CN1323139C - One-step super-depth method for removing arenes from natural gas synthetic oil - Google Patents
One-step super-depth method for removing arenes from natural gas synthetic oil Download PDFInfo
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- CN1323139C CN1323139C CNB2004100736312A CN200410073631A CN1323139C CN 1323139 C CN1323139 C CN 1323139C CN B2004100736312 A CNB2004100736312 A CN B2004100736312A CN 200410073631 A CN200410073631 A CN 200410073631A CN 1323139 C CN1323139 C CN 1323139C
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- 238000000034 method Methods 0.000 title claims abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 44
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 24
- 239000003345 natural gas Substances 0.000 title claims description 22
- 241001120493 Arene Species 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003350 kerosene Substances 0.000 abstract description 7
- 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
- 239000003921 oil Substances 0.000 description 54
- 238000005984 hydrogenation reaction Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 26
- 150000002431 hydrogen Chemical class 0.000 description 16
- 150000001336 alkenes Chemical class 0.000 description 13
- 239000002283 diesel fuel Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 238000007670 refining Methods 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 238000007790 scraping Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000004950 naphthalene Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000009795 derivation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009183 running Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- -1 actinide metals Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
一步超深度脱除天然气合成油中芳烃的方法，天然气合成油原料与氢气一起进入固定床反应器，在反应温度为200～400℃，总压为2.5～10.0MPa，氢分压为2.0～9.0MPa，氢油比为200～1000Nm3/m3，液时体积空速为1.0～10.0h-1的操作条件下与贵金属催化剂接触反应，反应后的油气混合物经分离、分馏得到目的产品，富含氢的气体则通过循环压缩机循环使用。该方法芳烃脱除率高达99w%以上，煤油和柴油产品的芳烃含量分别低于150μg/g和300μg/g，柴油馏分的十六烷值提高20多个单位。A one-step ultra-deep method for removing aromatics from natural gas-to-liquids. The raw materials of natural gas-to-liquids enter a fixed-bed reactor together with hydrogen. The reaction temperature is 200-400°C, the total pressure is 2.5-10.0 MPa, and the hydrogen partial pressure is 2.0-9.0 MPa, the ratio of hydrogen to oil is 200-1000Nm 3 /m 3 , and the liquid hourly volume space velocity is 1.0-10.0h -1 under the operating conditions of contacting and reacting with noble metal catalysts. After the reaction, the oil-gas mixture is separated and fractionated to obtain the target product, which is rich in Hydrogen-containing gas is recycled through a recycle compressor. The aromatics removal rate of the method is as high as over 99w%, the aromatics contents of kerosene and diesel products are respectively lower than 150 μg/g and 300 μg/g, and the cetane number of the diesel fraction is increased by more than 20 units.
Description
Technical field
The present invention relates to a kind of method with the refining hydrocarbon ils of hydrogen, more particularly, the present invention is a kind of method of hydrofining natural gas synthetic oil.
Background technology
Produce in the world wide with life the Fuel Demand amount is increased fast, national governments are also harsh day by day to the legislation of its quality from the angle of environmental protection and social sustainable development simultaneously, and producing the clean fuel that meets the environmental regulation requirement becomes the key that is related to the Petrochemical Enterprises survival and development.By the various cuts of traditional petroleum derivation, especially the middle runnings oil distillate is automobile-used and the main source of household fuel.Along with petering out of petroleum resources, various substitute energys obtain paying attention to and research just day by day, can satisfy the natural gas synthetic oil technology of severe rugged environment rules challenge and show one's talent, become a new way of new millennium production clean fuel as the efficient approach of gas utilization.
The technical process of Sweet natural gas system synthetic oil (GTL) comprising: removing sulphur, nitrogen etc. is CO and H to the natural gas conditioning step of the impurity of the toxic effect of follow-up building-up reactions catalyst system therefor, with conversion of natural gas
2The synthetic gas production stage and the Fischer-Tropsch synthesis step that synthetic gas is converted into hydro carbons such as straight-chain paraffin, alkene.
Above-mentioned production process makes Fischer-Tropsch synthetic reaction product have the compositing characteristic that is different from the fuel that obtains based on petroleum derivation.One of distinguishing feature is exactly to be substantially free of impurity such as sulphur, nitrogen in the synthetic product, following process to product is very favourable, the harshness that can satisfy the interior national governments of world wide or super low sulfur of organizing to set up even sulfur free fuel fully requires specification, but because the introducing of oxygen has determined wherein to contain a certain amount of oxygenatedchemicals in its building-up process, as alcohol, acid and ester etc., in follow-up hydro-upgrading, a certain amount of water can be generated, adverse influence can be produced the use of catalyzer; Second distinguishing feature that natural gas synthetic oil is formed is exactly that wherein olefin(e) centent is higher, because this production process is produced alkane by generating the alkene intermediate product.Oxidation not only himself takes place and superimposedly waits reaction in the existence of a large amount of alkene easily, but also can promote the oxidizing reaction of other hydro carbons, and generation has a strong impact on the products such as colloid of oil product use properties; Another compositing characteristic of natural gas synthetic oil is exactly that wherein aromaticity content is low.
Family heating furnace fuel (mainly being the coal diesel oil distillate) on the Northern Hemisphere especially Europe and Northeastern United States have the market requirement widely, and the production added value is higher; But its quality is had very strict requirement, especially aromaticity content, and wherein fire coal oil requires aromaticity content to be not more than 500 μ g/g, heating is not more than 1000 μ g/g with diesel oil requirement aromaticity content.Conventional oil deutero-coal diesel oil distillate is owing to contain more aromatic hydrocarbons and impurity such as sulphur, nitrogen, if produce heating furnace fuel by it, then need very harsh reaction conditions and complex treatment process, thereby investment and process cost are all very high, improper economically.Be applicable to that fine chemistry industry also needs aromaticity content is reduced to the utmost point low level with the low arene content solvent oil production of special solvent, raw material sources mainly are that catalytic reforming is raffinated oil and straight run oil, existing hydrogenation method takes off aromatic hydrocarbons technical process complexity, and is difficult to reduce to the level of tens μ g/g.
The content that natural gas synthetic oil contains a certain amount of alkene, be substantially devoid of impurity such as sulphur and nitrogen and aromatic hydrocarbons is low, it is the good raw material of producing ultralow aromaticity content product, producing the purpose product that obtains high yield under the demulcent reaction conditions relatively, have significant technical superiority and economic advantages.
USP5,868,921 disclose the one step process of the folded formula bed hydroprocessing handle hydrocarbon distillate cut that uses special-purpose hydrotreating catalyst, described method is included under the existence of hydrogen, make hydro carbons distillate cut flow through the folded formula bed of two kinds of hydrotreating catalysts of filling downwards successively, do not have the intermediate purification treatment step between two beds, this method can obtain having the liquid hydrocarbon oil product of the aromatic content and the content of heteroatoms of reduction.Preferred hydro carbons distillate cut requires its boiling range 10w% boiling point greater than 175 ℃, and the 90w% boiling point should be above 450 ℃.Wherein folded formula bed comprises that (a) handles the upper strata catalyst bed that catalyzer is formed by noble metal hydrogenation, used hydrotreating catalyst comprises that the content of appendix on acid refractory oxide carrier is that 0.1-15.0w% is selected from platinum, at least a precious metal in palladium and the iridium, with content be that 2-40w% is selected from tungsten, chromium, at least a metal in VIIB family metal and the actinide metals, described weight percent is represented based on the amount of the metal of total weight of carrier (down together), (b) handle lower floor's catalyst bed that catalyzer is formed by non-noble metal hydrogenation, used hydrotreating catalyst comprises that the content of appendix on the inorganic refractory oxide carrier of amorphous is that non-valuable VIII family's metal of 1-15w% and content are 1-25w%VIB family metal, also comprises the phosphorus of 0.1-5w%.This patented method is loaded precious metal (group vib metal) hydrotreating catalyst and conventional hydrotreating catalyst simultaneously in so-called " folded formula bed " lining, the using method that two kinds of catalyzer are different and may produce problems to the different requirements that process raw material in production application.
USP4,849,093 have proposed a kind of non-precious metal catalyst that adopts reaches the operational path that reduces aromaticity content in the raw material by the reaction division operation.In this operational path, through the reaction zone of two differential responses temperature, two reaction zones can comprise a plurality of reactors or beds respectively successively for stock oil and hydrogen.First reaction zone stock oil and hydrogen flow from bottom to top, catalyst system therefor amount more (accounting for more than the 60w% of total catalyst levels), and temperature of reaction is higher, obtains initial reaction rate faster in the hope of making the aromatic hydrocarbons saturated reaction; The reactant flow that first reaction zone comes out directly enters second reaction zone, this reaction zone gas-oil mixture flows from top to bottom, temperature of reaction is lower, it determines that foundation is to make about 10-20 times that the interior aromatic hydrogenation saturation rate constant of second reaction zone is this numerical value in first reaction zone, thereby the balance of the aromatic hydrogenation reaction that is subjected to Equilibrium limit is moved to helping the saturated direction of aromatic hydrocarbons.This method is applicable to the stock oil of aromaticity content higher (＞50%), and temperature of reaction is higher, and hydrocracking reaction has to a certain degree all taken place in two reaction zones.
USP5,435,907 disclose a kind of processing method of intermediate oil hydrogenation aromatics-removing.In fixed bed hydrogenation refining reaction device, be carried on nickel on the activity carbon carrier-tungsten catalyst sulfuration aftertreatment initial boiling point be 160～249 ℃, sulfur-bearing 0.5～5w%, nitrogenous 0.001～0.1w% contain aromatic hydrocarbons intermediate oil raw material.Operational condition: 299～454 ℃ of temperature of reaction (570～850 ), reaction pressure are that (600～2500psig), hydrogen-oil ratio is 178～891 Nm to 4.32～18MPa
3/ m
3(1000～5000SCFB).Under 380 ℃, 10.8MPa and hydrogen-oil ratio 712 (v/v) condition, can realize arene engaging scraping rate 70% (reducing to 9.6w%) from 32w%.
Above-mentioned the deficiencies in the prior art are that the aromaticity content of purpose product is still higher.
Summary of the invention
The objective of the invention is is providing a kind of at middle pressure with than carrying out super deeply hydrodearomatized method in to natural gas synthetic oil under the low reaction temperatures on the basis of existing hydro-upgrading technology.
Method provided by the invention comprises:
Raw material enters fixed-bed reactor with hydrogen, is 200～400 ℃ in temperature of reaction, and stagnation pressure is 2.5～10.0MPa, and the hydrogen dividing potential drop is 2.0～9.0MPa, and hydrogen-oil ratio is 200～1000 Nm
3/ m
3, volume space velocity is 1.0～10.0h during liquid
-1Operational condition under with the noble metal catalyst contact reacts; Reacted gas-oil mixture passes through the high and low pressure Separate System of Water-jet respectively, and the product liquid that obtains enters the reactor product that fractionating system obtains the different fractions section, and rich hydrogenous gas then recycles by recycle compressor.
The present invention is exactly the compositing characteristic that is different from mineral oil in conjunction with natural gas synthetic oil, on the basis of existing oil hydrogenation modifying process, natural gas synthetic oil is carried out the hydrogenation upgrading, realize removing to greatest extent the requirement of aromatic component, produce the products such as high-quality burning oil, diesel oil of ultralow aromaticity content.This method arene engaging scraping rate is up to more than the 99w%, and the aromaticity content of kerosene and diesel product is lower than 150 μ g/g and 300 μ g/g respectively, and the cetane value of diesel oil distillate improves more than 20 unit.
Embodiment
Method provided by the invention is so concrete enforcement:
Raw material enters fixed-bed reactor with hydrogen, is 200～400 ℃ in temperature of reaction, and stagnation pressure is 2.5～10.0MPa, and the hydrogen dividing potential drop is 2.0～9.0MPa, and hydrogen-oil ratio is 200～1000Nm
3/ m
3, volume space velocity is 1.0～10.0h during liquid
-1Operational condition under with the noble metal catalyst contact reacts; Reacted gas-oil mixture passes through the high and low pressure Separate System of Water-jet respectively, and the product liquid that obtains enters the reactor product that fractionating system obtains the different fractions section, and rich hydrogenous gas then recycles by recycle compressor.
Used raw material is a boiling range at 100～450 ℃ intermediate oil in present method, and natural gas via is crossed 100～450 ℃ of cuts in the synthetic oil that the fischer-tropsch building-up process obtains more precisely, is mainly kerosene and diesel oil distillate, and total aromaticity content is about 10w%.
Described noble metal catalyst is the VIII family noble metal catalyst that is carried on unformed aluminum oxide and/or the silica-alumina supports.Preferred platinum of hydrogenation metal active ingredient and/or palladium.
The reactor that only comes into operation in this invention is realized that olefin saturation and aromatic hydrogenation are reflected in the same reactor and is carried out by setting up two relatively independent conversion zones.Stock oil and hydrogen-containing gas enter behind the reactor at first together at first beds generation alkene heteroatomic hydrogenation and removing reactions such as saturated and oxygen, and the easily aromatics generation hydrogenation saturated reaction of reaction of part is also arranged simultaneously.Because heteroatomic hydrogenation and removing reaction such as olefin saturation and oxygen is carried out easily, and the olefin saturation thermal discharge is big, needed reaction conditions comparatively relaxes, therefore in the olefin saturation district, the catalyst system therefor amount is less, make reaction oil gas have bigger volume space velocity at this reaction zone, the degree difference that the reaction of bed upper, middle and lower different positions is carried out, thermal discharge also has very big difference, therefore the thermal discharge that needs the control reaction, guarantee the homogeneity of bed temperature of reaction, preventing that olefin saturation from concentrating acutely carries out, and emits a large amount of reaction heat, make bed temperature raise, high temperature of reaction can promote the generation of olefin saturation again, and vicious cycle like this causes the accident of beds overtemperature even temperature phenomenon out of hand to take place.
The aromatic hydrogenation reaction is the reversible thermopositive reaction that an amount of substance reduces.Rising along with temperature of reaction, the all corresponding increase of speed of reaction of positive reversed reaction, but, make the increment of dehydrogenation reaction speed greater than hydrogenation reaction, thereby cause its equilibrium constant to reduce rapidly because the hydrogenation activation energy of forward reaction (being hydrogenation reaction) is lower than its reversed reaction (dehydrogenation reaction).On the thermodynamics angle, under lower temperature, help the hydrogenation reaction of aromatic hydrocarbons, but its speed of reaction is relatively slow on reaction kinetics, react difficulty and carry out.Therefore, in second beds,, need to adopt comparatively harsh reaction conditions just in aromatic hydrocarbons saturated reaction district.Adopt relatively low temperature of reaction at this bed, the aromatic hydrogenation reaction is in the kinetic control zone in the temperature range that is adopted; The catalytic amount of filling is bigger, promptly adopt lower volume space velocity, the time that oil product contacts with catalyzer under the operational condition of low volume space velocity is longer, helps aromatic hydrocarbons and contacts comparatively fully with the activity of such catalysts center, guarantees fully carrying out of aromatic hydrocarbons saturated reaction.Between 1: 1～1: 15, will decide on the hydrocarbon composition situation of stock oil by this determination of ratio than scope for the catalyst volume of two beds.
The invention has the advantages that:
1 device flow process is simple.This method only adopts fixed-bed reactor, and technical process and hydro-refining unit are basic identical, can be formed by existing conventional hydro-refining unit transformation.
2, this method can be handled the different raw materials of forming flexibly, has stronger adaptability to raw material.The olefin(e) centent of being handled in the charging can be 10～50w%, and aromaticity content can be 1～15w%.
3, this method temperature of reaction is lower, and plant energy consumption is less.In temperature of reaction is 200～400 ℃, and stagnation pressure is 2.5～10.0MPa, and the hydrogen dividing potential drop is 2.0～9.0MPa, and hydrogen-oil ratio is 200～1000Nm
3/ m
3, volume space velocity is 1.0～10.0h during liquid
-1Concerning the balance of aromatic hydrogenation saturated reaction, such range of reaction temperature is in the kinetic control district, and is very favourable to the hydrogenation saturated reaction of aromatic hydrocarbons.
4, this processing method arene engaging scraping rate height can reach more than 99%.The kerosene product aromaticity content that obtains after the reactant flow cutting behind the hydrogenation can reach below the 150 μ g/g, and the aromaticity content in the diesel product can reach below the 300 μ g/g,, the cetane value of diesel oil distillate improves more than 20 unit.
5, this processing method has bigger flexibility of operation, can require according to the difference to reaction product to adjust reaction conditions, produces the middle runnings oil production of different aromaticity content specifications.
The following examples will give further instruction to present method, but therefore not limit present method.
Natural gas synthetic oil feedstock property in the embodiment is as shown in table 1.Total aromaticity content of this raw material is 7.6w%.Used noble metal catalyst is RLF-10 (being produced by Changling Refinery Chemical Industry Co., Ltd.'s catalyst plant) among the embodiment.
Embodiment 1
The natural gas synthetic oil raw material enters reactor with hydrogen, is that 8.0MPa, temperature of reaction are 220 ℃, volume space velocity is 0.8h during liquid in the hydrogen dividing potential drop
-1, hydrogen to oil volume ratio is 700Nm
3/ m
3Reaction conditions down and noble metal hydrogenation catalyst for refining RLF-10 contact reacts; Reacted logistics is isolated product liquid through high pressure, low-pressure gas-liquid separation system, and rich hydrogenous gas returns the reactor cycles utilization through recycle compressor.
Reaction conditions and main product property are listed in table 2.As can be seen from Table 2, the aromaticity content of reaction product is reduced to 621 μ g/g, and the arene engaging scraping rate that calculates thus is 99.18%.
Embodiment 2
The natural gas synthetic oil raw material enters reactor with hydrogen, is that 8.0MPa, temperature of reaction are 280 ℃, volume space velocity is 0.8h during liquid in the hydrogen dividing potential drop
-1, hydrogen to oil volume ratio is 700Nm
3/ m
3Reaction conditions down and noble metal hydrogenation catalyst for refining RLF-10 contact reacts; Reacted logistics is isolated product liquid through high pressure, low-pressure gas-liquid separation system, and rich hydrogenous gas returns the reactor cycles utilization through recycle compressor.
Reaction conditions and main product property are listed in table 2.As can be seen from Table 2, the aromaticity content of reaction product is reduced to 173 μ g/g, and the arene engaging scraping rate that calculates thus is 99.77%.
Reaction product is cut, and the kerosene(oil)fraction that obtains after the cutting and the aromaticity content of diesel oil distillate and main character are listed in table 3.The kerosene(oil)fraction aromaticity content is 92 μ g/g, and aromatic hydrocarbon content of diesel oil cut fraction is 239 μ g/g.
Embodiment 3
The natural gas synthetic oil raw material enters reactor with hydrogen, is that 6.4MPa, temperature of reaction are 260 ℃, volume space velocity is 0.8h during liquid in the hydrogen dividing potential drop
-1, hydrogen to oil volume ratio is 700 Nm
3/ m
3Reaction conditions down and noble metal hydrogenation catalyst for refining RLF-10 contact reacts; Reacted logistics is isolated product liquid through high pressure, low-pressure gas-liquid separation system, and rich hydrogenous gas returns the reactor cycles utilization through recycle compressor.
Reaction conditions and main product property are listed in table 2.As can be seen from Table 2, the aromaticity content of reaction product is reduced to 271 μ g/g, and the arene engaging scraping rate that calculates thus is 99.64%.
Embodiment 4
The natural gas synthetic oil raw material enters reactor with hydrogen, is that 8.0MPa, temperature of reaction are 280 ℃, volume space velocity is 1.6h during liquid in the hydrogen dividing potential drop
-1, hydrogen to oil volume ratio is 700Nm
3/ m
3Reaction conditions down and noble metal hydrogenation catalyst for refining RLF-10 contact reacts; Reacted logistics is isolated product liquid through high pressure, low-pressure gas-liquid separation system, and rich hydrogenous gas returns the reactor cycles utilization through recycle compressor.
Reaction conditions and main product property are listed in table 2.As can be seen from Table 2, the aromaticity content of reaction product is reduced to 440 μ g/g, and the arene engaging scraping rate that calculates thus is 99.42%; And 34.0 before the hydrogenation upgrading never of its cetane value is increased to 57.4.
Table 1 stock oil character
| Project | Natural gas synthetic oil |
| Density (20 ℃) | 0.7957 |
| Total sulfur, μ g/g | ＜1.0 |
| Total nitrogen, μ g/g | ＜1.0 |
| The bromine valency, gBr/100mL | 64.2 |
| Acidity, mgKOH/100mL | 1.8 |
| Alkylbenzene, w% | 7.27 |
| The naphthalene class, w% | 0.33 |
| Total aromatic hydrocarbons, w% | 7.60 |
| Boiling range (ASTM D86), ℃ | |
| Initial boiling point | 187 |
| 10％ | 201 |
| 30％ | 215 |
| 50％ | 226 |
| 70％ | 253 |
| 90％ | 297 |
| Do | 347 |
| Cutting back diesel oil distillate cetane value | 34.0 |
Table 2 processing condition and reaction product character
| Embodiment | 1 | 2 | 3 | 4 |
| Catalyzer | RLF-10 | RLF-10 | RLF-10 | RLF-10 |
| Processing condition | ||||
| The hydrogen dividing potential drop, MPa | 8.0 | 8.0 | 6.4 | 8.0 |
| Hydrogen-oil ratio, Nm 3/m 3 | 700 | 700 | 700 | 700 |
| Temperature of reaction, ℃ | 220 | 280 | 260 | 280 |
| Volume space velocity, h -1 | 0.8 | 0.8 | 0.8 | 1.6 |
| Product property | ||||
| Density, g/cm 3 | 0.7838 | 0.7820 | 0.7792 | 0.7812 |
| Alkylbenzene content, μ g/g | 560 | 173 | 271 | 440 |
| Naphthalene class content, μ g/g | 61 | |||
| Total aromaticity content, μ g/g | 621 | 173 | 271 | 440 |
Each cut main character of table 3 embodiment 2 reaction product cutting back
| Kerosene(oil)fraction | |
| Density, g/cm 3(20℃) | 0.7616 |
| Total aromaticity content, μ g/g | 92 |
| Aniline point, ℃ | 78.9 |
| Diesel oil distillate | |
| Density, g/cm 3(20℃) | 0.7981 |
| Condensation point, ℃ | ＜-50 |
| Alkylbenzene, μ g/g | 207 |
| Naphthalene class content, μ g/g | 32 |
| Total aromaticity content, μ g/g | 239 |
| Cetane value | 57.4 |
Claims (2)
1, an one-step super-depth removes the method for aromatic hydrocarbons in the natural gas synthetic oil, it is characterized in that raw material enters fixed-bed reactor with hydrogen, is 200～400 ℃ in temperature of reaction, and stagnation pressure is 2.5～10.0MPa, the hydrogen dividing potential drop is 2.0～9.0MPa, and hydrogen-oil ratio is 200～1000Nm
3/ m
3, volume space velocity is 1.0～10.0h during liquid
-1Operational condition under with the noble metal catalyst contact reacts; Reacted gas-oil mixture passes through the high and low pressure Separate System of Water-jet respectively, the product liquid that obtains enters the reactor product that fractionating system obtains the different fractions section, rich hydrogenous gas then recycles by recycle compressor, and described noble metal catalyst is the VIII family noble metal catalyst that is carried on unformed aluminum oxide and/or the silica-alumina supports.
2,, it is characterized in that described raw material is that natural gas via is crossed 100～450 ℃ of cuts in the synthetic oil that the fischer-tropsch building-up process obtains according to the method for claim 1.
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| CN1323139C true CN1323139C (en) | 2007-06-27 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849093A (en) * | 1987-02-02 | 1989-07-18 | Union Oil Company Of California | Catalytic aromatic saturation of hydrocarbons |
| JPH08283746A (en) * | 1995-02-14 | 1996-10-29 | Nippon Oil Co Ltd | Method for hydrogenating aromatic hydrocarbon in hydrocarbon oil and catalyst used therefor |
| CN1370814A (en) * | 2000-10-26 | 2002-09-25 | 中国石油化工股份有限公司 | Saturated loaded noble metal catalyst for distilling oil arenes and its prep. |
| CN1415705A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for producing good quality diesel oil |
-
2004
- 2004-08-31 CN CNB2004100736312A patent/CN1323139C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849093A (en) * | 1987-02-02 | 1989-07-18 | Union Oil Company Of California | Catalytic aromatic saturation of hydrocarbons |
| JPH08283746A (en) * | 1995-02-14 | 1996-10-29 | Nippon Oil Co Ltd | Method for hydrogenating aromatic hydrocarbon in hydrocarbon oil and catalyst used therefor |
| CN1370814A (en) * | 2000-10-26 | 2002-09-25 | 中国石油化工股份有限公司 | Saturated loaded noble metal catalyst for distilling oil arenes and its prep. |
| CN1415705A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for producing good quality diesel oil |
Non-Patent Citations (1)
| Title |
|---|
| 天然气制合成介绍 钱伯章，天然气工业，第22卷第4期 2002 * |
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