CN107760406A

CN107760406A - A kind of method for transformation of Fischer Tropsch waxes

Info

Publication number: CN107760406A
Application number: CN201610681637.0A
Authority: CN
Inventors: 李洪辉; 郭庆洲; 王鲁强; 高杰; 黄卫国; 李洪宝; 毕云飞
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-08-17
Filing date: 2016-08-17
Publication date: 2018-03-06
Anticipated expiration: 2036-08-17
Also published as: CN107760406B

Abstract

The present invention relates to Fischer Tropsch waxes manufacture field, discloses a kind of method for transformation of Fischer Tropsch waxes, including：Fischer Tropsch waxes are contacted with hydrotreating catalyst, raw material after obtained hydrotreating is fractionated, the second component that content by cut of the obtained carbon number more than 40 is more than 90 weight % contacts with hydrogenation conversion catalyst, the first component that content by the cut of the material after obtained hydro-conversion and carbon number less than or equal to 40 is more than 90 weight % contacts with isomerization-visbreaking catalyst separately or together, and obtained wax is converted into oil contacts with Hydrobon catalyst and be then fractionated.Cut of the carbon number in Fischer Tropsch waxes more than 40 can be converted into lube cut segment limit by method provided by the invention by hydro-conversion, reduce the dewaxing difficulty of follow-up isomerization-visbreaking course of reaction, the excessive fragmentation of heavy Fischer Tropsch waxes is avoided, and lube base oil yield can be improved.

Description

A kind of method for transformation of Fischer Tropsch waxes

Technical field

The present invention relates to Fischer Tropsch waxes manufacture field, in particular it relates to a kind of method for transformation of Fischer Tropsch waxes.

Background technology

As petroleum resources are increasingly reduced and the raising of environmental requirement, the life of clean fuel, top-grade lubricating oil base oil Production will be more and more by Fischer Tropsch waxes as raw material.

Fischer Tropsch waxes are that the hydro carbons produced by coal, natural gas and biomass by gas making and F- T synthesis technology mixes Thing, mainly it is made up of the different normal paraffins of carbon number and isomerization alkanes, not sulfur-bearing, nitrogen or metal impurities, is a kind of production The desirable feedstock of lube base oil.

F- T synthesis wax product is 1~120 by carbon number range, the hydrocarbon compound structure of even more than 120 carbon atoms Into.Because the carbon number range of lube cut section is C₂₀~C₄₀, carbon number is more than 20 normal paraffins or different in Fischer Tropsch waxes Paraffins can obtain the base oil of high viscosity index lubricant of different viscosities grade by converting.

CN101230290A discloses a kind of from the side of Fischer Tropsch waxes production solvent naphtha, lube base oil and heavy wax Method, including：A) Fischer Tropsch waxes are contacted with Hydrobon catalyst in hydrofining reaction area I, in distillation zone, I is by the product Separation, the end point of distillation is obtained less than 380 DEG C to 550 DEG C and initial boiling point is more than 380 DEG C to 550 DEG C two kinds of cuts；B) add in a wax Hydrogen conversion reaction zone contacts cut of the end point of distillation less than 380 DEG C to 550 DEG C with hydroisomerisation catalysts, prepares a kind of pour point The wax reduced is converted into oil；C) wax is converted into oily connecing with a kind of Hydrobon catalyst in hydrofining reaction area II Touch, and the product is separated in distillation zone II, obtain at least one solvent naphtha and at least one lube base oil；D) it is being hydrogenated with Refining reaction area III contacts cut of the initial boiling point more than 380 DEG C to 550 DEG C with a kind of Hydrobon catalyst, obtains one kind The wax of hydrogenated decolouring.The purpose of the method for the prior art is to process Fischer Tropsch waxes to produce with multifarious production Product, such as the multiple product such as solvent naphtha, base oil and heavy wax.Initial boiling point in Fischer Tropsch waxes is more than 380 DEG C to 550 by it DEG C cut as production heavy wax raw material, cause the total recovery of lube base oil product to decline to a great extent.The prior art The yield of lube base oil enumerated of embodiment part be not lube base oil total recovery, it is but small with the end point of distillation Yield on the basis of 380 DEG C to 550 DEG C of cut.Therefore, the total recovery of its lube base oil is not high.

CN102533329A discloses a kind of method that lube base oil is produced by f-t synthetic wax, including：A) adding Hydrogen refining reaction area I contacts Fischer Tropsch waxes with Hydrobon catalyst, obtains the expense after a kind of hydrogenated olefin saturation, deoxidation Hold in the palm synthetic wax；B) in a Ge La hydroconversion reactions area A by the obtained Fischer Tropsch waxes of step a) and hydroisomerisation catalysts Contact, the wax that obtaining a kind of pour point reduces are converted into oil；C) step b) is obtained in a Ge La hydroconversion reactions area B Wax is converted into oil and contacted with hydroisomerisation catalysts, obtains the wax that a kind of pour point reduce further and is converted into oil；d) The wax that the obtained pour points of step c) reduce further is converted into oil in hydrofining reaction area II to be catalyzed with hydrofinishing Agent contacts, and obtains the wax after a kind of hydrofinishing and is converted into oil, e) the generation oil that obtains step d) a distillation zone From obtaining lube base oil.The method of the prior art relaxes pour point depression by two sections of isomerization reaction zone substeps, can suitably carry Higher baseline oil yield, but due to containing the higher n-alkane of a large amount of carbon numbers in Fischer Tropsch waxes, it is directly entered isomerization reaction zone Or the reaction of excessive fragmentation can occur, cause lube base oil yield to decline, viscosity index (VI) reduces.

CN1761734A discloses a kind of method that base oil is produced by f-t synthetic wax, including：(a) by F- T synthesis It is intermediate oil scope and lower cut (i) that product, which is separated into boiling point, heavy ends (iii), and boiling point is between cut (i) Intermediate base oil precursor cut (ii) between cut (iii)；(b) make base oil precursor fraction (ii) experience catalytic hydrogenation different Structure and CATALYTIC DEWAXING TECHNIQUE, to produce one or more base oil grades；(c) heavy ends (iii) are made to undergo step of converting, To produce the cut (iv) that boiling point is less than heavy ends (iii)；The high boiling fraction (v) of cut (iv) is undergone catalysis (d) Hydroisomerization and CATALYTIC DEWAXING TECHNIQUE, to produce one or more base oil grades.The method of the prior art is through repeatedly dividing Evaporate, hydro-conversion can produce qualified lube base oil.Wherein heavy-tailed oil distillate experience hydro-conversion, fractionation, catalysis add Catalytic dewaxing produces base oil again after hydrogen isomerization, and flow is excessively complicated, can cause reduction, the viscosity of lube base oil yield Figure penalties increase.

Therefore, the above-mentioned different method for transformation for Fischer Tropsch waxes, high-viscosity index lubricating oil basis can be obtained Oil, but because Fischer Tropsch waxes boiling range is wider, it is converted, and procedure of processing is more, reaction is complicated, and base oil yield can be caused relatively low, and Flocculation phenomenon generally occurs in product.

In order to improve lube base oil product yield and quality, it is necessary to which further studying new Fischer Tropsch waxes converts work Skill.

The content of the invention

The present invention be directed to lube base oil yield in the Fischer Tropsch waxes conversion process of prior art is low, heavy Fischer-Tropsch Wax fraction be difficult to conversion the problems such as a kind of method for transformation of Fischer Tropsch waxes is provided, with improve lube base oil product yield and Quality.

To achieve these goals, the present invention provides a kind of method for transformation of Fischer Tropsch waxes, including：

(1) Fischer Tropsch waxes are contacted with hydrotreating catalyst, obtains the raw material after hydrotreating；

(2) raw material after the hydrotreating for obtaining step (1) is fractionated, and obtains cut of the carbon number less than or equal to 40 Content is that the content of the cut of more than 90 weight % the first component and carbon number more than 40 is more than 90 weight % the second component；

(3) the second component that step (2) obtains is contacted with hydrogenation conversion catalyst, obtains the material after hydro-conversion；

(4) the first component that the material after the hydro-conversion for obtaining step (3) and step (2) obtain is separately or together Contacted with isomerization-visbreaking catalyst, obtain wax and be converted into oil；

(5) wax that step (4) obtains is converted into oil to contact with Hydrobon catalyst, obtains the life after hydrofinishing Into oil；And

(6) the generation oil after the hydrofinishing for obtaining step (5) is fractionated, and obtains lube base oil.

Method provided by the invention carries out hydrogenation deoxidation and alkene saturation to Fischer Tropsch waxes first, then according to its cut Carbon number distribution corresponding to scope, Fischer Tropsch waxes are cut into predominant amount as first group of cut of carbon number less than or equal to 40 Divide the second component for cut of the carbon number more than 40 with predominant amount.Wherein predominant amount is cut of the carbon number less than or equal to 40 First component directly carries out isomerization-visbreaking；Predominant amount is that to be introduced into hydro-conversion anti-for the second component of cut of the carbon number more than 40 Area is answered, isomerization-visbreaking reaction zone is then passed through again and carries out pour point depression.The product of last isomerization-visbreaking reaction zone is by hydrofinishing, steaming Cut obtains the lube base oil of high viscosity index (HVI) from rear in high yield.

The present inventor has found under study for action, during the cracking reaction in hydroconversion reactions area, long-chain normal Alkane component is more beneficial in carbochain central breaks, so that heavy Fischer-Tropsch wax fraction of the carbon number more than 40 is converted into C₂₀~C₄₀ Lubricant base oil fraction segment limit.Therefore, the raw material after hydrotreating is fractionated, it is carbon to respectively obtain predominant amount First component of cuts of the number less than or equal to 40 and second component that predominant amount is cut of the carbon number more than 40, and will obtain Two kinds of cuts are processed using different subsequent machining technologies, reduce the dewaxing difficulty of follow-up isomerization-visbreaking course of reaction, The excessive fragmentation of heavy Fischer Tropsch waxes is avoided, improves lube base oil yield.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Brief description of the drawings

Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：

Fig. 1 is a kind of process chart of the method for transformation of Fischer Tropsch waxes of the present invention.

Fig. 2 is the process chart of the method for transformation of another Fischer Tropsch waxes of the present invention.

Embodiment

The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more New number range, these number ranges should be considered as specific open herein.

The invention provides a kind of method for transformation of Fischer Tropsch waxes, including：

Preferably, Fischer Tropsch waxes are contacted with hydrotreating catalyst to obtain a kind of hydrogenation deoxidation and alkene saturation Raw material, that is, the raw material after the hydrotreating can be a kind of hydrogenation deoxidation and the raw material of alkene saturation.

There is no particular limitation to the concrete operation method that is fractionated in step (2) for the method for the present invention, this area skill Art personnel can use conventional fractional method in the art to carry out, as long as the cut that carbon number is less than or equal to 40 can be respectively obtained Content be that the content of the cut of more than 90 weight % the first component and carbon number more than 40 is more than 90 weight % second group Point.For example, the fractionation can be carried out in fractionating column.Also, the distillation can be in one or more flash distillation, normal pressure Carried out in distillation and the operating unit being evaporated under reduced pressure.Specifically, in the present invention, those skilled in the art can be by using this The carbon number distribution situation of the conventional analytical feedstock oil in field, and determine that carbon number is less than according to the carbon number distribution situation The content of cut equal to 40 is that the content of the cut of the first component and carbon number more than 40 more than 90 weight % is 90 weight % The cut point of the second component above.

In the case of more preferably, in the first component stated before this invention, the content of cut of the carbon number less than or equal to 40 is More than 95 weight %；And in the second component, the content of cut of the carbon number more than 40 is more than 95 weight %.

It can be the wax that pour point reduces to be converted into oil by the wax obtained after being contacted with isomerization-visbreaking catalyst It is converted into oil.

Preferably, containing carrier and load active component on the carrier and appoint in the hydrotreating catalyst Choosing contains adjuvant component, and the carrier is selected from least one of silica, aluminum oxide, silica-alumina and molecular sieve, institute The metallic element for stating active component is selected from least one of nickel, cobalt, molybdenum and tungsten, and the active element of the adjuvant component is selected from At least one of fluorine, boron and phosphorus.It is described optionally to be represented containing adjuvant component, it can contain in the hydrotreating catalyst and help Agent component can also not contain adjuvant component.

Preferably, with the gross weight meter of the hydrotreating catalyst, contain in the hydrotreating catalyst with oxidation The total amount of thing meter be 1~5 weight % nickel and cobalt, molybdenum and tungsten using the total amount that oxide is counted as 10~40 weight %, with element The total amount of meter is 0~10 weight % adjuvant component.It should be strongly noted that contain in the hydrotreating catalyst with oxygen The total amount of compound meter is that 1~5 weight % nickel and cobalt refer to, nickel and/or cobalt can be contained in the hydrotreating catalyst, only Will be using the nickel and the total amount of cobalt that oxide is counted as 1~5 weight %.For containing in the hydrotreating catalyst with oxidation The total amount of thing meter is that 10~40 weight % molybdenum and tungsten also have and the explanation of the total amount identical of above-mentioned nickel and cobalt.It is foregoing in terms of element Total amount be 0~10 weight % adjuvant component represent, adjuvant component can be contained, adjuvant component can also not contained.

In a particular embodiment, the hydrotreating catalyst can selected from one kind in following catalyst, including： It is a kind of using silica-alumina as disclosed in the fluorine-containing of carrier, phosphorus hydrogenation catalyst, CN1853779A disclosed in CN1853780A A kind of using silica-alumina is one kind disclosed in the hydrogenation catalyst of containing fluorin of carrier, CN1853781A with silica-alumina For disclosed in the hydrogenation catalyst of containing phosphor of carrier, CN1872959A it is a kind of using aluminum oxide as the hydrogenation catalyst of containing fluorin of carrier and A kind of hydrogenation catalyst of containing phosphor using aluminum oxide as carrier disclosed in CN1872960A.

It is on the books in above-mentioned prior art literature on the more detailed preparation method of above-mentioned catalyst, here in the lump Using them as a part for present invention to quote.

Preferably, the active component in the hydrogenation conversion catalyst containing carrier and load on the carrier, it is described Carrier includes component A and component B, the component A are selected from least one of silica, aluminum oxide and silica-alumina, institute State component B and be selected from least one of beta-molecular sieve, Y type molecular sieve and USY molecular sieve, the metallic element in the active component Selected from least one of ruthenium, rhodium, platinum and palladium；Metallic element in more preferably described active component is platinum.

Preferably, with the gross weight meter of the hydrogenation conversion catalyst, contain in the hydrogenation conversion catalyst with metal 0.1~10 weight % of meter active component；It is highly preferred that contain 0.2~5 in terms of metal in the hydrogenation conversion catalyst Weight % active component.

According to a kind of preferred embodiment, in the hydrogenation conversion catalyst, the component A in the carrier is Silica-alumina, component B is USY molecular sieve, and on the basis of the total amount of the carrier, the content of the component B is 3-70 weights Measure %；It is highly preferred that the content of the component B is 10-60 weight %；It is particularly preferred that the content of the component B is 20-50 Weight %.

The present inventor has found under study for action, big from foregoing hydrogenation conversion catalyst of the invention and foregoing carbon number When the second component for being more than 90 weight % in the content of 40 cut is contacted, the lubrication of the present invention can be especially improved The yield of oil base oil.Especially, present inventor has further discovered that, using the hydrogenation in preceding preferred embodiment of the present invention When reforming catalyst is contacted with the second component that the content of cut of the foregoing carbon number more than 40 is more than 90 weight %, second Cut of the carbon number more than 40 in component more can be broken from the middle of carbochain, be converted into carbon number between 20-40 Lubricant base oil fraction segment limit so that the yield and quality for the lube base oil that method of the invention obtains reach most It is excellent.

Preferably, at least one of ruthenium, rhodium, platinum and palladium are selected from containing group VIII in the isomerization-visbreaking catalyst Active metallic element, more preferably platinum and/or palladium.

Preferably, in the isomerization-visbreaking catalyst, with the gross weight meter of the isomerization-visbreaking catalyst, described The content of group VIII metal element is 0.1~10 weight %, more preferably 0.1~5 weight %.

Preferably, the carrier of the isomerization-visbreaking catalyst is selected from least one of molecular sieve and aluminum oxide.

For example, CN1488733A, CN1448480A, CN1289643A, CN1228357A, CN1803998A and Isomerization-visbreaking catalyst disclosed in CN1382526A, all with good wax hygrogenating isomerization reaction performance, it can be used as different Structure pour point depression catalyst is used for the present invention.Isomerization-visbreaking catalyst disclosed in especially CN1382526A is when for the present invention, tool There are more preferable wax activity of conversion and the selectivity to lube base oil, therefore particularly suitable for the present invention.

It is on the books in the document of above-mentioned prior art on the more detailed preparation method of above-mentioned catalyst, here one And quoted them as a part for present invention.

According to method provided by the invention, the Hydrobon catalyst is mainly used in remaining in oil plant after removing dewaxes The impurity such as sulfur-bearing, nitrogen, oxygen, and saturation of olefins is to improve the stability of oil product and color.

Preferably, containing carrier and load active component on the carrier and appoint in the Hydrobon catalyst The adjuvant component contained is selected, the carrier is selected from least one of silica, aluminum oxide and silica-alumina, the work Property component in metallic element be selected from least one of vib element and group VIII element, the adjuvant component Active element is selected from least one of fluorine, phosphorus and boron.Likewise, in the Hydrobon catalyst, it is described optionally to contain Adjuvant component represent that can contain adjuvant component in the Hydrobon catalyst can also not contain adjuvant component.

For example, disclosed in CN1245204A, CN1105053A, CN1136069A, CN1169336A and CN1803283A Hydrobon catalyst, all with the full activity of fine hydrogenated olefin, can Hydrobon catalyst be used as to be used for the present invention.Especially Be Hydrobon catalyst disclosed in CN1245204A when for the present invention, there is higher hydrogenation activity and sulfur resistance, Therefore particularly suitable for the present invention.

Preferably, the condition that Fischer Tropsch waxes contact with hydrotreating catalyst includes：Pressure is 3~20MPa, and temperature is 300~420 DEG C, volume space velocity is 0.3~5h^-1, hydrogen to oil volume ratio is 100~2000；It is highly preferred that Fischer Tropsch waxes and hydrogenation The condition of processing catalyst contact includes：Pressure is 5~18MPa, and temperature is 320~400 DEG C, and volume space velocity is 0.5~2.5h^-1, hydrogen to oil volume ratio is 500~1500.

Preferably, the condition that the second component contacts with hydrogenation conversion catalyst includes：Pressure is 3~20MPa, and temperature is 280~400 DEG C, volume space velocity is 0.3~5h^-1, hydrogen to oil volume ratio is 100~2000；It is highly preferred that the second component turns with hydrogenation Changing the condition of catalyst contact includes：Pressure is 5~18MPa, and temperature is 300~380 DEG C, and volume space velocity is 0.5~3h^-1, hydrogen Oil volume ratio is 500~1500.

Preferably, in step (4), condition that material contacts with isomerization-visbreaking catalyst is 3~20MPa including pressure, Temperature is 300~390 DEG C, and volume space velocity is 0.3~5h^-1, hydrogen to oil volume ratio is 100~2000；It is highly preferred that material and isomery The condition of pour point depression catalyst contact is 5~18MPa including pressure, and temperature is 300~370 DEG C, and volume space velocity is 0.5~2.5h^-1, Hydrogen to oil volume ratio is 500~1500.Material and/or step after the hydro-conversion that " material " expression step (3) at this obtains (2) the first component obtained.

In the present invention, the first component that material and step (2) after the hydro-conversion that step (3) is obtained obtain respectively or Person contacts expression with isomerization-visbreaking catalyst together, can be by the material after hydro-conversion that step (3) obtain and step (2) To the first component contacted together with the isomerization-visbreaking catalyst of the same area, or the hydrogenation that step (3) can also be obtained The first component that material and step (2) after conversion obtain contacts with the isomerization-visbreaking catalyst of different zones respectively.If also, The first component that material and step (2) after the hydro-conversion that step (3) is obtained obtain drops with the isomery of different zones respectively Solidifying catalyst contact, the condition of contact can be with identical or different, as long as in the range of stating before this invention.

Preferably, the first component that material and step (2) after hydro-conversion step (3) obtained obtain together with it is different Structure pour point depression catalyst contacts.The contact can be carried out in the isomerization-visbreaking reaction zone containing the isomerization-visbreaking catalyst, It is highly preferred that the hydrogenation conversion catalyst is 0.1~10 with the isomerization-visbreaking Catalyst packing volume ratio：1, preferably 0.3 ~2.5：1.

Preferably, wax, which is converted into the condition that oil contacts with Hydrobon catalyst, includes：Pressure is 3~20MPa, temperature For 150~250 DEG C, volume space velocity is 0.3~5h^-1, hydrogen to oil volume ratio is 100~2000；It is highly preferred that wax be converted into oil with The condition of Hydrobon catalyst contact includes：Pressure is 5~18MPa, and temperature is 180~230 DEG C, volume space velocity is 0.5~ 3h^-1, hydrogen to oil volume ratio is 200~1000.

Preferably, the weight % of the content of the oxygen element in the Fischer Tropsch waxes≤1, and in the Fischer Tropsch waxes most High carbon number is less than or equal to 100, and preferably up to carbon number is less than or equal to 90.The highest carbon number refers to F- T synthesis less than or equal to 100 Carbon number not more than 100 in wax in each one-component.

Two kinds of preferred embodiments presented below further illustrate the method for transformation of the Fischer Tropsch waxes of the present invention：

Embodiment 1, the technique of the embodiment 1 are carried out using the technological process shown in Fig. 1, specifically：

A kind of method for transformation of Fischer Tropsch waxes, this method turn including hydrotreating reaction area I, distillation zone II, hydrogenation Change and implement in reaction zone III, isomerization-visbreaking reaction zone IV, hydrofining reaction area V and distillation zone VI system, including：

(1) Fischer Tropsch waxes are contacted with hydrotreating catalyst in hydrotreating reaction area I, obtains hydrogenation deoxidation and alkene The raw material of hydrocarbon saturation；

(2) raw material that step (1) obtains is fractionated in distillation zone II, obtains containing for cut of the carbon number less than or equal to 40 The content measured as cut of more than 90 weight % the first component and carbon number more than 40 is the second more than 90 weight % component；

(3) the second component that step (2) obtains is introduced into the hydroconversion reactions area III containing hydrogenation conversion catalyst to enter Row hydro-conversion, and will be introduced by obtaining material and first component after hydroconversion reactions area III reactions and be contained isomery The isomerization-visbreaking reaction zone IV of pour point depression catalyst carries out isomerization-visbreaking, and the wax for obtaining pour point reduction is converted into oil；

(4) wax that the pour point that step (3) obtains reduces is converted into oil and the hydrofinishing in hydrofining reaction area V Catalyst contacts, and obtains the oil of the generation after hydrofinishing；And

(5) the generation oil after the hydrofinishing for obtaining step (4) is fractionated in distillation zone VI, obtains lube base Oil.

Embodiment 2, the technique of the embodiment 2 are carried out using the technological process shown in Fig. 2, specifically： A kind of method for transformation of Fischer Tropsch waxes, this method is including hydrotreating reaction area I, distillation zone II, isomerization-visbreaking reaction zone IV-1, isomerization-visbreaking reaction zone IV-2, hydrofining reaction area V and distillation zone VI system in implement, including：

(3) the second component that step (2) obtains is introduced and contains hydrogenation conversion catalyst and isomerization-visbreaking catalyst successively Isomerization-visbreaking reaction zone IV-1 in carry out hydrogenation reaction, and first component is introduced and contains isomerization-visbreaking catalyst Isomerization-visbreaking reaction zone IV-2 carries out isomerization-visbreaking, goes out in the isomerization-visbreaking reaction zone IV-1 and isomerization-visbreaking reaction zone IV-2 The wax that pour point reduction is obtained at mouthful is converted into oil；

The present invention will be described in detail by way of examples below.In following examples, in the feelings being not particularly illustrated Under condition, the various raw materials that use are all from commercially available.Hydrotreating catalyst used below, hydrogenation conversion catalyst, isomery drop Solidifying catalyst and Hydrobon catalyst and preparation method thereof are as follows：

1st, hydrotreating catalyst

According to the preparation of example 6 in CN1853780A using fluorinated silicon oxide-aluminum oxide as carrier, fluorine, phosphorus are auxiliary agent group Point, nickel, molybdenum, tungsten are active component.Wherein on the basis of catalyst total amount, in terms of oxide, the mass fraction of nickel is 5%, molybdenum Mass fraction be 4%, the mass fraction of tungsten is 39.1%；In terms of element, the mass fraction of fluorine is 3.5%, the quality point of phosphorus Number is 1.1%, and remaining is silicaalumina carrier.

2nd, hydrogenation conversion catalyst

Hydrogenation conversion catalyst used below has three kinds, respectively hydrogenation conversion catalyst a, hydrogenation conversion catalyst b With hydrogenation conversion catalyst c.

Hydrogenation conversion catalyst a is carried on USY molecular sieve/silicaalumina carrier by active metal component of platinum Catalyst, wherein, on the basis of catalyst total amount, the mass fraction of platinum is 0.5%, and remaining is carrier；Using carrier as Benchmark, USY molecular sieve mass fraction are 30%, and remaining is silica-alumina.

Hydrogenation conversion catalyst b is carried on USY molecular sieve/silicaalumina carrier by active metal component of platinum Catalyst, wherein, on the basis of catalyst total amount, the mass fraction of platinum is 0.5%, and remaining is carrier；Using carrier as Benchmark, USY molecular sieve mass fraction are 60%, and remaining is silica-alumina.

Hydrogenation conversion catalyst c is carried on USY molecular sieve/silicaalumina carrier by active metal component of platinum Catalyst, wherein, on the basis of catalyst total amount, the mass fraction of platinum is 0.5%, and remaining is carrier；Using carrier as Benchmark, USY molecular sieve mass fraction are 80%, and remaining is silica-alumina.

3rd, isomerization-visbreaking catalyst

According to prepared by the example 6 in CN1382526A SAPO-11 molecular sieves/aluminum oxide is carried on by active component of platinum Supported catalyst, wherein on the basis of catalyst total amount, the mass fraction of platinum is 0.3%, and remaining is carrier.To carry On the basis of body, the mass fraction of SAPO-11 molecular sieves is 75% in the carrier, and remaining is aluminum oxide.

4th, Hydrobon catalyst

Prepared according to the example 3 in CN1245204A, wherein the mass fraction of platinum is 0.2%, the quality of palladium metal Fraction is 0.6%, and remaining is alumina support.

The yield of following lube base oil=(lube base oil quality/Fischer Tropsch waxes combined feed quality)

Embodiment 1

The present embodiment is using the Fischer Tropsch waxes in the technological process processing table 1 shown in Fig. 1, hydrotreating reaction area I dresses Hydrotreating catalyst is filled out, III filling hydrogenation conversion catalyst a, isomerization-visbreaking reaction zone IV fillings in hydroconversion reactions area are different Structure pour point depression catalyst, hydrofining reaction area V filling Hydrobon catalysts, operating condition is shown in Table 2, after distillation zone VI separation Lube base oil nature be shown in Table 3, wherein, cut of the carbon number less than or equal to 40 in the first component obtained in the II of distillation zone Content is 96.8 weight %, and the content of cut of the carbon number more than 40 is 97.6 weight % in the second obtained component.

Table 1

Project	Fischer Tropsch waxes
		Density (20 DEG C)/g.cm^{- 3}	0.8161
Fusing point/DEG C	85
		Sulfur content/μ gg^-1	<5
Nitrogen content/μ gg^-1	<1
		Oxygen content/weight %	0.82
Carbon number distribution/weight %
		≤C₄₀	51.03
C₄₀~C₈₃	48.97

Table 2

Process conditions	Hydrotreating zone I	Hydroconversion zone III	Isomerization-visbreaking area IV	Hydrofinishing district V
					Hydrogen dividing potential drop/MPa	8.0	10.0	10.0	10.0
Reaction temperature/DEG C	330	350	335	230
					Volume space velocity/h^-1	1.0	1.0	0.8	2.0
Hydrogen-oil ratio/(v/v)	800	500	500	500

Table 3

Product property
		Base oil yield/weight %	43.6
Kinematic viscosity/mm²·s^-1
		100℃	6.357
40℃	31.62
		Viscosity index (VI)	158
Pour point/DEG C	-38

Comparative example 1

This comparative example uses feedstock oil same as Example 1, identical catalyst, except that, saved in flow Hydroconversion reactions area III is removed, that is, not containing hydroconversion reactions area III in this comparative example, is also urged without using hydro-conversion Agent, carbon number are more than 40 cuts and carbon number and enter isomerization-visbreaking reaction zone IV processing less than or equal to 40 cuts, and operating condition is shown in Table 4, Lube base oil nature after distillation zone VI separation is shown in Table 5, wherein, carbon number is small in the first component obtained in the II of distillation zone It is 96.8 weight % in the content of the cut equal to 40, the content of cut of the carbon number more than 40 is 97.6 in the second obtained component Weight %.

Table 4

Process conditions	Hydrotreating zone I	Isomerization-visbreaking area IV	Hydrofinishing district V
				Hydrogen dividing potential drop/MPa	8.0	10.0	10.0
Reaction temperature/DEG C	330	335	230
				Volume space velocity/h^-1	1.0	0.8	2.0
Hydrogen-oil ratio/(v/v)	800	500	500

Table 5

Product property
		Base oil yield/weight %	28.4
Kinematic viscosity/mm²·s^-1
		100℃	6.132
40℃	30.98
		Viscosity index (VI)	150
Pour point/DEG C	-31

The result of analysis embodiment 1 and comparative example 1 can be seen that：Lube base oil product yield in embodiment 1 is more Height, pour point is lower, viscosity index (VI) is higher, hence it is evident that better than the lube base oil of the method acquisition of comparative example 1.

Embodiment 2

The present embodiment is using the Fischer Tropsch waxes in the technological process processing table 6 shown in Fig. 2, hydrotreating reaction area I dresses Hydrotreating catalyst is filled out, hydrogenation conversion catalyst a and isomery are loaded in layering to isomerization-visbreaking reaction zone IV-1 successively from top to bottom Pour point depression catalyst, both admission space ratios are 3：7, isomerization-visbreaking reaction zone IV-2 load isomerization-visbreaking catalyst, hydrogenation essence Reaction zone V processed loads Hydrobon catalyst, and operating condition is shown in Table 7, the lube base oil nature after distillation zone VI separation 8 are shown in Table, wherein, the content of cut of the carbon number less than or equal to 40 is 97.2 weight % in the first component obtained in the II of distillation zone, The content of cut of the carbon number more than 40 is 97.9 weight % in the second obtained component.

Table 6

Project	Fischer Tropsch waxes
		Density (20 DEG C)/g.cm^{- 3}	0.8395
Fusing point/DEG C	93
		Sulfur content/μ gg^-1	<5
Nitrogen content/μ gg^-1	<1
		Oxygen content/weight %	0.28
Carbon number distribution/weight %
		≤C₄₀	48.07
C₄₀~C₉₀	51.93

Table 7

Process conditions	Hydrotreating zone I	Isomerization-visbreaking area IV-1	Isomerization-visbreaking area IV-2	Hydrofinishing district V
					Hydrogen dividing potential drop/MPa	8.0	10.0	10.0	10.0
Reaction temperature/DEG C	350	340	340	230
					Volume space velocity/h^-1	1.0	0.8	0.8	2.0
Hydrogen-oil ratio/(v/v)	800	500	500	500

Table 8

Product property
		Base oil yield/weight %	41.8
Kinematic viscosity/mm²·s^-1
		100℃	5.967
40℃	29.15
		Viscosity index (VI)	156
Pour point/DEG C	-33

Comparative example 2

This comparative example uses work flow same as Example 2, identical feedstock oil, catalyst, except that Isomerization-visbreaking reaction zone IV-1 only loads isomerization-visbreaking catalyst, volume and the embodiment 2 of the isomerization-visbreaking catalyst loaded The cumulative volume of catalyst is identical in middle isomerization-visbreaking reaction zone IV-1, and operating condition is shown in Table 9, the lubrication after distillation zone VI separation Oil base oil property is shown in Table 10, wherein, the content of cut of the carbon number less than or equal to 40 in the first component obtained in the II of distillation zone For 97.2 weight %, the content of cut of the carbon number more than 40 is 97.9 weight % in the second obtained component.

Table 9

Table 10

Product property
		Base oil yield/weight %	25.7
Kinematic viscosity/mm²·s^-1
		100℃	5.864
40℃	29.33
		Viscosity index (VI)	149
Pour point/DEG C	-26

The result of analysis embodiment 2 and comparative example 2 can be seen that：Lube base oil product yield in embodiment 2 is more Height, pour point is lower, viscosity index (VI) is higher, hence it is evident that the lube base oil product obtained better than comparative example 2.

Embodiment 3

The present embodiment is using the Fischer Tropsch waxes in the technological process processing table 11 shown in Fig. 1, hydrotreating reaction area I dresses Hydrotreating catalyst is filled out, III filling hydrogenation conversion catalyst a, isomerization-visbreaking reaction zone IV fillings in hydroconversion reactions area are different Structure pour point depression catalyst, hydrofining reaction area V filling Hydrobon catalysts, operating condition are shown in Table 12, separated through distillation zone VI Lube base oil nature afterwards is shown in Table 13, wherein, carbon number evaporating less than or equal to 40 in the first component obtained in the II of distillation zone Point content be 96.9 weight %, the content that carbon number is more than 40 cut in the second obtained component is 97.2 weight %.

Table 11

Project	Fischer Tropsch waxes
		Density (20 DEG C)/g.cm^{- 3}	0.8225
Freezing point/DEG C	>50
		Sulfur content/μ gg^-1	<5
Nitrogen content/μ gg^-1	<1
		Oxygen content/weight %	0.6
Carbon number distribution/weight %
		≤C₄₀	87.61
C₄₀~C₆₈	12.39

Table 12

Process conditions	Hydrotreating zone I	Hydroconversion zone III	Isomerization-visbreaking area IV	Hydrofinishing district V
					Hydrogen dividing potential drop/MPa	8.0	10.0	10.0	10.0
Reaction temperature/DEG C	320	320	330	230
					Volume space velocity/h^-1	1.0	0.8	0.8	2.0
Hydrogen-oil ratio/(v/v)	800	500	500	500

Table 13

Product property
		Base oil yield/weight %	46.4
Kinematic viscosity/mm²·s^-1
		100℃	6.290
40℃	31.19
		Viscosity index (VI)	157
Pour point/DEG C	-45

Embodiment 4

The present embodiment is carried out using method similar to Example 1, except that：

The hydrogenation conversion catalyst used in the present embodiment is aforementioned hydrogenation reforming catalyst b, wherein, in the II of distillation zone To the first component in the content of cut of the carbon number less than or equal to 40 be 94.1 weight %, carbon number is more than in the second obtained component The content of 40 cut is 93.6 weight %.

Remaining is in the same manner as in Example 1.

As a result the lube base oil nature after distillation zone VI separation is shown in Table 14.

Table 14

Product property
		Base oil yield/weight %	40.2
Kinematic viscosity/mm²·s^-1
		100℃	6.187
40℃	30.97
		Viscosity index (VI)	154
Pour point/DEG C	-42

The result of analysis embodiment 4 and embodiment 1 can be seen that：Equally can be in high yield using hydrogenation conversion catalyst b Ground obtains lube base oil.But the present embodiment using with hydroconversion reactions area identical reaction temperature in embodiment 1 when, Cause decline, the reduction of viscosity index (VI) of base oil yield to a certain extent.If however, suitably it is hydrogenated with adjustment the present embodiment The temperature of conversion reaction zone, the product of property as shown in Example 1 can be equally obtained using hydrogenation conversion catalyst b.

Embodiment 5

The present embodiment is carried out using method similar to Example 2, except that：

The hydrogenation conversion catalyst used in the present embodiment is aforementioned hydrogenation reforming catalyst c, wherein, in the II of distillation zone To the first component in the content of cut of the carbon number less than or equal to 40 be 91.2 weight %, carbon number is more than in the second obtained component The content of 40 cut is 90.4 weight %.Namely turned with the hydrogenation in isometric hydrogenation conversion catalyst c alternative embodiments 2 Change catalyst a.Remaining is in the same manner as in Example 2.As a result the lube base oil nature after distillation zone VI separation see the table below 15。

Table 15

Product property
		Base oil yield/weight %	33.6
Kinematic viscosity/mm²·s^-1
		100℃	5.783
40℃	28.53
		Viscosity index (VI)	151
Pour point/DEG C	-39

The result of analysis embodiment 5 and embodiment 2 can be seen that：The lubrication oil base produced using hydrogenation conversion catalyst c Plinth oil, its base oil yield substantially reduce, viscosity index (VI) loss increase.

It is higher than by embodiment 5 with can be seen that the lube base oil yield in embodiment 5 in the result of comparative example 2 The yield of the lube base oil of comparative example 2, pour point are significantly lower than comparative example 2, and viscosity index (VI) is suitable, and combination property is substantially better than Comparative example 2.

Comparative example 3

This comparative example uses feedstock oil same as Example 1, but this comparative example uses CN101230290A implementation Method disclosed in example 1 handles the feedstock oil, after feedstock oil is refined by hydrofining reaction area, in distillation zone by hydrofinishing Wax separated afterwards, yield less than two kinds of materials of 500 DEG C of cuts and more than or equal to 500 DEG C cuts.500 DEG C of cuts will be less than to drop Solvent naphtha, lube base oil are obtained after solidifying, refined, fractionation；It will be greater than being equal to the refined production heavy wax of 500 DEG C of cut fraction hydrogenation. The lube base oil nature wherein obtained is shown in Table 16.

Table 16

Product property
		Base oil yield/weight %	25.7
Kinematic viscosity/mm²·s^-1
		100℃	5.211
40℃	23.62
		Viscosity index (VI)	160
Pour point/DEG C	-26

The result of analysis comparative example 3 and embodiment 1 can be seen that：Profit is produced according to the method disclosed in CN101230290A Lubricant base oil.In the case where comparative example 3 is suitable with the base oil viscosity index that embodiment 1 obtains, the embodiment of the present invention 1 The product that method obtains pour point is lower, yield is higher.

Comparative example 4

This comparative example uses feedstock oil same as Example 1, but this comparative example uses CN102533329A implementation Feedstock oil described in the table 1 of the method processing present invention disclosed in example 1, feedstock oil pass sequentially through two after hydrofinishing Wax hydroconversion reactions area, obtain lube base oil nature after final refining, fractionation and be shown in Table 17.

Table 17

Product property
		Base oil yield/weight %	34.8
Kinematic viscosity/mm²·s^-1
		100℃	5.752
40℃	28.50
		Viscosity index (VI)	149
Pour point/DEG C	-39

The result of analysis comparative example 4 and embodiment 1 can be seen that：Profit is produced according to the method disclosed in CN102533329A Lubricant base oil.In the case where comparative example 4 is suitable with the lube base oil pour point of embodiment 1, embodiments of the invention 1 The product that method obtains viscosity index (VI) is higher, yield is higher.

It can be seen from the results above that the dewaxing that method provided by the invention reduces follow-up isomerization-visbreaking course of reaction is difficult Degree, avoids the excessive fragmentation of heavy Fischer Tropsch waxes, improves lube base oil yield.

The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims

1. a kind of method for transformation of Fischer Tropsch waxes, including：

(2) raw material after the hydrotreating for obtaining step (1) is fractionated, and obtains the content of cut of the carbon number less than or equal to 40 The content of the cut of the first component and carbon number more than 40 for more than 90 weight % is the second more than 90 weight % component；

(4) the first component that the material after the hydro-conversion for obtaining step (3) and step (2) obtain separately or together with it is different Structure pour point depression catalyst contacts, and obtains wax and is converted into oil；

(5) wax that step (4) obtains is converted into oil to contact with Hydrobon catalyst, obtains the generation after hydrofinishing Oil；And

2. according to the method for claim 1, wherein, carrier is contained in the hydrotreating catalyst and is supported on the load Active component on body and optionally contain adjuvant component, the carrier be selected from silica, aluminum oxide, silica-alumina and At least one of molecular sieve, the metallic element of the active component is selected from least one of nickel, cobalt, molybdenum and tungsten, described to help The active element of agent component is selected from least one of fluorine, boron and phosphorus；Preferably,

With the gross weight meter of the hydrotreating catalyst, it is containing the total amount in terms of oxide in the hydrotreating catalyst 1~5 weight % nickel and cobalt, molybdenum and tungsten using the total amount that oxide is counted as 10~40 weight %, using the total amount that element is counted as 0~ 10 weight % adjuvant component.

3. method according to claim 1 or 2, wherein, carrier is contained in the hydrogenation conversion catalyst and is supported on institute The active component on carrier is stated, the carrier includes component A and component B, the component A are selected from silica, aluminum oxide and oxidation At least one of silicon-aluminum oxide, the component B are selected from least one of beta-molecular sieve, Y type molecular sieve and USY molecular sieve, Metallic element in the active component is selected from least one of ruthenium, rhodium, platinum and palladium；Preferably,

With the gross weight meter of the hydrogenation conversion catalyst, 0.1~10 in terms of metal is contained in the hydrogenation conversion catalyst Weight % active component；More preferably

In the hydrogenation conversion catalyst, the component A in the carrier is silica-alumina, and component B is USY molecular sieve, On the basis of the total amount of the carrier, the content of the component B is 3-70 weight %.

4. according to the method described in any one in claim 1-3, wherein, contain VIII in the isomerization-visbreaking catalyst The active metallic element selected from least one of ruthenium, rhodium, platinum and palladium of race；Preferably,

With the gross weight meter of the isomerization-visbreaking catalyst, the content of the group VIII metallic element is 0.1~10 weight %.

5. according to the method described in any one in claim 1-4, wherein, in the Hydrobon catalyst containing carrier and Load active component on the carrier and optionally contain adjuvant component, the carrier is selected from silica, aluminum oxide and oxygen At least one of SiClx-aluminum oxide, the metallic element in the active component are selected from vib element and group VIII member At least one of element, the active element of the adjuvant component are selected from least one of fluorine, phosphorus and boron.

6. according to the method described in any one in claim 1-5, wherein, Fischer Tropsch waxes contact with hydrotreating catalyst Condition include：Pressure is 3~20MPa, and temperature is 300~420 DEG C, and volume space velocity is 0.3~5h^-1, hydrogen to oil volume ratio 100 ~2000；Preferably,

The condition that Fischer Tropsch waxes contact with hydrotreating catalyst includes：Pressure is 5~18MPa, and temperature is 320~400 DEG C, Volume space velocity is 0.5~2.5h^-1, hydrogen to oil volume ratio is 500~1500.

7. according to the method described in any one in claim 1-6, wherein, what the second component contacted with hydrogenation conversion catalyst Condition includes：Pressure is 3~20MPa, and temperature is 280~400 DEG C, and volume space velocity is 0.3~5h^-1, hydrogen to oil volume ratio be 100~ 2000；Preferably,

The condition that second component contacts with hydrogenation conversion catalyst includes：Pressure is 5~18MPa, and temperature is 300~380 DEG C, body Product air speed is 0.5~3h^-1, hydrogen to oil volume ratio is 500~1500.

8. according to the method described in any one in claim 1-7, wherein, in step (4), material is catalyzed with isomerization-visbreaking The condition of agent contact includes：Pressure is 3~20MPa, and temperature is 300~390 DEG C, and volume space velocity is 0.3~5h^-1, hydrogen oil volume Than for 100~2000；Preferably,

The condition that material contacts with isomerization-visbreaking catalyst is 5~18MPa including pressure, and temperature is 300~370 DEG C, and volume is empty Speed is 0.5~2.5h^-1, hydrogen to oil volume ratio is 500~1500.

9. according to the method described in any one in claim 1-8, wherein, wax is converted into oil and connect with Hydrobon catalyst Tactile condition includes：Pressure is 3~20MPa, and temperature is 150~250 DEG C, and volume space velocity is 0.3~5h^-1, hydrogen to oil volume ratio is 100~2000；Preferably,

Wax, which is converted into the condition that oil contacts with Hydrobon catalyst, to be included：Pressure is 5~18MPa, and temperature is 180~230 DEG C, volume space velocity is 0.5~3h^-1, hydrogen to oil volume ratio is 200~1000.

10. according to the method for claim 1, wherein, the weight % of the content of the oxygen element in the Fischer Tropsch waxes≤1, And the highest carbon number in the Fischer Tropsch waxes is less than or equal to 100.