CN118685203A - Diesel oil blending component and preparation method thereof - Google Patents
Diesel oil blending component and preparation method thereof Download PDFInfo
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- 238000002156 mixing Methods 0.000 title claims abstract description 73
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 150000001336 alkenes Chemical class 0.000 claims abstract description 32
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 32
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 32
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 31
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- SHOVVTSKTTYFGP-UHFFFAOYSA-L butylaluminum(2+);dichloride Chemical compound CCCC[Al](Cl)Cl SHOVVTSKTTYFGP-UHFFFAOYSA-L 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 23
- 239000000306 component Substances 0.000 description 63
- 238000007710 freezing Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 12
- 238000009833 condensation Methods 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 230000005494 condensation Effects 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 230000008014 freezing Effects 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- -1 alkyl compound Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011280 coal tar Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 230000000881 depressing effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GZWBUHHBQIYWQI-UHFFFAOYSA-L tert-butyl(dichloro)alumane Chemical compound [Cl-].[Cl-].CC(C)(C)[Al+2] GZWBUHHBQIYWQI-UHFFFAOYSA-L 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a diesel oil blending component and a preparation method thereof, wherein the preparation method comprises the steps of carrying out polymerization reaction on a hydrocarbon-containing raw material under the catalysis of a catalyst, and washing and hydrotreating a reaction product to obtain the diesel oil blending component; the hydrocarbon-containing raw materials comprise a first olefin raw material and a second olefin raw material, wherein the first olefin raw material is at least one of C 4～C10 normal olefins, and the second olefin raw material is at least one of C 4～C10 isoolefins; the catalyst comprises a main catalyst and a phosphorus-containing compound. The diesel blending component obtained by the preparation method is also provided. The preparation method disclosed by the invention is simple in technological process, outstanding in product performance, low in raw material cost, high in yield and good in economy.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and relates to a production method of a diesel blending component.
Background
The condensation point is one of the main indexes of the diesel oil and is directly related to the low-temperature service performance of the diesel oil.
The research on the low-freezing diesel oil production technology is much published and reported at present, and a relatively mature industrialized technology exists. Wherein, CN103224810A describes a method for producing No. 10 to No. 35 low-freezing diesel oil by taking crude oil distillate oil as a raw material through a two-stage hydro-upgrading pour point depressing process. CN103805252a discloses a method for producing-35 # low-freezing diesel oil by a high-efficiency and low-cost hydrogenation pour point depressing process. CN1952042a describes a method for producing No. 30 low-freezing point diesel oil by hydro-upgrading-isomerism pour point depressing combined process using coal tar distillate as raw material. CN109666510a discloses a method for producing ultra-low-freezing diesel oil by using medium-temperature coal tar as raw material and through hydrocracking-hydro-upgrading combined process, the freezing point of the ultra-low-freezing diesel oil can reach the level of-60 ℃.
After researching the existing low-condensation-point diesel oil production technology in the field, the existing research mainly has the following common characteristics: based on the distillate oil raw material, the technical processes of hydrocracking, hydrofining, hydrodewaxing, isomerization dewaxing and the like are adopted to realize the chemical reaction processes of normal paraffin isomerization, polycyclic aromatic hydrocarbon saturation, heavy oil molecular cracking and the like, so that non-ideal components in the distillate oil are converted into ideal components. The problem of the prior researches is that the distillate oil of the prior researches is a complex hydrocarbon mixture, and contains a large amount of non-ideal components with high condensation point, for example, the crude oil and the coal tar distillate oil contain a large amount of polycyclic aromatic hydrocarbon, and more than 80% of the components of the heavy fraction of the Fischer-Tropsch synthetic oil are normal paraffins. Therefore, the upper limit achievable by process routes for producing low-freezing diesel on a distillate basis is limited; reflecting to actual industrial production, the difficulty of producing the No. 35 and No. 50 low-freezing diesel oil is relatively high, and a specific crude oil raw material is often required for processing and producing; or the production of low-grade low-freezing diesel oil can be realized by methods of tail cutting, blending aviation kerosene components and the like, but the method can reduce the combustion performance and stability of the diesel oil product.
Disclosure of Invention
Aiming at the problems in the existing low-freezing point diesel production process, in particular to the difficult problem that the quality of products is greatly limited by the influence of the properties of processing raw materials, through thorough and intensive research, a diesel blending component and a preparation method thereof are provided.
The technical scheme provided by the invention comprises the following aspects:
1. the invention provides a preparation method of a diesel blending component, which comprises the steps of carrying out polymerization reaction on a hydrocarbon-containing raw material under the catalysis of a catalyst, and washing and hydrotreating a reaction product to obtain the diesel blending component;
Wherein the hydrocarbonaceous feedstock comprises a first olefinic feedstock and a second olefinic feedstock, wherein the first olefinic feedstock is at least one of C 4～C10 n-olefins and the second olefinic feedstock is at least one of C 4～C10 isoolefins; the catalyst comprises a main catalyst and a phosphorus-containing compound; the molar ratio of the main catalyst to the phosphorus-containing compound is 1:0.003 to 0.2, preferably 1:0.01 to 0.03.
Further, in the above-mentioned method for producing a blended component for diesel oil, as a preferred embodiment, the phosphorus-containing compound is phosphotungstic acid and/or phosphomolybdic tungstic acid, preferably phosphotungstic acid.
Further, in the above method for preparing a diesel blending component, as a preferred embodiment, the main catalyst is one or a mixture of two or more of a metal-containing halide, a metal-containing alkyl halide, and a metal-containing alkyl compound, wherein the metal element is at least one of aluminum, iron, and titanium.
Further, in the above method for preparing a diesel blending component, as a preferred embodiment, the main catalyst may be one or more of aluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, n-butylaluminum dichloride, t-butylaluminum dichloride, triethylaluminum, ferric trichloride, and titanium tetrachloride; preferably one or more selected from aluminum chloride, diethyl aluminum chloride and triethyl aluminum.
Further, in the above method for preparing a diesel blending component, as a preferred embodiment, the first olefin feedstock is at least one of C 4～C6 normal olefins.
Further, in the above method for preparing a diesel blending component, as a preferred embodiment, the second olefinic feedstock is at least one of C 4～C6 isoolefins.
Further, in the above-described method for producing a diesel blending component, as a preferred embodiment, the first olefin feedstock includes an α -olefin (normal terminal olefin, normal olefin with an olefinic double bond at the terminal position) and a normal internal olefin (normal olefin with an olefinic double bond not at the terminal position).
Further, in the above-mentioned method for producing a diesel blending component, as a preferred embodiment, the mass fraction of α -olefin in the first olefin feedstock is 10% to 80%, preferably 25% to 75%, based on the total weight of the hydrocarbon feedstock; the mass fraction of normal internal olefins in the first olefin feedstock is 2% to 50%, preferably 5% to 40%.
Further, in the above-mentioned method for preparing a diesel blending component, as a preferred embodiment, the mass fraction of the second olefinic raw material is 2% to 50%, preferably 5% to 40%, based on the total weight of the hydrocarbonaceous raw material.
Further, in the above-mentioned method for producing a diesel blending component, as a preferred embodiment, the hydrocarbon-containing material may optionally contain a saturated alkane of C 4～C10, and the total mass of the alkane is not more than 50% of the total mass of the hydrocarbon-containing material, preferably not more than 40% of the total mass of the hydrocarbon-containing material.
Further, in the above-mentioned method for producing a diesel blending component, as a preferred embodiment, the molar ratio of the main catalyst in the catalyst to the olefin in the hydrocarbon-containing raw material is 1:20 to 200, preferably 1:70 to 150.
Further, in the preparation method of the diesel blending component, as a preferred embodiment, the polymerization temperature is 20 ℃ to 200 ℃, preferably 100 ℃ to 150 ℃; the pressure of the reaction is 1-30 MPa, preferably 2-10 MPa; the reaction time is 0.1 to 24 hours, preferably 0.5 to 8 hours.
Further, in the above method for preparing the diesel blending component, as a preferred embodiment, washing is generally water washing, the water washing temperature is generally controlled to be 20-80 ℃, and washing is carried out until the hydrogenation feeding index requirement is met.
Further, in the preparation method of the diesel blending component, as a preferred embodiment, the hydrotreating is to contact the reaction product with hydrogen in the presence of a hydrofining catalyst to perform hydrofining reaction, and the reaction effluent is distilled and separated under reduced pressure to collect the fraction with the initial distillation point of 150-200 ℃ and the final distillation point of 330-400 ℃ to obtain the diesel blending component.
Further, in the above-mentioned preparation method of the diesel blending component, as a preferred embodiment, the hydrofining reaction conditions are as follows: the reaction temperature is 100-350 ℃, preferably 150-250 ℃; the hydrogen partial pressure is 2.0-20.0 MPa, preferably 4.0-10.0 MPa; the volume airspeed is 0.1-2.5 h -1, preferably 0.5-2.0 h -1; the volume ratio of the hydrogen oil is 200-2000, preferably 500-1000.
Further, in the above method for preparing a diesel blending component, as a preferred embodiment, the hydrofining catalyst may be selected from commercial products or prepared by a method existing in the art, and in general, the hydrofining catalyst includes a carrier and an active metal component supported on the carrier, and the active metal component may be at least one of a group VIB metal and/or a group VIII metal, for example, one or more of molybdenum, nickel, cobalt, platinum, ruthenium, rhodium and palladium; the carrier is inorganic refractory metal oxide, and can be at least one of alumina, silica, magnesia, titania and zirconia.
The second aspect of the invention provides a diesel blending component obtained by the preparation method.
The third aspect of the invention provides low-freezing point diesel oil, which comprises diesel oil blending components obtained by the preparation method.
According to the invention, the existing problems in the field are analyzed and summarized, and in the field of low-freezing diesel oil, when the existing production process using distillate oil as a raw material is adopted, the condensation point of the diesel oil product is limited by the property of the raw material, and the condensation point is extremely difficult to reach below-50 ℃. If the high-purity low-condensation-point isoparaffin component is obtained through directional synthesis of hydrocarbons, the high-purity low-condensation-point isoparaffin component can be used as a blending component of special ultralow-condensation diesel oil, and the special performance of the high-condensation-point isoparaffin component has great application potential in the fields of alpine regions, polar scientific research, aerospace and the like. In the field of synthesizing isoparaffin, the technology for synthesizing isoparaffin by isobutene is developed more mature, and a diesel oil fraction product can be obtained, but the cetane number of the product is lower than 20 and the product cannot be used as a diesel oil component.
Compared with the prior art, the preparation process route of the diesel blending component provided by the invention mainly has the following technical effects and advantages:
1. In the research process, the condensation point and cetane number of paraffin molecules are positively correlated with the molecular weight, and are negatively correlated with the number of branched chains; in order to obtain the desired ultra low pour point diesel, the total number of branches is required to be moderate to reduce its negative impact on cetane number. The core of the invention is that the carbon number distribution and the branched chain length of the product, especially the branched chain number, are controlled by an innovative catalyst system and a raw material system, and the high-quality ultra-low-freezing diesel blending component with the condensation point lower than-70 ℃ and the cetane number higher than 40 is obtained. The hydrocarbon group of the product has single composition (isoparaffin), and the product is highly pure and almost free of high-condensation-point components such as aromatic hydrocarbon and the like and impurities such as sulfur, nitrogen and the like. The ultralow-freezing point diesel oil prepared by taking the ultralow-freezing point diesel oil as a core component is far superior to products produced by the existing process routes of distillate oil hydrogenation, isomerization pour point depression and the like in low-temperature performance indexes such as freezing point, cloud point and the like; the cetane number is higher, and the combustion performance is good; less harmful gas generated by combustion, safety and environmental protection, and is suitable for the requirement of continuously upgrading clean fuel.
2. The invention uses the low-carbon mixed hydrocarbon containing olefin as the raw material, and expands the raw material source in the field of low-freezing diesel oil; with the continuous advancement of petrochemical industry oil conversion, the low-carbon hydrocarbon byproducts produced by various related processes will grow greatly. The process route has the advantages of outstanding product performance, lower raw material cost, simple reaction process, high yield and good economy.
Detailed Description
In order to better illustrate the present invention, the operation and effects of the method of the present invention will be specifically described with reference to the following examples, which are not to be construed as limiting the scheme of the present invention.
The following examples and comparative examples were conducted under conventional conditions or conditions recommended by the manufacturer, where specific conditions were not noted.
In this context, the reagents or apparatus used are conventional products available commercially without the manufacturer's knowledge.
As used herein, the hydrofining catalyst is a Pt/Pd-Al 2O3 catalyst, the Pt content is 0.35wt% and the Pd content is 0.15wt%.
Example 1
The hydrocarbon-containing raw material is mixed hydrocarbon of C 4～C5, and the specific composition of the hydrocarbon-containing raw material is shown in Table 1. And synthesizing the ultra-low freezing point diesel oil blending component through a batch kettle reactor. The catalyst was 1mol of aluminum chloride and 0.01mol of phosphotungstic acid. The specific reaction conditions are shown in Table 2. The hydrofined product is distilled under reduced pressure, and the fraction with the boiling point of 180-360 ℃ is cut to obtain diesel oil blending components, and the indexes are shown in table 3.
Example 2
The hydrocarbon-containing raw material is mixed hydrocarbon of C 4～C5, and the specific composition of the hydrocarbon-containing raw material is shown in Table 1. And synthesizing the ultra-low freezing point diesel oil blending component through a batch kettle reactor. The catalyst is 0.5mol of aluminum chloride, 0.5mol of diethyl aluminum chloride and 0.03mol of phosphotungstic acid. The specific reaction conditions are shown in Table 2. The hydrofined product is distilled under reduced pressure, and the fraction with the boiling point of 180-360 ℃ is cut to obtain diesel oil blending components, and the indexes are shown in table 3.
Example 3
The hydrocarbon-containing raw material is mixed hydrocarbon of C 4～C5, and the specific composition of the hydrocarbon-containing raw material is shown in Table 1. And synthesizing the ultra-low freezing point diesel oil blending component through a batch kettle reactor. The catalyst was diethyl aluminum chloride 0.5mol, triethyl aluminum 0.5mol and phosphotungstic acid 0.02mol. The specific reaction conditions are shown in Table 2. The hydrofined product is distilled under reduced pressure, and the fraction with the boiling point of 180-360 ℃ is cut to obtain diesel oil blending components, and the indexes are shown in table 3.
Table 1 composition of hydrocarbonaceous feedstock in examples 1-3
TABLE 2 examples 1-3 reaction conditions
TABLE 3 Properties of the products of examples 1 to 3
| Example 1 | Example 2 | Example 3 | |
| Cetane number | 45 | 44 | 50 |
| Condensation point, DEG C | -80 | -78 | -75 |
| Cloud point, DEG C | -71 | -67 | -66 |
| Yield, wt% | 86.2 | 84.4 | 83.9 |
Example 4
The hydrocarbon-containing raw material is mixed hydrocarbon of C 5～C6, the specific composition of the hydrocarbon-containing raw material is shown in Table 4, and the total mole number of olefin is 100mol. And synthesizing the ultra-low freezing point diesel oil blending component through a batch kettle reactor. The catalyst was 1.0mol of aluminum chloride and 0.01mol of phosphotungstic acid. Wherein, the polymerization reaction condition is that the temperature is 115 ℃, the pressure is 5Mpa, the reaction time is 3h, and the hydrofining reaction condition is that: the temperature is 150 ℃, the hydrogen partial pressure is 6.0Mpa, the hydrogen-oil volume ratio is 600, and the airspeed is 2h -1. The hydrofining product is distilled under reduced pressure, and the fraction with the boiling point of 180-360 ℃ is cut to obtain the diesel oil blending component, the cetane number of the diesel oil blending component is 48, the condensation point of the diesel oil blending component is-76 ℃, the cloud point of the diesel oil blending component is-62 ℃, and the yield of the diesel oil blending component is 81.3wt%.
Table 4 composition of hydrocarbonaceous feedstock in example 4
| 1-Pentene | Isopentene | 2-Pentene | N-pentane | 1-Hexene | N-hexane |
| 30％ | 20％ | 10％ | 20％ | 10％ | 10％ |
Example 5
The hydrocarbon-containing raw material is mixed hydrocarbon of C 4～C10, the specific composition of the hydrocarbon-containing raw material is shown in table 5, and the total mole number of olefin is 100mol. And synthesizing the ultra-low freezing point diesel oil blending component through a batch kettle reactor. The catalyst was diethyl aluminum chloride 0.5mol, triethyl aluminum 0.5mol and phosphotungstic acid 0.01mol. Wherein, the polymerization reaction condition is that the temperature is 120 ℃, the pressure is 5Mpa, the reaction time is 2.5h, and the hydrofining reaction condition is that: the temperature is 200 ℃, the hydrogen partial pressure is 5.0Mpa, the hydrogen-oil volume ratio is 800, and the airspeed is 2h -1. The hydrofining product is distilled under reduced pressure, and the fraction with the boiling point of 180-360 ℃ is cut to obtain the diesel oil blending component, the cetane number of the diesel oil blending component is 52, the condensation point of the diesel oil blending component is-70 ℃, the cloud point of the diesel oil blending component is-57 ℃, and the yield of the diesel oil blending component is 79.6wt%.
TABLE 5 composition of hydrocarbonaceous feedstock in example 5
| 1-Butene | Isobutene (i-butene) | 2-Butene | 1-Hexene | 1-Octene | 1-Decene |
| 20％ | 30％ | 20％ | 10％ | 10％ | 10％ |
As can be seen from the analysis of the results of examples 1 to 5, when the catalyst, the raw materials and the process method are adopted, the yield of the diesel blending component (calculated by taking the olefin quality as the reference) is higher, the condensation point of the diesel blending component can be below-70 ℃, and the cloud point can be below-60 ℃, which indicates that the low-temperature performance of the blending component is extremely outstanding; meanwhile, the cetane number of the diesel blending component reaches more than 40, and the diesel blending component can meet the use requirement of the diesel blending component.
Comparative example 1
Substantially the same as in example 1, except that the composition of the hydrocarbonaceous feedstock was as follows: 45wt% of 1-butene, 25wt% of 2-butene, 5wt% of 1-pentene, 5wt% of n-butane, 10wt% of isobutane and 10wt% of n-pentane, and does not contain isoolefin. The reaction results are shown in Table 6.
Comparative example 2
Substantially the same as in example 2, except that the composition of the hydrocarbonaceous feedstock was as follows: 50wt% of 1-butene, 20wt% of isobutene, 5wt% of 1-pentene, 5wt% of n-butane, 10wt% of isobutane and 10wt% of n-pentane, and no n-internal olefin is contained. The reaction results are shown in Table 6.
Comparative example 3
Substantially the same as in example 3, except that the composition of the hydrocarbonaceous feedstock was as follows: 45wt% of 2-butene, 30wt% of isobutene, 5wt% of n-butane, 10wt% of isobutane and 10wt% of n-pentane, and no n-terminal olefin is contained. The reaction results are shown in Table 6.
Comparative example 4
Substantially the same as in example 1, except that the catalyst was only aluminum chloride. The reaction results are shown in Table 6.
Table 6 comparative example product properties
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Cetane number | 56 | 48 | 25 | 28 |
| Condensation point, DEG C | -55 | -66 | -75 | -63 |
| Cloud point, DEG C | -45 | -51 | -64 | -50 |
| Yield of diesel oil fraction, wt% | 61.0 | 68.2 | 80.5 | 23.1 |
Comparing the data in the table with the examples, the product of comparative example 1 has a higher congealing point than the examples and a lower yield than the examples; the diesel oil fraction yield of comparative example 2 and comparative example 4 is too low, and the cetane number is also low; the product of comparative example 3 has very low congealing point but too low cetane number to be used as a diesel blending component.
The foregoing description of the exemplary embodiments of the invention is not intended to limit the technical scope of the invention. The present invention is not limited to the above embodiments, and various modifications and adaptations may be made without departing from the spirit of the present invention.
Claims (16)
1. The preparation method comprises the steps of carrying out polymerization reaction on a hydrocarbon-containing raw material under the catalysis of a catalyst, and washing and hydrotreating a reaction product to obtain a diesel blending component; wherein the hydrocarbonaceous feedstock comprises a first olefin feedstock and a second olefin feedstock, wherein the first olefin feedstock is at least one of C 4～C10 n-olefins and the second olefin feedstock is at least one of C 4～C10 isoolefins; the catalyst comprises a main catalyst and a phosphorus-containing compound; the main catalyst is one or more than two of metal element-containing halide, metal element-containing alkyl halide and metal element-containing alkylate, the metal element is at least one of aluminum, iron and titanium, and the phosphorus-containing compound is phosphotungstic acid and/or phosphomolybdic tungstic acid.
2. The method for preparing a diesel blending component according to claim 1, wherein: the main catalyst is one or more than two of aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum chloride, diethyl aluminum chloride, n-butyl aluminum dichloride, tertiary butyl aluminum dichloride, triethyl aluminum, ferric trichloride and titanium tetrachloride; preferably one or more selected from aluminum chloride, diethyl aluminum chloride and triethyl aluminum.
3. The method for preparing a diesel blending component according to claim 1, wherein: the phosphorus-containing compound is phosphotungstic acid.
4. The method for preparing a diesel blending component according to claim 1, wherein: the molar ratio of the main catalyst to the phosphorus-containing compound is 1:0.003 to 0.2, preferably 1:0.01 to 0.03.
5. The method for preparing a diesel blending component according to claim 1, wherein: the first olefin feedstock is at least one of the C 4～C6 normal olefins.
6. The method for preparing a diesel blending component according to claim 1, wherein: the second olefinic feedstock is at least one of the C 4～C6 isoolefins.
7. The method for preparing a diesel blending component according to claim 1, wherein: the first olefin feedstock includes alpha olefins and normal internal olefins.
8. The method for preparing a diesel blending component according to claim 7, wherein: the mass fraction of alpha-olefin in the first olefin feed is 10-80%, preferably 25-75%, based on the total weight of the hydrocarbonaceous feed; the mass fraction of normal internal olefins in the first olefin feedstock is 2% to 50%, preferably 5% to 40%.
9. The method for preparing a diesel blending component according to claim 1, wherein: the mass fraction of the second olefin material is 2-50%, preferably 5-40% based on the total weight of the hydrocarbon-containing material.
10. The method for preparing a diesel blending component according to claim 1, wherein: the hydrocarbon-containing feedstock contains saturated alkanes of C 4～C10, the total mass of which is not more than 50wt%, preferably not more than 40wt% of the total mass of the hydrocarbon-containing feedstock.
11. The method for preparing a diesel blending component according to claim 1, wherein: the molar ratio of the main catalyst in the catalyst to the olefin in the hydrocarbon-containing raw material is 1:20-200, preferably 1:70-150.
12. The method for preparing a diesel blending component according to claim 1, wherein: the polymerization reaction temperature is 20-200 ℃, preferably 100-150 ℃; the pressure of the reaction is 1 to 30MPa, preferably 2 to 10MPa.
13. The method for preparing a diesel blending component according to claim 1, wherein: the hydrotreating is to contact the reaction product with hydrogen to carry out hydrofining reaction in the presence of hydrofining catalyst, the reaction effluent is distilled and separated under reduced pressure, and the fraction with the initial distillation point of 150-200 ℃ and the final distillation point of 330-400 ℃ is collected to obtain the diesel oil blending component.
14. The method for preparing a diesel blending component according to claim 1, wherein: the hydrofining reaction conditions are as follows: the reaction temperature is 100-350 ℃, preferably 150-250 ℃; the hydrogen partial pressure is 2.0-20.0 MPa, preferably 4.0-10.0 MPa; the volume airspeed is 0.1-2.5 h -1, preferably 0.5-2.0 h -1; the volume ratio of the hydrogen oil is 200-2000, preferably 500-1000.
15. A diesel blending component obtainable by the process of any one of claims 1 to 14.
16. A low pour point diesel comprising the diesel blending component of claim 15 or a diesel blending component obtained by the method of any one of claims 1-14.
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