KR101804663B1 - Method of Preparing Hydroprocessing Catalysts from in Waste Oil and Method of Converting Heavy oil using the same - Google Patents

Abstract

The present invention relates to a method for producing a hydrogenolysis reaction catalyst from waste oil and a method for converting heavy oil using the same. A method for producing a hydrogenolysis reaction catalyst from waste oil according to the present invention comprises the steps of: removing solid matter from the waste oil; Distilling the waste oil from which the solid matter has been removed in a distillation column to obtain an upper stream and a lower stream; Wherein the waste fluid comprises at least one metal component of molybdenum, iron, zinc and copper, and wherein the tower bottoms stream comprises the top tower stream The boiling point is higher and the metal content is higher.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrogenolysis reaction catalyst from waste oil and a method for converting heavy oil using the same,

The present invention relates to a method for producing a hydrogenolysis reaction catalyst from waste oil and a method for converting heavy oil using the same.

Waste oil is generally discharged with a specific gravity of 75 wt% or more of waste lubricating oil and may also include abrasive oil, cutting oil, fuel oil, asphalt oil, electric insulating oil, grease, rust preventive oil and the like.

At present, waste oil is separated into distillation component and residual component through non-incremental distillation process. The distillation component utilizes alternative fuel oil or reclaimed oil.

The residual components include various kinds of metal components contained in the waste lubricating oil and the like, and these include an expensive molybdenum component and the like. However, in the prior art, there is a problem in that the metal component in the residual component can not be utilized and the residual component is used only for low-cost applications.

Korean Published Patent Application No. 2007-0116074 (published on December 06, 2007)

It is another object of the present invention to provide a method for producing a hydrogenolysis reaction catalyst from waste oil and a method for converting heavy oil using the same.

According to another aspect of the present invention, there is provided a method of producing a catalyst for hydrocracking reaction from waste oil, comprising the steps of: removing solid matter from the waste oil; Distilling the waste oil from which the solid matter has been removed in a distillation column to obtain an upper stream and a lower stream; Wherein the waste fluid comprises at least one metal component of molybdenum, iron, zinc and copper, and wherein the tower bottoms stream comprises the top tower stream And has a high boiling point and a high metal content.

The tower bottoms stream may contain 50-3,000 ppm molybdenum.

The tower bottoms stream may further contain 100-5,000 ppm of iron, 1000-5,000 ppm of zinc and 50-5,000 ppm of copper.

The molybdenum can exist in the form of a sulphide.

VI (b), II (b), I (b), VI (a), V (a), VII (a) group element and a compound containing the group element.

The mixing may be performed such that the content of molybdenum increases and the content of molybdenum in the hydrocracking reaction catalyst is 150-5,000 ppm.

The mixing step may be performed at a temperature of about 50 to 200 DEG C in the tower bottom stream.

The mixing step may be performed in a state where ultrasonic waves are applied.

The tower bottoms stream may contain 90 to 99.5 weight percent organic matter.

It is an object of the present invention to provide a method for converting a heavy oil into a heavy oil, comprising the steps of: preparing a hydrocracking reaction catalyst by the method according to any one of claims 1 to 9; And converting the heavy oil using the hydrogenolysis reaction catalyst.

According to the present invention, there is provided a method for producing a catalyst for hydrocracking reaction from waste oil and a method for converting heavy oil using the same.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view for explaining a method of producing a hydrocracking reaction catalyst from waste oil according to an embodiment of the present invention. FIG.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings, and the inventor should appropriately interpret the concept of the term appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined. Therefore, the configuration of the embodiments described herein is merely the most preferred examples of the present invention, and does not represent all the technical ideas of the present invention, so that there are various equivalents and modifications that can be substituted at the time of the present application It should be understood.

First, a method for producing a hydrogenolysis reaction catalyst from waste oil according to an embodiment of the present invention will be described with reference to FIG.

The supplied waste oil 10 is subjected to a process 100 for physically separating the solid matter through a physical method such as centrifugation or filtration. The separated solid (11) is a solid-like material that is formed by mechanical friction or oxidation of oil, and may include giant polymers, salts, metals, and the like.

The wasted oil stream 20 from which the solid content has been removed is removed through the cryogenic still 101 maintained at 240 ° C or lower and supplied to the high temperature still 200 through the downstream of the tower. When continuous treatment of raw materials is not required, removal of moisture and separation of hydrocarbon oil can be carried out in a single still according to the temperature range at different boiling points.

In the high-temperature still 200, oil having a boiling point of 240 ° C to 590 ° C can be separated, and distillation can be performed under reduced pressure to reduce energy.

The hydrocarbon vapor stream (40, tower overhead stream, distillation component) at the top of the tower is recovered 41 as liquid oil via the container 300 and can be utilized as an alternative fuel oil, reclaimed oil or the like depending on the characteristics of the oil . The tower bottoms stream (50, residue component, residual component) is a residue component containing a high boiling point hydrocarbon fraction.

(A), VII (a), VII (b), IV (b), II At least one or more of the elements and the compound containing them are supplied (51, precursor supply) and mixed. In this process, the mixture is mixed in a stirring tank 400 heated to a temperature of 30 ° C to 200 ° C or 50 ° C to 200 ° C so as to have flowability, and then a finely dispersed hydrocracking catalyst is obtained (60). The precursor feed 51 may be omitted in other embodiments, in which case the tower bottoms stream 50 becomes the hydrocracking reaction catalyst 60.

A process of preparing the bottoms stream 50 by exposing the bottoms stream 50 to ultrasonic waves may be added as a step of pretreatment, and this may be performed through a mixing process in a stirring tank or an external device separately prepared.

The application of the ultrasonic waves may also be performed after the precursor supply 51 before being fed into the heavy oil conversion reaction. The dispersibility of the active metal component and the additive can be improved by application of ultrasonic waves.

Lubricating oil, which is the main component of waste oil, consists of more than 10 kinds of additives besides base oil. Base oil is a mineral oil obtained through chemical reaction process such as desulfurization, unsaturated hydrocarbon removal, ring opening reaction, isomerization reaction, poly-alpha-olefin, glycol, synthetic oils such as polyisobuthlene are common. Additives include clean dispersants that prevent the solid components generated by the oxidation or decomposition of oil from being deposited in the machine and induce dispersion, abrasion inhibitors that prevent excessive wear of machine parts, rust inhibitors that inhibit rust, oil A viscosity index improver for reducing viscosity change, a pour point depressant for improving low temperature fluidity, a defoaming agent for suppressing bubble formation to smooth fluid flow, an antioxidant for preventing oxidation of lubricant oil, a lubricant improving agent for reducing boundary friction, A solid lubricant for improving performance and lowering friction, a friction modifier, and the like. Among these, Mo-dialkyldithiocarbamate (Mo-DTC), which is designed to be in-situ with molybdenum disulfide dispersed well in oil or initially dispersed in molybdenum disulfide, Mo-dialkyldithiophosphate (Mo-DTP) and the like are generally used. Some of the dialkyldithiophosphate (Zn-DTP) is used to prevent partial oxidation and friction of oil. The clean dispersant acts as a surfactant to induce high dispersion of oil sludge, Magnesium salt and the like are added.

The tower bottoms stream 50 obtained from the distillation process may correspond to 5 to 50 wt% based on the input waste oil, and the API degree may be 5 to 30.

The tower bottoms stream 50 may contain 50-3,000 ppm molybdenum. In addition, the tower bottoms stream 50 may further contain 100-5,000 ppm of iron, 1000-5,000 ppm of zinc and / or 50-5,000 ppm of copper.

When the precursor feed (51) is performed, the molybdenum content of the hydrocracking reaction catalyst (60) may be increased to 150-5,000 ppm. In addition, the content of iron, zinc and / or copper may also increase.

In the hydrocracking reaction catalyst 60, the content of the organic matter may be 90% to 99.5% by weight. When the content of organic matter is less than 90% by weight, the dispersibility of the active metal is not ensured and the phenomenon of coagulation, coalescence, agglomeration, sedimentation and carbonization The catalytic properties can be lost. If the weight ratio of the organic matter is more than 99.5% by weight, the amount of the catalyst to be used may be excessively high, which may limit the throughput of the raw material, and the concentration of the active metal may be lowered to affect the conversion of heavy oil by the hydrocracking reaction have.

The hydrogenolysis reaction catalyst obtained by the above-described method can be used for heavy oil conversion. The heavy oil is converted to light oil by the hydrocracking reaction catalyst.

The heavy oil herein includes crude oil refining processes, petrochemical processes, heavy oil originating in the steel industry or low-cost crude oil classified as low crude oil.

The hydrocracking reaction can be carried out in a slurry-like high temperature and high pressure reactor. (1) removing impurities such as sulfur, nitrogen, nickel, vanadium, and iron present in the heavy oil, (2) removing impurities such as sulfur and nitrogen from the low-boiling point And high API synthetic oil or LPG, naphtha, kerosene, diesel oil, and gas oil under pressure.

The temperature of the hydrocracking reaction may be from 350 ° C to 500 ° C, and the pressure may be from 100 atmospheres to 150 atmospheres. And a stirring step at a temperature ranging from 50 ° C to 200 ° C where the flowability is maintained for uniform mixing with the raw material before the hydrocracking reaction is carried out.

According to the present invention, it is possible to provide economical operation of the hydrocracking reaction process according to the replacement of existing expensive metal catalysts by preparing a catalyst for the hardening of heavy oils from the low-cost separates generated in the refining process of waste oil. Concentrated metals are heavy metals harmful to the human body, which can reduce environmental emissions and improve the social environment.

It is possible to provide a method of significantly reducing the amount of the expensive metal when the catalyst according to the present invention is applied to the hydrocracking reaction.

According to the present invention, the clean dispersant among the components concentrated in the refining process of waste oil can increase or decrease the dispersibility of the hydrophilic metal precursor, thereby replacing or partially replacing the organometallic compound precursor which requires a separate synthesis process.

The catalysts prepared according to the present invention have chemical properties of high concentration heavy hydrocarbon fractions and physical properties of API and high viscosity are similar to raw materials and are applied to a fixed bed reactor, an applied reactor, a slurry bed reactor, It is possible.

According to the present invention, among the components concentrated in the refining process of the waste oil, the clean dispersant generates less fouling because the immersion of the carbon solid material, which can be generated as a macromolecule of metal and reaction byproduct, in the unit process is suppressed, Stable operation is possible.

The transition metals that are concentrated during the refining process of waste oil are highly dispersed in the residual oil and can be effective in the hydrocracking reaction and the light oil yield can be maximized by adding a small amount of catalyst precursor.

The waste oil-concentrated residue of the present invention contains various elements such as K, Na, Mg, Ca, Cu, Fe, Mo, Zn, S, P, , Zn), alkali metal (Na, K, Mg, Ca) sulfides, phosphates, and halides. These compounds decompose low-grade crude oil under high-temperature and high- .

In particular, the sulfides and phosphides of transition metals are expected to be effective catalyst components for hydrocracking, and even when there are trace amounts, each compound contributes synergistically to the hydrocracking reaction so that it is more effective than the contribution by the single transition metal compound .

Hereinafter, the present invention will be described in more detail by way of examples.

Experimental Example  1: From waste oil Hydrocracking reaction  Catalyst preparation

From the refining step of the waste oil according to FIG. 1, the liquefied hydrocarbon oil stream 41 and the distillation residue liquid stream 50 obtained by using the distillation process after purifying the impurity-separated stream 30 were taken. The wasted oil was separated from the recovery area by three refining companies whose impurity removal processes were different. Waste oil 1 was prepared by physical filtration using a filter to remove solid before distillation step. Waste oil 2 was prepared by centrifugation. Waste oil 3 was added with sulfuric acid as a coagulant to induce salt precipitation, and decanter was used And removing the sludge containing the precipitated salt. The water can be removed through a cryogenic still, which is maintained at 240 ° C or less. The liquefied hydrocarbon oil fraction and the distillation residue are mixed at a weight ratio of 80 to 90% by weight based on the charged mass of the refined waste oil, so that the waste oil from which the impurities have been removed is heated up to 10 ° C. per minute at 240 ° C. % And 10-20%, respectively. Samples 1 to 3 were prepared from waste oil 1 to 3 by taking the residue obtained in the bottom of the tower through the distillation process. Samples 4 to 6 were prepared by taking the distillate obtained from the overhead stream. Elemental components and their contents for these samples were analyzed by Elemental Analysis (Model: Thermo Scientific Flash 2000, Detector: X-ray fluorescence analysis (Model: Thermo / ARL QUANT'X ), inductively coupled plasma-atomic emission spectrometry (ICP-AES; model name: Thermo Fisher Scientific iCAP 6500 Duo), boiling point distribution was determined using ASTM D7169 (GC-Simdis) method, ; CCR) were analyzed using the ASTM D189 method.

Elemental Content of Waste Oil Separation by Elemental Analysis (%)

element Distillation residue
(Tower bottom residue) Liquefied hydrocarbon oil
(Top distillate) Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 C 79.5 81 79.5 85.3 85.5 85.3 H 12.1 12.6 12.1 13.7 13.9 13.7 O 3.2 1.6 2.1 - - - N 0.47 0.19 0.27 - - - S 0.94 0.58 0.91 0.08 0.05 0.08 Others 3.79 4.03 5.12 0.92 0.55 0.92

As shown in Table 1, it was confirmed that the distillate obtained from the top of the column and the bottom of the column had similar organic elements (C, H, O, N, S) distribution when distilled oil with impurities was distilled. The boiling point distributions of the tower top distillate and the tower bottom residue obtained from the sample 1 were analyzed according to the ASTM D7169 method. The results are shown in Table 2.

The boiling point distribution of the waste oil separation (Samples 1 and 4) according to ASTM D7169

Sample 1 Sample 4 Boiling point (캜) mass% Boiling point (캜) mass% 192.1 IBP 200.0 0.53 231.8 IBP 250.0 0.59 250.0 0.67 300.0 0.61 300.0 1.90 350.0 0.66 350.0 6.14 400.0 0.94 400.0 25.94 450.0 2.72 450.0 66.85 500.0 11.28 500.0 91.90 550.0 47.18 550.0 98.70 600.0 77.99 585.1 FBP 650.0 93.79 700.0 99.36 702.8 FBP

IBP: initial boiling point

FBP: final boiling point

From the boiling point distribution shown in Table 2, the tower top distillate has a relatively narrow boiling point (230-585 ° C), while the tower bottom residue (190-700 ° C) has a relatively high and broad boiling point Can be observed. In particular, it can be seen that the tower bottom residue is composed of a large amount of hydrocarbon compounds having a boiling point of 500 ° C or more, similar to a heavy raw material (eg, vacuum residue) that can be used as a raw material for hydrocracking reaction. Most of the hydrocarbon compounds in the waste oil start from the base oil component of the oil before use and are maintained physically and chemically stable hydrocarbon structure during use, so the change of boiling point may not be large. A base oil is a high boiling point oil obtained from crude oil (a reduced-pressure gas oil), which is subjected to a purification process such as a hydrotreating process to remove an unsaturated double bond or a cyclic compound, and is subjected to isomerization to obtain a colorless transparent mineral oil or a poly- ), Polyol esters, and wax cracking hydrocarbons. Therefore, when the distillation residue is partially mixed with the raw material in the hydrogenolysis reaction under high temperature and high hydrogen partial pressure conditions, non-ideal behavior such as increase of partial pressure due to decomposition hard gas, change of reaction heat, increase of hydrogen consumption It may not have a great influence. However, the amount of reformed residual carbon in distillation residues may increase the end product distribution of hydrocracking reaction, especially the amount of coke formation. Coke is a major byproduct of hydrocracking reaction, which is composed of large quantities of carbon and some hydrogens and is no longer decomposed into hard minerals. The formation of coke not only lowers the yield of the reaction but also deposits on the walls of the unit processes (hydrogenolysis reactor, separation process, transfer tube, etc.), which can cause serious operational problems in the process. Table 3 shows the results of measurement of the amount of residual decomposition of residual carbon in distillation residues.

Degradation Residual Carbon Content (%) on Waste Oil Distillation Residues

Sample 1 Sample 2 Sample 3 CCR (%) 9.8 7.1 13.4

On the other hand, X-ray fluorescence analysis was performed on distillation residues to observe the kinds of inorganic components including transition metals having activity in hydrocracking reaction, and the relative contents of the detected components are shown in Table 4.

Relative content (%) of metal elements in waste oil distillation residues by X-ray fluorescence analysis

element Sample 1 Sample 2 Sample 3 Na 17.2 22.6 0.0 Mg 1.5 0.0 0.0 Al 0.4 0.0 0.0 P 7.7 7.9 2.1 S 20.2 18.2 6.3 Cl 1.6 4.9 9.1 K 2.9 2.0 3.8 Ca 27.2 26.0 38.8 Fe 2.5 2.2 4.4 Cu 0.6 0.5 1.8 Zn 16.7 14.6 30.4 Br 0.3 0.2 0.2 Mo 1.4 1.1 3.0

Referring to Table 4, a large amount of various cations (Na, Mg, K, Ca) are contained due to the additives of the lubricating oil such as dispersant. On the other hand, molybdenum, copper, iron, zinc and the like corresponding to the transition metal exist, and they may be dispersed evenly in sulfide, phosphide and halide forms effective for the hydrogenolysis reaction derived from the organic metal additive. These enriched metals in the residue were quantified by ICP-AES analysis and the determined contents are shown in Table 5.

The metal content (ppm) of waste oil distillation residues determined by ICP-AES

element Sample 1 Sample 2 Sample 3 Mo 480 130 650 Cu 183 570 460 Fe 902 310 1,100 Zn 5,300 3,500 6,800

Referring to Table 5, it can be seen that the compositional distribution ratios of the prepared distillation residue samples are similar, but the absolute contents are slightly different according to the removal process of the impurities. In the case of Sample 2, the content of total transition metal was low, but the content of copper was somewhat high.

5 g of the distillation residue quantified by the above analysis method was prepared as a hydrocracking reaction catalyst.

Experimental Example  2: Of the hydrocracking catalyst Active metal amount  Change and Heating  Pretreatment

According to Experimental Example 1, an organometallic compound Mo-octoate (Shepherd Co., Mo content: 15%; oxidation number: 3.8) was quantitatively determined on the hydrocracking reaction catalyst prepared from Sample 1, and then the amount of active metal was changed. The mixture was stirred at 80 DEG C for 4 hours to prepare a hydrocracking catalyst having a different metal amount.

Experimental Example  3: Of the hydrocracking catalyst Active metal amount  Change and Heating  Pretreatment

According to Experimental Example 1, an organometallic compound hexacarbonyl molybdenum (Mo (CO) ₆ ) was quantitatively determined on the hydrocracking reaction catalyst prepared from Sample 1, and the amount of active metal was further changed. And the mixture was stirred at 80 DEG C for 4 hours to prepare a hydrocracking catalyst having a different metal amount.

Experimental Example  4: Of the hydrocracking catalyst  Pretreatment

The hydrocracking reaction catalyst was prepared in the same manner as in Experimental Example 3, except that it was exposed to ultrasound of 60 Hertz intensity in the stirring process.

Experimental Example  5: Non-catalyst  Evaluation of Hydrogenolysis of Heavy Oil Under Condition

The reaction conditions were an initial pressure of 80 bar at an initial temperature of 80 ° C, a reaction temperature of 430 ° C, a reaction time of 4 hours, and a stirring speed of 1,500 rpm. 40 g of vacuum residue was added to the 250 ml batch reactor, and the product was analyzed after the reaction under the above reaction conditions. The material used as the feedstock in the hydrocracking reaction evaluation is the reduced-pressure residuum obtained from Hyundai Oilbank and the characteristics are as shown in Table 6.

Characteristics of decompression residue

Analysis item result Elemental analysis
(wt.%) C 84.1 H 10.1 N 0.4 S 5.5 O - heavy metal
Content (mg / kg) Ni 36 V 151 SARA analysis
(Area%) S 4 A 47 R 18 A 31 API 5.84 Distillation curve > 524 ° C 82% CCR 23.2 wt% S: Saturates, A: Aromatic, R: Resin, A: Asphaltene

Experimental Example  6: Evaluation of Hydrogenolysis of Heavy Oil in the Presence of Catalyst

Hydrogenolytic decomposition was evaluated in the same manner as in Experimental Example 5, except that the catalyst prepared in Experimental Example 4 was mixed with 40 g of crude decompressed residual oil.

Experimental Example  7: Evaluation of hydrocracking reaction in the presence of catalyst

And the reaction time was changed to 2 hours. In the same manner as in Experimental Example 6, the hydrocracking reaction was evaluated.

< Comparative Example  And Example >

Comparative Example  One

According to Experimental Example 5, the hydrocracking reaction of the reduced residual oil was carried out without applying the catalyst.

Comparative Example  2

Mo-octoate was subjected to hydrocracking reaction according to Experimental Example 6 so that the molybdenum content had a concentration of 55 ppm relative to the reduced-pressure residual oil as the hydrocracking raw material.

Comparative Example  3

The hydrocracking reaction was carried out in the same manner as in Comparative Example 2 except that the molybdenum content of Mo-octoate was 250 ppm relative to the reduced-pressure residual oil.

Comparative Example  4

The hydrocracking reaction was carried out in the same manner as in Comparative Example 2 except that hexacarbonylmolybdenum had a molybdenum content of 250 ppm relative to the reduced-pressure residual oil.

Example  1 to 3

Hydrogenolysis reaction was carried out according to Experimental Example 6 using the hydrogenolysis reaction catalyst prepared from Samples 1 to 3 according to Experimental Example 1.

Example  4

The hydrocracking reaction catalyst was prepared according to Experimental Example 2, and hydrocracking reaction was carried out according to Experimental Example 6 so that the molybdenum content had a concentration of 250 ppm relative to the reduced pressure residual oil.

Example  5

The hydrocracking reaction catalyst was prepared according to Experimental Example 3, and hydrocracking reaction was carried out according to Experimental Example 6 so that the molybdenum content had a concentration of 250 ppm relative to the reduced pressure residual oil.

Example  6

The hydrocracking reaction was carried out in the same manner as in Example 6, except that the molybdenum content was 2,000 ppm relative to the reduced-pressure residual oil.

Example  7

A hydrocracking reaction catalyst pretreated according to Experimental Example 4 was prepared and subjected to hydrocracking reaction according to Experimental Example 6 so that the molybdenum content had a concentration of 55 ppm relative to the reduced residual oil.

Example  8

The hydrocracking reaction was carried out in the same manner as in Example 7, except that the molybdenum content was 250 ppm relative to the reduced-pressure residual oil.

Example  9

Hydrogenolysis was carried out in the same manner as in Example 7, except that the molybdenum content was 2,000 ppm relative to the reduced-pressure residual oil.

Example  10

The hydrocracking reaction catalyst was prepared according to Experimental Example 3, and the hydrocracking reaction was carried out according to Experimental Example 7 so that the molybdenum content was 2,000 ppm relative to the reduced pressure residual oil.

Example  11

The hydrocracking reaction catalyst was prepared according to Experimental Example 4, and the hydrocracking reaction was carried out according to Experimental Example 7 so that the molybdenum content was 2,000 ppm relative to the reduced-pressure residual oil.

Comparative Example  5

The hydrocracking reaction was carried out in the same manner as in Example 7, except that the molybdenum content was 11,000 ppm relative to the reduced-pressure residual oil.

The conditions according to Examples and Comparative Examples are shown in Table 7 below. Examples 1 to 3 used Samples 1 to 3, respectively, and Sample 4 was used in Examples 4 to 11.

Summary of catalyst preparation and hydrocracking reaction conditions according to Examples and Comparative Examples

division Raw material (VR)
(g) Used Oil
(g) Mo-Octoate
(Mo ppm) Mo (CO) ₆
(Mo ppm) Presence or absence
(Sonication @ 80 C for 4 hr) Total Mo contents
(Mo ppm) reaction
time
(hr) Comparative Example 1 40 0 0 0 X 0 4 Comparative Example 2 40 0 55 0 X 55 4 Comparative Example 3 40 0 250 0 X 250 4 Comparative Example 4 40 0 0 250 X 250 4 Example 1 40 5 0 0 X 55 4 Example 2 40 5 0 0 X 14 4 Example 3 40 5 0 0 X 72 4 Example 4 40 5 195 0 X 250 4 Example 5 40 5 0 195 X 250 4 Example 6 40 5 0 1,945 X 2,000 4 Example 7 40 5 0 0 O 55 4 Example 8 40 5 0 195 O 250 4 Example 9 40 5 0 1,945 O 2,000 4 Example 10 40 5 0 1,945 X 2,000 2 Example 11 40 5 0 1,945 O 2,000 2 Comparative Example 5 40 5 0 10,945 O 11,000 4

One example of the heavy crude residue is the heaviest oil fraction obtained from the atmospheric pressure and reduced pressure distillation process in the crude oil refining process, which is composed of 82% or more of residue components having a boiling point higher than 524 ° C. Because it has high viscosity and high impurity content, it is a relatively low value raw material and can be converted into liquid light oil with high value through pyrolysis reaction. High added liquid light oil can be classified into naphtha, middle distillate, and gas oil depending on the boiling point. On the other hand, when toluene insoluble (coke) is produced as a byproduct which can not be converted into the above-mentioned high-value liquid light oil by the progress of the hydrogenolysis reaction, it causes many problems in the process. In particular, deactivation of the used catalyst, deposition in the reactor and unit process interferes with the transfer of raw materials or reaction products, adversely affecting normal and stable operation. Therefore, it is desirable to design the catalyst so as to minimize the production of toluene insoluble.

Comparison of basic performance of hydrocracking using non-catalytic, Mo-octoate and waste oil distillation residues

Product distribution Raw material Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Gas product (%) 11.9 13.7 13.4 15.2 12.1 15.6 Liquid Product (%) 100.0 66.6 79.6 82.9 82.9 85.0 81.0   Naphtha (IBP-177 &lt; 0 &gt; C) 16.8 16.9 15.6 12.9 17.7 20.0   Middle distillate (177-343 ° C) 25.3 29.3 30.9 28.4 32.7 29.3   Gas oil (343-524 DEG C) 18.0 16.0 23.2 26.8 28.6 25.3 23.4   Residue (524 ° C-FBP) 82.0 8.5 10.1 9.7 12.8 9.3 8.2 Toluene insoluble (%) 21.6 6.7 3.7 1.9 2.9 3.4 Liquid Yield (%) ^a 58.0 69.4 73.2 70.0 75.7 72.8 Conversion (%) ^b 91.5 89.9 90.3 87.2 90.7 91.8

a. 100% -Gas product (%) - Residue (%) - Toluene insoluble (%)

b. 100% -Residue (%)

Table 8 shows the results obtained when the catalyst was not added (Comparative Example 1) and when it was added so as to be 55 ppm of Mo (Comparative Example 2), 250 ppm of Mo (Comparative Example 3), and 5 g of waste oil distillation residue, The results of the hydrocracking reaction are shown in Fig. The boiling points of the raw materials and liquid products shown in the above table were determined according to ASTM D7169, toluene insoluble was measured according to ASTM D4312, and gaseous products having a carbon number of 1 to 5 were measured by a thermal conductivity sensor (TCD) and a flame ionization detector (FID). &Lt; / RTI &gt; The yield of toluene insoluble was 22%, while the yield of liquid light oil was 58% or less, as shown in the results of hydrocracking reaction without catalyst (Comparative Example 1). On the other hand, when the organometallic precursor Mo-octoate proposed in the prior patents US20110139677, US20140291203, US7670984, US7842635, etc. is used at 250 ppm of Mo (Comparative Example 3), the yield of liquid light oil is remarkably improved to 73% or more. This is an efficient hydrocracking reaction catalyst that converts the precursor to a very homogeneous dispersion in the oil and then converts it to the active nano-form molybdenum disulfide (MoS ₂ ), which is active through in situ activation, to lower the activation energy barrier for hydrogenation . On the other hand, referring to the examples (Examples 1 to 3) in which the waste oil distillation residue is applied to the hydrocracking reaction, although the content of molybdenum is only about 14 to 72 ppm, when 250 ppm of Mo-octoate is applied 3) and the production of toluene insoluble. Comparing the results of the hydrocracking reaction in which the molybdenum content to be applied was adjusted to 55 ppm and the distillation residue of distillation oil (Example 1) and Mo-octoate (Comparative Example 2) were respectively added, a similar level of liquid light oil yield But the amount of toluene insoluble was decreased by 4.8% or more when waste oil distillation residue was applied. Comparing the results of applying the distillation residue of waste oil distillation to hydrocracking reaction (Examples 1 to 3), the reaction performance does not depend only on the Mo content, and as shown in Table 5, the sulfide of transition metal such as zinc, iron, Or a mixed form of the phosphates can be expected to be involved in the hydrocracking reaction in a complex manner.

Comparison of hydrocracking performance of catalysts with Mo contents of 250ppm relative to raw materials (decompression residue)

Product distribution Comparative Example 3 Comparative Example 4 Example 4 Example 5 Gas product (%) 13.4 16.4 19.7 17.8 Liquid Product (%) 82.9 78.6 78.6 80.5   Naphtha (IBP-177 ° C) (%) 15.6 15.8 12.3 13.0   Middle distillate (177-343 ° C) (%) 30.9 29.2 27.1 27.3   Gas oil (343-524 ° C) (%) 26.8 23.6 28.0 28.2   Residue (524 ° C -FBP) (%) 9.7 10.1 11.2 12.1 Toluene insoluble (%) 3.7 5.0 1.7 1.7 Liquid Yield (%) ^a 73.2 68.5 67.4 68.4 Conversion (%) ^b 90.3 89.9 88.8 87.9

a. 100% -Gas product (%) - Residue (%) - Toluene insoluble (%)

b. 100% -Residue (%)

Table 9 summarizes the results obtained by using the organic metal precursor Mo-octoate (Comparative Example 3), hexacarbonylmolybdenum (general precursor having no dispersibility) (Comparative Example 4), and the molybdenum content in the waste oil distillation residue In addition, the results are compared with the results obtained by adjusting the molybdenum concentration to 250 ppm in the hydrocracking reaction. The prior art document US 20130248422 suggests performance changes according to various species (carboxylate anion) of organic compounds coordinated to molybdenum for the design of the organometallic precursor for the hydrogenolysis reaction. The organic compound has a function of improving the dispersibility to oil and inducing effective catalytic decomposition of the active transition metal with the desired heavy molecule. Hexacarbonylmolybdenum does not have a long hydrocarbon chain and is relatively hydrophilic, and is not evenly dispersed in the heavy oil fraction as a raw material. Referring to the hydrocracking reaction results of Mo-octoate (Comparative Example 3) and hexacarbonyl molybdenum (Comparative Example 4) added with the molybdenum adjusted to 250 ppm in Table 9, It can be seen that the performance of Mo-octoate is excellent. On the other hand, it was found that the performance was very similar when the results were compared with those obtained by subjecting each of them to distillation residue of distillation (molybdenum 55ppm) (molybdenum 195ppm) and applying it to the hydrocracking reaction (Examples 4 and 5) . This is due to the role of the dispersing agent remaining in the distillation residue of waste oil, which is a result of greatly improving the dispersibility in the oil of the transition metal precursor which is hydrophilic. On the other hand, when molybdenum was added to the distillation residue of waste oil by the precursor, it showed an overcracking phenomenon in which the generation of the vapor phase was increased due to excessive activity, and Mo-octoate corresponding to molybdenum equivalent amount was applied The yield of the light liquid oil is slightly reduced.

Evaluation of the effect of hydrocracking reaction on the concentration of additional hydrophilic precursor

Product distribution Example 1 Example 5 Example 6 Gas product (%) 15.2 17.8 15.3 Liquid Product (%) 82.9 80.5 84.0   Naphtha (IBP-177 ° C) (%) 12.9 13.0 16.0   Middle distillate (177-343 ° C) (%) 28.4 27.3 27.4   Gas oil (343-524 ° C) (%) 28.6 28.2 28.7   Residue (524 ° C -FBP) (%) 12.8 12.1 11.9 Toluene insoluble (%) 1.9 1.7 0.8 Liquid Yield (%) ^a 70.0 68.4 72.0 Conversion (%) ^b 87.2 87.9 88.1

a. 100% -Gas product (%) - Residue (%) - Toluene insoluble (%)

b. 100% -Residue (%)

Table 10 shows the results obtained by adding hexacarbonylmolybdenum, a common precursor, to 55 ppm, 250 ppm, and 2,000 ppm (Example 1, Example 4, and Example 6, respectively) to distillation residue of waste oil (molybdenum content 55 ppm) The molybdenum content is controlled and then the hydrocracked residue is subjected to hydrocracking reaction. As the molybdenum content increases, the conversion rate increases and the amount of toluene insoluble decreases. This is because the hydrogenation activity is increased as the amount of the added transition metal is increased, and the radicals generated from pyrolysis are effectively inhibited from hydrogenation or the generation of coke by capping of the terminal group. On the other hand, when the amount of hexacarbonylmolybdenum added to reach 2,000 ppm based on the molybdenum content was increased (Example 4), only a small amount of 250 ppm was added based on the molybdenum content 1), and it is possible to obtain a highly liquid liquid light oil.

The transition metals in waste oil distillation residues are either grown by phenomena such as coagulation, coalescence, agglomeration, sedimentation and carbonization during use and purification, And the like. For example, in the prior art non-patent documents (Giuseppe Bellussi, Giacomo Rispoli, Alberto Landoni, Roberto Millini, Daniele Molinari, Erica Montanari, Daniele Moscotti, Paolo Pollesel / Hydroconversion of heavy residues in slurry reactors: Developments and perspectives / J. Catal. -200 / 308 (2013)) suggest that molybdenum disulfide, which is an active species of the hydrocracking reaction, forms a stacking layer bound by van der Waals force as a result of prolonged exposure to the process . The activity of the hydrogenation reaction is not high except for the rim of the multi-layered basal site, and the growth of the molybdenum disulfide results in greatly lowering the activity of the reaction. Transition metals other than molybdenum also lose their activity as a catalyst unless the size of the crystal constituting them is increased or the dispersion is poor. See also other prior non-patent documents (Millan M. Mdleleni, Taeghwan Hyeon, and Kenneth S. Suslick / Sonochemical Synthesis of Nanostructured Molybdenum Sulfide / J. Am. Chem. Soc. / 120 / 6189-6190 , It can be grown to an exfoliated structure or not agglomerated when exposed to ultrasonic waves during the synthesis of molybdenum disulfide, and the thus prepared catalyst has excellent performance in hydrogenation reaction.

Based on the results of the above document, the catalysts used in the results of Table 10 were subjected to a hydrocracking reaction by adding pretreatment for 4 hours at 80 DEG C while exposed to ultrasound of 60 Hertz intensity. The results are shown in Table 11 Respectively. The added precursor was hexacarbonyl molybdenum, which was quantitatively prepared so as to have a molybdenum content of 55 ppm, 250 ppm, and 2,000 ppm (Examples 7, 8, and 9, respectively) relative to the raw material. It can be seen that the conversion rate and the yield of the liquid light crude oil are improved in comparison with the results in Table 9, which is applied without performing the pretreatment in the catalyst preparation step. Further, referring to the two cases (Example 8 and Example 9) prepared by adding hexacarbonylmolybdenum, the amount of toluene insoluble produced was slightly increased when the pretreatment was carried out. However, The production amount of the product is remarkably reduced. On the other hand, when the hydrocracking reaction was carried out by adding a large amount of hexacarbonyl molybdenum so that the content of molybdenum relative to the raw material reached 11,000 ppm (Comparative Example 5), no significant change in performance was observed. This explains that the performance is not improved in proportion as the molybdenum amount consumed in the actual hydrocracking reaction is consumed.

Performance evaluation of hydrocracking reaction by pretreatment

Product distribution Example 7 Example 8 Example 9 Comparative Example 5 Gas product (%) 15.6 12.9 12.2 11.9 Liquid Product (%) 82.9 84.7 85.3 85.5   Naphtha (IBP-177 ° C) (%) 16.2 18.0 19.5 19.7   Middle distillate (177-343 ° C) (%) 29.4 28.5 27.8 27.8   Gas oil (343-524 ° C) (%) 26.6 26.7 27.8 27.9   Residue (524 ° C -FBP) (%) 10.8 11.5 10.2 10.1 Toluene insoluble (%) 1.6 2.4 2.5 2.6 Liquid Yield (%) ^a 72.1 73.2 75.1 75.4 Conversion (%) ^b 89.2 88.5 89.8 89.9

a. 100% -Gas product (%) - Residue (%) - Toluene insoluble (%)

b. 100% -Residue (%)

The commercial process of hydrocracking reaction is generally designed and operated so that raw materials and reactants are continuously injected and the product has a continuous flow according to the separation process. In such a continuous process, the hydrogenolysis reactor is designed to have a low residence time in order to ensure high throughput, so that high conversion rate in short time and yield of liquid light oil can be guaranteed for efficient operation do. Table 12 shows the results obtained by adding hexacarbonylmolybdenum to the waste oil distillation residue to adjust it to 2,000 ppm and then performing the pretreatment (Example 10 and Example 6) (Example 11 and Example 9 ) Catalysts were applied to hydrocracking reaction of reduced pressure residues at different reaction times. When the reaction time was reduced to half, the conversion and the yield of liquid light oil decreased, but the amount of toluene insoluble was greatly decreased while the decrease was not significant. On the other hand, the catalysts pretreated showed a higher conversion ratio and yield of the light oil, and this can be interpreted as a result of the improvement of catalyst activity by pretreatment.

Changes in Product Distribution of Hydrogenolysis by Reaction Time

Reaction time
Product distribution 2 hours 4 hours Example 10 Example 11 Example 6 Example 9 Gas product (%) 8.0 10.4 15.3 12.2 Liquid Product (%) 91.9 89.3 84.0 85.3   Naphtha (IBP-177 ° C) (%) 10.8 11.2 16.0 19.5   Middle distillate (177-343 ° C) (%) 22.1 23.9 27.4 27.8   Gas oil (343-524 ° C) (%) 35.5 33.5 28.7 27.8   Residue (524 ° C -FBP) (%) 23.6 20.7 11.9 10.2 Toluene insoluble (%) 0.1 0.3 0.8 2.5 Liquid Yield (%) ^a 68.3 68.6 72.0 75.1 Conversion (%) ^b 76.4 79.3 88.1 89.8

a. 100% -Gas product (%) - Residue (%) - Toluene insoluble (%)

b. 100% -Residue (%)

The above-described embodiments are illustrative of the present invention, and the present invention is not limited thereto. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims.

10: Waste oil supply flow
11: solids removal flow
20: distillation feed stream
30: Waste oil stream to remove impurities
31: Moisture flow
40: De-metal hydrocarbons vapor
41: Refined hydrocarbon oil
50: distillation residue flow
51: Metal precursor supply flow
60: Product (hydrocracking reaction catalyst) flow
100: solids remover
101: Cryogenic still (water removal)
200: High temperature distiller (hydrocarbon oil fraction)
300: capacitor
400: Mixer

Claims (10)

A method for producing a hydrogenolysis reaction catalyst from waste oil,
Removing solid matter from the waste oil;
Distilling the waste oil from which the solid matter has been removed in a distillation column to obtain an upper stream and a lower stream;
And obtaining a hydrocracking reaction catalyst comprising the tower bottoms stream,
Wherein the waste oil contains at least one metal component of molybdenum, iron, zinc and copper,
The tower bottom stream has a higher boiling point and a higher metal content than the tower top stream,
Wherein the tower bottoms stream comprises 50-3,000 ppm of molybdenum,
VI (b), II (b), I (b), VI (a), V (a), VII (a) at least one of the group elements and the compound containing the group element,
Wherein the mixing step is performed in a state where ultrasonic waves are applied. delete The method according to claim 1,
Wherein the tower bottoms stream further comprises 100-5,000 ppm of iron, 1000-5,000 ppm of zinc, and 50-5,000 ppm of copper. The method according to claim 1,
Wherein the molybdenum is present in sulfided form. delete The method according to claim 1,
Wherein the mixing is performed such that the molybdenum content is increased and the molybdenum content in the hydrocracking reaction catalyst is 150-5,000 ppm. The method according to claim 1,
Wherein the mixing step is performed at a temperature of 50 to 200 DEG C in the tower bottom flow. delete The method according to claim 1,
Wherein the tower bottoms stream comprises 90 to 99.5 weight percent organic matter. In the heavy oil conversion method,
Preparing a hydrocracking reaction catalyst by the process according to any one of claims 1, 3, 4, 6, 7, and 9;
Wherein said heavy oil is converted using said hydrogenolysis reaction catalyst.

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