid system, and is a combination of two unit operations of evaporation and condensation.
9. The oxidation treatment method for the deep desulfurization process of fuel according to claim 1, characterized in that: the material of the catalyst comprises a titanium silicalite molecular sieve.
CN202111569071.XA 2021-12-21 2021-12-21 Oxidation treatment method for fuel oil deep desulfurization process Pending CN114292668A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1912060A (en) * 2006-07-07 2007-02-14 中国石油化工股份有限公司 Highly sulfur removal method of diesel oil
CN102086403A (en) * 2009-12-07 2011-06-08 武侯区巅峰机电科技研发中心 Method for extracting and desulfurizing oxidated diesel oil

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1912060A (en) * 2006-07-07 2007-02-14 中国石油化工股份有限公司 Highly sulfur removal method of diesel oil
CN102086403A (en) * 2009-12-07 2011-06-08 武侯区巅峰机电科技研发中心 Method for extracting and desulfurizing oxidated diesel oil

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