CN115181588B - System and method for producing high-melting-point wax by Fischer-Tropsch synthesis of heavy products - Google Patents
System and method for producing high-melting-point wax by Fischer-Tropsch synthesis of heavy products Download PDFInfo
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- CN115181588B CN115181588B CN202110373912.3A CN202110373912A CN115181588B CN 115181588 B CN115181588 B CN 115181588B CN 202110373912 A CN202110373912 A CN 202110373912A CN 115181588 B CN115181588 B CN 115181588B
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 48
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 135
- 238000004821 distillation Methods 0.000 claims abstract description 79
- 238000002844 melting Methods 0.000 claims description 159
- 230000008018 melting Effects 0.000 claims description 155
- 239000002904 solvent Substances 0.000 claims description 86
- 238000000034 method Methods 0.000 claims description 47
- 239000002245 particle Substances 0.000 claims description 29
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 12
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 4
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 229940094933 n-dodecane Drugs 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 31
- 239000007921 spray Substances 0.000 abstract description 8
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 3
- 238000000638 solvent extraction Methods 0.000 abstract description 2
- 239000001993 wax Substances 0.000 description 155
- 239000000047 product Substances 0.000 description 116
- 238000000926 separation method Methods 0.000 description 36
- 238000002156 mixing Methods 0.000 description 30
- 239000000295 fuel oil Substances 0.000 description 22
- 238000001704 evaporation Methods 0.000 description 18
- 230000008020 evaporation Effects 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- 239000003921 oil Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003245 coal Substances 0.000 description 8
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000011085 pressure filtration Methods 0.000 description 6
- 238000000526 short-path distillation Methods 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 238000003828 vacuum filtration Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
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- 238000010992 reflux Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 naphtha Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
- C10G73/06—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of solvents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/40—Physical treatment of waxes or modified waxes, e.g. granulation, dispersion, emulsion, irradiation
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a system and a method for producing high-melting-point wax by Fischer-Tropsch synthesis of heavy products, comprising a reduced pressure distillation tower, a granulating system connected with a bottom discharge port of the reduced pressure distillation tower and a multistage extraction system connected with the granulating system; the multistage extraction system comprises an extractor and a solid-liquid separator; the granulating system is selected from one of a granulator or a spray granulating device. The method for producing the high-melting-point wax by using the Fischer-Tropsch synthesis heavy product adopts the conventional technical route of reduced pressure distillation coupled with solvent extraction, has mild operation conditions, avoids the technical requirement of high vacuum degree, has low equipment requirement, has not harsh requirement on the sealing performance of a pipeline, has large operation elasticity and easier engineering amplification, and is suitable for large-scale industrialized application.
Description
Technical Field
The invention relates to the field of Fischer-Tropsch synthesis, in particular to a system and a method for producing high-melting-point wax from a Fischer-Tropsch synthesis heavy product.
Background
The Fischer-Tropsch synthesis technology is a core technology of coal indirect liquefaction, and refers to heterogeneous hydrogenation of coal at high temperature to generate synthetic gas under the action of a solid catalyst and under proper reaction conditions to generate hydrocarbon mixtures (C) 1 ~C 100 ) And oxygen-containing compounds, can produce large-scale oil products such as liquefied gas, naphtha, diesel oil and the like, and can continuously produce target oil products after the heavy fraction is subjected to secondary pyrolysis.
Fischer-Tropsch wax is a heavy fraction of coal-based synthetic oil, and mainly comprises linear saturated alkane with relative molecular weight of 500-1000, and the carbon number distribution is generally C 12 ~C 120 . Compared with the traditional petroleum wax, the Fischer-Tropsch wax has the characteristics of high crystallinity, high melting point, narrow melting point range, low oil content, low penetration, low melt viscosity, high stability, low aromatic hydrocarbon content, almost no sulfur and nitrogen and other impurities, hardness, wear resistance and the like. The high-melting-point wax product is widely applied to the fields of candles, food packaging coatings, daily chemicals, PVC product processing lubricants, hot melt adhesives, plastic processing, printing ink and paint, bright wax, warm mix asphalt additives and the like, and the product value is as high as 1-3 ten thousand yuan/ton. Long-chain alkane in the Fischer-Tropsch synthesis heavy fraction is separated to produce a high-melting-point refined wax product with the melting point higher than 80 ℃, so that the raw material advantages of the Fischer-Tropsch synthesis oil can be fully exerted, and the economical efficiency of the Fischer-Tropsch synthesis process is improved.
Patents CN110066680A, CN103980940a and CN104673383a provide a method for producing high melting point refined wax by distillation separation of fischer-tropsch synthesis products by means of very high vacuum distillation. The common characteristics of the methods are that Fischer-Tropsch synthetic oil is subjected to multistage distillation separation under the ultimate vacuum of less than 50Pa and the distillation temperature of 120-320 ℃ to obtain the high-melting-point wax product. Even further, in order to obtain wax products with a melting point higher than 100 ℃, distillation at absolute pressures lower than 10Pa is required. Therefore, the process technology has great difficulty and high equipment requirement, the large-scale industrial application of tens of thousands of tons is difficult, and meanwhile, the ultrahigh-melting-point wax with the melting point of more than 105 ℃ and higher product purity is difficult to produce.
Patent CN110066680A discloses a fine separation method and a fine separation system for a Fischer-Tropsch wax crude product, wherein the raw material of the Fischer-Tropsch wax crude product enters a primary separation system, and is separated in a thin film evaporator at 220-260 ℃ under the absolute pressure of 10-50 Pa to obtain a 1# light phase product and a 1# heavy phase product; the No. 1 heavy phase product enters a secondary separation system, and is separated in a primary short-range distiller at the temperature of 230-270 ℃ and the absolute pressure of 0.5-10 Pa to obtain a No. 2 light phase product and a No. 2 heavy phase product; the 2# heavy phase product enters a three-stage separation system, and is separated in a two-stage short-range distiller at 240-280 ℃ under the absolute pressure of 0.5-10 Pa to obtain a 3# light phase product and a 3# heavy phase product; and (3) the 3# heavy phase product enters a four-stage separation system, and is separated in a three-stage short-path distiller at 240-290 ℃ under the absolute pressure of 0.5-10 Pa to obtain a 4# light phase product and a 4# heavy phase product.
However, the process is significantly characterized by subjecting the crude Fischer-Tropsch wax to thin film distillation or short path distillation at ultra-high vacuum and higher temperatures, and thus has problems such as: (1) The vacuum degree of the technical requirement is extremely high, the distillation area is large, the processing capacity of raw materials is limited, the technical requirement on equipment is high, the sealing performance of a pipeline is extremely high, the operation elasticity is low, the engineering amplification is difficult, and the large-scale industrial application is difficult; (2) Because the thin film distillation is limited by the distillation separation precision, the purity of the product is lower, and particularly, the product of the high-melting-point wax has wide carbon number distribution and melting temperature distribution; (3) The distillation process is carried out at high temperature, and the wax is required to be vaporized at high temperature, so that the energy consumption is relatively high; (4) Fischer-Tropsch wax is a long-chain alkane molecule, has the characteristic of easy cracking, and a small amount of olefin, oxygen-containing compound and other impurities existing in the raw material are easy to crack, coke formation and other chemical changes caused by heating in the high-temperature distillation process, so that the separation operation is influenced, the technical index of wax products is influenced, and especially the chromaticity of the wax products is poor; (5) Fischer-Tropsch wax is mainly composed of long-chain alkane molecules, has the characteristic of easy cracking, and the longer the alkane chain is, the higher the melting point is, and the lower the cracking temperature is, so that the temperature of thin film distillation cannot be excessively high, usually is lower than 280 ℃, and even in a extreme vacuum state, the wax product with the melting point exceeding 105 ℃ cannot be directly produced.
Disclosure of Invention
In view of the above problems in the prior art, it is an object of the present invention to provide a system for preparing a high melting point wax from a heavy fischer-tropsch synthesis product, which is capable of obtaining a high quality high melting point wax product by treating the heavy fischer-tropsch synthesis product using a reduced pressure distillation column, a granulation system and a multistage extraction system which are sequentially connected.
It is a further object of the present invention to provide a process for producing high melting waxes from Fischer-Tropsch derived heavy products.
It is a further object of the present invention to provide a high melting point wax product produced according to the method.
In order to achieve one of the above purposes, the technical scheme adopted by the invention is as follows:
a system for preparing high-melting-point wax from Fischer-Tropsch synthesis heavy products comprises a reduced pressure distillation tower, a granulating system connected with a bottom discharge port of the reduced pressure distillation tower and a multistage extraction system connected with the granulating system.
In some preferred embodiments of the present invention, the multistage extraction system has a stage number of 3 stages or more, preferably 3-5 stages.
In some preferred embodiments of the present invention, the multi-stage extraction system comprises an extractor and a solid-liquid separator. Wherein each stage of extraction system is provided with an extractor and a solid-liquid separator.
In some preferred embodiments of the present invention, the auxiliary equipment of the vacuum distillation column comprises a raw material heating furnace, a heat exchanger, a transfer pump, a drawn fraction condenser, a reflux pump and a fraction storage tank.
In some preferred embodiments of the present invention, the solid-liquid separator is selected from one of a filtration type solid-liquid separator or a centrifugal type solid-liquid separator.
In some preferred embodiments of the invention, the solid-liquid separator further comprises an extractant recovery unit; preferably, the extractant recovery unit is a flash evaporator.
In some preferred embodiments of the invention, the granulation system is selected from one of a granulator or a spray granulation apparatus.
In order to achieve the second purpose, the technical scheme adopted by the invention is as follows:
a process for producing a high melting point wax from a fischer-tropsch synthesis heavy product comprising:
s1, performing reduced pressure distillation on a Fischer-Tropsch synthesis heavy product, so as to separate high-melting-point crude wax with a melting point higher than 70 ℃;
s2, granulating the high-melting-point coarse wax to obtain coarse wax particles;
s3, carrying out primary extraction treatment on the crude wax particles by adopting a primary extraction solvent to obtain a primary raffinate and a primary extract, wherein the primary extract is subjected to solvent recovery treatment to obtain a primary high-melting-point wax product;
s4, carrying out secondary extraction treatment on the I-level raffinate by adopting a secondary extraction solvent to obtain a II-level raffinate and a II-level extract, wherein the II-level extract is subjected to solvent recovery treatment to obtain a II-level high-melting-point wax product;
s5, performing three-stage extraction treatment on the II-stage raffinate by using a three-stage extraction solvent to obtain a III-stage raffinate and a III-stage extract, wherein the III-stage extract is subjected to solvent recovery treatment to obtain a III-stage high-melting-point wax product.
In some preferred embodiments of the invention, further comprising S6, subjecting the III-stage raffinate to a four-stage extraction process using a four-stage extraction solvent to yield a IV-stage raffinate and a IV-stage extract.
According to the invention, five-stage extraction solvent can be used for carrying out five-stage extraction treatment on the IV-stage raffinate to obtain V-stage raffinate and V-stage extract, and the like until the production requirement is met.
According to the invention, the III-level extract can be directly distilled, and the IV-level high-melting-point wax product with the melting point range of 105-135 ℃ can be obtained after the solvent is recovered.
According to the invention, in the step S1, the Fischer-Tropsch synthesis heavy product is subjected to reduced pressure distillation, and the high-melting-point crude wax with the melting point higher than 70 ℃ is separated, and meanwhile, the low-melting-point cerate with the melting point range lower than 50 ℃ and the medium-low-melting-point wax with the melting point range of 50-70 ℃ can be obtained.
In some preferred embodiments of the present invention, reduced pressure distillation may be performed in a reduced pressure distillation column to obtain high melting point crude wax at the bottom outlet, middle and low melting point wax at the middle side of the column, and low melting point wax at the top outlet.
In some preferred embodiments of the present invention, in step S1, the operating conditions of the reduced pressure distillation include: the absolute pressure is 100 Pa-5000 Pa; and/or the temperature of the bottom of the tower is 200-350 ℃.
In some preferred embodiments of the present invention, in step S1, the operating conditions of the reduced pressure distillation include: the absolute pressure is 100 Pa-2000 Pa; and/or the temperature of the bottom of the tower is 200-310 ℃.
In some preferred embodiments of the present invention, in step S1, the operating conditions of the reduced pressure distillation include: the absolute pressure is 100 Pa-1000 Pa.
The purpose of carrying out reduced pressure distillation on the Fischer-Tropsch synthesis heavy product is to cut high-melting-point wax coarse wax with proper melting point from the Fischer-Tropsch synthesis heavy product as a raw material for finely separating the high-melting-point wax, thereby ensuring the stability of the raw material in the classifying extraction process. Meanwhile, a byproduct of low-melting-point cerate with a melting point lower than 50 ℃ and medium-low-melting-point wax with a melting point of 50-70 ℃ is produced in the Fischer-Tropsch synthesis heavy product.
In some preferred embodiments of the invention, the fraction of the Fischer-Tropsch heavy product is cut by distillation under reduced pressure at a temperature greater than 480 ℃.
In some preferred embodiments of the invention, the fraction of the Fischer-Tropsch synthesis heavy product is cut by reduced pressure distillation at a temperature of greater than 500 ℃.
In some preferred embodiments of the present invention, in step S2, the particle size of the coarse wax particles is less than 1mm, preferably 0.03mm to 0.15mm, more preferably 0.038mm to 0.125mm, and even more preferably 0.045mm to 0.1mm.
The high-melting-point wax coarse wax is granulated, so that the subsequent extraction and solid-liquid separation are convenient. The inventors of the present application have found that smaller particle size is more advantageous for extraction but disadvantageous for solid-liquid separation. In view of the above, the particle diameter of the coarse wax particles is preferably set to 0.045mm to 0.1mm.
In some preferred embodiments of the present invention, the primary extraction solvent, the secondary extraction solvent, the tertiary extraction solvent and the quaternary extraction solvent are the same or different and are each independently selected from one or more of saturated hydrocarbons having a boiling point range of 50 ℃ to 220 ℃, esters, alcohols, fischer-Tropsch synthesis light oil fractions having a distillation range of 50 ℃ to 220 ℃ and a saturated hydrocarbon content of greater than 60%, naphtha having a distillation range of 50 ℃ to 220 ℃, and petroleum ether having a distillation range of 60 ℃ to 120 ℃.
In some preferred embodiments of the present invention, the primary extraction solvent, the secondary extraction solvent, the tertiary extraction solvent and the quaternary extraction solvent are the same or different and are each independently selected from one or more of saturated hydrocarbons having a boiling point range of 60 ℃ to 220 ℃, esters, alcohols, fischer-Tropsch synthesis light oil fractions having a distillation range of 50 ℃ to 220 ℃ and a saturated hydrocarbon content of greater than 60%, naphtha having a distillation range of 50 ℃ to 220 ℃, and petroleum ether having a distillation range of 60 ℃ to 120 ℃.
In some preferred embodiments of the present invention, the saturated hydrocarbon is selected from at least one of n-hexane, cyclohexane, n-heptane, isoheptane, methylcyclohexane, n-octane, isooctane, n-decane, isodecane, n-dodecane, and n-hexadecane.
In some preferred embodiments of the present invention, the esters are selected from at least one of methyl acetate, ethyl propionate, butyl acetate, isobutyl acetate, isopropyl acetate, and ethyl butyrate.
In some preferred embodiments of the present invention, the alcohol is selected from at least one of ethanol, isopropanol, butanol, pentanol, hexanol, ethylene glycol, and propylene glycol.
In some preferred embodiments of the present invention, in step S3, the operating conditions of the primary extraction process include: the temperature is 60-90 ℃, preferably 70-90 ℃; the absolute pressure is 0.08-0.5 MPa; the time is 10 min-120 min.
In some preferred embodiments of the present invention, the mass ratio of the slack wax particles to the primary extraction solvent is (1-8): 1, preferably (1.1-8): 1.
In some preferred embodiments of the present invention, in step S4, the operating conditions of the secondary extraction process include: the temperature is 70-100 ℃, preferably 80-100 ℃; the absolute pressure is 0.08-0.5 MPa; the time is 10 min-120 min.
In some preferred embodiments of the invention, the mass ratio of the I-stage raffinate to the secondary extraction solvent is (1-8): 1, preferably (1.1-8): 1.
In some preferred embodiments of the present invention, in step S5, the operating conditions of the three-stage extraction process include: the temperature is 100-130 ℃; the absolute pressure is 0.08-0.5 MPa; the time is 10 min-120 min.
In some preferred embodiments of the invention, the mass ratio of the stage II raffinate to the tertiary extraction solvent is (1-8): 1, preferably (1.1-8): 1.
In some preferred embodiments of the present invention, the grade I extract, the grade II extract, and the grade III extract are distilled respectively, and the solvent is recovered to obtain a grade I high melting point wax product, a grade II high melting point wax product, and a grade III high melting point wax product having melting point ranges of 60 ℃ to 90 ℃, 70 ℃ to 100 ℃, and 100 ℃ to 130 ℃, respectively; preferably, the conditions of the distillation treatment include: the temperature is 100-250 ℃; the absolute pressure is 10 KPa-100 KPa.
According to the present invention, the recovered solvent can be recycled.
In some preferred embodiments of the invention, the Fischer-Tropsch synthesis heavy product may be subjected to a pre-heat treatment prior to the reduced pressure distillation operation described in step S1. The conditions of the preheating treatment are as follows: and heating the Fischer-Tropsch heavy product to 200-310 ℃ and then sending the Fischer-Tropsch heavy product into a reduced pressure distillation tower.
In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:
a high melting point wax product made in accordance with the method of any of the preceding embodiments, the high melting point wax product comprising at least one of a grade I high melting point wax product, a grade II high melting point wax product, and a grade III high melting point wax product, and the high melting point wax product having an oil content of less than 0.8wt%.
A high melting point wax product made in accordance with the method of any of the preceding embodiments, the high melting point wax product comprising at least one of a grade I high melting point wax product, a grade II high melting point wax product, a grade III high melting point wax product, and a grade V high melting point wax product, and the high melting point wax product having an oil content of less than 0.8wt%.
In the invention, the melting point ranges of the I-level high-melting point wax product, the II-level high-melting point wax product, the III-level high-melting point wax product and the V-level high-melting point wax product are 60 ℃ to 90 ℃, 70 ℃ to 100 ℃, 100 ℃ to 130 ℃ and 105 ℃ to 135 ℃ respectively.
In the present invention, the term "Fischer-Tropsch heavy product" is also referred to as "Fischer-Tropsch heavy oil fraction" and refers to a fraction of the Fischer-Tropsch product that is greater than 350 ℃.
In the present invention, the term "low melting point cerate" means a cerate having a melting point range of less than 50 ℃ or a fraction lower than 420 ℃ during distillation under reduced pressure.
In the invention, the term "medium-low melting point wax" refers to wax with a melting point range of 50-70 ℃ or fractions with a melting point range of 420-510 ℃ in a reduced pressure distillation process.
The beneficial effects of the invention are at least the following aspects:
the method for producing the high-melting-point wax by using the Fischer-Tropsch synthesis heavy product adopts a conventional technical route of reduced pressure distillation coupled with solvent extraction, has mild operation conditions, avoids the technical requirement of high vacuum degree, has low equipment requirement, has not strict requirement on the sealing performance of a pipeline, has large operation elasticity and easier engineering amplification, and is suitable for large-scale industrial application.
Secondly, the method adopts a multistage extraction process to realize fine separation of the crude wax product, and synchronously realizes the control of the melting point and the oil content of the wax product in the separation process, so that the oil content of the product is low; the selectivity of the extractant to the extract is high, and the purity of the obtained wax product is higher.
Thirdly, the method adopts mild extraction temperature to avoid chromaticity change of wax and oxygen-containing compounds caused by high-temperature pyrolysis and coking carbon deposition, and the product chromaticity is good; the mild extraction temperature can not cause cracking reaction of long-chain alkane molecules, and can directly produce ultrahigh-melting-point wax with melting point higher than 105 ℃.
Fourth, the method adopts the conventional reduced pressure distillation coupling multistage extraction process, so that the raw material adaptability is good, the product scheme is more flexible, and the extraction stage number and the extraction process parameters can be flexibly adjusted according to the characteristics of the raw materials and the requirements of the product scheme.
Fifthly, the high-melting-point wax obtained by the method has a melting point of 70-130 ℃, an oil content of less than 0.8%, and a high product purity.
Drawings
Fig. 1 is a process flow diagram of example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.
In the following embodiments, each performance index test standard and method is as follows:
1. melting point test: according to ASTM D3954 method;
2. chromaticity: according to GB/T3555 method;
3. oil content: according to the GB/T3554 method, butanone is used as a solvent for samples with the melting point lower than 78 ℃, and methyl isobutyl ketone is used as a solvent for samples with the melting point higher than 78 ℃;
4. yield: the mass of the high melting point wax product/total amount of Fischer-Tropsch heavy oil x100%;
5. filtration rate: filtration rate = filtrate mass/(filtration time x filtration area), filtrate refers to the text the solid-liquid separation after mixing wax liquid;
6. melting process: measured by a Differential Scanning Calorimeter (DSC), the sample is taken at N 2 And in the gas atmosphere, the temperature is reduced from the melting point temperature T+50 ℃ to the melting point temperature T-60 ℃ at a speed of 10 ℃/min, a temperature reduction curve is measured, the initial temperature point of the exothermic peak is used as a first temperature point, the low temperature point at the area of 95% of the exothermic peak is used as a second temperature point, and the temperature difference is the melting range temperature.
In the following embodiments, unless otherwise specified, the system employed: the device comprises a reduced pressure distillation system (mainly comprising a reduced pressure distillation tower), a granulating system connected with a bottom discharge port of the reduced pressure distillation tower and a three-stage extraction system connected with the granulating system. The three-stage extraction system comprises a first-stage extraction device, a second-stage extraction device and a third-stage extraction device. The primary extraction device comprises a primary extractor and a primary solid-liquid separation device, such as a centrifugal filter; the secondary extraction device comprises a secondary extractor and a secondary solid-liquid separation device, such as a vacuum drum filter; the three-stage extraction device comprises a three-stage extractor and a three-stage solid-liquid separation device, such as a pressurized bag filter. The auxiliary equipment of the vacuum distillation tower comprises a raw material conveying pump, a heating furnace, a heat exchanger, a conveying pump, a pumped fraction condenser, a reflux pump and a fraction storage tank.
The conveying pump is connected with the heating furnace, the heating furnace is connected with the heat exchanger, the inlet of the conveying pump is connected with the heat exchanger, and the outlet of the conveying pump is connected with the feed inlet of the vacuum distillation tower. The middle section of the vacuum distillation tower body is provided with a side line extraction outlet. The top outlet, side outlet and bottom outlet of the vacuum distillation tower are respectively connected with the extraction fraction condenser. The extraction fraction condensers are respectively connected with the fraction storage tanks for storing low-melting-point cerate, medium-low-melting-point wax and high-melting-point crude wax. Wherein, the outlet of the fraction storage tank for storing the high-melting-point crude wax is connected with a spray granulator. The outlet of the granulator is connected with a three-stage extraction system after passing through buffer equipment. Wherein, the top fraction is partially refluxed by a reflux pump to ensure the separation precision.
In the three-stage extraction system, an outlet of a first-stage extractor is connected with an inlet of a first-stage solid-liquid separation system-a centrifugal filter, and a solid material outlet of the centrifugal filter is connected with a feed inlet of a second-stage extractor; the outlet of the secondary extractor is connected with the inlet of a secondary solid-liquid separation system-vacuum rotary drum filter, and the solid outlet of the vacuum rotary drum filter is connected with the feed inlet of the tertiary extractor; the outlet of the three-stage extractor is connected with the inlet of a three-stage solid-liquid separation system, namely a pressurized bag filter, and the solid outlet of the pressurized bag filter is connected with a dryer.
The liquid outlets of the centrifugal filter, the vacuum rotary drum filter and the pressurized bag filter are respectively connected with the first flash evaporator, the second flash evaporator and the third flash evaporator, and the gas phase outlet and the liquid phase outlet of each flash evaporator are respectively connected with the extraction solvent recovery tanks of all levels and the high-melting-point wax product storage tanks.
Example 1
The raw materials adopt Fischer-Tropsch synthesis heavy oil of Ningxia coal industry company of national energy group, and the distillation range is 350-710 ℃; carbon number distribution C 18 ~C 102 Melting point 91 ℃ and melting range 65 ℃.
S1, preheating a Fischer-Tropsch synthesis heavy oil fraction to 300 ℃, sending the Fischer-Tropsch synthesis heavy oil fraction into a reduced pressure distillation tower, performing reduced pressure distillation at 300Pa absolute pressure, separating out a fraction with the temperature less than 420 ℃ from the tower top, taking the fraction with the partial extraction temperature of 420-510 ℃ as a 2# medium-low melting wax with the medium melting point of 65 ℃ as a 1# low melting wax, and obtaining a fraction with the temperature greater than 510 ℃ from the tower bottom as a high melting crude wax;
s2, carrying out spray granulation on the high-melting-point crude wax to obtain crude wax particles with the diameters of 0.045 mm-0.075 mm;
s3, mixing the crude wax particles with a primary extraction solvent n-heptane according to a mass ratio of 3:1, carrying out primary extraction treatment for 30min at 75 ℃ and normal pressure, centrifuging the extracted mixture to obtain a class I raffinate and a class I extract, carrying out flash evaporation on the class I extract under the conditions of 20KPa (absolute pressure) and 120 ℃, and recovering the primary extraction solvent to obtain a 3# high melting point wax product with the melting point of 83 ℃;
s4, mixing the I-level raffinate and the second-level extraction solvent n-octane according to the mass ratio of 2:1, mixing, carrying out secondary extraction treatment at 90 ℃ and 0.1MPa for 60min, and carrying out solid-liquid separation by vacuum filtration to obtain a II-stage raffinate and a II-stage extract; carrying out flash evaporation treatment on the II-level extract at 15KPa (absolute pressure) and 130 ℃, and recovering a second-level extraction solvent to obtain a No. 4 high-melting-point wax product with a melting point of 98 ℃;
s5, mixing the II-stage raffinate and the three-stage extraction solvent n-hexadecane according to a mass ratio of 8:1, mixing, performing three-stage extraction treatment at 105 ℃ and 0.1MPa for 45min, and performing solid-liquid separation by pressure filtration to obtain a III-stage raffinate and a III-stage extract; carrying out flash evaporation treatment on the III-level extract under the conditions of 10KPa (absolute pressure) and 140 ℃ to recover the solvent, and obtaining a No. 5 high-melting-point wax product with the melting point of 111 ℃; the III-grade raffinate was dried to give a 6# high melting wax product.
The properties of the high melting wax product obtained by the reaction are shown in Table 1.
TABLE 1
Example 2
The raw materials adopt Fischer-Tropsch synthesis heavy oil of an Itai group, the raw materials adopt Fischer-Tropsch synthesis heavy oil of the Itai group, and the distillation range is 365-690 ℃; carbon number distribution C 20 ~C 95 Melting point 88 ℃ and melting range 63 ℃.
S1, preheating a Fischer-Tropsch synthesis heavy oil fraction to 280 ℃, sending the Fischer-Tropsch synthesis heavy oil fraction into a reduced pressure distillation tower, performing reduced pressure distillation at 100Pa absolute pressure, separating out a fraction with the temperature less than 420 ℃ from the tower top, taking the fraction with the partial extraction temperature of 420-510 ℃ as a low-melting-point wax with the middle melting point of 67 ℃ and taking the fraction with the temperature greater than 510 ℃ as a high-melting-point crude wax at the tower bottom;
s2, carrying out spray granulation on the high-melting-point crude wax to obtain crude wax particles with the diameters of 0.045 mm-0.075 mm;
s3, mixing the crude wax particles with a mixture of a first-stage extraction solvent butyl acetate and n-octane (1:1) according to a mass ratio of 5:1, carrying out primary extraction treatment for 90min at 65 ℃ and normal pressure, centrifuging the extracted mixture to obtain a class I raffinate and a class I extract, carrying out flash evaporation on the class I extract under the conditions of 20KPa (absolute pressure) and 120 ℃, and recovering a primary extraction solvent to obtain a 3# high melting point wax product with the melting point of 75 ℃;
s4, mixing the I-stage raffinate with a mixture (1:1) of isopropyl alcohol and n-octane serving as a secondary extraction solvent according to a solvent ratio of 8:1, mixing, carrying out secondary extraction treatment for 120min at 80 ℃ and 0.5MPa, and carrying out solid-liquid separation by vacuum filtration to obtain a class II raffinate and a class II extract; carrying out flash evaporation treatment on the II-level extract at the temperature of 100 ℃ under the pressure of 20KPa (absolute pressure), and recovering a second-level extraction solvent to obtain a No. 4 high-melting-point wax product with the melting point of 90 ℃;
s5, mixing the II-stage raffinate and light naphtha with the third-stage extraction solvent fraction of 70-145 ℃ according to the mass ratio of 6:1, mixing, performing three-stage extraction treatment at 105 ℃ and 0.3MPa for 60min, and performing solid-liquid separation by pressure filtration to obtain a III-stage raffinate and a III-stage extract; carrying out flash evaporation treatment on the III-level extract under the conditions of 20KPa (absolute pressure) and 180 ℃ to recover the solvent, and obtaining a No. 5 high-melting-point wax product with the melting point of 110 ℃; the III-grade raffinate was dried to give a 6# high melting wax product.
The properties of the high melting wax product obtained by the reaction are shown in Table 2.
TABLE 2
Example 3
The raw materials adopt Fischer-Tropsch synthesis heavy oil of a future energy group, and the distillation range is 355-760 ℃; carbon number distribution C 20 ~C 110 Melting point 108 ℃ and melting range 71 ℃.
S1, preheating a Fischer-Tropsch synthesis heavy oil fraction to 290 ℃, sending the Fischer-Tropsch synthesis heavy oil fraction into a reduced pressure distillation tower, carrying out reduced pressure distillation at 200Pa absolute pressure, separating out a fraction with the temperature less than 420 ℃ from the tower top, taking the fraction as a 1# low-melting-point cerate with the melting point of 48 ℃, partially extracting the fraction with the temperature of 420-505 ℃ from the tower as a 2# medium-low-melting-point wax with the melting point of 68 ℃, and taking the fraction with the temperature greater than 505 ℃ from the tower bottom as a high-melting-point crude wax;
s2, carrying out spray granulation on the high-melting-point crude wax to obtain crude wax particles with the diameters of 0.045 mm-0.075 mm;
s3, mixing the coarse wax particles with a primary extraction solvent isooctane according to a mass ratio of 4.5:1, carrying out primary extraction treatment for 45min at 80 ℃ and 0.2MPa, centrifuging the extracted mixture to obtain a I-level raffinate and an I-level extract, carrying out flash evaporation on the I-level extract under the conditions of 20KPa (absolute pressure) and 180 ℃, and recovering the primary extraction solvent to obtain a 3# high melting point wax product with the melting point of 85 ℃;
s4, mixing the I-level raffinate and the second-level extraction solvent n-octane according to the solvent ratio of n-decane of 5:1 (mass ratio), and carrying out secondary extraction treatment at 95 ℃ and 0.3MPa for 75min, and carrying out solid-liquid separation by vacuum filtration to obtain a class II raffinate and a class II extract; carrying out flash evaporation treatment on the II-level extract at the temperature of 150 ℃ under 80KPa (absolute pressure), and recovering a second-level extraction solvent to obtain a No. 4 high-melting-point wax product with the melting point of 96 ℃;
s5, mixing the II-level raffinate and the three-level extraction solvent n-hexadecane according to a mass ratio of 6:1, mixing, performing three-stage extraction treatment at 110 ℃ and 0.3MPa for 30min, and performing solid-liquid separation by pressure filtration to obtain a III-stage raffinate and a III-stage extract; carrying out flash evaporation treatment on the III-level extract under 30KPa (absolute pressure) and 220 ℃ to recover the solvent, and obtaining a No. 5 high-melting-point wax product with a melting point of 115 ℃; the III-grade raffinate was dried to give a 6# high melting wax product.
The properties of the high melting wax product obtained by the reaction are shown in Table 3.
TABLE 3 Table 3
Example 4
The raw materials adopt Fischer-Tropsch synthesis heavy oil of Ningxia coal industry company of national energy group, and the distillation range is 350-710 ℃; carbon number distribution C 18 ~C 102 Melting point 91 ℃ and melting range 65 ℃.
S1, preheating a Fischer-Tropsch synthesis heavy oil fraction to 300 ℃, sending the Fischer-Tropsch synthesis heavy oil fraction into a reduced pressure distillation tower, performing reduced pressure distillation at 300Pa absolute pressure, separating out a fraction with the temperature less than 420 ℃ from the tower top, taking the fraction with the partial extraction temperature of 420-510 ℃ as a 2# medium-low melting point wax with the melting point of 65 ℃ as a 1# low melting point cerate, and obtaining a fraction with the temperature greater than 510 ℃ from the tower bottom as a high melting point crude wax;
s2, spraying and granulating the high-melting-point crude wax to obtain crude wax particles with diameters of 0.5 mm-0.75 mm;
s3, mixing the crude wax particles with a primary extraction solvent n-heptane according to a mass ratio of 3:1, carrying out primary extraction treatment for 30min at 75 ℃ under normal pressure, centrifuging the extracted mixture to obtain a class I raffinate and a class I extract, carrying out flash evaporation on the class I extract under the conditions of 20KPa (absolute pressure) and 120 ℃, and recovering the primary extraction solvent to obtain a 3# high melting point wax product with the melting point of 75 ℃;
s4, mixing the I-level raffinate and the second-level extraction solvent n-octane according to a mass ratio of 2:1, mixing, carrying out secondary extraction treatment at 90 ℃ and 0.1MPa for 60min, and carrying out solid-liquid separation by vacuum filtration to obtain a II-stage raffinate and a II-stage extract; carrying out flash evaporation treatment on the II-level extract under 15KPa (absolute pressure) and 130 ℃, and recovering a second-level extraction solvent to obtain a No. 4 high-melting-point wax product with a melting point of 86 ℃;
s5, mixing the II-stage raffinate and the three-stage extraction solvent n-hexadecane according to the proportion of 8:1, mixing, performing three-stage extraction treatment at 105 ℃ and 0.1MPa for 45min, and performing solid-liquid separation by pressure filtration to obtain a III-stage raffinate and a III-stage extract; carrying out flash evaporation treatment on the III-level extract under the conditions of 10KPa (absolute pressure) and 140 ℃ to recover the solvent, and obtaining a No. 5 high-melting-point wax product with the melting point of 102 ℃; the III-grade raffinate was dried to give a 6# high melting wax product.
The properties of the high melting wax product obtained by the reaction are shown in Table 4.
TABLE 4 Table 4
From the data in tables 1 and 4, it is found that the melting point of the high melting point wax fraction is significantly reduced, the yield is reduced, the yield of the residual fraction is increased, and the melting range of the residual fraction is increased, indicating that the separation effect is deteriorated, under the same conditions, after the particle size of the pellets is increased.
Example 5
The raw materials adopt Fischer-Tropsch synthesis heavy oil of Ningxia coal industry company of national energy group, and the distillation range is 350-710 ℃; carbon number distribution C 18 ~C 102 Melting point 91 ℃ and melting range 65 ℃.
S1, preheating a Fischer-Tropsch synthesis heavy oil fraction to 300 ℃, sending the Fischer-Tropsch synthesis heavy oil fraction into a reduced pressure distillation tower, performing reduced pressure distillation at 300Pa absolute pressure, separating out a fraction with the temperature less than 420 ℃ from the tower top, taking the fraction with the partial extraction temperature of 420-510 ℃ as a 2# medium-low melting point wax with the melting point of 65 ℃ as a 1# low melting point cerate, and obtaining a fraction with the temperature greater than 510 ℃ from the tower bottom as a high melting point crude wax;
s2, carrying out spray granulation on the high-melting-point crude wax to obtain crude wax particles with the diameters of 0.005 mm-0.010mm;
s3, mixing the crude wax particles with a primary extraction solvent n-heptane according to a mass ratio of 3:1, carrying out primary extraction treatment for 30min at 75 ℃ and normal pressure, centrifuging the extracted mixture to obtain a class I raffinate and a class I extract, carrying out flash evaporation on the class I extract under the conditions of 20KPa (absolute pressure) and 120 ℃, and recovering the primary extraction solvent to obtain a 3# high melting point wax product with the melting point of 78 ℃;
s4, mixing the I-level raffinate and the second-level extraction solvent n-octane according to a mass ratio of 2:1, mixing, carrying out secondary extraction treatment at 90 ℃ and 0.1MPa for 60min, and carrying out solid-liquid separation by vacuum filtration to obtain a II-stage raffinate and a II-stage extract; carrying out flash evaporation treatment on the II-level extract under 15KPa (absolute pressure) and 130 ℃, and recovering a second-level extraction solvent to obtain a No. 4 high-melting-point wax product with a melting point of 92 ℃;
s5, mixing the II-stage raffinate and the three-stage extraction solvent n-hexadecane according to the proportion of 8:1, mixing, performing three-stage extraction treatment at 105 ℃ and 0.1MPa for 45min, and performing solid-liquid separation by pressure filtration to obtain a III-stage raffinate and a III-stage extract; carrying out flash evaporation treatment on the III-level extract under the conditions of 10KPa (absolute pressure) and 140 ℃ to recover the solvent, and obtaining a No. 5 high-melting-point wax product with the melting point of 108 ℃; the III-grade raffinate was dried to give a 6# high melting wax product.
The properties of the high melting wax product obtained by the reaction are shown in Table 5.
TABLE 5
From the data in tables 1 and 5, it was found that the melting point of the high melting point wax fraction was significantly increased under the same conditions after the particle size of the pellets was reduced, and the yield was increased, but the filtration rate was significantly reduced by melting Cheng Biankuan.
Comparative example 1
The raw materials adopt Fischer-Tropsch synthesis heavy oil of Ningxia coal industry company of national energy group, and the distillation range is 350-710 ℃; carbon number distribution C 18 ~C 102 Melting point 91 ℃ and melting range 65 ℃.
The liquid Fischer-Tropsch wax is cut and separated according to the short-path distillation method described in patent CN110066680A, and is subjected to multistage short-path distillation treatment under the absolute pressure of 10Pa, 5 components of <220 ℃, 220-240 ℃, 240-270 ℃, 270-290 ℃ and >290 ℃ are respectively cut, and the product properties are shown in table 6.
TABLE 6
As can be seen from comparative example 1, in the short path distillation process, the distillation temperature of 290 ℃ has reached the decomposition temperature of the Fischer-Tropsch wax, and further raising the temperature will cause the Fischer-Tropsch wax to decompose; therefore, the short path distillation method is not suitable for continuously carrying out fine separation on the distilled heavy components with the temperature of more than 290 ℃, and only can be used as a byproduct in the form of a mixture, and the product has the problems of Cheng Kuan melting point, low melting point, high oil content, low chromaticity and the like; that is, the conventional short path distillation method cannot finely separate the high melting point wax fraction. Meanwhile, the oil content of the high melting wax prepared by the method provided by the comparative example is higher than that of the high melting wax product prepared by the method provided by the invention.
Comparative example 2
The raw materials are adopted by ChinaFischer-Tropsch synthesis heavy oil of Ningxia coal industry company is carried out, and the distillation range is 350-710 ℃; carbon number distribution C 18 ~C 102 Melting point 91 ℃ and melting range 65 ℃.
S1, preheating a Fischer-Tropsch synthesis heavy oil fraction to 300 ℃, sending the Fischer-Tropsch synthesis heavy oil fraction into a reduced pressure distillation tower, performing reduced pressure distillation at 300Pa absolute pressure, separating out a fraction with the temperature less than 420 ℃ from the tower top, taking the fraction with the partial extraction temperature of 420-510 ℃ as a 2# medium-low melting point wax with the melting point of 65 ℃ as a 1# low melting point cerate, and obtaining a fraction with the temperature greater than 510 ℃ from the tower bottom as a high melting point crude wax;
s2, carrying out spray granulation on the high-melting-point crude wax to obtain crude wax particles with the diameters of 0.045 mm-0.075 mm;
s3, mixing the crude wax particles with a mixed solution of a primary extraction solvent butanone and toluene (mass ratio 3:7) according to mass ratio 3:1, carrying out primary extraction treatment for 30min at 75 ℃ and normal pressure, centrifuging the extracted mixture to obtain a class I raffinate and a class I extract, carrying out flash evaporation on the class I extract under the conditions of 20KPa (absolute pressure) and 120 ℃, and recovering the primary extraction solvent to obtain a 3# high melting point wax product with the melting point of 83 ℃;
s4, mixing the I-level raffinate with a mixed solution of a second-level extraction solvent butanone and toluene (mass ratio 3:7) according to mass ratio 2:1, mixing, carrying out secondary extraction treatment at 90 ℃ and 0.3MPa for 60min, and carrying out solid-liquid separation by vacuum filtration to obtain a II-stage raffinate and a II-stage extract; carrying out flash evaporation treatment on the II-level extract under 15KPa (absolute pressure) and 130 ℃, and recovering a second-level extraction solvent to obtain a No. 4 high-melting-point wax product with a melting point of 98 ℃;
s5, mixing the II-stage raffinate with a mixed solution of a third-stage extraction solvent butanone and toluene (mass ratio 3:7) according to the ratio of 8:1, mixing, performing three-stage extraction treatment at 105 ℃ and 0.3MPa for 45min, and performing solid-liquid separation by pressure filtration to obtain a III-stage raffinate and a III-stage extract; carrying out flash evaporation treatment on the III-level extract under the conditions of 10KPa (absolute pressure) and 140 ℃ to recover the solvent, and obtaining a No. 5 high-melting-point wax product with the melting point of 111 ℃; the III-grade raffinate was dried to give a 6# high melting wax product.
The properties of the high melting wax product obtained by the reaction are shown in Table 7.
TABLE 7
As can be seen from the comparison example, the conventional ketone benzene system solvent is adopted, under the same condition, the melting point of the high-melting-point wax part is obviously reduced, the yield is reduced, the melting point of the residual part is reduced, the yield is increased, and the melting point is Cheng Biankuan, so that the extractant cannot effectively separate the high-melting-point wax.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (23)
1. A method for producing high melting point wax from a heavy fischer-tropsch product, the system for producing high melting point wax from a heavy fischer-tropsch product comprising a reduced pressure distillation column, a pelletizing system connected to a bottom outlet of the reduced pressure distillation column, and a multistage extraction system connected to the pelletizing system, the method comprising:
s1, performing reduced pressure distillation on a Fischer-Tropsch synthesis heavy product, so as to separate high-melting-point crude wax with a melting point higher than 70 ℃;
s2, granulating the high-melting-point coarse wax to obtain coarse wax particles;
s3, carrying out primary extraction treatment on the crude wax particles by adopting a primary extraction solvent to obtain a primary raffinate and a primary extract, wherein the primary extract is subjected to solvent recovery treatment to obtain a primary high-melting-point wax product;
s4, carrying out secondary extraction treatment on the I-level raffinate by adopting a secondary extraction solvent to obtain a II-level raffinate and a II-level extract, wherein the II-level extract is subjected to solvent recovery treatment to obtain a II-level high-melting-point wax product;
s5, performing three-stage extraction treatment on the II-stage raffinate by using a three-stage extraction solvent to obtain a III-stage raffinate and a III-stage extract, wherein the III-stage extract is subjected to solvent recovery treatment to obtain a III-stage high-melting-point wax product;
optionally S6, carrying out four-stage extraction treatment on the III-stage raffinate by adopting four-stage extraction solvent to obtain IV-stage raffinate and IV-stage extract;
the grain diameter of the coarse wax particles is 0.03 mm-0.15 mm;
the primary extraction solvent, the secondary extraction solvent, the tertiary extraction solvent and the quaternary extraction solvent are the same or different, and are each independently selected from one or more of saturated hydrocarbon, esters, alcohols with the boiling point range of 50-220 ℃ and Fischer-Tropsch synthesis light oil fraction with the distillation range of 50-220 ℃ and the saturated hydrocarbon content of more than 60%, naphtha with the distillation range of 50-220 ℃ and petroleum ether with the distillation range of 60-120 ℃.
2. The method according to claim 1, wherein in step S1, the reduced pressure distillation is performed in a reduced pressure distillation column, whereby the high melting point crude wax is separated at a bottom of the reduced pressure distillation column.
3. The method according to claim 2, wherein the operating conditions of the reduced pressure distillation include: the absolute pressure is 100 Pa-5000 Pa; and/or the bottom temperature is 200-350 ℃.
4. A process according to claim 3, wherein the operating conditions of the reduced pressure distillation comprise: the absolute pressure is 100 Pa-2000 Pa.
5. The method of claim 4, wherein the operating conditions of the reduced pressure distillation comprise: the absolute pressure is 100 Pa-1000 Pa.
6. The process according to claim 2, wherein the bottom temperature is 200 ℃ to 310 ℃.
7. The method according to claim 1, wherein in step S2, the particle size of the coarse wax particles is 0.038mm to 0.125mm.
8. The process according to claim 1, wherein the primary extraction solvent, the secondary extraction solvent, the tertiary extraction solvent and the quaternary extraction solvent are the same or different and are each independently selected from one or more of saturated hydrocarbons having a boiling point range of 60 ℃ to 220 ℃, esters, alcohols and fischer-tropsch light oil fractions having a distillation range of 50 ℃ to 220 ℃ and a saturated hydrocarbon content of more than 60%, naphtha having a distillation range of 50 ℃ to 220 ℃ and petroleum ether having a distillation range of 60 ℃ to 120 ℃.
9. The method according to claim 1, wherein the saturated hydrocarbon is selected from at least one of n-hexane, cyclohexane, n-heptane, isoheptane, methylcyclohexane, n-octane, isooctane, n-decane, isodecane, n-dodecane, and n-hexadecane; the esters are at least one selected from methyl acetate, ethyl propionate, butyl acetate, isobutyl acetate, isopropyl acetate and ethyl butyrate; the alcohol is at least one selected from ethanol, isopropanol, butanol, amyl alcohol, hexanol, ethylene glycol and propylene glycol.
10. The method according to claim 1, wherein in step S3, the operating conditions of the primary extraction process include: the temperature is 60-90 ℃; the absolute pressure is 0.08MPa to 0.5MPa; the time is 10 min-120 min.
11. The method according to claim 9, wherein in step S3, the operating conditions of the primary extraction process include: the temperature is 70-90 ℃.
12. The method according to claim 9, wherein in step S3, the mass ratio of the raw wax particles to the primary extraction solvent is (1 to 8): 1.
13. The method according to claim 12, wherein in step S3, the mass ratio of the raw wax particles to the primary extraction solvent is 1.1 to 8:1.
14. The method according to claim 1, wherein in step S4, the operating conditions of the secondary extraction process comprise: the temperature is 70-100 ℃; the absolute pressure is 0.08MPa to 0.5MPa; the time is 10 min-120 min.
15. The method according to claim 14, wherein in step S4, the operating conditions of the secondary extraction process comprise: the temperature is 80-100 ℃.
16. The process of claim 14, wherein in step S4 the mass ratio of the stage I raffinate to the secondary extraction solvent is (1-8): 1.
17. The process of claim 16, wherein in step S4 the mass ratio of the stage I raffinate to the secondary extraction solvent is (1.1-8): 1.
18. The method according to claim 1, wherein in step S5, the operating conditions of the three-stage extraction process comprise: the temperature is 100-130 ℃; the absolute pressure is 0.08MPa to 0.5MPa; the time is 10 min-120 min.
19. The process of claim 18, wherein in step S5 the mass ratio of the stage II raffinate to the tertiary extraction solvent is (1-8): 1.
20. The process of claim 19, wherein in step S5 the mass ratio of the stage II raffinate to the tertiary extraction solvent is (1.1-8): 1.
21. The process according to claim 1, wherein the grade I extract, the grade II extract and the grade III extract are distilled respectively, and the solvent is recovered to obtain a grade I high melting point wax product, a grade II high melting point wax product and a grade III high melting point wax product having melting point ranges of 60 ℃ to 90 ℃, 70 ℃ to 100 ℃ and 100 ℃ to 130 ℃ respectively.
22. The method of claim 21, wherein the distillation process conditions comprise: the temperature is 100-250 ℃; the absolute pressure is 10 KPa-100 KPa.
23. A high melting point wax product made by the method of any of claims 1-22, the high melting point wax product comprising at least one of a grade I high melting point wax product, a grade II high melting point wax product, and a grade III high melting point wax product, and the high melting point wax product having an oil content of less than 0.8wt%.
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