CN103772095B

CN103772095B - The method of preparing hexane by disproportionating butylene

Info

Publication number: CN103772095B
Application number: CN201210412530.8A
Authority: CN
Inventors: 宣东; 张惠明; 刘苏; 沈伟; 李木金
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2012-10-25
Filing date: 2012-10-25
Publication date: 2015-09-09
Anticipated expiration: 2032-10-25
Also published as: CN103772095A

Abstract

The present invention relates to a kind of method of preparing hexane by disproportionating butylene, the problem that the catalyst life mainly existed in solution conventional art is short.The present invention is raw material by adopting with butylene, butene feedstock obtains the butene stream containing 1-butylene and 2-butylene respectively after lightness-removing column, weight-removing column, butene stream obtains through isomerization reactor the logistics being rich in 1-butylene, butene stream obtains the technical scheme of product hexene through disproportionation reactor, tripping device, can be used for the industrial production of preparing hexane by disproportionating butylene.

Description

The method of preparing hexane by disproportionating butylene

Technical field

The present invention relates to a kind of method of preparing hexane by disproportionating butylene.

Background technology

As a kind of olefin product of high added value, the synthesis of hexene is paid attention to very much.The customary preparation methods of current industrial hexene generates 1-hexene by ethylene polymerization, and the catalyzer of employing is alkylating metal catalyst.By olefin metathesis technology, C4 conversion of olefines low value-added for relative surplus can be become hexene and the ethene of high added value.

Olefin metathesis (Olefin metathesis) is a kind of conversion of olefines process.By under the effect of transition-metal catalyst (as W, Mo, Re etc.), in alkene C=C double bond fracture and again formed, thus new olefin product can be obtained.We can represent the dismutation of alkene simply from following reaction formula:

R in reaction formula ₁, R ₂, R ₃, R ₄represent different alkyl or hydrogen atom respectively.If wherein the disproportionation reaction (such as formula 1) of same alkene is called self disproportionation (self-metathesis); Disproportionation reaction (formula 2) between different alkene is then called cross disproportionation (cross-metathesis).

The control of self disproportionation reaction of 1-butylene is the most key, because 1-butylene double bond isomerization reaction generates 2-butylene, and 1-butylene and 2-butylene cross disproportionation cause hexene optionally to reduce, so the key of this technology is that in suppression raw material, 1-butylene is at the double-bond isomerization of catalyst surface.

WO02059066 reports the automatic disproportionation technology of 1-butylene.The catalyzer that this technology adopts be Tungsten oxide 99.999 load on silicon oxide, at the temperature of 200 DEG C ~ 350 DEG C, 1-butylene self disproportionation generates ethene and 3-hexene.3-hexene is converted into 1-hexene in isomerization reaction subsequently.This patent is pointed out, adds 2-amylene and be conducive to 3-hexene in product and optionally improve in reactant.

It is the technology that raw material prepares propylene and hexene that WO03076371A1 reports with butylene.This technology adopt catalyzer be Tungsten oxide 99.999 load on silicon oxide, temperature of reaction is 343 DEG C, and reaction pressure is 5bar.

When reacting for preparing hexane by disproportionating butylene, all there is the problem that catalyst life is short in the method in above document.

Summary of the invention

Technical problem to be solved by this invention is the short problem of the catalyst life that exists in prior art, provides a kind of method of new preparing hexane by disproportionating butylene.When the method is used for preparing hexane by disproportionating butylene reaction, there is the advantage that catalyst life is long.

For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing hexane by disproportionating butylene, take butylene as raw material, comprises the following steps: (a) butene feedstock obtains material I after the dme in lightness-removing column removing raw material; B () material I obtains material II after the components such as weight-removing column removing stopper wherein; C () logistics II and isomerization catalyst contact reacts obtain the logistics III being rich in 1-butylene; D () logistics III and disproportionation catalyst contact reacts obtain containing product hexene, ethene and butene stream IV; E () logistics IV enters tripping device, be separated and obtain product hexene, ethene and unreacted butylene.

In technique scheme, the preferred version of lightness-removing column operational condition is: theoretical plate number 60 ~ 70 pieces, tower pressure: 0.5 ~ 0.6MPa, tower top temperature 45 ~ 55 DEG C, bottom temperature 55 ~ 60 DEG C.The preferred version of weight-removing column operational condition is: theoretical plate number 160 ~ 180 pieces, tower pressure 1.7 ~ 1.9MPa, tower top temperature 40 ~ 45 DEG C, bottom temperature 50 ~ 55 DEG C.The preferred version of the isomerization catalyst described in step (c) is Ni/Al ₂o ₃, the charge capacity of Ni is 5 ~ 20%, and preferable range is 8 ~ 15; Operational condition: temperature of reaction 40 ~ 60 DEG C, reaction pressure in absolute pressure 1 ~ 2MPa, the mass space velocity of carbon 41 ~ 8 hour ^-1.The preferred version of disproportionation catalyst described in step (d) is WO ₃/ SiO ₂, WO ₃charge capacity be 4 ~ 15%, preferable range is .5 ~ 12%; Operational condition is: temperature of reaction 350 ~ 450 DEG C, reaction pressure in absolute pressure 1 ~ 4MPa, the mass space velocity of carbon 46 ~ 20 hours ^-1.The butylene obtained in step (e) utilizes as reaction raw materials again with the form of circulation butylene.

The present invention by increasing lightness-removing column and weight-removing column before reactor, the reaction such as dme and stopper poisonous substance effectively can be removed in reaction process, effectively to reduce in raw material impurity to the impact of catalyst activity, improve the work-ing life of catalyzer, with 1-butylene low conversion rate in 50% for catalyst deactivation calculate, the life-span not adding lightness-removing column and weight-removing column catalyzer is 700 hours, and the life-span of adding lightness-removing column and weight-removing column rear catalyst can rise to 1200 hours, compare raising 40%, achieve good technique effect.

Accompanying drawing explanation

Fig. 1 is the schema of the technological system of the present invention of butylene material for the production of hexene.

In Fig. 1,1 is butene feedstock, and 2 is dme, and 3 for removing the C 4 materials of dme, 4 is heavy constituent, and 5 for removing the butylene material of heavy constituent, and 6 is mixed butene material, 7 for being rich in the feed stream of 1-butylene, and 8 is reaction product, and 9 is hexene product, 10 is carbon four by product, and 11 is circulation butylene, and 21 is lightness-removing column, 22 is weight-removing column, 23 is isomerization reactor, and 24 is disproportionation reactor, and 25 is tripping device.

With reference to Fig. 1, method of the present invention is briefly stated in flow charts.

As shown in Figure 1, butene feedstock 1 is through obtaining C 4 materials 3 after dme in lightness-removing column removing raw material, logistics 3 obtains C 4 materials 5 through heavy constituents such as weight-removing column removing stoppers wherein, material 5 and circulation butylene 11 mix rear formation mixing raw material 6, mixing raw material enters the logistics 7 that isomerization reactor obtains being rich in 1-butylene, logistics 7 enters disproportionation reactor reaction, be obtained by reacting target product propylene, amylene and unreacted butylene, reaction product 8 obtains polymerization-grade hexene 9 and circulation butylene 11 through tripping device, remaining carbon four byproduct 10 can use as liquefied gas.

Below by embodiment, the present invention is further elaborated.

Embodiment

[embodiment 1]

By the technical process shown in Fig. 1, the catalyzer in isomerization reactor is 12%Ni/Al ₂o ₃, operational condition: temperature of reaction 50 DEG C, reaction pressure in absolute pressure 1.5MPa, the mass space velocity 2h of carbon four ^-1; Disproportionation catalyst in disproportionation reactor is 8%WO ₃/ SiO ₂, operational condition is: temperature of reaction 350 DEG C, reaction pressure in absolute pressure 3MPa, the mass space velocity of carbon 42 hours ^-1.Reaction conditions is as shown in table 1, and the operational condition of lightness-removing column and weight-removing column is as shown in table 2, and reaction result is as shown in table 3.

[embodiment 2 ~ 6]

Each condition and the step of pressing [embodiment 1] are reacted, and just change different operating parameterss, its reaction conditions lists in table 1, and reaction conditions is as shown in table 1, and the operational condition of lightness-removing column and weight-removing column is as shown in table 2, and reaction result is as shown in table 3.

[comparative example 1]

By the technical process shown in Fig. 1, just not through lightness-removing column and weight-removing column process.Catalyzer in isomerization reactor is 12%Ni/Al ₂o ₃, operational condition: temperature of reaction 50 DEG C, reaction pressure in absolute pressure 1.5MPa,

The mass space velocity of carbon 42 hours ^-1; Disproportionation catalyst in disproportionation reactor is 8%WO ₃/ SiO ₂, operational condition is: temperature of reaction 350 DEG C, reaction pressure in absolute pressure 3MPa, the mass space velocity of carbon 42 hours ^-1.Reaction result is as shown in table 3.

Table 1

Note: the data of isomerization catalyst and disproportionation catalyst are all the mass percentage of active ingredient.

Table 2

[comparative example 2]

By the technical process shown in Fig. 1, each condition and the step of pressing [embodiment 2] are reacted, just not through lightness-removing column and weight-removing column process.Reaction conditions is as shown in table 1; Reaction result is as shown in table 3.

[comparative example 3]

By the technical process shown in Fig. 1, each condition and the step of pressing [embodiment 3] are reacted, just not through lightness-removing column and weight-removing column process.Reaction conditions is as shown in table 1; Reaction result is as shown in table 3.

Table 3

	1-butylene transformation efficiency (%)	Hexene weight selectivities (%)	Life-span (hour)
				Embodiment 1	62.2	60.5	1230
Embodiment 2	61.5	61.3	1220
				Embodiment 3	58.3	62.3	1250
Embodiment 4	59.5	61.0	1180
				Embodiment 5	61.8	62.6	1270
Embodiment 6	61.2	63.4	1240
				Comparative example 1	56.5	58.3	720
Comparative example 2	57.2	57.5	700
				Comparative example 3	55.3	58.9	710

Claims

1. a method for preparing hexane by disproportionating butylene, is raw material with butylene, comprises the following steps:

A () butene feedstock obtains material I after the dme in lightness-removing column removing raw material;

B () material I removes after stopper heavy constituent wherein through weight-removing column and obtains material II;

C () logistics II and isomerization catalyst contact reacts obtain the logistics III being rich in 1-butylene;

D () logistics III and disproportionation catalyst contact reacts obtain containing product hexene, ethene and butene stream IV;

E () logistics IV enters tripping device, be separated and obtain product hexene, ethene and unreacted butylene.

Described lightness-removing column operational condition: theoretical plate number 60 ~ 70 pieces, tower pressure: 0.5 ~ 0.6MPa, tower top temperature 45 ~ 55 DEG C, bottom temperature 55 ~ 60 DEG C; Described weight-removing column operational condition: theoretical plate number 60 ~ 70 pieces, tower pressure: 0.4 ~ 0.5MPa, tower top temperature 43 ~ 53 DEG C, bottom temperature 50 ~ 60 DEG C.

2. the method for preparing hexane by disproportionating butylene according to claim 1, is characterized in that isomerization reaction operational condition: temperature of reaction 40 ~ 60 DEG C, reaction pressure in absolute pressure 1 ~ 2MPa, the mass space velocity of carbon 41 ~ 8 hour ^-1.

3. the method for preparing hexane by disproportionating butylene according to claim 1, is characterized in that described isomerization catalyst is Ni/Al ₂o ₃, the charge capacity of Ni is 5 ~ 20%.

4. the method for preparing hexane by disproportionating butylene according to claim 3, is characterized in that the charge capacity of Ni is 8 ~ 15%.

5. the method for preparing hexane by disproportionating butylene according to claim 1, is characterized in that disproportionation reaction operational condition: temperature of reaction 350 ~ 450 DEG C, reaction pressure in absolute pressure 1 ~ 4MPa, the mass space velocity of carbon 46 ~ 20 hours ^-1.

6. the method for preparing hexane by disproportionating butylene according to claim 1, is characterized in that described disproportionation catalyst is WO ₃/ SiO ₂, WO ₃charge capacity be 4 ~ 15%.

7. the method for preparing hexane by disproportionating butylene according to claim 6, is characterized in that WO ₃charge capacity be 6.5 ~ 12%.

8. the method for preparing hexane by disproportionating butylene according to claim 1, is characterized in that the butylene obtained in step (e) utilizes as reaction raw materials again with the form of circulation butylene.