CN1323140C - Two-step super-depth method for removing arenes from natural gas synthetic oil - Google Patents
Two-step super-depth method for removing arenes from natural gas synthetic oil Download PDFInfo
- Publication number
- CN1323140C CN1323140C CNB2004100736327A CN200410073632A CN1323140C CN 1323140 C CN1323140 C CN 1323140C CN B2004100736327 A CNB2004100736327 A CN B2004100736327A CN 200410073632 A CN200410073632 A CN 200410073632A CN 1323140 C CN1323140 C CN 1323140C
- Authority
- CN
- China
- Prior art keywords
- reaction
- oil
- hydrogen
- catalyst
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to a two-step super-depth method for eliminating aromatics in natural gas synthetic oil. The natural gas synthetic oil as a raw material and hydrogen are together supplied into a first fixed bed reactor to contact a hydrofining catalyst in a reaction; a reactant flow generated by the first reactor, which is not separated, is directly supplied into a second fixed bed reactor to contact an aromatic saturation catalyst in a reaction; the target product is obtained by separating and fractionating an oil-gas mixture after the reaction, and hydrogen-enriched gas is circularly used by a circulating compressor. The method has the advantage of high yield of the target product. The aromatic elimination rate is higher than 99 w%, the aromatic content of a coal oil product and the aromatic content of a diesel oil product are respectively lower than 100 mu g/g and 200 mu g/g, and the cetane value of a diesel oil fraction is improved 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
Enter 21st century; world's oil refining industry faces petroleum resources crisis of petering out and the dual-pressure that adopts environmentally friendly technology production clean fuel; can satisfy the natural gas synthetic oil technology of rigorous environment rules challenge day by day and just show one's talent, become a new way of new millennium production clean fuel as the efficient approach that utilizes of Sweet natural gas.
Adopt the Fischer-Tropsch process synthesis technique conversion of natural gas to be become cuts such as the kerosene that obtains behind the synthetic oil, diesel oil must just can become the liquid fuel that meets the engine service requirements through hydro-upgrading correspondingly.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 conventional mineral fuel.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, can satisfy the super low sulfur of formulation in the world wide even the harshness of sulfur free fuel fully and require 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 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, oxidation and reaction such as superimposed not only himself take place in the existence of a large amount of alkene easily, but also can promote the oxidizing reaction of other hydro carbons, generate the products such as colloid that have a strong impact on the 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, under relative demulcent reaction conditions, can produce and obtain ideal purpose product, and have the high remarkable advantage of purpose product yield, have bigger technical superiority and economic advantages.
USP5,068,025 to disclose a kind of be the saturated dual-step type processing method of aromatic hydrogenation in 93～482 ℃ the sulfur-bearing raw material with the cut scope, reaction raw materials and hydrogen are successively by two placed in-line hydrogenation catalyst beds.First reaction bed operational condition: temperature of reaction is that 316～399 ℃ of (600～750 ), stagnation pressures are that (650～2500psi), the hydrogen dividing potential drop is that (500～2200psig), hydrogen-oil ratio is 178～891Nm to 3.6～15.84MPa to 4.68～18.0MPa
3/ m
3(1000～5000SCF/BBL), volume space velocity is 0.1～5h during liquid
-1The hydrogenation activity component of catalyst system therefor is nickel, tungsten and the phosphorus that is carried on the gamma-alumina carrier, and the nickel metal content is 2～4w% (accounting for the weight percentage of catalyzer, down together), and W content is 20～30w%, and phosphorus content is 2～4w%.Reaction oil gas directly enters second beds without operations such as stripping, separation, this bed catalyst activity metal component is cobalt and/or nickel, molybdenum and the phosphorus that is carried on the alumina supporter, the hydrogenation metal component concentration is 2～4w%, and molybdenum content is 12～16w%, and phosphorus content is 2～4w%.Operational condition is that (600～2500psi), the hydrogen dividing potential drop is that (500～2200psig), hydrogen-oil ratio is 178～891Nm to 3.6～15.84MPa for 316～399 ℃ (600-750 ), 4.32～18.0MPa
3/ m
3(1000～5000SCF/BBL), volume space velocity is 0.1～5h during liquid
-1When aromatics conversion rate requires greater than 50% the time, the reaction pressure of this technology must be greater than 10.0MPa, and the construction cost of device and running operation expense are higher.
USP5,183,556 disclose a kind of two step hydrogenation aromatics-removing methods of diesel oil, the first step raw material and hydrogen-rich gas following current are by a kind of non-precious metal catalyst, remove gaseous fraction in the logistics that obtains by the first step by gas-liquid separation device then, liquid phase then entered for second step and new hydrogen counter current contact is carried out deep hydrogenation, and the second step catalyst system therefor is noble metal catalyst normally, also can be non-precious metal catalyst.Two step hydrogenation processes can be carried out in same reactor, also can carry out in two different reactors.Do not establish high pressure hot separator in the first step and between second step, the liquid phase of coming out from the first step directly entered for second step.This method can be produced the low sulfur and low aromatics diesel of aromaticity content less than 5～10v%.
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 178～891Nm 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%.
EP0699733 has proposed a kind of two-stage hydrogenation process of distillate, first section employing is the Hydrobon catalyst of active component with cobalt-molybdenum, nickel-molybdenum or nickel-cobalt, make the outlet sulphur content not be higher than 0.05w%, second section is adopted noble metal catalyst to reduce aromaticity content.Between one, two section, have two high pressure hot separators at least, and the bottom of two separators is all introduced hydrogen or hydrogen-rich gas and is carried out gas and carry.One, two sections high-temperature high-pressure separators that two one-tenth series are set are in order to remove dissolved hydrogen sulfide in one section liquid product more up hill and dale.This technology in depress operation, first section for feed sulphur content being taken off below 500 μ g/g, adopted higher temperature of reaction, enters the saturated performance of high aromatic hydrocarbons of utilizing noble metal catalyst after second section and operate under the relative low temperature.In the example that text provides, adopt above-mentioned flow process and catalyzer, at stagnation pressure 55kg/cm
2, first section 369 ℃ of temperature of reaction, air speed 4.5h
-1The time, feed sulphur content can be dropped to 0.033w%, aromatic hydrocarbons drops to 36w%, then through two intermediate heat high scores (with one section uniform temp, pressure are arranged) liquid product enters two sections and carries out the degree of depth and take off virtue behind the stripping, final product aromatic hydrocarbons can drop to 17w%, and sulphur content drops to 0.03w% (two sections sweetening poweies are very limited).
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 first fixed-bed reactor with hydrogen, is 150～300 ℃ 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 Hydrobon catalyst contact reacts; The reactant flow that first reactor generates directly enters second fixed-bed reactor without separating, and is 250～400 ℃ 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 0.5～5.0h during liquid
-1Operational condition under with the aromatic hydrocarbon saturation 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, 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 100 μ g/g and 200 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 first fixed-bed reactor with hydrogen, is 150～300 ℃ 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 Hydrobon catalyst contact reacts; The reactant flow that first reactor generates directly enters second fixed-bed reactor without separating, and is 250～400 ℃ 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 0.5～5.0h during liquid
-1Operational condition under with the aromatic hydrocarbon saturation 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, 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%.
In the present invention, two direct serial operations of fixed-bed reactor all comprise one or more beds.
First fixed-bed reactor adopt comparatively demulcent operational condition, temperature of reaction is lower, volume space velocity is higher during liquid, correspondingly the raw material treatment capacity is bigger, used Hydrobon catalyst is group vib and/or the VIII family non-precious metal catalyst that is carried on amorphous silicon aluminium and/or the alumina supporter, the preferred nickel of hydrogenation metal active ingredient of the used Hydrobon catalyst of the present invention.Because the temperature in whole reactor or the beds is lower, be about 150～250 ℃, the principal reaction of carrying out is the hydrogenation and removing reaction and the hydrogenation of olefins saturated reaction of oxygen, while is some aromatic hydrocarbons generation hydrogenation saturated reaction also, but does not have the generation of hydrocracking and/or heat cracking reaction basically.The principal reaction that this reaction zone takes place is thermopositive reaction, has a large amount of reaction heat to generate in the reaction process, and the temperature control of reactor or beds seems particularly important.
Operational condition is harsh relatively in second fixed-bed reactor, and volume space velocity is lower during liquid, and temperature of reaction is higher relatively, and the aromatic hydrocarbons saturated reaction mainly takes place.Described aromatic hydrocarbon saturation catalyst be carried on amorphous silicon aluminium or or alumina supporter on group vib and/or the non-precious metal catalyst or the noble metal catalyst of VIII family.Catalyzer can adopt the non-precious metal catalyst identical with first reaction zone, because the compositing characteristic of the stock oil of handling, be substantially free of impurity such as sulphur nitrogen in this reaction zone feeds, therefore also can adopt the noble metal catalyst of stronger platiniferous of aromatic hydrocarbons saturability and/or palladium.
The invention has the advantages that:
1. the device flow process is simple.Adopt two fixed-bed reactor serial operations, in first reactor, under the non-precious metal catalyst effect, the natural gas synthetic oil raw material is carrying out the hydrogenation and removing reaction of hydrogenation of olefins saturated (hydrogenation of olefins saturation exponent up to 99w% more than) and oxygenatedchemicals under the reaction conditions of low temperature, high-speed; In second reactor, reactant flow is carried out the aromatic hydrocarbons saturated reaction under at relative comparatively high temps, than the low-speed reaction conditions.This technical process is identical with conventional hydrofining flow process, can utilize in addition appropriate reconstruction of existing full scale plant, increase a reactor and accordingly heat-exchange equipment can implement.
2. temperature of reaction is lower, and plant energy consumption is less.The temperature of reaction of first reactor is 150～250 ℃, and volume space velocity can reach 3～5h
-1The temperature of reaction of second reactor is 250～350 ℃.Concerning 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.
3. this processing method arene engaging scraping rate height can reach more than the 99w%.The kerosene product aromaticity content that obtains after the reactant flow cutting behind the hydrogenation can reach below the 100 μ g/g, and the aromaticity content in the diesel product can reach below the 200 μ g/g, and the cetane value of diesel oil distillate improves more than 20 unit.
4. 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%.The used Hydrobon catalyst trade mark is RA-1A among the embodiment, and aromatic hydrocarbon saturation catalyst is the RLF-10 (being produced by Fushun petrochemical corporation (complex) catalyst plant and Changling Refinery Chemical Industry Co., Ltd.'s catalyst plant respectively) that contains non-noble metal RA-1A, contains precious metal.
Embodiment 1
Natural gas synthetic oil raw material and hydrogen enter first reactor, are that 8.0MPa, temperature of reaction are 220 ℃, volume space velocity is 3.0h during liquid in the hydrogen dividing potential drop
-1, hydrogen to oil volume ratio is 700Nm
3/ m
3Reaction conditions down and non-noble metal hydrogenation catalyst for refining RA-1A contact reacts; Reacted logistics directly enters second reactor without separating, and volume space velocity is 1.1h when the hydrogen dividing potential drop is 8.0MPa, 260 ℃ of temperature of reaction, liquid
-1, hydrogen to oil volume ratio is 700Nm
3/ m
3Reaction conditions down with non-noble metal hydrogenation catalyst for refining RA-1A reaction, reaction effluent passes through high pressure, the low-pressure gas-liquid separation system is isolated product liquid, rich hydrogenous gas returns two reactor cycles utilizations 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 0.09w%, and the arene engaging scraping rate that calculates thus is 98.82%.
Embodiment 2
Natural gas synthetic oil raw material and hydrogen enter first reactor, are that 8.0MPa, temperature of reaction are 220 ℃, volume space velocity is 3.0h during liquid in the hydrogen dividing potential drop
-1, hydrogen to oil volume ratio is 700Nm
3/ m
3Reaction conditions down and non-noble metal hydrogenation catalyst for refining RA-1A contact reacts; Reacted logistics directly enters second reactor without separating, and volume space velocity is 1.1h when the hydrogen dividing potential drop is 8.0MPa, 260 ℃ of temperature of reaction, liquid
-1, hydrogen to oil volume ratio is 700Nm
3/ m
3Reaction conditions down with noble metal hydrogenation catalyst for refining RLF-10 reaction, reaction effluent passes through high pressure, the low-pressure gas-liquid separation system is isolated product liquid, rich hydrogenous gas returns two reactor cycles utilizations 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 364 μ g/g, and the arene engaging scraping rate that calculates thus is 99.52%.
Embodiment 3
Natural gas synthetic oil raw material and hydrogen enter first reactor, are that 8.0MPa, temperature of reaction are 220 ℃, volume space velocity is 3.0h during liquid in the hydrogen dividing potential drop
-1, hydrogen to oil volume ratio is 700Nm
3/ m
3Reaction conditions down and non-noble metal hydrogenation catalyst for refining RA-1A contact reacts; Reacted logistics directly enters second reactor without separating, and volume space velocity is 1.1h when the hydrogen dividing potential drop is 8.0MPa, 280 ℃ of temperature of reaction, liquid
-1, hydrogen to oil volume ratio is 700Nm
3/ m
3Reaction conditions down with noble metal hydrogenation catalyst for refining RLF-10 reaction, reaction effluent passes through high pressure, the low-pressure gas-liquid separation system is isolated product liquid, rich hydrogenous gas returns two reactor cycles utilizations 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 86 μ g/g, and the arene engaging scraping rate that calculates thus is 99.89%.
To carry out fractionation from the product liquid that the low-pressure gas-liquid separation system obtains and obtain corresponding kerosene and diesel oil distillate, its main property analysis the results are shown in table 3.By data in the table 3 as seen, the total aromaticity content in the kerosene(oil)fraction is 35 μ g/g, and the total aromaticity content in the diesel oil distillate is 129 μ g/g, and 34.0 before the hydrogenation upgrading never of its cetane value is increased to 56.7.
Embodiment 4
Natural gas synthetic oil raw material and hydrogen enter first reactor, are that 8.0MPa, temperature of reaction are 220 ℃, volume space velocity is 3.0h during liquid in the hydrogen dividing potential drop
-1, hydrogen to oil volume ratio is 700Nm
3/ m
3Reaction conditions down and non-noble metal hydrogenation catalyst for refining RA-1A contact reacts; Reacted logistics directly enters second reactor without separating, and volume space velocity is 2.0h when the hydrogen dividing potential drop is 8.0MPa, 280 ℃ of temperature of reaction, liquid
-1, hydrogen to oil volume ratio is 700Nm
3/ m
3Reaction conditions down with noble metal hydrogenation catalyst for refining RLF-10 reaction, reaction effluent passes through high pressure, the low-pressure gas-liquid separation system is isolated product liquid, rich hydrogenous gas returns two reactor cycles utilizations 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 293 μ g/g, and the arene engaging scraping rate that calculates thus is 99.61%.
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 | RA-1A/ RA-1A | RA-1A/ RLF-10 | RA-1A/ RLF-10 | RA-1A/ RLF-10 |
| Processing condition | ||||
| The hydrogen dividing potential drop, MPa | 8.0 | 8.0 | 8.0 | 8.0 |
| Hydrogen-oil ratio, Nm 3/m 3 | 700 | 700 | 700 | 700 |
| Temperature of reaction, ℃ | ||||
| First reactor | 220 | 220 | 220 | 220 |
| Second reactor | 260 | 260 | 280 | 280 |
| Volume space velocity, h -1 | ||||
| First reactor | 3.0 | 3.0 | 3.0 | 3.0 |
| Second reactor | 1.1 | 1.1 | 1.1 | 2.0 |
| Product property | ||||
| Density, g/cm 3 | 0.7841 | 0.7824 | 0.7793 | 0.7802 |
| Alkylbenzene content, μ g/g | 830 | 364 | 86 | 293 |
| Naphthalene class content, μ g/g | 109 | - | - | - |
| Total aromaticity content, μ g/g | 939 | 364 | 86 | 293 |
Each cut main character of table 3 embodiment 3 reaction product cutting back
| Kerosene(oil)fraction | |
| Density, g/cm 3(20℃) | 0.7601 |
| Total aromaticity content, μ g/g | 35 |
| Aniline point, ℃ | 79.2 |
| Diesel oil distillate | |
| Density, g/cm 3(20℃) | 0.7982 |
| Condensation point, ℃ | ＜-50 |
| Alkylbenzene, μ g/g | 108 |
| Naphthalene class content, μ g/g | 21 |
| Total aromaticity content, μ g/g | 129 |
| Cetane value | 56.7 |
Claims (4)
1, a kind of two-step super-depth removes the method for aromatic hydrocarbons in the natural gas synthetic oil, it is characterized in that raw material enters first fixed-bed reactor with hydrogen, is 150～300 ℃ 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 Hydrobon catalyst contact reacts; The reactant flow that first reactor generates directly enters second fixed-bed reactor without separating, and is 250～400 ℃ 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 0.5～5.0h during liquid
-1Operational condition under with the aromatic hydrocarbon saturation 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, and rich hydrogenous gas then recycles by recycle compressor.
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.
3,, it is characterized in that described Hydrobon catalyst is to be carried on the group vib on unformed aluminum oxide or the silica-alumina supports and/or the non-precious metal catalyst of VIII family according to the method for claim 1.
4,, it is characterized in that described aromatic hydrocarbon saturation catalyst is to be carried on the group vib on amorphous silicon aluminium and/or the alumina supporter and/or the non-precious metal catalyst or the noble metal catalyst of VIII family according to the method for claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100736327A CN1323140C (en) | 2004-08-31 | 2004-08-31 | Two-step super-depth method for removing arenes from natural gas synthetic oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100736327A CN1323140C (en) | 2004-08-31 | 2004-08-31 | Two-step super-depth method for removing arenes from natural gas synthetic oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1743427A CN1743427A (en) | 2006-03-08 |
| CN1323140C true CN1323140C (en) | 2007-06-27 |
Family
ID=36138952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100736327A Active CN1323140C (en) | 2004-08-31 | 2004-08-31 | Two-step super-depth method for removing arenes from natural gas synthetic oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1323140C (en) |
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 contained in hydrocarbon oil and catalyst therefor |
| CN1351118A (en) * | 2000-10-30 | 2002-05-29 | 中国石油化工股份有限公司 | Medium-pressure hydrogenating process for removing arylhydrocarbon from diesel oil fraction |
| 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 CNB2004100736327A patent/CN1323140C/en active Active
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 contained in hydrocarbon oil and catalyst therefor |
| CN1351118A (en) * | 2000-10-30 | 2002-05-29 | 中国石油化工股份有限公司 | Medium-pressure hydrogenating process for removing arylhydrocarbon from diesel oil fraction |
| 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 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1743427A (en) | 2006-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101045884B (en) | Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil | |
| CN112143522B (en) | Hydrogenation method and system for production chemical material | |
| CN103059972B (en) | Combined hydrogenation method of producing chemical materials | |
| CN101747935B (en) | Method for producing light olefins and monocyclic aromatic hydrocarbons from heavy hydrocarbons | |
| CN101117596B (en) | Hydrogenation method capable of producing diesel oil and chemical materials flexibly | |
| CN101880549A (en) | Hydrogenation method for liquefied gas fraction | |
| CN103013559A (en) | Hydrocracking method for selective increasing of aviation kerosene yield | |
| CN104611056A (en) | Hydrotreatment method of low-temperature Fischer-Tropsch synthesis product | |
| CN102453535B (en) | Hydrocracking method for reforming material yield increase | |
| CN103059986B (en) | Hydrocracking method for producing chemical materials | |
| CN107987879A (en) | A kind of and method for hydrogen cracking of production heavy naphtha and tail oil | |
| CN104004541B (en) | A kind of preparation method of coal-based high arene underwater content stock oil | |
| CN100489067C (en) | Multistage hydrogeneration operation reaction chamber with intemediate flash section | |
| CN100425675C (en) | Hydrogenation method for producing catalytic reforming raw material | |
| CN101230291B (en) | Low consumption energy method for processing fischer-tropsch synthesis | |
| CN101177623A (en) | Hydro-cracking method for Fisher-Tropsch synthesis fuels | |
| CN109988609B (en) | Flexible shale oil hydrocracking process | |
| CN102344829B (en) | Combination method for residue hydrotreatment, catalytic cracking heavy oil hydrogenation and catalytic cracking | |
| CN112143521B (en) | Hydrogenation method and system for producing catalytic reforming raw material | |
| CN103305273B (en) | A kind of catalysis conversion method reducing coke and dry gas yied | |
| CN100448955C (en) | Hydrogenization method for deep desulfurization of gasoline, and lowering olefin | |
| CN1323140C (en) | Two-step super-depth method for removing arenes from natural gas synthetic oil | |
| CN111484875B (en) | Catalytic cracking method and reaction system | |
| CN109988635B (en) | Hydrotreatment and hydrocracking combined process | |
| CN109988625B (en) | Hydrofining and hydrocracking combined process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |