WO2022042508A1 - 吸附精馏分离乙苯的复合吸附剂及应用 - Google Patents

吸附精馏分离乙苯的复合吸附剂及应用 Download PDF

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WO2022042508A1
WO2022042508A1 PCT/CN2021/114167 CN2021114167W WO2022042508A1 WO 2022042508 A1 WO2022042508 A1 WO 2022042508A1 CN 2021114167 W CN2021114167 W CN 2021114167W WO 2022042508 A1 WO2022042508 A1 WO 2022042508A1
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xylene
ethylbenzene
adsorbent
composite adsorbent
tower
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PCT/CN2021/114167
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English (en)
French (fr)
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郄思远
唐文成
赵明
田龙胜
高思亮
庞伟伟
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中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Priority to US18/042,312 priority Critical patent/US20230322648A1/en
Priority to JP2023513399A priority patent/JP2023540227A/ja
Priority to EP21860343.9A priority patent/EP4206169A4/en
Priority to KR1020237010338A priority patent/KR20230056758A/ko
Publication of WO2022042508A1 publication Critical patent/WO2022042508A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/073—Ethylbenzene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/08—Xylenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique

Definitions

  • the present invention relates to a composite adsorbent for adsorption and rectification separation and its application, in particular to a method for separating ethylbenzene from C 8 aromatic hydrocarbons by using the composite adsorbent by adsorption and rectification.
  • Ethylbenzene is an important chemical basic raw material, mainly used for the production of styrene. At present, ethylbenzene is mainly produced by alkylation of benzene and ethylene. In the refining and chemical industry, ethylbenzene is rich in resources. Ethylbenzene accounts for about 18 % by mass in the reformed C8 fraction, and ethylbenzene in the ethylene cracking C8 fraction accounts for about 50% by mass.
  • this part of ethylbenzene can be directly separated , it can save the consumption of ethylene and benzene, and optimize the allocation of chemical resources; in addition, after the ethylbenzene in the C 8 fraction is separated, using xylene without ethylbenzene or with greatly reduced ethylbenzene content as the raw material of the aromatics complex will significantly increase the Efficiency of aromatics complexes. Therefore, it is very necessary to develop a new process for the efficient separation of ethylbenzene from mixed C8 aromatics.
  • GB1198592 describes a process for the separation of C8 aromatics using single or multiple rectification columns, requiring at least 250 trays, preferably 365 trays, and a reflux ratio of 100 to 250:1.
  • the method can separate ethylbenzene, ortho-xylene and the mixture of para-xylene and meta-xylene by distillation, and then separate para-xylene from the mixture of para-xylene and meta-xylene by crystallization, and isomerize the remaining components, which can High consumption, no economic advantage.
  • the separation of ethylbenzene by adsorption can be divided into two categories.
  • One is to preferentially adsorb non-ethylbenzene components in C aromatic hydrocarbons, and obtain ethylbenzene products from the extract.
  • US3917734 , US4079094 and US4108915 use Ca-X/Y, Sr -KX or Sr-X zeolite, preferentially adsorbs xylene isomers in C aromatic hydrocarbons, and obtains ethylbenzene products from extracts, but it is difficult to obtain high-purity ethylbenzene products using such adsorbents, and its purity is easily affected by the composition of raw materials Impact.
  • CN100577617C discloses a method for separating ethylbenzene and p-xylene in mixed C aromatic hydrocarbons by adopting pressure swing adsorption technology.
  • the adsorbent used is ZSM-5 molecular sieve. This adsorbent can only take p-xylene and ethylbenzene as the absorbent and cannot separate them. The selectivity of the adsorbent to the target products p-xylene and ethylbenzene lower.
  • the extractive distillation process is a method that uses an extractant to increase the relative volatility of the components to be separated to improve the separation efficiency.
  • the reported solvent for extractive distillation separation of ethylbenzene is difficult to provide ideal selectivity, and the separation efficiency is low.
  • US4292142 discloses a method for separating ethylbenzene from p-xylene and m-xylene by extractive rectification, using maleic anhydride and phthalic anhydride as a composite solvent for extractive rectification, in order to reduce maleic anhydride and phthalic anhydride the freezing point, and oxygen-containing compounds can also be added. Under the condition that the solvent ratio is 1.5, the relative volatility of ethylbenzene and p-xylene can reach 1.22.
  • US5135620 discloses a method for separating ethylbenzene from C 8 aromatic hydrocarbons by extractive rectification, using a hydrocarbon sulfonate of monovalent copper as an entrainer, and extractive rectification to separate ethylbenzene in C 8 aromatic hydrocarbons, and the sulfonic acid includes paraffin Toluenesulfonic acid, p-dodecylbenzenesulfonic acid, p-hexadecylbenzenesulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, naphtholsulfonic acid or halobenzenesulfonic acid.
  • the object of the present invention is to provide a composite adsorbent for separating ethylbenzene by adsorption and rectification from C aromatics and its application.
  • the composite adsorbent can improve the volatility of ethylbenzene relative to other C aromatics , so that the Rectification separates high-purity ethylbenzene from C8 aromatics.
  • the composite adsorbent for adsorbing, rectifying and separating ethylbenzene from C 8 aromatic hydrocarbons provided by the present invention comprises 1-50 mass % of xylene adsorbent and 50-99 mass % carrier liquid, wherein the carrier liquid is selected from alkanes , one or both of aryl-substituted alkanes, decalin and alkyl-substituted decalin, the alkanes are C 10 -C 26 alkanes, and the aryl-substituted alkanes are C 13 -C alkanes 16 Aryl-substituted alkanes.
  • the carrier liquid is selected from alkanes , one or both of aryl-substituted alkanes, decalin and alkyl-substituted decalin
  • the alkanes are C 10 -C 26 alkanes
  • the aryl-substituted alkanes are C
  • the composite adsorbent provided by the invention is obtained by mixing the xylene adsorbent and an appropriate amount of carrier liquid, and can be used to separate ethylbenzene and xylene in C8 aromatic hydrocarbons by means of adsorption and rectification, and obtain a high-purity ethylbenzene product.
  • the method can reduce fixed investment and energy consumption for separating ethylbenzene.
  • Fig. 1 is the schematic flow sheet of the method for the adsorption and rectification separation of ethylbenzene from C 8 aromatic hydrocarbons provided by the present invention.
  • the composite adsorbent provided by the present invention includes a xylene adsorbent and a carrier liquid, wherein the xylene adsorbent adsorbs xylene in the process of adsorption and rectification, so as to easily separate ethylbenzene from xylene in C aromatics , so
  • the carrier liquid is used to carry the xylene adsorbent to flow, it does not react with C aromatic hydrocarbons, and the boiling point is preferably greater than 180 ° C, so that in the process of adsorption and rectification, the carrier liquid does not volatilize to the top of the adsorption and rectification tower, and
  • the adsorbent carrying adsorbed xylene enters the distillation and desorption tower, where the xylene in the adsorbent is desorbed, and the carrier liquid carries the regenerated xylene adsorbent and returns to the adsorption and rectification tower for reuse
  • the composite adsorbent can significantly increase the relative volatility of ethylbenzene relative to each isomer of xylene, so that high-purity ethylbenzene can be separated from C 8 aromatics by adsorption and rectification.
  • the xylene adsorbent in the composite adsorbent of the present invention is used to increase the relative volatility of ethylbenzene to each isomer of xylene, and the carrier liquid is used to carry the xylene adsorbent to flow.
  • the composite adsorbent preferably comprises 5-35 mass % of xylene adsorbent and 65-95 mass % of carrier liquid.
  • the xylene adsorbent is preferably a Y molecular sieve in which a metal ion of Group IA and/or Group IIA occupies a cationic position, the metal ion of Group IA is preferably Li + or Na + , and the metal ion of Group IIA is preferably Sr 2+ or Ba 2 + , more preferably NaY molecular sieve.
  • the grain size of the Y molecular sieve is preferably 0.1-2 microns, more preferably 0.2-1.5 microns.
  • Described carrier liquid is selected from one or any two in alkane, aryl-substituted alkane, decalin or alkyl-substituted decalin, wherein the alkane can be normal alkane or iso-alkane, preferably C 10 -C 24 n-paraffin, more preferably C 11 -C 20 n-paraffin.
  • the aryl-substituted alkane is preferably a C 13 -C 16 diphenyl alkane.
  • the alkyl group of the alkyl-substituted decalin may be a C 1 -C 12 alkyl group, preferably a C 3 -C 10 alkyl group, more preferably a C 2 -C 6 alkyl group, and the number of substituted alkyl groups It can be 1-4, preferably 1-2.
  • the method for separating ethylbenzene by adsorption and rectification comprises the steps of introducing a C aromatic hydrocarbon mixture into the middle of an adsorption and rectification tower, the composite adsorbent of the present invention is introduced into the upper part of the adsorption and rectification tower, and after adsorption and rectification, ethylbenzene is removed from the
  • the adsorption distillation tower is discharged from the top of the tower, and the xylene-enriched composite adsorbent is discharged from the bottom of the tower and enters the middle of the distillation and desorption tower.
  • the mixed xylene is discharged from the top of the tower, and the regenerated composite adsorption is obtained at the bottom of the tower.
  • the agent is returned to the upper part of the adsorption rectification tower for reuse.
  • the pressure at the top of the adsorption distillation column is preferably 0.01 to 0.2 MPa
  • the number of theoretical plates is preferably 30 to 100, more preferably 30 to 80
  • the temperature of the composite adsorbent entering the tower is preferably 90 to 130 ° C
  • the temperature at the bottom of the column is preferably 140-250°C
  • the top temperature is preferably 70-100°C.
  • the mass ratio of the composite adsorbent entering the adsorption rectification tower and the C 8 aromatic hydrocarbon mixture is preferably 5 to 30, more preferably 8 to 23, and the mass ratio of the xylene adsorbent in the composite adsorbent to the C 8 aromatic hydrocarbon mixture is preferably 1.5 ⁇ 6. More preferably 2-5, the mass ratio of the carrier liquid to the xylene adsorbent is preferably 1.5-20, more preferably 2-10.
  • the reflux ratio in the upper part of the column is preferably 1-15, and more preferably 1-8.
  • the column top pressure of the distillation desorption column is preferably 0.01-0.15MPa, more preferably 0.01-0.06MPa, the number of theoretical plates is preferably 20-50, more preferably 25-45, the temperature at the bottom of the column is preferably 160-280°C, and the temperature at the top of the column is preferably 60 ⁇ 90°C.
  • the reflux ratio of the upper part of the distillation and desorption column is preferably 0.3 to 3, and more preferably 0.5 to 2.
  • the reflux ratio is the mass ratio of the material returned to the column at the top of the column to the material discharged at the top of the column.
  • the adsorption rectification tower and the distillation and desorption tower can be packed towers or tray towers.
  • the content of ethylbenzene in the C 8 aromatic hydrocarbon mixture is preferably 10-85% by mass, more preferably 15-60% by mass.
  • Relative volatility refers to the ratio of the volatility of the volatile component i to the volatility of the less volatile component j in the separated solution, which can reflect the precise The ease of separation of the two components during distillation.
  • the relative volatility of the two components i and j to be separated when they reach gas-liquid equilibrium is calculated by formula (1):
  • x is the liquid phase mole fraction of the component in equilibrium
  • y is the gas phase mole fraction of the component in equilibrium.
  • the C 8 aromatic hydrocarbon mixture from pipeline 1 is introduced into the middle of the adsorption rectification tower 3, the composite adsorbent is introduced into the upper part of the adsorption rectification tower from pipeline 2, and the C 8 aromatic hydrocarbons are in countercurrent contact with the composite adsorbent in the tower for adsorption.
  • the xylene in the C 8 aromatics is adsorbed by the xylene adsorbent, and the ethylbenzene is distilled to the top of the tower and discharged from the top line 7, and the ethylbenzene product is obtained after condensation.
  • the composite adsorbent that has adsorbed xylene is discharged from the bottom of the adsorption rectification tower, and enters the middle of the distillation and desorption tower 4 through the pipeline 5, and the xylene is desorbed from the composite adsorbent by distillation to realize the desorption of the xylene adsorbent.
  • Regeneration the xylene after desorption is discharged from the top line 8 of the distillation and desorption tower, and the xylene is obtained by condensation, and the regenerated composite adsorbent is discharged from the bottom of the distillation and desorption tower, and returns to the adsorption essence through pipeline 6 and pipeline 2.
  • the xylene basically does not contain ethylbenzene, and can be used as an isomerization raw material to produce p-xylene.
  • the method for determining the relative volatility of each component of C aromatics is as follows: add the sample to be tested into an Agilent 7694 headspace sampler, place it for a certain period of time, and analyze it by an Agilent 7890 chromatographic analysis when the gas-liquid equilibrium is reached. The composition of the gas and liquid phases in the injector was measured, and the relative volatility of the components was calculated from equation (1).
  • Ethylbenzene, p-xylene, o-xylene and m-xylene were mixed in equal mass ratios to prepare a C 8 aromatic hydrocarbon mixture as feedstock oil, and the ethylbenzene content in the feedstock oil was 25% by mass.
  • a C 8 aromatic hydrocarbon mixture as feedstock oil
  • ethylbenzene content in the feedstock oil was 25% by mass.
  • NaY molecular sieve powder with a grain size of 0.2-1 micron as the xylene adsorbent
  • n-tetradecane as the carrier liquid
  • mix the xylene adsorbent and the carrier liquid to make a composite adsorbent
  • the xylene in the composite adsorbent adsorbs xylene
  • the agent content was 20% by mass
  • the carrier liquid content was 80% by mass.
  • the composite adsorbent and the raw oil were added to the headspace sampler, wherein the mass ratio of carrier liquid/xylene adsorbent/raw oil was 8:2:1, and the mass ratio of composite adsorbent to raw oil was 10:1. Place at 80°C for 45 minutes to achieve gas-liquid equilibrium, and take gas and liquid phases for composition analysis.
  • the measured relative volatility of ethylbenzene to xylene isomers in the feedstock oil after adding the composite adsorbent is shown in Table 1. .
  • the relative volatility of ethylbenzene relative to each isomer of xylene in the feedstock oil after adding the composite adsorbent was measured according to the method of Example 1, except that the mass ratio of the carrier liquid/xylene adsorbent/feedstock oil used was 8:4 : 1, the mass ratio of the composite adsorbent to the feed oil was 12: 1, and the results are shown in Table 1.
  • the use of the composite adsorbent of the present invention can significantly improve the relative volatility of ethylbenzene relative to each isomer of xylene, compared with the method of not using the composite adsorbent or only using the carrier liquid.
  • the composite adsorbent of the invention can separate ethylbenzene in C 8 aromatic hydrocarbons.
  • Example 1 Use the composite adsorbent and feedstock oil described in Example 1 , separate ethylbenzene and xylene in the C aromatics according to the flow process shown in Figure 1, and see Table 2 for the operating conditions of the adsorption rectification tower, the distillation and desorption tower and the purity of the resulting product. .
  • the feedstock oil is the C 8 fraction of the reformed oil, wherein the mass ratio of ethylbenzene: p-xylene: m-xylene: o-xylene is 18: 19: 39: 24, according to Fig.
  • the flow process shown in 1 separates ethylbenzene and xylene in the C8 cut, and the operating conditions of the adsorption rectification tower, the distillation and desorption tower and the purity of the obtained product are shown in Table 3.
  • the feedstock oil is ethylene pyrolysis gasoline C 8 fraction, wherein the mass ratio of ethylbenzene: p-xylene: m-xylene: o-xylene is 52: 10: 23: 15, according to Figure 1
  • the shown flow process separates ethylbenzene and xylene in the C8 cut, and the operating conditions of the adsorption rectification tower, the distillation and desorption tower and the purity of the obtained product are shown in Table 4.
  • the use of the adsorption rectification of the present invention to separate ethylbenzene from a C 8 aromatic hydrocarbon mixture can greatly reduce energy consumption and improve Separation efficiency of benzene and xylene.

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Abstract

一种从C 8芳烃中吸附精馏分离乙苯的复合吸附剂，包括1～50质量％的二甲苯吸附剂和50～99质量％的载液，其中所述的载液选自烷烃、芳基取代烷烃、十氢萘和烷基取代的十氢萘中的一种或两种，所述的烷烃为C 10～C 26的烷烃，所述的芳基取代烷烃为C 13～C 16的芳基取代烷烃。所述的复合吸附剂可提高乙苯相对其它C 8芳烃的挥发度，从而可通过吸附精馏从C 8芳烃中分离高纯度乙苯。

Description

吸附精馏分离乙苯的复合吸附剂及应用 技术领域
本发明涉及用于吸附精馏分离的复合吸附剂及其应用，具体地说，涉及利用所述复合吸附剂通过吸附精馏分离C 8芳烃中乙苯的方法。
背景技术
乙苯是一种重要的化工基础原料，主要用于生产苯乙烯。目前主要采用苯与乙烯进行烷基化反应生产乙苯。而在炼油化工行业中，乙苯资源丰富，重整C 8馏分中乙苯占18质量％左右，乙烯裂解C 8馏分中乙苯占50质量％左右，如果能直接将这部分乙苯分离出来，可以节省乙烯、苯的消耗，优化配置化工资源；另外将C 8馏分中的乙苯分离后，用不含乙苯或乙苯含量大幅降低的二甲苯作为芳烃联合装置的原料，将显著提高芳烃联合装置的效能。因此开发从混合C 8芳烃中高效分离乙苯的新工艺是十分必要的。
目前，从C 8芳烃中分离乙苯有三种方法：超精馏法、吸附法以及抽提法。其中利用超精馏法从C 8馏分中分离乙苯是一个传统工艺，因为混合C 8芳烃的四种同分异构体沸点相近，其中乙苯和对二甲苯沸点差仅为2.2℃，使用精馏方法分离难度较大。
GB1198592描述了使用单个或多个精馏塔分离C 8芳烃的方法，需要至少250个塔板，优选365个塔板，回流比为100～250∶1。该方法通过蒸馏可分离乙苯、邻二甲苯以及对二甲苯和间二甲苯的混合物，对二甲苯和间二甲苯的混合物再通过结晶分离对二甲苯，其余组分进行异构化，其能耗高，没有经济优势。
吸附法分离乙苯可分为两类，一类为优先吸附C 8芳烃中的非乙苯组分，从抽佘物中得到乙苯产品，如US3917734、US4079094及US4108915分别使用Ca-X/Y、Sr-K-X或Sr-X沸石，优先吸附C 8芳烃中二甲苯异构体，从抽佘物中获得乙苯产品，但使用此类吸附剂得到高纯度乙苯产品较为困难，并且其纯度易受到原料组成的影响。另一类为优先吸附乙苯，CN100577617C公开了一种采用变压吸附技术分离混合C 8芳烃中乙苯和对二甲苯的方法，其变压吸附分离过程中使用吹扫气对吸附床层进行吹扫，使用的吸附剂为ZSM-5分子筛，这种吸附剂只能将对二甲苯和乙苯共同作为吸出物而不能将其分离，吸附剂对 目的产物对二甲苯和乙苯的选择性较低。
萃取精馏工艺是一种利用萃取剂增大待分离组分间的相对挥发度以提高分离效率的方法。目前，已报道的萃取蒸馏分离乙苯的溶剂难以提供理想的选择性，分离效率较低。
US4292142公开了通过萃取精馏将乙苯与对二甲苯和间二甲苯分离的方法，使用马来酸酐和邻苯二甲酸酐作为萃取精馏复合溶剂，为降低马来酸酐和邻苯二甲酸酐的凝固点，还可加入含氧化合物。在溶剂比为1.5的条件下，乙苯与对二甲苯的相对挥发度可达到1.22。
US5135620公开了使用萃取精馏从C 8芳烃中分离乙苯的方法，采用一价铜的烃磺酸盐为夹带剂，萃取精馏分离C 8芳烃中的乙苯，所述的磺酸包括对甲苯磺酸，对十二烷基苯磺酸，对十六烷基苯磺酸，萘磺酸，苯酚磺酸，萘酚磺酸或卤代苯磺酸。先将夹带剂通入萃取精馏塔，富含乙苯的组分从塔顶排出，溶于二甲苯的夹带剂从塔底排出，可通过蒸馏塔分离二甲苯和夹带剂，二甲苯从塔顶排出，溶有二甲苯的夹带剂从塔底排出返回萃取精馏塔。在溶剂比为2的条件下，乙苯与二甲苯的相对挥发度达到1.16。
发明内容
本发明的目的是提供一种从C 8芳烃中吸附精馏分离乙苯的复合吸附剂及其应用，所述的复合吸附剂可提高乙苯相对其它C 8芳烃的挥发度，从而可通过吸附精馏从C 8芳烃中分离高纯度乙苯。
本发明提供的从C 8芳烃中吸附精馏分离乙苯的复合吸附剂，包括1～50质量％的二甲苯吸附剂和50～99质量％的载液，其中所述的载液选自烷烃，芳基取代烷烃、十氢萘和烷基取代的十氢萘中的一种或两种，所述的烷烃为C 10～C 26的烷烃，所述的芳基取代烷烃为C 13～C 16的芳基取代烷烃。
本发明提供的复合吸附剂是通过将二甲苯吸附剂和适量载液混合得到，可用于通过吸附精馏的方法分离C 8芳烃中的乙苯和二甲苯，并得到高纯度乙苯产品。所述方法可降低固定投资和分离乙苯的能耗。
附图说明
图1为本发明提供的从C 8芳烃中吸附精馏分离乙苯的方法的流程示意图。
具体实施方式
本发明提供的复合吸附剂包括二甲苯吸附剂和载液，其中所述的二甲苯吸附剂在吸附精馏过程中吸附二甲苯，从而易使乙苯与C 8芳烃中的二甲苯分离，所述的载液用于携带二甲苯吸附剂流动，其不与C 8芳烃反应，并且沸点优选大于180℃，如此，可使吸附精馏过程中，载液不挥发至吸附精馏塔顶，并携带吸附二甲苯的吸附剂进入蒸馏脱附塔中，在蒸馏脱附塔中脱附吸附剂中的二甲苯，载液携带再生的二甲苯吸附剂返回吸附精馏塔重复利用。所述复合吸附剂可显著提高乙苯相对二甲苯各异构体的相对挥发度，从而可通过吸附精馏从C 8芳烃中分离高纯度乙苯。
本发明所述的复合吸附剂中的二甲苯吸附剂用于提高乙苯相对二甲苯各异构体的相对挥发度，载液用于携带二甲苯吸附剂流动。所述的复合吸附剂优选包括5～35质量％的二甲苯吸附剂和65～95质量％的载液。
所述的二甲苯吸附剂优选为IA族和/或IIA族金属离子占据阳离子位的Y分子筛，所述的IA族金属离子优选Li +或Na +，IIA族金属离子优选Sr 2+或Ba 2+，更优选为NaY分子筛。
所述的Y分子筛的晶粒粒径优选0.1～2微米、更优选0.2～1.5微米。
所述的载液选自烷烃，芳基取代烷烃、十氢萘或烷基取代的十氢萘中的一种或任意两种，其中所述的烷烃可为正构烷烃或异构烷烃，优选C 10～C 24的正构烷烃、更优选C 11～C 20的正构烷烃。
所述的芳基取代烷烃优选C 13～C 16的二苯基烷烃。
所述的烷基取代的十氢萘的烷基可为C 1～C 12的烷基、优选C 3～C 10的烷基、更优选C 2～C 6的烷基，取代烷基个数可为1～4，优选1～2。
本发明提供的吸附精馏分离乙苯的方法，包括将C 8芳烃混合物引入吸附精馏塔的中部，本发明所述的复合吸附剂引入吸附精馏塔上部，经过吸附精馏，乙苯从吸附精馏塔塔顶排出，富集二甲苯的复合吸附剂从塔底排出，进入蒸馏脱附塔的中部，经过蒸馏脱附，混合二甲苯从塔顶排出，塔底得到再生后的复合吸附剂，返回吸附精馏塔上部重新利用。
上述方法中，吸附精馏塔的塔顶压力优选0.01～0.2MPa，理论塔板数优选30～100、更优选30～80，复合吸附剂的入塔温度优选90～130℃，塔底温度优选140～250℃，塔顶温度优选70～100℃。
进入吸附精馏塔的复合吸附剂与C 8芳烃混合物的质量比优选为5～30、更优选8～23，复合吸附剂中的二甲苯吸附剂与C 8芳烃混合物的质量比优选为1.5～6、更优选2～5，载液与二甲苯吸附剂的质量比优选为1.5～20、更优选2～10。塔上部回流比优选1～15、更优选1～8。
蒸馏脱附塔的塔顶压力优选0.01～0.15MPa、更优选0.01～0.06MPa，理论塔板数优选20～50、更优选25～45，塔底温度优选160～280℃，塔顶温度优选60～90℃。蒸馏脱附塔上部的回流比优选0.3～3、更优选0.5～2。
上述方法中，所述回流比为塔上部回流入塔物料与塔顶排出物料的质量比。
所述吸附精馏塔和蒸馏脱附塔可为填料塔或者板式塔。
本发明方法中，所述C 8芳烃混合物中乙苯含量优选为10～85质量％、更优选15～60质量％。
在吸附蒸馏中，用相对挥发度衡量溶剂的分离效果，相对挥发度(α)是指被分离溶液中易挥发组分i的挥发度与难挥发组分j的挥发度之比，可以反映精馏过程中两组分分离的难易程度。待分离的i、j两组分在达到气液平衡时的相对挥发度用式(1)计算：
Figure PCTCN2021114167-appb-000001
式(1)中，x为平衡状态下组分的液相摩尔分数，y为平衡状态下组分的气相摩尔分数。当α为1时，两组分的挥发度相等，说明两组分不能用吸附精馏方法分离，当α大于1，且α值越大时，两组分就越易用吸附精馏方法分离。
下面通过附图进一步说明本发明。
图1中，将来自管线1的C 8芳烃混合物引入吸附精馏塔3的中部，复合吸附剂由管线2引入吸附精馏塔的上部，C 8芳烃在塔内与复合吸附剂逆流接触进行吸附与精馏，C 8芳烃中的二甲苯被二甲苯吸附剂吸附，乙苯则被蒸馏至塔顶，并从塔顶管线7排出，经冷凝后得到乙苯产品。吸附了二甲苯的复合吸附剂从吸附精馏塔塔底排出，由管线5进入蒸馏脱附塔4的中部，通过蒸馏使二甲苯从复合吸附剂中脱附，实现二甲苯吸附剂的脱附再生，脱附后的二甲苯从蒸馏脱附塔的塔顶 管线8排出，经冷凝得到二甲苯，再生后的复合吸附剂从蒸馏脱附塔塔底排出，经管线6和管线2返回吸附精馏塔重新利用。所述的二甲苯中基本不含乙苯，可作为异构化原料生产对二甲苯。
下面通过实例进一步详细说明本发明，但本发明并不限于此。
实例和对比例中，测定C 8芳烃各组分相对挥发度的方法为：将被测样品加入安捷伦7694顶空进样器中，放置一定时间，待达到气液平衡时，由安捷伦7890色谱分析测定所述进样器中的气相和液相组成，由式(1)计算组分的相对挥发度。
实例1
将乙苯、对二甲苯、邻二甲苯、间二甲苯按等质量比混合，配成C 8芳烃混合物作为原料油，原料油中乙苯含量为25质量％。取晶粒粒径为0.2～1微米的NaY分子筛粉末作为二甲苯吸附剂，正十四烷为载液，将二甲苯吸附剂与载液混合制成复合吸附剂，复合吸附剂中二甲苯吸附剂含量为20质量％，载液含量为80质量％。
将复合吸附剂与原料油加入顶空进样器中，其中载液/二甲苯吸附剂/原料油质量比为8∶2∶1，复合吸附剂与原料油的质量比为10∶1，于80℃放置45分钟，使达到气液平衡，分别取气、液相进行组成分析，测得的加入复合吸附剂后的原料油中乙苯相对二甲苯各异构体的相对挥发度见表1。
实例2
按实例1的方法测定加入复合吸附剂后的原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是所用载液/二甲苯吸附剂/原料油的质量比为8∶3∶1，复合吸附剂与原料油的质量比为11∶1，结果见表1。
实例3
按实例1的方法测定加入复合吸附剂后的原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是所用载液/二甲苯吸附剂/原料油的质量比为8∶4∶1，复合吸附剂与原料油的质量比为12∶1，结果见表1。
实例4
按实例1的方法测定加入复合吸附剂后的原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是所用载液/二甲苯吸附剂/原料油的 质量比为13∶2∶1，复合吸附剂与原料油的质量比为15∶1，结果见表1。
实例5
按实例1的方法测定加入复合吸附剂后的原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是所用载液/二甲苯吸附剂/原料油的质量比为18∶2∶1，复合吸附剂与原料油的质量比为20∶1，结果见表1。
实例6
按实例1的方法测定加入复合吸附剂后的原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是所用载液为正十一烷，结果见表1。
实例7
按实例1的方法测定加入复合吸附剂后的原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是所用载液为正十六烷，结果见表1。
实例8
按实例1的方法测定加入复合吸附剂后的原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是所用载液为二苯甲烷，结果见表1。
实例9～10
按实例1的方法测定加入复合吸附剂后的原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是所用载液分别为丁基十氢萘和十氢萘，结果见表1。
实例11
按实例1的方法测定加入复合吸附剂后的原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是所用原料油中乙苯∶对二甲苯∶邻二甲苯∶间二甲苯的质量比为1∶2∶1∶1，原料油中乙苯含量为20质量％，结果见表1。
实例12
按实例1的方法测定加入复合吸附剂后的原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是所用原料油中乙苯∶对二甲苯∶邻二甲苯∶间二甲苯的质量比为2∶1∶1∶1，原料油中乙苯含量为40质量％，结果见表1。
表1
Figure PCTCN2021114167-appb-000002
对比例1
按实例1的方法测定原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是不用复合吸附剂，结果见表1。
对比例2
按实例1的方法测定原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是不用复合吸附剂，所用原料油中乙苯∶对二甲苯∶邻二甲苯∶间二甲苯的质量比为1∶2∶1∶1，结果见表1。
对比例3
按实例1的方法测定原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是不用复合吸附剂，所用原料油中乙苯∶对二甲苯∶邻二甲苯∶间二甲苯的质量比为2∶1∶1∶1，结果见表1。
对比例4
按实例1的方法测定原料油中乙苯相对二甲苯各异构体的相对挥发度，不同的是在原料油中只加入正十四烷，正十四烷与原料油的质 量比为8∶1，结果见表1。
由表1可知，使用本发明所述的复合吸附剂，较之不使用复合吸附剂或仅使用载液的方法，可显著提高乙苯相对二甲苯各异构体的相对挥发度，说明使用本发明所述的复合吸附剂可分离C 8芳烃中的乙苯。
实例13
使用实例1所述的复合吸附剂和原料油，按照图1所示的流程分离C 8芳烃中的乙苯和二甲苯，吸附精馏塔、蒸馏脱附塔操作条件及所得产品纯度见表2。
对比例5
使用普通精馏塔分离实例1所述原料油中的乙苯与二甲苯，精馏塔操作条件及所得产品纯度见表2。
对比例6
使用萃取精馏方法分离C 8芳烃中的乙苯，将C 8芳烃通入萃取精馏塔中部，萃取溶剂通入塔上部，经萃取精馏，乙苯从塔顶排出，富含二甲苯的富溶剂从塔底排出，进入溶剂回收塔，经过精馏，二甲苯从塔顶排出，贫溶剂从塔底排出返回萃取精馏塔。使用1，2，4-三氯苯作为萃取溶剂，C 8芳烃原料油按实例1方法配制，萃取精馏塔、溶剂回收塔的操作条件及所得产品纯度见表2。
表2
Figure PCTCN2021114167-appb-000003
*萃取溶剂/原料油质量比
实例14
使用实例1所述的复合吸附剂，原料油为重整生成油C 8馏分，其中乙苯∶对二甲苯∶间二甲苯∶邻二甲苯的质量比为18∶19∶39∶24，按照图1所示的流程分离所述C 8馏分中的乙苯和二甲苯，吸附精馏塔、蒸馏脱附塔的操作条件及所得产品纯度见表3。
对比例7
使用普通精馏塔分离实例14所述原料油中的乙苯与二甲苯，精馏塔操作条件及所得产品纯度见表3。
表3
Figure PCTCN2021114167-appb-000004
买例15
使用实例1所述的复合吸附剂，原料油为乙烯裂解汽油C 8馏分，其中乙苯∶对二甲苯∶间二甲苯∶邻二甲苯的质量比为52∶10∶23∶15，按照图1所示的流程分离所述C 8馏分中的乙苯和二甲苯，吸附精馏塔、蒸馏脱附塔的操作条件及所得产品纯度见表4。
对比例8
使用普通精馏塔分离实例15所述原料油中的乙苯与二甲苯，精馏塔操作条件及所得产品纯度见表4。
表4
Figure PCTCN2021114167-appb-000005
由表2～4可知，利用本发明所述的吸附精馏从C 8芳烃混合物中分离乙苯，较之单独使用普通精馏塔或萃取精馏分离乙苯，可大幅降低能耗，提高乙苯与二甲苯的分离效率。

Claims (13)

  1. 一种从C 8芳烃中吸附精馏分离乙苯的复合吸附剂，包括1～50质量％的二甲苯吸附剂和50～99质量％的载液，其中所述的载液选自烷烃、芳基取代烷烃、十氢萘和烷基取代的十氢萘中的一种或两种，所述的烷烃为C 10～C 26的烷烃，所述的芳基取代烷烃为C 13～C 16的芳基取代烷烃。
  2. 按照权利要求1所述的复合吸附剂，其特征在于所述的复合吸附剂包括5～35质量％的二甲苯吸附剂和65～95质量％的载液。
  3. 按照权利要求1所述的复合吸附剂，其特征在于所述的二甲苯吸附剂为IA族和/或IIA族金属离子占据阳离子位的Y分子筛。
  4. 按照权利要求3所述的复合吸附剂，其特征在于所述的二甲苯吸附剂为NaY分子筛。
  5. 按照权利要求3或4所述的复合吸附剂，其特征在于所述的Y分子筛的晶粒粒径为0.1～2微米。
  6. 按照权利要求1所述的复合吸附剂，其特征在于所述的烷烃为C 10～C 24的正构烷烃，所述的芳基取代烷烃为C 13～C 16的二苯基烷烃，所述烷基取代的十氢萘的烷基为C 1～C 12的烷基，取代烷基个数为1～4。
  7. 按照权利要求6所述的复合吸附剂，其特征在于所述的烷烃为C 11～C 20的正构烷烃，所述的烷基取代的十氢萘的烷基为C 3～C 10的烷基。
  8. 一种吸附精馏分离乙苯的方法，包括将C 8芳烃混合物引入吸附精馏塔(3)的中部，权利要求1所述的复合吸附剂引入吸附精馏塔(3)上部，经过吸附精馏，乙苯从吸附精馏塔塔顶排出，富集二甲苯的复合吸附剂从塔底排出，进入蒸馏脱附塔(4)的中部，经过蒸馏脱附，混合二甲苯从塔顶排出，塔底得到再生后的复合吸附剂，返回吸附精馏塔上部重新利用。
  9. 按照权利要求8所述的方法，其特征在于吸附精馏塔的塔顶压力为0.01～0.2MPa，理论塔板数为30～100，复合吸附剂的入塔温度为90～130℃，塔底温度为140～250℃。
  10. 按照权利要求9所述的方法，其特征在于进入吸附精馏塔的复合吸附剂中二甲苯吸附剂与C 8芳烃混合物的质量比为1.5～6，载液与 二甲苯吸附剂的质量比为1.5～20，回流比为1～15。
  11. 按照权利要求8所述的方法，其特征在于蒸馏脱附塔的塔顶压力为0.01～0.15MPa、理论塔板数为20～50、塔底温度为160～280℃。
  12. 按照权利要求11所述的方法，其特征在于蒸馏脱附塔的回流比为0.3～3。
  13. 按照权利要求8所述的方法，其特征在于所述C 8芳烃混合物中乙苯含量为10～85质量％。
PCT/CN2021/114167 2020-08-26 2021-08-24 吸附精馏分离乙苯的复合吸附剂及应用 WO2022042508A1 (zh)

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