CN111088070A - Inferior heavy oil treatment method - Google Patents
Inferior heavy oil treatment method Download PDFInfo
- Publication number
- CN111088070A CN111088070A CN201811241395.9A CN201811241395A CN111088070A CN 111088070 A CN111088070 A CN 111088070A CN 201811241395 A CN201811241395 A CN 201811241395A CN 111088070 A CN111088070 A CN 111088070A
- Authority
- CN
- China
- Prior art keywords
- oil
- unit
- catalytic
- heavy oil
- inferior heavy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000295 fuel oil Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 79
- 239000003921 oil Substances 0.000 claims abstract description 178
- 230000003197 catalytic effect Effects 0.000 claims abstract description 106
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 106
- 239000002002 slurry Substances 0.000 claims abstract description 103
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 46
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 238000000926 separation method Methods 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 238000005194 fractionation Methods 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 6
- 238000004062 sedimentation Methods 0.000 claims abstract description 4
- 239000011280 coal tar Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- 238000005352 clarification Methods 0.000 claims description 11
- 239000003502 gasoline Substances 0.000 claims description 9
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002283 diesel fuel Substances 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 20
- 239000011593 sulfur Substances 0.000 abstract description 20
- 239000007787 solid Substances 0.000 abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 11
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 25
- 238000001914 filtration Methods 0.000 description 20
- 239000012535 impurity Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000571 coke Substances 0.000 description 7
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000010426 asphalt Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000011331 needle coke Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229920006395 saturated elastomer Chemical group 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010747 number 6 fuel oil Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses an inferior heavy oil treatment method, which comprises the steps that inferior heavy oil enters a first hydrotreating unit, hydrogenation reaction is carried out in the presence of hydrogen and a first hydrotreating catalyst, liquid phase effluent obtained after reaction directly enters a catalytic cracking unit without fractionation, catalytic oil slurry obtained after reaction product separation is mixed with a first auxiliary agent, and the first auxiliary agent is subjected to sedimentation separation after mixing treatment to obtain a first material and residue after separation; and (3) allowing the first material to enter a second hydrotreating unit, performing a hydrogenation reaction under the action of a second hydrotreating catalyst and hydrogen, allowing a liquid phase effluent obtained by the reaction to enter a clarifying unit, separating to obtain clarified oil, and further performing solid-liquid separation to obtain purified oil slurry. The treatment method not only can realize the clean treatment of the heavy oil, but also can purify, remove solid and sulfur from the catalytic slurry oil generated by catalytic cracking, thereby greatly improving the economic value of the catalytic slurry oil.
Description
Technical Field
The invention belongs to the field of oil refining chemical industry, and particularly relates to a method for treating inferior heavy oil.
Background
With the trend of increasing the heaviness and deterioration of crude oil, the proportion of the residual oil as the heaviest component in the crude oil is increased, and the environmental protection requirement is increasingly strict, so that the efficient utilization of the heavy oil, especially the residual oil, is not only concerned about meeting the requirement of clean production, but also becomes an important factor influencing the economic benefit of enterprises and even survival and death. From the traditional processing means of the residual oil, the residual oil processing can be divided into two routes of hydrogenation and decarburization, wherein decarburization mainly refers to thermal cracking, visbreaking, solvent deasphalting and the like, the hydrogenation route can be divided into fixed bed hydrogenation, suspension bed hydrogenation, fluidized bed hydrogenation, moving bed hydrogenation and the like, the decarburization process is relatively simple overall, the technology is mature, but the problems of low liquid yield, serious pollution and the like exist, and the method is gradually not suitable for the clean production requirements of enterprises; the hydrogenation means is a main direction and trend of heavy oil processing at present and in a future period of time due to the advantages of environment-friendly process, high liquid yield and the like, and is more and more concerned by enterprises. From the product structure, as the demand for fuel oil is slowly increased and the demand for chemical raw materials is increased, the product structure of the traditional oil refining enterprise is changed from the prior pure fuel type to the fuel chemical type and even the purification chemical type, the product tends to be diversified and high in value, such as low-sulfur bunker fuel oil, low-sulfur petroleum coke and the like, and the product is diversified and pays more attention to the quality and environmental protection requirements of the product. For example, MAPPOL convention gives detailed regulations on the emission control region of fuel oil sulfur content used by ships, the limit value and the implementation time of the fuel oil sulfur content, and the sulfur content of the fuel oil for the ships should not exceed 0.5% when the ships are sailing in a general region at sea after 1 month 1 day 2020; if the MAPPOL convention is strictly executed to meet the requirement on the low-sulfur fuel oil, the annual low-sulfur fuel oil demand is about 300 ten thousand tons, but from the current market situation, because the sulfur content of crude oil in most production places is high, almost no refineries which can produce fuel oil with the sulfur content of 0.5 percent or even below 0.1 percent are available all over the world, the market gap of the low-sulfur fuel oil is large, and the production enterprises have urgent needs on the low-sulfur fuel oil production technology. Therefore, how to combine the efficient utilization of the residual oil with the production of high-end products is a problem to be considered by current researchers.
The catalytic cracking of heavy oil is an important part in the process of processing the heavy oil in China, and makes an important contribution to the production of clean fuel oil in China, but some low-end raw materials which are difficult to solve, such as catalytic slurry oil, are also produced in the production process of a catalytic cracking device. China has the catalytic cracking processing capacity of more than 150Mt/a, the catalytic cracking slurry oil yield accounts for 6-8% of the catalytic cracking processing amount, the catalytic slurry oil yield is very large, meanwhile, the catalytic slurry oil has the characteristics of large density, high sulfur content, high colloid content and the like, and most importantly, the catalytic slurry oil contains a large amount of catalyst powder which is difficult to remove, so that the subsequent processing difficulty of the catalytic slurry oil is large, the utilization value is low, and the problem which needs to be solved urgently by enterprises is formed. If the catalytic slurry oil is used as a blending component of low-sulfur fuel oil, the catalytic slurry oil must be treated to reduce the density, sulfur content and solid content, so that the slurry oil de-solidification becomes a key step for realizing efficient utilization of the slurry oil, which is also an important problem in the industry at present. The utilization of catalytic cracking slurry oil mainly focuses on the following aspects, the blending of the catalytic cracking slurry oil is used as a delayed coking raw material, the blending is carried out in an atmospheric and vacuum device to improve the yield of wax oil, the blending is used as a solvent deasphalting raw material, asphalt components are separated by distillation to blend and produce road asphalt, aromatic-rich components are separated by using a solvent to produce chemical products, and asphalt modification components are produced by direct thermal cracking.
The method for removing solid from catalytic slurry oil is mainly a filtering solid-removing method, and Huangfu et al, application of slurry oil filtering technology in heavy oil catalytic cracking unit, introduces a method for filtering solid from catalytic slurry oil. Wherein, the core element of the oil slurry filtering system is a porous metal powder sintered filter element. As the hot slurry passes through the filter element, the slurry liquid can pass through the filter element, clean slurry (filtrate) enters the downstream equipment, and solid catalyst particles are trapped on the inner surface of the filter element. The filtered solid catalyst filter cake is back flushed with dry gas and discharged
And a filter cake receiving tank. During the deslagging process, the rapid pressure release and the reverse flow of the filtrate can rapidly strip the solids off the inner surface of the filter element and allow all of the media inside the filter to flow out of the filter through the reject valve. The method needs to be provided with a pre-filtering device and a fine filtering device, and also needs to be provided with auxiliary equipment such as back flushing oil, so that the operation is complicated, the back flushing is frequent, and the actual operation has certain difficulty.
Patent CN 103789028A introduces a method for producing needle coke raw material by using catalytic cracking slurry oil, in the patent technology, firstly, filtering the catalytic cracking slurry oil by using a filtering technology to remove catalyst powder in the slurry oil, secondly, hydrogenating the solid-removed slurry oil by using a hydrogenation means to remove part of sulfur and saturated part of aromatic hydrocarbon, and then, obtaining ideal components by distillation and cutting to be used as raw materials for producing needle coke. In the technology, the filtering means is a relatively common oil slurry de-solidification means, but because the particle size of catalyst powder in the catalytic oil slurry is small, and the catalytic oil slurry contains certain viscosity, the catalyst powder is wrapped in the heavy component of the catalytic oil slurry and is difficult to remove through the filtering means, and meanwhile, the heavy component of the catalytic oil slurry is still easy to intercept on a filter screen in the filtering process, so that the filtering effect is poor, and meanwhile, the loss of the heavy component is also caused.
Disclosure of Invention
The traditional heavy oil thermal processing technology has the problems of low liquid yield and serious pollution, the catalytic slurry oil obtained by the heavy oil catalytic cracking technology has the problems of high solid content and small particle size, the conventional filtering and other means have the conditions of high liquid yield loss, incomplete catalyst powder removal, easy blockage of a filter, frequent back washing and unstable operation of a filtering device when the catalytic slurry oil is treated, most catalytic slurry oil can only be used as the feed of a coking device, a large amount of coke with low value is produced as a byproduct, and the value of the catalytic slurry oil cannot be fully exerted. The traditional heavy oil processing means can not realize the purpose of deep, efficient and complete conversion of heavy oil, and how to process inferior heavy oil and obtain added-value products is also an urgent problem to be solved.
Compared with the traditional heavy oil processing technology, the treatment method can realize the clean treatment of the heavy oil, can purify and remove solid and sulfur from catalytic slurry oil generated by a catalytic cracking process, and greatly improves the economic value of the catalytic slurry oil. Meanwhile, high liquid yield in the catalytic slurry oil treatment process can be ensured, and deep, efficient and clean production of heavy oil is really realized.
The invention provides an inferior heavy oil treatment method, which comprises the following steps:
(1) the inferior heavy oil enters a first hydrotreating unit, and is subjected to hydrogenation reaction in the presence of hydrogen and a first hydrotreating catalyst;
(2) directly feeding the liquid phase effluent obtained after the reaction in the step (1) into a catalytic cracking unit without fractionation, and separating the reaction product to obtain dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, catalytic heavy cycle oil and catalytic slurry oil;
(3) mixing the catalytic slurry oil obtained in the step (2) with a first auxiliary agent, performing sedimentation separation after mixing treatment, and obtaining a first material and residue after separation;
(4) the first material obtained by separation in the step (3) and hydrogen enter a second hydrotreating unit and react under the action of a second hydrotreating catalyst;
(5) the liquid phase effluent obtained in the step (4) enters a clarification unit, and clarified oil is obtained after separation;
(6) and (5) carrying out solid-liquid separation on the clarified oil obtained in the step (5) to obtain purified oil slurry after separation.
In the method for treating the inferior heavy oil, the inferior heavy oil can be atmospheric residual oil and/or vacuum residual oil, and usually contains one or more of straight-run wax oil, vacuum wax oil, secondary processing wax oil and catalytic cycle oil.
In the method for treating inferior heavy oil of the present invention, the inferior heavy oil in the first hydrotreatment unit can be hydrogenated by one or more of the existing fixed bed hydrogenation process, boiling bed hydrogenation process, suspension bed hydrogenation process and moving bed hydrogenation process; preferably, a fixed bed hydrogenation process and/or an ebullated bed hydrogenation process is used. The first hydrotreatment unit is provided with more than 1 hydrotreatment reactor. Taking the fixed bed residual oil hydrotreating process as an example, each hydrotreating reactor may be filled with one or more of a hydrogenation protective agent, a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodenitrogenation residual carbon conversion catalyst, which are all catalysts used in the fixed bed residual oil hydrotreating process. The above catalysts are generally catalysts in which a porous refractory inorganic oxide such as alumina is used as a carrier, oxides of metals of group VIB and/or group VIII such as W, Mo, Co, Ni and the like are used as active components, and other various additives such as elements P, Si, F, B and the like are selectively added, for example, residual oil hydrotreating catalysts of FZC series produced by catalyst division of petrochemical Co., Ltd.
In the method for treating the inferior heavy oil, the operating conditions of the first hydrotreating unit are that the reaction temperature is 370-450 ℃, preferably 380-440 ℃, and the reaction pressure is 10-25 MPa, preferably 15-20 MPa; the volume ratio of the hydrogen to the oil is 300-1500, preferably 400-800; the hourly space velocity of the raw oil is 0.15h-1～0.80h-1Preferably 0.2h-1～0.60h-1。
In the method for treating the inferior heavy oil, the catalytic cracking can adopt the conventional technology in the field. The catalytic cracking device can be one set or more than one set, each set of catalytic cracking device at least comprises a reactor and a regenerator, the catalytic cracking device is required to be provided with a fractionating tower, each set of catalytic cracking device can be respectively provided with a fractionating tower, and the fractionating towers can also be shared. The fractionating tower fractionates the catalytic cracking reaction effluent into dry gas, liquefied gas, catalytic gasoline fraction, catalytic diesel fraction, catalytic heavy cycle oil, catalytic slurry oil, etc. The catalytic cracking fractionator may be designed in accordance with conventional knowledge.
In the method for treating the inferior heavy oil, the operating conditions of the catalytic cracking unit in the step (2) are as follows: the reaction temperature is 450-600 ℃, and preferably 480-550 ℃; the regeneration temperature is 600-800 ℃, preferably 650-750 ℃, the weight ratio of the solvent to the oil is 2-30, preferably 4-10; the contact time with the catalyst is 0.1-15 seconds, preferably 0.5-5 seconds; the pressure is 0.1-0.5 MPa. The catalytic cracking catalyst used includes catalysts generally used for catalytic cracking, such as silica-alumina catalysts, silica-magnesia catalysts, acid-treated clays, and molecular sieve cracking catalysts such as X-type, Y-type, ZSM-5, M-type, layered column, etc., and is preferably a molecular sieve cracking catalyst, because of its high activity, low coke formation, high gasoline yield, and high conversion rate. The reactor of the catalytic cracking unit can be various types of catalytic cracking reactors, and is preferably a riser reactor or a riser plus bed reactor. The process flow generally comprises the following steps: raw oil is injected from the bottom of the riser reactor and contacts with the high-temperature regenerated catalyst from the regenerator, and the catalyst mixture of oil gas and deposited coke generated by the cracking reaction moves upwards along the riser reactor to complete the catalytic cracking reaction of the whole raw oil.
In the method for treating the inferior heavy oil, part or all of the catalytic diesel oil, part or all of the catalytic heavy cycle oil and part or all of the catalytic slurry oil in the step (2) can be recycled to the first hydrotreatment unit.
In the method for treating the inferior heavy oil, a step (3.1) can be added between the step (3) and the step (4), wherein in the step (3.1), the first material obtained by separating in the step (3) and hydrogen firstly enter a hydrogenation pretreatment unit, hydrogenation reaction is carried out in the presence of a hydrogenation pretreatment catalyst, and a reaction effluent enters a second hydrogenation treatment unit to carry out the step (4).
In the method for treating the inferior heavy oil, the first auxiliary agent in the step (3) is coal tar and/or coal tar distillate oil, and specifically can be one or more of full-fraction medium-low temperature coal tar, full-fraction high-temperature coal tar, medium-low temperature coal tar distillate oil and high-temperature coal tar distillate oil.
In the method for treating the inferior heavy oil, the weight ratio of the first auxiliary agent to the catalytic slurry oil in the step (3) is 1: 10-1: 30, preferably 1: 15-1: 25; the mixing treatment temperature is 50-150 ℃, and the preferable mixing treatment temperature is 60-120 ℃; the mixing treatment time is 0.5-4 h, and preferably 1-2 h.
In the method for treating the inferior heavy oil, a second auxiliary agent can be added in the step (3), wherein the second auxiliary agent is one or more of tetrahydronaphthalene, decahydronaphthalene, formic acid, formaldehyde and methanol, and is preferably one or more of tetrahydronaphthalene and decahydronaphthalene; the weight ratio of the second auxiliary agent to the catalytic slurry oil is 1: 30-1: 100, and preferably 1: 50-1: 80.
In the method for treating inferior heavy oil, the hydrogenation pretreatment unit in the step (3.1) can adopt one or more of a fixed bed hydrogenation process, a boiling bed hydrogenation process, a suspension bed hydrogenation process and a moving bed hydrogenation process. The hydrogenation pretreatment unit is provided with more than 1 hydrogenation pretreatment reactor, and when more than 2 hydrogenation pretreatment reactors are arranged, more than 2 reactors can be connected in series and/or in parallel.
In the inferior heavy oil treatment method of the invention, the operation conditions of the hydrogenation pretreatment unit are as follows: the reaction temperature is 300-380 ℃, the reaction pressure is 4-9 Mpa, and the volume airspeed is 0.4-2.0 h-1The hydrogen-oil volume ratio is 400-1000, the preferable reaction temperature is 320-360 ℃, the reaction pressure is 6-8 Mpa, and the volume airspeed is 0.6-1.2 h-1The volume ratio of hydrogen to oil is 500-800.
In the method for treating the inferior heavy oil, the second hydrotreating unit in the step (4) can adopt one or more of a fixed bed hydrogenation process, a boiling bed hydrogenation process, a suspended bed hydrogenation process and a moving bed hydrogenation process, and preferably adopts the boiling bed hydrogenation process. The second hydrotreatment unit is provided with more than 1 hydrotreatment reactor, and when more than 2 hydrotreatment reactors are provided, more than 2 reactors can be connected in series and/or in parallel.
In the method for treating the inferior heavy oil, the operating conditions of the second hydrotreating unit in the step (4) are as follows: the reaction temperature is 360-420 ℃, the reaction pressure is 6.0-14.0 Mpa, and the volume airspeed is 0.5-2.5 h-1The hydrogen-oil volume ratio is 300-1000, preferably, the reaction temperature is 370-410 ℃, the reaction pressure is 7.0-11.0 Mpa, the volume space velocity is 0.8-1.5 h < -1 >, and the hydrogen-oil volume ratio is 500-800.
In the method for treating inferior heavy oil of the present invention, the hydrotreating unit and the second hydrotreating unit may be in one reactor, or may be provided with separate reactors.
In the method for treating the inferior heavy oil, the catalyst used by the hydrogenation pretreatment unit can be any one of the existing hydrogenation pretreatment catalysts, for example, a commercially available catalyst, such as a hydrogenation pretreatment catalyst developed by the research institute of petrochemical industry, can be adopted.
In the method for treating inferior heavy oil, when the second hydrotreatment unit adopts an ebullated bed hydrogenation process, the waste catalyst discharged by the second hydrotreatment unit can be used as a hydrogenation pretreatment catalyst of a hydrogenation pretreatment unit.
In the method for treating inferior heavy oil of the present invention, the catalyst used in the second hydrotreatment unit is a conventional hydrotreating catalyst in the art, wherein the active metal of the catalyst can be one or more of nickel, cobalt, molybdenum or tungsten. For example, the catalyst composition may comprise, in weight percent: 0.1-12% of nickel or cobalt (calculated according to the oxide thereof), 5-15% of molybdenum or tungsten (calculated according to the oxide thereof), and the carrier can be one or more of alumina, silica, alumina-silica or titanium oxide. The catalyst is in the shape of extrudate or sphere, and the bulk density is 0.4-0.9 g/cm3The particle diameter (spherical diameter or strip diameter) is 0.08-0.8 mm, and the specific surface area is 100-200 m2/g。
In the method for treating the inferior heavy oil, the clarifying unit in the step (5) can be one or more of a standing clarifying unit and a forced clarifying unit by means of external force; the clarifying units are at least one, and can be operated in series or in parallel. The clarifying unit is mainly used for separating large-particle catalysts larger than 25 microns, and the separated large-particle catalysts can be treated with the waste catalysts of the catalytic cracking unit.
In the method for treating inferior heavy oil of the present invention, the solid-liquid separation unit in step (6) is mainly used for separating the small particle catalyst which cannot be clarified in step (5), the solid-liquid separation unit can adopt one of the existing methods in the field for realizing solid-liquid separation, preferably adopts an external force means of a high speed centrifuge to forcibly realize solid-liquid separation, and the operation conditions of the centrifuge are as follows: the rotating speed is 1500-3000 r/min, the temperature is 60-80 ℃, and the operation conditions are preferably as follows: the rotating speed is 1900-2500 r/min, and the temperature is 65-75 ℃. The separated catalyst powder may be sent out for treatment together with the catalyst particles obtained in step (4).
Compared with the prior art, the inferior heavy oil treatment method has the following advantages:
1. in the method for treating the inferior heavy oil, the inferior heavy oil is subjected to combined treatment by means of hydrotreating, catalytic cracking, catalytic slurry oil solid removal and the like, so that the utilization rate of the heavy oil is greatly improved, the liquid yield is obviously improved, products such as high-value light fuel oil and the like can be produced, and the economic value of the heavy oil is greatly improved; in addition, the defects of environmental pollution, low liquid yield, unavailable catalytic slurry oil or low utilization value in the processing process of the traditional technical means are overcome, and the overall value is improved.
2. In the method for treating the inferior heavy oil, the catalytic oil slurry is subjected to graded treatment by using the first auxiliary agent and the second auxiliary agent, and the steps of hydrogenation pretreatment, hydrotreating, clarification treatment and solid-liquid separation are performed, so that the graded removal of solid impurities with different sizes in the catalytic oil slurry is realized. Firstly, under the combined action of a first auxiliary agent and a second auxiliary agent, the aggregation, sedimentation and separation of large-particle catalyst particles in catalytic slurry oil are promoted; and then the catalytic slurry oil treated by the auxiliary agent is subjected to hydrogenation treatment through the hydrogenation pretreatment unit and the second hydrogenation treatment unit, unsaturated hydrocarbons such as colloid and the like influencing the system viscosity and subsequent filtration are subjected to hydrogenation saturation, the reduction of the viscosity of heavy components is facilitated, and the second hydrogenation treatment unit uses a fluidized bed reactor, so that the bed layer can be prevented from being blocked by catalyst powder, and the long-period operation of the device can be ensured.
3. In the method for treating the inferior heavy oil, the second auxiliary agent can generate a synergistic effect with the first auxiliary agent to promote the settling separation of solid impurities in the catalytic oil slurry, and can release active hydrogen under the condition of hydrogenation pretreatment in the hydrogenation pretreatment unit to carry out hydrogenation saturation on the easily-coked precursor contained in the first auxiliary agent, and simultaneously carry out hydrogenation pretreatment on the catalytic oil slurry to promote the complex use of the hydrogenation treatment unit, alleviate the hydrogenation reaction of the second hydrogenation treatment unit and reduce the operation difficulty.
4. In the method for treating the inferior heavy oil, the second hydrotreating unit uses the fluidized bed reactor, the waste catalyst discharged by the fluidized bed reactor can be used as a hydrogenation pretreatment catalyst of the hydrogenation pretreatment unit, the waste catalyst discharged by the second hydrotreating unit still has certain hydrogenation activity, and meanwhile, as the catalyst has already undergone hydrogenation reaction and has already passed an initial activity period, the possibility of coking and carbon deposition of aromatic hydrocarbons such as unsaturated hydrocarbons and the like on the surface of the waste catalyst is greatly reduced; on the other hand, the catalytic slurry oil has a high content of unsaturated hydrocarbons, and the structure and the content of the unsaturated hydrocarbons have a certain distribution rule, wherein the catalytic slurry oil contains a part of components which are easily condensed to form coke when being heated, for example, if the catalytic slurry oil is completely and directly fed into the second hydrotreating unit for hydrogenation reaction, on one hand, the hydrogenation reaction of the unsaturated hydrocarbons can release a large amount of heat, a large amount of cold hydrogen needs to be injected, the energy consumption is high, and on the other hand, the unsaturated hydrocarbons which are easily condensed to form coke when being heated partially coke on the surface of the. The waste catalyst discharged by the second hydrotreatment unit is adopted to carry out mild hydrogenation pretreatment on the catalytic slurry oil in advance, so that the problems can be effectively avoided, and the recycling of the waste catalyst is realized.
5. The method can obviously improve the utilization rate of the catalytic slurry oil, the traditional filtering method has low solid impurity removal efficiency, the yield of the catalytic slurry oil after filtering is damaged due to the interception and recombination of the filter screen, and meanwhile, the operation period of the filtering equipment is shortened due to the rapid increase of the pressure drop of the filter screen. The method combines the property characteristics of the catalytic slurry oil, and by adding a certain auxiliary agent, the viscosity of the catalytic slurry oil is reduced, meanwhile, the aggregation and precipitation of small particles in the catalytic slurry oil are realized, and the operation complexity is reduced; meanwhile, the heavy component wrapped with the small particle impurities is hydrogenated by adopting a hydrogenation means, so that the small particle impurities are resolved and precipitated from the heavy component, and finally the solid impurities are efficiently removed.
6. In the catalytic slurry oil treatment method, the catalytic slurry oil prehydrogenation reaction depth is controlled by adjusting the reaction pressure and the reaction temperature, the catalytic slurry oil is firstly subjected to shallow hydrogenation to improve the thermal stability of the slurry oil, the hydrogenation depth is too deep, the reaction hydrogen consumption is large, and the cost is high; meanwhile, the softening point and the viscosity of the hydrogenated oil slurry are greatly reduced, and the blending proportion of high-grade road asphalt or low-sulfur fuel oil is influenced.
Detailed Description
The invention is further described below by means of specific embodiments without limiting the scope of protection of the invention.
The inferior heavy oil treatment method comprises the following steps: the inferior heavy oil enters a first hydrotreating unit, and is subjected to hydrogenation reaction in the presence of hydrogen and a first hydrotreating catalyst; the liquid phase effluent obtained after the reaction directly enters a catalytic cracking unit without fractionation, and dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, catalytic heavy cycle oil and catalytic slurry oil are obtained after the reaction product is separated; the catalytic slurry oil is fully mixed with a first auxiliary agent according to a certain proportion, whether a second auxiliary agent is added or not can be determined according to needs, and the fully mixed raw materials are subjected to settling separation to obtain a first material and large-particle residues; the first material and hydrogen are mixed and firstly enter a hydrogenation pretreatment unit, the mixed material is subjected to shallow hydrogenation, components which are easy to generate coke in a hydrogenation saturated system are hydrogenated, the mixed material subjected to shallow hydrogenation continuously enters a second hydrogenation treatment unit for deep hydrogenation to remove sulfur and nitrogen impurities and reduce the content of unsaturated hydrocarbons, the material obtained after hydrogenation treatment enters a clarification unit to remove partial large particles precipitated due to viscosity reduction, clarified oil after removal of a small amount of large particles enters a solid-liquid separation unit, the viscosity and solid content of the system are greatly reduced at the moment, small particle substances are thoroughly removed under the action of external force, and finally, low-sulfur, low-aromatic hydrocarbon and solid-free purified oil slurry is obtained.
The first hydrotreating catalyst used in the invention can be FZC series catalyst developed by the comforting petrochemical research institute, and the catalyst types are hydrogenation protection catalyst FZC-100, demetallization catalyst FZC-103, desulfurization catalyst FZC-13 and denitrification catalyst FZC-33 respectively; the hydrogenation pretreatment catalyst used can be FF-36 catalyst developed by the comforting petrochemical research institute; the second hydrotreating catalyst used is microspherical aluminaSupported molybdenum-nickel catalyst containing MoO313.8 wt%, NiO content 6.2 wt%, and bulk density of the catalyst 0.78g/cm3Surface area 205m2The catalyst particles had an average diameter of 0.31 mm/g.
The properties of the residual oil and the first auxiliary agent (including coal tar whole fraction and coal tar distillate) used in the examples and comparative examples of the present invention are shown in table 1.
Example 1
Example 1 using residual oil as a raw material, according to the method for treating inferior heavy oil of the present invention, inferior heavy oil enters a first hydrotreating unit (the first hydrotreating unit employs a fixed bed reactor), and undergoes a hydrogenation reaction in the presence of hydrogen and a first hydrotreating catalyst, where the reaction conditions in the first hydrogenation reactor are as follows: the reaction temperature is 385 ℃, the reaction pressure is 15.5Mpa, and the volume space velocity is 0.28h-1Hydrogen to oil volume ratio of 450; the liquid phase effluent obtained after the reaction directly enters a catalytic cracking unit without fractionation, and dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, catalytic heavy cycle oil and catalytic slurry oil are obtained after the reaction product is separated; firstly, mixing catalytic slurry oil with a first auxiliary agent coal tar full fraction, wherein the ratio of the catalytic slurry oil to the first auxiliary agent is 16:1, the mixing treatment temperature and the mixing treatment time of the catalytic slurry oil and the first auxiliary agent are respectively 65 ℃ and 1.2h, removing part of large-particle substances, then feeding the large-particle substances and hydrogen into a hydrogenation pretreatment reactor together for carrying out shallow hydrogenation reaction to remove easily condensed coke-forming substances, and the reaction conditions of the hydrogenation pretreatment reactor are as follows: the reaction temperature is 335 ℃, the reaction pressure is 6.5Mpa, and the volume space velocity is 0.75h-1Hydrogen to oil volume ratio 550; then the mixture enters a hydrotreating reactor for deep impurity removal reaction, wherein the reaction conditions of the hydrotreating reactor are as follows: the reaction temperature is 385 ℃, the reaction pressure is 8.5Mpa, and the volume space velocity is 1.0h-1Hydrogen to oil volume ratio 630, where the hydroprocessing reactor uses an ebullated bed reactor. The mixed system after the impurity removal reaction is respectively treated by a clarification unit and a forced solid-liquid separation unit to obtain purified oil slurry, and the operation conditions of the forced solid-liquid separation unit are as follows: the rotation speed is 2150r/min, and the temperature is 68 ℃. The reaction results are shown in Table 2.
Example 2
Example 2 using residual oil as a raw material, according to the method for treating inferior heavy oil of the present invention, inferior heavy oil enters a first hydrotreating unit (the first hydrotreating unit employs a fixed bed reactor), and undergoes a hydrogenation reaction in the presence of hydrogen and a first hydrotreating catalyst, where the reaction conditions in the first hydrogenation reactor are as follows: the reaction temperature is 385 ℃, the reaction pressure is 15.8Mpa, and the volume space velocity is 0.30h-1Hydrogen-oil volume ratio 500; the liquid phase effluent obtained after the reaction directly enters a catalytic cracking unit without fractionation, and dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, catalytic heavy cycle oil and catalytic slurry oil are obtained after the reaction product is separated; firstly, mixing catalytic slurry oil with a first auxiliary agent coal tar full fraction and a second auxiliary agent tetrahydronaphthalene, wherein the ratio of the catalytic slurry oil to the first auxiliary agent to the second auxiliary agent is 19:1 and 62:1, the mixing treatment temperature and the mixing treatment time of the catalytic slurry oil with the first auxiliary agent to the second auxiliary agent are 82 ℃ and 1.6 hours respectively, removing part of large-particle substances, and then, feeding the large-particle substances and hydrogen into a hydrotreating reactor together for deep impurity removal reaction, wherein the reaction conditions of the hydrotreating reactor are as follows: the reaction temperature is 388 ℃, the reaction pressure is 8.5Mpa, and the volume space velocity is 1.2h-1And a hydrogen to oil volume ratio of 650, wherein the hydroprocessing reactor uses an ebullated bed reactor. The mixed system after the impurity removal reaction is respectively treated by a clarification unit and a forced solid-liquid separation unit to obtain purified oil slurry, and the operation conditions of the forced solid-liquid separation unit are as follows: the rotation speed is 2250r/min and the temperature is 70 ℃. The reaction results are shown in Table 2.
Example 3
Example 3 using residual oil as a raw material, according to the method for treating inferior heavy oil of the present invention, inferior heavy oil enters a first hydrotreating unit (the first hydrotreating unit employs a fixed bed reactor), and undergoes a hydrogenation reaction in the presence of hydrogen and a first hydrotreating catalyst, where the reaction conditions in the first hydrogenation reactor are as follows: the reaction temperature is 390 ℃, the reaction pressure is 16.5Mpa, and the volume space velocity is 0.32h-1Hydrogen to oil volume ratio 550; the liquid phase effluent obtained after the reaction directly enters a catalytic cracking unit without fractionation, and dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, catalytic heavy cycle oil and catalytic slurry oil are obtained after the reaction product is separated;mixing catalytic slurry oil with coal tar distillate oil (fraction below 500 ℃) as a first auxiliary agent, wherein the ratio of the catalytic slurry oil to the first auxiliary agent is 23:1, the mixing treatment temperature and the mixing treatment time of the catalytic slurry oil and the first auxiliary agent are 90 ℃ and 1.6 hours respectively, removing part of large-particle substances, and then, feeding the large-particle substances and hydrogen into a hydrotreating reactor together for deep impurity removal reaction, wherein the reaction conditions of the hydrotreating reactor are as follows: the reaction temperature is 392 ℃, the reaction pressure is 9.5Mpa, and the volume space velocity is 1.2h-1Hydrogen to oil volume ratio of 700, wherein the hydroprocessing reactor uses an ebullated bed reactor. The mixed system after the impurity removal reaction is respectively treated by a clarification unit and a forced solid-liquid separation unit to obtain purified oil slurry, and the operation conditions of the forced solid-liquid separation unit are as follows: the rotation speed is 2350r/min, and the temperature is 75 ℃. The reaction results are shown in Table 2.
Example 4
Example 4 using residual oil as a raw material, according to the method for treating inferior heavy oil of the present invention, inferior heavy oil enters a first hydrotreating unit (the first hydrotreating unit employs a fixed bed reactor), and undergoes a hydrogenation reaction in the presence of hydrogen and a first hydrotreating catalyst, where the reaction conditions in the first hydrogenation reactor are as follows: the reaction temperature is 398 ℃, the reaction pressure is 17.5Mpa, and the volume space velocity is 0.38h-1Hydrogen to oil volume ratio 580; the liquid phase effluent obtained after the reaction directly enters a catalytic cracking unit without fractionation, and dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, catalytic heavy cycle oil and catalytic slurry oil are obtained after the reaction product is separated; firstly, mixing catalytic slurry oil with a first auxiliary agent coal tar distillate oil (fraction less than 500 ℃) and a second auxiliary agent tetrahydronaphthalene, wherein the ratio of the catalytic slurry oil to the first auxiliary agent to the second auxiliary agent is 24:1 and 75:1 respectively, the mixing treatment temperature and the mixing treatment time of the catalytic slurry oil to the first auxiliary agent and the second auxiliary agent are respectively 95 ℃ and 1.8 hours, removing part of large-particle substances, and then, feeding the catalytic slurry oil and hydrogen together into a hydrogenation pretreatment reactor to perform shallow hydrogenation reaction to remove easily condensed coke-forming substances, wherein the reaction conditions of the hydrogenation pretreatment reactor are as follows: the reaction temperature is 345 ℃, the reaction pressure is 8.0Mpa, and the volume space velocity is 0.9h-1Hydrogen to oil volume ratio of 700; then the mixture enters a hydrotreating reactor to carry out deep impurity removal reaction, and the reaction condition of the hydrotreating reactor is: the reaction temperature is 395 ℃, the reaction pressure is 9.8Mpa, and the volume space velocity is 1.4h-1Hydrogen to oil volume ratio of 700, wherein the hydroprocessing reactor uses an ebullated bed reactor. The mixed system after the impurity removal reaction is respectively treated by a clarification unit and a forced solid-liquid separation unit to obtain purified oil slurry, and the operation conditions of the forced solid-liquid separation unit are as follows: the rotation speed is 2400r/min, and the temperature is 78 ℃. The reaction results are shown in Table 2.
Comparative example 1
The same as example 1 except that the catalytic slurry oil of comparative example 1 was directly subjected to hydrotreating without any treatment in the hydrotreating pretreatment unit and the hydrotreating unit, the reaction results are shown in table 2.
Comparative example 2
The method is substantially the same as that of example 1, except that the catalytic slurry oil in comparative example 2 is first filtered by a conventional filtering method (the filtering diameter is 25 μm), and then enters a hydrogenation pretreatment unit and a hydrogenation treatment unit for hydrogenation reaction, and the reaction results are shown in Table 2.
TABLE 1 heavy oil and coal tar feedstock Properties
TABLE 2 naphtha Properties
TABLE 3 Diesel Properties
TABLE 4 catalytic slurry oil purification effect under different cases
Through the above description and comparative analysis of the embodiment, it is found that for the inferior heavy oil and catalytic slurry oil which are the inferior raw materials with high solid content and high aromatic hydrocarbon, the method of the invention emphasizes the combined action of the conversion of the inferior heavy oil, the de-solid of the auxiliary agent and the hydro-de-solid, ensures the deep conversion of the inferior heavy oil, the high-efficiency de-impurity and de-solid of the catalytic slurry oil and the long-term operation of the device, and provides a good technical means for improving the value of the heavy oil and the catalytic slurry oil.
Claims (17)
1. An inferior heavy oil treatment method comprises the following steps:
(1) the inferior heavy oil enters a first hydrotreating unit, and is subjected to hydrogenation reaction in the presence of hydrogen and a first hydrotreating catalyst;
(2) directly feeding the liquid phase effluent obtained after the reaction in the step (1) into a catalytic cracking unit without fractionation, and separating the reaction product to obtain dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, catalytic heavy cycle oil and catalytic slurry oil;
(3) mixing the catalytic slurry oil obtained in the step (2) with a first auxiliary agent, performing sedimentation separation after mixing treatment, and obtaining a first material and residue after separation;
(4) the first material obtained by separation in the step (3) and hydrogen enter a second hydrotreating unit and react under the action of a hydrotreating catalyst;
(5) the liquid phase effluent obtained in the step (4) enters a clarification unit, and clarified oil is obtained after separation;
(6) and (5) carrying out solid-liquid separation on the clarified oil obtained in the step (5) to obtain purified oil slurry after separation.
2. The method for treating inferior heavy oil according to claim 1, wherein: the inferior heavy oil is atmospheric residue and/or vacuum residue.
3. The method for treating inferior heavy oil according to claim 2, wherein: the inferior heavy oil contains one or more of straight-run wax oil, vacuum wax oil, secondary processing wax oil and catalytic cycle oil.
4. The method for treating inferior heavy oil according to claim 1, wherein: and (3) adding a step (3.1) between the step (3) and the step (4), wherein in the step (3.1), the first material obtained by separating in the step (3) and hydrogen firstly enter a hydrogenation pretreatment unit, hydrogenation reaction is carried out in the presence of a hydrogenation pretreatment catalyst, and the reaction effluent enters a second hydrogenation treatment unit to carry out the step (4).
5. The method for treating inferior heavy oil according to claim 1, wherein: the first auxiliary agent in the step (3) is coal tar and/or coal tar distillate oil.
6. The method for treating inferior heavy oil according to claim 1 or 5, wherein: the first auxiliary agent in the step (3) is one or more of full-fraction medium-low temperature coal tar, full-fraction high-temperature coal tar, medium-low temperature coal tar distillate oil and high-temperature coal tar distillate oil.
7. The method for treating inferior heavy oil according to claim 1, wherein: the weight ratio of the first auxiliary agent to the catalytic slurry oil in the step (3) is 1: 10-1: 30, and preferably 1: 15-1: 25.
8. The method for treating inferior heavy oil according to claim 1, wherein: the mixing treatment temperature in the step (3) is 50-150 ℃, and preferably 60-120 ℃; the mixing treatment time is 0.5-4 h, preferably 1-2 h.
9. The method for treating inferior heavy oil according to claim 1, wherein: and (3) adding a second auxiliary agent, wherein the second auxiliary agent is one or more of tetrahydronaphthalene, decahydronaphthalene, formic acid, formaldehyde and methanol, and is preferably one or more of tetrahydronaphthalene and decahydronaphthalene.
10. The method for treating inferior heavy oil according to claim 1, wherein: the weight ratio of the second auxiliary agent to the catalytic slurry oil is 1: 30-1: 100, and preferably 1: 50-1: 80.
11. The method for treating inferior heavy oil according to claim 1, wherein: the operating conditions of the first hydrotreating unit are that the reaction temperature is 370-450 ℃, preferably 380-440 ℃, and the reaction pressure is 10-25 MPa, preferably 15-20 MPa; the volume ratio of the hydrogen to the oil is 300-1500, preferably 400-800; the hourly space velocity of the raw oil is 0.15h-1～0.80h-1Preferably 0.2h-1～0.60h-1。
12. The method for treating inferior heavy oil according to claim 1, wherein: the operating conditions of the catalytic cracking unit in the step (2) are as follows: the reaction temperature is 450-600 ℃, and preferably 480-550 ℃; the regeneration temperature is 600-800 ℃, preferably 650-750 ℃, the weight ratio of the solvent to the oil is 2-30, preferably 4-10; the contact time with the catalyst is 0.1-15 seconds, preferably 0.5-5 seconds; the pressure is 0.1-0.5 MPa.
13. The method for treating inferior heavy oil according to claim 1, wherein: the operating conditions of the hydrogenation pretreatment unit are as follows: the reaction temperature is 300-380 ℃, the reaction pressure is 4-9 Mpa, and the volume airspeed is 0.4-2.0 h-1The hydrogen-oil volume ratio is 400-1000, the preferable reaction temperature is 320-360 ℃, the reaction pressure is 6-8 Mpa, and the volume airspeed is 0.6-1.2 h-1The volume ratio of hydrogen to oil is 500-800.
14. The method for treating inferior heavy oil according to claim 1, wherein: in the step (4), the second hydrotreating unit adopts one or more of a fixed bed hydrogenation process, a boiling bed hydrogenation process, a suspended bed hydrogenation process and a moving bed hydrogenation process, and preferably adopts the boiling bed hydrogenation process.
15. The method for treating inferior heavy oil according to claim 1, wherein: the second hydrotreatment unit in the step (4) is operated under the conditions: the reaction temperature is 360-420 ℃, the reaction pressure is 6.0-14.0 Mpa, and the volume airspeed is 0.5-2.5 h-1The hydrogen-oil volume ratio is 300-1000, preferably, the reaction temperature is 370-410 ℃, the reaction pressure is 7.0-11.0 Mpa, the volume space velocity is 0.8-1.5 h < -1 >, and the hydrogen-oil volume ratio is 500-800.
16. The method of treating inferior heavy oil according to claim 12, wherein: when the second hydrotreatment unit adopts an ebullated bed hydrogenation process, the waste catalyst discharged from the second hydrotreatment unit is used as a hydrogenation pretreatment catalyst of a hydrogenation pretreatment unit.
17. The method for treating inferior heavy oil according to claim 1, wherein: the clarification unit in the step (5) is one or more of a standing clarification unit and a forced clarification unit with the help of external force; at least one clarifying unit is arranged, and the clarifying units are operated in series or in parallel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811241395.9A CN111088070A (en) | 2018-10-24 | 2018-10-24 | Inferior heavy oil treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811241395.9A CN111088070A (en) | 2018-10-24 | 2018-10-24 | Inferior heavy oil treatment method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111088070A true CN111088070A (en) | 2020-05-01 |
Family
ID=70392353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811241395.9A Pending CN111088070A (en) | 2018-10-24 | 2018-10-24 | Inferior heavy oil treatment method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111088070A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215649A (en) * | 1990-05-02 | 1993-06-01 | Exxon Chemical Patents Inc. | Method for upgrading steam cracker tars |
| CN1955261A (en) * | 2005-10-24 | 2007-05-02 | 中国石油化工股份有限公司 | Hydrocracking method of midbarrel oil circulation |
| CN102041095A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Resid hydrotreating and catalytic cracking combined processing method |
| CN103540353A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Combined hydrogenation process method for treating coal tar and residual oil |
| CN104212489A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Processing method for high nitrogen content heavy oil |
| CN108102710A (en) * | 2016-11-25 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of method for preparing needle coke |
-
2018
- 2018-10-24 CN CN201811241395.9A patent/CN111088070A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215649A (en) * | 1990-05-02 | 1993-06-01 | Exxon Chemical Patents Inc. | Method for upgrading steam cracker tars |
| CN1955261A (en) * | 2005-10-24 | 2007-05-02 | 中国石油化工股份有限公司 | Hydrocracking method of midbarrel oil circulation |
| CN102041095A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Resid hydrotreating and catalytic cracking combined processing method |
| CN103540353A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Combined hydrogenation process method for treating coal tar and residual oil |
| CN104212489A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Processing method for high nitrogen content heavy oil |
| CN108102710A (en) * | 2016-11-25 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of method for preparing needle coke |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11421166B2 (en) | Process for the production of fuels of heavy fuel type from a heavy hydrocarbon-containing feedstock using a separation between the hydrotreatment stage and the hydrocracking stage | |
| CN101210200B (en) | Hydrogenation treatment and catalytic cracking combined process for residual oil | |
| JP6670856B2 (en) | Feedstock conversion method for producing fuel oil, comprising a hydrotreating step, a hydrocracking step, a precipitation step, and a precipitate separation step | |
| CN111088068A (en) | Production method of low-sulfur marine fuel oil | |
| KR20180014776A (en) | Method for converting feedstocks comprising a hydrocracking step, a precipitation step and a sediment separation step, in order to produce fuel oils | |
| CN107557064B (en) | Coal tar combined bed hydrogenation method and system for coal tar combined bed hydrogenation | |
| CN103805247B (en) | A kind of combined technical method processing poor ignition quality fuel | |
| CN110938467B (en) | Hydrocracking method | |
| CN111088070A (en) | Inferior heavy oil treatment method | |
| CN102465035B (en) | Combined process for processing wax oil | |
| CN114437792B (en) | Method and device for processing residual oil | |
| CN101942339A (en) | Boiling-bed residual-oil hydrocracking and catalytic-cracking combined process method | |
| CN111088074A (en) | Coal tar and residual oil combined treatment process | |
| CN111378491B (en) | Inferior heavy oil hydrotreating process | |
| CN110408432B (en) | Method for treating inferior residual oil by combined process | |
| CN114574240A (en) | Method for preparing bunker fuel oil by hydrogenation | |
| CN114574239A (en) | Preparation method of marine fuel oil | |
| CN114437808B (en) | Method and system for processing heavy oil | |
| CN111088071A (en) | Catalytic slurry oil treatment method | |
| CN114437795B (en) | Method and system for processing heavy oil | |
| CN114437800B (en) | Two-stage hydrocracking method | |
| CN113862035B (en) | Method for producing high-end needle coke raw material from catalytic cracking slurry oil | |
| CN112210401B (en) | Tandem and alternative residual oil hydrotreating-catalytic cracking combined process method and system | |
| CN110408428B (en) | Method for treating residual oil by combined process | |
| CN113736509B (en) | Treatment method for hydrogenation residual oil of slag oil slurry bed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240322 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant after: CHINA PETROLEUM & CHEMICAL Corp. Country or region after: China Applicant after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant before: CHINA PETROLEUM & CHEMICAL Corp. Country or region before: China Applicant before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |