阅读说明：本技术 一种模拟移动床分离α-烯烃的方法 (Method for separating alpha-olefin by simulated moving bed ) 是由 李俊诚 钱震 武靖为 张晓龙 菅青娥 高源� 邬学霆 陈浩庭 于 2019-03-04 设计创作，主要内容包括：本发明提供一种模拟移动床分离α-烯烃的方法,该方法包括以煤基费托合成油为原料,目标烯烃碳数N的范围为9-18,原料经过预处理,馏分切割,烷烯分离,异构体分离等处理步骤,得到高纯度α-烯烃产品。与传统的精馏、萃取工艺相比,本发明的方法得到的产品纯度更高、收率更高,能耗较低,生产成本显著降低。(The invention provides a method for separating alpha-olefin by a simulated moving bed, which comprises the steps of taking coal-based Fischer-Tropsch synthetic oil as a raw material, wherein the carbon number N of target olefin is 9-18, and carrying out pretreatment, fraction cutting, alkane-alkene separation, isomer separation and other treatment steps on the raw material to obtain a high-purity alpha-olefin product. Compared with the traditional rectification and extraction process, the method has the advantages of higher product purity, higher yield, lower energy consumption and obviously reduced production cost.)

1. A method for separating alpha-olefin by a simulated moving bed is characterized in that coal-based Fischer-Tropsch synthetic oil is used as a raw material, the range of the carbon number N of target olefin is 4-18, and the method specifically comprises the following steps:

(1) and (3) cutting fractions: cutting the fraction of the pretreated raw material to obtain a component with the carbon number of N;

(2) and (3) alkane and alkene separation: performing alkane-alkene separation on the components in the step (1) by adopting a first simulated moving bed, and separating alkane and alkene to obtain alkene-rich components;

(3) isomer separation: separating isomers of the olefin-rich component obtained in the step (2) by adopting a second simulated moving bed, and separating out a high-purity alpha-olefin product with the content of more than 99.2 wt%;

the alkane and alkene separation step does not comprise a step of removing oxygen-containing compounds.

2. A method for separating alpha-olefin according to claim 1, wherein the first simulated moving bed process parameters in step (2) are: the operation temperature is 50-110 ℃, the operation pressure is 0.3-0.8MPa, and the mass ratio of the agent to the oil is 0.5-4: 1; preferably, the operation temperature is 60-100 ℃, the operation pressure is 0.4-0.6MPa, and the mass ratio of the agent to the oil is 0.5-2: 1.

3. A process for the separation of alpha-olefins according to any of the claims 1-2, wherein the second simulated moving bed process parameters in step (3) are: the operation temperature is 50-110 ℃, the operation pressure is 0.3-0.8MPa, and the mass ratio of the agent to the oil is 0.5-4: 1; preferably, the operation temperature is 60-100 ℃, the operation pressure is 0.4-0.6Mpa, and the mass ratio of the agent to the oil is 0.5-2: 1.

4. A process for separation of alpha-olefins according to any of the claims 1-3, characterized in that the loading agent in the first simulated moving bed is a series a molecular sieve, preferably a 5A molecular sieve and/or a modified 5A molecular sieve.

5. A process for separation of alpha-olefins according to any of the claims 1-4, characterized in that the loading agent in the second simulated moving bed is a X series molecular sieve, preferably a 13X molecular sieve and/or a modified 13X molecular sieve.

6. A simulated moving bed separation process of alpha-olefins according to any of claims 1 to 5, characterized in that the target olefin carbon number N is in the range of 9 to 18, preferably 9 to 16, more preferably 10 to 14, even more preferably 10 to 12.

7. The simulated moving bed separation method of alpha-olefins according to any of the claims 1 to 6, wherein the coal-based Fischer-Tropsch synthesis oil has an olefin content of 73 to 75 wt%, an alkane content of 22 to 25 wt% and an oxygen-containing compound content of 3 to 5 wt%.

8. A process for the separation of alpha-olefins according to any of the claims 1-7, wherein the pre-treatment step comprises the step of deacidifying the feedstock.

9. The process for separation of alpha-olefins according to any of the claims 1 to 8, wherein the first and second SMB units each comprise an adsorbent bed, a feedstock feed system, a desorbent feed system, a recycle system, a liquid withdrawal system, a raffinate withdrawal system, a valve stack and an automatic control system; wherein, the adsorption bed comprises a plurality of adsorption columns which are divided into an adsorption area, a purification area, a desorption area and a buffer area;

the upper end of each adsorption column is provided with a raw material feed valve, a desorbent feed valve and a circulating liquid feed valve;

the lower end of each adsorption column is provided with a raffinate discharge valve and an extract discharge valve;

a one-way valve is arranged between every two adjacent adsorption columns;

the raw material feeding system is connected with a raw material feeding valve of each adsorption column;

the desorbent feed system is connected with a desorbent feed valve of each adsorption column;

the circulating system comprises a circulating pump, and is connected with a circulating liquid feeding valve of each adsorption column through the circulating pump;

the extract system is connected with an extract discharge valve of each adsorption column;

the raffinate system is connected with a raffinate discharge valve of each adsorption column;

all valves form a program control valve group, the program control valve group is connected with an automatic control system, and the automatic control system can control the opening and closing state of each valve in the program control valve group.

Technical Field

The invention relates to a method for separating alpha-olefin by a simulated moving bed, in particular to a method for separating high-purity alpha-olefin from coal-based Fischer-Tropsch synthetic oil by adopting a two-stage simulated moving bed mode.

Background

The Fischer-Tropsch synthetic oil product contains a large amount of valuable chemical raw materials, namely olefin, which is a key raw material for producing other fine chemical products and has extremely important influence on downstream industries. At present, the subsequent processing method for Fischer-Tropsch synthetic oil products at home and abroad mainly focuses on the aspects of distillation and rectification.

Patents US7217852 and US7294253 propose a process for the distillation of fischer-tropsch oils and an intermediate distillate obtained by distillation, which contains branches such as methyl, ethyl, propyl, etc., and the C9-C16 components account for more than 90% of the total distillate, which is the main component constituting diesel oil and which has good low temperature fluidity, but the product obtained by this process has low purity and cannot be used directly in polymerization reactions.

EP1835011 proposes a method for the distillation treatment of a fischer-tropsch synthesis crude and the resulting middle distillate, the main process being to cut the FTS crude into naphtha and middle distillate. The south Africa SASOL company develops a combined process route of alkaline washing, etherification, rectification and extraction in 1994 to realize the preparation of polymerization-grade 1-hexene and 1-octene. However, the process has complicated route and high operation energy consumption, so that the investment and operation cost is very high, and the technology can only separate C6 and C8 components, but cannot separate high-carbon-number components.

In document CN104370678, a light distillate oil of carbon five synthesized by fischer-tropsch is used as a raw material, the raw material is extracted and rectified, an extracting agent is N, N-dimethylformamide, and a 1-pentene enriched material obtained from the top of an extractive rectification tower is further purified by precision rectification to obtain a 1-pentene product. The carbon number of the olefin obtained by the method is single, and the basic method is extraction and rectification, so that the energy consumption is high, the solvent consumption is high, and the production cost is high.

In addition, the south Africa SASOL company develops a combined process route of alkaline washing, etherification, rectification and extraction in 1994 to realize the preparation of polymerization-grade 1-hexene and 1-octene. However, the process has complicated route and high operation energy consumption, so that the investment and operation cost is very high, and the technology can only separate C6 and C8 components, but cannot separate high-carbon-number components.

The simulated moving bed is a separation apparatus which performs a separation operation using the adsorption principle. The simulated moving bed technology is taken as a main representative of continuous chromatography, has the advantages of high production efficiency, low organic solvent consumption, large mass transfer driving force, convenience for automatic continuous production and the like, is widely applied to the fields of petrochemical industry, food industry, pharmacy and the like, and is a complex industrial process and a periodic process with a plurality of non-linearity, non-equilibrium, non-ideal and multi-degree of freedom of influencing factors.

The separation processes in the technical documents all adopt the traditional extraction rectification process, and because the difference between the boiling points of alpha-olefin and impurities (isoolefin) is very small, the separation cost by adopting the extraction rectification process is very high, the using amount of a solvent is large, the recovery is difficult, and the requirements of the current social development are not met. Although current technology enables separation of liquid olefins from liquid alkanes, there is still a need to provide more improved methods for separating olefins from alkanes.

In order to overcome the defects, the application firstly proposes the combination of two-stage separation of the Fischer-Tropsch synthetic oil raw material and the simulated moving bed, efficiently and economically separates the alpha-olefin with a wide carbon chain range from the Fischer-Tropsch synthetic oil, and breaks through the conventional path of separating the alpha-olefin with a specific carbon number and a narrow carbon chain range by extraction and rectification.

Disclosure of Invention

The invention aims to solve the problem of efficiently and economically separating alpha-olefin from coal-based Fischer-Tropsch synthetic oil to obtain an olefin product meeting the purity requirement, and particularly provides an alpha-olefin separation method which has simple process and low energy consumption and can meet the requirements of different purity and carbon number distribution (such as C4-C18) of olefin on the market.

In order to achieve the purpose of the invention, the adopted technical scheme is as follows:

a method for separating alpha-olefin by a simulated moving bed takes coal-based Fischer-Tropsch synthetic oil as a raw material, the range of the carbon number N of target olefin is 4-18, and the method specifically comprises the following steps:

(1) and (3) cutting fractions: cutting the fraction of the pretreated raw material to obtain a component with the carbon number of N;

(2) and (3) alkane and alkene separation: performing alkane-alkene separation on the components in the step (1) by adopting a first simulated moving bed, and separating alkane and alkene to obtain alkene-rich components;

(3) isomer separation: separating isomers of the olefin-rich component obtained in the step (2) by adopting a second simulated moving bed, and separating out a high-purity alpha-olefin product with the content of more than 99.2 wt%;

the separation step of alkane and alkene does not comprise a step of removing oxygen-containing compounds.

In general terms, the amount of the solvent to be used,

the first simulated moving bed process parameters in the step (2) are as follows: the operation temperature is 50-110 ℃, the operation pressure is 0.3-0.8MPa, and the mass ratio of the agent to the oil is 0.5-4: 1; preferably, the operation temperature is 60-100 ℃, the operation pressure is 0.4-0.6MPa, and the mass ratio of the agent to the oil is 0.5-2: 1.

The second simulated moving bed process parameters in the step (3) are as follows: the operation temperature is 50-110 ℃, the operation pressure is 0.3-0.8MPa, and the mass ratio of the agent to the oil is 0.5-4: 1; preferably, the operation temperature is 60-100 ℃, the operation pressure is 0.4-0.6Mpa, and the mass ratio of the agent to the oil is 0.5-2: 1.

The packing agent in the first simulated moving bed is an A series molecular sieve, preferably a 5A molecular sieve and/or a modified 5A molecular sieve.

The filler in the second simulated moving bed is an X series molecular sieve, preferably a 13X molecular sieve and/or a modified 13X molecular sieve.

The target olefin carbon number N is preferably in the range of 9 to 18, preferably 9 to 16, more preferably 10 to 14, and further preferably 10 to 12.

The coal-based Fischer-Tropsch synthetic oil contains 73-75 wt% of olefin, 22-25 wt% of alkane and 3-5 wt% of oxygen-containing compound.

The pretreatment step includes a step of deacidifying the feedstock.

The first and second simulated moving beds employ the following equipment:

comprises an adsorption bed, a raw material feeding system, a desorbent feeding system, a circulating system, a liquid pumping system, a raffinate pumping system, a program control valve group and an automatic control system; wherein, the adsorption bed comprises a plurality of adsorption columns which are divided into an adsorption area, a purification area, a desorption area and a buffer area;

the upper end of each adsorption column is provided with a raw material feed valve, a desorbent feed valve and a circulating liquid feed valve;

the lower end of each adsorption column is provided with a raffinate discharge valve and an extract discharge valve;

a one-way valve is arranged between every two adjacent adsorption columns;

the raw material feeding system is connected with a raw material feeding valve of each adsorption column;

the desorbent feed system is connected with a desorbent feed valve of each adsorption column;

the circulating system comprises a circulating pump, and is connected with a circulating liquid feeding valve of each adsorption column through the circulating pump;

the extract system is connected with an extract discharge valve of each adsorption column;

the raffinate system is connected with a raffinate discharge valve of each adsorption column;

all valves form a program control valve group, the program control valve group is connected with an automatic control system, and the automatic control system can control the opening and closing state of each valve in the program control valve group.

Advantageous effects

1. In the alkane-alkene mixture, the alkene is a polar substance, the alkane is a nonpolar or weak polar substance, and the adsorption performance of the polarity of the alkane on a specific adsorbent has certain difference. Compared with the traditional rectification and extraction process, the method adopts the mode of serial simulated moving beds for separation, and the obtained alpha-olefin product has higher purity, higher yield, lower energy consumption and about 15 percent of the production cost of the traditional process.

2. The method is particularly suitable for the separation process of alpha-olefin in the coal-based Fischer-Tropsch synthetic oil, and the combination of various process parameters of the method is closely related to the composition of the raw material, namely the process of continuously adjusting and perfecting the raw material through analysis of the raw material, adjustment of the parameters and small to medium tests.

3. According to the market demand, in order to reduce the production cost, the method of the invention does not arrange an oxygen compound removing step after the cut fraction cutting, although the existence of a small amount of oxygen compound can cause the service life of the adsorbent in the simulated moving bed to be reduced and the catalyst-oil ratio to be increased, compared with the method comprising the oxygen compound removing step, the method can reduce the whole production cost and can obtain the alpha-olefin product with high purity meeting the requirement.

4. The program control valve group is adopted to replace the traditional multi-channel rotary valve to control the cycle switching of the simulated moving bed, so that the equipment cost is reduced; the program control valve group can be flexibly cut out according to the maintenance requirement, so that the equipment maintenance is facilitated; each adsorption column can be cut out for maintenance, and the system is cut in after the adsorbent is replaced, so that the long-period running capacity of the device is greatly improved.

Drawings

FIG. 1 is a schematic diagram of a simulated moving bed process for separating alpha-olefins in accordance with the present invention.

Detailed Description

The technological process of the invention is shown in figure 1, and alpha-olefin products are obtained after raw materials are pretreated, cut, separated into alkane-olefin by a simulated moving bed I and separated into straight chain-isoolefin by a simulated moving bed II.

After the raw material is subjected to deacidification pretreatment, distillate oil enters a light component removing tower, components with carbon number less than N are separated from the top of the light component removing tower, and components at the bottom of the tower enter a heavy component removing tower; the component with carbon number more than N is separated from the bottom of the heavy component removing tower, and the component with carbon number N is separated from the top of the heavy component removing tower. The content of oxygen-containing compounds in the distillate oil is further reduced after fraction cutting.

The simulated moving bed divides the fixed adsorption bed into a plurality of sections, the sections are filled with adsorbents, and liquid between the sections cannot directly flow through. Each section is provided with an inlet and outlet pipeline, and the inlet and outlet of the pipeline are controlled by a valve. Typically, in a simulated moving bed with 8 adsorption columns, 20 of 24 inlets and outlets only play a role in connection between sections, the other 4 inlets and outlets are used for the inlet or outlet of four strands of materials, the positions of the inlets and outlets of the materials at a certain moment divide the whole adsorption bed layer into four zones, the distances of the zones are unequal, and the mass transfer of each zone is different. The inlet and outlet of four materials in the simulated moving bed move upwards at a speed synchronous with the change of solid phase concentration, thus forming a closed loop, and the total result is basically the same as the effect of keeping the inlet and outlet positions still and the solid adsorbent moving from top to bottom in the adsorber, thereby achieving the separation effect.

The simulated moving bed operating parameters are as follows:

a first simulated moving bed: the temperature is 50-110 ℃, the operating pressure is 0.3-0.8MPa, the filler of the simulated moving bed is an A series molecular sieve (such as a 3A, 4A, 5A or modified 5A molecular sieve), the mass ratio of the agent to the oil is 0.5-4: 1, and the content of the obtained olefin component is more than 99.5 wt%.

A second simulated moving bed: the temperature is 50-110 ℃, the operating pressure is 0.3-0.8MPa, the filler of the simulated moving bed is X series molecular sieve (such as 13X molecular sieve or modified 13X molecular sieve), the mass ratio of the filler to the oil is 0.5-4: 1, and the content of the obtained alpha-olefin component is more than 99.6 wt%.

The invention adopts a distillate oil raw material source which is a 120-million ton/year coal oil production device of the chemical industry Limited liability company of inner Mongolia Yitai, and the components are shown in Table 1.

TABLE 1 distillate feedstock composition

Numbering	Species of matter	Content/wt%
			1	Alkanes (normal/iso-alkanes)	23.17
2	Olefins (normal/iso olefins)	71.83
			3	Acids substances	0.5
4	Alcohols	4
			5	Aldehydes, esters, ketones	0.5

The raw material composition of the distillate obtained after deacidification is shown in table 2.

TABLE 2 Deacidification distillate composition

Numbering	Species of matter	Content/wt%
			1	Alkanes (normal/iso-alkanes)	23.90
2	Olefins (normal/iso olefins)	74.10
			3	Acids (acids)	--
4	Aldehydes, esters, ketones	2

Distillate cut the feed composition in the distillate is shown in table 3.

Table 3 distillate composition after cut

Comparative example 1

The target carbon number is 9, and the alkane and the alkene are separated in an extraction and rectification mode after pretreatment and fraction cutting treatment without simulated moving bed separation. Wherein the operation temperature of the separation of the alkane and the alkene is 100-105 ℃, the temperature at the top of the tower is 48-50 ℃, the reflux ratio is 5, the agent-oil ratio is 1: 1 (the mass ratio of the filling agent to the oil), the extracting agent is NMP (the fourth extracting agent in the example 1 of the reference CN 105777467A), and the content of the obtained alkene component is 98.08 wt%; straight chain hydrocarbon and branched chain hydrocarbon are not separated, the boiling points are only 3 ℃ lower, and the separation by using a rectification method is very difficult.