CN107312569B

CN107312569B - A kind of isoparaffin solvent oil that F- T synthesis naphtha produces the method for isoparaffin solvent oil and obtained by this method

Info

Publication number: CN107312569B
Application number: CN201610265309.2A
Authority: CN
Inventors: 金环年; 李丽; 马辉; 赵效洪; 高浩华; 李景; 艾军; 苗强
Original assignee: Shenhua Group Corp Ltd; National Institute of Clean and Low Carbon Energy
Current assignee: China Energy Investment Corp Ltd; National Institute of Clean and Low Carbon Energy
Priority date: 2016-04-26
Filing date: 2016-04-26
Publication date: 2019-05-21
Anticipated expiration: 2036-04-26
Also published as: CN107312569A

Abstract

The present invention relates to solvent naphtha preparation fields, disclose a kind of isoparaffin solvent oil that F- T synthesis naphtha produces the method for isoparaffin solvent oil and obtained by this method.The method comprise the steps that F- T synthesis naphtha is carried out dehydration of alcohols reaction in the presence of a catalyst to prepare alkene by (1)；(2) product that step (1) obtains is subjected to polymerization reaction in the presence of polymerization catalyst；(3) product that step (2) obtains is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst；(4) by the way that initial boiling point in the product of fractionation cutting step (3) is not less than 160 DEG C and the end point of distillation is not more than 340 DEG C of fraction, isoparaffin solvent oil is obtained.The method of F- T synthesis naphtha production isoparaffin solvent oil of the invention, the yield and purity is high of isoparaffin solvent oil, and it is good by the of light color of isoparaffin solvent oil product, oxidation stability and the thermal stability that this method obtains, the content of aromatic hydrocarbons, sulphur and nitrogen compound is negligible.

Description

The method of a kind of F- T synthesis naphtha production isoparaffin solvent oil and by this method Obtained isoparaffin solvent oil

Technical field

The present invention relates to solvent naphtha preparation fields, and in particular, to a kind of F- T synthesis naphtha production isoparaffin is molten The method of agent oil and the isoparaffin solvent oil obtained by this method.

Background technique

Solvent oil product is one of five major class oil products, solvent oil product can be divided into aromatic hydrocarbon, Porous deproteinized bone aliphatic category, Isomeric alkane hydro carbons, cycloalkane and N-alkanes hydro carbons etc., wherein isomeric alkane hydro carbons solvent naphtha is with condensation point is low, smell is small, toxicity The features such as low and good security, is widely used in print and dye diluent, printing ink solvent, intermetallic composite coating cleaning agent, antirust oil, tasteless spray Mist agent, tasteless oil paint, paint, organosol formula, high-grade clothing dry cleaner's naphtha, peroxide organic compound carrier, washing daily use chemicals Product etc..

Currently, the production of isomeric alkane hydro carbons solvent naphtha is mainly using isoparaffin and alkene as raw material, it is anti-by being alkylated It answers, hydrogenated redistillation obtains isoparaffin solvent oil, and the Isopars of gasoline fraction range generally can be obtained in this method Oil, and the isoparaffin solvent oil for producing kerosene or diesel oil distillate range is then more difficult.

Fischer-Tropsch synthesis oil have the undesirable components content such as sulphur, nitrogen, aromatic hydrocarbons it is extremely low, main group become chain type hydrocarbon, cycloalkane The features such as seldom with the content of aromatic hydrocarbons.Fraction is lighter in Fischer-Tropsch synthesis oil, and the olefin(e) centent in oil product is higher, and Determination of Alkane Content is got over It is low.The olefin(e) centent highest of F- T synthesis light fraction oil, olefin(e) centent can reach 40% or more.These features of Fischer-Tropsch oil make Obtain its alkane solvent oil for being relatively suitble to prepare low-sulfur, low virtue.

Existing research discovery, F- T synthesis light distillate can directly obtain solvent naphtha by hydro-upgrading, solvent naphtha tool There is the features such as high selection dissolubility, high stability, colorless and odorless, low-viscosity, but product is almost made of n-alkane, has There is higher condensation point.It needs thus using hydrofinishing-hydroisomerizing joint processing scheme, such as patent application US5,866,748 In be previously mentioned using C8-C20 Fischer-Tropsch synthesis oil carry out hydroisomerizing prepare isomery-normal alkane solvent oil method, it is made The cryogenic property and viscosity of standby solvent naphtha are obviously improved.It will be apparent that the alkene being possessed of higher values in Fischer-Tropsch synthesis oil Hydrocarbon is thoroughly wasted.

In order to which using the alkene in Fischer-Tropsch synthesis oil, patent application US6,605,206 are disclosed to F- T synthesis light fraction Oily (end point of distillation is at 300 DEG C or higher) carries out polymerization reaction, but its purpose product is lubricating oil.It specifically discloses a kind of increasing Add the method for C10 or more hydrocarbon products, comprising: (1) Fischer-Tropsch product being divided into Fischer-Tropsch wax and light liquid hydrocarbons, (end point of distillation is less than 370℃)；(2) the hydrogenated isomery of Fischer-Tropsch wax prepares the hydrocarbon component of higher boiling, low pour point；(3) in Fischer-Tropsch light hydrocarbon prepared by alcohol deoxidation Alkene；(4) olefinic polymerization prepares high-molecular-weight hydrocarbons；(5) cutting separation diesel oil, lube base oil component.It is different according to boiling point, The lube base oil of different viscosity ranks can be prepared.However, the patent application publication with F- T synthesis light distillate most In the method for a large amount of production lube base oil, though it is related to the oxygenatedchemicals dehydration in Fischer-Tropsch synthesis oil generating alkene Hydrocarbon, but the purpose product of this application is lube base oil, thus using similar to by α-alkene in subsequent polymerization reaction Hydrocarbon produces the poly reaction of synthetic lubricant base oil.

Patent application US2,004,267,071 discloses a kind of processing method of F- T synthesis light oil, specifically discloses: Fischer-Tropsch light fraction oily (C5-C19) through dehydroxylation converts alcohol in alkene and with after molecular sieve adsorbing and removing oxygenatedchemicals, Through ionic liquid-catalyzed olefinic polymerization, diesel oil and lubricating oil component are obtained using hydrofinishing.

Summary of the invention

The purpose of the invention is to overcome drawbacks described above in the prior art, a kind of F- T synthesis naphtha production is provided The method of isoparaffin solvent oil and the isoparaffin solvent oil obtained by this method, wherein in F- T synthesis feed naphtha Contained pure and mild alkene is utilized well, without being abandoned and wasting as the prior art, to increase raw material Effective rate of utilization also improves the yield of isoparaffin solvent oil.

The present inventor has found in surprise under study for action, using F- T synthesis naphtha as raw material, by F- T synthesis stone brain Oil successively carries out dehydration of alcohols reaction, polymerization reaction and hydrogenation reaction, and it is available preferably to control specific polymeric reaction condition More dimerisation products can obtain yield and the significantly higher isoparaffin solvent oil of isoparaffin purity.

Therefore, to achieve the goals above, in a first aspect, the present invention provides a kind of F- T synthesis naphthas to produce isomery The method of alkane solvent oil, this method comprises:

(1) F- T synthesis naphtha is subjected to dehydration of alcohols reaction in the presence of a catalyst, is made in F- T synthesis naphtha Alcohol is converted into alkene；

(2) product that step (1) obtains is subjected in the presence of polymerization catalyst polymerization reaction, obtains step (1) Alkene in product is converted into the polymerizate that target product is dimerization object；

(3) product that step (2) obtains is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst, obtains step (2) Polymerizate in product is converted into saturated alkane；

(4) by the way that initial boiling point in the product of fractionation cutting step (3) is not less than 160 DEG C and the end point of distillation is not more than 340 DEG C Fraction obtains isoparaffin solvent oil.

Second aspect, the present invention provides by isoparaffin solvent oil obtained by the above method.

In the method for F- T synthesis naphtha production isoparaffin solvent oil of the invention, the yield of isoparaffin solvent oil Height can reach 80% or more (yield is on the basis of the alkene in polymerization reaction raw material)；And in solvent naphtha isoparaffin purity Height, content can reach 98% or more.Meanwhile the color of the isoparaffin solvent oil product produced by the method for the present invention Shallowly, oxidation stability and thermal stability are good, and the content of aromatic hydrocarbons, sulphur and nitrogen compound is negligible.

Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.

Specific embodiment

Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

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

In a first aspect, the present invention provides a kind of method of F- T synthesis naphtha production isoparaffin solvent oil, the party Method includes:

(1) F- T synthesis naphtha is subjected to dehydration of alcohols reaction under the action of catalyst, is made in F- T synthesis naphtha Alcohol is converted into alkene；

In method of the invention, the purity of isoparaffin in the yield and solvent naphtha in order to improve isoparaffin solvent oil, Under preferable case, F- T synthesis naphtha is the F- T synthesis feed naphtha that the end point of distillation is not more than 160 DEG C.

In method of the invention, F- T synthesis naphtha contains alkene, organic oxygen-containing compound and alkane, with the Fischer-Tropsch On the basis of synthetic naphtha total weight, olefin(e) centent preferably more than 20 weight %, further preferably exists more than 10 weight % 40 weight % or more；Organic oxygen-containing compound content is more than 1 weight %, preferably more than 5 weight %, further preferably 10 Weight % or more；Determination of Alkane Content is more than 10 weight %, preferably more than 20 weight %.Wherein, under preferable case, taken with described On the basis of holding in the palm synthetic naphtha total weight, olefin(e) centent is 20-70 weight %, further preferably 40-60 weight %；It is organic to contain Oxygen compound content is 1-30 weight %, further preferably 5-25 weight %；Determination of Alkane Content is 10-50 weight %, further Preferably 20-35 weight %.Wherein, on the basis of the F- T synthesis naphtha total weight, contain in organic oxygen-containing compound Alcohol content be 1-25 weight %, preferably 10-20 weight %；Normal paraffin content is 10-40 weight %, preferably 20-30 Weight %；Isoparaffin content is 0-10 weight %, preferably 0-7 weight %；N-alkanol content is 5-15 weight %, preferably 10-15 weight %.

In the method for the present invention, under preferable case, in step (1), dehydration of alcohols reaction condition includes: that temperature is 300-450 DEG C, Further preferably 350-400 DEG C；Volume space velocity is 0.2-5h when liquid^-1, further preferably 0.5-3h^-1。

In the method for the present invention, under preferable case, in step (1), F- T synthesis naphtha urge used in dehydration of alcohols reaction Agent include aluminium oxide, natural mordenite zeolite, Y type molecular sieve, solid super strong acid substance, in large hole cation exchanger resin extremely Few one kind, preferably activated alumina, such as gama-alumina.

In the method for the present invention, above-mentioned dehydration of alcohols reaction can increase the olefin(e) centent in F- T synthesis feed naphtha, together When alcohol removing can reduce influence to subsequent polymerisation reaction catalyst.

In the method for the present invention, the present inventor has further been found that in polymerization process low point under study for action The alkene of son is converted into heavier product, while the carbon backbone structure of polymer forms branch at molecule addition point, passes through control The specific reaction temperature of polymerization reaction processed and specific reaction time, can more generate dimerisation products, reduce trimerization, four it is poly- with And the generation of poly product, i.e., so by controlling, extent of polymerization can obtain more high yield and the isoparaffin of higher purity is molten Agent oil.Therefore, in the yield and solvent naphtha in order to further increase isoparaffin solvent oil isoparaffin purity, preferable case Under, in step (2), polymeric reaction condition includes: that temperature is 50-150 DEG C, further preferably 100-130 DEG C；Time is 30- 120min, further preferably 30-50min.Wherein, temperature can be 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, the arbitrary value between 130 DEG C or aforementioned value, the time can be 30min, 35min, 40min, 45min, 50min or aforementioned Arbitrary value between numerical value.

In method of the invention, for polymerization catalyst, there is no particular limitation, can be various use commonly used in the art Under the catalyst of olefinic polymerization, preferable case, polymerization catalyst is Lewis acid catalyst, it is further preferred that Lewis is sour Catalyst is aluminum halide, alkyl aluminium halide, alkyl aluminum, halogenation boron, tin halides, iron halide, copper halide, halogenated titanium, antimony halides, halogen Change one of zinc and gallium halide or a variety of, further preferably one in aluminum halide, alkyl aluminium halide, alkyl aluminum and halogenation boron Kind or it is a variety of, be still more preferably boron trifluoride, one of alchlor, aluminium ethide and Chloroethyl aluminium or a variety of. Halo groups in Lewis acid catalyst can be fluorine and/or chlorine, preferably chlorine.

Preferably, the mass ratio of alkene is 0.01-0.1:1 in the product that polymerization catalyst and step (1) obtain, further Preferably 0.02-0.05:1.

Wherein, since Lewis acid catalyst is more sensitive to water, so then being needed if necessary depending on raw material condition First raw material is dried before reactions.Specific drying process condition is well known to those skilled in the art, herein It repeats no more.

In step (2), it is preferable that after polymerization reaction, lye is added and washes, again to polymerizate after settle and separate It is post-processed.

In the case of process of the present invention it is preferred, in step (3), hydrogenation conditions include: that hydrogen partial pressure is 3-10MPa, Further preferably 4-8MPa；Temperature is 150-350 DEG C, and further preferably 160-300 DEG C, be still more preferably 230- 260℃；The volume ratio (i.e. hydrogen to oil volume ratio) for the product that hydrogen and step (2) obtain is 100-2000:1, further preferably 250-1000:1；Volume space velocity is 0.2-5h when liquid^-1, further preferably 0.5-3h^-1。

In the method for the present invention, under preferable case, in step (3), hydrogenation catalyst is the group vib metal being carried on carrier And/or group VIIIB metallic catalyst, it is further preferred that carrier be silica, aluminium oxide, clay, magnesia, titanium oxide and One of zirconium oxide is a variety of；Group vib metal includes molybdenum and/or tungsten, and group VIII metal includes cobalt and/or nickel.

Under preferable case, in hydrogenation catalyst, on the basis of the weight of hydrogenation catalyst, the oxide of group vib metal Content is 15-25 weight %, and the oxide content of group VIIIB metal is 3-6 weight %.

In method of the invention, the product of step (2) is contacted with hydrogen in the presence of a hydrogenation catalyst, be may be implemented pair The saturation of alkene and the removal of impurity, impurity are mainly the remaining micro amount of oxygen in raw material.

Second aspect, the present invention also provides by isoparaffin solvent oil obtained by the above method.

Fractionation cutting is carried out by the product obtained to step (3), obtaining boiling range in the reaction product of step (3) is 160- 340 DEG C of fraction, the fraction are high-purity isoparaffin composition, and the solvent of different model can be prepared according to different demands Oil.In the present invention, also 160-340 DEG C of fraction further can be cut as needed, it is different to obtain more boiling ranges Fraction is used as the solvent naphtha of different purposes.

Embodiment

The present invention will be described in detail by way of examples below.In following embodiment and comparative example, such as nothing is especially said Bright, each material is commercially available, and each method is method commonly used in the art.

F- T synthesis naphtha A used in embodiment 1-5, the end point of distillation is 160 DEG C, total with F- T synthesis naphtha A On the basis of weight, hydro carbons composition (weight %) is shown in Table 1, and organic oxygen-containing compound composition (weight %) is shown in Table 2.

Table 1

Carbon number	N-alkane	Isoparaffin	Alkene	Cycloalkane	Aromatic hydrocarbons	It is total
							2	0	0	0	0	0	0
3	0	0	0	0	0	0
							4	0.05	0	0	0	0	0.05
5	0.97	0.15	3.52	0	0	4.64
							6	3.25	0.46	8.4	0.02	0	12.13
7	5.36	1.2	13.08	0.05	0.79	20.48
							8	6.15	1.3	16.34	0.31	0.05	24.15
9	6.23	1.67	15.71	0.15	0.07	23.83
							10	0.66	0.2	0.67	0	0	1.53
It is total	22.67	4.98	57.72	0.53	0.91	86.81

Table 2

F- T synthesis naphtha B used in embodiment 6, the end point of distillation is 200 DEG C, with F- T synthesis naphtha B gross weight On the basis of amount, hydro carbons composition (weight %) is shown in Table 3, and organic oxygen-containing compound composition (weight %) is shown in Table 4.

Table 3

Carbon number	N-alkane	Isoparaffin	Alkene	Cycloalkane	Aromatic hydrocarbons	It is total
							2	0	0	0	0	0	0
3	0	0	0	0	0	0
							4	0.03	0	0.05	0	0	0.08
5	0.59	0.09	1.09	0	0	1.77
							6	1.97	0.28	4.65	0.01	0	6.91
7	3.25	0.97	7.89	0.03	0.48	12.62
							8	3.86	0.87	9.9	0.19	0.03	14.85
9	3.91	1.01	10.69	0.09	0.04	15.74
							10	3.8	1.06	10.15	0	0.43	15.44
11	3.21	1	8	0	0.16	12.37
							12	1.72	0.61	2.63	0	0	4.96
It is total	22.34	5.89	55.05	0.32	1.14	84.74

Table 4

The calculation formula of isoparaffin solvent oil yield are as follows: the yield=[(fraction that boiling range is 160 DEG C~340 DEG C in product Quality)-(boiling range is 160 DEG C~340 DEG C of fraction quality in raw material)] quality of alkene in/raw material.

Embodiment 1

The method that the present embodiment is used to illustrate F- T synthesis naphtha production isoparaffin solvent oil of the invention.

(1) F- T synthesis naphtha A is subjected to dehydration of alcohols reaction under the action of catalyst, is made in F- T synthesis naphtha Alcohol is converted into alkene, wherein dehydration of alcohols reaction condition includes: that temperature is 400 DEG C, and volume space velocity is 1.5h when liquid^-1, catalyst is γ-Al₂O₃.Theatotal olefinsacontent is 67.49 weight % in the product obtained after dehydration of alcohols reaction.The production obtained after dehydration of alcohols reaction The hydro carbons composition (weight %) of object is shown in Table 5, and organic oxygen-containing compound composition (weight %) is shown in Table 6.

Table 5

Carbon number	N-alkane	Isoparaffin	Alpha-olefin	Other alkene	Cycloalkane	Aromatic hydrocarbons	It is total
								2	0	0	0	0	0	0	0
3	0	0	0	0	0	0	0
								4	0.20	0	0	0.08	0	0	0.28
5	1.74	0.15	0.52	3.8	0	0	6.21
								6	3.47	0.46	0.63	8.67	0.02	0	13.25
7	5.39	1.6	2.68	12.01	0.05	0.79	22.52
								8	6.21	1.43	4.56	13.32	0.31	0.05	25.88
9	6.12	1.67	5.71	14.62	0.15	0.07	28.34
								10	0.67	0.2	0.26	0.63	0	0	1.76
It is total	23.80	5.51	14.36	53.13	0.53	0.91	98.24

Table 6

Carbon number	N-alkanol	Isomery alcohol	Aldehyde	Ketone	Ester	It is total
							2	0.2	0	0	0	0	0.2
3	0.1	0	0	0	0	0.1
							4	0.19	0.27	0	0.07	0	0.53
5	0.18	0.08	0	0.08	0.16	0.5
							6	0.12	0.07	0	0.01	0.11	0.31
7	0.02	0.03	0	0.01	0.06	0.12
							It is total	0.81	0.45	0	0.17	0.33	1.76

From the data of table 5 and table 6: being reacted by the above-mentioned dehydration of alcohols of step (1), in F- T synthesis feed naphtha Most alcohol be converted into the alkene useful to subsequent polymerisation reaction.

(2) product that step (1) obtains is subjected in the presence of polymerization catalyst polymerization reaction, obtains step (1) Alkene in product is converted into the polymerizate that target product is dimerization object, wherein polymeric reaction condition includes: that temperature is 100 DEG C, time 50min, polymerization catalyst is alchlor, the matter of alkene in the product that alchlor and step (1) obtain Amount is than being 0.03:1.Obtained product is separated off catalyst, and is used as polymeric reaction product after NaOH alkali cleaning and washing.

By the above-mentioned polymerization reaction of step (2), the most alkene in product for obtaining step (1) are converted into Useful and target product is reacted for the polymerizate of dimerization object to follow-up hydrogenation.

(3) product that step (2) obtains is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst, obtains step (2) Polymerizate in product is converted into saturated alkane, wherein hydrogenation conditions include: that hydrogen partial pressure is 6.4MPa；Temperature is 260 ℃；The volume ratio for the product that hydrogen and step (2) obtain is 800:1；Volume space velocity is 2h when liquid^-1, hydrogenation catalyst NiMo/ Al₂O₃(with hydrogenation catalyst NiMo/Al₂O₃Weight on the basis of, the content of NiO is 4 weight %, MoO₃Content be 24 weights Measure %, Al₂O₃Content be 72 weight %, similarly hereinafter)；

By the above-mentioned hydrogenation reaction of step (3), the overwhelming majority in product for obtaining step (2) is mainly dimerization The polymerizate of object is changed into saturated alkane, and a considerable amount of target product-use of the present invention are contained in the saturated alkane in product Make the isoparaffin of solvent naphtha.

On the basis of the alkene total weight contained in the product that dehydration of alcohols reacts, calculating boiling range is 160- The yield of 340 DEG C of fraction is 83.5%.And 160-340 DEG C of fraction product, appearance colorless is transparent, oxygen content < 0.2%, virtue Hydrocarbon content is 0.03 volume %.It is 98.4 weight % by the isoparaffin content in the product known to chromatography, is high-quality Isoparaffin solvent oil.

Embodiment 2

(1) F- T synthesis naphtha A is subjected to dehydration of alcohols reaction under the action of catalyst, is made in F- T synthesis naphtha Alcohol is converted into alkene, wherein dehydration of alcohols reaction condition includes: that temperature is 350 DEG C, and volume space velocity is 3h when liquid^-1, catalyst is γ-Al₂O₃.The total content of alkene is 64.94 weight % in the product obtained after dehydration of alcohols reaction.It is obtained after dehydration of alcohols reaction The hydro carbons composition (weight %) of product is shown in Table 7, and organic oxygen-containing compound composition (weight %) is shown in Table 8.

Table 7

Carbon number	N-alkane	Isoparaffin	Alpha-olefin	Alkene	Cycloalkane	Aromatic hydrocarbons	It is total
								2	0	0	0	0	0	0	0
3	0	0	0	0	0	0	0
								4	0.05	0	0	0	0	0	0.05
5	1.1	0.15	3.2	2.04	0	0	6.49
								6	3.5	0.46	7.5	2.5	0.02	0	13.98
7	6.36	1.4	12.3	2.59	0.05	0.79	23.49
								8	6.15	1.3	15.2	2.14	0.31	0.05	25.15
9	6.5	1.67	15	1.8	0.15	0.07	25.19
								10	0.66	0.2	0.05	0.62	0	0	1.53
It is total	24.32	5.18	53.25	11.69	0.53	0.91	95.88

Table 8

(2) product that step (1) obtains is subjected in the presence of polymerization catalyst polymerization reaction, obtains step (1) Alkene in product is converted into the polymerizate that target product is dimerization object, wherein polymeric reaction condition includes: that temperature is 120 DEG C, time 40min, polymerization catalyst is alchlor, the matter of alkene in the product that alchlor and step (1) obtain Amount is than being 0.05:1.Obtained product is separated off catalyst, and is used as polymeric reaction product after NaOH alkali cleaning and washing.

(3) product that step (2) obtains is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst, obtains step (2) Polymerizate in product is converted into saturated alkane, wherein hydrogenation conditions include: that hydrogen partial pressure is 4.5MPa；Temperature is 240 ℃；The volume ratio for the product that hydrogen and step (2) obtain is 1000:1；Volume space velocity is 3h when liquid^-1, hydrogenation catalyst is NiMo/Al₂O₃；

On the basis of the alkene total weight contained in the product that dehydration of alcohols reacts, calculating boiling range is 160- The yield of 340 DEG C of fraction is 89.2%.And 160-340 DEG C of fraction product, appearance colorless is transparent, oxygen content < 0.2%, virtue Hydrocarbon content is 0.04 volume %.It is 99.1 weight % by the isoparaffin content in the product known to chromatography, is high-quality Isoparaffin solvent oil.

Embodiment 3

(1) F- T synthesis naphtha A is subjected to dehydration of alcohols reaction under the action of catalyst, is made in F- T synthesis naphtha Alcohol is converted into alkene, wherein dehydration of alcohols reaction condition includes: that temperature is 380 DEG C, and volume space velocity is 0.8h when liquid^-1, catalyst is γ-Al₂O₃.The total content of alkene is 66.06 weight % in the product obtained after dehydration of alcohols reaction.It is obtained after dehydration of alcohols reaction The hydro carbons composition (weight %) of product is shown in Table 9, and organic oxygen-containing compound composition (weight %) is shown in Table 10.

Table 9

Carbon number	N-alkane	Isoparaffin	Alpha-olefin	Alkene	Cycloalkane	Aromatic hydrocarbons	It is total
								2	0	0	0	0	0	0	0
3	0	0	0	0	0	0	0
								4	0.05	0	0	0	0	0	0.05
5	1.12	0.15	2.6	4.48	0	0	8.35
								6	3.56	0.46	5.3	7.35	0.02	0	16.69
7	6.33	1.41	10.5	2.82	0.05	0.79	21.9
								8	6.15	1.29	13.1	3.34	0.31	0.05	24.24
9	6.55	1.67	10.6	5.3	0.15	0.07	24.34
								10	0.66	0.2	0.09	0.58	0	0	1.53
It is total	24.42	5.18	42.19	23.87	0.53	0.91	97.1

Table 10

Carbon number	N-alkanol	Isomery alcohol	Aldehyde	Ketone	Ester	It is total
							2	0.2	0	0	0	0	0.2
3	0.26	0	0	0	0	0.26
							4	0.56	0.07	0	0.15	0	0.78
5	0.59	0.23	0	0	0.14	0.96
							6	0.36	0.19	0	0.02	0.12	0.69
7	0.01	0	0	0	0	0.01
							It is total	1.98	0.49	0	0.17	0.26	2.9

(2) product that step (1) obtains is subjected in the presence of polymerization catalyst polymerization reaction, obtains step (1) Alkene in product is converted into the polymerizate that target product is dimerization object, wherein polymeric reaction condition includes: that temperature is 130 DEG C, time 30min, polymerization catalyst is alchlor, the matter of alkene in the product that alchlor and step (1) obtain Amount is than being 0.02:1.Obtained product is separated off catalyst, and is used as polymeric reaction product after NaOH alkali cleaning and washing.

(3) product that step (2) obtains is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst, obtains step (2) Polymerizate in product is converted into saturated alkane, wherein hydrogenation conditions include: that hydrogen partial pressure is 8MPa；Temperature is 230 ℃；The volume ratio for the product that hydrogen and step (2) obtain is 300:1；Volume space velocity is 0.8h when liquid^-1, hydrogenation catalyst is NiMo/Al₂O₃；

On the basis of the alkene total weight contained in the product that dehydration of alcohols reacts, calculating boiling range is 160- The yield of 340 DEG C of fraction is 84.2%.And 160-340 DEG C of fraction product, appearance colorless is transparent, oxygen content < 0.2%, virtue Hydrocarbon content is 0.03 volume %.It is 99.1 weight % by the isoparaffin content in the product known to chromatography, is high-quality Isoparaffin solvent oil.

Embodiment 4

According to the method for embodiment 1, unlike: polymeric reaction condition includes: that temperature is 80 DEG C, time 50min.

In step (4), on the basis of the alkene total weight contained in the product that dehydration of alcohols reacts, calculates and evaporate The yield for the fraction that journey is 160-340 DEG C is 77.6%.And 160-340 DEG C of fraction product, appearance colorless is transparent, and oxygen content < 0.2%, arene content is 0.03 volume %.It is 98.2 weights by the isoparaffin content in the product known to chromatography % is measured, is good isoparaffin solvent oil.

Embodiment 5

According to the method for embodiment 1, unlike: polymeric reaction condition includes: that temperature is 100 DEG C, time 80min.

In step (4), on the basis of the alkene total weight contained in the product that dehydration of alcohols reacts, calculates and evaporate The yield for the fraction that journey is 160-340 DEG C is 75.3%.And 160-340 DEG C of fraction product, appearance colorless is transparent, and oxygen content < 0.2%, arene content is 0.03 volume %.It is 98.3 weights by the isoparaffin content in the product known to chromatography % is measured, is good isoparaffin solvent oil.

Embodiment 6

According to the method for embodiment 1, unlike: replacing the end point of distillation by 200 DEG C of F- T synthesis naphtha B with the end point of distillation For 160 DEG C of F- T synthesis naphtha A.

In step (4), on the basis of the alkene total weight contained in the product that dehydration of alcohols reacts, calculates and evaporate The yield for the fraction that journey is 160-340 DEG C is 72.3%.And 160-340 DEG C of fraction product, appearance colorless is transparent, and oxygen content is 0.65%, arene content is 1.2 volume %.It is 42.2 weights by the isoparaffin content in the product known to chromatography Measure %.

By embodiment 1 compared with embodiment 4-5 it is found that the temperature of polymerization reaction be 100-130 DEG C, time 30-50min When, the yield for the isoparaffin solvent oil that can be further increased.

Using embodiment 1 compared with embodiment 6 it is found that using the end point of distillation no more than 160 DEG C F- T synthesis naphtha as When raw material, the yield and purity of the isoparaffin solvent oil that can be further increased.

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.

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 also be regarded as the disclosure of the present invention.

Claims

1. a kind of method of F- T synthesis naphtha production isoparaffin solvent oil, comprising:

(1) F- T synthesis naphtha is subjected to dehydration of alcohols reaction in the presence of a catalyst, turns the alcohol in F- T synthesis naphtha Turn to alkene；

(2) product that step (1) obtains is subjected to polymerization reaction in the presence of polymerization catalyst, the product for obtaining step (1) In alkene be converted into target product be dimerization object polymerizate；

(3) product that step (2) obtains is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst, the product for obtaining step (2) In polymerizate be converted into saturated alkane；

(4) by the way that initial boiling point in the product of fractionation cutting step (3) is not less than 160 DEG C and the end point of distillation is not more than 340 DEG C of fraction, Isoparaffin solvent oil is obtained,

Wherein, the F- T synthesis naphtha is the F- T synthesis naphtha that the end point of distillation is not more than 160 DEG C.

2. according to the method described in claim 1, wherein, the F- T synthesis naphtha contains alkene, organic oxygen-containing compound And alkane, on the basis of the F- T synthesis naphtha total weight, the olefin(e) centent is 20-70 weight %；It is described organic to contain Oxygen compound content is 1-30 weight %；The Determination of Alkane Content is 10-50 weight %.

3. according to the method described in claim 2, wherein, on the basis of the F- T synthesis naphtha total weight, the alkene Content is 40-60 weight %；The organic oxygen-containing compound content is 5-25 weight %；The Determination of Alkane Content is 20-35 weight Measure %.

4. described organic on the basis of the F- T synthesis naphtha total weight according to the method described in claim 2, wherein Alcohol content is 1-25 weight % in oxygenatedchemicals.

5. described organic on the basis of the F- T synthesis naphtha total weight according to the method described in claim 4, wherein Alcohol content is 10-20 weight % in oxygenatedchemicals.

6. method described in any one of -5 according to claim 1, wherein in step (1), the dehydration of alcohols reaction condition packet Include: temperature is 300-450 DEG C；Volume space velocity is 0.2-5h when liquid^-1。

7. according to the method described in claim 6, wherein, in step (1), the dehydration of alcohols reaction condition includes: that temperature is 350-400℃；Volume space velocity is 0.5-3h when liquid^-1。

8. method described in any one of -5 according to claim 1, wherein in step (1), F- T synthesis naphtha carries out alcohol The catalyst of dehydration includes aluminium oxide, natural mordenite zeolite, Y type molecular sieve, solid super strong acid substance and macroporous cation At least one of exchanger resin.

9. according to the method described in claim 8, wherein, the catalyst that F- T synthesis naphtha carries out dehydration of alcohols reaction is γ- Aluminium oxide.

10. method described in any one of -5 according to claim 1, wherein in step (2), the polymeric reaction condition packet Include: temperature is 50-150 DEG C；Time is 30-120min.

11. according to the method described in claim 10, wherein, in step (2), the polymeric reaction condition includes: that temperature is 100-130℃；Time is 30-50min.

12. method described in any one of -5 according to claim 1, wherein in step (2), the polymerization catalyst is Lewis acid catalyst.

13. according to the method for claim 12, wherein the Lewis acid catalyst is aluminum halide, alkyl aluminium halide, alkane One of base aluminium, halogenation boron, tin halides, iron halide, copper halide, halogenated titanium, antimony halides, zinc halide and gallium halide are a variety of.

14. according to the method for claim 13, wherein the Lewis acid catalyst is aluminum halide, alkyl aluminium halide, alkane One of base aluminium and halogenation boron are a variety of.

15. according to the method for claim 14, wherein the Lewis acid catalyst is boron trifluoride, alchlor, second One of base aluminium and Chloroethyl aluminium are a variety of.

16. according to the method for claim 15, wherein alkene in the product that the polymerization catalyst is obtained with step (1) Mass ratio be 0.01-0.1:1.

17. according to the method for claim 16, wherein alkene in the product that the polymerization catalyst is obtained with step (1) Mass ratio be 0.02-0.05:1.

18. method described in any one of -5 according to claim 1, wherein in step (3), the hydrogenation conditions packet It includes: hydrogen partial pressure 3-10MPa；Temperature is 150-350 DEG C；The volume ratio for the product that hydrogen and step (2) obtain is 100-2000: 1；Volume space velocity is 0.2-5h when liquid^-1。

19. according to the method for claim 18, wherein in step (3), the hydrogenation conditions include: that hydrogen partial pressure is 4-8MPa；Temperature is 160-300 DEG C；The volume ratio for the product that hydrogen and step (2) obtain is 250-1000:1；Volume is empty when liquid Speed is 0.5-3h^-1。

20. according to the method for claim 19, wherein in step (3), the hydrogenation conditions include: that temperature is 230-260℃。

21. method described in any one of -5 according to claim 1, wherein in step (3), the hydrogenation catalyst is negative The group vib metal and/or group VIIIB metallic catalyst being loaded on carrier.

22. according to the method for claim 21, wherein the carrier is silica, aluminium oxide, clay, magnesia, oxidation One of titanium and zirconium oxide are a variety of.

23. according to the method for claim 21, wherein the group vib metal includes molybdenum and/or tungsten, the VIII group gold Belong to includes cobalt and/or nickel.

24. the isoparaffin solvent oil that method described in any one of -23 obtains according to claim 1.