CN103420759B

CN103420759B - The production method of propylene

Info

Publication number: CN103420759B
Application number: CN201210150410.5A
Authority: CN
Inventors: 宣东; 刘苏; 董静
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: 2012-05-16
Filing date: 2012-05-16
Publication date: 2015-12-16
Anticipated expiration: 2032-05-16
Also published as: CN103420759A

Abstract

The present invention relates to a kind of production method of propylene, the problem of mainly solving to need consumption of ethylene present in conventional art.The present invention is the raw material of carbon four by using the material comprising 1- butylene, 2- butylene, iso-butane and normal butane, the raw material of carbon four obtains the butene stream of butylene containing 1- and 2- butylene through extract and separate flow respectively, butene stream obtains the technical scheme of product propylene, the industrial production available for the propylene processed of carbon four through disproportionation reactor, de- ethylene column and depropenizer.

Description

The production method of propylene

Technical field

The present invention relates to a kind of production method of propylene.

Background technology

Traditional ethene coproduction and refinery's Propylene recovery method is obviously difficult to meet growing propylene demand, and C can be digested while naphtha pyrolysis severity is not reduced using olefin(e) disproportionation technology₄Cut, and can propylene enhancing, thus preparing propylene through olefin disproportionation technology research and development not only to improving the yield of propylene, while to promoting low value-added C₄The comprehensive utilization of cut has great significance, wherein butylene disproportionation production propylene involved in the present invention makes a kind of up-and-coming technique.

Olefin dismutation reaction is also known as olefinic double bonds displacement reaction, it is a kind of alkene Transformation Phenomenon found 1960s, olefin dismutation reaction just turns into the class significant process that alkene is converted since then, and olefin feedstock that can be relatively inexpensive by some, abundant using olefin dismutation reaction is converted into the higher olefin product of a variety of added values.Olefin dismutation reaction process can be represented by the following formula：

Wherein R and R ' represents alkyl or hydrogen atom.Simplest olefin dismutation reaction is that propylene disproportionation generates ethene and butene-2.

WO2005009929 is reported in a kind of processing method of the C4 olefin streams for maximum production of propylene, the method without ethene, including conventional metathesis reaction and automatic metathesis reaction.

WO2006052688 reports the Catalyst And Method that a kind of ethene and butylene double decomposition produce propylene, and this method makes described charging and contact ethylene production propylene under metathesis reaction conditions in the metathesis reaction area containing metathesis catalyst.

CN97121426 reports a kind of preparation method of propylene, and this method makes 2- amylenes and ethylene reaction in the presence of being included in metathesis catalyst, and above-mentioned catalyst at least contains the compound of the VIth b, VII b or VIII group 4 transition metal in a kind of element, periodic table.

There is the problem of needing consumption of ethylene when being reacted for the propylene processed of carbon four in the method in document above.

The content of the invention

The technical problems to be solved by the invention are that there is provided a kind of new propylene production the problem of consumption of ethylene is needed present in prior art.When this method is used for the reaction of the propylene processed of carbon four, have the advantages that to be not required to consumption of ethylene.

In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of production method of propylene, with butylene containing 1-, 2- butylene, the carbon four of normal butane and iso-butane is raw material, is comprised the following steps：(a) olefin stream I is obtained after the raw material of carbon four to be removed to iso-butane and normal butane in raw material through extraction procedure；(b) logistics I obtains the logistics II containing product ethylene, propylene, carbon four and light dydrocarbon with disproportionation catalyst haptoreaction；(c) logistics II enters de- ethylene column, and tower top obtains ethene, and tower reactor obtains the logistics III containing propylene and carbon four and light dydrocarbon；(d) logistics III enters depropenizer, and tower top obtains product propylene, and tower reactor obtains carbon four and light dydrocarbon logistics.

In above-mentioned technical proposal, the preferred scheme of extractant used is n-formylmorpholine and the mixed solvent of MEK in extraction procedure described in step (a), and both weight ratios are 1:1；The preferred scheme of disproportionation catalyst described in step (b) is WO₃/SiO₂, WO₃Load capacity be 4~15%, the preferred scheme of operating condition is 250~350 DEG C of reaction temperature, reaction pressure 1~4MPa in terms of absolute pressure, 1~8h of mass space velocity of carbon four^-1；The preferred scheme of de- ethylene column operating condition：100~120 pieces of theoretical cam curve, tower presses 1.8~2.2MPa, tower top temperature -35~-30 DEG C, bottom temperature -10~-5 DEG C；The preferred scheme of depropenizer operating condition：160~180 pieces of theoretical cam curve, tower presses 1.7~1.9MPa, 40~45 DEG C of tower top temperature, 50~55 DEG C of bottom temperature.

The present invention before reactor by increasing extraction procedure by alkene and alkane separation, the utilization rate of C 4 olefin can be effectively improved and butane is rationally reclaimed, 5% can be improved compared to the technique propylene weight yield not using extraction procedure, 1- butylene and the reaction of 2- butylene disproportionations generate propylene and amylene in disproportionation reactor simultaneously, under the conditions of production equal amount propylene, and do not need ethene as reaction raw materials, economic benefit is improved, preferable technique effect is achieved.

Brief description of the drawings

Fig. 1 is the flow chart for producing the technological system of the invention of the C 4 materials of propylene.

1 is the raw material of carbon four in Fig. 1, and 2 be iso-butane and normal butane, and 3 be 1- butylene and 2- butylene, and 4 be reaction product, and 5 be ethene, and 6 be propylene, carbon four and light dydrocarbon logistics, and 7 be propylene, and 21 be extraction procedure, and 22 be disproportionation reactor, and 23 be de- ethylene column, and 24 be depropenizer.

Reference picture 1, the method for the present invention is briefly stated in flow charts.

As shown in Figure 1, the raw material 1 of carbon four obtains C 4 olefin logistics 3 after iso-butane and normal butane 2 in raw material are removed through extraction procedure, olefin stream 3 and disproportionation catalyst haptoreaction, reaction obtains target product propylene, carbon four and light dydrocarbon logistics, and reaction product 4 is through de- ethylene column, the ethene 5 that tower top is obtained, the component 6 that tower reactor is obtained enters depropenizer and handled, tower top obtains polymerization-grade propylene 7, carbon four and light dydrocarbon that tower reactor is obtained, can be used as liquefied gas.

Below by embodiment, the present invention is further elaborated.

Embodiment

【Embodiment 1】

Technological process as shown in Figure 1, extractant is the mixed solvent of n-formylmorpholine and MEK, and weight ratio is 1：1；Disproportionation catalyst in disproportionation reactor is 8%WO₃/SiO₂, operating condition is：300 DEG C of reaction temperature, reaction pressure 3MPa in terms of absolute pressure, the mass space velocity 2h of carbon four^-1.As shown in table 1, the operating condition for taking off ethylene column and depropenizer is as shown in table 2, and reaction result is as shown in table 3 for the operating condition of extraction procedure.

【Embodiment 2~6】

Reacted by each condition of embodiment 1 with step, simply change different operating parameters, as shown in table 1, the operating condition for taking off ethylene column and depropenizer is as shown in table 2, and its reaction condition and reaction result are listed in shown in table 3 for the operating condition of extraction procedure.

【Comparative example 1】

Technological process as shown in Figure 1, extraction procedure is not passed through simply.Disproportionation catalyst preferred scheme in disproportionation reactor is 8%WO₃/SiO₂, operating condition is：300 DEG C of reaction temperature, reaction pressure 3MPa in terms of absolute pressure, the mass space velocity 2h of carbon four^-1.As shown in table 2, reaction result is as shown in table 3 for the operating condition of de- ethylene column and depropenizer.

【Comparative example 2】

Technological process as shown in Figure 1, extractant is the mixed solvent of n-formylmorpholine and MEK, and weight ratio is 1：1；Disproportionation catalyst in disproportionation reactor is 4%WO₃/SiO₂, operating condition is：350 DEG C of reaction temperature, reaction pressure 2MPa in terms of absolute pressure, the mass space velocity 4h of carbon four^-1, the mol ratio of ethene and carbon four is 2:1.As shown in table 1, the operating condition for taking off ethylene column and depropenizer is as shown in table 2, and reaction result is as shown in table 3 for the operating condition of extraction procedure.

【Comparative example 3】

Technological process as shown in Figure 1, extractant is the mixed solvent of n-formylmorpholine and MEK, and weight ratio is 1：1；Disproportionation catalyst in disproportionation reactor is 12%WO₃/SiO₂, operating condition is：400 DEG C of reaction temperature, reaction pressure 4MPa in terms of absolute pressure, the mass space velocity 1h of carbon four^-1, the mol ratio of ethene and carbon four is 1:1.As shown in table 1, the operating condition for taking off ethylene column and depropenizer is as shown in table 2, and reaction result is as shown in table 3 for the operating condition of extraction procedure.

Table 1

Table 2

Table 3

Note：The data of disproportionation catalyst are all the weight/mass percentage composition of active component.

Claims

1. a kind of production method of propylene, with butylene containing 1-, 2- butylene, the carbon four of normal butane and iso-butane is raw material, is comprised the following steps：

(a) olefin stream I is obtained after the raw material of carbon four to be removed to iso-butane and normal butane in raw material through extraction procedure；

(b) logistics I obtains the logistics II containing product ethylene, propylene, carbon four and light dydrocarbon with disproportionation catalyst haptoreaction；

(c) logistics II enters de- ethylene column, and tower top obtains ethene, and tower reactor obtains the logistics III containing propylene and carbon four and light dydrocarbon；

(d) logistics III enters depropenizer, and tower top obtains product propylene, and tower reactor obtains carbon four and light dydrocarbon logistics；

Extractant used is the mixed solvent of n-formylmorpholine and MEK in the extraction procedure, and both weight ratios are 1:1；

Disproportionation catalyst described in step (b) is WO₃/SiO₂, WO₃Load capacity be 4~15%, operating condition is：300~450 DEG C of reaction temperature, reaction pressure 1~4MPa in terms of absolute pressure, the mass space velocity of carbon four is more than 1 and is less than or equal to 8h^-1。

2. a kind of production method of propylene according to claim 1, it is characterised in that the operating condition of de- ethylene column：100~120 pieces of theoretical cam curve, tower presses 1.8~2.2MPa, tower top temperature -35~-30 DEG C, bottom temperature -10~-5 DEG C；The operating condition of depropenizer：160~180 pieces of theoretical cam curve, tower presses 1.7~1.9MPa, 40~45 DEG C of tower top temperature, 50~55 DEG C of bottom temperature.