CN102746895A - Single-reactor hydrogenation technology of Fischer-Tropsch synthetic full fraction products - Google Patents
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Abstract
The invention relates to a single-reactor hydrogenation technology of Fischer-Tropsch synthetic full fraction products. The single-reactor hydrogenation technology is characterized in that a single reactor is used to carry out pre-hydrogenation and hydrofining of Fischer-Tropsch synthetic full fraction products; carbon distribution of the Fischer-Tropsch synthetic full fraction products is in a range of C4-C100; a catalyst is filled into the single reactor in a two or more-section filling way; and a protective agent is filled into a first section and other sections are filled with hydrogenation catalysts. Raw materials pass through the protective agent and then undergo a hydrofining reaction with olefins and organic oxygen-containing compounds in the presence of the hydrogenation catalysts. High-quality naphtha, solvent naphtha, liquid paraffin, a diesel fraction, a lubricant base oil fraction and high-quality wax are separated out from reaction products. The single-reactor hydrogenation technology has characteristics of high thermal efficiency of reaction processes, small temperature rise of a catalyst bed and less investment of equipment, and is especially suitable for hydrofining of Fischer-Tropsch synthetic full fraction products containing olefins and a certain amount of organic oxygen-containing compounds.
Description
Technical field
The present invention relates to an a kind of reactor drum hydrogenation technique of Fischer-Tropsch synthetic, specifically, the present invention relates to the hydrocracking technology of Fischer-Tropsch synthetic, described hydrogenation technique is accomplished at the hydrogenation technique of a fixed bed or similar reaction unit.
Background technology
Fischer-Tropsch synthetic; Or the composition of claiming oil from Fischer-Tropsch synthesis and oil has a great difference; Mainly form by straight-chain paraffin, alkene; And contain a certain amount of organic oxygen-containing compound, the highest 50wt% that accounts for total amount of olefin(e) centent wherein, the high-content of organic oxygen-containing compound can account for the 20wt% of total amount.High olefin(e) centent makes it in hydroconversion process, cause catalyzer localized heat release amount excessive easily, causes catalyzer coking inactivation; Simultaneously, big thermal discharge can cause that the beds temperature rise is too fast, and this also is unfavorable for the temperature control of bed.And the existence of acid organic oxygen-containing compound in the oil product; Not only influence the stability of oil product; And the meeting severe corrosion equipment, be unfavorable for the further processing of synthetic oil product, so must adopt appropriate means that oil from Fischer-Tropsch synthesis is carried out unifining; To improve the quality of oil product, improve value-added content of product.
At present, the oil product hydrogen refining process mainly is that the Hydrobon catalyst that is adopted is an active ingredient with group vib (like Mo or W) and VIII family (like Ni, Co) metallic element generally, with γ-Al to oil and edible oil in the industry
2O
3Or SiO
2-Al
2O
3Be carrier, catalyzer has higher unifining activity and stable through prevulcanized, and mostly the technology that is adopted is two reactor process, comprises pre-hydrogenator and hydrofining reactor.
The hydrogenation modification method of a kind of light constituent oil from Fischer-Tropsch synthesis of Chevron company public reported (U.S.Patent 6,709,569), the Hydrobon catalyst of employing are to be active ingredient with one or both metals among Co, W, Mo and the Ni, Al
2O
3For preparing carriers forms.This method requires before to the oil from Fischer-Tropsch synthesis hydro-upgrading, and hydrogenation catalyst needs prevulcanized.
Mobil company also a kind of method that is used for the hydrocracking of oil from Fischer-Tropsch synthesis of public reported (U.S.Patent 4; 500,417), this method requires hydrogenation catalyst presulfurizing; But also required before the Fischer-Tropsch oil hydrogenation transforms, add sulphur to improve activity of such catalysts and stability.
CN 1958740 A disclose a kind of method of hydrotreating of deep desulfurization olefin hydrocarbon reduction of gasoline, adopt two hydrogenators to carry out hydrotreatment, have improved flexibility of operation for producing clean gasoline.
CN 1769380A discloses the one-stage hydrogenation method of producing top grade article white oil, is to adopt pre-refining reactor drum and refining reaction device serial operation, and the catalyzer and the operational condition of two reactor drums have nothing in common with each other, and have guaranteed that the pour point of white oil product does not reduce.
CN 100345944C discloses a kind of technology that is used for unvulcanised oil from Fischer-Tropsch synthesis hydrocracking; Preparatory hydrogenation and deep hydrogenation two-stage hydrogenation reactor drum have been adopted; Reaction raw materials at first carries out the preparatory hydrogenation of low temperature at first reactor drum; Carry out the deep hydrogenation deoxygenation at second reactor drum then, the catalyzer that two-stage reaction adopts is unvulcanised attitude hydrogenation catalyst.
Existing patent and the technology all without exception employing two reactor drums or multiple reactor technology; Because the Fischer-Tropsch synthetic olefin(e) centent mainly is distributed in the lighting end interval; Existing two reactor process exist the pre-hydrogenator thermal discharge big; Need a large amount of cold shock hydrogen to reduce the beds temperature rise, and the raw material of entering hydrofining reactor also need carry out preheating, has increased energy expenditure again.This has not only increased facility investment, has also increased running cost, also is unfavorable for the reasonable utilization of reaction heat simultaneously.
The present invention adopts a reactor drum hydrogenation technique, is raw material with the synthetic full cut product of Fischer-Tropsch, and heavy ends plays the accumulation of heat effect; With light ends hydrogenation reaction liberated heat on second section catalyzer; Take catalyzer more than the 3rd section or the 3rd section to, effectively reduce second section beds temperature rise, guaranteed that also catalyzer has enough temperature of reaction to carry out hydrogenation reaction more than the 3rd section or the 3rd section simultaneously; Thereby both helped the temperature control of beds, reduced energy expenditure again.
The present invention possibly exist metal or mechanical impurity to coming from the full cut product of Fischer-Tropsch synthesis oil raw material; First section in a reactor drum is provided with the guard catalyst section; Be used for removing metal or mechanical impurity, guarantee second section catalyzer or the normal use of section catalyzer afterwards.
In addition, the oil from Fischer-Tropsch synthesis hydrogenation catalyst general requirement prevulcanized (except the CN100345944C) of public reported.And oil from Fischer-Tropsch synthesis is different from oil and edible oil, except containing paraffinic hydrocarbons and alkene, also contains a certain amount of organic oxygen-containing compound in the oil product, has the characteristics of no sulphur, no nitrogen and low aromatic hydrocarbons.In oil from Fischer-Tropsch synthesis hydro-upgrading process, introduce element sulphur, not only make hydrogenation technique complicated, but also have the potential environmental pollution.In order to overcome above deficiency; The present invention provides a kind of Fischer-Tropsch to synthesize full cut product hydrogenation technique; Catalyzer can not need sulfidizing; Through oil from Fischer-Tropsch synthesis is carried out unifining, can obtain high-quality petroleum naphtha, solvent oil, whiteruss, diesel oil distillate, lubricant base oil fraction and high-quality wax etc.According to the different routes of chiral process, coal liquefaction can be divided into direct liquefaction and indirect liquefaction two big classes.DCL/Direct coal liquefaction is directly to change into liquid product to coal.Its technology mainly contains Exxon (Exxon) Exxon donor solvent process (being called for short the EDS method), H-coal process etc.The EDS method is the effect by hydrogen supply dissolvent, under certain temperature and pressure, coal hydrogenation is liquefied as liquid fuel; H-coal process is to adopt the pressurized catalysis fluidized-bed reactor, by the effect of high temperature and catalyzer, makes coal under hydrogen pressure, be cracked into micromolecular liquid hydrocarbon fuel.The diesel yield of Hydrogenation liquefaction process is about 70%; LPG and gasoline account for 20%, and all the other also contain heteroatomss such as a considerable amount of oxygen, nitrogen, sulphur for being main intermediates with the polycyclic aromatic hydrocarbons; Aromaticity content is also higher, further is processed as products such as high-quality gasoline, diesel oil than difficulty.
At an a kind of reactor drum hydrogenation technique that is used for the synthetic full cut product of Fischer-Tropsch provided by the invention; Because the Fischer-Tropsch synthetic olefin(e) centent mainly is distributed in the light ends interval; When adopting light ends, middle runnings and heavy ends parallel feeding; When having reduced by second section beds temperature rise, guaranteed that also beds has enough temperature of reaction more than the 3rd section or the 3rd section, thereby helped the temperature control of beds; Hydrogenation reaction in the whole reactor is being carried out under the demulcent condition relatively, also help prolonging simultaneously the work-ing life of catalyzer.
The objective of the invention is to contain the characteristics of a large amount of alkene and a certain amount of organic oxygen-containing compound to oil from Fischer-Tropsch synthesis; An a kind of reactor drum hydrogenation technique that is suitable for the synthetic full cut product of Fischer-Tropsch is provided; Alkene in the oil from Fischer-Tropsch synthesis is saturated, and the organic oxygen-containing compound in the hydrocracking oil product.This technology has been simplified technical process greatly; Reduce facility investment and process cost, reduced energy expenditure, guaranteed the quality of hydrogenated products simultaneously; When the processing oil from Fischer-Tropsch synthesis; Can through changing operational condition and processing parameter, obtain higher alkene saturation exponent and organic oxygen-containing compound decreasing ratio according to different requirement.
The applicant is to the deficiency of prior art; According to long-term practical experience, proposed a kind ofly Fischer-Tropsch synthesis oil to be carried out hydrorefined novel process, this process using one reactor drum hydrogenation technique; Compare with original technology, have the advantages that technology is simple, process cost is low.
Summary of the invention
The purpose of this invention is to provide a kind of method that fischer-tropsch synthesis product is processed as high-quality oil fuel and industrial chemicals; Promptly the invention provides a kind of hydrogenation technique of Fischer-Tropsch synthetic; It is characterized in that described hydrogenation technique is the unifining of in single hydrogenator, accomplishing Fischer-Tropsch synthetic; Said hydrogenator adopts the catalyzer more than two sections or two sections, and wherein first section is protective material, and all the other sections are hydrogenation catalyst; Said hydrogenation technique comprises the Fischer-Tropsch synthetic warp mixed with hydrogen and feeds said reactor drum; At first make said raw material pass through protective material; Under the hydrogenation catalyst existence condition, carry out hydrogenation reaction then; The processing condition of said hydrogenation reaction are: temperature of reaction is 200～320 ℃, and pressure is 2.0～10MPa, and air speed is 0.3～8.0h
-1, hydrogen to oil volume ratio is 300～1500 under the standardpressure; Can obtain high-quality petroleum naphtha, solvent oil, whiteruss, diesel oil distillate, lubricant base oil fraction and high-quality wax by said unifining and after separating.
The processing condition of preferred hydrogenator are: temperature of reaction is 220～300 ℃, and pressure is 4.0～8.0MPa, and air speed is 0.5～2.0h
-1, the hydrogen to oil volume ratio under the standardpressure is 600～1000.
In a reactor drum hydrogenation technique of Fischer-Tropsch synthetic provided by the invention; Fischer-Tropsch synthetic is mixed into reactor drum with hydrogen after the volume pump metering; With conversion of olefines is stable hydrocarbon; Oxygen acid can be converted into alcohol and/or ester and/or saturated alkane (according to catalyzer and reaction conditions decision), and reaction product can obtain high-quality petroleum naphtha, solvent oil, whiteruss, diesel oil distillate, lubricant base oil fraction and high-quality wax etc. after separating.
In a reactor drum hydrogenation technique of Fischer-Tropsch synthetic provided by the invention, the processing condition of hydrogenator are: temperature of reaction is 200～320 ℃, is preferably 220～300 ℃, and pressure is 2.0～10MPa, is preferably 4.0～8.0MPa, and air speed is 0.3～8.0h
-1, be preferably 0.5～2.0h
-1, hydrogen to oil volume ratio (under the standardpressure) is 300～1500, is preferably 600～1000.
In a reactor drum hydrogenation technique of Fischer-Tropsch synthetic provided by the invention, described reactor drum can adopt this area reactor drum commonly used, for example fixed-bed reactor or other reaction bed, and preferred, method of the present invention more is applicable to fixed-bed reactor.
Preferably, the hydrogenator described in the inventive method adopts the catalyzer more than three sections or three sections, and for example, described reactor drum adopts three sections or four sections catalyzer.Wherein, one section is protective material, and described protective material is commercially available demetalization protective material, or homemade demetalization protective material.
In a reactor drum hydrogenation technique of the synthetic full cut product of a kind of Fischer-Tropsch provided by the invention; Hydrogenation unit is fixed bed or similar reactor drum; Wherein the demetalization protective material of filling is commercially available protective material, perhaps is homemade according to conventional methods demetalization protective material.Used protective material can remove the mechanical impurity in the raw material, and alkalies and alkaline earth impurity effectively reduces the beds pressure drop, and prolongs the work-ing life of hydrogenation catalyst.
It is understandable that according to foregoing; In the employed reactor drum of the inventive method; At least loaded the one-stage hydrogenation catalyzer, wherein said each section hydrogenation catalyst can be a kind of hydrogenation catalyst, or the mixing of two or more hydrogenation catalyst; Usually, described hydrogenation catalyst is the conventional hydrogenation catalyst that uses in this area; For example, described hydrogenation catalyst can be sulphided state or unvulcanised attitude hydrogenation catalyst; Preferably, said hydrogenation catalyst is a unvulcanised attitude hydrogenation catalyst; More preferably described unvulcanised hydrogenation catalyst is to load on the hydrogenation catalyst that group vib, VIIB family and VIII family metal and non-metal kind on aluminum oxide and/or molecular sieve and/or the silica supports are formed.
In a reactor drum hydrogenation technique of the synthetic full cut product of a kind of Fischer-Tropsch provided by the invention, wherein load two kinds of hydrogenation catalysts at least.Can satisfy requirement of the present invention though in fact be applied to any catalyzer of hydrogenation, some catalyzer is better than other catalyzer.As containing VIII family non-precious metal such as nickel, cobalt, other can or also can not comprise group vib metal such as tungsten, molybdenum etc., also can add iron, lanthanum, copper etc. simultaneously and help catalyst component; It can be one or more the arbitrary combination in silicon-dioxide, aluminum oxide, silica-alumina, zirconium white, titanium oxide, the molecular sieve that carrier is formed.Two or more component in wherein being made up of above-mentioned carrier is mixed and the carrier processed is called complex carrier; Wherein said alumina supporter can adopt acid or alkali to carry out pre-treatment, such as through peroxophosphoric acid or sulfuric acid or the pretreated alumina supporter of organic acid, is called modified aluminium oxide supports; Molecular sieve wherein can be the molecular sieve of beta-molecular sieve, MCM series molecular sieve, Y series molecular sieve, ZSM series molecular sieve or SAP0 series etc., also can be the wherein combination of one or more molecular sieves.In addition, the loaded catalyst that contains one or more noble metals such as metals such as platinum and palladium also can satisfy requirement of the present invention.
In a reactor drum hydrogenation technique of the synthetic full cut product of a kind of Fischer-Tropsch provided by the invention; Hydrogenation catalyst can adopt multiple type of feed according to practical situation, such as the one section type of feed that adopts multiple hydrogenation catalyst proportional mixing, perhaps adopt above-mentioned two kinds of types of feed that form combines by the catalyst property different mining with the segmentation type of feed.
In the one reactor drum hydrogenation technique of the synthetic full cut product of a kind of Fischer-Tropsch of the present invention, the oil from Fischer-Tropsch synthesis of use mainly is made up of straight chain hydrocarbon, alkene and a certain amount of organic oxygen-containing compound, is forming and evident difference is arranged in nature with oil.
In the inventive method be; Employed raw material Fischer-Tropsch synthetic can be this area Fischer-Tropsch synthetic commonly used; Or be called oil from Fischer-Tropsch synthesis, for example, used raw material Fischer-Tropsch synthetic is the full cut product of Fischer-Tropsch synthesis oil; Or a kind of cut in the Fischer-Tropsch synthetic or the mixture of several fractions, for example can be one or more the mixture in light ends, middle runnings, the heavy ends.
For example, used raw material Fischer-Tropsch synthetic is the synthetic full cut product of Fischer-Tropsch in the hydrogenation technique of Fischer-Tropsch synthetic of the present invention, and its carbon distribution is C4～C100; When used Fischer-Tropsch synthesis oil raw material was the synthetic full cut product of above-mentioned Fischer-Tropsch, said hydrogenation reaction processing condition are: temperature of reaction was 220～300 ℃, and pressure is 4.0～8.0MPa, and air speed is 0.5～2.0h
-1, the hydrogen to oil volume ratio under the standardpressure is 600～1000.
And for example, used raw material Fischer-Tropsch synthetic is a Fischer-Tropsch synthetic mesophase cut product in the hydrogenation technique of Fischer-Tropsch synthetic of the present invention, and its carbon distribution is C6～C50; When raw materials used Fischer-Tropsch synthetic was above-mentioned Fischer-Tropsch synthetic mesophase cut product, the processing condition of said hydrogenation reaction are: temperature of reaction was 200～280 ℃, and pressure is 4.0～8.0MPa, and air speed is 0.5～2.0h
-1, the hydrogen to oil volume ratio under the standardpressure is 600～1000.
And for example, used raw material Fischer-Tropsch synthetic is a Fischer-Tropsch synthetic heavy cut in the hydrogenation technique of Fischer-Tropsch synthetic of the present invention, and its carbon distribution is C8～C100; When used Fischer-Tropsch synthetic raw material was above-mentioned Fischer-Tropsch synthetic heavy cut, the processing condition of said hydrogenation reaction are: temperature of reaction was 220～300 ℃, and pressure is 4.0～8.0MPa, and air speed is 0.5～2.0h
-1, the hydrogen to oil volume ratio under the standardpressure is 600～1000.
Compare with original multiple reactor hydrogenation technique, a reactor drum hydrogenation technique of the present invention has following characteristics:
1, Fischer-Tropsch synthetic one reactor drum hydrogenation technique provided by the invention adopts a reactor drum that Fischer-Tropsch synthetic is carried out unifining, has simplified technical process, has reduced facility investment, has reduced energy expenditure.
2, a reactor drum hydrogenation technique of Fischer-Tropsch synthetic provided by the invention is through using the catalyzer of different performance; Realization is to the substep hydrocracking of the synthetic full feedstock of Fischer-Tropsch; Make exothermic heat of reaction mitigation, controlled; Effectively reduce the beds temperature rise, also prolonged the work-ing life of catalyzer simultaneously.
3, to be directed against the Fischer-Tropsch synthetic raw material can be the synthetic full distillate oil article of Fischer-Tropsch to a reactor drum hydrogenation technique of Fischer-Tropsch synthetic provided by the invention, but also can be in light ends, middle runnings, the heavy ends one or more, and feeding manner is flexible.
When 4, application hydrogenation reaction device of the present invention carries out hydrocracking to Fischer-Tropsch synthetic, can obtain higher alkene saturation exponent and hydrogenation deoxidation rate through changing processing parameter.This technology is effective especially for the oil product processing of being made up of straight chain hydrocarbon, alkene and a certain amount of organic oxygen-containing compound.
5, use a reactor drum hydrogenation technique of Fischer-Tropsch synthetic provided by the invention; Oil quality through after the unifining is good; Acid number is low, and colourity is good, can obtain high-quality petroleum naphtha, solvent oil, whiteruss, diesel oil distillate, lubricant base oil fraction and high-quality wax etc.
Description of drawings
Accompanying drawing 1 is the process flow sheet of Fischer-Tropsch synthetic one reactor drum hydrogenation technique of the present invention.
Embodiment
A kind of embodiment of this programme is briefly described below in conjunction with the process flow sheet of accompanying drawing 1:
Its dynamic flow is following: the Fischer-Tropsch synthetic raw material mixes with hydrogen after the volume pump metering; Get into hydrogenator through pipeline again, raw material at first through the first segment protect agent, removes mechanical impurity; Alkalies and alkaline earth impurity; Then on second section hydrogenation catalyst, carry out part or all of hydrogenation of olefins, on hydrogenation catalyst more than the 3rd section or the 3rd section, carry out the unifining of surplus alkene and organic oxygen-containing compound then, hydrorefined reaction conditions is: temperature of reaction is 260 ℃; Pressure is 4.0MPa, and air speed is 1.0h
-1, hydrogen to oil volume ratio (under the standardpressure) is 600; Product behind the hydrogenation is flowed out by reactor drum; Get into separator through pipeline; Through after the simple separation; The hydrogen partial recycle, all the other products get into separation column, after separating, can obtain high-quality petroleum naphtha, solvent oil, whiteruss, diesel oil distillate, lubricant base oil fraction and high-quality wax etc.
In order to further specify all main points of the present invention, below in conjunction with specific embodiment the present invention is done further explanation, but be not limited to following embodiment; The percentage composition that relates among the said wherein embodiment is a weight percentage.
Embodiment 1
With the synthetic full cut product of Fischer-Tropsch is raw material; First section filling protective material in the reactor drum; Second section is the bimetallic catalyst of alumina load, molecular sieve carried bimetallic catalyst and the trimetallic catalyst mixed packing of alumina load; The synthetic full cut product of Fischer-Tropsch mixes with hydrogen after the volume pump metering, gets into hydrogenator, through controlling suitable reaction conditions; Under relatively mild condition, raw material is carried out unifining, the product after the unifining can obtain high-quality petroleum naphtha, solvent oil, whiteruss, diesel oil distillate, lubricant base oil fraction and high-quality wax etc. through separating.Olefin conversion is 100.0%; The transformation efficiency of organic oxacid is 98.5%, and the organic oxygen-containing compound decreasing ratio is 95%, and diesel product acidity is 0.20mgKOH/100ml; Metals content impurities such as Fe, Cu, Mn, K, Ca are all less than 0.1ppm, and concrete experimental result is seen table 3.Processing condition are seen table 1, and feedstock property is seen table 2.
Table 1
Table 2
Embodiment 2
With the synthetic full cut product of Fischer-Tropsch is raw material; First section filling protective material in the reactor drum; Second section is the bimetallic catalyst of alumina load, and the 3rd section is the molecular sieve carried bimetallic catalyst and the trimetallic catalyst mixed packing of silica-alumina load, and the synthetic full cut product of Fischer-Tropsch mixes with hydrogen after the volume pump metering; Get into hydrogenator; Through controlling suitable reaction conditions, under relatively mild condition, raw material is carried out unifining, the product after the unifining can obtain high-quality petroleum naphtha, solvent oil, whiteruss, diesel oil distillate, lubricant base oil fraction and high-quality wax etc. after separating.Olefin conversion is 100.0%; The transformation efficiency of organic oxacid is 99.0%, and the organic oxygen-containing compound decreasing ratio is 96.2%, and diesel product acidity is 0.15mgKOH/100ml; Metals content impurities such as Fe, Cu, Mn, K, Ca are all less than 0.1ppm, and concrete experimental result is seen table 3.Processing condition are seen table 1, and feedstock property is seen table 2.
Embodiment 3～10
Embodiment 3～10th, are raw material with the synthetic full cut product of Fischer-Tropsch; Carrying out on the fixed-bed reactor continuously; Operating process is with embodiment 1, and metals content impurities such as Fe, Cu, Mn, K, Ca are all less than 0.1ppm in the product, and catalyzer all adopts four sections types of feed; First section filling protective material in the reactor drum, the synthetic full cut product unifining result of the catalyst type of second section, the 3rd section, the 4th section use and Fischer-Tropsch sees table 3.Processing condition are seen table 1, and feedstock property is seen table 2.
The result shows that technical process provided by the invention is fit to contain alkene and contains the unifining of the synthetic full cut product of Fischer-Tropsch of a certain amount of organic oxygen-containing compound very much.
Below described embodiment of the present invention in detail, can do a lot of improvement and variation obviously for a person skilled in the art and can not deviate from essence spirit of the present invention.All these variations and improvement are all within protection scope of the present invention.
Claims (10)
1. the hydrogenation technique of a Fischer-Tropsch synthetic; The hydrogen refining process that it is characterized in that said Fischer-Tropsch synthetic is in single hydrogenator, to accomplish; This hydrogenator adopts the catalyzer more than two sections or two sections, and wherein first section is protective material, and all the other sections are hydrogenation catalyst; Said hydrogenation technique comprises the Fischer-Tropsch synthetic warp mixed with hydrogen and feeds said reactor drum; At first make said raw material pass through protective material; Under the hydrogenation catalyst existence condition, carry out hydrogenation reaction then; The processing condition of said hydrogenation reaction are: temperature of reaction is 200～320 ℃, and pressure is 2.0～10MPa, and air speed is 0.3～8.0h
-1, hydrogen to oil volume ratio is 300～1500 under the standardpressure; Can obtain high-quality petroleum naphtha, solvent oil, whiteruss, diesel oil distillate, lubricant base oil fraction and high-quality wax by said unifining and after separating.
2. according to the hydrogenation technique of the said Fischer-Tropsch synthetic of claim 1, it is characterized in that described protective material is commercially available demetalization protective material, or homemade demetalization protective material.
3. according to the hydrogenation technique of the said Fischer-Tropsch synthetic of claim 2, it is characterized in that described hydrogenator adopts the catalyzer more than three sections or three sections, preferably adopts four sections catalyzer.
4. according to the hydrogenation technique of the said Fischer-Tropsch synthetic of claim 3, it is characterized in that described each section hydrogenation catalyst can be a kind of hydrogenation catalyst, or the mixing of two or more hydrogenation catalyst.
5. according to the hydrogenation technique of the said Fischer-Tropsch synthetic of claim 4, it is characterized in that said hydrogenation catalyst is sulphided state or unvulcanised attitude hydrogenation catalyst; Preferred said hydrogenation catalyst is a unvulcanised attitude hydrogenation catalyst.
6. according to the hydrogenation technique of the said Fischer-Tropsch synthetic of claim 6, it is characterized in that said unvulcanised hydrogenation catalyst is to load on the hydrogenation catalyst that group vib, VIIB family and VIII family metal and non-metal kind on aluminum oxide and/or molecular sieve and/or the silica supports are formed.
7. according to the hydrogenation technique of any said Fischer-Tropsch synthetic of claim 1-6, it is characterized in that used raw material Fischer-Tropsch synthetic is the full cut product of Fischer-Tropsch synthesis oil, or a kind of cut in the Fischer-Tropsch synthetic or the mixture of several fractions.
8. according to the hydrogenation technique of the said Fischer-Tropsch synthetic of claim 7, it is characterized in that used raw material Fischer-Tropsch synthetic is the synthetic full cut product of Fischer-Tropsch, its carbon distribution is C4～C100; When used raw material Fischer-Tropsch synthetic was the synthetic full cut product of Fischer-Tropsch, said hydrogenation reaction processing condition are: temperature of reaction was 220～300 ℃, and pressure is 4.0～8.0MPa, and air speed is 0.5～2.0h
-1, the hydrogen to oil volume ratio under the standardpressure is 600～1000.
9. according to the hydrogenation technique of the said Fischer-Tropsch synthetic of claim 7, it is characterized in that used raw material Fischer-Tropsch synthetic is a Fischer-Tropsch synthetic mesophase cut product, its carbon distribution is C6～C50; When raw materials used Fischer-Tropsch synthetic was Fischer-Tropsch synthetic mesophase cut product, the processing condition of said hydrogenation reaction were: temperature of reaction is 200～280 ℃, and pressure is 4.0～8.0MPa, and air speed is 0.5～2.0h
-1, the hydrogen to oil volume ratio under the standardpressure is 600～1000.
10. according to the hydrogenation technique of the said Fischer-Tropsch synthesis oil of claim 7, it is characterized in that used raw material Fischer-Tropsch synthetic is a Fischer-Tropsch synthetic heavy cut, its carbon distribution is C8～C100; When used raw material Fischer-Tropsch synthetic was Fischer-Tropsch synthetic heavy cut, the processing condition of said hydrogenation reaction were: temperature of reaction is 220～300 ℃, and pressure is 4.0～8.0MPa, and air speed is 0.5～2.0h
-1, the hydrogen to oil volume ratio under the standardpressure is 600～1000.
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| CN104673384A (en) * | 2015-03-02 | 2015-06-03 | 武汉凯迪工程技术研究总院有限公司 | Hydrofining method for much production of middle distillate obtained from low-temperature Fischer-Tropsch full-range oil |
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| CN104611059A (en) * | 2015-02-12 | 2015-05-13 | 武汉炼化工程设计有限责任公司 | Method for preparing liquid paraffin, paraffin precursor and lubricant base oil precursor from Fischer-Tropsch synthesis products |
| RU2678443C1 (en) * | 2015-03-02 | 2019-01-29 | Ухань Кайди Инджиниринг Текнолоджи Рисерч Инститьют Ко., Лтд. | Fisher-tropsh low-temperature distillate hydraulic cleaning method having the medium distillates high output |
| CN104673384A (en) * | 2015-03-02 | 2015-06-03 | 武汉凯迪工程技术研究总院有限公司 | Hydrofining method for much production of middle distillate obtained from low-temperature Fischer-Tropsch full-range oil |
| WO2016138832A1 (en) * | 2015-03-02 | 2016-09-09 | 武汉凯迪工程技术研究总院有限公司 | Method of hydrofining low-temperature fischer-tropsch distillate having high yield of middle distillates |
| US10450519B2 (en) * | 2015-03-02 | 2019-10-22 | Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. | Method for hydrofining of middle distillates of Fischer-Tropsch synthetic full-range distillates |
| KR20170116108A (en) * | 2015-03-02 | 2017-10-18 | 우한 카이디 엔지니어링 테크놀로지 리서치 인스티튜트 코오퍼레이션 엘티디. | A method for hydrogen purification of a low temperature Fischer-Tropsch flow with a high yield of intermediate oil |
| KR101960627B1 (en) | 2015-03-02 | 2019-03-20 | 우한 카이디 엔지니어링 테크놀로지 리서치 인스티튜트 코오퍼레이션 엘티디. | A method for hydrogen purification of a low temperature Fischer-Tropsch flow with a high yield of intermediate oil |
| CN106635161A (en) * | 2016-12-28 | 2017-05-10 | 神华集团有限责任公司 | Method for preparing coal-based heavy liquid paraffin from coal indirect liquefaction oil product and coal-based heavy liquid paraffin prepared through method |
| CN106675649A (en) * | 2016-12-28 | 2017-05-17 | 神华集团有限责任公司 | Method for preparing coal-based light liquid paraffin from coal indirect liquefied oil product and coal-based light liquid paraffin obtained through method |
| CN108203598A (en) * | 2017-12-15 | 2018-06-26 | 赛鼎工程有限公司 | A kind of technique of F- T synthesis light hydrocarbon hydrofinishing |
| CN108165307A (en) * | 2017-12-15 | 2018-06-15 | 赛鼎工程有限公司 | A kind of technique of Fischer-Tropsch synthesis of heavy hydrocarbon hydrofinishing |
| CN110016363A (en) * | 2018-01-08 | 2019-07-16 | 神华集团有限责任公司 | Fischer-Tropsch synthesis oil processing produces the method and system of diesel oil and lube base oil |
| CN110016363B (en) * | 2018-01-08 | 2020-12-18 | 神华集团有限责任公司 | Method and system for producing diesel oil and lubricant base oil by processing Fischer-Tropsch synthetic oil |
| CN110964563A (en) * | 2018-09-28 | 2020-04-07 | 中国科学院大连化学物理研究所 | Hydrofining method for preparing mixed alcohol crude product from synthesis gas |
| CN110964563B (en) * | 2018-09-28 | 2021-08-31 | 中国科学院大连化学物理研究所 | Hydrofining method for preparing mixed alcohol crude product from synthesis gas |
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Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Applicant after: Zhongke Synthetic Oil Technology Co., Ltd. Address before: Jiahua hi tech Development Zone, Shanxi province Taiyuan city 030032 Street No. 6 Applicant before: Zhongke Synthetic Oil Technology Co., Ltd. |
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