CN103102952A - Production method of diesel oil - Google Patents
Production method of diesel oil Download PDFInfo
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- CN103102952A CN103102952A CN2011103508021A CN201110350802A CN103102952A CN 103102952 A CN103102952 A CN 103102952A CN 2011103508021 A CN2011103508021 A CN 2011103508021A CN 201110350802 A CN201110350802 A CN 201110350802A CN 103102952 A CN103102952 A CN 103102952A
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Abstract
The invention discloses a production method of diesel oil. The method consists of: leaving the reaction effluent from diesel oil raw material hydrofining and straight-run gasoline to enter a second reaction zone to contact a hydrodewaxing catalyst, subjecting the diesel oil raw material to a shape selective cracking reaction, and making the straight-run gasoline to undergo dehydrogenation and isomerization reactions, and separating the product so as to obtain a diesel oil product. The method adjusts the operating temperature of the second reaction zone by adjusting the amount of the straight-run gasoline injected into the second reaction zone so as to achieve flexible switch among different pour point depressing depths, and also can make the straight-run gasoline undergo dehydrogenation and isomerization reactions so as to effectively enhance the octane number of the straight-run gasoline. With the characteristics of simple and convenient operation, flexibility and controllability, the method provided in the invention overcomes the security risk of switch between different processes, and is especially suitable for the summer mode for hydrodewaxing production of low pour point diesel oil. Compared with the existing process switching schemes, the method involved in the invention makes full use of existing reactors, and is free of idle reactors.
Description
Technical field
The present invention relates to a kind of production method of diesel oil, particularly produced flexibly the method for different trade mark high-grade low-freezing diesel oil by inferior distillate oil.
Background technology
In present oil refining field, due to the good production that stimulates diesel oil of economical efficiency, in recent years the diesel oil equilibrium of supply and demand, crude oil cost and the clean fuel legislation production diesel oil that will impel refiner's maximum particularly.In addition, along with the raising of people's environmental consciousness and the increasingly stringent of environmental regulation, produce and use clear gusoline more and more to become a kind of development trend.
Along with developing rapidly of world economy, society's economic behaviour in winter is increasingly active, and the world market increases the demand of low-coagulation diesel oil and has a very strong seasonality; Along with the significantly investment of integrated and various countries, the world to traffic, will promote the significantly intercommunication of north and south in winter, thing goods and materials, this also can promote the demand of low-coagulation diesel oil.In addition, along with the development of world's crude oil heaviness and in poor quality, the diesel quality variation, this will ask for help seek and a kind ofly can produce high-grade low-freezing diesel oil, the flexible production technique of production in summer clean diesel winter by inferior distillate oil.
CN1257107A, US4436614 and CN101724459A disclose the method by the low solidifying lubricating oil of distillate production or intermediate oil, and the method adopts hydrofining-hydrodewaxing single hop hydrogenation or single hop tandem process.US6413412 and CN1289831A disclose the combined hydrogenation method of producing high hexadecane value, low-coagulation diesel oil, and the method adopts the flow process of hydrofining-hydro-upgrading-hydrodewaxing single hop series connection.US4394249 discloses a kind of hydrogenating desulfurization and hydrodewaxing combination process, a kind of two-stage process of this process using directly is provided with recycle hydrogen amine at hydrogenating desulfurization and two reactors of hydrodewaxing and washes system with the impact of impurity in reducing recycle hydrogen on Hydrodewaxing catalyst.These techniques and technical products yield are high, and some is widely used industrial, can produce the low solidifying fine-quality diesel oil that meets the demands.These techniques winter need to be by the pour point depression mode operation, and produce fine-quality diesel oil as common hydro-refining unit summer, and reducing the diesel oil loss, and these patents all not have the how problem of flexible conversion between the different trades mark of introduction.
Present many refinerys adopt the mode that flow process is switched to carry out the conversion of summer mode and winter mode, but this mode needs increase shutdown valve and cross-line on flow process, exist the risk in safe and idle reactor management.Delivered one piece in world NPRA in 2009 meeting and be entitled as the article of " BEYOND ULSD:TECHNOLOGY ENHANCEMENTS TO IMPROVE DISTILLATE PRODUCT QUALITY ", this article has been introduced a kind of method of winter mode and summer mode conversion.The method adopts single hop hydrogenation catalyst dewaxing technique, and in a reactor, when do not need to carry out dewaxing treatment summer, the dewaxing bed can remove the dewaxing function by annotating cold hydrogen with catalyst for refining and pour point depression catalyst loading.Inferior distillate oil has the large characteristics of hydrogenation thermal discharge, and make the pour point depression catalyzer be in dormant state, need to inject a large amount of cold hydrogen, the temperature of pour point depression catalyzer could be reduced to desired degree, exist the problem that hydrogen-consuming volume is large, increase recycle hydrogen load and difficult control of temperature.
Summary of the invention
For the problem that exists in above-mentioned technology, the invention provides a kind of production method of diesel oil.The method technique is simple, energy consumption is lower, can switch flexibly between different trade mark diesel oil scheme, thereby reach the flexible switching between the different pour point depression degree of depth, and can make straight-run spirit generation dehydrogenation and isomerization reaction, thereby can effectively improve the octane value of straight-run spirit.
The production method of diesel oil provided by the invention comprises:
(1) after diesel raw material and hydrogen mix, contact with Hydrobon catalyst at the first reaction zone, main purpose is sulphur, the nitrogen impurity that removes in raw material, and carries out part alkene and aromatic saturation reaction;
Reaction effluent and the straight-run spirit of (2) first reaction zones enter second reaction zone, contact with Hydrodewaxing catalyst, and diesel raw material is selected the shape scission reaction, and straight-run spirit carries out dehydrogenation and isomerization reaction; Wherein the add-on of straight-run spirit is the 0.1wt% ~ 20.0wt% of diesel raw material weight, is preferably 2.0wt% ~ 15.0wt%; The temperature that straight-run spirit enters before second reaction zone is 10 ~ 100 ℃, is preferably 20 ~ 80 ℃; The operational condition of second reaction zone is as follows: 250 ~ 420 ℃ of temperature of reaction are preferably 300 ~ 400 ℃; Reaction pressure is 2.0 ~ 15.0MPa, is preferably 3.0 ~ 10.0MPa; Hydrogen to oil volume ratio is 100 ~ 1000, is preferably 200 ~ 600; Volume space velocity 0.5 ~ 4.0h during liquid
-1, be preferably 0.5 ~ 3.0h
-1
(3) reaction effluent of second reaction zone is through gas-liquid separation, and liquid phase enters the product fractionating system, obtains diesel product.
In the inventive method, described straight-run spirit can be mixed into second reaction zone with the reaction effluent of the first reaction zone, also can enter separately second reaction zone, and straight-run spirit need not heat before entering second reaction zone or only heat or heat exchange get final product a little.
When the first reaction zone and second reaction zone can be arranged in different reactors, also can be arranged in same reactor.In the time of in same reactor is set, straight-run spirit can enter reactor between the first reaction zone and second reaction zone.When the first reaction zone and second reaction zone are arranged in two reactors, straight-run spirit can inject the pipeline between two reactors, also can inject from the second reaction zone entrance.
Method provided by the invention can be produced the diesel oil of the different trades mark, thereby realize the flexible switching between variant production trade mark scheme as required by adjusting the injection rate of straight-run spirit, also can according to the flexible in season, realize the purpose of maximum increasing output of diesel oil.
In the inventive method, it is as follows that the first reaction zone carries out the hydrofining condition: 250 ~ 420 ℃ of temperature of reaction are preferably 300 ~ 400 ℃; Reaction pressure is 2.0 ~ 15.0MPa, is preferably 3.0 ~ 10.0MPa; Hydrogen to oil volume ratio is 100 ~ 1000, is preferably 200 ~ 600; Volume space velocity 0.8 ~ 6.0h
-1, be preferably 1.0 ~ 4.0h
-1
In the inventive method, two reaction zones can be arranged in two or more beds of a reactor, also can be arranged in two or more tandem reactors.
In the inventive method, when switching between the different trades mark, only need the straight-run spirit amount that enters second reaction zone by adjustment, regulate the temperature of reaction of second reaction zone, impel the pour point depression catalyzer to make gasoline and diesel oil that corresponding reaction in various degree occurs under different temperature of reaction, when realizing the different trade mark diesel product of flexible production high-quality, improve the character of straight-run spirit, especially improve its octane value.
In the present invention, diesel raw material used is one or more the mixture in straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, visbreaking diesel oil.Therefore the present invention is applicable to various types of diesel oil distillates and composition thereof.
The first hydroconversion reaction zone filling Hydrobon catalyst, the second hydroconversion reaction zone filling Hydrodewaxing catalyst.According to method provided by the invention, described Hydrobon catalyst refers to have hydrogenating desulfurization, the non-precious metal catalyst of hydrodenitrification, hydrogenation of olefins and aromatic saturation function.This non-precious metal catalyst is generally with γ-Al
2O
3Or contain a small amount of SiO
2γ-Al
2O
3Be carrier, take group vib and/or VIII family metal as active ingredient, the group vib metal is generally Mo and/or W, and the group VIII metal is generally Co and/or Ni, and catalyzer can use suitable auxiliary agent as required.Take the weight of catalyzer as benchmark, the group vib metal content is counted 4.0wt% ~ 28.0wt% with oxide compound, and the group VIII metal content is counted 2.0wt% ~ 15.0wt% with oxide compound.The specific surface area of catalyzer is generally 100 ~ 650m
2/ g, pore volume are 0.15 ~ 0.80ml/g.
The Hydrodewaxing catalyst that second reaction zone is selected is with shape slective cracking molecular sieve and γ-Al
2O
3Or contain a small amount of SiO
2γ-Al
2O
3Jointly as carrier, the shape slective cracking molecular sieve can be one or more in ZSM type molecular sieve, beta-molecular sieve, is preferably ZSM-5 molecular sieve.The active metal component of Hydrodewaxing catalyst is group VIII metal component in the metallic element periodictable, is generally Ni or Co.Take the weight of catalyzer as benchmark, the content of ZSM-5 molecular sieve is 60% ~ 85%, and the group VIII metal content is counted 0.5wt% ~ 5.0wt% with oxide compound.The specific surface area of catalyzer is generally 200 ~ 800m
2/ g, pore volume are 0.15 ~ 0.50ml/g, and side pressure strength is 100 ~ 300N/cm.
Compared with prior art, the advantage and disadvantage of the inventive method is:
(1) the inventive method injects by adjusting the service temperature that the amount of second reaction zone straight-run spirit is regulated second reaction zone, thereby reach the flexible switching between the different pour point depression degree of depth, and can make straight-run spirit generation dehydrogenation and isomerization reaction, effectively improve the octane value of straight-run spirit.The inventive method is simple to operation, and is controlled flexibly, the risk when having overcome different flow process conversion on safety;
(2) straight-run spirit as the heat-absorbing body of second reaction zone, can reduce the quenching hydrogen consumption of second reaction zone greatly, thereby lowers the load of recycle compressor;
(3) the inventive method, when diesel oil pour point depression amplitude not quite or not needs pour point depression (being summer mode), under the prerequisite that guarantees the hydrofining degree of depth, by regulating the straight-run spirit injection rate, the Hydrodewaxing catalyst bed temperature is remained on shallow degree pour point depression occurs or the pour point depression reaction does not occur, and can make straight-run spirit generation dehydrogenation and isomerization reaction, thereby can effectively improve the octane value of straight-run spirit.Winter mode can adopt the pattern of the conventional hydrodewaxing production low-coagulation diesel oil that does not inject straight-run spirit.Compare with existing flow process handover scheme, take full advantage of existing reactor, do not have the problem of idle reactor;
(4) the inventive method, the pour point depression amplitude of Hydrodewaxing catalyst can be regulated in the scope of 0 ~ 60 ℃, and handiness is large.Octane number of direct distillation gasoline improves 5 ~ 30 units.The Hydrodewaxing catalyst that the present invention adopts not only can have been given play to the effect of different pour point depression amplitudes at different temperature, but also can make straight-run spirit generation dehydrogenation and isomerization reaction, improve the octane value of straight-run spirit, the function of catalyzer is given full play to.And, when adopting different production decision, can not produce large impact to the performance and used life of catalyzer.Switching between different pour point depression schemes is very easy to, and can complete the blocked operation between scheme in several hours, and the life-span of catalyzer is not subjected to the impact of the frequent cooling that heats up substantially.
Embodiment
Further set forth below in conjunction with embodiment and comparative example, but the present invention is not limited to this embodiment.In the present invention, wt% is massfraction.
The raw materials used oily A of embodiment and comparative example and stock oil C are wax distillate oil, and stock oil B is wax-containing distillate inferior, and its character sees Table 1.Test the character of Hydrobon catalyst used and Hydrodewaxing catalyst and list in table 2, wherein Hydrobon catalyst is designated as respectively HT-1, HT-2, HT-3, and Hydrodewaxing catalyst is designated as respectively HDW-1, HDW-2.
The technical process of embodiment 1 ~ 4 under summer mode is: at first the mixture of stock oil and hydrogen contacts with the Hydrobon catalyst of the first reaction zone, effluent with enter second reaction zone after straight-run spirit mixes, reaction product is through gas-liquid separation, gas phase with continue to recycle after new hydrogen mixes, liquid phase goes out device and obtains product through fractionation.Its reaction conditions and reaction result see Table 3 and table 4.
Comparative example 1 and 2 adopts the method that flow process is switched to test under summer mode, its technical process is: stock oil and hydrogen are introduced into the first reaction zone after mixing, and carry out the reactions such as desulfurization, denitrogenation and aromatic hydrocarbons fractional saturation under suitable reaction conditions and Hydrobon catalyst effect; The first reaction zone effluent is directly all walked cross-line, namely gets rid of second reaction zone, and the cross-line effluent separates with recycle hydrogen through separation system, then enters separation column and tells vapour, diesel oil and portion gas hydro carbons.Its reaction conditions and reaction result see Table 3 and table 4.
Embodiment 5 ~ 8th, respectively with embodiment 1 ~ 4 after summer mode running, adjusting flow process and operational condition turns round under pattern in the winter time, the concrete technology flow process is: stock oil is introduced into the first reaction zone after being heated to certain temperature and hydrogen mixing, carries out the reactions such as desulfurization, denitrogenation and aromatic saturation under suitable reaction conditions and Hydrobon catalyst effect; The first reaction zone effluent directly enters second reaction zone, under the effect of suitable processing condition and Hydrodewaxing catalyst, mainly selects the shape scission reaction.Reaction product is separated with recycle hydrogen through separation system, then enters separation column and tells vapour, diesel oil and portion gas hydro carbons.Its reaction conditions and reaction result are listed in table 5 and table 6.
Comparative example 3 and 4 be respectively with comparative example 1 and 2 after summer mode running, adjust flow process and operational condition and turn round under pattern in the winter time, flow process is with embodiment 5 ~ 8, its reaction conditions and reaction result are listed in table 5 and table 6.
Table 1 stock oil character
| Analysis project | Raw material A | Raw material B | Raw material C | Straight-run spirit |
| Density (20 ℃), kg/m 3 | 854 | 871 | 821 | 741 |
| The boiling range scope, ℃ | 181~372 | 204~368 | 146~370 | 57~192 |
| Sulphur, μ g/g | 789 | 1344 | 1500 | 230 |
| Nitrogen, μ g/g | 686 | 975 | 532 | 53 |
| Research octane number (RON) | - | - | - | 60 |
| Cetane value | 39 | 33 | - | - |
| Condensation point, ℃ | 8 | -2 | 18 | - |
Table 2 test used catalyst character
| The catalyzer numbering | HT-1 | HT-2 | HT-3 | HDW-1 | HDW-2 |
| Catalyzer forms, wt% | ? | ? | ? | ? | ? |
| WO 3 | 19 | - | 22 | - | - |
| NiO | 6 | 4.5 | 8 | 1.2 | 2.5 |
| MoO 3 | 0 | 20.0 | 3 | - | - |
| CoO | - | 2.6 | - | 1.2 | - |
| ZSM-5 molecular sieve | - | - | - | 67 | 76 |
| Aluminum oxide | Surplus | Surplus | Surplus | Surplus | Surplus |
| Pore volume, mL/g | 0.340 | 0.360 | 0.380 | 0.200 | 0.290 |
| Specific surface area, m 2/g | 242 | 250 | 254 | 289 | 302 |
| Side pressure strength, N/cm | 190 | 178 | 180 | 145 | 173 |
| Profile | Herba Galii Bungei shape | Cylindrical | Cloverleaf pattern | Cloverleaf pattern | Cylindrical |
| Tap density, g/cm 3 | 0.88 | 0.85 | 0.91 | 0.71 | 0.74 |
Table 3 test technology condition (summer mode)
| Test number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| The stock oil type | Raw material A | Raw material B | Raw material B | Raw material C | Raw material B | Raw material C |
| The first reaction zone (hydrofining section) | ? | ? | ? | ? | ? | ? |
| The hydrogen dividing potential drop, MPa | 6.5 | 8.5 | 11.0 | 4.5 | 6.5 | 4.5 |
| Hydrogen to oil volume ratio | 600 | 500 | 700 | 300 | 500 | 500 |
| Volume space velocity, h -1 | 2.4 | 3.2 | 4.0 | 1.5 | 3.2 | 1.5 |
| Temperature of reaction, ℃ | 345 | 325 | 330 | 358 | 340 | 335 |
| The catalyzer numbering | HT-1 | HT-2 | HT-2 | HT-3 | HT-1 | HT-3 |
| Second reaction zone (hydrodewaxing section) | ? | ? | ? | ? | ? | ? |
| The hydrogen dividing potential drop, MPa | 6.5 | 8.5 | 11.0 | 4.5 | - | - |
| Hydrogen to oil volume ratio | 600 | 500 | 700 | 300 | - | - |
| Volume space velocity, h -1 | 2.3/14.7 | 2.5/11.0 | 3.5/11.0 | 1.8/15.5 | - | - |
| Temperature of reaction, ℃ | 330 | 300 | 300 | 340 | - | - |
| The catalyzer numbering | HDW-1 | HDW-1 | HDW-2 | HDW-2 | HDW-1 | HDW-2 |
| The straight-run spirit injection rate, wt%(is to diesel raw material) | 4.0 | 7.0 | 6.2 | 2.4 | - | - |
| Temperature before straight-run spirit injects, ℃ | 28 | 50 | 39 | 78 | - | - |
The main character of each routine product of table 4 (summer mode)
| The embodiment numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Naphtha yield, wt%(is to diesel raw material) | 5.4 | 6.1 | 5.5 | 8.1 | 1 | 1.5 |
| Diesel yield, wt%(is to diesel raw material) | 97.3 | 99.5 | 99.4 | 93.2 | 98.5 | 98.4 |
| The diesel oil main character | ? | ? | ? | ? | ? | ? |
| Density (20 ℃), kg/m 3 | 845.3 | 860.0 | 846.5 | 828.0 | 861.0 | 824.0 |
| Boiling range, ℃ | ? | ? | ? | ? | ? | ? |
| IBP/10% | 155/218 | 148/215 | 151/215 | 146/238 | 150/215 | 145/238 |
| 50%/90% | 278/348 | 260/338 | 261/341 | 308/362 | 260/339 | 307/362 |
| 95% | 365 | 362 | 365 | 366 | 363 | 365 |
| Sulphur, μ g/g | 18 | 20 | 23 | 32 | 27 | 18 |
| Nitrogen, μ g/g | 22 | 9 | 14 | 11 | 13 | 12 |
| Cetane value | 48 | 46 | 51 | 53 | 46 | - |
| Condensation point, ℃ | -5 | -2 | -2 | -1 | -1 | 19 |
| Cold filter clogging temperature, ℃ | -1 | 2 | 1 | 2 | 2 | - |
| Oxidation stability, mg/ (100mL) | 1.2 | 1.0 | 0.5 | 0.7 | 1.1 | 0.9 |
| The petroleum naphtha main character | ? | ? | ? | ? | ? | ? |
| Density (20 ℃), kg/m 3 | 698.0 | 697.0 | 695.0 | 701.6 | 701.6 | 698.0 |
| The boiling range scope/℃ | 45-156 | 42-155 | 40-155 | 40-155 | 40-155 | 45-156 |
| Research octane number (RON) | 78 | 79 | 78 | 79 | 74 | 75 |
| Sulphur, μ g/g | 8 | 10 | 2 | 7 | 7 | 8 |
Table 5 test technology condition (winter mode)
| Test number | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 3 | Comparative example 4 |
| The stock oil type | Raw material A | Raw material B | Raw material B | Raw material C | Raw material A | Raw material C |
| The first reaction zone (hydrofining section) | ? | ? | ? | ? | ? | ? |
| The hydrogen dividing potential drop, MPa | 5.4 | 6.5 | 10.5 | 4.5 | 5.4 | 4.5 |
| Hydrogen to oil volume ratio | 600 | 500 | 700 | 300 | 600 | 300 |
| Volume space velocity, h -1 | 2.4 | 3.2 | 4.0 | 1.5 | 2.4 | 1.5 |
| Temperature of reaction, ℃ | 348 | 345 | 341 | 355 | 348 | 355 |
| The catalyzer numbering | HT-1 | HT-2 | HT-2 | HT-3 | HT-1 | HT-3 |
| Second reaction zone (hydrodewaxing section) | ? | ? | ? | ? | ? | ? |
| The catalyzer numbering | HDW-1 | HDW-1 | HDW-2 | HDW-2 | HDW-1 | HDW-2 |
| The hydrogen dividing potential drop, MPa | 5.4 | 6.5 | 10.5 | 4.5 | 5.4 | 4.5 |
| Hydrogen to oil volume ratio | 600 | 500 | 700 | 300 | 600 | 300 |
| Volume space velocity, h -1 | 2.3/14.7 | 2.5/8.0 | 3.5/11.0 | 1.8/15.5 | 2.3/14.7 | 1.8/15.5 |
| Temperature of reaction, ℃ | 348 | 345 | 340 | 355 | 347 | 355 |
The main character of each routine product of table 6 (winter mode)
| Test number | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 3 | Comparative example 4 |
| Naphtha yield, wt%(is to diesel raw material) | 9.5 | 4.8 | 5.6 | 13.7 | 9.7 | 13.4 |
| Diesel yield, wt%(is to diesel raw material) | 89.6 | 94.5 | 93.8 | 85.7 | 89.5 | 85.9 |
| The diesel oil main character | ? | ? | ? | ? | ? | ? |
| Density (20 ℃), kg/m 3 | 857.1 | 869.0 | 851.1 | 836.0 | 857.3 | 835.8 |
| The cut scope, ℃ | ? | ? | ? | ? | ? | ? |
| IBP/10% | 156/218 | 152/216 | 151/215 | 146/237 | 155/218 | 146/238 |
| 50%/90% | 279/348 | 263/340 | 261/341 | 308/363 | 278/348 | 308/362 |
| 95% | 365 | 362 | 365 | 367 | 364 | 366 |
| Sulphur, μ g/g | 37 | 35 | 7 | 35 | 30 | 32 |
| Nitrogen, μ g/g | 41 | 65 | 11 | 42 | 34 | 39 |
| Cetane value | 43 | 36 | 45 | 52 | 44 | 53 |
| Condensation point, ℃ | -23 | -39 | -23 | -37 | -23 | -38 |
| Cold filter clogging temperature, ℃ | -15 | -30 | -14 | -29 | -15 | -30 |
| Oxidation stability, mg/ (100mL) | 1.2 | 1.0 | 0.5 | 0.9 | 1.2 | 0.8 |
| The petroleum naphtha main character | ? | ? | ? | ? | ? | ? |
| Density (20 ℃), kg/m 3 | 699.0 | 697.0 | 698.0 | 700.2 | 698.0 | 699.6 |
| The boiling range scope, ℃ | 40-155 | 40-155 | 40-155 | 40-155 | 40-155 | 40-155 |
| Research octane number (RON) | 75 | 74 | 73 | 75 | 75 | 74 |
| Sulphur, μ g/g | 8 | 10 | 2 | 7 | 7 | 9 |
Embodiment 1 ~ 4th, particular embodiment of the present invention.Comparative example 1 ~ 2nd, summer, oil was walked cross-line, and stock oil only passes through the example of hydrofining reaction bed.All can find out from table 3 and table 4, under summer mode, fine-quality diesel oil that embodiment 1 ~ 4 all can the production condensation point meets the demands, diesel yield is higher than under winter mode, and the octane value of petroleum naphtha improves 10 more than unit than straight-run spirit; The diesel quality that comparative example 1 ~ 2 is produced is produced diesel quality a little less than the inventive method, and can not reduce the condensation point of diesel oil, when the raw material condensation point is higher, can not produce the satisfactory diesel oil of condensation point with the method for comparative example.Under summer mode, by adjusting reaction conditions, in diesel product, sulphur content can be reduced to less than 50mg/g, condensation point of diesel oil can be dropped to the pour point depression amplitude of requirement by regulating two anti-entrance straight-run spirit injection rates, diesel yield is high, and the octane number of direct distillation gasoline increase rate is large.
Can find out from table 5 and listed test conditions and the test-results of table 6, under pattern, by adjusting reaction conditions, the condensation point range of decrease of diesel oil can reach more than 60 ℃ in the winter time, and in diesel product, sulphur content can be reduced to less than 50mg/g, and diesel yield is higher.Embodiment 5 ~ 8 and comparative example 3 and 4 all can be produced high-grade low-freezing diesel oil, and as seen, the performance of embodiment of the present invention catalyzer is not injected the impact of straight-run spirit substantially.
Claims (9)
1. the production method of a diesel oil comprises:
(1) after diesel raw material and hydrogen mix, contact with Hydrobon catalyst at the first reaction zone, main purpose is sulphur, the nitrogen impurity that removes in raw material, and carries out part alkene and aromatic saturation reaction;
Reaction effluent and the straight-run spirit of (2) first reaction zones enter second reaction zone, contact with Hydrodewaxing catalyst, and diesel raw material is selected the shape scission reaction, and straight-run spirit carries out dehydrogenation and isomerization reaction; Wherein the add-on of straight-run spirit is the 0.1wt% ~ 20.0wt% of diesel raw material weight, and the temperature that straight-run spirit enters before second reaction zone is 10 ~ 100 ℃; The operational condition of second reaction zone is as follows: 250 ~ 420 ℃ of temperature of reaction, reaction pressure are 2.0 ~ 15.0MPa, and hydrogen to oil volume ratio is 100 ~ 1000, volume space velocity 0.5 ~ 4.0h during liquid
-1
(3) reaction effluent of second reaction zone is through gas-liquid separation, and liquid phase enters the product fractionating system, obtains diesel product.
2. in accordance with the method for claim 1, it is characterized in that in step (2), the add-on of straight-run spirit is the 2.0wt% ~ 15.0wt% of diesel raw material weight.
3. in accordance with the method for claim 1, it is characterized in that it is 20 ~ 80 ℃ that described straight-run spirit enters the front temperature of second reaction zone.
4. in accordance with the method for claim 1, it is characterized in that in step (2), the operational condition of second reaction zone is as follows: temperature of reaction is 300 ~ 400 ℃; Reaction pressure is 3.0 ~ 10.0MPa; Hydrogen to oil volume ratio is 200 ~ 600; During liquid, volume space velocity is 0.5 ~ 3.0h
-1
5. in accordance with the method for claim 1, it is characterized in that in step (1), it is as follows that the first reaction zone carries out the hydrofining condition: temperature of reaction is 250 ~ 420 ℃, and reaction pressure is 2.0 ~ 15.0MPa, hydrogen to oil volume ratio is 100 ~ 1000, and during liquid, volume space velocity is 0.8 ~ 6.0h
-1
6. in accordance with the method for claim 1, it is characterized in that in step (1), it is as follows that the first reaction zone carries out the hydrofining condition: temperature of reaction is 300 ~ 400 ℃, and reaction pressure is for being 3.0 ~ 10.0MPa, hydrogen to oil volume ratio is for being 200 ~ 600, and during liquid, volume space velocity is 1.0 ~ 4.0h
-1
7. in accordance with the method for claim 1, it is characterized in that diesel raw material used is one or more the mixture in straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, visbreaking diesel oil.
8. in accordance with the method for claim 1, it is characterized in that, the first hydroconversion reaction zone filling Hydrobon catalyst is with γ-Al
2O
3Be carrier, take group vib and VIII family metal as active ingredient, take the weight of catalyzer as benchmark, the group vib metal content is counted 4.0wt% ~ 28.0wt% with oxide compound, and the group VIII metal content is counted 2.0wt% ~ 15.0wt% with oxide compound; The character of catalyzer is as follows: specific surface area is 100 ~ 650m
2/ g, pore volume are 0.15 ~ 0.80ml/g.
9. in accordance with the method for claim 1, it is characterized in that, second reaction zone filling Hydrodewaxing catalyst is with ZSM-5 molecular sieve and γ-Al
2O
3Be carrier, active metal component is the group VIII metal component, and take the weight of catalyzer as benchmark, the content of ZSM-5 molecular sieve is 60% ~ 85%, and the group VIII metal content is counted 0.5wt% ~ 5.0wt% with oxide compound; The character of catalyzer is as follows: specific surface area is 200 ~ 800m
2/ g, pore volume are 0.15 ~ 0.50ml/g, and side pressure strength is 100 ~ 300N/cm.
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|---|---|---|---|
| CN201110350802.1A CN103102952B (en) | 2011-11-09 | 2011-11-09 | Production method of diesel oil |
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|---|---|---|---|
| CN201110350802.1A CN103102952B (en) | 2011-11-09 | 2011-11-09 | Production method of diesel oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109704275A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Organic liquid hydrogen storage system and hydrogen storage method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066870A (en) * | 1992-06-17 | 1992-12-09 | 洛阳市石油化工研究所 | Non-hydro isomerizaiton process |
| CN1111586C (en) * | 1998-12-16 | 2003-06-18 | 中国石油化工集团公司 | Method for producing high-grade low-freezing diesel oil from fraction oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1066870A (en) * | 1992-06-17 | 1992-12-09 | 洛阳市石油化工研究所 | Non-hydro isomerizaiton process |
| CN1111586C (en) * | 1998-12-16 | 2003-06-18 | 中国石油化工集团公司 | Method for producing high-grade low-freezing diesel oil from fraction oil |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109704275A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Organic liquid hydrogen storage system and hydrogen storage method |
| CN109704275B (en) * | 2017-10-26 | 2021-08-03 | 中国石油化工股份有限公司 | Organic liquid hydrogen storage system and hydrogen storage method |
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