TW466268B - Method for manufacturing cleaner fuels - Google Patents

Abstract

A method is provided for manufacturing cleaner fuels, in which NPC (natural polar compounds), naturally existing in small quantities within various petrolic hydrocarbon fractions, are removed from the petrolic hydrocarbon fractions ranging, in boiling point, from 110 to 560 DEG C and preferably from 200 to 400 DEG C, in advance of catalytic hydroprocessing. The removal of NPC improves the efficiency of the catalytic process and produces environment-friendly products, such as diesel fuel with a sulfur content of 50 ppm (wt) or lower. Also the NPC can be used to improve fuel lubricity.

Description

A7 4 6 626 8 _B7__ V. Description of the invention (I) Field of the invention The present invention relates to a method for preparing clean fuels, and in particular, to a stagnation point of 110 to 560 before a catalytic hydroprocessing process Method for removing NPC (natural polar compounds) from petroleum hydrocarbon raw materials at ° C. The removal of NPC improves the efficiency of the catalyst and produces environmentally friendly products, especially those related to diesel with less than 50 ppm (wt) sulfur content. In addition, the present invention also guides the use of, for example, NPC to improve fuel lubricity. Prior Art of Invention The problems of past environmental pollution, especially the deterioration of air quality, have led to strict environmental regulations around the world, and developed countries have also implemented strict controls on the fuel used in transportation vehicles. Among these fuels, diesel is considered to be a major source of harmful pollutants such as Sox, NOx, and PM (particulate matters, special substances). Therefore, the most stringent regulatory standards are preparing to implement diesel. Many diesel specifications, such as sulfur content, aromatic content, polyaromatic content, colorless and transparent saturated hydrocarbon content (cetane) content, T95 (95 ° /. Distillation temperature), density and viscosity affect the aforementioned pollutants Production, but sulfur content becomes the most important issue, because it will form sulfur dioxide during combustion. What's more, part of the sulfur dioxide is easily converted into sulfur trioxide, which will form PM (special substance) with water vapor. In addition to the formation of PM (special substances), sulfur-containing compounds such as sulfur dioxide and sulfates can harm the exhaust gas aftertreatment equipment by poisoning precious metal catalysts. Recently, automakers have claimed that diesel sulphur content should be lower than the long-term legacy * 3 Oppm (wt) to be suitable for new engines that comply with future exhaust specifications. As a result, the self-zhang scale applies the national standard (CNS) A4 specification (210 X 297 public room 4) -----; --- I ---- 1 > equipment-(Please read the precautions on the back first ^ Write this page) Order. -Line-

Printed by the Intellectual Property Bureau's Consumer Cooperatives of the Ministry of Economic Affairs-M 4 6 626 8 A7 B7 Printed by the Employees' Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (Y) ULSD (ultra-low sulfur content) diesel market is enthusiastic, especially in the Western Europe. This fuel is expected to eventually replace the traditional diesel market with 500 ppm (wt) sulfur content. To keep up with tighter regulations, oil companies have invested heavily in producing environmentally friendly petroleum products. Such as retrofitting existing equipment or installing new processes. However, from an economic point of view, there is no existing or novel process that is economically cost-effective under the current price structure. Therefore, the United States and European countries have implemented policies to encourage refineries such as tax incentives to compensate for the additional production of clean fuels. cost. HDS (hydrodesulfurization ’gas desulfurization reaction) process is the most common process to reduce the sulfur content of diesel by converting sulfur compounds into hydrogen sulfide. In the late 1950s, the HDS process was originally used as a pretreatment for naphtha refining because sulfur compounds are extremely toxic to catalysts. Since then, various HDS processes have been developed. In the I960s, the HDS process of LGO (light gas oil) appeared for the first time, and now most of them have HDS process. Statistics show that in 1994, 21% of the world's crude oil distillation unit capacity was kerosine and LGO HDS process unit capacity. The HDS process used by many refineries today is a non-licensed process, and most of the related patents belong to the preparation and upgrading of catalysts. Generally speaking, when the process variables and catalysts are appropriately modified, diesel with a sulfur content of 0.1% by weight can be produced. However, to produce diesel with a sulfur content below 50 ppm (wt), operating variables such as catalyst activity, reaction temperature, bed volume, and hydrogen partial pressure require innovative improvements. Since the first generation of LGO HDS was introduced into production in the 1960s, the catalyst activity has more than doubled. The catalyst activity was modified in deep HDS to achieve the required level. The so-called deep HDS refers to the hydrogen-sulfur-removal anti-reflective sheet paper scale _ house mark (CNS) .- Vi specification (210 χ 297) Reading-Note on the back · Note Ψ Item t Write page binding 〇4 6 62 6 8 a7 ^ ________ B7________ 5. Explanation of the invention (>) The rate of hydrodesulfurization should be greater than 95%. Reduce the sulfur content from 2000ppm to 500ppm, compared with the first-generation catalyst, the catalyst activity needs to be improved by about 3.2 times, and reduce the sulfur content from 500ppm to 50ppm, compared to the first-generation catalyst. The catalyst activity needs to be improved by about 17.6 times. This means that unless catalyst activity can be dramatically improved, in a deep HDS process, the number of reactors must be increased or the charging rate must be reduced. What's worse, when the reaction conditions become strict, the catalyst life will be shortened to I / 2 to I / 5 of the traditional catalyst life, and the catalyst will become more important because it requires more metal to be embedded in the catalyst. Expensive, and more complex modifications to the supported structure. Increasing the reaction temperature can reduce the sulfur content, but because most HDS processes are designed to have 0-2% sulfur content, these boilers or reactors cannot be operated beyond the design limit. In addition, increasing the reaction temperature will result in poor product and color travel and reduced catalyst life. In the past, many refineries tended to install additional reactors to meet regulatory requirements, as this seemed simple and straightforward. However, due to space constraints, the huge capital required to add reactors, and the pressure drop in the reactor, only a very limited number of reactors can be added. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and increasing the pressure on large reactors, as mentioned earlier, is another option. However, the cost of retrofitting high-pressure reactors, compressors, pumps, and heat exchangers is very high, let alone increasing hydrogen consumption. In addition to sulfur, whether the aromatic content should also be used as the quality standard for diesel has been debated for a long time. However, low-aromatic diesel for automobiles has been manufactured and sold in the United States and parts of Northern Europe. However, 'to saturate aromatic compounds, a large amount of hydrogen and precious metal catalysts are needed, and energy consumption will also be significantly larger. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 male 4) Λ7 '46 626 8 V. Description of invention (flat) Increased. In addition, the use of precious metal catalysts requires an additional HDS process for hydrogen treatment to prevent sulfur or nitrogen compounds from deactivating the catalyst. Only a few of the hydrogen treatment processes designed to remove sulfur compounds and aromatic and aromatic compounds from LGO to produce clean diesel oil can be commercialized. Among these, they can be classified into the following three categories. The first type is to perform HDS (hydrogen desulfurization reaction) & HDA (hydrogen removal of aromatic reaction) simultaneously in a single reactor under high temperature and high pressure in the presence of a highly active nickel-molybdenum-based catalyst. However, this process has not been widely used, because its high temperature and high pressure equipment, accompanied by a low process rate, increase the cost of investment in vain. Moreover, its conversion rate of aromatic compounds is not high. The second is to use a series reactor. Deep HDS is completed in the former reactor, while the latter reactor is filled with precious metal catalysts to reduce the aromatic compound content. This process usually involves adding an HDA unit after an existing HDS unit. Compared with the HAD unit alone, the HDA conversion rate is significantly improved. However, investment costs and operating costs have also increased significantly. The third is the Syn-Sat process. This is the use of countercurrent flow for HDS and HDA in a single reactor. The Syn-Sat process has a higher conversion rate than any printed by its Consumer Cooperative in the Intellectual Property Bureau of the Ministry of Economic Affairs, and it is also more economical than other processes. However, compared with the deep HDS process, the Syn-Sat process requires a lot of investment costs and operating costs. In addition, special attention must be paid to the poisoning effect of HDA catalyst, so that the sulfur compound content of the HDS export is not higher than 1 Oppj ^ wt). As mentioned above, the traditional LGO processing process has its technical limitations before the catalyst activity has made a big breakthrough. Therefore, research on the use of raw materials different from LGO, or the use of novel reaction paths to produce clean diesel fuel is being accelerated. This paper size applies to China National Standard Sheep (CNS) A 'specifications χ Guan Gong Ai Ai)' 46626 8

V. Description of the Invention (f) Plant, taking hydrogen cracking processes as an example, using VGO (Vacimm Gas Oil) instead of LG0 to illustrate these methods. Because VG0 has a high sulfur content and nitrogen compound content, the HDS process and nitrogen cracking process are completed in a two-stage reactor at high temperature and pressure. The kerosene and diesel distillate obtained from the hydrogen cracking process contain almost no sulfur and contain less than 50% of aromatic compounds compared to the products obtained from the [GO HDS process]. However, due to the high viscosity of the feed, the reaction efficiency is low and its investment cost is almost three times higher than that of traditional deep HDS. There is also a process for polymerizing natural gas to produce diesel distillate, such as Shell ’s middle distillate (Symthesis, SMDS) process. In the SMDS process, natural gas is converted into syn-gas' by Fisher_Tropsch reaction, and then it is polymerized to produce a diesel distillate that does not contain sulfur and aromatic compounds. However, because the feed is very expensive and the reaction needs to be completed in three steps, high investment is inevitable. Therefore, there is no economic benefit to most refineries unless they own a natural gas field and their gas-liquid conversion process is near the natural gas field. Du Printing by Employees of Intellectual Property Bureau of the Ministry of Economic Affairs Recently, a new technology using biocatalyst (bio-catalySt), namely the biodesulfurization process, is being developed. The biological desulfurization system selectively removes sulfur compounds that are difficult to handle, that is, sulfur compounds that are difficult to remove in the traditional HDS process, and is applied as an auxiliary process of the HDS process. However, the report points out that the biological desulfurization reaction process does not have sufficient reaction efficiency (space rate is about 0.1hr-1) to be applied to mass production scale refineries. Biological desulfurization also produces by-products such as hope. This paper size applies the national standard (CNS) A4 specification (210 ^ 297 4 6 626 8 A7 _; _. B7_ V. Description of the invention (t) US5,454,933 reveals an adsorption process to process LGO fluid from HDS Sulfur compounds are removed to produce sulfur-free diesel. Although similar adsorption principles are used, the present invention differs from this case in that it is upstream from the HDS unit to remove NPC instead of removing sulfur compounds to improve the HDS unit. The sulfur conversion rate is different from this case. As is generally known, adsorption is not effective in removing sulfur compounds from petroleum hydrocarbons. Sulfur compounds have a low polarity with respect to nitrogen and oxygen, and sulfur adsorption from the feed reaches 0.05 % Of the adsorbent is difficult to obtain. When the adsorption is repeated, the adsorption efficiency of activated carbon tends to gradually disappear. Therefore, in order to maintain the sulfur removal rate, the adsorbent V .... needs to be regenerated more frequently However, this will result in lost productivity and increased operating costs, as fewer feeds can be processed and more solvents consumed in the operating cycle. Because the technique disclosed in US 5,454,933 fails to indicate whether sulfur migration can be maintained The removal rate, so a series of experiments with activated carbon with similar physical properties used in US5,454,933. It was found that the sulfur removal rate of US5,454,933 could not meet the requirements. When the desorption was repeated, the sulfur removal rate decreased and the desorption Liquid, that is, by-products, is generated too much. The results of this experiment are listed in Comparative Example 18 below. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, US 5,730,860 reveals that a conventional hydrogen treatment process cannot overcome the inability to generate sulfur content below 30 ppm ) Or less gasoline products. According to the technology of US 5,730,860, it contains high concentrations of sulfur compounds, nitrogen compounds and oxygen compounds (such as mercaptans, amines, moons and peroxides, fluidized cracked gasoline, semi-refined gasoline). Products) hydrocarbons are processed by counter current-type fluidizing adsorption process and the adsorbent is regenerate with hot hydrogen. The adsorbed liquid is condensed with heterogeneous compounds and then applied to this country on the paper scale. Standard (CNS) A4 specification (210x 297 male: g) 46626 8 A7 —--------- §z ____ ___ V. Description of the invention (7) HDS processing. But this The process has the limitation that it cannot be applied to hydrocarbon fluids with a boiling point higher than 2601 or higher. In addition, because the by-products generated by it need to be processed by the diesel HDS process, the performance of sulfur removal under deep HDS conditions will have a negative impact . Therefore, the application of this technology to the current generation of gasoline and ultra-low sulfur fuel is very problematic. In addition, the biodiesel product prepared by the presence of oil products and about 20% of the extracted vegetable oil phase formula It has been found that these biodiesel products can significantly reduce the production of pollutants. These bio-diesel products have developed into alternative fuels in some countries where crops are problematic. This is why they are led to add 20% of traditional diesel. However, in this case, the stability of storage also caused great problems. 0 As mentioned above, various attempts to produce clean oil have been proposed, but they must be invested or technically limited. They are not cost-effective. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The inventor made a concentrated and thorough research on the production of clean fuels, and found that the conventional technologies such as LGO pretreatment for adsorption or extraction can greatly improve the use in deep HDS Regional catalyst us HDS performance. The petroleum distillates removed during the pretreatment step of the present invention include various functional groups having functions such as _COOH (naphthoic acid), -OH (phenol), -N (p-pyridine), and _NI1 (this) Compounds, and compounds different from the following benzylphene and the like in Example 4 below. Nitrogen-containing compounds are mainly heterocyclic compounds such as u-carbazole, benzophenone, and other compounds. Acridine and tetrahydrobian. Although these distillates also contain saturated and aromatic compounds, these distillates exhibit a high polarity characteristic due to the high concentration of the above-mentioned polar compounds. These polar compounds constitute only a small amount in petroleum hydrocarbons. Therefore, these polar compounds are defined as NPC (Natural Polar Compounds) to avoid the application of the Chinese National Standard (CNS) A4 specification (210 x297) on this paper scale. 46 626 8 A7 B7 V. Description of the invention (); Exemptions and processes such as Additives, chemicals, or similar synthetic polar compounds are confused. 0 NPCs will have different physical properties and compositions depending on the crude oil source, viscosity, and pretreatment of the distillate. NPCs separated from LGO are almost electrically neutral and can be divided into groups such as acidic, basic, and neutral compounds. The high NPC content of petroleum products with high stagnation points becomes higher, but the existence of NPC is still relatively small, so the removal of these compounds has only a small amount of physical and chemical properties such as viscosity range and sulfur content and aromatic compounds. influences. Therefore, NPC does not like by-products and impurities, and NPC does not harm the catalyst or the catalytic process. Although NPC has a relatively high polarity and density compared to the distillate from which NPC is removed, the completion of the sulfur conversion target of the NPC in the HDS process will not cause a burden. However, according to the present invention, it is found that even if a small amount of NPC is present, the deep desulfurization in the HDS process should have a significant negative impact. The deep desulfurization reaction only occurs in compounds such as diphenylmethylphene (DBT) and 4,6. -Dimethylbenzophene (46 DMDBT) conversion can be completed. Extensive research on the removal of npc by the inventors of this case found that these well-known technologies such as adsorption and effective pre-treatment of the solvent HDS units upstream to produce clean fuel. Extraction can be printed by the Intellectual Property Office of the Ministry of Economic Affairs and the Consumer Affairs Agency. To remove impurities and polar compounds from hydrocarbon feedstocks, adsorption and solvent extraction have been widely used for a long time. For example, U.S. Patent No. 5,300,218 discloses the use of an appropriate adsorbent, such as a carbon molecular complex, to remove diesel smoke from diesel fuel. U.S. Patent No. 4,912,873 also discloses an adsorption process that uses polymer resin to process diesel or spray oil to reduce color and filtration problems. However, the complex molecular salt complex polymer resin is not effective for the present invention.

1 This paper size applies the Yin Guozheng standard (CNS > A4 regulations ^ " ^ 210 X 297.) 4 6 626 8 A7 B7 V. Description of the invention (<]) Benefits of NPC color! In addition to the proportion and the adsorbent used Too expensive. In addition, the application range of the carbon molecular complex or the polymer resin is different from those of the present invention related to improving the catalytic activity of the hydrogen process. For petroleum and petrochemical processes, the catalytic reaction process occupies an important position, and protecting the catalyst from permanent deactivation is also an important chapter. In order to avoid permanent inactivation caused by previous steps or raw materials by-products or impurities, various pretreatment processes have been proposed. In these pretreatment processes, the principles of adsorption and solvent extraction are the most commonly applied. Typical examples include mechanical filtration to prevent the accumulation of tiny impurities, naphthoic acid in raw materials used in alkaline washing columns to be neutralized and extracted with alkaline catalysts in the Merox process, and adsorption of sulfur or olefins in activated mud columns before the nano-reforming process. Group of hydrocarbons. Especially in the process of isomerization and etherification reaction, the catalyst is susceptible to impurities. The pretreatment technology of removing these cones of plutonium is widely studied. Representative previous cases include: US Patent Nos. 5,516,963, 5,336,834, and 5,264,187 No. 5,271,834, 5,120,881, 5,082,987, 4,795,545, and 4,409,421. However, the scope of application, raw materials or processes of these documents are different from this case. U.S. Patent Nos. 4,344,841, 4,343,693, and 4,269,694 are related to adsorption technologies that prevent the formation of water, precipitates, and additives from forming deposits and pollution reduction equipment in catalytic processes such as subsequent hydrogen treatment processes. U.S. Patent No. 4,176,047 discloses a pretreatment process using an aluminum catalyst in the Delayed Coker process to prevent silicon-based antifoaming from adversely affecting subsequent HDS processes and improving the octane process. This paper size applies to Chinese national standards (CNSM4 specifications (210 X 297 must not -----.-------- vlk —— (Please read the precautions on the back first to write this page)) On the 0th line · Economic Printed by the Consumers' Cooperative of the Ministry of Intellectual Property Bureau 4β 626 8 Α7 B7 V. Description of the Invention (丨.) US Patent No. 4, 〇33,861 discloses a method for reducing the nitrogen content in hydrocarbon raw materials, by making it difficult for these to pass through hydrogen The nitrogen compounds removed by the denitrification reaction are polymerized and separated by their increased boiling point. US Patent No. 3,954,603 discloses a removal of hydrogen-breaking materials such as Shale oil, Syncrude, and bitumen, such as kun or magnetic, which will poison Method for catalyst contamination using iron, cobalt, or oxidation or sulfide of these metals, or mixtures thereof in a two-step pretreatment process. Review the previous techniques in detail, as previously described, adsorption and / or solvent extraction It is only used to improve product quality and the situation that the catalytic reaction process does not work properly due to additives, impurities, or by-products from previous steps and / or raw materials. Until now, the present invention The basic facts of NPC removal have never been proposed, and the present invention has a great impact on the catalyst activity of deep HDS processes. ΛV Please read the precautions on the back before writing this page) Binding- Summary of Inventions Printed by Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics The purpose of this invention is to improve the catalytic process by removing naturally occurring NPCs from crude oil. The components of NPCs do not affect the activity of catalysts used in general processes. Causes a fatal effect, which usually changes according to its own reaction pathway in the catalytic process. However, when a specific sulfide requires high reaction energy for its removal, it needs desulfurization to obtain a desulfurization rate of 97 ° /. At or above, NPC was found to have a significant effect on the effectiveness of the reaction with the sulfide in the reaction pathway. According to the present invention, the influencing factors of the NPC form can be easily obtained through adsorption / desorption or falling agent extraction techniques. Removal and removal of raw materials of Npc can increase i · 2% iHDS rate. This improvement seems to be not much, however, this increase-line 〇Ι A7 A 6 62 6 8____B7 It shows that (U) 1-2% is significant in the deep HDS region, making it possible to produce diesel with a sulfur content of less than 50 ppm (wt) by a more economical method than any conventional method. Although the diesel fraction is concerned Various technologies for desulfurization and dearomatization of materials have been developed, but the fact is that the company does not consider them to be economically feasible. In order to economically produce petroleum products with low sulfur 'nitrogen and aromatic content to reduce vehicle harmful gas emissions, The present invention provides the removal of NPC to improve the efficiency of the catalyst. It is not found in other prior art documents and is superior to the previous process. The previous process requires excessive investment and high operating costs. As a result of the intensive and thoughtful experience of the inventors, continuous efforts have been made to apply the theory of the present invention to commercialization, which also shows that some adsorbents can be continuously regenerated in applications such as adsorption / desorption, and the removal and improvement of the NPC is subsequently Implementation of various raw materials catalytic reaction process. In addition, regarding the reduction of the frictional force caused by the result of the deep desulfurization reaction, it has been found that the concentrated NPC obtained by adsorption is effective as a natural friction modifier. Although the 'fixed bed absorption technique' is used to prove many cases of the present invention, it is applied to other forms of pretreatment, which can be selected according to raw materials, including fluid bed adsorption and solvent extraction, and are also included in the scope of the present invention. Printed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs for cooperation in printing [Simplified illustration]: Figure 1: Flow chart of the basic concept of the present invention. Figure 2: Simple flowchart of the adsorption process according to the present invention. Fig. 3: Curves of sulfur concentration vs. reaction temperature according to the two products of NPC-removed raw material and alkali raw material removed in Example 13. Figure 4. Graph of nitrogen removal rate versus number of regenerations according to Example 10. 'This paper size applies to China National Standard (CNS) A4 specification (210 X 297 JM6 62 6 8 A7 __B7. V. Description of the invention ([>). :: r Drawing number description: None [preferable specific embodiment Detailed description] The present invention is related to the substantial removal of NPC from petroleum hydrocarbon raw materials, which can improve the catalyst activity of the subsequent catalytic hydrogen treatment process, is helpful for the economical production of clean fuels, and can reduce pollutants, especially PM, NOx. And SOX pollutants after combustion in the engine. The entire concept of the present invention is illustrated in Figure 1. The petroleum hydrocarbon raw material used in the present invention has a boiling point between 110 and 560. (:, preferably between 200 to 400 ° C. These naturally occurring NPCs of petroleum hydrocarbon distillates can be removed by adsorption or solvent extraction. According to a series of experimental research results of the present invention, the use of one or more adsorbents to adsorb NPCs is the best way to remove NPCs. Effective method. The hydrocarbon fuel produced according to the present invention preferably has a boiling point range of 110 ° C to 400 ° C, and preferably has a sulfur content of less than 500 ppm (wt) and most preferably less than 50. ppm (wt) 〇 Adsorption is widely used in Example, while operating in a single column to briefly illustrate the invention. The actual procedure can be converted into two or more fixed beds for continuous operation of adsorption and desorption. Printed by Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives In the present invention, the NPC is removed from the petroleum raw material distillate to substantially reduce the NPC concentration in the petroleum raw material distillate. The so-called substantial reduction of the NPC concentration is at least 50%, that is, at least 50% of the NPC is removed from the petroleum raw material distillate. In addition, preferably, about 60% to 90% of the NPC is removed from the petroleum feed fraction. As shown in the following examples, 'the interaction is performed through a single adsorption column. Adsorption and desorption, NPC Can be easily removed from hydrocarbon feedstocks. NPCs that are removed or extracted from petroleum feedstock distillates, preferably from 5.0 to 50% by weight of oxidation-containing '^ Paper Standard Chinese National Standard (CNS) A4 Specification ( 210 X 297 41½) '' 4 6 626 8 A7 at V. Description of the invention (13), 50 to 50 wt% nitrogen-containing heterocyclic compound, and sulfur content ranging from 0.1 to 5.0 wt ° /. 0 1 of NPC-based petroleum feedstock distillates removed or extracted 5_0 Comment 丨% composition. 'In general, the viscosity of raw materials will increase when the boiling point increases, and the amount of NPC (and nitrogen content in NPC) extracted will increase. Therefore, according to the raw materials used, adsorption. Pretreatment procedures For example, the operating parameters of RPA (Ratio of Product to Ads.orbent), temperature, and LHSV (liquid hourly space velocity, 1 ι · ι) also change accordingly. Among these parameters, RPA is the most important operating parameter in the preprocessing step. RP A is more defined: defined as the ratio of the treated product to the adsorbent under an operating cycle that includes a series of steps of adsorption, cleaning and regeneration. When RpA is low, strict adsorption procedures and adsorption work also increase. The adsorbents in the examples include activated aluminum, aci (i white clay), Fuller's earth, activated carbon, zeolite, aluminum hydroxide, silicone, and ion exchange resin. Aluminum hydroxide and silicone The strong adsorption position, its adsorption mechanism like hydrogen bonding system is particularly suitable for reproducibility. The aforementioned adsorbent can be selected from two or more combinations, and the correct combination can increase the adsorption efficiency; the simultaneous use of silicone gel and ion exchange resin in the adsorption column requires It is more efficient than removing NPC by using a kind of Shixijiao ion exchange resin. + Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. -. Γ .. (Please read the precautions on the back before filling this page) ί Line: The preferred silicone adsorbent has a pore size of 40 to 2000 A., a specific surface area of 100 to 1000 m2 / g, and The pore volume is 0.5 to 1.5 cc / g. Please refer to Fig. 2, which shows an adsorption system according to the present invention. Process. First, liquid hydrocarbons flow into one of two or more adsorption tubing columns at a predetermined time and interact with each other. Make NPC sucked When the carbon gas of the NPC has been removed, and the night is entered into the subsequent catalytic process, the adsorption column with the NPC is desorbed, and the paper size is compliant with the Chinese National Standard (CNS) A4 specification (210x297 ' ii) 4 6 626 8 A7 B7 V. Description of the invention (I) The desorption is performed to regenerate the adsorption column. The desorption solvent is usually an alcohol, ether or net containing six or less carbon atoms. Specific examples There are methanol, methyl-tert-butyl ether and acetone. In general, the aforementioned solvents have low boiling points and are therefore easily distilled and recovered from raw materials or NPCs. The two fixed beds used in the aforementioned process can be changed to-liquid beds or A moving bed is used instead to obtain the same result. The catalytic reaction process after the adsorption pretreatment step can be HDS, HAD, mild hydrogen cracking, hydrogen cracking, or a combination thereof. The catalyst used in these processes has an acid activation site on the surface of the catalyst. Although the heteroatom-containing polar compounds do not permanently deactivate the catalyst, the activity of the catalyst is reduced because these compounds tend to be adsorbed on the activation sites of the fluorinating agents. The invention also discloses that the use of NPC as a natural friction modifier can combat the degradation of friction caused by the result of deep desulfurization. In these applications, the NPC is concentrated to a nitrogen content in the NPC that becomes 10 times or more than that of the raw material. High (preferably more than 50 times), and the content of oxygen-containing organic acid or phenol is about 10% or higher, preferably 15% or higher. NPC is preferably concentrated by an adsorption process, and more preferably The adsorbent used is selected from the group consisting of activated carbon, zeolite, hydroxide, silica gel, ion exchange resin, and combinations thereof. Most of the NPCs extracted by adsorption have nitrogen content, sulfur content, and all acids. The number will decrease. In particular, the nitrogen content becomes closely related to the NPC removal ratio 'as shown in Example 4. Although it is expected that the content of oxygenates will change with the removal of NPC, it is very difficult to capture the changes in oxygen content of treated hydrocarbons because the change occurs on the margin of error in oxygen content analysis. If NPC weight changes can be measured and compared, the NPC removal ratio can be accurately quantified ' However, this measurement must take an unrealistically long time. So please read the note on the back first and then write the booklet and bookbinding. Printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size is applicable to China Guokuan De Pange 4 A 1 / ^ Public 7 9 2 A7 4 6 626 8 5 Explanation of the invention (丨 5) The NPC removal ratio is expressed by the change of nitrogen content in the following examples, because the nitrogen content is relatively easy to analyze, as shown in the examples, the error range is relatively reasonable. Example 1 LGO and light cycle Oil (LCO) is used as the raw material of the present invention, and its properties are changed according to the form of crude oil. In Table 1, the properties and composition of various LGOs and an LCO are listed. These oils are uniquely used in connection with the present invention. As mentioned before, the composition and properties of NPC; can be changed with the use of raw materials, but these changes are not intended to limit the present invention. In Table 1, "A", "B" and "C" are LGOs with different boiling point sulfur and nitrogen contents, and "D" is LCO produced from the atmospheric residue (AR) fluid catalytic conversion (FCC) process . -----; ------- Th Pack ---- (Please read the notes on the back first to write this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, consumer cooperation Du printed material characteristics ABCD sulfur, ppm (wt) 12,286 15,420 14,056 8,738 Nitrogen, ppm (wt) 2 26 173 15 6 2,503 Distilled V IBP 228 220 227 285 10% 270 26 1 274 323 50% 3 11 308 306 90% 367 375 353 355 EP 388 382 368 n / a IBP = initial boiling point EP = ending boiling point (last boiling point)-line; 4 6 626 8 A7 R7 Five invention description (丨 L) Example 2 The adsorbent of the present invention is selected from those commonly used in column color Layer analysis of silicon molybdenum and ion exchange resin. The physical properties of these adsorbents are shown in Table 2. Gel —'— IP adsorbent pore volume average pore specific surface area cc / g size, A0 m ^ / ga 'silica gel 0.38 20.19 7 3 3.2 b ~ ** ——— 0.45 25.9 700.27. C 0.74 48.55 607.95 d 1.05 68.98 608.05 e 1.07 104.39 410.94 f 1.16 164.34 283.47 g 1.16 234.4 198.24 h aluminum 0.7 9 50 to 70 100-200 i ion exchange resin 0.55 450 to 500 > 400 ί 111 — ------ * --- 1 ---- ^ iln Γ '(Please read the precautions on the back before writing this page) Line-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs I This Example 3 In Table 2 a series of experiments were performed using hard glue for comparison The effect of different adsorbents on the removal of NPC. The diameters of "a" to "g" range from 0.3 to 0.5 mm. The steps for adsorption / desorption are as follows: 1) 40cc of adsorbent "a" is packed into a condensed glass tube. 2) The temperature of the adsorption bed is maintained at 50 ° C by circulating water outside the condensed glass tube. The degree applies to the standard of the House of Representatives < CNS) A4 (21Q x 297 46 626 8 4) 5) 6) 7) A7 B7 V. Description of the invention (/; >) * 3) 400cc LGO "A" to The flow rate was 200 cc / hr into the inner tube filled with the adsorbent. When step 3) was completed, 80 cc of non-polar solvent hexane was injected into the inner tube at a flow rate of 200 cc / hr. Clean the inner tube with nitrogen. The products from steps 3), 4), and 5 are mixed. The product of step 6) was separated from the solvent by a rotary pressure reducer, and the residue was "NPC-removed LGO". 8) Complete step 5) 80 cc of highly polar solvent 曱 tert-butyl ether is injected into the inner tube at a flow rate of 200 cc / hr. 9) Clean the inner tube again with nitrogen. 10) The products of steps 8) and 9) are mixed together. 11) The product of step 10) was separated from the solvent by a rotary pressure reducer, and the residue was "NPC". 12) Repeat the procedure of steps 3) to 1 1) more than twice. 13) Repeat the above steps 1) to 12) with the adsorbents "b" to "g", respectively. V pack --- one (please read the precautions on the back ^ 'Fill this page first); 5 · The paper size printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (' 210 X 297 4 6 626 8 A7 B7 V. Description of the invention (| <?) Table 3 Removal ratio of adsorbent nitrogen (%) 1st 2nd 3a 6 5 7 b 22 2 1 21 c 53 52 52 d 62 6 1 60 e 5 1 54 53 f 46 47 4 7 g 49 50 50 --------- Loading ... (Please read the precautions on the back before filling this page) Nitrogen removal ratio is based on [(feed N -Product N) xl0〇] / (feed N content) decision, where product N (Product N) is the nitrogen content of the dehydrogenation raw material after adsorption treatment. The actual implementation status and physical properties of the adsorbents are compared to show their actual implementation status It is closely related to their pore volume, pore size and specific surface area: when the pore volume is larger, the actual adsorption effect is better. When the pore volume is increased, the pore size is increased when the specific surface area is reduced. According to the results, the silicone adsorbent has Pore volume 0 5 to 15 (^ / §, pore size 40 to 200 A. and specific surface area 10 to 10,000 m2 / g is more suitable for treating LG0. For example, if the pore volume is less than 0.5 cc / g or if the pore size is less than 40 A °, adsorption will be less effective. In other words, if adsorption If the pore volume of the agent is too large, the physical strength of the absorbent will be significantly fragile and the surface area will be greatly reduced. Specifications (210 X 297) 46 626 8 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (^) Example 4 The NPC obtained in Example 3 was performed-column chemical species analysis: 1) 10.34 grams (200ml) Shixijiao (Merck Silica (0.60, 7-20_mesh ASTM) was filled in a glass column Umx2.5cm) as a medium pressure color layer analysis 0.2) NPC 10.00 obtained in Example 3 Grams were dissolved in n-methane, and the solution was poured into a glass column, and then 500 ml of n-methane, 500 mi of 1: 1 n-gastric methane: toluene mixed solvent, 500 ml of toluene, and 500 ml of methanol were flowed into the column. 3) Of the 7T outflow parts F1 to F6, the number of each of the first four parts can be divided by 250ml, 500ml for F5 and 300ml for F6. 4) Rotary pressure reducer for each part The solvent was removed and the residue was weighed. 5) Qualitative analysis of nitrogen and sulfur content with Antek Analyzer, and qualitative analysis of nitrogen and sulfur species with FT-IR Analyzer, GC-MSD, and GG-AED. 6) A field desorption (FD) mass spectrometer is used for semi-quantitative analysis of specific chemical species of each part by molecular weight comparison. A series of mass spectrum peaks are selected according to the mass spectrum interval I4. If the consistency is within the allowable limit of the mass difference of 0.05 compared with the calculated tritium, the chemical group can be considered to have an alkyl component. To determine the correctness of the mass spectrometry measurement, the mass spectrometry calibration standard (polyethylene glycol: PEG) was used as the analysis after the mass spectrometry measurement of the sample. Consistency of PEG mass spectrometry and calculation of tritium The error range is within 0.3. The results are shown in Table 4. This paper is again applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 · 4¾) ------------ M.-*. + (Please read the precautions on the back #. 犯 write first This page) Order: β. Line 46 626 8 A7 B7 V. Description of the invention (> 〇) Printing of clothing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs- ¢. ”Table 4 FI F2 F3 F4 F5 F6 Yield% 18.0 2.8 Π.8 5.0 19.5 42.9 S, ppm (wt) 1746 44496 42514 31077 16365 17569 N, ppm (wt) 0 0 1688 30450 20434 27798 FI-IR Typical-Aromatic d: fc Hid: Dagger NH COOH n-alkane Base NH Aromatic Compound Spectrum Aromatic Compound COOH GC-AED Non- DBTs DBTs DBTs: ad DBTs: nd -MSD DBTs DBTs CBZs nd C | B2s CBZs: ndnd CBZs Amine FD-Mass Acid, Phenol: 29% d wood, 4 spit, benzene farming, 4 voices, nfe, π bite: .32% paraffin wax: 5% naphthalene: 4% aromatic compounds, sulfur compounds and unknowns: 30% * DBTs (Dibenzuthiophenes); CBZs (Carbazules) nd (not detected) As shown in Table 4, it can be found that NPC is a polar mixture formed by polar compounds. Nitrogen-containing compounds such as pyridine, oxazole, carbazole, carbamide, and acetone, and oxygen-containing compounds such as organic acids and phenols account for the total weight. The national standard (CNSM4 specification (210 X 297) (please read first) Note on the back page of this page) J5J.-Line · 46 626 8 A7 B7 V. Description of the invention (> 1)-more than half. In fact, LG〇 before and after adsorption, the composition and properties of The change is mainly due to the changes in its nitrogen and oxygen content. The data in Table 4 also shows that the sulphide in large Npc has a longer residence time than dbts, that is, from the viewpoint of the number of knives, sulfur compounds are twice as concentrated as T3DBTs. The polysulfide compounds, like everyone else, have a 3-variety aromatic ring, which has a stronger adsorption force in oil and gas than DBTs. Therefore, it can be inferred that the polysulfide compounds are concentrated in NPC. However, the sulfur content before and after adsorption is The change is only a small amount, and the reason is because of the content of polysulfide compounds in the surface position. From this analysis of data, it can be inferred that oxygen, nitrogen, and polycyclic sulfur compounds will be in the desulfurization and denitrification reaction. Adsorption on the active site of the catalyst The processing is separated and concentrated in NPC, the reaction rate and Npc reactant remained in the role as "active inhibitor" as compared to the reaction rate significantly increased, especially in the deep desulfurization reaction of hydrogen. In order to further examine the relationship between the physical properties of LGO removal NPC and the proportion of npc removal, the following experimental operation method, such as implementation 3, is to use the adsorbent "c" to absorb the raw material "B" ° Analysis and physical properties of LGO removal NPC The comparison changes with RpA. Table 5 (please read the precautions on the back before writing this page). Install. Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs RPA 10 20 40 NPC divided by the supply 4.86 3.11 1.99 LGO (gr iter) nitrogen Removal ratio,% 5 5 39 29 TAN reduction ratio 94 74 6 6 Sulfur removal ratio, 3.7 2.3 0.7 26 Chinese National Standard (CNS) AJ specification (210 X 297 ft

0.973 0.849 1.72 1 46 626 8 A7 B7 V. Description of the invention (: > w Example 5 The same procedure as in Example 3 was repeated, except that the raw material b and 40cc were selected from "d", "h" and "i" "And its combined use with adsorbents. 2.0" ("raw material B is injected into a bed filled with adsorbents with a diameter ranging from 0.3 to 0.5 mm at a rate of 200 cc / hr. This procedure is repeated 12 times to test The regenerability of the adsorbent. Table 6 shows the nitrogen removal ratio of the adsorbent to remove NPC from the raw material B. Filled adsorbent nitrogen removal ratio 3rd 6th 9th 12 d 72 73 74 73 i 4 8 n / a N / an / ad: 1: 1 92 90 85 80 d: i = 1: 1 76 73 74 n / ad: i = 1: 2 77 77 77 n / a (Please read the notes on the back before filling this page ) _ Printed by a Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs> Examples 2, 3, and 4 above show that NPC removal can be done with different adsorbents, such as ion exchange resins; and the nitrogen removal ratio will vary with different adsorption The use of the agent is changed. In addition, the combination of two or more adsorbents can enhance the nitrogen removal ratio. For example, in the case of d: i in Table 6, the column is filled with silicone "d Immediately after filling the ion exchange resin, the nitrogen removal ratio is improved by about 3 to 5% compared to the case of using silicone "d" alone. The Zhang scale is applicable to China Standard (CNS) A4 (210 X—297 1¾) -------- Order ...! Line, 46 626 8 A7 B7 V. Description of the invention Example 6 The same procedure of 3 is repeated, except that the raw materials "a", "b", "c" and "D" are Use with 40cc of stored particles directly controlled from 0.3 to 0.5mrr ^ adsorbent "d". The outflow from the raw materials "A", "B", "C" and "D" are marked as A-1 , Bl, cl, and D-1. The nitrogen removal ratios of some A-1, B-1, C-1, and D-1 are shown in Table 7. A-1 B-1 C-1 D-1 nitrogen removal Ratio 60 ———— 61 61 13 As shown in Table 7, 'The nitrogen removal ratio is not different among various lg0s, but the nitrogen removal ratio in LCO is very low, and lc0 contains more than 10 times Nitrogen compounds contain! And have South viscosity and aromatic compound content. Therefore, adsorption is an effective pretreatment technology for LGO with relatively low levels of nitrogen content, viscosity and aromatic compounds' but for LC0 Example 7 __ | The consumer co-operatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the same procedures as in Example 3, except that 2,000, 3,000, and 4,000 cc of raw materials A were 10,000, 2,000, and 4,000, respectively. The rate of cc / hr was injected into a bed packed with 400 cci adsorbent having a diameter of 0.85 to 1.0 mm. The pressure difference of the adsorbent bed and the amount of polar solvent used are shown in Table 8 together with LG nitrogen. It also shows changes in pressure differential and space velocity. The Zhang scale is applicable to China Solid Standard (CNS) A4 specification (210 X 297? Ιτ 4 6 62 6 8 A7 B7 V. Description of the invention (> ρ Table 8 Flow rate treatment LGO RPA Removal of proportional solvent to LGO pressure difference ( cc / hr) (CC) (%) Volume ratio (lcg / cm2) 2,000 5.0 74 0.40 0.75 1,000 3,000 7.5. 64 0.27 4,000 10.0 58 0.20 2,000 5.0 66 0.40 0.95 2,000 3,000 7.5 62 0.27 4,000 10.0 52 0.20 2,000 5.0 59 0.40 1.50 4,000 3,000 7.5 50 0.27 4,000 10.0 46 0.20 (Please read the notes on the back before writing this page). When the space velocity increases the same as RP Α, the pressure drop increases as the nitrogen removal rate decreases. In other words When the reduction of RPA is the same as the space velocity, the nitrogen removal ratio increases. This tendency of removing NPC by adsorption constitutes a basic operating rule trend, and it can be expected in other adsorption forms and technologies as well. The diameter of an adsorbent particle It is closely related to the pressure difference: the pressure difference is inversely proportional to the square of the particle diameter. Increasing the particle size can reduce the pressure difference, but at the same time it will reduce the attractor capacity of the adsorbent. When the particle size increases, The nitrogen removal ratio is significantly more sensitive to space velocity. In other words, the NPC removal tendency changes with the adsorption temperature. For LGO, the appropriate bed temperature range is 40 to 80 ° C, which is very similar to the LGO storage temperature. Similar. This paper size applies to 0 Chinese standards (CNS) A4 specifications (210 X 297 male. ¾)-line. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 14 6 6 2 6 8 A7 B7 V. Description of the invention ( > () Example 8 The same procedure as in Example 3 was repeated except that only one polar solvent was used with 40 cc of the adsorbent "d" having a particle diameter of 0.3 to 0.5 mm. The nitrogen removal rate of raw material A is shown in Table 9 The test conditions are as follows: 1) 40cc of adsorbent d is filled in the inner tube of the concentrated glass tube column. 2) The temperature of the adsorption bed is maintained at 5 (TC constant temperature) by circulating water outside the concentrated glass tube. 3) 400cc of LGO "A" is injected into the inner tube filled with the adsorbent at a flow rate of 200cc / hr. 4) When step 3) is completed, 400cc of MTBT vapor is passed into the adsorption bed at a rate of 200cc / hr. Preheat the tube and heat it to 90 ° C. The temperature of the bed is concentrated by Xuan outer tube to maintain the circulating water at 80 ° C. 5) The products of steps 3) and 4) are mixed together, and the solvent residue is removed by applying a pressure reducer to "MPC-removedLGO". 6) After completing step 5), 80cc liquid MTBT is injected into the inner tube at a rate of 200cc / hr. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 7) Step 6) The product is removed by a rotary pressure reducer, and the residue is "NPC". _ Table 9_ Nitrogen removal ratio (%) _ 62_ In contrast to the two solvents used in Example 4, only one solvent was used in Example 8, but the nitrogen removal ratio was the same. This result provides a decision on what kind of adsorbent should be used. This paper size applies Chinese National Standards (CNS) A4 specifications (2〗 0 X 297 g t) 4 6 626 8 A7 B7 Employees ’Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printing V. Description of Invention (> t) Production Technology. For example, an ebullating or fluid bed that cannot be operated with different solvents at the same time can be applied to an adsorption pretreatment step. Example 9 In addition to adsorption, a series of solvent extraction experiments were completed. The use of a polar solvent demonstrated the same degree of improvement in whether solvent extraction removes NPC and solvent extraction as well as adsorption in the HDS process. The following procedure was used: 1) 500 cc of the raw material "B" was placed in a mixer with an equivalent volume of methanol and stirred. 2) After the stirring and mixing are completed, the mixture is left to stand for 5 minutes to cause phase separation, and then LGO is sucked from the bottom of the mixer and extracted with a solvent. 3) The extracted LGO was removed with a rotary pressure reducer to remove the residual methanol, and pure LGO from NPC was obtained. The nitrogen removal ratio was changed. The ratio of the raw material "B" to the volume ratio of methanol is shown in Table 10. _ 4) Repeat the same procedure as steps 1) to 3), except that "B" is replaced with "D" as the raw material. The nitrogen removal ratio is shown in Table 10 as the ratio of the raw material "D" to the volume ratio of methanol is changed. 5) In order to prepare the raw materials for the deep desulfurization reaction test, steps 1) to 3) are repeated to reach 14 liters of LGO de-NPC labeled "B-SX". 6) Repeat step 5), except that the raw material "D" is used to replace the raw material "B" to obtain 14 liters of LGO denominated "D-SX" de-NPC. (Please read the precautions on the back before filling in this page) I. .Line σ X 297 crystal) 466268 A7 B7_ V. Description of the invention (>;?) Raw material: MeOH B-SX, nitrogen removal ratio (%)- -------- D-SX, nitrogen removal ratio ^ 1 250cc: 750cc 72 65 — 333cc: 667cc 65 — 500cc: 500cc 55 23 _ ---- 667cc: 333cc 40 750cc: 250cc 31 Duck 7 ) In order to determine the nitrogen removal ability of methanol, repeat steps 1) to 3) to prepare the labelled: B-SX1 "NPC-free LGO 〇8) Fresh raw material" B "and the methanol left in step 2) are injected and mixed again In the mixer, stir and mix for 20 minutes. From the mixture, separate the LGO labeled "B-SX2" 〇9) Repeat the procedure of step 8) to prepare "B-SX3". Other fresh feeds with the same methanol solvent The nitrogen removal ratio is shown in Table 11 below. Table 11. Raw material B-SX1 B-SX2 B-SX3 Nitrogen removal ratio 55 32 22_ As shown in Table 7 of Example 6, the nitrogen removal ratio of raw material "D" Very low. But by using solvent extraction method, for those fluids that are not easy to adsorb and remove Npc. Catalytic cracking (FCC) cycle oil, nitrogen removal of coke gasoline, empty gasoline raw materials The rate can be improved to the same LGO obtained from the same Misaki — the sample level, the relevant information can be seen in Table 1. This paper size is applicable to Chinese national standards (CNS > A4 specifications (210 X 297 centimeters)) Please read the precautions for £ r first • Binding. Printed by the page. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 46 626 8 V. Description of the invention (^) Solvent extraction is allowed to contain heavy gasoline, FCC circulating oil and coke gasoline with a point exceeding 4Gm. Petroleum raw materials undergo NPC removal. As shown in Tables 10 and 11, the proportion of the amount of g oil to the solvent used for extraction increases, or as the number of solvent cycles increases, the nitrogen removal ratio gradually decreases, which means the solubility of NPC in the solvent phase Close to the saturation point. With the correct choice of solvents to promote high NPC solubility, perhaps solvent extraction can be a good process for removing NPCs from heavy distillates. Example 10 Using Raw Material B "to Test Silicone" d "(Example Magic For regenerative properties, LGO filled 40cc of colorimetric analysis silica gel into the inner tube of an enrichment column with 50 ° C circulating water through an adsorption bed labeled "B1". 200 (> c ^ 々Lg〇B was also introduced into the bed, followed by 80cc MTBE. After repeating the above procedure 10 times, the isolates "B1 + mtbE" and "NPC + MTBE" were collected, MTBE was then removed by rotating the pressure reducer. By measuring the nitrogen content of "B" and Bl ". The nitrogen removal ratio can be calculated, and the result is shown in Figure 4. As shown in Figure 4, after 400 operating cycles, the nitrogen transfer of the adsorbent Except for the printing of employee cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs, the proportion has not declined at all. This reproducibility is very important in industrial applications and economics.-Generally speaking, the adsorption mechanism of silicone rubber is considered to be via oxygen bonds. There is no strong adsorption site, unlike activated aluminum, which has many strong acid sites. This characteristic can explain why second gum has better reproducibility. Adsorption to strong acid or alkali sites makes reversible reactions (desorption) difficult. This can be done by examples 5 Table 6 data to understand, 4. 6 62 6 8 A7 B7 V. Description of the invention (> v where d: h = 1: l absorbent shows a high nitrogen removal rate in the initial stage, fast but when As the number of regeneration and reuse increases, the nitrogen removal rate decreases rapidly. The regeneration of these adsorbents can be achieved by heating or using highly polar solvents, which is also included in the scope of the present invention, but their application is somewhat limited. Favorite Absorbent, therefore, must have re-absorbable properties such as silicon bond and aluminum hydroxide with hydrogen bonding. The performance of the adsorbent is also determined by the structural characteristics of the adsorbent and the properties of the raw materials, such as boiling point range, NPC content and raw material composition Example 11 • In order to check whether the removal and how it affects the performance of the catalyst in the HDS process, the raw material of the HDS reaction unit was prepared as follows: 1) 400cc of adsorbent d with a particle diameter of 0.88 to 1.00mm was charged to Concentrated glass tube column. 2) The temperature of the adsorption bed is maintained at a constant temperature of 50 ° C by circulating water outside the concentrated glass tube. 3) 400cc of LGO "A" is injected at a flow rate of 200 (^ / dagger) filled with the adsorbent. Inner tube. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4) When step 3) is completed, 80cc non-polar solvent pinane is injected into the inner tube at a flow rate of 200ec / hri. 5) The inner tube is purged with nitrogen. 6) The products obtained in steps 3), 4), and 5 are mixed. 7) The product of step 6) is separated from the solvent by a rotary pressure reducer, and the residue is "NPC-removedLGO". This paper size applies China National Standard (CNS) A4 Specification (210 x 297 mm) 46 626 8 A7 B7 V. Description of the invention (today) 8) Complete step 5) 80cc of highly polar solvent methyl tert-butyl ether is injected into the inner tube at a flow rate of 200cc / hr. 9) Clean the inner tube again with nitrogen. 1) Mix the products of steps 8) and 9). 11) The product of step 10) is separated from the solvent by a rotary pressure reducer, and the residue is "NPC". I2) Repeat steps 3) to 11) The procedure is more than 2 times. 13) Repeat the above steps ii) to) with adsorbent "b" @ "g". The results of the nitrogen removal ratio are shown in Table 12. A-2 C-2 .B-2 B-3 D-SX Nitrogen removal ratio (%) 55 60 ------- 1 60 72 64 Example 12

In order to check the improvement of the catalyst of Example 11, the raw material A of Example 1 and the material "A_2 of Example U" were used to test. The catalyst used in the printing test of the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of this example is At present, it is popularly used in commercial process. Its physical properties and chemical composition are listed in Table 13. ^ Paper rule, money, wealth and miscellaneous standard (CNS) A4 (210 46 826 8 A7 B7) 5. Description of the invention (: > 丨) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 13 Chemical composition physical properties IPC, CoO 4.09wt% Specific surface area 214m2 / g M0O3 16.35wt% Pore volume 0'41cc / 8 NiO O.Olwt% Average pore size 76A〇 Na2〇0.09wt% Packing density 836kg / m3 AI2O3 Equilibrium average length l / 20inch 400cc catalyst was loaded into a HDS test factory equipment for deep desulfurization reaction, and 1% dimethyl, disulfide and The LGO phase was mixed for pre-sulfidation. The raw material LGO "A" was then introduced into the reactor, and product samples were collected for sulfur analysis at three different reaction temperatures. The catalyst bed was stable at the same temperature before testing the products. It was maintained for 24 hours. The determination of the catalyst activity of the LGO "A-2" after adsorption treatment was completed in the same way. The results are shown in Table 14 ° Table 14 Reaction conditions Η 'Partial pressure, kgf / cm2 H2 / oil ratio, Nm3 / kl LHSV, hr-l catalyst volume, cc 58.8 170 1.88 400 Rxn. As a result, the sulfur product Feed A A-2 BAT 300 3,943ppm 2,547ppm BAT 320 l, 960ppm l, 298ppm BAT 340 756PPM 325ppm * BAT: Bed Average Temperature (average bed temperature) The paper size applies the Chinese National Standard (CNS) A4 specification (210 χ 297) iiilll — — — — — — — I · (Please read the precautions on the back flr ^ ·· Write this page ·- -Line; 6 4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 626 8 A7 B7 V. Description of the invention (The product shows that the sulfur level of the product has been reduced. The raw material of adsorption pretreatment has significantly improved its sulfur reduction level. Example 13 In order to examine and compare the improvement of catalyst activity, different RPAs treated with adsorption: "B" in Example 1 and "B" in Example 11 B-2 "and" B-3 "are three different NPC removed materials for deep desulfurization reaction tests. 100 cc of the same catalyst as in Example 12 was charged into a high-pressure continuous reactor and mixed with LGO in an amount of 1% of difluorenyl-disulfide to perform presulfidation. Deep HDS was performed under the same conditions as in Example 12. After the sample was stably maintained at the same reaction temperature for 24 hours, product samples were collected for sulfur analysis. The results are shown in Table 15 below. Table 15 Product sulfur content vs. reaction temperature (w.ppm) Raw materials B B-2 B, 3 BAT 324〇C 1503 756 470 BAT 334〇C 671 399 182 BAT 344 ° C 301 99 63 BAT 354〇C 108 39 18 Table 15 shows that the LGO product of the LGO raw material having a nitrogen removal of 60% or more after the adsorption pretreatment with the present invention has a sulfur content of less than 100 ppm (wt), and the same LGO raw material under the same HDS operation The sulfur content of the product is 300ppm (wt). ○ The standard of Chinese paper (CNS) A4 standard (210 X 297 mm) for private paper. (Please read the precautions on the back first # rFill this page j US * Γ _ _

€ Λ 丨 626 8 A7 B7 V. Description of the invention 〇 >) Example 14 Taken from each of the products described in Example 13 at 334cC hydrogen desulfurization reaction wlOOcc 'Sayboh color analysis with Minolta Digital Colorimeter CT-320 The results are shown in Table 16 below. Raw material B raw material B-2 raw material B-3 raw material product color + 12 +20 + 18 sulfur product 671 ppm 399 ppm 182ppm Frequent color degradation of the product is often encountered in deep HDS, and the adsorption pretreatment raw material significantly improves the product color as shown in Table 16. Show. The above results show that the deep HDS after the adsorption pretreatment of the present invention can bring about substantial improvement in product color and product sulfur content. Example 15 A deep HDS reaction test was performed using the raw materials "A" and "C" of Example 1 and LG0s "A_2" and "C-2" removed by NPC of Example 11. The same high pressure, continuous reactor and catalyst as those used in Example 12 were used. The results and operating conditions are shown in Table 17 below. ----: --------- Equipped · — 1 ί Please read the notes on the back to write this page} • 17 ..-· # Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 6 626 8 B7 V. Description of the invention U +) Table 17 Reaction conditions Η 分 partial pressure, kgf / cra2 Η / / oil ratio, Nm3 / kl LHSV, hr-1 catalyst volume, cc 40.0 250 1.35 100 reaction result, raw material A A-2 C C-2 Product sulfur, ppm BAT 324 ° C 1.348 779-1,355 846 BAT 334 ° C 684 281 774 426 BAT 344 ° C 296 155 355 180 BAT 354 ° C 115 40 158 75 Despite the boiling point, sulfur content, and Different levels of nitrogen 'can also achieve deep HDS improvement. < Please read the precautions on the back first ^ 1 Write this page) Binding: Example 16 NPC removal of tLGO B ~ SX prepared by solvent extraction in Example 9 "Deep HDS reaction test, the same as described in Example 12 111 ^ conditions and the same reactor, the results are shown in Table 丨 8. The paper printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is compatible with the Chinese National Standard (ctviS) A4 specification (210 x 297 Sr 4 6 626 8 A7 Description of invention (shirt) B7 Table 18 Raw material nitrogen, ppm (wt) 57 sulfur, ppm (wt) 15,400 product sulfur BAT 334 ° C 680 BAT 344 ° C * 279 ppm (wt) BAT 354〇C 118 Please read first Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

The purpose of this embodiment is to examine whether other NPC removal methods such as solvent extraction can achieve the same or similar effects. If the nitrogen removal ratio is the same, the improvement effect of the HDS catalytic activity of the 1 G O s obtained in Example 9 is similar to that of the LGOs obtained by adsorption. Therefore, the nitrogen removal ratio of the solvent extraction is the same as that of the adsorption example. For deep HDS, solvent extraction can be one of the good pretreatment methods, however, when using the same nitrogen removal ratio as that obtained by adsorption, excess solvent must be used. In fact, solvent extraction requires two or more distillation columns to recover the solvent, and its processing capacity can be the same as the subsequent deep HDS process. Therefore, the solvent extraction method is not advantageous in terms of operation and investment price. If only a small amount of raw materials are to be processed by solvent extraction, these disadvantages can be overcome by using appropriate solvents. The aforementioned commercial disadvantages should not be taken as a limitation of the scope of the present invention. I Example 17 A series of experiments were performed to view the deep HDS effect of NPC-removed LCO. Note: Applicable to China National Standard (CNS) A-l specification (210 X 297)

A7 4. 6 6 2 6 8 _B7 _; _ 5. Description of the invention (batch) First, the LCO raw material "D" and the raw material "B" are mixed at a volume ratio of 3: 7, and then the mixture is subjected to deep HD S. The same catalysts and HDS conditions as in Example 12 were used. The NPC-removed LCO "D-SX" prepared by the solvent extraction in Example 11 was mixed with the raw material "B" in a volume ratio of 3: 7, and then the mixture was subjected to deep HDS. The results are shown in Table 19. Table 19

Reaction BAT product sulfur content Raw material B 70V.% + Raw material D30V.% Raw material B 70 V.% + Raw material D-SX30V.% @ 334〇C 2,449 PPM S 1.859 PPMS @ 344〇C 1,649 PPM S. 1,201 PPMS @ 354〇 C 1,060 PPMS 749 PPM S @ 364 ° C 665 PPM S 393 PPM S Even with the increase in circulating oil power up to 30% of the raw material, there are still significant deep HDS improvement results, which can be attributed to NPC removal. This is believed to be a desulfurization refining operation for middle distillates of feedstocks with a high proportion of circulating oil. It has significant economic significance. Comparative Example 18 A series of experiments were designed to investigate the differences between U.S. Patent No. 5,454,933 and the present invention: the regenerability of the adsorbent, the amount of RPA and by-products. To be effective, the surface shape of the adsorbent used is very similar to that of the Filtrosorb 400 adsorbent used in the previously disclosed invention. The BET properties of the two absorbents are shown in Table 20 below. The paper size is applicable to the national standard (CNS) A4 specification (210 X 297). Please read it before you read it again.-装 装 装 Binding, printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the consumer co-operative society 46 626 8 A7 B7 V. Description of the invention (%). Table 20 BET properties US Pat. 5,454,933 Activated carbon suggested by activated carbon DARC0 Surface area m2 / g 800 ~ 1200 627 Pore size A ° 20 ~ 100 43.5 The adsorption / desorption procedure is as follows. 1) ACROS organics (DARCO 20-40 mesh) are dried at 150 ° C for 6 hours. 2) 40cc dry activated carbon is packed into the inner tube of the condensed glass column. The activated carbon bed is maintained at 90 ° C with circulating hot water outside the tube. 3) 25 0cc of toluene is injected into the adsorption bed at a flow rate of 8cc / min. 4) After step 3) is completed, 240 ppm (wt) sulfur-containing deep hydrogen desulfurization LG0 manufactured by SK's LGOHDS process is injected at a flow rate of 15 cc / min. 5) The first 75cc product mixture of LG0 and toluene, which is equivalent to 33cc LG0, was collected and separated by a rotary pressure reducer, and the residue was labeled T1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6) The remaining product mixture is collected and separated into toluene by a rotary reducer, and the residue is labeled T2. 7) After completing step 4), add 250cc methylbenzyl to the active breaker at a flow rate of 8cc / min. 8) The sulfur content of "T1" and "T2" is analyzed by ANTEK sulfur analyzer. 9) Repeat steps 4) to 8) once. This paper size applies the Chinese National Standard (Ci \ S) AJ specification (21CU 297 public love) ϊ 626 8 Α7 Β7 V. Description of the invention (poor) 10) Except step 4) With 100 < ^ deep hydrogen desulfurization LG0 Replace 400 (; (; except, repeat steps 4) to 8) three times. The results are shown in Table 21 below. Regeneration number 0 1 2 3 4 Tl, cc 35 35 35 35 35 RPA 0.88 0.88 0.88 0.88 0.88 Desulfurization reaction,% 80 64 66 47 48 T1 + T2, cc 400 400 100 100 100 RPA 10 10 2.5 2.5 2.5 Desulfurization reaction ,% 26 23 55 43 42 Extraction, g 33.0 32.3 32.1 31.7 32.4 Extraction to raw material ratio (w / w%) 9.7 9.5 37.8 37.3 38.1 400 was not available, and DARLO activated carbon has similar physical properties to FiltfQsorb 400, so it was used in experiments. For 0.88 RPA, the absorbent removes more than 80% of the sulfide from LG0 treated with deep hds ... However, after repeated desorption treatments, the adsorbent will lose its adsorption effect, 'Even with Filtrosorb 400, can the present invention There are also concerns about continuous operation at 1 to 1.75 RP2. U.S. Patent No. 5,454,933 also does not provide examples of treatments for adsorption and 4 adsorption over one cycle. As shown in Table 21, about 40% of the raw materials were converted into by-products at 2.5 RPA. Is Filtrosorb 400 more selective for the adsorption of sulfides, and the by-products from 1 to 1.75 RPA can be considered. By-products cannot be used as CNS A4 specifications (210 X 297 '& ---------- 1') (Please read the notes on the back first to fill in this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, the printed products of the consumer cooperatives are therefore 4 6 626 8 A? 5. Description of the invention (^) Uses other than oil mixture raw materials. Patents are very unfavorable. From an economic point of view, this implementation of the aforementioned disclosure has a low score. The friction force is 100 ppm (wt) and the NPC obtained in Example 4 is divided into u 300 ppm (wt) diesel oil "LL" φ. 'The obtained sample was subjected to HFRR (high frequent reciprocating rigw, ^ ^ friction test, HFRR is -IS 〇 Diesel friction standard measuring instrument. The results are shown in the following table. ____Table 22 Addition amount ppm (wt)

Average friction diameter, HFRR.jCBase) 588 100 300 498 415 Ministry of Economic Affairs, Intellectual Property, Economics, and Consumer Affairs Agency The above results show that NpC, a by-product of the adsorption pretreatment method, can be used as an effective fuel friction additive for ultra-low sulfur diesel with poor friction. The pretreatment method of the present invention not only improves the subsequent catalytic process to produce low-sulfur fuel, but also provides the problem of improving frictional degradation of fuel by using by-products as frictional additives. Example 20. An experiment was performed to examine the effect of NPC removal on the exhaust characteristics of diesel. Removal of NPC diesel and ordinary diesel with the same sulfur content level was used for exhaust test. The test method is as follows: The raw material "A" was subjected to deep HDS at 356 ° C under the same conditions as in Example 12 to produce the system. Desulfurized LGO, which is marked as "A-em- Γ. Printed [____ This paper size applies to Chinese national standard (Ci \ S) Ai specification (2 丨 〇, 297 issued) 4 6 626 8 A7

Printed by the Intellectual Property Office of the Ministry of Economic Affairs and Consumer Affairs Co., Ltd. V. Description of the invention (4 °) 2) The raw material “A” is pre-processed in the same manner as in reality_6 to remove the NPC, at 339. (: Deep delete reaction is carried out below to produce desulfurized LGO, which is marked as "A" em_2 ,. ^ 3) Commercial kerosene with sulfur content iOppmbt) 30% emmem-2 "to prepare exhaust test fuel, Its meteomating characteristics are similar to commercial diesel, marked as "A-em-hD ,, ..:" A-em-2-D "〇4) The above two samples were used with a reference fuel to maintain engine stability and perform Diesel engine test. Commercial diesel (SK diesel) was used as the reference fuel. The sample characteristics are shown in Table 23 below. ^ .5) Exhaust test is carried out with a displacement of 丨 丨, 056cc, such as the 02366 bus diesel engine sold by Korea Daewoo Automobile. ;?] ^ Exhaust 1: The measurement is based on the D-13 model, which is a Korean high-efficiency diesel vehicle exhaust test mode. In addition, smoke measurements were performed on three samples according to the Smoke 3 mode. Details and measurements are shown in Tables 24 and 25, respectively. Consecutive surveys are performed to reduce the error of environmental changes, and the repeatability of the engine is checked with reference to fuel before and after each test. In addition, 4 pre-tests were performed with the same reference diesel to evaluate the reproducibility of MDT (Mini Dilution Tunnel) and consumption gas analyzer for PM measurement. 6) (CNS) Al (210 x 297 < I --------- I ----- install i — (Please read the note on the back ^: fill out this page first) 46 626 8 A7 B7 V. Description of the invention (afternoon I) Table 23 Characteristics SK diesel A-em-lD A-em-2-D Specific gravity 15/4 ° C 0.8374 0.8218 0.8209 ASTM D86, ° C IBP 152 159 165 10% 190 200 204 50% 259 278 282 90% 344 351 353 95% 368 370 EP 376 382 378 Residue, νοΐ.% 0.8 1.6 1.5 Ignition point, ° C 63 63 S ppm (wt) 330 220 220 N ppm (wt)-23 8 10% Residues, wt% 0.10 0.04 0.02 SK Diesel: Commercial SK Diesel Products ---- 1 ------- r --- (Please read the unintentional matter on the back ¥ Please fill in this page) · Ministry of Economy Wisdom The printed standard for employees 'cooperatives of the Property Bureau applies the Chinese National Standard (CNS) Al specification (210 X 297) 4 6 62 6 8 A7 B7 V. Description of the invention (dipper) Table 24. Printed by the employees' cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs D-13 (PM Measurement) mode engine RPM% Load Wt. Factor 1 Idle — 025 2 1920 10 0.08 3 1920 25 0.08 4 1920 50 0.08 5 1920 75 0.08 6 1920 100 0.25 7 Idle 0 .25 8 3200 100 0.1 9 3200 75 0.02 10 3200 50 0.02 11 3200 25 0.02 12 3200 10 0,02 13 Idle-0.25 / 3 Smoke 3 (Smoke measurement) Mode engine RPM% Load 1 1000 100 2 1320 100 3 2200 100 * Maximum engine output RPM: 3200 rpm 60% of maximum engine output RPM · 1920 rpm (Please read the precautions on the back first ^ Fill out this page) Binding ------: ---. This paper size is applicable 0 National Standard (CNS) Ai Specification (2) 〇297297 46 46626 8 A7 B7 V. Description of Invention (43) Table 25 Test Subjects All PM SOF Sulfate Smoke (%) (gr / kw-h) (g / kw-h) (g / kw-h) A-em-1-D 0.766 0.051 0.007 50 A-em-2-D 0.596 0.040 0.005 48% improvement 22 21 28 4 * SOF (dissolved organic matter ratio) as shown in Table 25 It is shown that the deep hydrogen desulfurized diesel after NPC removal shows 22% lower PM exhaust compared with other diesels with the same sulfur content. The improvement of the exhaust characteristics may be the result of the removal of PM precursor materials, which may be removed as one of the NPCs. The exhaust characteristics make the pretreatment process of the present invention more attractive because it can It produces clean diesel with low sulfur content, and it has less exhaust pollution than other diesels with the same sulfur content. Although the present invention can be applied to various different catalytic processes to produce hydrocarbon fuel, it is preferably applied upstream of the deep HDS process to produce kerosene and diesel to improve the effect of the HDS process and the quality of the product. Due to increasingly stringent environmental regulations, refineries require efficient and economical deep desulfurization technology to produce clean diesel. The present invention provides a simple but effective pretreatment process that can make the conventional HDS process economically produce ULSO from high sulfur LGO raw materials. In addition, the present invention provides, for example, extending catalyst life, reducing hydrogen consumption, and reducing operating costs by using low-grade raw materials. Etc. Moreover, at the same level of sulfur content, the diesel treated with adsorption showed better exhaust characteristics than traditional diesel. When burning, the adsorption-treated diesel is better than the conventional one. The paper size applies the Chinese National Standard (CNS) A.l specifications (210 X 297 (please read the precautions on the back before filling this page).

L-pack -------- Order--I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 46 626 8 A7 _____B7_____ V. Description of the invention (4 buckets) Diesel emits less PM and NOx, PM and NOX Two of the most restrictive pollutants are specified. Because the HDS reaction temperature is reduced and the amount of color body precursors in the pretreatment process is substantially reduced, the color of diesel improves. The operating conditions of the pretreatment process are very close to the surrounding temperature and pressure. In addition, the pretreatment process can process hydrocarbons at a higher space velocity than the HDS process, so the size needs to be substantially smaller than traditional reaction units. The investment cost of the pre-processing process is estimated to be about 10% of the HDS process. Because the crew process uses ordinary adsorbents and solvents without catalysts and hydrogen, its operating cost is estimated to be about 10% to 20% of the HDS process. It is understood that the terminology used in describing the present invention in a detailed manner is to clarify the essence of the present invention and not to limit it. With the above guidance, the present invention can be easily modified and changed. Therefore, it is also included in the scope of patent application of the present invention, and the present invention can be implemented in a manner different from that described in the specific examples of the specification. ---- 丨 — 丨 丨 丨 I — yJ * pack · ------- " Order-I 丨 丨 丨-丨 丨-. (Please read the notes on the back first # Fill this page > i : The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints a moderate rule sheet. The booklet 7 i29 X I10 (2 grid 4 _ _N l (c J quasi-standard home country)

Claims (1)

4 6 626 8 Φ September 27th, revised page A8 B8 C8 D8 Printed by the Consumers' Cooperatives, Intellectual Property Bureau of the Ministry of Economic Affairs 6. Application for patent scope 1. A method for manufacturing hydrocarbon fuels, the method includes: (a) in petroleum Before the raw material distillate is subjected to catalytic hydrogen processing, the natural polar compounds are removed from the petroleum raw material distillate to substantially reduce the concentration of the natural polar compound in the petroleum raw material distillate. The boiling point range of the petroleum raw material distillate is introduced. Between 110 ° C and 560 ° C; and (b) catalytically treating the petroleum feedstock distillate to produce a hydrocarbon fuel. 2. The method according to item 1 of the patent application range, wherein the boiling point range of the hydrocarbon fuel is between 110 ° C and 400 ° C and its sulfur content is less than 5000 ppm (wt). 3. The method according to item 1 of the patent application range, wherein the boiling point range of the hydrocarbon fuel is between 110 ° C and 400 ° C and its sulfur content is less than 50 ppm (wt). 4_ The method according to item 1 of the patent application range, wherein the boiling point range of the petroleum feed distillate is between 200 ° C and 400 ° C. 5. The method according to item 1 of the scope of patent application, wherein the petroleum raw material fraction obtained in step (a) has a nitrogen content reduction greater than 30% and a sulfur content reduction greater than 0.5% compared with the original petroleum raw material distillate. The total acid amount is reduced by more than 60%. 〇6_ As described in the method of patent application No. 1, wherein the natural polar compound includes 5.0 to 50% (wt) oxygen-containing compounds, 5.0 to 50% (wt). Nitrogen-containing heterocyclic compounds, and 0.1 to 5.0% (wt) sulfur. 7. The method according to item 1 of the scope of patent application, wherein the natural polar compound portion removed from the petroleum raw material distillate constitutes 0.001 to 5.0% (wt) of the petroleum raw material residue. CN (CNS) A4 specifications (21. X 297 private release j ----- Please read the precautions on the back and fill in this page. A8SD8. * 46 626 8 VI. Patent Application Scope 8 · If you apply for a patent park The method of item 1, wherein the hydrogen treatment is selected from the group consisting of hydrogen desulfurizing, hydrodearomatizing, miid hydrocracking, hydrocracking, or a mixture thereof. The method of applying for the first paragraph of the patent application park, wherein the natural polar compound is removed from the petroleum raw material by solvent extraction. .10. The method of claim 9 of the patent application scope, wherein the petroleum raw material contains a final boiling point of more than 400 C Heavy oil, fiuidi2ed catalytic cracking cycle oil, and coke gasoline. 11. The method according to item 丨 of the patent application, wherein the natural polar compound is obtained by at least Adsorption of adsorbents is removed from petroleum feedstocks. 12. The method according to item 丨 丨 of the scope of patent application, wherein the adsorption takes place in two or more adsorption towers. 13. As described in item 11 of the scope of patent application Method, wherein the adsorption process occurs in a fluid bed adsorption process or an ebullated bed adsorption process. 14. The method according to item i of the patent application scope, wherein the adsorbent is selected from the group consisting of activated aluminum, acid white mud ( acid white clay), Fuller's earth, activated carbon, zeolite, aluminum hydroxide, silicone, ion exchange resin family and mixtures thereof. 15 · The method according to item 14 of the patent application, wherein the adsorbent is selected from Including silica gel, ion exchange resin group and mixtures thereof. 16. The method according to item 5 of the patent application range, wherein the adsorbent is a silica gel with a pore size of 40 to 200 A and a specific surface area of 100 to 10,000. 〇〇m2 / g, and the pore volume is 0.5cc / g to 1.5. The size of this paper is the National Standard of Finance (CNS) A4 (210 X 297 Lin). -------- Line: (Please read the notes on the back first (Fill in this page again.) .0. Printed by the Ministry of Economic Affairs% · The Intellectual Property Bureau employee consumer cooperative M 4 Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumer cooperative 6 6 626 8 as B8 C8 D8 The method includes adding a natural polar compound extracted from a petroleum raw material having a boiling point in the range of 200 to 400 ° C, wherein the natural polar compound includes 5.0 to 50% (wt) of an oxygen-containing compound, 5.0 to 50 % (wt) of nitrogen-containing heterocyclic compounds, and 0_1 to 5.0% (wt) of sulfur. 18. The method according to claim 17 in which the natural polar compound is concentrated by an adsorbent. 19. The method of claim 18, wherein the adsorption system is selected from the group consisting of a fixed bed adsorption process using two or more absorption towers, a fluid bed adsorption process, or an ebullating bed adsorption process. 20. The method according to item 19 of the patent application park, wherein the adsorption process uses an adsorbent to select from activated activator, acid white clay, Fuller's earth, activated carbon, loose rock, hydrogen A family of oxides, dream gums, ion exchange resins and their blends. 21. The method according to item 20 of the patent application park, wherein the adsorbent is silicon gel, the pore size is 40 to 200 A, the specific surface area is 100 to 1,000 m2 / g, and the pore volume is 0.5 cc / g to 1,5. 22. The method of claim 18, wherein the natural polar compound has a nitrogen content more than 50 times greater than the nitrogen content of petroleum hydrocarbons and includes more than 10 ° /. Oxygenated organic acids and phenols. ------------- Q -11 (Please read the precautions on the back before filling this page} Order: Line 1 paper size applies to China National Standard (CNS) A4 (210 X 297 Hurry)