CN110655954A - Ultra-deep desulfurization method for residual oil hydrogenated diesel oil - Google Patents

Ultra-deep desulfurization method for residual oil hydrogenated diesel oil Download PDF

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CN110655954A
CN110655954A CN201810691538.XA CN201810691538A CN110655954A CN 110655954 A CN110655954 A CN 110655954A CN 201810691538 A CN201810691538 A CN 201810691538A CN 110655954 A CN110655954 A CN 110655954A
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fraction
diesel oil
oil
diesel
ultra
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丁石
张锐
王哲
渠红亮
鞠雪艳
葛泮珠
习远兵
张乐
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a super-deep desulfurization method of residue hydrogenated diesel oil, which comprises the following steps: a. fractionating residual oil hydrogenated diesel oil to obtain a light fraction and a heavy fraction, wherein the cutting point temperature of the light fraction and the heavy fraction is 331-355 ℃; b. b, carrying out hydrodesulfurization treatment on the light fraction obtained in the step a to obtain a first part of ultra-low sulfur diesel oil fraction; c. and c, carrying out oxidation desulfurization treatment on the heavy fraction obtained in the step a to obtain a second part of ultra-low sulfur diesel fraction. The method can effectively remove the sulfur-containing compounds in the residual oil hydrogenated diesel oil, reduces the severity of a diesel oil hydrogenation device, prolongs the running time of the diesel oil hydrogenation device, can reduce the use amount of an oxidant and an extractant, has high oil product yield and good economic benefit compared with the prior art.

Description

Ultra-deep desulfurization method for residual oil hydrogenated diesel oil
Technical Field
The present disclosure relates to a super-deep desulfurization method for residual oil hydrogenated diesel oil.
Background
The exhaust gas discharged after combustion of diesel contains Sulfur Oxides (SO)X) Nitrogen Oxide (NO)X) And a large amount of harmful substances such as Particulate Matter (PM), which not only form acid rain in cities and surrounding areas, destroy the ozone layer of the earth, but also may cause carcinogenesis of human bodies. To reduce SO in automobile exhaustX、NOXAnd the emission of pollutants such as PM, the sulfur content in the diesel oil needs to be reduced, and the aromatic hydrocarbon content in the diesel oil needs to be reduced.
Therefore, the diesel oil standard is increasingly strict worldwide, and the production of environment-friendly low-sulfur or ultra-low-sulfur diesel oil becomes a problem which is generally regarded by governments and oil refining enterprises worldwide. The Europe IV emission standard diesel oil, the specified sulfur content is less than 50 mug/g; while the Euro V emission standard diesel oil, the specified sulfur content is further reduced to less than 10 mug/g. It can be seen that the worldwide development trend of diesel quality is as follows: the sulfur content of diesel fuels is continually reduced to meet more stringent emissions regulations.
The residual hydrogenated diesel oil is a diesel oil fraction generated in the production process of a residual hydrogenated device, and the sulfur content of the residual hydrogenated diesel oil is generally 50-300 mu g/g. Although the sulfur content of the residual hydrogenated diesel oil is much lower than that of straight-run diesel oil, coker diesel oil and catalytic cracking diesel oil, the sulfur contained in the residual hydrogenated diesel oil is hydrogen partial pressure of a residual hydrogenation device above 15MPa, and 0.2h-1The sulfur content of the sulfide remaining after hydrogenation at the airspeed of (2) is difficult to reduce to below 10 mu g/g by introducing the sulfide into a diesel hydrogenation device, and the sulfide is often required to be mixed with straight-run diesel oil and the like for processing. But even so, due to residue hydrogenated dieselThe dibenzothiophene containing a large amount of polysubstituents is difficult to remove sulfides, the operation severity of the diesel hydrogenation device is obviously improved, and further the operation period of the diesel hydrogenation device is shortened and the economy is deteriorated.
The oxidation desulfurization mechanism is that the oxygen atom in the oxidant carries out electrophilic addition reaction on the sulfur atom in the sulfur-containing compound to produce sulfone or sulfoxide substances, and the more the substituents are, the stronger the electronic effect is, and the easier the sulfur-containing compound is oxidized. Thus, the difficulty of sulfide removal in oxidative desulfurization is directly opposite to that of hydrodesulfurization. Hydrodesulfurization is suitable for removing sulfur-containing compounds of thiophene and benzothiophene, and oxidative desulfurization is suitable for removing dibenzothiophene and dibenzothiophene compounds containing substituent groups.
At present, many technologies are developed for the oxidative desulfurization of diesel fractions:
CN1412280A discloses an ultrasonic-catalytic-oxidative desulfurization method for producing ultra-low sulfur diesel oil, which comprises mixing diesel oil, hydrogen peroxide and a phase transfer catalyst into emulsion under the action of ultrasonic waves, so as to oxidize most sulfides in the diesel oil into sulfones, and then obtaining the ultra-low sulfur diesel oil meeting the national IV discharge standard by an extraction mode.
CN1952050B discloses a diesel oil oxidation desulfurization method, in which diesel oil raw materials are subjected to oxidation desulfurization reaction in the presence of hydrogen peroxide, an extracting agent and an inorganic solid catalyst, and the continuous operation of a fixed bed is adopted, so that the temperature can be-20-150 ℃, and the liquid hourly space velocity can be 1-50 h-1(ii) a The intermittent operation is carried out at the temperature of-20 to 150 ℃, the reaction time is 0.05 to 1.0 hour, and the production of national V diesel oil is realized.
By adopting the two modes to directly carry out oxidative desulfurization treatment on the diesel fraction, dibenzothiophene compounds which are easy to oxidize and dibenzothiophene compounds containing substituent groups can be effectively converted into sulfones, and thiophene substances which are difficult to oxidize have lower oxidation rate, so that the reaction efficiency is reduced. In addition, when the whole-fraction diesel is processed, the consumed amount of the oxidant is large, the produced sulfones and sulfoxides are very many, and a large amount of extractant is needed to remove the produced sulfones and sulfoxides from the diesel, so that the liquid yield of the diesel product is low, and the energy consumption of the large amount of extractant in the regeneration process is huge, and the process is poor in economy. In addition, when hydrogen peroxide is used as an oxidant, the oxidant and diesel oil are poor in compatibility, the oxidation reaction efficiency is low, the oil phase and the hydrogen peroxide are emulsified by using ultrasonic waves, the oxidation reaction efficiency is improved, and the liquid phase separation after the reaction is difficult.
CN200510047498.8 discloses a method for oxidative desulfurization of hydrogenated diesel oil, which comprises the steps of fractionating hydrogenated diesel oil into light fraction and heavy fraction according to a cutting point of 250-330 ℃, wherein the light fraction is not processed, and the heavy fraction is subjected to oxidative desulfurization by hydrogen peroxide and extraction and then is mixed with the light fraction to obtain an ultra-low sulfur diesel oil product. The method reduces the distillate oil loss caused by the diesel oil oxidation desulfurization process to a certain extent, and reduces the dosage of an extracting agent and an oxidizing agent. However, the cutting point is light, which results in that the total amount of heavy fraction is large, and the proportion of dibenzothiophene compounds containing substituent groups in the heavy fraction is low, so that not only is the oxidation reaction rate low, but also the total amount of processed heavy fraction oil is large, and the problems of large fraction oil loss and large using amount of extractant and oxidant also exist.
Disclosure of Invention
The method can effectively remove sulfur-containing compounds in the residual hydrogenated diesel oil, and has high oil product yield and good economic benefit.
In order to achieve the above object, the present disclosure provides a method for ultra-deep desulfurization of residue hydrogenated diesel oil, comprising the steps of:
a. fractionating residual oil hydrogenated diesel oil to obtain a light fraction and a heavy fraction, wherein the cutting point temperature of the light fraction and the heavy fraction is 331-355 ℃;
b. b, carrying out hydrodesulfurization treatment on the light fraction obtained in the step a to obtain a first part of ultra-low sulfur diesel oil fraction;
c. and c, carrying out oxidation desulfurization treatment on the heavy fraction obtained in the step a to obtain a second part of ultra-low sulfur diesel fraction.
Optionally, in the step a, the temperature of the cutting point of the light fraction and the heavy fraction is 335-345 ℃.
Optionally, in step b, the hydrodesulphurization treatment comprises: contacting the light fraction with a hydrogenation catalyst to carry out hydrogenation reaction;
the hydrogenation catalyst comprises a carrier and metal active components loaded on the carrier, wherein the carrier is amorphous alumina and/or amorphous silica-alumina, the metal active components are VIB group non-noble metals and/or VIII group non-noble metals, the VIB group non-noble metals are Mo and/or W, and the VIII group non-noble metals are Ni and/or Co.
Alternatively, the conditions of the hydrogenation reaction are as follows: the temperature is 320-420 ℃, the pressure is 3.0-15.0 MPa, and the liquid hourly space velocity is 0.5-6.0 h-1The volume ratio of hydrogen to oil is 100-1000 Nm3/m3。
Optionally, in step c, the oxidative desulfurization treatment comprises: and (3) contacting the heavy fraction with a mixture containing an oxidant and an acidic auxiliary agent to perform an oxidation desulfurization reaction, and separating the reacted material to remove sulfone compounds and/or sulfoxide compounds to obtain the second part of the ultra-low sulfur diesel fraction.
Optionally, the oxidant is 25-35 wt% aqueous hydrogen peroxide, and the molar ratio of the oxidant to the sulfur in the heavy fraction is (1-10): 1;
the acid auxiliary agent is at least one selected from formic acid, acetic acid and acetic anhydride, and the molar ratio of the acid auxiliary agent to sulfur in the heavy fraction is (0.5-5): 1.
optionally, the oxidative desulfurization reaction is carried out in a microchannel reactor, the microchannel reactor having a plurality of sets of feed channels, each set of feed channels including a first feed channel and a second feed channel, the first feed channel and the second feed channel converging to communicate with a microchannel; said heavy fraction being fed by said first feed path and said mixture comprising oxidant and acidic adjuvant being fed by said second feed path; the sizes of the minimum dimensions of the micro-reaction channels are respectively 0.1 mm-2 mm, and the sizes of the secondary minimum dimensions are respectively 0.5 mm-10 mm;
the reaction conditions of the oxidative desulfurization reaction include: the temperature is 30-80 ℃, and preferably 40-60 ℃; the retention time is 0.5-10 min, preferably 1-8 min.
Optionally, the residual hydrogenated diesel oil is a diesel oil fraction produced by a residual hydrogenation process and having a distillation range of 160-390 ℃, and the sulfur content of the residual hydrogenated diesel oil is 50-2000 [ mu ] g/g.
Optionally, the method further comprises: in the step b, the light fraction and an externally produced diesel oil fraction are mixed for the hydrodesulfurization treatment, wherein the externally produced diesel oil fraction is a diesel oil fraction with the distillation range of 160-390 ℃ produced by a straight-run diesel oil process, a coking diesel oil process or a catalytic cracking diesel oil process or a combination of two or three of the straight-run diesel oil process, the coking diesel oil process and the catalytic cracking diesel oil process.
Optionally, the process further comprises the step of blending said first portion of the ultra low sulfur diesel fraction obtained in step b with said second portion of the ultra low sulfur diesel fraction obtained in step c.
Through the technical scheme, the residual oil hydrogenated diesel oil is fractionated at a high cutting point temperature, so that the total amount of the obtained light fraction is relatively large, and the total amount of the obtained heavy fraction is relatively small. Therefore, on one hand, more light fractions are subjected to hydrodesulfurization at a lower severity level to produce the ultra-low sulfur diesel, so that the product yield can be improved, and the process operation cost is obviously reduced; on the other hand, the reaction time of the heavy fraction for oxidation desulfurization is short, the consumption of the oxidant and the catalyst is low, the dosage of the adsorbent or the extractant further required by product separation is low, and the effects of improving the product yield and reducing the cost are achieved. The method can effectively remove the sulfur-containing compounds in the residual oil hydrogenated diesel oil, and the obtained ultra-low sulfur diesel oil product can meet the national V emission index, has high yield and good economic benefit.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The ultra-deep desulfurization method of the residue hydrogenated diesel oil is characterized by comprising the following steps of:
a. fractionating residual oil hydrogenated diesel oil to obtain a light fraction and a heavy fraction, wherein the cutting point temperature of the light fraction and the heavy fraction is 331-355 ℃;
b. b, carrying out hydrodesulfurization treatment on the light fraction obtained in the step a to obtain a first part of ultra-low sulfur diesel oil fraction;
c. and c, carrying out oxidation desulfurization treatment on the heavy fraction obtained in the step a to obtain a second part of ultra-low sulfur diesel fraction.
The present disclosure fractionates the resid hydrogenated diesel at a higher cut point temperature, resulting in a relatively high total amount of light fractions and a relatively low total amount of heavy fractions. Therefore, on one hand, more light fractions are subjected to hydrodesulfurization at a lower severity level to produce the ultra-low sulfur diesel, so that the product yield can be improved, and the process operation cost is obviously reduced; on the other hand, the reaction time of the heavy fraction for oxidation desulfurization is short, the consumption of the oxidant and the catalyst is low, the dosage of the adsorbent or the extractant further required by product separation is low, and the effects of improving the product yield and reducing the cost are achieved.
The method disclosed by the invention is suitable for diesel distillate oil produced by various residual oil hydrogenation processes, such as fixed bed residual oil hydrogenated diesel oil, suspended bed residual oil hydrogenated diesel oil, boiling bed residual oil hydrogenated diesel oil and the like. Specifically, the residual hydrogenated diesel oil can be diesel oil fraction produced by a residual hydrogenation process and having a distillation range of 160-390 ℃, and the sulfur content of the residual hydrogenated diesel oil can be 50-2000 mu g/g.
According to the present disclosure, in order to further improve the product yield and optimize the desulfurization effect, the cut point temperature of the light fraction and the heavy fraction in step a may be 335 to 345 ℃.
In step b, the meaning of hydrodesulfurization treatment is well known to those skilled in the art in light of this disclosure. Specifically, the hydrodesulfurization treatment may include: and contacting the light fraction with a hydrogenation catalyst to carry out hydrogenation reaction.
The hydrogenation catalyst may be of a conventional kind for hydrodesulphurisation, among others. For example, the hydrogenation catalyst may include a support and a metal active component supported on the support; the carrier can be amorphous alumina and/or amorphous silica-alumina; the metal active component can be a VIB group non-noble metal and/or a VIII group non-noble metal, the VIB group non-noble metal can be Mo and/or W, and the VIII group non-noble metal can be Ni and/or Co. Specifically, the hydrogenation catalyst may include 50 to 85 wt% of a carrier, 1 to 10 wt% of cobalt and/or nickel in terms of oxide, and 5 to 45 wt% of molybdenum and/or tungsten in terms of oxide, based on the dry weight of the hydrogenation catalyst. The hydrogenation catalyst can be prepared by adopting a method in the prior art or can be obtained commercially.
Wherein, the hydrogenation reaction conditions can be as follows: the temperature is 320-420 ℃, the pressure is 3.0-15.0 MPa, and the liquid hourly space velocity is 0.5-6.0 h-1The volume ratio of hydrogen to oil is 100-1000 Nm3/m3。
According to the present disclosure, in step c, the oxidative desulfurization treatment may include: and (3) contacting the heavy fraction with a mixture containing an oxidant and an acidic auxiliary agent to perform an oxidation desulfurization reaction, and separating the reacted material to remove sulfone compounds and/or sulfoxide compounds to obtain the second part of the ultra-low sulfur diesel fraction.
Wherein the oxidant is generally an aqueous hydrogen peroxide solution, the concentration of the oxidant can be 25 to 35 weight percent, and the molar ratio of the oxidant to the sulfur in the heavy fraction can be (1 to 10): 1.
wherein the acidic auxiliary agent can be at least one selected from formic acid, acetic acid and acetic anhydride, and the molar ratio of the acidic auxiliary agent to sulfur in the heavy fraction can be (0.5-5): 1.
wherein, the condition of the oxidation desulfurization reaction can comprise: the temperature is 30-80 ℃, and the reaction time is 0.5-80 min.
In order to further increase the product yield and optimize the desulfurization effect, in a preferred embodiment of the present disclosure, the oxidative desulfurization reaction may be performed in a microchannel reactor. Further, the microchannel reactor may have a plurality of sets of feed channels, each set of feed channels may include a first feed channel and a second feed channel, and the first feed channel and the second feed channel converge and communicate with a microchannel. The heavy fraction may be fed through the first feed channel (or second feed channel), and the mixture containing the oxidizing agent and the acidic assistant may be fed through the second feed channel (or first feed channel), which meet, mix, and undergo the oxidative desulfurization reaction in the micro-reaction channel. The minimum dimension of the micro-reaction channel is 0.1 mm-2 mm, and the minor dimension is 0.5 mm-10 mm. Wherein the definition of the smallest dimension and the next smallest dimension is well known to those skilled in the art, for example, when the cross-sectional shape of the micro reaction channel is circular, the diameter thereof is the smallest dimension; when the cross section of the micro reaction channel is rectangular, the width of the rectangle is the minimum dimension, and the length of the rectangle is the minor dimension; when the cross section of the micro reaction channel is in an ellipse shape, the short diameter of the ellipse is the minimum dimension, and the long diameter is the minor dimension; and so on. The small-size micro-reaction channel can obviously improve the contact surface between the heavy fraction and the mixture containing the oxidant and the acid auxiliary agent, thereby promoting the oxidative desulfurization reaction and effectively improving the product yield and the desulfurization effect. Furthermore, the first feed channel and the second feed channel may be arranged at an angle, e.g. 60 °, 90 °, 180 °, etc. The number of the feed channel groups can be designed according to actual needs. The heavy fraction of the oil phase can be fully mixed with the oxidant and the acid auxiliary agent of the water phase through the enhanced mixing effect of the microchannel reactor, and the oxidative desulfurization reaction can be completed within a relatively low severity and a relatively short time, specifically, in the preferred embodiment, the reaction conditions of the oxidative desulfurization reaction can include: the temperature is 30-80 ℃, and the retention time is 0.5-10 min.
After the oxidation desulfurization reaction is finished, the reacted materials can be neutralized and washed by alkali liquor, and then separated by an adsorption or extraction method to oxidize the generated sulfone compounds and/or sulfoxide compoundsAnd removing to obtain the second part of ultra-low sulfur diesel oil fraction. When the extraction method is used for separation, the extraction agent used can be any suitable polar solvent, such as N, N-dimethylformamide, methanol, dimethyl sulfoxide, etc., and the extraction conditions can be as follows: the temperature is 20-40 ℃, the pressure is 0.1-0.2 MPa, and the volume ratio of the agent oil is (0.5-3): 1. when the separation is carried out by adopting an adsorption method, the adsorbent can be silica gel, alumina and the like, and the adsorption conditions can be as follows: the temperature is 20-40 ℃, the pressure is 0.1-0.2 MPa, and the volume airspeed of the diesel oil is 0.2-0.6 h-1。
According to the present disclosure, the method may further comprise: in the step b, the light fraction and the exo-diesel fraction are mixed to carry out hydrodesulfurization treatment, the exo-diesel fraction is a diesel fraction with the distillation range of 160-390 ℃ produced by a straight-run diesel process, a coker diesel process or a catalytic cracking diesel process or a combination of two or three of the above processes, the light fraction and the exo-diesel fraction are mixed to carry out hydrodesulfurization treatment, and the exo-diesel fraction is a diesel fraction with the distillation range of 160-390 ℃ produced by a straight-run diesel process, a coker diesel process or a catalytic cracking diesel process or a combination of two or three of the above processes.
According to the present disclosure, the process may further comprise the step of blending the first portion of the ultra low sulfur diesel fraction obtained in step b with the second portion of the ultra low sulfur diesel fraction obtained in step c.
The method can effectively remove sulfur-containing compounds in the residual oil hydrogenated diesel oil, and the obtained ultra-low sulfur diesel oil product can meet the national V emission index (the sulfur content is not higher than 10 mu g/g), has high yield and has good economic benefit.
The following examples further illustrate the methods provided by the present disclosure, but are not intended to limit the disclosure thereto.
In the examples and comparative examples, the sulfur content of the diesel fuel stock was measured using an X-ray fluorescence instrument manufactured by XOS corporation by the following test method: ASTM-7039; the sulfur content of the diesel oil product is measured by adopting an EA5000 type instrument produced by Jena, and the test method comprises the following steps: SH-0689.
The hydrogenation catalyst C used in the examples and comparative examples was sold under the trade designation RS-2100, manufactured by China petrochemical catalyst division.
The overall yield of the diesel product was calculated using the following formula:
total yield (%) — light fraction mass fraction × hydrodesulfurization yield + heavy fraction mass fraction × oxidative desulfurization yield.
The basic properties of the raw oils used in examples and comparative examples are shown in Table 1.
TABLE 1
Raw oil Raw oil A Raw oil B
Origin of origin Fixed bed residual oil hydrogenated diesel oil Slurry bed residual oil hydrogenated diesel oil
Density (20 ℃ C.), g/cm3 0.8886 0.8580
Sulfur content, μ g/g 127 376
Nitrogen content,. mu.g/g 385 2210
Distillation Range ASTM D-86, deg.C
IBP 206 175
10％ 242 221
30％ 274 248
50％ 290 275
70％ 310 305
90％ 338 332
FBP 362 352
Example 1
Fractionating raw oil A according to the cutting point temperature of 340 ℃ to obtain a light fraction and a heavy fraction, wherein the light fraction accounts for 89.8 wt%, the sulfur content is 98 mu g/g, and the nitrogen content is 305 mu g/g; the heavy fraction accounted for 10.2 wt.%, the sulfur content was 382. mu.g/g, and the nitrogen content was 1089. mu.g/g.
Feeding the light fraction and hydrogen into a reactor filled with a hydrogenation catalyst together, and contacting the light fraction and the hydrogen with the hydrogenation catalyst to perform hydrodesulfurization reaction under the following reaction conditions: the temperature is 350 ℃, and the hourly space velocity of the raw oil is 2.0h-1Hydrogen partial pressure of 6.4MPa and hydrogen-oil volume ratio of 300Nm3/m3. The sulfur content of the liquid product (i.e., the first portion of the ultra low sulfur diesel fraction) in the resulting reactor effluent was 6.8 μ g/g, with a hydrodesulfurization yield of 99.9 wt.%.
A T-shaped microchannel reactor with 50 groups of feed channel groups is adopted, and a first feed channel and a second feed channel of each group of feed channel groups are arranged at an angle of 90 degrees and are converged and communicated with a micro-reaction channel; the smallest dimension of the micro-reaction channel is 0.3mm, and the next smallest dimension is 1 mm. The above-mentioned heavy fraction was fed from the first feed passage, and a mixture obtained by mixing a 30 wt% aqueous hydrogen peroxide solution and formic acid at a weight ratio of 1:0.5 was fed from the second feed passage, H2O2The molar ratio to sulfur in the heavy fraction was 2: 1, the molar ratio of formic acid to sulfur in the heavy fraction is 1: 1. the temperature in the microchannel reactor was 60 ℃ and the residence time was 2 min. Neutralizing the effluent of the microchannel reactor with 5 wt% sodium hydroxide solution, separating oil phase, and adsorbing with silica gel (adsorption conditions: 25 deg.C, pressure of 0.1MPa, and diesel volume space velocity of 0.4 h)-1) And the sulfur content of the finally obtained second part of ultra-low sulfur diesel fraction product is 7.1 mu g/g, and the yield of oxidative desulfurization is 91.8 percent by weight.
The first part of the ultra-low sulfur diesel oil fraction and the second part of the ultra-low sulfur diesel oil fraction are mixed to obtain the ultra-low sulfur diesel oil product with the sulfur content of 6.8 mu g/g and the total yield of 99.1 weight percent.
Comparative example 1
This comparative example is intended to illustrate a process in which the residue hydrogenated diesel oil is not fractionated, but is directly subjected to hydrodesulfurization treatment.
Feeding the raw oil A and hydrogen together into a reactor filled with a hydrogenation catalyst, and contacting with the hydrogenation catalyst for hydrogenation and dehydrationAnd (3) carrying out sulfur reaction under the following reaction conditions: the temperature is 350 ℃, and the hourly space velocity of the raw oil is 2.0h-1Hydrogen partial pressure of 6.4MPa and hydrogen-oil volume ratio of 300Nm3/m3. The sulfur content of the liquid product in the resulting reactor effluent was 17.2 μ g/g, with a hydrodesulfurization yield of 99.9 wt%.
When the reaction temperature was raised to 370 ℃ and other conditions were unchanged, the sulfur content of the liquid product in the resulting reactor effluent was 14.6. mu.g/g, and the hydrodesulfurization yield was 99.5% by weight.
As can be seen from a comparison of example 1 and comparative example 1, the light fraction obtained after fractionating a residual hydrogenated diesel oil according to the process of the present disclosure is subjected to hydrodesulfurization treatment to obtain a product having a lower sulfur content.
Comparative example 2
This comparative example is intended to illustrate the process of oxidative desulfurization treatment without fractionation of the residue hydrogenated diesel oil.
Using the same microchannel reactor as in example 1, feed oil A was fed from the first feed channel, a mixture obtained by mixing 30 wt% aqueous hydrogen peroxide and formic acid at a weight ratio of 1:0.5 was fed from the second feed channel, and H2O2The molar ratio to sulfur in the heavy fraction was 2: 1, the molar ratio of formic acid to sulfur in the heavy fraction is 1: 1. the temperature in the microchannel reactor was 60 ℃ and the residence time was 2 min. Neutralizing the effluent of the microchannel reactor with 5 wt% sodium hydroxide solution, separating oil phase, and adsorbing with silica gel (adsorption conditions: 25 deg.C, pressure of 0.1MPa, and diesel volume space velocity of 0.4 h)-1) The sulfur content of the finally obtained diesel product is 21.1 mu g/g, and the oxidative desulfurization yield is 92.3 weight percent.
As can be seen from a comparison of example 1 and comparative example 2, the sulfur content of the resulting product is lower when the heavy fraction obtained by fractionating the residual hydrogenated diesel oil is subjected to oxidative desulfurization according to the process of the present disclosure.
Comparative example 3
This comparative example serves to illustrate the effect of fractionating a residual hydrogenated diesel at a different cut point temperature than the present disclosure.
Fractionating the raw oil A according to the cutting point temperature of 325 ℃ to obtain a light fraction and a heavy fraction, wherein the light fraction accounts for 78.0 weight percent, the sulfur content is 74 mu g/g, and the nitrogen content is 258 mu g/g; the heavy fraction accounted for 22.0 wt%, the sulfur content was 315. mu.g/g, and the nitrogen content was 835. mu.g/g.
Feeding the light fraction and hydrogen into a reactor filled with a hydrogenation catalyst together, and contacting the light fraction and the hydrogen with the hydrogenation catalyst to perform hydrodesulfurization reaction under the following reaction conditions: the temperature is 350 ℃, and the hourly space velocity of the raw oil is 2.0h-1Hydrogen partial pressure of 6.4MPa and hydrogen-oil volume ratio of 300Nm3/m3. The liquid product (i.e., the first portion of the diesel fraction) in the resulting reactor effluent had a sulfur content of 6.3 μ g/g and a hydrodesulfurization yield of 99.9 wt%.
Using the same microchannel reactor as in example 1, the above-mentioned heavy fraction was fed from the first feed channel, a mixture obtained by mixing 30% by weight of an aqueous solution of hydrogen peroxide and formic acid in a weight ratio of 1:0.5 was fed from the second feed channel, and H was fed from the first feed channel2O2The molar ratio to sulfur in the heavy fraction was 2: 1, the molar ratio of formic acid to sulfur in the heavy fraction is 1: 1. the temperature in the microchannel reactor was 60 ℃ and the residence time was 2 min. Neutralizing the effluent of the microchannel reactor with 5 wt% sodium hydroxide solution, separating oil phase, and adsorbing with silica gel (adsorption conditions: 25 deg.C, pressure of 0.1MPa, and diesel volume space velocity of 0.4 h)-1) The sulfur content of the second portion of the diesel fraction finally obtained was 12.1. mu.g/g, and the oxidative desulfurization yield was 91.9% by weight.
The first portion of the diesel fraction and the second portion of the diesel fraction were mixed to obtain a diesel product having a sulfur content of 7.6 μ g/g and a total yield of 98.1 wt%.
As can be seen from a comparison of example 1 and comparative example 3, the product obtained using the process of the present disclosure has a lower sulfur content and a higher overall yield.
Example 2
Fractionating the raw oil B according to the cutting point temperature of 335 ℃ to obtain a light fraction and a heavy fraction, wherein the light fraction accounts for 88.9 weight percent, the sulfur content is 290 mu g/g, and the nitrogen content is 1525 mu g/g; the heavy fraction accounted for 11.1 wt%, the sulfur content was 1064. mu.g/g, and the nitrogen content was 7690. mu.g/g.
Feeding the light fraction and hydrogen into a reactor filled with a hydrogenation catalyst together, and contacting the light fraction and the hydrogen with the hydrogenation catalyst to perform hydrodesulfurization reaction under the following reaction conditions: the reaction temperature is 350 ℃, and the hourly space velocity of the raw oil is 1.5h-1Hydrogen partial pressure of 6.4MPa and hydrogen-oil volume ratio of 300Nm3/m3. The liquid product (i.e., the first ultra low sulfur diesel fraction) in the resulting reactor effluent had a sulfur content of 7.4 μ g/g and a hydrodesulfurization yield of 99.9 wt.%.
Using the same microchannel reactor as in example 1, the above-mentioned heavy fraction was fed from the first feed channel, and a mixture obtained by mixing 30% by weight of an aqueous solution of hydrogen peroxide and formic acid in a weight ratio of 1:1 was fed from the second feed channel, H2O2The molar ratio to sulfur in the heavy fraction was 3: the molar ratio of formic acid to sulfur in the heavy fraction was 3: 1. the temperature in the microchannel reactor was 50 ℃ and the residence time was 3 min. Neutralizing the effluent of the microchannel reactor with 5 wt% sodium hydroxide solution, separating out oil phase, and extracting with N, N-Dimethylformamide (DMF) (extraction conditions are 30 ℃, pressure is 0.15MPa, and solvent-oil ratio is 2: 1), wherein the sulfur content of the second part of the ultra-low sulfur diesel oil fraction is 6.9 mug/g, and the yield of oxidative desulfurization is 91.4 wt%.
The first part of the ultra-low sulfur diesel oil fraction and the second part of the ultra-low sulfur diesel oil fraction are mixed to obtain the ultra-low sulfur diesel oil product with the sulfur content of 7.4 mu g/g and the total yield of 99.0 weight percent.
Comparative example 4
This comparative example is intended to illustrate a process in which the residue hydrogenated diesel oil is not fractionated, but is directly subjected to hydrodesulfurization treatment.
Feeding the raw oil B and hydrogen into a reactor filled with a hydrogenation catalyst together, and contacting the raw oil B and the hydrogen with the hydrogenation catalyst to perform hydrodesulfurization reaction under the following reaction conditions: the temperature is 350 ℃, and the hourly space velocity of the raw oil is 1.5h-1Hydrogen partial pressure of 6.4MPa and hydrogen-oil volume ratio of 300Nm3/m3. Of the liquid product in the resulting reactor effluentThe sulfur content was 21.7. mu.g/g, and the hydrodesulfurization yield was 99.8% by weight.
When the reaction temperature was raised to 370 ℃ and other conditions were unchanged, the sulfur content of the liquid product in the resulting reactor effluent was 16.2. mu.g/g, and the hydrodesulfurization yield was 99.4% by weight.
As can be seen from a comparison of example 2 and comparative example 4, the light fraction obtained after fractionation of the residual hydrogenated diesel oil is hydrodesulfurized to obtain a product with a lower sulfur content according to the disclosed method.
Comparative example 5
This comparative example is intended to illustrate the process of oxidative desulfurization treatment without fractionation of the residue hydrogenated diesel oil.
Raw oil B, 30 wt% aqueous hydrogen peroxide solution and formic acid were mixed in accordance with the formula H2O2: formic acid: the molar ratio of sulfur in the feed oil B is 3: 3: 1, introducing the mixture into a reactor with the diameter of 500mm and filled with inert solid fillers for oxidation desulfurization reaction, wherein the temperature of the reactor is 50 ℃, the retention time is 80min, the effluent of the reactor is neutralized by 5 weight percent of sodium hydroxide solution, oil phase N, N-Dimethylformamide (DMF) is separated for extraction (the extraction conditions are 30 ℃, the pressure is 0.15MPa and the solvent-oil ratio is 2: 1), the sulfur content of the finally obtained diesel oil product is 9.8 mu g/g, and the oxidation desulfurization yield is 90.1 weight percent.
As can be seen from a comparison of example 2 and comparative example 5, according to the process of the present disclosure, the heavy fraction obtained by fractionating the residue hydrogenated diesel oil is subjected to oxidative desulfurization treatment in a microchannel reactor, the treatment time is greatly shortened, and the sulfur content of the obtained product is lower.
Example 3
Fractionating raw oil A according to the cutting point temperature of 340 ℃ to obtain a light fraction and a heavy fraction, wherein the light fraction accounts for 89.8 wt%, the sulfur content is 98 mu g/g, and the nitrogen content is 305 mu g/g; the heavy fraction accounted for 10.2 wt.%, the sulfur content was 382. mu.g/g, and the nitrogen content was 1089. mu.g/g.
Feeding the light fraction and hydrogen into a reactor containing hydrogenation catalyst, contacting with hydrogenation catalyst to perform hydrodesulfurization reactionThe conditions are as follows: the temperature is 350 ℃, and the hourly space velocity of the raw oil is 2.0h-1Hydrogen partial pressure of 6.4MPa and hydrogen-oil volume ratio of 300Nm3/m3. The sulfur content of the liquid product (i.e., the first portion of the ultra low sulfur diesel fraction) in the resulting reactor effluent was 6.8 μ g/g, with a hydrodesulfurization yield of 99.9 wt.%.
The above heavy fraction, a 30% by weight aqueous solution of hydrogen peroxide and formic acid are mixed according to H2O2: formic acid: the molar ratio of sulfur in the raw oil B is 2: 1: 1) introducing into a reactor with the diameter of 500mm and filled with inert solid filler for oxidation desulfurization reaction, wherein the temperature of the reactor is 60 ℃, the retention time is 30min, the effluent of the reactor is neutralized by 5 weight percent sodium hydroxide solution, and the separated oil phase is adsorbed by silica gel (the adsorption conditions are as follows: at 25 ℃, the pressure is 0.1MPa, and the volume space velocity of the diesel oil is 0.4h-1) The sulfur content of the second part of the ultra-low sulfur diesel oil fraction finally obtained is 14.8 mu g/g, and the yield of the oxidative desulfurization is 90.5 percent by weight.
The first part of the ultra-low sulfur diesel oil fraction and the second part of the ultra-low sulfur diesel oil fraction are mixed to obtain the ultra-low sulfur diesel oil product with the sulfur content of 7.6 mu g/g and the total yield of 98.9 weight percent.
Example 4
Fractionating the raw oil B according to the cutting point temperature of 335 ℃ to obtain a light fraction and a heavy fraction, wherein the light fraction accounts for 88.9 weight percent, the sulfur content is 290 mu g/g, and the nitrogen content is 1525 mu g/g; the heavy fraction accounted for 11.1 wt%, the sulfur content was 1064. mu.g/g, and the nitrogen content was 7690. mu.g/g.
Feeding the light fraction and hydrogen into a reactor filled with a hydrogenation catalyst together, and contacting the light fraction and the hydrogen with the hydrogenation catalyst to perform hydrodesulfurization reaction under the following reaction conditions: the reaction temperature is 350 ℃, and the hourly space velocity of the raw oil is 1.5h-1Hydrogen partial pressure of 6.4MPa and hydrogen-oil volume ratio of 300Nm3/m3. The liquid product (i.e., the first ultra low sulfur diesel fraction) in the resulting reactor effluent had a sulfur content of 7.4 μ g/g and a hydrodesulfurization yield of 99.9 wt.%.
The above heavy fraction, a 30% by weight aqueous solution of hydrogen peroxide and formic acid are mixed according to H2O2: formic acid: the molar ratio of sulfur in the feed oil B is 3: 3: 1) introducing the mixture into a reactor with the diameter of 500mm and filled with inert solid filler for oxidation desulfurization reaction, wherein the temperature of the reactor is 50 ℃, the retention time is 80min, the effluent of the reactor is neutralized by 5 weight percent of sodium hydroxide solution, and oil phase N, N-Dimethylformamide (DMF) is separated for extraction (the extraction conditions are as follows: 30 ℃, the pressure of 0.15MPa, the ratio of agent to oil of 2: 1) the sulfur content of the second part of the ultra-low sulfur diesel oil fraction finally obtained is 9.9 mu g/g, and the yield of the oxidative desulfurization is 90.4 weight percent.
And mixing the first part of the ultra-low sulfur diesel fraction with the second part of the ultra-low sulfur diesel fraction to obtain the ultra-low sulfur diesel product with the sulfur content of 7.7 mu g/g and the total yield of 98.8 percent by weight.
As can be seen from a comparison of examples 1-2 and examples 3-4, when the oxidative desulfurization treatment is carried out in a microchannel reactor, not only can the treatment time be shortened, but also the sulfur content of the resulting product is lower and the overall yield is higher.
Example 5
Fractionating the raw oil A according to the cutting point temperature of 331 ℃ to obtain a light fraction and a heavy fraction, wherein the light fraction accounts for 81.8 weight percent, the sulfur content is 78 mu g/g, and the nitrogen content is 268 mu g/g; the heavy fraction accounted for 18.2 wt.%, the sulfur content was 347 μ g/g, and the nitrogen content was 911 μ g/g.
Feeding the light fraction and hydrogen into a reactor filled with a hydrogenation catalyst together, and contacting the light fraction and the hydrogen with the hydrogenation catalyst to perform hydrodesulfurization reaction under the following reaction conditions: the temperature is 350 ℃, and the hourly space velocity of the raw oil is 2.0h-1Hydrogen partial pressure of 6.4MPa and hydrogen-oil volume ratio of 300Nm3/m3. The sulfur content of the liquid product (i.e., the first portion of the ultra low sulfur diesel fraction) in the resulting reactor effluent was 6.3 μ g/g, with a hydrodesulfurization yield of 99.9 wt.%.
Using the same microchannel reactor as in example 1, the above-mentioned heavy fraction was fed from the first feed channel, a mixture obtained by mixing 30% by weight of an aqueous solution of hydrogen peroxide and formic acid in a weight ratio of 1:0.5 was fed from the second feed channel, and H was fed from the first feed channel2O2The molar ratio to sulfur in the heavy fraction was 2: 1,the molar ratio of formic acid to sulfur in the heavy fraction was 1: 1. the temperature in the microchannel reactor was 60 ℃ and the residence time was 2 min. Neutralizing the effluent of the microchannel reactor with 5 wt% sodium hydroxide solution, separating oil phase, and adsorbing with silica gel (adsorption conditions: 25 deg.C, pressure of 0.1MPa, and diesel volume space velocity of 0.4 h)-1) And the sulfur content of the finally obtained second part of ultra-low sulfur diesel fraction product is 10.7 mu g/g, and the yield of oxidative desulfurization is 91.9 weight percent.
The first part of the ultra-low sulfur diesel oil fraction and the second part of the ultra-low sulfur diesel oil fraction are mixed to obtain the ultra-low sulfur diesel oil product with the sulfur content of 7.1 mu g/g and the total yield of 98.4 weight percent.
Example 6
Fractionating the raw oil A according to the cutting point temperature of 350 ℃ to obtain a light fraction and a heavy fraction, wherein the light fraction accounts for 94.5 weight percent, the sulfur content is 106 mu g/g, and the nitrogen content is 327 mu g/g; the heavy fraction accounted for 5.5 wt%, the sulfur content was 488 μ g/g, and the nitrogen content was 1381 μ g/g.
Feeding the light fraction and hydrogen into a reactor filled with a hydrogenation catalyst together, and contacting the light fraction and the hydrogen with the hydrogenation catalyst to perform hydrodesulfurization reaction under the following reaction conditions: the temperature is 360 ℃, and the hourly space velocity of the raw oil is 2.0h-1Hydrogen partial pressure of 6.4MPa and hydrogen-oil volume ratio of 300Nm3/m3. The liquid product (i.e., the first ultra low sulfur diesel fraction) in the resulting reactor effluent had a sulfur content of 7.2 μ g/g and a hydrodesulfurization yield of 99.9 wt.%.
Using the same microchannel reactor as in example 1, the above-mentioned heavy fraction was fed from the first feed channel, a mixture obtained by mixing 30% by weight of an aqueous solution of hydrogen peroxide and formic acid in a weight ratio of 1:0.5 was fed from the second feed channel, and H was fed from the first feed channel2O2The molar ratio to sulfur in the heavy fraction was 2: 1, the molar ratio of formic acid to sulfur in the heavy fraction is 1: 1. the temperature in the microchannel reactor was 60 ℃ and the residence time was 2 min. Neutralizing the effluent of the microchannel reactor with 5 wt% sodium hydroxide solution, separating oil phase, and adsorbing with silica gel (adsorption conditions: 25 deg.C, pressure of 0.1MPa, and diesel volume space velocity of 0.4 h)-1) And the sulfur content of the finally obtained second part of ultra-low sulfur diesel fraction product is 4.1 mu g/g, and the yield of oxidative desulfurization is 91.7 weight percent.
The first part of the ultra-low sulfur diesel oil fraction and the second part of the ultra-low sulfur diesel oil fraction are mixed to obtain the ultra-low sulfur diesel oil product with the sulfur content of 7.0 mu g/g and the total yield of 99.4 weight percent.
As can be seen from the comparison of example 1 with examples 5-6, the sulfur content of the resulting product is lower when the cut point temperature is 335-345 ℃.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (10)

1. The ultra-deep desulfurization method of the residue hydrogenated diesel oil is characterized by comprising the following steps of:
a. fractionating residual oil hydrogenated diesel oil to obtain a light fraction and a heavy fraction, wherein the cutting point temperature of the light fraction and the heavy fraction is 331-355 ℃;
b. b, carrying out hydrodesulfurization treatment on the light fraction obtained in the step a to obtain a first part of ultra-low sulfur diesel oil fraction;
c. and c, carrying out oxidation desulfurization treatment on the heavy fraction obtained in the step a to obtain a second part of ultra-low sulfur diesel fraction.
2. The method according to claim 1, wherein in step a, the cut point temperature of the light fraction and the heavy fraction is 335-345 ℃.
3. The process of claim 1, wherein in step b, the hydrodesulfurization treatment comprises: contacting the light fraction with a hydrogenation catalyst to carry out hydrogenation reaction;
the hydrogenation catalyst comprises a carrier and metal active components loaded on the carrier, wherein the carrier is amorphous alumina and/or amorphous silica-alumina, the metal active components are VIB group non-noble metals and/or VIII group non-noble metals, the VIB group non-noble metals are Mo and/or W, and the VIII group non-noble metals are Ni and/or Co.
4. The process of claim 3, wherein the hydrogenation reaction conditions are: the temperature is 320-420 ℃, the pressure is 3.0-15.0 MPa, and the liquid hourly space velocity is 0.5-6.0 h-1The volume ratio of hydrogen to oil is 100-1000 Nm3/m3。
5. The method of claim 1, wherein in step c, the oxidative desulfurization treatment comprises: and (3) contacting the heavy fraction with a mixture containing an oxidant and an acidic auxiliary agent to perform an oxidation desulfurization reaction, and separating the reacted material to remove sulfone compounds and/or sulfoxide compounds to obtain the second part of the ultra-low sulfur diesel fraction.
6. The method of claim 5, wherein the oxidizing agent is a 25-35 wt% aqueous hydrogen peroxide solution, and the molar ratio of the oxidizing agent to the sulfur in the heavy fraction is (1-10): 1;
the acid auxiliary agent is at least one selected from formic acid, acetic acid and acetic anhydride, and the molar ratio of the acid auxiliary agent to sulfur in the heavy fraction is (0.5-5): 1.
7. the process of claim 5, wherein the oxidative desulfurization reaction is carried out in a microchannel reactor having a plurality of sets of feed channels, each set of feed channels including a first feed channel and a second feed channel, the first feed channel and the second feed channel converging to communicate with a microchannel; said heavy fraction being fed by said first feed path and said mixture comprising oxidant and acidic adjuvant being fed by said second feed path; the sizes of the minimum dimensions of the micro-reaction channels are respectively 0.1 mm-2 mm, and the sizes of the secondary minimum dimensions are respectively 0.5 mm-10 mm;
the reaction conditions of the oxidative desulfurization reaction include: the temperature is 30-80 ℃, and preferably 40-60 ℃; the retention time is 0.5-10 min, preferably 1-8 min.
8. The method according to claim 1, wherein the residue hydrogenated diesel oil is a diesel oil fraction produced by a residue hydrogenation process and having a distillation range of 160-390 ℃, and the sulfur content of the residue hydrogenated diesel oil is 50-2000 μ g/g.
9. The method of claim 1, wherein the method further comprises: in the step b, the light fraction and an externally produced diesel oil fraction are mixed for the hydrodesulfurization treatment, wherein the externally produced diesel oil fraction is a diesel oil fraction with the distillation range of 160-390 ℃ produced by a straight-run diesel oil process, a coking diesel oil process or a catalytic cracking diesel oil process or a combination of two or three of the straight-run diesel oil process, the coking diesel oil process and the catalytic cracking diesel oil process.
10. The process of claim 1 further comprising the step of combining said first portion of the ultra low sulfur diesel fraction from step b with said second portion of the ultra low sulfur diesel fraction from step c.
CN201810691538.XA 2018-06-28 2018-06-28 Ultra-deep desulfurization method for residual oil hydrogenated diesel oil Pending CN110655954A (en)

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