CN103805237B - A kind of method utilizing catalyzer grating technology to produce low-coagulation diesel oil - Google Patents
A kind of method utilizing catalyzer grating technology to produce low-coagulation diesel oil Download PDFInfo
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- CN103805237B CN103805237B CN201210440354.9A CN201210440354A CN103805237B CN 103805237 B CN103805237 B CN 103805237B CN 201210440354 A CN201210440354 A CN 201210440354A CN 103805237 B CN103805237 B CN 103805237B
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- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000007710 freezing Methods 0.000 claims abstract description 19
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000005336 cracking Methods 0.000 claims description 11
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 6
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- 150000002431 hydrogen Chemical class 0.000 abstract description 4
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- -1 VIB group metals Chemical class 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of method utilizing catalyzer grating technology to produce low-coagulation diesel oil.After diesel raw material mixes with hydrogen, successively by the hydroconversion reaction zone of at least two series connection, the refining pour point depression catalyzer composite bed comprising Hydrodewaxing catalyst bed successively by hydroconversion reaction zone described in Flow of Goods and Materials direction and loaded by Hydrobon catalyst and hydro-upgrading isomerization-visbreaking catalyst mix; Last hydroconversion reaction zone gained reaction effluent is through being separated and after fractionation, obtaining low freezing point diesel fuel product.Hydrofining and the temperature rise of upgrading and pour point reducing process and the temperature drop of hydrodewaxing process are reasonably combined utilization by the inventive method, yield and the cetane value of diesel oil is improve while producing low solidifying low-sulfur diesel-oil, reduce the hot(test)-spot temperature of device, extend running period; In addition reduce the consumption of cold hydrogen or the combustion gas loss of process furnace, joint has also economized process cost.
Description
Technical Field
The invention relates to a production method of low freezing point diesel oil, in particular to a hydrogenation method for producing low freezing point diesel oil by a catalyst grading technology and a composite filling technology.
Background
Diesel oil is used as fuel of a compression ignition engine, plays an irreplaceable role as an irreproducible resource in the modern production and life process, can be used as fuel of vehicles such as automobiles, tanks, airplanes, tractors, railway vehicles and the like or other machines, and can also be used for power generation, heating and the like. According to different use industries and environments, users have great difference on the quality requirements of diesel oil products, for people living in alpine regions or winter, the demand of low-freezing-point diesel oil is always high, the traditional shape-selective cracking process can process heavy diesel oil fractions containing wax, the pour point depression range can reach 20-50 ℃, the range of the diesel oil fractions can be widened while the low-freezing-point diesel oil is obtained, the yield is improved, and the method is a very useful and advanced technology for solving the production problem of the low-freezing-point diesel oil.
The conditions of China are similar, particularly in recent years, along with the continuous improvement of national economic development and environmental awareness, the requirement on the quality of diesel oil is higher and higher, the popularization rate of diesel oil refining is increased year by year, and in addition, in northern cold regions, in addition to the requirement on the conventional refining property of the diesel oil, the condensation point becomes one of essential requirement indexes, so that the yield and the quality of low-condensation diesel oil can be improved, and the market demand is met, thus becoming an important problem concerned by oil refining enterprises in the cold regions. The cracking and the combined process thereof are selected as one of the main means for reducing the condensation point of the diesel oil, can be used for producing low-sulfur low-condensation diesel oil, and is beneficial to improving the economic benefit of oil refining enterprises.
The diesel oil shape-selective cracking technology is also called hydrodewaxing, and means that in the presence of hydrogen, a diesel oil raw material containing wax passes through the surface of a bifunctional catalyst containing active metal and a molecular sieve, so that the wax molecule content in the diesel oil raw material is reduced. The dewaxing principle is that under certain operation condition, the raw material is mixed with hydrogen and contacted with hydrodewaxing catalyst, and the high-condensation-point components of paraffin, short-side paraffin, long-side chain cycloparaffin and long-side chain arene in the raw material are selectively cracked into small molecules, while other components are basically unchanged, so that the aim of reducing the condensation point of oil product is finally achieved. The method has the advantages of low hydrogen consumption in the reaction process, strong raw material adaptability, low energy consumption, simple process flow, capability of forming a combined process with other hydrogenation processes or independent use and the like, so the method is widely applied. At present, many oil refining enterprises in northern cold regions of China adopt the technology to produce low freezing point diesel oil.
CN1257107A describes a method for producing high-quality low-freezing diesel oil by distillate oil. The method adopts a one-stage series flow of hydrofining and hydrodewaxing, wherein the one-stage series flow comprises two catalyst beds of hydrofining catalyst and hydrodewaxing catalyst, and the hydrodewaxing adopts Ni/ZSM-5 catalyst. The method has the advantages that the temperature drop of the hydrodewaxing catalyst bed layer is large, the improvement of the yield and the dewaxing effect of the diesel oil fraction is limited to a certain extent, and the service life of the hydrodewaxing catalyst is shortened.
CN102051232A introduces a diesel oil hydrogenation pour point depression method, which adjusts the property of catalyst to make diesel oil pour point depression effect good and diesel oil fraction yield high, but because the combined process of hydrogenation refining and hydrodewaxing in series is still adopted, the contradiction between pour point depression effect and diesel oil fraction yield still exists.
CN102453531A describes a diesel hydrodewaxing method, which increases the average reaction temperature of the hydrodewaxing catalyst and the utilization rate of the hydrodewaxing catalyst by using the temperature rise of a refining agent, but the method has the advantages of improving the average reaction temperature of the hydrodewaxing catalyst and improving the utilization rate of the hydrodewaxing catalyst
The reaction temperature at the outlet of each bed layer is still relatively high, and the period is limited to a certain extent.
CN01134271.4 discloses a hydrogenation combination method for producing high-cetane number and low-freezing point diesel oil. Raw oil and hydrogen are firstly contacted with a hydro-upgrading catalyst or a hydrocracking catalyst, reaction effluent is not separated and then contacted with a hydrodewaxing catalyst, the reaction effluent is cooled and enters a high-pressure separator, a separated liquid product enters a fractionation system, and gas rich in hydrogen is circulated back to the reactor. The method can simultaneously improve the cetane number of the diesel oil and reduce the condensation point of the diesel oil in the same set, and the cetane number of a diesel oil product is improved by more than 6 units compared with that of raw oil.
CN99113293.9 discloses a method for producing high-cetane number, high-quality and low-freezing point diesel oil by distillate oil. The method directly connects the hydrodewaxing with the hydrofining and the hydro-upgrading in series to realize the hydrofining-hydro-upgrading-hydrodewaxing-segment series flow, and adopts the hydrofining catalyst with strong coking resistance and the hydro-upgrading and hydrodewaxing catalyst with strong ammonia resistance and acid resistance, so that the process has the characteristics of good refining/dewaxing effect, high diesel oil yield, strong raw material adaptability, high diesel oil cetane number, simple process flow and flexible product scheme.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for producing low freezing point diesel. The method of the invention carries out grading on the hydrodewaxing catalyst and the mixed catalyst which is filled by hydrofining and hydrogenation modification isomerization pour point depressing compositely, and reasonably combines and utilizes the temperature drop in the hydrodewaxing process and the temperature rise in the hydrogenation process, thereby improving the yield of diesel oil while producing low-freezing-point low-sulfur diesel oil, reducing the hot point temperature of the device and prolonging the running period; in addition, the consumption of cold hydrogen or the fuel gas consumption of the heating furnace is reduced, and the operation cost is saved.
The invention provides a method for producing low freezing point diesel oil by utilizing a catalyst grading technology, which comprises the following steps:
the diesel raw material and hydrogen are mixed and then sequentially pass through at least two hydrogenation reaction zones which are connected in series, and the hydrogenation reaction zones sequentially comprise a hydrodewaxing catalyst bed layer and a refined dewaxing catalyst composite bed layer filled by mixing a hydrofining catalyst and a hydro-upgrading heterogeneous dewaxing catalyst according to the material flowing direction; and separating and fractionating the reaction effluent obtained in the last hydrogenation reaction zone to obtain the low-condensation-point diesel oil product.
In the method, in each hydrogenation reaction zone, diesel raw material and hydrogen firstly pass through a hydrodewaxing catalyst bed layer to carry out pour point depression reaction; and the reaction effluent passes through a refined pour point depressing catalyst composite bed layer filled by mixing a hydrofining catalyst and a hydro-upgrading heterogeneous pour point depressing catalyst to carry out hydrodesulfurization, hydrodenitrogenation, aromatic saturation and pour point depressing reactions.
According to the hydrogenation method of the invention, the diesel oil raw material is conventional pour point depressing raw material, namely high pour point diesel oil, and the pour point is generally above 0 ℃, preferably above 5 ℃. The nitrogen content of the diesel raw material is less than 2000 mu g/g, generally 50-1200 mu g/g, and most preferably 100-500 mu g/g. If the organic nitrogen content in the diesel fuel stock is too high, for example, the nitrogen content is above 2000 mug/g, the diesel fuel stock can be partially denitrified by passing through a hydrofining or hydrodenitrogenation catalyst bed before passing through the hydrodewaxing catalyst bed in the first hydrogenation reaction zone. The diesel oil raw material can be various straight-run or secondary processed diesel oil obtained by processing naphthenic base crude oil, intermediate base crude oil or paraffin base crude oil, and the like, and preferably is the component obtained by processing paraffin base crude oil. The dry point of the diesel fuel raw material is generally 350-440 ℃, preferably 370-400 ℃. For example, the diesel raw material can be one or more of various straight-run diesel, coked diesel, catalytic diesel and the like obtained by processing Daqing crude oil.
The hydrodewaxing catalyst adopts a catalyst containing a shape-selective cracking molecular sieve, and comprises a carrier and a loaded metal component. The catalyst generally takes shape selective cracking molecular sieve and adhesive as carriers, and metals in VIB group and/or VIII group as hydrogenation active metal components. The shape-selective cracking molecular sieve is a hydrogen type molecular sieve, and the molecular sieve can be one or more of hydrogen type ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieves, and is preferably a ZSM-5 molecular sieve; the silica-alumina molar ratio of the shape-selective cracking molecular sieve is generally 10-150, and preferably 20-120.
The VIB group metal is Mo and/or W, and the VIII group metal is Co and/or Ni. Based on the weight of the catalyst, the content of the hydrogenation active metal component is 1-16 percent calculated by oxide, the content of the shape-selective cracking molecular sieve is 50-85 percent, and the content of the adhesive is 10-40 percent. The hydrodewaxing catalyst can be selected from various existing commercial catalysts, such as hydrodewaxing catalysts, such as FDW-1 and FDW-3 developed by the Fushun petrochemical research institute (FRIPP); the catalyst may be prepared according to conventional knowledge in the art, for example, a satisfactory hydrodewaxing catalyst may be prepared by referring to the contents disclosed in CN1952074A, CN1352231A, CN101143333A and CN 102451748A.
The hydro-upgrading heterogeneous pour point depressing catalyst is a conventional catalyst in the technical field and generally comprises 29-50 w% of amorphous silica-alumina, 1-9 w% of modified β molecular sieve, 15-35 w% of VIB group metal calculated as oxide, 3-9 w% of VIII group metal calculated as oxide and 0-45 w% of porous refractory oxide by taking the weight ratio of the catalyst as a reference, wherein SiO of the modified β molecular sieve is prepared from the following components of amorphous silica-alumina, modified β molecular sieve, refractory porous oxide and oxide of VIB group and VIII group metals2/Al2O3The weight ratio is 50-90, the average size of crystal grains is 0.1-0.5 micron, and the infrared acidity is 0.1-0.4 mmol/g.
The porous refractory oxide may be one or more selected from alumina, titania, zirconia, boria, and composite oxides of the above elements (aluminum, titanium, zirconium, and boron), and preferably alumina. If the porous alumina can contain a macroporous alumina and a microporous alumina adhesive, the content of the macroporous alumina is generally 0 w-22 w%; the content of the small-hole alumina is generally 0-23 w%. The specific surface area of the catalyst is generally 160-230 m2The pore volume is 0.32-0.45 mL/g, and the modified β molecular sieve has the general property of SiO2/Al2O3The weight ratio is generally 50 to 90, the crystallinity is generally 90 to 110, the average size of crystal grains is generally 0.1 to 0.5 micron, and the specific surface area is 400 to 750m2A pore volume of 0.25 to 0.50mL/g, Na2The O content is less than 0.10w%, the infrared acidity is 0.1-0.4 mmol/g, and the secondary pore volume of 2-10 nm accounts for 30-60% of the total pore volume.
SiO in the amorphous silicon-aluminum2The content of (B) is generally 20 to 75w%, preferably 35 to 60 w%. The pore volume of the amorphous silica-alumina is 0.5-1.1 mL/g, preferably 0.6-0.8 mL/g; the specific surface area is 200-500 m2A ratio of 280 to 500 m/g is preferred2/g。
The pore volume of the macroporous alumina is 0.6-1.2 mL/g, preferably 0.8-1.2 mL/g, and the specific surface area is 200-550 m2A ratio of 300 to 500 m/g is preferred2(ii) in terms of/g. The pore volume of the microporous alumina is 0.3-0.5 mL/g, and the specific surface area is 180-350 m2(ii) in terms of/g. The group VIB metal is typically W and/or Mo, and the group VIII metal is typically Ni and/or Co.
The conventional hydro-upgrading isomerization pour point depression catalyst can be selected from various existing commercial catalysts, such as FC-14, FC-20 and the like developed by FRIPP. It is also possible to prepare specific hydroupgrading isomerization pour point depressing catalyst according to the common knowledge in the art, for example, the satisfactory hydroupgrading isomerization pour point depressing catalyst can be prepared by referring to the disclosure in CN 1712498A.
The hydrofining catalyst can adopt a conventional diesel hydrofining catalyst, generally uses VIB group and/or VIII group metals as active components, uses alumina or silicon-containing alumina as a carrier, and uses Mo and/or W as the VIB group metals and Co and/or Ni as the VIII group metals. Based on the weight of the catalyst, the content of the VIB group metal is 8-28 wt% calculated by oxide, the content of the VIII group metal is 2-15 wt% calculated by oxide, and the properties are as follows: the specific surface area is 100 to 650m2The pore volume is 0.15-0.8 mL/g, and the types of the selectable commercial catalysts are various, such as hydrofining catalysts such as FH-98 and FH-UDS developed by the petrochemical research institute (FRIPP); conventional hydrotreating oxidation state catalysts may also be prepared as desired according to common general knowledge in the art.
The operating conditions of the hydrodewaxing catalyst bed layer are as follows: the reaction pressure is 6.0-20.0 MPa, and the volume ratio of hydrogen to oil is 200: 1-1500: 1, the volume airspeed is 0.1-10.0 h-1Reaction temperature 260DEG C to 455 ℃; the preferable operation conditions are that the reaction pressure is 7.0-15.0 MPa, and the volume ratio of hydrogen to oil is 300: 1-1000: 1, the volume airspeed is 0.3-8.0 h-1The reaction temperature is 310-410 ℃.
The operation conditions of the refined pour point depressing catalyst composite bed layer consisting of the hydrofining and hydro-upgrading heterogeneous pour point depressing catalyst are as follows: the reaction pressure is 6.0-20.0 MPa, and the volume ratio of hydrogen to oil is 200: 1-1500: 1, the volume airspeed is 0.1-10.0 h-1The reaction temperature is 270-460 ℃; the preferable operation conditions are that the reaction pressure is 7.0-15.0 MPa, and the volume ratio of hydrogen to oil is 300: 1-1000: 1, the volume airspeed is 0.3-8.0 h-1The reaction temperature is 315-415 ℃.
According to the method, in each hydrogenation reaction zone, the filling volume ratio of the hydrodewaxing catalyst bed layer to the refined dewaxing catalyst bed layer filled by mixing the hydrofining catalyst and the hydro-upgrading isomerization dewaxing catalyst is 1: 10-10: 1, and preferably 1: 5-5: 1.
In the refined pour point depressing catalyst composite bed layer, a hydrofining catalyst and a hydro-upgrading heterogeneous pour point depressing catalyst are filled in a composite mode, and the filling volume ratio is 1: 10-10: 1, preferably 1: 5-5: 1.
For the at least two hydrogenation reaction zones, the hydrodewaxing catalyst bed layer and the refined dewaxing catalyst composite bed layer can be respectively arranged in more than two bed layers of a reactor; or may be separately disposed in more than two hydrogenation reactors in series.
Compared with the prior art, the method has the following advantages:
1. in each hydrogenation reaction zone, raw oil firstly passes through a hydrodewaxing catalyst bed layer to carry out pour point depression reaction, the diesel oil raw material is treated, the reaction is shown as endothermic reaction, the raw oil treated by the hydrodewaxing process passes through a refined pour point depression catalyst composite bed layer to carry out hydrodesulfurization, hydrodenitrogenation, aromatic saturation and pour point depression reaction, and the hydrogenation reaction is shown as exothermic effect. In general, as the hydrogenation reaction appears to be an exothermic reaction, the process generates a temperature rise; the hydrodewaxing reaction is a selective molecular sieve cracking reaction, the heat effect is shown as an endothermic reaction, and the temperature is reduced in the process; the two catalysts are graded and filled, the respective heat release and heat absorption effects can be fully utilized, the comprehensive utilization of heat in the reaction process is realized, and the pour point depression effect is not influenced by the excessive temperature rise and temperature drop effects, so that the hot point temperature of the whole catalyst bed is reduced, the yield of diesel oil is ensured, and a better pour point depression effect is obtained. In addition, the invention adopts hydrofining catalyst for grading, and the diesel raw material is firstly contacted with the hydrodewaxing catalyst, thus having the characteristics of strong adaptability of raw material and low cost of catalyst.
2. Substantially the same effect is exhibited in each hydrogenation reaction zone in terms of process. So that in at least two hydrogenation reaction zones connected in series, the hydrogenation reaction has an optimization effect of comprehensive accumulation. Compared with the prior art, the invention effectively and reasonably utilizes the high-temperature point and the low-temperature point of the device from part to part only by grading combination and composite filling of the catalyst on the basis of not changing the flow of the device, thereby reducing the hot point temperature of the device, reasonably reducing the integral temperature gradient of the device and prolonging the service life of the catalyst. In addition, compared with the conventional hydrodewaxing combined process, the combination has the advantages that the heat in the reaction process is more reasonably utilized, and less or no cold hydrogen is added between the two reaction zones, so the consumption of the cold hydrogen and the gas consumption of a heating furnace are reduced, and the operation cost is saved.
Drawings
FIG. 1 is a schematic diagram of a graded fill in accordance with one embodiment of the process of the present invention; the operation mode of filling a single reactor in layers with two hydrogenation reaction zones is selected.
Detailed Description
The method for producing low freezing point diesel oil by using the catalyst grading technology is described in detail below with reference to the accompanying drawings.
As shown in FIG. 1, the diesel oil production method of the invention comprises the following steps:
raw oil 1 and hydrogen 2 are mixed at the inlet of a reactor and then enter the reactor 3, sequentially pass through a hydrodewaxing catalyst bed layer 4, a hydrofining and hydroupgrading heterogeneous dewaxing composite catalyst bed layer 5, a hydrodewaxing catalyst bed layer 6 and a hydrofining and hydroupgrading heterogeneous dewaxing composite bed layer 7 which are connected in series step by step from top to bottom to obtain a reaction effluent 8, the reaction effluent 8 is discharged from the bottom of the reactor, enters a high-pressure separator 10 after being injected with water 9, and a gas 11 obtained at the upper part passes through a recycle hydrogen compressor 12 and is mixed with new hydrogen 13 to obtain recycle hydrogen 14 which is used as make-up hydrogen or cold hydrogen; the liquid phase obtained from the middle and lower parts enters a low-pressure separator 17, the low-pressure gas 18 discharged from the upper part is subjected to subsequent treatment, and the liquid phase 20 obtained from the middle and lower parts enters a subsequent fractionation system; the acid water 15 discharged from the bottom of the high-pressure separator 10 is mixed with the acid water 19 discharged from the bottom of the low-pressure separator 17, and then the acid water treatment device is subjected to subsequent processing.
The process for producing low freezing point diesel oil of the present invention will be further described with reference to the following examples.
Comparative example 1
Comparative example 1 is a device for producing low freezing point diesel oil by adopting one-stage series process of hydrodewaxing, hydrofining and hydro-upgrading isomerization dewaxing. Comprises a hydrodewaxing catalyst bed layer and a refined dewaxing catalyst bed layer which is filled with a hydrofining catalyst and a hydro-upgrading heterogeneous dewaxing catalyst layer in a layered manner. Comparative example 1 the same grade of low pour point diesel was produced as in example 1. The used catalyst, feed oil, and diesel product congealing points were the same as in example 1. The operating results are shown in Table 2.
Comparative example 2
Comparative example 2 is a device for producing low freezing point diesel oil by adopting one-stage series process of hydrodewaxing, hydrofining and hydro-upgrading isomerization dewaxing. The yield of diesel oil is controlled to be basically the same as that of the example 1, and low freezing point diesel oil with different grades is produced. The yields of the catalyst, feed oil and diesel oil used in the comparative example were the same as those in example 1, and the catalyst loading was the same as that in comparative example 1. The operating results are shown in Table 2.
Example 1
The process flow shown in figure 1 is adopted, and the low freezing point diesel oil is produced by utilizing the grading series connection and mixed loading flow. The embodiment 1 comprises two hydrogenation reaction zones connected in series, the mixed volume ratio of the hydrofining catalyst and the hydro-upgrading isomerization pour point depressing catalyst in the refined pour point depressing catalyst composite bed layer of each reaction zone is 1:4, and the total using amount of the catalyst is the same as that of the comparative examples 1 and 2. The hydro-upgrading isomerization pour point depressing catalyst used in the example 1 is an FC-14 catalyst, the hydrofining catalyst is an FH-98 catalyst, the hydrodewaxing catalyst is an FDW-3 catalyst, and the catalysts are all commercial catalysts developed and produced by the comforting petrochemical research institute.
The operating conditions and test results are shown in Table 2.
Table 1 raw oil properties table.
| Item | Raw oil |
| Origin of origin | Normal-pressure and third-line diesel oil |
| Density (20 ℃ C.)/g-cm-3 | 0.8810 |
| Range of distillation range/. degree.C | 280～400 |
| Nitrogen/. mu.g.g-1 | 220 |
| Sulfur/. mu.g.g-1 | 1200 |
| Freezing point/. degree.C | 13 |
| Cetane number | 35.0 |
Table 2 process conditions and results.
| Comparative example 1 | Comparative example 2 | Example 1 | |
| Catalyst composition | FDW-3/(FH-98/FC-14) | FDW-3/(FH-98/FC-14) | FDW-3/(FH-98+FC-14) |
| Reaction pressure/MPa | 9.0 | 9.0 | 9.0 |
| Average reaction temperature/. degree.C | 375/380* | 367/380* | 375/381*/375/381* |
| LHSV/h-1 | 3.0/2.5** | 3.0/2.5** | 6.0/5.0**/6.0/5.0** |
| Inlet hydrogen to oil volume ratio | 600:1 | 600:1 | 600:1 |
| Diesel oil product pour point/° c | -37 | -22 | -35 |
| Yield of diesel oil, wt% | 73.7 | 82.0 | 81.8 |
| Diesel oil sulfur content/microgram g-1 | 30 | 33 | 29 |
| Cetane number of diesel oil | 39 | 41.9 | 39 |
| Maximum temperature of bed/. degree.C | 390 | 378 | 379 |
| Cold hydrogen consumption/baseline | 0.9 | 1.7 | 1.0 |
The average reaction temperature is the weighted average temperature of the refined pour point depressing catalyst bed layer;
volume space velocity is the volume space velocity of the refined pour point depression catalyst bed.
The embodiment can show that the method has the greatest characteristics that aiming at processing diesel raw materials, the method has the characteristics of extremely strong raw material adaptability and low catalyst cost, the produced low-condensation product has low impurity content and good desulfurization effect, and the condensation point of the raw materials can be reduced to the greatest extent under the condition of ensuring a certain diesel yield; in addition, the method has the characteristics of low hot spot temperature, long running period and low cold hydrogen consumption; for enterprises, the method has great advantages in manpower, material resources and energy consumption while completing the production task of high-quality products.
Claims (8)
1. A method for producing low freezing point diesel oil by utilizing a catalyst grading technology comprises the following steps:
the diesel raw material and hydrogen are mixed and then sequentially pass through at least two hydrogenation reaction zones which are connected in series, and the hydrogenation reaction zones sequentially comprise a hydrodewaxing catalyst bed layer and a refined dewaxing catalyst composite bed layer filled by mixing a hydrofining catalyst and a hydro-upgrading heterogeneous dewaxing catalyst according to the material flowing direction; separating and fractionating the reaction effluent obtained in the last hydrogenation reaction zone to obtain a low-freezing point diesel oil product; wherein,
the dry point of the diesel raw material is 350-440 ℃; in each hydrogenation reaction zone, the filling volume ratio of the hydrodewaxing catalyst bed layer to the refined dewaxing catalyst composite bed layer is 1: 10-10: 1; in the refined pour point depressing catalyst composite bed layer, the filling volume ratio of the hydrofining catalyst to the hydro-upgrading heterogeneous pour point depressing catalyst is 1: 10-10: 1;
the hydro-upgrading heterogeneous pour point depression catalyst comprises 29-50 w% of amorphous silica-alumina, 1-9 w% of modified β molecular sieve, 15-35 w% of VIB group metal, 3-9 w% of VIII group metal and 0-45 w% of porous refractory oxide, wherein the weight of the catalyst is taken as a reference, and SiO of the modified β molecular sieve is not included by 0w%2/Al2O3The weight ratio is 50-90, the average size of crystal grains is 0.1-0.5 micron, and the infrared acidity is 0.1-0.4 mmol/g.
2. A process according to claim 1, wherein the diesel fuel feedstock has a pour point above 0 ℃ and a nitrogen content below 2000 μ g/g.
3. The method according to claim 1, wherein the diesel fuel feedstock has a pour point of above 5 ℃ and a nitrogen content of 50 to 1200 μ g/g.
4. The process of claim 1 wherein the diesel feedstock has a nitrogen content of greater than 2000 μ g/g and is partially denitrified by passing the diesel feedstock through a bed of hydrodenitrogenation catalyst prior to passing the diesel feedstock through the bed of hydrodewaxing catalyst in the first hydrogenation zone.
5. The process of claim 1 wherein the hydrodewaxing catalyst bed is operated at conditions such that: the reaction pressure is 6.0-20.0 MPa, and the volume ratio of hydrogen to oil is 200: 1-1500: 1, and the volume space velocity is 0.1-10.0h-1The reaction temperature is 260-455 ℃.
6. The method as set forth in claim 1, characterized in that the operating conditions of the composite bed of the refined pour point depressing catalyst filled with the mixture of the hydrofining catalyst and the hydro-upgrading isomerization pour point depressing catalyst are as follows: the reaction pressure is 6.0-20.0 MPa, and the volume ratio of hydrogen to oil is 200: 1-1500: 1, the volume airspeed is 0.1-10.0 h-1The reaction temperature is 270-460 ℃.
7. The method as claimed in claim 1, wherein the hydrodewaxing catalyst takes a shape-selective cracking molecular sieve and a binder as carriers, and a VIB-group and/or VIII-group metal as a hydrogenation active metal component, and the weight of the catalyst is taken as a reference, the content of the hydrogenation active metal is 1% -16% in terms of oxide, the content of the shape-selective cracking molecular sieve is 50% -85%, and the content of the binder is 10% -40%.
8. The process as claimed in claim 1, wherein the hydrorefining catalyst comprises 8-28 w% of group VIB metal and 2-15 w% of group VIII metal, calculated as oxide, based on the weight of the catalyst, and/or active component of group VIB and/or group VIII metal, and alumina or siliceous alumina as carrier.
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| CN1417298A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Combined hydrogenation method of producing diesel oil with high cetane number and low solidifying point |
| CN1896187A (en) * | 2005-07-15 | 2007-01-17 | 中国石油化工股份有限公司 | Hydrogenation for producing high-bioctyl-value and low-freezing-point diesel oil |
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