JPS60173091A - Hydrogenation of petroleum residual fraction - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for hydroconversion of heavy hydrocarbon fractions or residual oils, and more particularly to a two-stage conversion process using hydrothermal reaction and catalytic hydrogenation reaction of petroleum residues. .

High temperature on heavy hydrocarbons or residual oils obtained from petroleum, oil shells, tar sands, coal, etc.

The production of liquid products by hydrogenation under high pressure is well known. However, the resulting liquid production efficiency is often not as good as compared to light fractions that are gaseous under normal conditions due to consumption of hydrogen and catalyst or production in excess.

In a specific example of a two-stage hydroconversion process for heavy hydrocarbons, 5
The heavy material is first heated to about 40% in the presence of hydrogen.
From 0°C to 480°C (approximately 750°F to 900'F),
It is subjected to a hydrothermal reaction treatment under severe conditions, preferably without the use of catalysts or contacting substances. The entire effluent from the first stage (gases, liquids, solids) is then passed directly to the catalytic hydrocracking zone at a temperature below 800'F and below the hydrothermal reaction zone. In a preferred embodiment of this process, the hydrothermal reaction zone and the catalytic reactor are paired in close proximity. Although the conversion of residual oil and the production of distillate fraction are set to be maximum, it is possible to operate under more severe conditions in the hydrothermal reaction stage, and even more decomposition products are produced. It can generate and emit light gas.

Furthermore, the distillation fraction formed in the hydrothermal reaction stage is once again subjected to hydrogenation in a catalytic reactor. However, while this method improves product quality, it also increases hydrogen consumption. In addition, hydrothermal reactions at high temperatures produce saturated light hydrocarbons, which tend to form unstable mixtures with undecomposed residual 1i substances, which are thought to be aromatic hydrocarbons or unsaturated hydrocarbons. .

Here, most of the heavy parts in the residual oil are asphaltene, and an aromatic medium is required to dissolve this. Furthermore, most of the substances containing undecomposed heavy asphaltene in solution do not have sufficient solubility. As a result, phase separation and asphaltene precipitation tend to occur as the temperature decreases from the hydrothermal reaction stage to the lower temperature hydrocracking stage.

Regarding the case of coal liquefaction with petroleum residue added.

U.S. Pat. No. 4,330,393 discloses that in order to increase the water ice partial pressure in the hydrocracking stage, a small amount of water and This suggests that it is better to separate gases from C1 to 04. In U.S. Pat. No. 4,330,393, the physical configuration of the hydrothermal reaction zone is such that a slurry of coal and residual oil flows through the zone in one direction, either upwardly or downwardly. Additionally, the multi-stage coal liquefaction process shown in U.S. Pat. It is known that this structure is convenient for exhausting most of the gas.

In general, a two-step process (hydrothermal reaction - hydrocracking) usually requires much more hydrogen.Hydrogen is produced and supplied from relatively expensive natural gas or coal using known processes. Regarding the zero expenses that will be incurred, please refer to the following 3.
If these conditions are met, it will be possible to reduce prices without losing profits.

(1) Light products that consume hydrogen in the catalytic reactor are separated before the catalytic hydrocracking stage. (11) Some heavy oil material is removed before the catalytic hydrocracking stage.

010 Selecting milder operating conditions 0If the hydrogen utilization efficiency in the -C, two-stage residual oil hydrogenation process could be improved by reducing hydrogen addition to the middle distillate produced in the two-stage process, it would be a significant improvement. This would be possible by continuously removing relatively light cuts, possibly up to middle cuts, from the dissolver stage product.

In addition, the light fraction containing light saturated hydrocarbons produced in the hydrothermal reaction stage of the two-stage residual oil hydroconversion process causes inconsistency and is harmful to the process in the catalytic hydrocracking stage, - It would be a great advantage if it could be continuously removed from the residual liquid along with other substances such as carbon oxide. By taking such measures, the υ second stage will be operated more efficiently and the inconsistency of the product due to asphaltene precipitation will be overcome. All of the advantages indicated herein are achieved by the process of the present invention.

SUMMARY OF THE INVENTION The present invention relates to a process for hydrotreating petroleum residues. Hydrothermal reaction treatment - In the stripping zone,
A mixture consisting of the petroleum residue and hydrothermal reaction products is formed, and a majority of the produced light fractions are removed from the mixture by simultaneous countercurrent contact of the mixture with a first hydrogen gas stream at an elevated temperature. Stripped. The gas stream containing the product light fractions is withdrawn from the hydrothermal treatment-stripping zone, leaving the product heavy effluent stream intact.

At least a portion of the produced heavy effluent stream is subjected to % secondary hydrogen gas and externally supplied hydrogenation in a catalytic reaction zone under hydrocracking conditions at a temperature lower than that of the hydrothermal reaction-stripping zone. Contact with decomposition catalyst. A secondary effluent stream is then recovered from the hydrocracking zone.

Detailed description of preferred embodiments of generation A preferred embodiment of the present invention will be explained with reference to the drawings.

The heated (bo/p transportable) petroleum residue enters the hydrothermal treatment-dripping zone 10 via flow path 1.

Here, the petroleum residue generally flows downward and comes into countercurrent contact with the added hydrogen gas which enters the hydrothermal treatment and stripping zone 10 through flow path 5. The petroleum residue is heated and hydrotreated in the presence of added hydrogen gas, thus forming a mixture of petroleum, residue, and materials produced by the hydrothermal reaction. Hydrogen gas passes through zone 10, generally as an upward flow, to strip most of the light fractions produced from the mixture and to the process via flow path 15.
Carried out of the stripping band. The mixture remaining in zone 10 is conveyed through channel 20 to zone 25, where it can be removed if required.

It is cooled to a temperature p below the temperature of the hydrothermal reaction stage, preferably about 85°C below the hydrothermal reaction stage. The cooled mixture is further conveyed through channel 30 to hydrocracking zone 35 where it is catalytically hydrocracked in the presence of hydrogen supplied via channel 40 to produce a relatively low viscosity liquid product. generate things. This is easily separated from any remaining solid residue.

To explain in more detail with reference to the diagram, the petroleum residue can be mixed with a solvent to form a slurry that can be pumped, or it can be heated and pumped using conventional methods. It may be made into liquid form. The basic raw materials of the present invention are 1 petroleum, 1 petroleum residue, heavy oil derived from coal, oil shell, tar sands, bituminous coal, lignite and mixtures thereof.

Carbohydrate bulk materials, etc. Maya (Mexico), Be
ta, Hondo, Pt, Arguello
Residual oils from heavy crude oils such as (both off the coast of California) are particularly preferred. The solvent used for the preparation of the raw materials may be selected from a variety of solvents based on known techniques or derived from the process.

Even when the metal content in the hydrocracking zone is relatively high, the process of the present invention can be carried out by mixing the feedstock with up to about SWECH of pulverized coal to form a slurry, which can be achieved by prior demetalization or pretreatment. It can be used without taking any measures.

By doing so, a substantial portion of the metals in the crude oil will either combine with the coal clouded in the liquid raw material or deposit on the finished coal, but will not deposit on the cracking catalyst.

The raw oil passes through flow path 1 to one or more treatment tanks.
Hydrothermal reaction treatment with stripper - fed or pumped to stripping zone 10. The feedstock is then heated from about 400°C to 480°C (about 750'F to 90°C) until some of the feedstock reacts with the added hydrogen.
0'F), preferably about 425°C to 455°C (about 8
Heated at temperatures ranging from 00'F to 850°F. A mixture of raw materials and hydrothermal reaction products containing light fractions is thereby formed. Such light products, commonly known as middle distillates, contain acid gases such as carbon monoxide and light saturated hydrocarbons such as methane, ethane, and butane with boiling points up to about 670'C (below 700C). Contains a light hydrocarbon fraction containing components that

Preferably, the feedstock is heated to at least 400°C (750°F) to achieve sufficient conversion in the hydrothermal reaction zone. Furthermore, in order to prevent excessive thermal decomposition, it is preferable not to heat above about 480° C. (about 900° C. or lower). by this.

This is because under standard conditions the overall yield of liquid product is substantially reduced.

Hydrothermal Reaction Processing The IJ Zubing zone 10 basically consists of one or more elongated vessels, preferably without externally supplied catalysts or contacting substances. Also, in at least one hinoki of the zone, the feedstock is designed to flow downward while the hydrogen gas flows upward and makes countercurrent contact with the heated feedstock and the mixture resulting from the hydrothermal reaction. There is. More generally, the tank in which the hydrogen gas and the raw material are in continuous contact is a column filled with solid packing, or an empty column through which the raw material is sprayed and the gas is passed.
or a column with multiple bubble cap sheep or valve trays. However, in any case, the structure is such that the gas and the raw material are in countercurrent contact with each other in order to obtain the maximum driving force due to the concentration difference, in other words, the maximum dissipation rate, for example, the stripping rate. The design factors for this unit operation are covered in Chapters 4, 14, and 18 of the 5th edition of "Chemical Engineer's Handbook" by Perri and Chilton, published by McGraw-Hill, and are reproduced here. shall be incorporated.

Hydrothermal Reaction Treatment - The stripping zone 10 includes one or more treatment vessels in which the feedstock and added hydrogen are in countercurrent or cocurrent flow, but essentially at least one
Basic Treatment - In the dripping tank, the mixture of raw materials and hydrothermal reaction products is in countercurrent flow with the flow of hydrogen gas. Processing-sdripping vessels are operated as level-controlled liquid-filled vessels due to the need to maintain a constant level of the liquid mixture and thereby adjust the residence time of the mixture in the hydrothermal reaction zone. Level control is illustrated in Chapter 22 of the book by Berry and Chilton mentioned above, so that part will be incorporated here. The latter operation is preferably carried out under conditions where substantial backmixing is not detrimental to the process and its products. Furthermore, the treatment-sdripping vessel can be operated as a vertical multi-stage continuous reactor (Chapter 4, p. 21 of Berry and Chilton, supra) by using the reactor internals described above. is preferred. It is also preferred that the latter operation be carried out under conditions that result in minimal backmixing.

Hydrothermal Reaction Processing - The yield of each component of the product obtained from the stripping zone 10 is determined by successive temperature steps in each of the zones 10, e.g., all temperatures within zone 10 are maintained within the aforementioned temperature ranges. Then, the temperature is set at the side near the channel 1 on the inlet side of the zone 100.

If the temperature of the tank closer to the flow path 20 on the outlet side of the region 10 is lowered, improvements such as reducing the amount of light products, which are gaseous under normal conditions, can be achieved. Decreasing the temperature towards the exit side of zone 10 prepares the zone 25 and 350 stages and also prevents decomposition reactions.

Temperature control along the series can be facilitated by interphase cooling by means such as heat exchangers or jets of cooling gas. Furthermore, similar benefits can be obtained by using the above-mentioned multi-stage continuous reactor in the processing and stripping zone 10 consisting of a single cell.

Eliminate or reduce back-mixing in multi-stage reactors and reduce temperature distribution in the IJ tubing tank?
In order to obtain this, for example, a method is used in which the preheated raw material 1 gold is made to flow downward and the cooled hydrogen gas stream 5 is made to flow upward.

Alternatively, a method may be adopted in which hydrogen gas is blown into the longitudinally long treatment-stripping tank from several locations along the vertical direction. Additionally, in another embodiment, such temperature stepwise dissolution-strisoping zones are employed to achieve the lower temperatures required for the hydrocracking stage 35 within a specified temperature range. In some cases, the cooling stage 25 may not necessarily be necessary.The countercurrent flow of hydrogen gas, including fresh and recycled hydrogen, through the flow path 5 is within the knowledge of those skilled in the art. Depending on the operating conditions considered within the range and the aforementioned design factors, the stripping of the actual mixture may be made deeper or deeper compared to the amount and boiling point of the light products that are originally to be stripped from the mixture. It could be done shallowly.

Hydrothermal reaction treatment of most of the intermediate lees with a boiling point as low as about 260°C (about 500°F) - Strisoping Zone 1
It may be preferable in some cases to strip it from zero and remove it via channel 15. Also, about 20
It is preferred that the majority of light hydrocarbons having boiling points below about 70° F. be stripped from the hydrothermal treatment-strisoping zone 10 and removed via flow path 15. Additionally, it is most preferred that all gases having boiling points below about 62 DEG F. be stripped from the process-strithoping zone 10 and removed through the channels 15. Hydrogen in the product gas 15 should be separated and recycled to the process. On the other hand, the light hydrocarbons in the product gas 15 should be fractionated and used as is, or further processed if necessary for special use.

Hydrothermal reaction treatment) The operating conditions in the IJ Zubing zone can vary widely, except for temperature. Other operating conditions in the hydrothermal reaction treatment-strisoping zone are as follows. Residence time is 0.01 to 3.0
time, preferably 0.1 to 1 hour. Pressure is O to 10
,000 psig, preferably 1,500 to 5,000 psig
000 psig, more preferably 1.500 to 2,000 psig O hydrogen gas flow rate is 0 to 20,000 Nft per barrel of feedstock, preferably 3%.
The hourly superficial velocity of the 000 to 10.000 Nft3 o feedstock is about 0.6 to 100 hr-1; preferably about 1 to 1 Q hr'0. While the hydrogen supply to the hydrocracking stage 35 is separate, the processing stage 10 and the hydrocracking stage 35 can desirably remain paired in close proximity. As a result, an optimum hydrogen pressure and gas flow rate are provided for the hydrothermal reaction treatment zone 10, while different optimum values of hydrogen pressure and gas flow rate are provided for the catalytic hydrocracking zone 35. Such flexibility cannot be achieved with a process in which hydrogen gas and liquid flow in parallel.

In general, hydrogen consumption is higher in the hydrogen cracking zone;
The hydrogen gas flow rate is high. By installing a bonder (not shown in the figure) in the flow path 30.

Zone 10 can be operated with low hydrogen pressure and zone 35 with high hydrogen pressure.

In the treatment zone, although it is possible that substances contained in the added coal may have some catalytic effect, generally no externally supplied catalyst is used.

The mixture of heavy products and unconverted feedstock, along with the remaining light products, is conveyed via flow path 20 to cooling zone 25.

In cooling zone 25, a heat exchanger or similar means cools the product from processing vessel 10 to a temperature below the temperature of the processing stage, at least 425°C (800'F). In zone 25, some cooling effect may be added by adding fresh hydrogen, if desired. Cooling zone 25 is an optional step in this aspect, and zone 10
This may not necessarily be necessary to create a temperature gradient between zone 35 and zone 35. In some cases, band 25
may include a flash unit to separate the light solvent components from the heavy remaining in the heavy product stream.The separated light solvent components are combusted and process heat)
The mixture of heavy reaction products giving k, feedstock and remaining light products is fed through flow path 30 to reaction zone 35 containing the hydrocracking catalyst. Hydrogen, including fresh hydrogen and/or recycled hydrogen, is fed to the hydrocracking zone 35 via flow path 40.

In the hydrocracking reaction zone, hydrogenation and cracking occur simultaneously;
A high molecular weight compound is converted to a low molecular weight compound, and the sulfur in the compound is converted to hydrogen sulfide, the nitrogen to ammonia, and the oxygen to water. The catalytic reaction zone is preferably of the fixed bed type, although ebullated or moving beds may also be used. The mixture of heavy product and unconverted feedstock passes through the catalytic reaction zone preferably as an upflow, but it may also be a downflow. Similarly, it is optional whether the added hydrogen gas flows countercurrently or cocurrently with respect to the liquid flow. The first advantage of passing such a mixture as an upward flow through a fixed bed of catalyst particles is that the possibility of blockage is reduced.

A particularly desirable method of operating the process is to provide an upward flow to the fixed catalyst bed and to remove the catalyst from the bottom of the fixed bed as the catalyst deteriorates. Fresh catalyst is replenished from the top of the fixed bed and replaced with catalyst removed from the bottom. This replenishment and removal of the catalyst is carried out periodically or in a continuous or semi-continuous manner.

The continuous catalyst exchange according to the invention is carried out at such a slow rate that the catalyst bed can be said to be a fixed bed.

The catalyst used in the hydrocracking zone is a well known commercially available hydrocracking catalyst. Catalysts suitable for use in the hydrocracking reaction step are those containing a hydrogenating component and a cracking component. Among these, it is preferable that the hydrogenation component be supported by a fire-resistant decomposition carrier. Suitable supports are, for example, silica, alumina or compositions of two or more refractory oxides, ie silica-alumina, silica-magnesia.

Silica-zirconia, alumina-boria, silica-titania, silica-zirconia-titania, acid-treated clay, etc. Phosphates of metal acids, such as alumina phosphate, are also often used. Preferably, the decomposition carrier contains alumina and a composition of silica and alumina. Suitable hydrogenation components are selected from Group 6 B metals, Group 8 metals and their oxides or mixtures of the aforementioned. Particularly useful are silica-alumina or alumina-supported cobalt materials.
Hydrocracking zone 35 has one or more hydrocracking reactors containing any combination of one or more of the aforementioned catalysts.

The temperature in the hydrocracking zone is 425°C to prevent catalyst deterioration.
It is better to maintain the temperature lower than 800°F (640°C to 800°F), preferably in the range of 640°C to 425°C (645° to 800°F), and more preferably in the range of 640°C to 400°C (645°C to 800°F).
750°F). The temperature of the hydrocracking zone should preferably be about 55°C to 85°C lower than the temperature of the hydrothermal reaction zone. Other conditions for water bulking and decomposition are as follows. Pressure is 500 to 5,000
p81gb preferably 1,000 to 3,000 p
sig s More preferably from 1.500 to 2,50
0 psig s hydrogen gas flow rate per barrel of slurry 2.000 to 20.000 Nft3, preferably 3,000 to 10.000 Nft” k slurry superficial velocity per hour 0.1 to 2.0 , preferably 0.2 to 0.5° product effluent 5 from reaction zone 35
0 is 5 separation zone 55 with a boiling point of approximately 150°C to 260°C (
(approximately 6000F to 500°F), preferably 2
It is separated into gaseous components at standard conditions such as light oils below 00°C (400°F) and hydrogen, carbon oxides, carbon dioxide, hydrogen sulfide, and C1 to 04 hydrocarbons.

The hydrogen is preferably separated from other gaseous components and recycled. The liquid fraction 65 is passed to fractional distillation or further processing steps.

The process of the invention produces a liquid product under very clean standard conditions. Products that are liquid under standard conditions, i.e.
Any product fraction with a boiling point lower than 0.04 has an exceptionally low specific gravity and a sulfur content of 0.2 w
The nitrogen content is as low as 0.5 wt %.

[Brief explanation of the drawing]

The figure is a block flow diagram of suitable steps used in the specific implementation of the present invention. Band, 55... Separate band agent Asamura Kozu iMi's I'J1. ! ) (No change in content) Residual Distillate Eaves Rage Product Continued from Page 1 0 Inventor Dennis Earl, Kiya American Congregation 1
Tsushu 19 m Novato, California, Medul Lane Procedural amendment (method) March 1985 1z Dear Commissioner of the Japan Patent Office 1, Indication of the case 1932 Patent Application No. 23ZZQ No. 2, Name of the invention Oro Awa V 笈The relationship between the fraction A and the enemy Ibida 13σAku 3, and the person making the correction 1'1 Special 3'1 To the person's address Attention to the person's address /4
, Agent 5, Date of amendment order I J Showa ω 1st month - 6th day of construction 6, Number of inventions increased by amendment 7, Drawings subject to amendment Purification of drawings i! j (no changes to the content)

Claims (1)

[Claims] (1) In a method for hydrotreating petroleum residue, (1)
Hydrothermal Reaction Treatment - Forming a mixture of the petroleum residue and hydrothermal reaction products in a stripping zone by simultaneously contacting the mixture with a first hydrogen gas stream countercurrently at an elevated temperature. (b) recovering a light fraction-containing gas stream from the hydrothermal reaction treatment stripping zone leaving a heavy effluent stream; (0) in a catalytic reaction zone; The hydrothermal reaction treatment - under hydrocracking conditions comprising a temperature below the temperature of the stripping zone, at least a portion of the heavy effluent stream is treated with a second hydrogen gas stream and an externally supplied water volumizing cracking catalyst. (d) and recovering a secondary effluent stream from the catalytic reaction zone. (2) The hydrothermal reaction treatment-stripping zone comprises at least one treatment-stripping vessel equipped with internals that substantially sufficiently suppress back-mixing. Method 0(3) The hydrothermal reaction treatment - Method 0(4) The hydrothermal reaction treatment according to claim 1, in which no catalyst or contact particles are supplied externally to the stripping zone. 2. The method of claim 1, wherein the hydrogen partial pressure in the dripping zone is lower than the hydrogen partial pressure in the reaction zone. (5) The scale decomposition conditions are such that the pressure is from 20 to 1.00.
0 atm, liquid surface velocity of oil residue from 0.1 to 10 per hour
A method according to claim 1, comprising: (6) The method according to claim 1, wherein the temperature of the reaction zone is about 85° C. lower than the temperature of the hydrothermal reaction treatment-sdripping zone. (7) The hydrothermal reaction treatment. -The temperature of the stripping zone is approximately 600°F to 10°C.
00'F. (8) A method according to claim 1, wherein the temperature of the melting-sdripping zone is lowered stepwise, being lower at the inlet side of the zone than at the outlet side.