CN1417291A - Technological process of preparing diesel oil fraction selectively with Fischer-tropsch synthetic gas - Google Patents
Technological process of preparing diesel oil fraction selectively with Fischer-tropsch synthetic gas Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000002283 diesel fuel Substances 0.000 title claims description 111
- 230000008569 process Effects 0.000 title claims description 33
- 239000007789 gas Substances 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 238000010189 synthetic method Methods 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 10
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- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
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- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 229930195733 hydrocarbon Natural products 0.000 claims description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims description 23
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- 229910052799 carbon Inorganic materials 0.000 claims description 14
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- 239000007788 liquid Substances 0.000 claims description 11
- 150000003138 primary alcohols Chemical class 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
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- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 description 64
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 24
- 238000009835 boiling Methods 0.000 description 20
- 239000003921 oil Substances 0.000 description 14
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- 239000002808 molecular sieve Substances 0.000 description 9
- 238000011160 research Methods 0.000 description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
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- 150000001336 alkenes Chemical class 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000009508 confectionery Nutrition 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- -1 arene compound Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
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- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 244000144725 Amygdalus communis Species 0.000 description 1
- 235000011437 Amygdalus communis Nutrition 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020641 Co Zr Inorganic materials 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
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- 240000003133 Elaeis guineensis Species 0.000 description 1
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- WXOMTJVVIMOXJL-BOBFKVMVSA-A O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)OS(=O)(=O)OC[C@H]1O[C@@H](O[C@]2(COS(=O)(=O)O[Al](O)O)O[C@H](OS(=O)(=O)O[Al](O)O)[C@@H](OS(=O)(=O)O[Al](O)O)[C@@H]2OS(=O)(=O)O[Al](O)O)[C@H](OS(=O)(=O)O[Al](O)O)[C@@H](OS(=O)(=O)O[Al](O)O)[C@@H]1OS(=O)(=O)O[Al](O)O Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)OS(=O)(=O)OC[C@H]1O[C@@H](O[C@]2(COS(=O)(=O)O[Al](O)O)O[C@H](OS(=O)(=O)O[Al](O)O)[C@@H](OS(=O)(=O)O[Al](O)O)[C@@H]2OS(=O)(=O)O[Al](O)O)[C@H](OS(=O)(=O)O[Al](O)O)[C@@H](OS(=O)(=O)O[Al](O)O)[C@@H]1OS(=O)(=O)O[Al](O)O WXOMTJVVIMOXJL-BOBFKVMVSA-A 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- IOYNQIMAUDJVEI-BMVIKAAMSA-N Tepraloxydim Chemical compound C1C(=O)C(C(=N/OC\C=C\Cl)/CC)=C(O)CC1C1CCOCC1 IOYNQIMAUDJVEI-BMVIKAAMSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 150000001728 carbonyl compounds Chemical class 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
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- VLWBWEUXNYUQKJ-UHFFFAOYSA-N cobalt ruthenium Chemical compound [Co].[Ru] VLWBWEUXNYUQKJ-UHFFFAOYSA-N 0.000 description 1
- GNEMDYVJKXMKCS-UHFFFAOYSA-N cobalt zirconium Chemical compound [Co].[Zr] GNEMDYVJKXMKCS-UHFFFAOYSA-N 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
一种通过费托合成由合成气选择制备主要以柴油馏分烷烃的合成方法，该生产方法采用一段法，由合成气直接制备以柴油馏分烷烃为主的产物；合成气主要组成为H2和CO，并且H2/CO体积比为1.0～4.0；费托合成催化剂为含金属钴/活性炭载体催化剂；费托合成的反应条件为：反应温度为120～400℃，反应压力为0.05～10Mpa，合成气空速为100～5000h－1。利用该方法可得到柴油馏分产物为180－380℃馏分，该馏分按重量至少含有95％的烷烃，其异构烃与正构烃的比例在0.03至0.3范围内，硫和氮含量低于50ppm，不饱和烃含量低于2％，氧含量低于0.001至0.3％。A synthetic method for selective preparation of mainly diesel fraction alkanes from synthesis gas through Fischer-Tropsch synthesis. The production method adopts a one-stage method to directly prepare products mainly of diesel fraction alkanes from synthesis gas; the main components of synthesis gas are H2 and CO , and the H 2 /CO volume ratio is 1.0-4.0; the Fischer-Tropsch synthesis catalyst is a metal-containing cobalt/activated carbon carrier catalyst; The air velocity is 100~5000h -1 . Using this method, the diesel fraction product can be obtained as a 180-380°C fraction, which contains at least 95% alkanes by weight, the ratio of isohydrocarbons to normal alkanes is in the range of 0.03 to 0.3, and the content of sulfur and nitrogen is less than 50ppm , the unsaturated hydrocarbon content is less than 2%, and the oxygen content is less than 0.001 to 0.3%.
Description
Technical field
The invention provides a kind of be used for by Fischer-Tropsch synthetic with the synthetic gas be the raw material one-stage process directly optionally the straight-chain paraffin carbon number of preparation mainly concentrate on the Catalytic processes process of fraction of diesel oil 20 with interior and hydro carbons carbon number.
Background technology
The main component of associated gas is the lower carbon number hydrocarbons based on methane, because these hydrocarbon resourceses are away from the consumption market, the transportation of the Sweet natural gas of this part and utilization are just quite difficult, therefore the main at present indirect reformer technology that adopts Sweet natural gas, it is the GTL technology, so-called GTL technology transfers Sweet natural gas to liquid fuel exactly, promptly the natural gas via synthetic gas is converted into the core process of cleaning liquid fluid fuel (as gasoline, diesel oil, alcohols etc.) by Fischer-Tropsch synthesis (Fischer-Tropsch Synthesis).In recent years, the continuous increase of coal/Sweet natural gas proven reserve, the exhaustion day by day of petroleum resources makes the research in this field very active.Yet its efficient core that transforms remains and the relevant catalysis problem of fischer-tropsch synthetic catalyst research.
Strict day by day along with people's more and more dark and environmental regulation to the understanding of environment protection importance, low-sulfur, low nitrogen, the demand of diesel oil of hanging down aromatic hydrocarbons and low-heavy metal content are more and more big.Traditional from the improvement of petroleum resources by the technologies such as hydrogenation desulfurization and denitrogenation of oil, be difficult to satisfy specification of quality to high-quality diesel oil.The natural gas via synthetic gas is earlier by the synthetic long-chain heavy paraffin hydrocarbon (wax) that is converted into of Fischer-Tropsch, is converted into research report and the patent that the low nitrogen of low-sulfur hangs down the diesel oil distillate technical process of aromatic hydrocarbons high hexadecane value by hydrocracking or hydroisomerization again through cutting apart after and can finds in disclosed document.Still there is not bibliographical information but be the raw material one-stage process carbon number that directly optionally prepares straight-chain paraffin with the synthetic gas up to now in the 20 new catalytic processs that mainly concentrate on fraction of diesel oil with interior and hydro carbons carbon number.
In the research of nearly 80 years fischer-tropsch catalysts, people have found that Fe, Co and Ru are the effective active ingredients of fischer-tropsch catalysts, auxiliary elements such as Ru, Zr, K and Cu play an important role to activity, the stability of fischer-tropsch catalysts, and the characteristics of these a few class catalyzer are synthetic gas can be converted into the hydro carbons of wide region products distribution (as C under the Fischer-Tropsch operational condition
100More than).At present, precipitated iron fischer-tropsch catalysts and cobalt zirconium/silicon-dioxide fischer-tropsch catalysts adopt slurry attitude bed or fixed-bed process successfully to realize industrialization in the Fischer-Tropsch factory of the Fischer-Tropsch factory of South Africa Sosal and Dutch Shell company respectively, and Fischer-Tropsch high-carbon hydrocarbon (wax) product that the parallel-series hydroeracking unit is fastened iron system or cobalt is cracked into gasoline, diesel oil or lubricated wet goods related fluid fluid fuel and chemical.The rarer products distribution of research on laboratory or the pilot scale fischer-tropsch synthetic catalyst drops in the narrow carbon number (as C
20In) reported in literature, once the someone attempted making carrier loaded cobalt-base catalyst with molecular sieve, was used for synthetic oil product fuel, but found to have a large amount of aromatic hydrocarbons in oil-phase product, reduced the quality of petrol and diesel oil greatly.But select for use gac to make the synthetic C of cobalt-base catalyst of carrier
20The research of interior hydrocarbon also end appears in the newspapers and leads.Thereby, utilize two-stage method or multiple process that coal/natural gas via synthetic gas is converted into the complex process of liquid fuel, cost is higher, thereby because difficult and petroleum-based energy competition has to a certain degree limited coal/Sweet natural gas prepares the technology of gasoline or diesel oil by Fischer-Tropsch realization.Study the catalyzer of optionally directly synthetic or directed synthetic mesophase cut hydro carbons (diesel component), make synthetic gas be converted into liquid hydrocarbon fuel, simple for process, might develop earlier in 21st century produce coal/natural gas energy resource substitutes the catalyzer and the technology of petroleum resources.
It is that unstripped gas generates lower carbon number hydrocarbons (＜C through the Fischer-Tropsch reaction with the synthetic gas that USP.4478954 has reported a kind of
4) and pure iron/gac slurry attitude fischer-tropsch catalysts.Done following explanation about catalyzer: vector contg 20～90%, active ingredient iron level 5～50%, selection of auxiliary chromium, magnesium, its content 5～40%, reaction conditions are typical Fischer-Tropsch synthesis condition.
It is that feedstock production is mainly C with methyl alcohol or synthetic gas that USP.4542122 has invented a kind of
10 +Co～the Th/TiO of fraction
2Catalyzer.Patent also introduced by the high-carbon hydrocarbon that makes by fischer-tropsch reaction on this catalyzer further hydrotreatment make middle distillate diesel oil or aviation diesel oil etc.Done following explanation about catalyzer: carrier by Rutile:Anatase be about 3: 2～100: 1, Primary Catalysts Co:2～25%, Th:0.1～10%.Patent research is the result show, the working conditions of this catalyzer, 140～400psig, H
2: CO=2: 1～3: 1, V
SP=300～1500h
-1, 190～260 ℃, it is active and with high C that this catalyzer has very high methanol hydrogenation and co hydrogenation
10 +The advantage of selectivity of product.
It is that unstripped gas generates the Co-Zr/SiO that pyroparaffine is the master through the Fischer-Tropsch reaction with the synthetic gas that USP.4579986 has reported a kind of
2Fischer-tropsch catalysts, this catalyzer is C under typical fischer-tropsch conditions
5 +Selectivity can reach more than 82%.
Venter and Vannice are that the fischer-tropsch synthetic catalyst of carrier had research (J.Catal. to gac, 1987,103:450, Catal.Lett., 1990,7:219, J.Phys.Chem., 1992,96:9944), behind the carbonyl compound of dipping a certain amount of Fe, Mn, K on the gac, and behind hydrogen reducing, find that catalyzer has higher CO hydrogenation activity and C under typical fischer-tropsch conditions
2 =～C
4 =The selectivity of hydrocarbon, research simultaneously shows that all the adding of Mn/K auxiliary agent has improved the selective power of catalyzer to alkene significantly.
USP.6274029,5689031,5378348 grades have been invented the heavy synthetic oil of natural gas via synthetic gas by the fischer-tropsch reaction generation of non-water gas shift reation, separate after hydroisomerization is produced the new process and the reaction process of high-quality diesel oil and coproduction lubricating oil.But, do not see as yet based on cobalt metal at present being supported on the production method of gac as the direct combined diesel oil cut of catalyzer.
Summary of the invention
The object of the present invention is to provide that a kind of to be used for synthetic by Fischer-Tropsch be the Catalytic processes process that the preparation of material choice ground mainly concentrates on diesel oil distillate by synthetic gas.
Another object of the present invention is for above-mentioned technological process provides a kind of reactive system, to carry out above-mentioned reaction.
To achieve these goals, the invention provides a kind of synthetic by the main synthetic method of synthetic gas selection preparation with diesel oil distillate alkane by Fischer-Tropsch, it is characterized in that: this production method adopts one-stage process, by the product of the direct preparation of synthetic gas based on diesel oil distillate alkane; Synthetic gas mainly consists of H
2And CO.
Synthetic gas derive from Sweet natural gas, coal, oil field gas, coal-seam gas or hydro carbons be raw material gas making process gained mainly consist of H
2And CO, and H
2/ CO volume ratio is 1.0～4.0; Fischer-tropsch synthetic catalyst is catalyzer such as cobalt metal/absorbent charcoal carrier; Fischer-Tropsch synthetic reaction conditions is: 120～400 ℃, reaction pressure is 0.05～10Mpa, and the synthetic gas air speed is 100～5000h
-1
In addition, in the synthetic method of the invention described above, by the direct synthetic production method of the Fischer-Tropsch building-up process of the non-steam conversion of carrying out on the activated carbon supported cobalt-base catalyst.
In addition, in the synthetic method of the invention described above, directly synthetic diesel oil distillate product is a 180-380 ℃ of cut, this cut contains 95% alkane by weight at least, the ratio of its isomeric hydrocarbon and positive structure hydrocarbon is in 0.03 to 0.3 scope, sulphur and nitrogen content are lower than 50ppm, and unsaturated hydrocarbons content is lower than 2%, and oxygen level is lower than 0.001 to 0.3%.
In addition, in the synthetic method of the invention described above, directly the existence of the oxygen that this diesel oil distillate contains in the synthetic diesel oil distillate product is mainly with the form of high carbon number straight chain primary alcohol, and this straight chain primary alcohol is C
12And C
12Above alcohol, the cetane value of this oil product reaches about 60 to 70, and the weight content of nitrogen and sulphur is less than or equal to 15ppm at least in this oil product.
In addition, in the synthetic method of the invention described above, directly in the synthetic diesel oil distillate product in this oil product the weight content of nitrogen and sulphur be preferably lower than or equal 10ppm.
Being suitable for catalyst system of the present invention is by VIII family element, as, cobalt, iron or nickel are that main active element, particularly cobalt are that active element is with IVB family element, as Zr, Ti, or IIIB family metallic element, as La, Ce etc., be auxiliary agent, be carried on a kind of porous support, this carrier is optimum with gac, and this catalyzer is made up of main active ingredient, auxiliary agent and carrier three parts.Carrier can be selected almond gac, cocoanut active charcoal, oil palm gac, coal activated carbon for use.Preparation of catalysts can adopt soaks altogether or divides the method for soaking, and the nitrate of its metal is impregnated on the absorbent charcoal carrier under the condition of finding time, and airing at room temperature then at 80～90 ℃ of dry 1-8 hours, got final product at 110～120 ℃ of dry 1-10 hours at last earlier.The content of VIII family metal is preferably in 5～15wt% at 0.01-20%, and IVB family metal or IIIB family be as auxiliary agent, and its content is: with the molar ratio of VIIIB metal be about 1: 2～1: 20.Shown in its ideal catalyzer composed as follows:
Co，wt％???????7～25，
Zr，wt％???????0～6.5，
Ti，wt％???????0～6.5，
Ta，wt％???????0～2.0，
Ce，wt％???????0～3.0，
Ru，wt％???????0～1.0，
Gac, wt% 60～90
Specific surface area 800～1100m
3/ g
Pore volume 0.35～0.75ml/g
Bulk density 0.30～0.60g/ml
Be associated by the synthetic process of directly producing high-quality diesel oil distillate by the synthetic gas one-stage process of Fischer-Tropsch with the present invention, its fischer-tropsch synthetic catalyst preferably adopts non-steam conversion (promptly not having the water-gas shift activity) catalyzer, such as activated carbon supported cobalt-based or ruthenium-based catalyst or cobalt ruthenium mixed catalyst, than appropriate catalyst is cobalt-base catalyst, only catalyzer is activated carbon supported, and zirconium dioxide or titanium dioxide are the cobalt-base catalyst of auxiliary agent.This catalyzer at first reduces in the nitrogen atmosphere on fixed bed or paste state bed reactor, and its optimum reductive condition is the reduction temperature scope: 250～500 ℃; Reduction pressure range: 0.3～1.5Mpa; The space-time speed range of hydrogen: 100～1000h
-1The stir speed (S.S.) scope of paste state bed reactor: 400～1000 rev/mins.The only reaction conditions of Fischer-Tropsch synthesis is a range of reaction temperature: 120～350 ℃; Reaction pressure scope: 0.5～10.0Mpa; The space-time speed range of synthetic gas: 100～1500h
-1The stir speed (S.S.) scope of paste state bed reactor: 400～1000 rev/mins, the volume ratio scope of hydrogen/carbon monoxide in the synthetic gas: 1～3.
Fischer-Tropsch synthetic primary products are alkane, and the primary products that ruthenium-based catalyst produces are middle runnings, are C
10～C
20Straight-chain paraffin, and traditional cobalt-base catalyst are as Co/SiO
2, generally produce the heavy straight-chain paraffin, i.e. C
20 +Alkane, so cobalt-base catalyst is suitable for production wax product.But the Fischer-Tropsch synthesis oil phase product of the activated carbon supported cobalt-base catalyst of using among the present invention drops on C
5～C
21In the scope, mainly drop on C
10～C
19The straight-chain paraffin scope in, its reason is the shape selectivity in the duct of fischer-tropsch synthetic catalyst, has limited the further generation of wax, thereby makes product depart from the Schulz-Flory distribution.
In general, combined diesel oil has higher cetane value, usually up to 60, in addition up to 70, oilness, oxidative stability and other physical properties can both satisfy the particular requirement of pipeline transportation.
Synthetic diesel oil of the present invention can directly be used as high-quality diesel oil, or use with the hydro carbons blending in other low-grade diesel oil or the identical boiling spread, when using as blending agents, synthetic diesel oil consumption of the present invention can be relatively low, as 10% or more some more, although consumption is few, can improve the quality of concocted diesel oil greatly.Though synthetic diesel oil of the present invention can improve the character of nearly all various diesel product, ideal is the low-grade reformed diesel fuel product of blending, i.e. the diesel oil that hydrogenation catalyst cracking or thermo-cracking are produced.
Utilize the advantage of Fischer-Tropsch building-up process, the diesel oil distillate that is obtained has low-sulfur, the characteristics of low nitrogen and low aromatic hydrocarbons.These heteroatomic compounds are Fischer-Tropsch synthetic poisonous substances, have removed before the gas renormalizing preparing synthetic gas.And, this process do not produce aromatic hydrocarbon or under common condition operation the time do not have aromatic hydrocarbon produce.Because the growth of carbochain is undertaken by the alkene intermediate, so contain a spot of alkene in final product, the concentration of alkene is generally lower.Past, people wished once that Fischer-Tropsch last handling process synthetic and product is incorporated in the single operating unit and carried out, once attempting to adopt molecular sieve carried cobalt-base catalyst to carry out Fischer-Tropsch synthesizes, but because the duct shape selectivity of molecular sieve is difficult to play a role to long chain alkane, and the intermediate--alkene--of carbochain growth-in the carrier molecule sieve, be converted into arene compound, and this aromatic hydrocarbon will reduce the quality of diesel oil.The catalyzer that the present invention adopts is activated carbon supported cobalt-base catalyst, and the shape selectivity of gac has limited the generation of wax in the Fischer-Tropsch building-up process, and the alkene intermediate that carbochain increases is difficult to be converted into aromatic product at absorbent charcoal carrier.
Comprise that pureer and milder organic acid oxygenatedchemicalss also can produce in traditional Fischer-Tropsch building-up process, it is very low that employing catalyzer of the present invention produces oxygenatedchemicals, and mainly exist at aqueous phase, but content in water for being lower than 2%.Advantage of the present invention need not further to do hydrotreatment at the cut of generation diesel oil, can directly be used as diesel oil fuel.Not doing in the straight-chain paraffin of hydrotreatment, have only the oxygenatedchemicals of trace, mainly is the primary alconol class of straight chain.
Be considered to promote in the oxygenatedchemicals of diesel fuel lubricity that the intensity of its hydrogen bond is greater than the HYDROGEN BOND INTENSITY of hydrocarbon product (all cpds bonding strength data can be found) in standard database.Both difference are big more, and its lubrication is big more.Oxygenatedchemicals has lipophilic group and hydrophilic radical, and therefore, the lubricity of diesel oil increases.Optimum oxygenatedchemicals is the long-chain primary alconol, as C
12～C
24Straight chain primary alcohol.
When its oxygenatedchemicals was organic acid, well-known, organic acid had corrosive nature, but the organic acid growing amount is very micro-in the Fischer-Tropsch synthesis of non-steam conversion.Be difficult to infrared spectra and detect, therefore, its content will be lower than the oxygen of 15ppm.
The Fischer-Tropsch synthesis of non-water gas shift reation is characterized in making by product CO by the control reaction conditions
2Growing amount minimize.These reaction conditionss comprise the whole bag of tricks, carry out as dividing to depress at relatively low CO, that is to say, at H
2/ CO volume ratio is more than 1.7/1, and only scope is in 1.9/1～2.3/1 the scope.The carbochain growth factor is only to be 0.87.Only range of reaction temperature is 220～265 ℃, and the catalyst system of employing is only to be activated carbon supported cobalt-based or ruthenium-based catalyst.
The content of oxygenatedchemicals in the synthetic oil (in oxygen level in the anhydrous synthetic oil) is relatively less than the required minimum value of diesel fuel lubricity, also be, at least being higher than the more suitable oxygen level of 0.001%wt% (in oxygen level in the anhydrous synthetic oil) is 0.001～0.3% (in oxygen level in the anhydrous synthetic oil), and only oxygen level is 0.0025～0.3% (in oxygen level in the anhydrous synthetic oil).
The present invention also provides a kind of reactive system (equipment) that is used for above-mentioned Fischer-Tropsch synthesis, by the CO and the H of certain proper ratio
2Synthetic gas is from pipeline 1, and this gas is at first through interior dress silica gel, and the purification pipe 2 of 5A molecular sieve and gac purifies, its flow after preheater 4 is preheating to about 200 ℃, enters F-T synthesis reactor 5 by mass flowmeter 3 controls, the reaction hydrocarbon product is collected via product holding tank 6,7 and 8 respectively.Lighter hydrocarbons are difficult to condensation liquefaction in hot holding tank, and the product of 180-245 ℃ of cut is collected in the holding tank 6, and the product of 80-180 ℃ of cut is collected in the holding tank 7, and the product of 0-80 ℃ of cut is collected in the holding tank 8.And the heavy constituent cut that is higher than 245 ℃ still is stranded in the paste state bed reactor, can be periodically the heavy constituent product be extracted with whiteruss slurry attitude liquid (initial reaction stage) by a strainer 9 (the strainer micro-pore diameter is 50 μ m), catalyzer with still be stranded in the paste state bed reactor after liquid product separates after filtration.
In addition, in above-mentioned reactive system, reactor 5 is preferably paste state bed reactor 5.
Hydrogen and carbon monoxide synthetic gas (H
2/ CO=1.95/2.15) in paste state bed reactor, under the effect of activated carbon supported cobalt-base catalyst, at the alkane that can be converted into middle runnings.In temperature of reaction is 230～245 ℃, 2.0～2.5MPa, and linear velocity is 12～17.5 cels, carbochain growth factor α value is about 0.875.Fischer-Tropsch synthesizing alkanes series products separates by primary flash distillation by its different boiling point.Four kinds of cuts with different boiling ranges are respectively: 1) C
5 +The cut of 0～80 ℃ of boiling range, be referred to as the cold separating tank liquid of Fischer-Tropsch; 2) cut of 80～180 ℃ of boiling ranges is referred to as heating and separating jar liquid; 3) cut of 180～245 ℃ of boiling ranges is referred to as hot knock-out pot liquid; 4) heavy ends (250～380 ℃ of boiling ranges), this part product must come out by millipore filter (50 μ m) press filtration termly.Wherein the cut of 180～380 ℃ of boiling ranges accounts for more than 65% of total cut weight.By the following examples technology of the present invention is described further.
Description of drawings
Fig. 1 is typical process flow figure of the present invention.
Embodiment
Embodiment 1
Utilize the described technical process of Fig. 1, under following reaction conditions, react.
Production method of the present invention adopts one-stage process, by the product of the direct preparation of synthetic gas based on diesel oil distillate alkane.Synthetic gas mainly consists of H
2And CO, and H
2/ CO volume ratio is 1.0～4.0; Fischer-tropsch synthetic catalyst is containing metal cobalt/carried by active carbon body catalyst; Fischer-Tropsch synthetic reaction conditions is: temperature of reaction is 120～400 ℃, and reaction pressure is 0.05～10Mpa, and the synthetic gas air speed is 100～5000h
-1
In addition, in flow process shown in Figure 1, by the CO and the H of certain proper ratio
2Synthetic gas is from pipeline (1), this gas at first purifies through purification pipe (2), its flow is controlled by mass flowmeter (3), after preheater (4) preheating, enter F-T synthesis reactor (5), the reaction hydrocarbon product is collected via product holding tank (6), (7) and (8) respectively, and wherein the product of 180-245 ℃ of cut is collected in the holding tank (6), the product of 80-180 ℃ of cut is collected in the holding tank (7), and the product of 0-80 ℃ of cut is collected in the holding tank (8).And the heavy constituent cut that is higher than 245 ℃ still is stranded in the paste state bed reactor (5), can periodically heavy constituent product and whiteruss be starched attitude liquid (in initial reaction stage by a strainer (9), mainly be the heavy constituent product afterwards) extract together, catalyzer with still be stranded in the reactor (5) after liquid product separates after filtration.
Embodiment 2
The cut of 180～245 ℃ of boiling ranges of 40% (weight), this cut is from Fischer-Tropsch synthetic hot knock-out pot, heavy ends (250～380 ℃ of boiling ranges) with 60% (weight), this part product must come out by millipore filter (50 μ m) press filtration termly, mix the diesel oil fuel that obtains mutually, be referred to as diesel oil fuel A, therefore the boiling range of this blended diesel oil fuel is 180～380 ℃, diesel oil fuel A be among the present invention to be set forth by activated carbon supported cobalt-base catalyst by the synthetic directly representative of synthetic fully typical diesel oil fuel of Fischer-Tropsch.
Embodiment 3
The cut of 180～245 ℃ of boiling ranges of 45% (weight), this cut is from Fischer-Tropsch synthetic hot knock-out pot, heavy ends (250～380 ℃ of boiling ranges) with 55% (weight), this part product must come out by millipore filter (50 μ m) press filtration termly, mix the diesel oil fuel that obtains mutually, be referred to as diesel oil fuel B, therefore the boiling range of this blended diesel oil fuel is 180～380 ℃, and diesel oil fuel B is a representative example among the present invention.
Embodiment 4
Diesel oil fuel C and D are respectively two portions cuts that diesel oil fuel B is divided into through distillation, and wherein diesel oil fuel C represents 180～260 ℃ of cuts of diesel oil fuel B, and diesel oil fuel D then represents 260～380 ℃ of cuts of diesel oil fuel B.
Embodiment 5
50 gram diesel oil fuel B handle through 16 gram 8～12 order Si-Al molecular sieves (13X molecular sieve), and diesel oil fuel E is its treatment solution liquid fuel of gained after filtration, and this processing can remove alcohol and other oxygenatedchemicals wherein effectively.
Embodiment 6
Petroleum base diesel oil fuel after the diesel oil fuel F hydrotreatment, straight(-run) diesel distillate by about 40% catalytic cracking diesel oil cut and 60% is formed, be actually a kind of common commercial Dissel oil, its boiling range scope is 180～430 ℃, and contains sulphur (X diffraction mensuration) and 40%FIA (fluorescent indicator adsorption method) aromatic hydrocarbons of 655ppm.Diesel oil fuel F represents the object of reference of PetroChina Company Limited. of the present invention base diesel oil fuel.
Embodiment 7
Diesel oil fuel G is mixed by the diesel oil fuel B and the diesel oil fuel F of equivalent, should contain the total oxygen level of 590ppm among the diesel oil fuel G, the 90ppm boiling point be 260 ℃ of alcohols (GC/MS) wherein the total oxygen of 340ppm be primary alconol (
1H NMR, 180～380 ℃).Diesel oil fuel G has represented the example of concocted diesel oil that is used for combined diesel oil of the present invention and petroleum base diesel oil.
Embodiment 8
Diesel oil fuel A, the oxygenatedchemicals among B and the E (comprising organic acid and alcohol) by
1H NMR spectrum, IR, methods such as GC/MS are measured.Wherein
1H NMR spectrum is carried out on Bruker DRX-400, and the experiment of quantitative data is carried out by the following method, at first at room temperature is dissolved in CDCl
3In, pulse width is 2.9.mu.s, stops 60 seconds, scans 64 times.Trimethyl silane is as object of reference, and dioxane is interior mark.Primary alconol, secondary alcohol, the content of ester and acid directly by it at 3.6 (2H), 3.4 (1H), the peak area of 4.1 (2H) and 2.4 (2H) ppm and the comparison of internal standard substance and get.IR spectrographic experiment is carried out on Bruker EQUINOX 55 spectrographs, sample be pressed into the ingot sheet after KBr mixes mutually, scan through 4000 times that (resolving power is 0.3cm
-1) obtaining infrared data, the content of its carboxylic acid and ester is respectively by 1720 and 1738cm
-1Specific absorption measure.Being determined on the 5973N MS/6890GC instrument of GC/MS carried out.Selected m/z=31 (CH
3O
+) quasi-molecular ions is as the content of primary alconol, takes by weighing C
2-C
14, C
16And C
18Primary alconol and normal paraffin C
8-C
16Mixed solution is as external standard.The mensuration of alkene adopts bromine valency index method, and with reference to ASTM D2710, all analytical resultss are listed in table 1.In diesel oil fuel A and B, contain the straight chain primary alcohol of some amount, be mainly C
12-C
18Primary alconol.The existence of these alcohols is of great benefit to for the oilness of improving diesel oil.Molecular sieve is handled, as, diesel oil fuel E is one of method of a kind of effective elimination alcohols.All detect existence in all these diesel oil fuels less than oxygenatedchemicalss such as carboxylic acid and ester classes.
Table 1 diesel oil fuel A, B and molecular sieve are handled oxygenatedchemicals (alcohols, carboxylic acid esters) among the diesel oil fuel E of back
Content
Embodiment 9
| Measuring method | Diesel oil fuel A | Diesel oil fuel B | Diesel oil fuel E |
| Oxygen level in the carboxylic acid esters, ppm, IR | Do not have | Do not have | Do not have |
| ??C 5-C 18Oxygen level in the primary alconol, ppm, 1HNMR | Do not have | Do not have | Do not have |
| ??C 5-C 18Oxygen level in the primary alconol, ppm, GC/MS | ??6.3 | ????7.7 | Do not have |
| ??C 12-C 18Oxygen level in the primary alconol, ppm, GC/MS | ??4.3 | ????6.5 | Do not have |
| The alkene total amount, mmol/g (bromine valency index method) | ??0.008 | ????0.006 | Do not have |
Diesel oil fuel A-G all samples all adopts standard oilness evaluation assessment (BOCLE method) to consult ASTM D 5001 standards, the result collects in table 2, its data are the percentage ratio of the oilness of itself and standard reference diesel oil sample, wherein consult ASTM D 5001 with reference to the preparation of diesel oil sample.Diesel oil fuel A and B have preferable oilness.Diesel oil fuel E is the sample of diesel oil fuel B after molecular sieve 13X processing removes oxygenatedchemicals, and therefore, its oilness is relatively poor, shows the C of straight chain
5-C
24Primary alconol plays an important role for the oilness that improves diesel oil fuel B.Diesel oil fuel C and D represent two samples of diesel oil fuel B after 260 ℃ of cut cuttings respectively, and its boiling range is respectively 180～260 ℃ and 260～380 ℃.Contain the C that boiling point is lower than 260 ℃ among the diesel oil fuel C
5-C
11Straight chain primary alcohol, contain the C that boiling point is higher than 260 ℃ among the diesel oil fuel D
12-C
24Straight chain primary alcohol.Relatively and diesel oil fuel C, diesel oil fuel D has better oilness.These results show that clearly boiling range is at 260～380 ℃ C
12-C
24Straight chain primary alcohol play an important role for the oilness that improves stable hydrocarbon diesel oil.Diesel oil fuel F has oilness preferably as low-sulfur petroleum base diesel oil fuel, but slightly poorer than the oilness of diesel oil fuel B.To be diesel oil fuel B and diesel oil fuel F form in 1: 1 ratio blending diesel oil fuel G, and its oilness improves to some extent than diesel oil fuel F.These results show: directly synthetic alkyl B not only has hyperpure component, and has superior blending ability, can improve the performance of doctor negative petroleum base diesel oil fuel.
The lubricity of table 2 diesel oil fuel A-G relatively
| Diesel oil fuel | The oilness percentage ratio of reference standard diesel oil sample, % |
| ????A | ????91.8 |
| ????B | ????90.9 |
| ????C | ????43.7 |
| ????D | ????99.7 |
| ????E | ????35.6 |
| ????F | ????86.0 |
| ????G | ????87.4 |
Claims (10)
1. select preparation mainly with the synthetic method of diesel oil distillate alkane by Fischer-Tropsch is synthetic by synthetic gas for one kind, it is characterized in that:
(1) this production method adopts one-stage process, by the product of the direct preparation of synthetic gas based on diesel oil distillate alkane;
(2) synthetic gas mainly consists of H
2And CO, and H
2/ CO volume ratio is 1.0～4.0;
(3) fischer-tropsch synthetic catalyst is containing metal cobalt/carried by active carbon body catalyst;
(4) Fischer-Tropsch synthetic reaction conditions is: temperature of reaction is 120～400 ℃, and reaction pressure is 0.05～10Mpa, and the synthetic gas air speed is 100～5000h
-1
2. according to the described synthetic method of claim 1, it is characterized in that by the direct synthetic production method of the Fischer-Tropsch building-up process of the non-steam conversion of carrying out on the activated carbon supported cobalt-base catalyst.
3. according to the described synthetic method of claim 1, it is characterized in that direct synthetic diesel oil distillate product is a 180-380 ℃ of cut, this cut contains 95% alkane by weight at least, the ratio of its isomeric hydrocarbon and positive structure hydrocarbon is in 0.03 to 0.3 scope, sulphur and nitrogen content are lower than 50ppm, unsaturated hydrocarbons content is lower than 2%, and oxygen level is lower than 0.001 to 0.3%.
4. according to the described synthetic method of claim 3, it is characterized in that this diesel oil distillate contains in the direct synthetic diesel oil distillate product oxygen mainly with the form of high carbon number straight chain primary alcohol, this straight chain primary alcohol is C
12And C
12Above alcohol, the cetane value of this oil product reaches 60 to 70, and the weight content of nitrogen and sulphur is less than or equal to 15ppm in this oil product.
5. according to the described synthetic method of claim 4, it is characterized in that in the direct synthetic diesel oil distillate product that the weight content of nitrogen and sulphur is less than or equal to 10ppm in this oil product.
6. equipment that is used to implement the described synthetic method of claim 1-5 comprises:
CO and H by certain proper ratio
2Synthetic gas is from pipeline (1), this gas at first purifies through purification pipe (2), its flow is controlled by mass flowmeter (3), after preheater (4) preheating, enter F-T synthesis reactor (5), the reaction hydrocarbon product is respectively via product holding tank (6), (7) and (8) collect, wherein the product of 180-245 ℃ of cut is collected in the holding tank (6), the product of 80-180 ℃ of cut is collected in the holding tank (7), the product of 0-80 ℃ of cut is collected in the holding tank (8), and the heavy constituent cut that is higher than 245 ℃ still is stranded in the paste state bed reactor (5), can be periodically the heavy constituent product be extracted with whiteruss slurry attitude liquid by a strainer (9), catalyzer with still be stranded in the reactor (5) after liquid product separates after filtration.
7. according to the described equipment of claim 6, it is characterized in that reactor (5) is a paste state bed reactor (5).
8. according to claim 6 or 7 described equipment, it is characterized in that the fischer-tropsch synthetic catalyst that loads in the reactor (5) is cobalt metal/carried by active carbon body catalyst.
9. according to the described setting of claim 8, it is characterized in that the catalyzer that loads in the reactor (5) at first upward reduces in the nitrogen atmosphere at reactor (5), reductive condition is a reduction temperature: 250～500 ℃; Reduction pressure: 0.3～1.5Mpa; The space-time speed of hydrogen: 100～1000h
-1
10. according to the described setting of claim 7, it is characterized in that the stir speed (S.S.) of paste state bed reactor (5): 400～1000 rev/mins.
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| CN104263400B (en) * | 2014-08-22 | 2016-01-20 | 芜湖市纽泰知识产权信息咨询有限公司 | A kind of technique of methanol conversion |
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| CN104263400A (en) * | 2014-08-22 | 2015-01-07 | 赵锦玲 | A methanol conversion process |
| CN104152170A (en) * | 2014-08-25 | 2014-11-19 | 安徽工程大学 | Preparation method of diesel oil |
| CN106268816A (en) * | 2015-06-12 | 2017-01-04 | 中国科学院大连化学物理研究所 | Activated carbon supported cobalt-based synthetic oil catalyst and its preparation method and application |
| CN107099321A (en) * | 2017-05-03 | 2017-08-29 | 中为(上海)能源技术有限公司 | The method that expense opens up synthetic fuel product is produced using underground coal gasification(UCG) product gas |
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