阅读说明：本技术 低硫石油焦的制备方法 (Preparation method of low-sulfur petroleum coke ) 是由 刘必心 申海平 任磊 李子锋 陈煜� 于 2019-08-28 设计创作，主要内容包括：本发明涉及石油焦制备领域,公开了一种低硫石油焦的制备方法,其中,所述方法包括：(1)在氧化反应条件下,以及在溶剂和液相催化剂的存在下,将渣油与氧化剂接触反应,得到含有氧化渣油的产物；(2)在热转化条件下,将步骤(1)得到的含有氧化渣油的产物进行热转化反应,得到低硫石油焦。本发明的效果和益处是提供了一个温和条件下对渣油中含硫化合物的氧化方法,通过对渣油原料进行预氧化处理,结合热转化(焦化)工艺,达到制备低硫石油焦的目的。(The invention relates to the field of petroleum coke preparation, and discloses a preparation method of low-sulfur petroleum coke, wherein the method comprises the following steps: (1) under the condition of oxidation reaction and in the presence of solvent and liquid-phase catalyst, residual oil and oxidant are contacted and reacted to obtain product containing oxidized residual oil; (2) and (2) carrying out thermal conversion reaction on the oxidized residual oil-containing product obtained in the step (1) under the thermal conversion condition to obtain low-sulfur petroleum coke. The invention has the effects and benefits that the method for oxidizing the sulfur-containing compounds in the residual oil under mild conditions is provided, and the aim of preparing the low-sulfur petroleum coke is achieved by carrying out pre-oxidation treatment on the residual oil raw material and combining a thermal conversion (coking) process.)

1. A process for the production of low sulfur petroleum coke, comprising:

(1) under the condition of oxidation reaction and in the presence of solvent and liquid-phase catalyst, residual oil and oxidant are contacted and reacted to obtain product containing oxidized residual oil;

(2) and (2) carrying out thermal conversion reaction on the oxidized residual oil-containing product obtained in the step (1) under the thermal conversion condition to obtain low-sulfur petroleum coke.

2. The method as claimed in claim 1, wherein in the step (1), the weight ratio of the residual oil, the solvent, the oxidant in terms of effective component and the liquid phase catalyst in terms of effective component is 100-800:1-50:1, preferably 100-500:10-30: 1.

3. The process according to claim 1 or 2, wherein in step (1), the oxidizing agent is selected from one or more of hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, tert-hexyl peroxypivalate, concentrated nitric acid and peroxyacetic acid.

4. The process of claim 1 or 2, wherein in step (1), the solvent is selected from one or more of benzene, toluene, chloroform, pyridine, N dimethylformamide, dichloromethane, catalytic diesel, coker diesel, reformed gasoline, and coker gasoline.

5. The process according to claim 1 or 2, wherein in step (1), the liquid phase catalyst is selected from one or more of nickel naphthenate, iron naphthenate, acetic acid, trifluoroacetic acid, benzoic acid, iron isooctanoate, and molybdenum isooctanoate.

6. The method according to any one of claims 1 to 5, wherein in step (1), the oxidation reaction conditions comprise: the reaction temperature is 45-130 ℃, preferably 50-120 ℃; the reaction time is 2 to 20 hours, preferably 3 to 15 hours; the reaction pressure was normal pressure in gauge pressure.

7. The method as claimed in any one of claims 1 to 6, wherein the residual oil is reacted with the oxidant in the presence of the solvent and the liquid phase catalyst in the step (1) by contacting them in a manner comprising: heating the residual oil to the temperature of 100-220 ℃, preferably 120-200 ℃, uniformly mixing the residual oil with the solvent, the liquid-phase catalyst and the oxidant, and then carrying out an oxidation reaction.

8. The method of any of claims 1-7, wherein the method further comprises: before subjecting the oxidized residuum-containing product obtained in step (1) to a thermal conversion reaction, subjecting the product to fractional distillation to separate the solvent therein, and returning the separated solvent as at least a portion of the solvent used in step (1).

9. The method according to any one of claims 1 to 8, wherein in step (2), the conditions of the thermal conversion reaction comprise: the reaction temperature is 250-550 ℃, and preferably 370-525 ℃; the reaction time is from 0.5 to 10 hours, preferably from 1 to 5 hours, and the reaction pressure is normal pressure in terms of gauge pressure.

10. A process according to any one of claims 1 to 9 in which the resid is a vacuum resid.

Technical Field

The invention relates to the field of petroleum coke preparation, in particular to a method for preparing low-sulfur petroleum coke, and more particularly relates to a method for preparing low-sulfur petroleum coke by carrying out oxidation pretreatment on residual oil and then carrying out thermal conversion reaction.

Background

With the heavy and inferior crude oil resources, the deep processing technology of heavy oil becomes the key point for the development of oil refining technology. At present, the processes of coking, heavy oil catalytic cracking, residual oil hydrogenation and the like are still taken as main processes, and delayed coking is the heavy oil conversion technology which is most applied in the world at present. Since the first set of delayed coking device was put into production in the united states in 1930, the delayed coking process has developed rapidly, delayed coking is one of the main means of inferior heavy oil processing, the processing capacity thereof increases year by year, a large amount of petroleum coke is inevitably generated, and besides a part of high-quality petroleum coke can be used as electrodes, fuels and other fields of aluminum smelting and steel making, the utilization problem of high-sulfur petroleum coke (such as petroleum coke produced by enterprises processing imported high-sulfur crude oil in China, with the sulfur content of more than 7%) generated by increasing sulfur-containing crude oil is urgently needed to be solved. How to reduce the sulfur content in high-sulfur petroleum coke generated by delayed coking is a very concerned problem for researchers and enterprises at home and abroad at present.

At present, the production of low-sulfur petroleum coke mainly aims at raw material pretreatment, namely, sulfur-containing compounds in raw oil are removed and then the low-sulfur petroleum coke is produced by a coking device.

The hydrotreating technology is the most widely used desulfurization technology in the petroleum refining industry at present, the hydrotreating not only requires a high-temperature and high-pressure reaction environment but also requires a large amount of noble metal catalysts, and in addition, the hydrogen consumption of the hydrotreating is large, and the hydrotreating process causes great burden and pressure on some refineries in terms of hydrogen source and economic cost, so that the development of other desulfurization technologies is urgent.

The problems of large investment of devices, harsh operating conditions and the like exist in the hydrodesulfurization technology. Non-hydrodesulfurization techniques have received increasing attention. From the current research situation, the non-hydrodesulfurization technology mainly comprisesIncluding adsorption desulfurization, complex desulfurization, extractive desulfurization, biological desulfurization, ionic liquid desulfurization, membrane separation desulfurization, alkylation desulfurization, and the like, as well as combinations thereof. Compared with other traditional non-hydrodesulfurization technologies (including adsorption desulfurization, complex desulfurization, extraction desulfurization and biological desulfurization), the oxidative desulfurization technology has the advantages of high desulfurization efficiency, mild reaction conditions and the like, and has become a research focus of the non-hydrodesulfurization technology in recent years and is paid more and more attention. Some researchers and companies abroad develop corresponding researches on the oxidation desulfurization technology, but the current researches mainly focus on the oxidation desulfurization of light oil products (gasoline and diesel oil), such as H utilized by the Japanese Petroleum Energy Company (PEC)₂O₂Acetic acid or carboxylic acid of trifluoroacetic acid is used as catalyst for oxidation, then washed by NaOH aqueous solution, and silica gel or alumina gel is used for absorbing oxidized sulfide, thus achieving the purpose of removing sulfide in diesel oil. The sulfur content of the diesel oil treated by the process can be reduced from 500-600 mu g/g to 10 mu g/g, the process conditions are mild (50 ℃, the reaction lh is carried out under 0.1 MPa), and the desulfurization rate is high, but the yield of the product is very high. As another example, Petro star in the United states started to research from 1996 on how to remove sulfur compounds from diesel fuel using a conversion-extraction desulfurization process (CED technology for short). At present, a novel continuous desulfurization combined process is developed, wherein H is used at normal pressure and below 100 DEG C₂O₂Acetic acid is used as oxidant, and sulfur in light oil is extracted through selective oxidation and liquid-liquid extraction to reduce sulfur content from 400 microgram/g to below 10 microgram/g.

Furthermore, a few companies have studied the oxidative desulfurization technology of heavy oil, for example, the FlexUPTM oxidative desulfurization technology developed by Auterra corporation in the United states can treat heavy sulfur-containing crude oil, oil sand bitumen and coal liquefaction oil, and can also treat residual oil from oil refinery, straight run wax oil, coker wax oil, catalytic cracking slurry oil and heavy cycle oil.

For example, CN100429295C discloses a fixed bed oxidative desulfurization method, which comprises oxidizing a petroleum fraction containing alkylaromatic hydrocarbons with oxygen at 80-150 ℃ and 0.1-5MPa for 10-50 hours to oxidize the alkylaromatic hydrocarbons therein into organic peroxides, mixing the petroleum fraction containing organic peroxides with the petroleum fraction or chemical raw materials to be desulfurized, feeding the mixture into a fixed bed reactor filled with a supported molybdenum-phosphorus oxide catalyst, performing an oxidation reaction of sulfur-containing compounds at normal pressure and 40-90 ℃, wherein the oxidation reaction products are sulfoxides and sulfones corresponding to the sulfur-containing compounds, and separating the generated sulfoxides and sulfones from the petroleum fraction by solvent extraction or solid adsorbent adsorption.

As another example, CN103827264A discloses a process for catalytic cracking and oxidative desulfurization of a hydrocarbon feedstock containing organic sulfides whereby a product stream containing lower boiling hydrocarbon components and having a reduced concentration of organic sulfides as compared to the hydrocarbon feedstock is recovered, the process comprising: a. combining a hydrocarbon feedstock, an effective amount of an oxygen-containing gas, an effective amount of a heated cracking catalyst, and optionally an effective amount of a heterogeneous catalytic additive comprising an oxidation function to form a suspension; b. maintaining the suspension through a reaction zone of a fluid catalytic cracking reactor unit such that: oxidizing at least a portion of the organosulfur compounds in the hydrocarbon feedstock to form oxidized organosulfur compounds, breaking the carbon-sulfur bonds of the oxidized organosulfur compounds to form sulfur-free hydrocarbon compounds and sulfur oxides, and catalytically cracking the oxidized and nonoxidized compounds, including nonoxidized sulfur-free hydrocarbon compounds, nonoxidized organosulfur compounds, and oxidized organosulfur compounds, to lower boiling hydrocarbon compounds; wherein the catalytic cracking occurs under conditions that are more favorable to the catalytic cracking of compounds of the hydrocarbon feedstock than the thermal cracking; c. separating and recovering the cracked components and the cracking catalyst particles; d. regenerating at least a portion of the separated cracking catalyst particles; returning at least a portion of the regenerated cracking catalyst particles to the hydrocarbon feedstock and oxygen-containing gas in step a.

As another example, CN104395435A discloses a method for modifying a heteroatom-containing hydrocarbon stream by removing heteroatom contaminants, the method comprising: contacting a heteroatom-containing hydrocarbon feed with an oxidant and an immiscible acid; the oxidized heteroatom-containing hydrocarbon feed is contacted with at least one caustic and at least one selectivity promoter comprising an organic compound having at least one acidic proton prior to removal of the heteroatom contaminants from the heteroatom-containing hydrocarbon feed. The method disclosed in example 2 describes in detail: at 85 ℃, mixing straight-run light normal pressure oil and cumyl peroxide, carrying out contact reaction with a pellet-shaped titanyl catalyst in a fixed bed reactor to carry out oxidation reaction, and heating the reaction product to 50 ℃ again to carry out reaction. And separating by gravity to obtain light normal pressure oil with light phase with fully reduced heteroatoms and heavy phase by-products (containing oxidation products). In addition, the cumyl peroxide is recovered and reused by means of vacuum distillation.

Therefore, the related reports on the oxidation desulfurization of the residual oil are few, and only the report is introduced in CN104395435A of Odela corporation in the United states. Therefore, the technology for oxidative desulfurization of residual oil, particularly the technology for preparing low-sulfur petroleum coke from residual oil, is still under further research and development.

Disclosure of Invention

The invention aims to overcome the problem of residual oil oxidative desulfurization in the prior art, and provides a method for preparing low-sulfur petroleum coke by oxidative desulfurization of residual oil.

In the prior art, the method for preparing petroleum coke from residual oil is generally to directly subject the residual oil to a thermal conversion reaction. However, if a lower sulfur content of the petroleum coke is desired, the residuum needs to be desulfurized. The inventor of the invention finds that when the residual oil is subjected to oxidative desulfurization treatment by adopting the prior art, the residual oil has a boiling point of over 500 ℃ and a high viscosity, and the mass transfer efficiency of the reaction can be remarkably reduced when the oxidative desulfurization reaction of the residual oil is carried out at an oxidative desulfurization temperature of usually not higher than 130 ℃, so that the oxidative desulfurization effect of the residual oil is poor. Therefore, how to achieve effective oxidative desulfurization of residuum is the key to making low sulfur petroleum coke. In addition, if the solid-phase catalyst is adopted for catalytic oxidation desulfurization according to the report of the prior art, not only the catalyst residue in the oxidation product is high, but also the catalyst is extremely easy to inactivate because heavy oil macromolecules such as asphaltene exist in the residual oil and the like and the catalyst is also greatly damaged. Not only can the continuous oxidation and desulfurization treatment of the residual oil be realized, but also the recycling of the solid phase catalyst is not facilitated. Therefore, the inventor of the invention can well realize the sufficient oxidation of sulfur-containing substances in the residual oil, such as the oxidation of thiophene into sulfone, by mixing the residual oil with the solvent to reduce the viscosity of the residual oil system and adopting the liquid-phase catalyst to catalyze, oxidize and desulfurize on the basis of ensuring the mass transfer efficiency of the system. In the subsequent thermal conversion reaction process, the oxidation product is converted into sulfur dioxide under the thermal conversion condition and is fully removed, so that low-sulfur petroleum coke is obtained, and the problem that the catalyst is difficult to filter after reaction due to the adoption of a solid-phase catalyst is also avoided.

In order to achieve the above object, the present invention provides a method for preparing low sulfur petroleum coke, wherein the method comprises:

(1) under the condition of oxidation reaction and in the presence of solvent and liquid-phase catalyst, residual oil and oxidant are contacted and reacted to obtain product containing oxidized residual oil;

(2) and (2) carrying out thermal conversion reaction on the oxidized residual oil-containing product obtained in the step (1) under the thermal conversion condition to obtain low-sulfur petroleum coke.

The method has the advantages that the method for oxidizing the sulfur-containing compounds in the residual oil under mild conditions is provided, the oxidant is green and clean, the process is relatively simple, and the aim of preparing the low-sulfur petroleum coke is fulfilled by pre-oxidizing the residual oil raw material and combining a thermal conversion (coking) process.

In addition, the method provided by the invention preferably recycles the solvent through a fractionating device after the oxidation reaction, thereby further reducing the reaction cost.

Drawings

FIG. 1 is a schematic diagram of a process for preparing low-sulfur petroleum coke from residual oil, which mainly comprises two parts of oxidizing pretreatment of residual oil and thermal conversion of oxidized products to remove sulfur.

Description of the reference numerals

1-a resid feed vessel in which resid, solvent, and catalyst are mixed;

2-an oxidation reactor;

3-solvent fractionation equipment;

4-oxidation residual oil thermal conversion device.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the present invention, the "low sulfur petroleum coke" refers to petroleum coke having a sulfur content of not more than 3 wt%.

According to the invention, the preparation method of the low-sulfur petroleum coke comprises the following steps:

(1) under the condition of oxidation reaction and in the presence of solvent and liquid-phase catalyst, residual oil and oxidant are contacted and reacted to obtain product containing oxidized residual oil;

(2) and (2) carrying out thermal conversion reaction on the oxidized residual oil-containing product obtained in the step (1) under the thermal conversion condition to obtain low-sulfur petroleum coke.

The invention uses residual oil as raw material, and prepares low-sulfur petroleum coke with sulfur content not higher than 3 wt% by pre-oxidizing sulfur-containing compounds in the residual oil and combining thermal conversion (coking) reaction.

According to the present invention, in the step (1), the solvent is various solvents capable of diluting and/or dissolving the residual oil under the oxidation condition to improve the fluidity of the residual oil, thereby achieving an improvement in the mass transfer efficiency of the oxidation reaction during the oxidation reaction and an improvement in the desulfurization effect of the residual oil. Preferably, the solvent is selected from one or more of benzene, toluene, chloroform, pyridine, N-dimethylformamide, dichloromethane, catalytic diesel, coker diesel, reformate gasoline and coker gasoline.

According to the present invention, in the step (1), the liquid phase catalyst is various liquid phase catalysts capable of catalyzing oxidation of the residue. The liquid phase catalyst refers to a catalyst generally used in the form of a liquid phase, for example, a catalyst itself is liquid, or a mixed solution of a catalyst and a solvent. Preferably, the liquid phase catalyst is selected from one or more of nickel naphthenate, iron naphthenate, acetic acid, trifluoroacetic acid, benzoic acid, iron isooctanoate, and molybdenum isooctanoate.

According to the present invention, in step (1), the oxidizing agent is various oxidizing agents capable of effecting oxidation of the residual oil, i.e., oxidation of sulfur-containing compounds in the residual oil. Preferably, the oxidizing agent is selected from one or more of hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, tert-hexyl peroxypivalate, concentrated nitric acid and peroxyacetic acid.

According to the invention, in the step (1), the dosage of the solvent is based on the improvement of the fluidity of the residual oil, and the dosage of the liquid phase catalyst is based on the catalytic oxidation of the residual oil, namely the oxidation of sulfur-containing compounds in the residual oil. Preferably, the weight ratio of the residual oil, the solvent, the oxidant in terms of effective components and the liquid phase catalyst in terms of effective components is 100-800:1-50:1, and preferably 100-500:10-30: 1. Herein, the effective component of the liquid phase catalyst refers to the amount of solute or pure substance (catalyst) in the liquid phase catalyst when the liquid phase catalyst is used in the form of a solution or is liquid itself. The effective component of the oxidizing agent refers to the amount of solute or pure substance (oxidizing agent) in the oxidizing agent when the oxidizing agent is used in the form of an aqueous solution or is liquid itself, for example, the mass percentage of commercially available concentrated nitric acid is usually 68%, and the amount of the effective component refers to the value obtained by multiplying the mass of the concentrated nitric acid solution by the mass fraction thereof. For example, hydrogen peroxide is usually used in the form of hydrogen peroxide, and for example, the mass fraction of hydrogen peroxide commercially available is usually 30%, and the amount of the active ingredient is a value obtained by multiplying the mass of the hydrogen peroxide aqueous solution by the mass fraction thereof.

According to the present invention, in the step (1), the conditions of the oxidation reaction generally include a reaction temperature and a reaction time, and a reaction pressure. The conditions for the oxidation reaction can be selected from a wide range and can be selected according to the routine reference in the art. Preferably, the reaction temperature of the oxidation reaction is 45 to 130 ℃, more preferably 50 to 120 ℃; the reaction time of the oxidation reaction is 2 to 20 hours, more preferably 3 to 15 hours; the reaction pressure of the oxidation reaction was normal pressure in terms of gauge pressure.

According to the present invention, since the boiling point of the residue is generally above 500 ℃ and the viscosity is large. Therefore, in order to further improve the mass transfer effect of the reaction and improve the effect of oxidative desulfurization of the residual oil, the residual oil needs to be preheated first so that the residual oil can flow. Therefore, in the preferred case, in step (1), the residual oil is reacted with the oxidant in the presence of the solvent and the liquid phase catalyst by a contact reaction method comprising: heating the residual oil to the temperature of 100-220 ℃, preferably 120-200 ℃, uniformly mixing the residual oil with the solvent, the liquid-phase catalyst and the oxidant, and then carrying out an oxidation reaction. The heated residual oil, the solvent and the liquid phase catalyst can be uniformly mixed under stirring, and the specific stirring condition is not particularly limited as long as the three components are uniformly mixed.

According to the invention, the method further comprises: before subjecting the oxidized residuum-containing product obtained in step (1) to a thermal conversion reaction, subjecting the product to fractional distillation to separate the solvent therein, and returning the separated solvent as at least a portion of the solvent used in step (1). The cost of the reaction can be further reduced by fractionating the solvent for reuse. Wherein the conditions of the fractionation may be selected based on the boiling points of the different solvents to effect separation of the solvent from the product containing the oxidized sulfur-containing compounds.

According to the invention, in the step (2), the oxidized sulfur-containing compounds in the oxidized residual oil in the step (1) can be further decomposed and removed through a thermal conversion reaction, and meanwhile, low-sulfur petroleum coke is prepared through a coking process. Wherein, the thermal conversion reaction refers to the process of deep cracking and condensation of organic matters and carbonization zooming at high temperature. Specifically, in the step (2), the conditions of the thermal conversion reaction generally include a reaction temperature and a reaction time, and a reaction pressure. The conditions for the thermal conversion reaction can be selected from a wide range and can be selected according to the routine skill in the art. Preferably, the reaction temperature of the thermal conversion reaction is 250-550 ℃, more preferably 370-525 ℃; the reaction time of the thermal conversion reaction is 0.5 to 10 hours, more preferably 1 to 5 hours; the reaction pressure was normal pressure in gauge pressure.

The present invention will be described in further detail below with reference to fig. 1.

According to one embodiment of the invention, the method for preparing low sulfur petroleum coke comprises the following steps: heating residual oil to make the residual oil be able to flow, uniformly mixing the heated residual oil with solvent, liquid-phase catalyst and oxidant in residual oil raw material tank 1, then feeding the mixture into oxidation reactor 2 to make oxidation reaction. The oxidized residuum containing product is passed to a solvent fractionation unit 3 for fractionation to effect distillative separation of solvent therefrom and to return separated solvent to at least a portion of the solvent used in residuum feed drum 1. And (3) feeding the oxidized residual oil subjected to solvent separation into an oxidized residual oil thermal conversion device 4 for thermal conversion reaction to prepare low-sulfur petroleum coke.

The present invention will be described in detail below by way of examples.

In the following examples and comparative examples:

the amounts of oxidant and catalyst are given as effective amounts thereof;

the feedstock used was vacuum residue, the properties of which are shown in table 1;

the sulfur content of petroleum coke is determined by elemental analysis methods;

a small-sized simulated coking device is adopted in the thermal conversion experiment of the oxidation residual oil.

TABLE 1

Example 1

This example illustrates the process of the present invention for making low sulfur petroleum coke from resid.

The method comprises the steps of putting the vacuum residue into an oven, heating to 150 ℃ until the residue can flow, pouring 50g of the residue into a 250mL three-neck flask while the residue is hot, adding 50g of solvent toluene, simultaneously adding 3g of oxidant hydrogen peroxide and 0.15g of catalyst nickel naphthenate, and stirring to fully and uniformly mix the residue, the solvent, the oxidant and the catalyst. The three-necked flask is heated to 70 ℃ for oxidation reaction, and the reaction time is 5 hours. After the reaction is finished, the solvent toluene in the residual oil system is distilled off. And respectively taking out 1g of oxidized residual oil and original residual oil, and carrying out a residual oil thermal conversion experiment on a small-sized green coke evaluation device at the reaction temperature of 500 ℃ for 1.5 hours to obtain coke. And finally, carrying out sulfur content test on the obtained coke, and comparing the change of the sulfur content in the petroleum coke before and after oxidation, wherein the specific result is shown in table 2.

Example 2

This example illustrates the process of the present invention for making low sulfur petroleum coke from resid.

The vacuum residue is put into an oven and heated to 165 ℃ until the residue can flow, 50g of the residue is poured into a 250mL three-neck flask while the residue is hot, about 50g of solvent catalytic diesel oil is added, 5g of oxidant cumene hydroperoxide and 0.3g of catalyst iron isooctanoate are added, and the residue, the solvent, the oxidant and the catalyst are stirred to be fully and uniformly mixed. The three-necked flask is heated to 80 ℃ for oxidation reaction, and the reaction time is 7 hours. After the reaction is finished, solvent catalytic diesel oil in a residual oil system is distilled off, 1g of oxidized residual oil and original residual oil are respectively taken out, a residual oil thermal conversion experiment is carried out on a small green coke evaluation device, the reaction temperature is 480 ℃, and the reaction time is 2 hours, so that coke is obtained. And finally, carrying out sulfur content test on the obtained coke, and comparing the change of the sulfur content in the petroleum coke before and after oxidation, wherein the specific result is shown in table 2.

Example 3

This example illustrates the process of the present invention for making low sulfur petroleum coke from resid.

The vacuum residue is put into an oven and heated to 135 ℃ until the residue can flow, 50g of the residue is poured into a 250mL three-neck flask while the residue is hot, 50g of solvent coking diesel oil is added, 7.5g of oxidant cyclohexanone peroxide and 0.25g of catalyst molybdenum isooctanoate are added, and the mixture is stirred to fully and uniformly mix the residue, the solvent, the oxidant and the catalyst. The three-necked flask is heated to 90 ℃ for oxidation reaction, and the reaction time is 7 hours. After the reaction is finished, the solvent coking diesel oil in the residual oil system is distilled off, 1g of oxidized residual oil and original residual oil are respectively taken out, a residual oil thermal conversion experiment is carried out on a small-sized green coke evaluation device, the reaction temperature is 525 ℃, and the reaction time is 2.5 hours, so that coke is obtained. And finally, carrying out sulfur content test on the obtained coke, and comparing the change of the sulfur content in the petroleum coke before and after oxidation, wherein the specific result is shown in table 2.

Example 4

This example illustrates the process of the present invention for making low sulfur petroleum coke from resid.

The method comprises the steps of putting vacuum residue into an oven, heating to 170 ℃ until the residue can flow, pouring 50g of residue into a 250mL three-neck flask while the residue is hot, adding 50g of solvent N, N-dimethylformamide, simultaneously adding 6g of oxidant tert-hexyl peroxypivalate and 0.2g of catalyst trifluoroacetic acid, and stirring to fully and uniformly mix the residue with the solvent, the oxidant and the catalyst. Heating the three-necked flask to 100 ℃ for oxidation reaction for 10 hours. After the reaction is finished, the solvents N and N dimethylformamide in the residual oil system are removed by distillation, 1g of oxidized residual oil and original residual oil are respectively taken out, a residual oil thermal conversion experiment is carried out on a small-sized green coke evaluation device, the reaction temperature is 390 ℃, and the reaction time is 3 hours, so that coke is obtained. And finally, carrying out sulfur content test on the obtained coke, and comparing the change of the sulfur content in the petroleum coke before and after oxidation, wherein the specific result is shown in table 2.

Example 5

This example illustrates the process of the present invention for making low sulfur petroleum coke from resid.

The vacuum residue is put into an oven and heated to 150 ℃ until the residue can flow, 50g of residue is poured into a 250mL three-neck flask while the residue is hot, 50g of solvent pyridine is added, 3g of oxidant tert-butyl hydroperoxide and 0.15g of catalyst benzoic acid are added at the same time, and the mixture is stirred to be fully and uniformly mixed with the solvent, the oxidant and the catalyst. The three-necked flask is heated to 70 ℃ for oxidation reaction, and the reaction time is 5 hours. After the reaction is finished, the solvent pyridine in the residual oil system is distilled off. And respectively taking out 1g of oxidized residual oil and original residual oil, and carrying out a residual oil thermal conversion experiment on a small-sized green coke evaluation device at the reaction temperature of 500 ℃ for 1.5 hours to obtain coke. And finally, carrying out sulfur content test on the obtained coke, and comparing the change of the sulfur content in the petroleum coke before and after oxidation, wherein the specific result is shown in table 2.

Example 6

This example illustrates the process of the present invention for making low sulfur petroleum coke from resid.

The vacuum residue is put into an oven and heated to 150 ℃ until the residue can flow, 50g of the residue is poured into a 250mL three-neck flask while the residue is hot, 300g of solvent dichloromethane is added, 3g of oxidant hydrogen peroxide and 0.5g of catalyst acetic acid are added simultaneously, and the mixture is stirred to be fully and uniformly mixed with the solvent, the oxidant and the catalyst. The three-necked flask is heated to 70 ℃ for oxidation reaction, and the reaction time is 5 hours. After the reaction is finished, the solvent dichloromethane in the residual oil system is distilled off. And respectively taking out 1g of oxidized residual oil and original residual oil, and carrying out a residual oil thermal conversion experiment on a small-sized green coke evaluation device at the reaction temperature of 500 ℃ for 1.5 hours to obtain coke. And finally, carrying out sulfur content test on the obtained coke, and comparing the change of the sulfur content in the petroleum coke before and after oxidation, wherein the specific result is shown in table 2.

Comparative example 1

This comparative example is illustrative of a reference process for making petroleum coke from residuum.

The vacuum residue is put into an oven and heated to 150 ℃ until the residue can flow, 50g of the residue is poured into a 250mL three-neck flask while the residue is hot, 50g of solvent toluene is added, 3g of oxidant hydrogen peroxide is added at the same time, and the mixture is stirred to fully and uniformly mix the residue, the solvent and the oxidant. The three-necked flask is heated to 70 ℃ for oxidation reaction, and the reaction time is 5 hours. After the reaction is finished, the solvent toluene in the residual oil system is distilled off. And respectively taking out 1g of oxidized residual oil and original residual oil, and carrying out a residual oil thermal conversion experiment on a small-sized green coke evaluation device at the reaction temperature of 500 ℃ for 1.5 hours to obtain coke. And finally, carrying out sulfur content test on the obtained coke, and comparing the change of the sulfur content in the petroleum coke before and after oxidation, wherein the specific result is shown in table 2.

Comparative example 2

This comparative example is illustrative of a reference process for making petroleum coke from residuum.

The vacuum residue is put into an oven and heated to 150 ℃ until the residue can flow, 50g of the residue is poured into a 250mL three-neck flask while the residue is hot, 3g of hydrogen peroxide serving as an oxidant and 0.15g of nickel naphthenate serving as a catalyst are added, and the mixture is stirred to fully and uniformly mix the residue, the solvent, the oxidant and the catalyst. The three-necked flask is heated to 70 ℃ for oxidation reaction, and the reaction time is 5 hours. After the reaction is finished, the solvent toluene in the residual oil system is distilled off. And respectively taking out 1g of oxidized residual oil and original residual oil, and carrying out a residual oil thermal conversion experiment on a small-sized green coke evaluation device at the reaction temperature of 500 ℃ for 1.5 hours to obtain coke. And finally, carrying out sulfur content test on the obtained coke, and comparing the change of the sulfur content in the petroleum coke before and after oxidation, wherein the specific result is shown in table 2.

Comparative example 3

This comparative example is illustrative of a reference process for making petroleum coke from residuum.

And (3) directly carrying out a residue oil thermal conversion experiment on the vacuum residue oil on a small-sized green coke evaluation device, wherein the reaction temperature is 470 ℃, and the reaction time is 3 hours, so as to obtain the coke. Finally, the obtained coke was subjected to sulfur content test, and the specific results are shown in table 2.

TABLE 2

As can be seen from the results in table 2, the method provided by the present invention can prepare low sulfur petroleum coke, and the sulfur content in the low sulfur petroleum coke is reduced by at least 13.2% compared with the sulfur content in the residual oil feedstock.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.