CN111088072A - Hydrocracking method for reducing heavy naphtha bromine index and increasing aviation kerosene smoke point - Google Patents
Hydrocracking method for reducing heavy naphtha bromine index and increasing aviation kerosene smoke point Download PDFInfo
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- 239000003350 kerosene Substances 0.000 title claims abstract description 138
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 61
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 29
- 239000000779 smoke Substances 0.000 title abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 15
- 238000005336 cracking Methods 0.000 claims abstract description 14
- 239000002283 diesel fuel Substances 0.000 claims abstract description 10
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- 230000008569 process Effects 0.000 claims description 19
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- 238000004821 distillation Methods 0.000 claims description 2
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- 229930195733 hydrocarbon Natural products 0.000 abstract description 17
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- 238000001833 catalytic reforming Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
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- 230000008901 benefit Effects 0.000 description 3
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a hydrocracking method for reducing the bromine index of heavy naphtha, which comprises the following steps: raw oil and hydrogen are mixed and then enter a hydrofining reactor to carry out hydrofining reaction, reaction effluent enters a hydrocracking reactor, hydrocracking generated oil enters a fractionating tower through a high-pressure separator and a low-pressure separator to obtain dry gas, liquefied gas, light naphtha, heavy naphtha, light aviation kerosene, heavy aviation kerosene, diesel oil and tail oil, and part or all of the light aviation kerosene is recycled to the hydrocracking reactor. The method can effectively improve the content of aromatic hydrocarbon and naphthenic hydrocarbon and the partial pressure of ammonia in reactants, and inhibit the secondary cracking reaction of the paraffinic hydrocarbon, thereby achieving the purposes of reducing the bromine index of heavy naphtha and increasing the smoke point of aviation kerosene.
Description
Technical Field
The invention relates to a hydrocracking method for reducing the bromine index of heavy naphtha and increasing the smoke point of aviation kerosene, which is particularly suitable for processing paraffin-based wax oil in the medium-pressure hydrocracking process, does not need to carry out large-scale transformation on a device, and can realize the aims of reducing the bromine index of heavy naphtha and increasing the smoke point of aviation kerosene only by adjusting a process operation method.
Background
The hydrocracking technology has the characteristics of high production flexibility, strong raw material adaptability and high product quality, and plays a role of a medium-flow column in the aspect of adjusting the production balance of a whole plant. The products of the hydrocracking process include natural gas, liquefied gas, naphtha, jet fuel, diesel, and tail oil. The traditional hydrocracking technology mainly produces naphtha or middle distillate according to market change. The hydrocracking device is divided into high-pressure hydrocracking (12 Mpa) and medium-pressure hydrocracking (6-12 Mpa) according to different design pressures. The traditional high-pressure hydrocracking device has the advantages of strong raw material adaptability, high adjustment flexibility, high product quality and the like. However, for the medium-pressure hydrocracking device, the partial hydrogen pressure is low, the aromatic hydrocarbon saturation depth in the raw oil is insufficient, and the aromatic hydrocarbon content in the product is high, so that the defect of low quality of part of products is caused. When the medium-pressure hydrocracking device is used for processing wax oil, the problems of high heavy naphtha bromine index, low aviation kerosene smoke point, low diesel cetane number, high tail oil BMCI value and the like can occur.
The hydrocracking heavy naphtha mainly comprises C6-C10 alkane and cycloalkane, and the bromine index of the heavy naphtha reflects the olefin content. For a refinery integrated refinery, heavy naphtha is often used as catalytic reforming raw oil, and the heavy naphtha has a high bromine index, i.e., a high olefin content, which increases the surface carbon deposition rate of a catalytic reforming agent, reduces the activity of the catalytic reforming agent, and shortens the regeneration time. The internal control index of the catalytic reforming device to the bromine index of the raw oil is generally no more than 150 mgBr/100 g. The higher bromine index of heavy naphtha is mainly due to the following reasons: (1) the hydrocracking unit has lower operation pressure; (2) under the condition of a hydrocracking catalyst system with poor hydrogenation activity and strong cracking activity, the operation temperature is higher, the paraffin cracking reaction is intensified, and the olefin content in the product is increased; (3) when the paraffin-based raw oil is processed, the raw oil contains a large amount of paraffin, the content of aromatic hydrocarbon and naphthene is low, and the secondary cracking reaction of the paraffin is facilitated, so that a large amount of olefin is generated; (4) the last bed of the hydrocracking reactor is often provided with a post-refining agent, which is the same as the hydrofinishing agent, but is more acidic. And the bed has the lowest hydrogen partial pressure and the highest reaction temperature, so that the olefin saturation depth generated by secondary cracking is insufficient and the olefin saturation depth is accumulated in a heavy naphtha product.
The hydrocracking aviation kerosene mainly comprises C10-C12 naphthenic hydrocarbon and paraffin hydrocarbon, and when the reaction pressure is low, the content of aromatic hydrocarbon in the aviation kerosene is high, so that the requirement that the smoke point of high-quality No. 3 jet fuel is not less than 25mm cannot be met. The hydrocarbon of the aviation kerosene component between 165 and 220 ℃ is relatively large, the content of naphthenic hydrocarbon and the content of aromatic hydrocarbon are relatively high, the hydrocarbon ratio of the aviation kerosene component between 165 and 220 ℃ is reduced, namely the saturation depth of the component is increased, and the content of aromatic hydrocarbon and naphthenic hydrocarbon is reduced, so that the method is a key point for improving the aviation kerosene smoke point.
For a medium-pressure hydrocracking device, because the medium-pressure hydrocracking device is limited by design pressure and raw oil type, in order to solve the problems of higher bromine index of heavy naphtha and lower smoke point of aviation kerosene, only improvement can be made on the process flow or the operation method, so that the problem of low product quality is solved. The hydrocracking reaction is a competitive adsorption reaction, and the polarity sequence of different hydrocarbons is as follows: aromatic hydrocarbons > naphthenes > paraffins, the more polar hydrocarbons will preferentially adsorb on the catalyst active sites and undergo hydrocracking reactions. The aromatic hydrocarbon and the naphthenic hydrocarbon have higher polarity, so that the reaction is preferentially carried out, the cracking reaction of the paraffinic hydrocarbon is not easy to carry out, and the aromatic hydrocarbon and the naphthenic hydrocarbon are reserved in the product. Therefore, it is very effective to increase the contents of aromatic hydrocarbons and naphthenic hydrocarbons in the reactants in order to avoid the occurrence of deep cracking reaction of paraffinic hydrocarbons.
In the hydrocracking technology, more reports are made about methods and technologies for increasing yield and quality of aviation kerosene, but less reports are made about how to reduce the bromine index of heavy naphtha. CN 103421537 a discloses a hydrogenation process to ensure that heavy naphtha meets the reforming feed requirements. The method comprises the steps of enabling the hydrocracking reaction effluent to enter a hot high-pressure separator for gas-liquid separation, filling a hydrofining catalyst bed layer at the upper part in the hot high-pressure separator for mercaptan removal reaction, and then cooling the reaction product to enter a cold high-pressure separator. The method can effectively reduce the sulfur content of the heavy naphtha and meet the feeding requirement of a catalytic reforming device. However, the hot high-pressure gas contains a large amount of water vapor, which has great influence on the activity and mechanical strength of the hydrofining agent, and if the catalyst is crushed and gelatinized, the pressure difference of the hot high-pressure gas outlet and the inlet is increased, which is very unfavorable for the safe and smooth operation of the equipment. In addition, secondary refining of the heavy naphtha fraction results in a reduction in aromatic hydrocarbon potential.
CN 103013559A discloses a hydrocracking method for selectively increasing yield of aviation kerosene. According to the method, raw oil and hydrogen are mixed and then subjected to hydrofining reaction and hydrocracking reaction in sequence, reaction effluent is cooled and separated, and obtained 10% -100% of heavy diesel oil fraction with the temperature of 320-370 ℃ is returned to a raw material tank for continuous reaction. The method is effective in improving aviation kerosene yield and aviation kerosene smoke point. But the yield of heavy diesel oil fraction is lower, and the yield and quality improvement of aviation kerosene are limited.
CN 104560169 a discloses a hydrocracking process for producing heavy naphtha from a high nitrogen feedstock. The method adopts a single-stage series flow and is provided with two hydrocracking reactors, wherein tail oil fraction is mixed with recycle hydrogen after being pressurized and enters a second reaction zone for hydrocracking reaction. The method can improve the selectivity of heavy naphtha and reduce the yield of light components. However, the tail oil contains a large amount of paraffin and naphthene, the aromatic potential of the heavy naphtha produced after recycling is reduced, the equipment investment is large, and the economic benefit is not high.
CN 106520199 a discloses a hydrocracking method for producing aviation kerosene under medium pressure. The method is provided with two hydrofining reactors and one hydrocracking reactor. Under the condition that the pressure is less than or equal to 12.0MPa, the kerosene fraction is divided into a light aviation kerosene fraction, a medium aviation kerosene fraction and a heavy aviation kerosene fraction, and at least part of the medium aviation kerosene fraction is pumped out to the second-stage hydrofining reaction zone for circulation. The invention can effectively reduce the smoke point of aviation kerosene, but one hydrofining reactor is additionally arranged, so that the equipment investment and the operation cost are higher.
CN 106520197A discloses a hydrocracking method for producing aviation kerosene from inferior raw oil. The method comprises the steps of introducing the obtained kerosene fraction into a kerosene fractionating tower for fractionating to obtain a light aviation kerosene fraction and a heavy aviation kerosene fraction, recycling at least part of the heavy aviation kerosene fraction into the raw material tank and/or a hydrofining reaction zone, and taking the light aviation kerosene fraction and the optional rest of the heavy aviation kerosene fraction as aviation kerosene products out of the device. The method can reduce the smoke point of the aviation kerosene to a certain extent. However, the heavy aviation kerosene fraction is a fraction with higher smoke point and less aromatic hydrocarbon, and the aviation kerosene smoke point cannot be greatly improved after circulation.
Disclosure of Invention
The invention aims to solve the problem that the bromine index of heavy naphtha and the smoke point of aviation kerosene of a medium-pressure hydrocracking device are unqualified, and provides a hydrocracking method for reducing the bromine index of heavy naphtha and increasing the smoke point of aviation kerosene.
The invention relates to a hydrocracking method for reducing the bromine index of heavy naphtha, which comprises the following steps: raw oil and hydrogen are mixed and then enter a hydrofining reactor to carry out hydrofining reaction, reaction effluent enters a hydrocracking reactor, hydrocracking generated oil enters a fractionating tower through a high-pressure separator and a low-pressure separator to obtain dry gas, liquefied gas, light naphtha, heavy naphtha, light aviation kerosene, heavy aviation kerosene, diesel oil and tail oil, and part or all of the light aviation kerosene is recycled to the hydrocracking reactor.
In the method, the raw oil is a conventional wax oil raw material, the distillation range is generally 200-550 ℃, and the raw oil can be wax oil obtained by fractionating paraffin-based, naphthenic-based and intermediate-base crude oil, and can also be blended with coking wax oil with the concentration of less than 20%. The sulfur content in the raw oil is less than or equal to 30000 mu g/g, and the nitrogen content is less than or equal to 2000 mu g/g. When processing inferior raw materials, protective agents including demetallization agents, carbon residue removal agents, silicon capture agents and the like are filled before a hydrofining agent.
In the method, the dry point of the heavy naphtha is 132-165 ℃, the dry point of the heavy aviation kerosene is 240-282 ℃, and the cutting point of the light aviation kerosene and the heavy aviation kerosene is 200-230 ℃.
In the method, the mass ratio of the light aviation kerosene for circulation to the light aviation kerosene products discharged from the device is 0.5-2: 1. Preferably, the recycled light aviation kerosene and an aromatic nitrogen compound are mixed and then enter a hydrocracking reactor, the mass ratio of the aromatic nitrogen compound to the light aviation kerosene is 0.005-0.1, and the aromatic nitrogen compound is generally one or more of pyrrole, pyridine, quinoline or indole.
In the method, the hydrofining reactor is divided into one or more reaction zones along the material flow direction, preferably 1 to 6 reaction zones, and further preferably 2 to 4 reaction zones; the hydrocracking reactor is divided into 2 or more reaction zones along the material flow direction, preferably 2 to 6 reaction zones, and further preferably 3 to 5 reaction zones.
In the method, the light aviation kerosene can be uniformly circulated back to each hydrocracking catalyst bed layer or circulated back to each hydrocracking catalyst bed layer according to a mode that the circulation quantity is gradually increased, the circulation quantity of the next catalyst bed layer adjacent to the catalyst bed layer along the material flow direction is 1.2-1.5 times of the circulation quantity of the previous catalyst bed layer, and further, the circulation is preferably started from the second catalyst bed layer.
In the method, the hydrofining reactor is filled with hydrofining catalyst which is conventional in the field, and the hydrofining catalyst comprises a carrier and hydrogenation active metal; wherein the carrier is inorganic refractory oxide, generally selected from one or more of alumina, amorphous silicon-aluminum, silicon dioxide or titanium oxide, etc.; the hydrogenation active metal comprises metal components of VIB and/or VIII groups, wherein the VIB group is selected from tungsten and/or molybdenum and calculated by oxide is 10-35%, preferably 15-30%, and the VIII group is selected from nickel and/or cobalt and calculated by oxide is 1-7%, preferably 1.5-6%. The carrier is inorganic refractory oxide, and is generally selected from alumina, amorphous silica-alumina, silica, titanium oxide and the like. The hydrofining catalyst can be selected from conventional hydrocracking pretreatment catalysts, wherein the conventional hydrocracking pretreatment catalysts can be selected from various existing commercial catalysts, such as hydrotreating catalysts developed and developed by the Fushu petrochemical industry research institute (FRIPP), such as 3936, 3996, FF-36, FF-46, FF-56 and FF-66; it can also be prepared according to the common knowledge in the field, if necessary.
In the above process, the reaction conditions in the hydrorefining reactor are generally: the reaction pressure is 5.0-35.0 MPa, preferably 6.0-19.0 MPa; the average reaction temperature is 200-480 ℃, and preferably 270-450 ℃; the volume space velocity is 0.1-15.0 h-1Preferably 0.2 to 3.0 hours-1(ii) a The volume ratio of hydrogen to oil is 100: 1-2500: 1, preferably 400: 1-2000: 1.
in the above process, the hydrocracking catalyst generally comprises a cracking component, a hydrogenation component and a binder. Such as any suitable hydrocracking catalyst including those known in the art. The cracking component typically comprises amorphous silica-alumina and/or molecular sieves, typically molecular sieves such as Y-type or USY-type molecular sieves. The binder is typically alumina or silica. The hydrogenation component is a metal, a metal oxide or a metal sulfide of a metal in a VI group, a VII group or a VIII group, and more preferably one or more of iron, chromium, molybdenum, tungsten, cobalt, nickel or sulfides or oxides thereof. The hydrogenation component content is usually 5 to 40wt% based on the weight of the catalyst. Specifically, the existing hydrocracking catalyst may be selected, or a specific hydrocracking catalyst may be prepared as required. Commercial hydrocracking catalysts are mainly: HC-12, HC-14, HC-24, HC-39, etc. by UOP, 3905, 3955, FC-12, FC-16, FC-24, FC-32, 3971, 3976, FC-26, FC-28, etc. by FRIPP, and ICR126, ICR210, etc. by CHEVRON.
In the above process, the hydrocracking operation conditions include: the reaction pressure is 5.0-35.0 MPa, preferably 6.0-19.0 MPa; the average reaction temperature is 200-480 ℃, preferably 270-450 ℃; the volume space velocity is 0.1-15.0 h-1Preferably 0.2 to 3.0 hours-1(ii) a The volume ratio of hydrogen to oil is 100: 1-2500: 1, preferably 400: 1-2000: 1.
the method of the invention divides the aviation kerosene into light aviation kerosene with high aromatic content and heavy aviation kerosene with high paraffin content, returns the light aviation kerosene to the position between the bed layers of the hydrocracking reactor, sets a nitrogen injection point in the pipeline for introducing the light aviation kerosene, inhibits the activity of the hydrocracking agent by introducing aromatic nitrogen compound, and can increase the contents of aromatic hydrocarbon and cyclane in reactants. And mixing part of the light aviation kerosene and the heavy aviation kerosene to obtain a qualified product pipeline. Finally, the purposes of inhibiting secondary cracking of paraffin, reducing the bromine index of heavy naphtha and increasing the smoke point of aviation kerosene can be realized.
The method of the invention has the following advantages:
(1) the light aviation kerosene fraction and the aromatic nitrogen compound are mixed and then enter a hydrocracking reactor, so that the transitional cracking of paraffin can be effectively inhibited, and the bromine index of heavy naphtha can be reduced.
(2) As the content of the aromatic hydrocarbon and the naphthenic hydrocarbon in the reactants is increased, the content of the aromatic hydrocarbon and the naphthenic hydrocarbon in the heavy naphtha is increased, and the aromatic potential of the heavy naphtha can be obviously improved.
(3) The aviation kerosene fraction is divided into two fractions of light aviation kerosene and heavy aviation kerosene, the light aviation kerosene with higher aromatic hydrocarbon content is circulated to the hydrocracking reactor, the aviation kerosene smoke point can be effectively improved, and the qualified aviation kerosene can be obtained under the medium-pressure hydrocracking condition.
(4) The mixture of the light aviation kerosene and the aromatic nitrogen compound is circulated to each reaction zone of hydrocracking, and can replace cold hydrogen as a cooling medium, thereby playing the roles of reducing the cold hydrogen amount and reducing the energy consumption.
Drawings
FIG. 1 is a flow diagram of a hydrocracking process for reducing the bromine index of heavy naphtha. Wherein, 1, a raw oil tank; 2, a raw material oil pump; 3, new hydrogen; 4 a hydrofining reactor; 5 a hydrocracking reactor; 6, generating oil; 7 high pressure separator; 8, cooling high-pressure gas; 9 a recycle hydrogen desulfurization system; 10 recycle hydrogen compressor; 11 a low pressure separator; 12, low gas separation; 13 low oil fraction; 14 a fractionation column; 15 gas; 16 light naphtha; 17 heavy naphtha; 18 aviation kerosene; 19 diesel oil; 20 a separator; 21 tail oil; 22 light aviation kerosene; 23-fold sailing coal; and 24 nitrogen injection points.
Detailed Description
The following examples further illustrate the process of the present invention, but are not intended to limit the invention thereto.
As shown in fig. 1, the raw oil in the tank 1 is mixed with mixed hydrogen 3 by a pump 2, and then enters a hydrofining reactor 4 and a hydrocracking reactor 5, and sequentially passes through a catalyst bed layer from top to bottom. The reaction effluent 6 enters a high-pressure separator 7, the high-pressure gas 8 obtained at the upper part enters a recycle hydrogen desulfurization system 9, and is used as cold hydrogen and recycle hydrogen after being pressurized by a recycle hydrogen compressor 10; the liquid phase obtained from the middle lower part of the high-pressure separator enters a low-pressure separator 11, the low-fraction gas 12 discharged from the upper part is subjected to subsequent treatment, the liquid phase 13 obtained from the middle lower part enters a subsequent fractionation system 14, and the gas 15, the light naphtha 16, the heavy naphtha 17, the aviation kerosene 18, the diesel oil 19 and the tail oil 20 are obtained; the aviation kerosene fraction enters a separator 21 to obtain light aviation kerosene 22 and heavy aviation kerosene 23. Aromatic nitrogen compounds are injected at the nitrogen injection point 24 and mixed with the light aviation kerosene before being introduced between the reaction zones of the hydrocracking reactor. And mixing part of the light aviation kerosene and the heavy aviation kerosene to obtain a product qualified line.
Example 1
Chongqing VGO is used as raw oil, FF-36 is used as a hydrofining agent, FC-46 is used as a hydrocracking agent, the actual operation process conditions are shown in Table 3, and the reaction pressure is set to be 12 MPa. After the low-fraction oil enters a fractionating tower, the aviation kerosene fraction enters a separator to be cut into light aviation kerosene and heavy aviation kerosene, and the cutting point is 220 ℃. The mass ratio of the light aviation kerosene to the aviation kerosene product discharged from the device is 1.0, pyrrole is injected into the nitrogen injection point, and the mass ratio of the injection amount to the light aviation kerosene is 0.01. The mixture of aromatic nitrogen compounds and light aviation kerosene enters each hydrocracking reactor zone from the first bed layer uniformly.
Example 2
Chongqing VGO is used as raw oil, FF-36 is used as a hydrofining agent, FC-46 is used as a hydrocracking agent, the actual operation process conditions are shown in Table 3, and the reaction pressure is set to be 12 MPa. After the low-fraction oil enters a fractionating tower, the aviation kerosene fraction enters a separator to be cut into light aviation kerosene and heavy aviation kerosene, and the cutting point is 220 ℃. The mass ratio of the light aviation kerosene to the aviation kerosene product discharged from the device is 1.0, pyrrole is injected into the nitrogen injection point, and the mass ratio of the injection amount to the light aviation kerosene is 0.01. The mixture of aromatic nitrogen compounds and light aviation kerosene enters each hydrocracking reactor zone from the first bed layer, and the circulation ratio in the material flow direction is 1.5.
Example 3
Chongqing VGO is used as raw oil, FF-36 is used as a hydrofining agent, FC-46 is used as a hydrocracking agent, the actual operation process conditions are shown in Table 3, and the reaction pressure is set to be 12 MPa. After the low-fraction oil enters a fractionating tower, the aviation kerosene fraction enters a separator to be cut into light aviation kerosene and heavy aviation kerosene, and the cutting point is 220 ℃. The mass ratio of the light aviation kerosene to the aviation kerosene product discharged from the device is 1.0, pyrrole is injected into the nitrogen injection point, and the mass ratio of the injection amount to the light aviation kerosene is 0.01. The mixture of aromatic nitrogen compounds and light aviation kerosene enters each hydrocracking reactor zone from the second bed layer, and the circulation ratio in the material flow direction is 1.5.
Example 4
Chongqing VGO is used as raw oil, FF-36 is used as a hydrofining agent, FC-46 is used as a hydrocracking agent, the actual operation process conditions are shown in Table 3, and the reaction pressure is set to be 12 MPa. After the low-fraction oil enters a fractionating tower, the aviation kerosene fraction enters a separator to be cut into light aviation kerosene and heavy aviation kerosene, and the cutting point is 220 ℃. The mass ratio of the light aviation kerosene to the aviation kerosene product discharged from the device is 1.0, pyridine is injected into the nitrogen injection point, and the mass ratio of the injection amount to the light aviation kerosene is 0.01. The mixture of aromatic nitrogen compounds and light aviation kerosene enters each hydrocracking reactor zone from the second bed layer, and the circulation ratio in the material flow direction is 1.5.
Example 5
Chongqing VGO is used as raw oil, FF-36 is used as a hydrofining agent, FC-46 is used as a hydrocracking agent, the actual operation process conditions are shown in Table 3, and the reaction pressure is set to be 12 MPa. After the low-fraction oil enters a fractionating tower, the aviation kerosene fraction enters a separator to be cut into light aviation kerosene and heavy aviation kerosene, and the cutting point is 220 ℃. The mass ratio of the light aviation kerosene to the aviation kerosene product discharged from the device is 1.0, and nitrides are not injected into the nitrogen injection points. The mixture of aromatic nitrogen compounds and light aviation kerosene enters each hydrocracking reactor zone from the second bed layer, and the circulation ratio in the material flow direction is 1.5.
Comparative example 1
Chongqing VGO is used as raw oil, FF-36 is used as a hydrofining agent, FC-46 is used as a hydrocracking agent, the actual operation process conditions are shown in Table 3, and the reaction pressure is set to be 12 MPa. After the low-fraction oil enters the fractionating tower, the obtained aviation kerosene product is directly discharged out of the device without being cut.
Comparative example 2
Chongqing VGO is used as raw oil, FF-36 is used as a hydrofining agent, FC-46 is used as a hydrocracking agent, the actual operation process conditions are shown in Table 3, and the reaction pressure is set to be 10 MPa. After the low-fraction oil enters the fractionating tower, the obtained aviation kerosene product is directly discharged out of the device without being cut.
The properties of the catalysts used in the examples are listed in table 1. The properties of the raw oils used are shown in Table 2. Table 3 shows the process conditions for the operation of the apparatus.
TABLE 1 physicochemical Properties of the catalyst
TABLE 2 Properties of the feed oils
TABLE 3 Process operating conditions
Hydrorefining catalyst;
light oil hydrocracking catalyst;
post-refining agent.
TABLE 4 hydrocracking liquid product distribution
Table 5 comparative and examples bromine index of heavy naphtha vs. smoke point of aviation kerosene
| Product(s) | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Bromine index of heavy naphtha mgBr/100g | 257 | 298 | 120 | 75 | 46 | 66 | 178 |
| Smoke point of aviation kerosene, mm | 22.5 | 19.6 | 27.0 | 26.5 | 25.9 | 25.6 | 26.8 |
At substantially the same tail oil yield, the hydrocracking liquid product was divided as shown in table 4, and when light aviation kerosene was circulated to the hydrocracking reactor and nitrides were injected, the yields of light naphtha and heavy naphtha were slightly decreased, and the yields of aviation kerosene and diesel oil were slightly increased, which were caused by the increase of nitrides in the reactants, the decrease of cracking activity and light oil selectivity. Table 5 shows the analysis results of the heavy naphtha bromine index and the aviation kerosene smoke point corresponding to the comparative example and the example, and it can be seen from table 5 that the heavy naphtha bromine index and the aviation kerosene smoke point can not meet the production requirements when processing paraffin-based wax oil (daqing VGO) under the medium-pressure hydrocracking condition. After the method disclosed by the patent is adopted, the reduction range of the bromine index of the heavy naphtha is obvious, and the smoke point of the aviation kerosene is obviously increased. Comparing example 1 with example 2, it can be seen that when the recycle ratio is increased along the material flow direction, the yield of light naphtha and heavy naphtha is reduced, the yield of aviation kerosene and diesel oil is increased, the bromine index of heavy naphtha is obviously reduced, and the smoke point of aviation kerosene is slightly reduced. Comparing example 3 with example 4, it can be seen that the yields of light naphtha and heavy naphtha are reduced, the yields of aviation kerosene and diesel oil are slightly increased, the bromine index of heavy naphtha is increased, and the smoke point of aviation kerosene is slightly reduced by injecting the basic nitrides as compared with injecting the non-basic nitrides. Comparing example 5 with other examples, it can be seen that, when the light aviation kerosene is directly circulated to the hydrocracking reactor without injecting nitrides, the yields of light naphtha and heavy naphtha are high, the smoke point of aviation kerosene is high, but the bromine index is high, and the product quality requirement cannot be met. When the non-alkaline nitride pyrrole is injected, the cutting point is 220 ℃, the circulation is started from the 1 st bed layer, and the circulation ratio along the material flow direction is 1.5, the aviation kerosene smoke point is the highest. When the non-basic pyrrole nitride is injected, the cut point is 220 ℃, the circulation is started from the second bed, and the circulation ratio along the material flow direction is 1.5, and the bromine index of the heavy naphtha is lowest.
Claims (12)
1. A hydrocracking method for reducing the bromine index of heavy naphtha is characterized in that: the method comprises the following steps: raw oil and hydrogen are mixed and then enter a hydrofining reactor to carry out hydrofining reaction, reaction effluent enters a hydrocracking reactor, hydrocracking generated oil enters a fractionating tower through a high-pressure separator and a low-pressure separator to obtain dry gas, liquefied gas, light naphtha, heavy naphtha, light aviation kerosene, heavy aviation kerosene, diesel oil and tail oil, and part or all of the light aviation kerosene is recycled to the hydrocracking reactor.
2. The method of claim 1, wherein: the raw oil is wax oil raw material, and the distillation range is 200-550 ℃.
3. The method of claim 1, wherein: the dry point of the heavy naphtha is 132-165 ℃, the dry point of the heavy aviation kerosene is 240-282 ℃, and the cutting point of the light aviation kerosene and the heavy aviation kerosene is 200-230 ℃.
4. The method of claim 1, wherein: the mass ratio of the recycled light aviation kerosene to the light aviation kerosene products discharged from the device is 0.5-2: 1.
5. The method of claim 1, wherein: and (2) mixing the recycled light aviation kerosene with an aromatic nitrogen compound, and then feeding the mixture into a hydrocracking reactor, wherein the mass ratio of the aromatic nitrogen compound to the light aviation kerosene is 0.005-0.1, and the aromatic nitrogen compound is one or more of pyrrole, pyridine, quinoline or indole.
6. The method of claim 1, wherein: the hydrocracking reactor is divided into 2-6 reaction zones along the material flow direction.
7. The method of claim 1, wherein: the light aviation kerosene is uniformly circulated back to each bed layer of the hydrocracking catalyst or is circulated back to each bed layer of the hydrocracking catalyst according to a mode that the circulation quantity is gradually increased.
8. The method of claim 7, wherein: the circulation amount of the next catalyst bed layer adjacent to the catalyst bed layer along the material flow direction is 1.2 to 1.5 times of the circulation amount of the previous catalyst bed layer.
9. The method of claim 1, wherein: the hydrofining catalyst comprises a carrier and hydrogenation active metal; wherein the carrier is an inorganic refractory oxide; the hydrogenation active metal comprises a group VIB and/or group VIII metal component.
10. The method of claim 1, wherein: the reaction conditions in the hydrofining reactor are as follows: the reaction pressure is 5.0-35.0 MPa; average inverseThe temperature is 200-480 ℃; the volume space velocity is 0.1-15.0 h-1(ii) a The volume ratio of hydrogen to oil is 100: 1-2500: 1.
11. the method of claim 1, wherein: the hydrocracking catalyst comprises a cracking component, a hydrogenation component and a binder, wherein the cracking component usually comprises amorphous silica-alumina and/or a molecular sieve, the binder usually is alumina or silica, and the hydrogenation component is an oxide or sulfide of a metal in a VI group, a VII group or a VIII group.
12. The process of claim 1, wherein the hydrocracking operating conditions comprise: the reaction pressure is 5.0-35.0 MPa; the average reaction temperature is 200-480 ℃; the volume space velocity is 0.1-15.0 h-1(ii) a The volume ratio of hydrogen to oil is 100: 1-2500: 1.
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