CN107973687B - Method for removing oxygen-containing compounds in mixed aromatics of methanol aromatization product - Google Patents
Method for removing oxygen-containing compounds in mixed aromatics of methanol aromatization product Download PDFInfo
- Publication number
- CN107973687B CN107973687B CN201610918528.6A CN201610918528A CN107973687B CN 107973687 B CN107973687 B CN 107973687B CN 201610918528 A CN201610918528 A CN 201610918528A CN 107973687 B CN107973687 B CN 107973687B
- Authority
- CN
- China
- Prior art keywords
- aromatic hydrocarbon
- oxygen
- tower
- material flow
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
-
- 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
-
- 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
Abstract
The invention relates to a method for removing oxygen-containing compounds in mixed aromatics of a methanol aromatization product, which comprises the step of enabling reaction products flowing out of a methanol aromatization reactor to sequentially pass through a three-phase separator, an alkaline washing tower, a water washing tower, an aromatic extraction tower and an oxygen-containing compound adsorption tower. The mixed aromatic hydrocarbon obtained by the method has low content of oxygen-containing compounds, is convenient for subsequent treatment, and effectively improves the economic value of the mixed aromatic hydrocarbon of the methanol aromatization product.
Description
Technical Field
The invention relates to a method for removing oxygen-containing compounds in aromatic hydrocarbons, in particular to a method for removing oxygen-containing compounds in mixed aromatic hydrocarbons of methanol aromatization products.
Background
Aromatic hydrocarbons (wherein benzene, toluene and xylene are respectively referred to as B, T and X, and the three are collectively referred to as BTX) are important basic organic chemical raw materials. Aromatics are mainly derived from catalytic reforming and steam cracking by-products pyrolysis gasoline (nearly 90%) -petroleum route, only around 10% from coal route. With the economic development, BTX aromatics, especially in the asia-pacific region, still maintain a vigorous market demand. However, with the continuous consumption of petroleum resources and the increasing price, the production cost of aromatic hydrocarbons using petroleum as a raw material has greatly increased. Thus, in the long run, the preparation of aromatics from coal-based methanol conversion is a very promising route for aromatics production.
Patent CN200610012703.1 discloses a process for preparing aromatic hydrocarbon by methanol conversion, a catalyst and a catalyst preparation method. The process takes methanol as a raw material and a modified ZSM-5 molecular sieve as a catalyst, and the operation pressure is 0.1-5.0 Mpa, the operation temperature is 300-460 ℃, and the airspeed of the raw material liquid is 0.1-6.0 h-1Catalytically converting the aromatic hydrocarbon into a product mainly containing aromatic hydrocarbon under the condition; cooling and separating to obtain gasPhase product low carbon hydrocarbon and liquid phase product C5+Separating the hydrocarbons; liquid phase product C5+The hydrocarbons are extracted and separated to obtain aromatic hydrocarbons and non-aromatic hydrocarbons.
Patent CN201010146915.5 discloses a system and a process for preparing aromatic hydrocarbons by converting methanol or dimethyl ether. The process comprises the following steps: the raw material methanol or dimethyl ether is firstly reacted in an aromatization reactor, after the reaction product is separated, H2, methane, mixed C8 aromatic hydrocarbon and partial C9+ hydrocarbon are used as product output system, and C2+Non-aromatic and mixed C8 aromatic and part C9+The aromatic hydrocarbons except the hydrocarbons are used as a circulating material flow to return to the corresponding reactor for further aromatization reaction. By adopting the system and the process, the product in the aromatization process of the methanol or the dimethyl ether is separated and recycled, so that the yield and the selectivity of the aromatic hydrocarbon are improved, the process is flexible, and the target product can be changed according to the market demand.
However, unlike the petroleum route for the production of aromatics, the aromatization of methanol also poses a problem. Since methanol is an oxygen-containing compound, there are inevitably unreacted methanol in the reaction product, and oxygen-containing compounds produced by side reactions, such as formic acid, ethanol, acetic acid, acetaldehyde, propionaldehyde, acetone, butyraldehyde, methyl ethyl ketone, pentanone, hexanone, alkylphenyl ethanol, alkylphenol, and the like. On one hand, the oxygen-containing compounds can cause corrosion to equipment, such as formic acid and acetic acid; on the other hand, the presence of the oxygen-containing compound can seriously affect the normal operation of the subsequent operation units of the product mixed aromatic hydrocarbon entering the aromatic hydrocarbon integrated device, including an adsorption separation unit, a disproportionation unit, an isomerization unit and the like, thereby reducing the quality and the economic value of the mixed aromatic hydrocarbon.
Chinese patent CN101993321 discloses a process for removing oxygenates from an olefin stream comprising passing the olefin stream sequentially through three deoxygenator columns of different pressures. Since ethylene and propylene are in a gaseous form under a relatively low pressure condition and the boiling point of the oxygen-containing compound is relatively high, the ethylene and propylene can be effectively separated from each other by gas-liquid separation by controlling the temperature and the pressure. For liquid phase aromatics, this process is less suitable.
Chinese patent CN103191754 discloses a catalyst for Fischer-Tropsch synthetic oil hydrofining and a preparation method and application thereof. The catalyst uses alumina as carrier, nickel and tungsten as hydrogenation active component, and contains at least one of titanium oxide, silicon oxide, zirconium oxide, fluorine, boron, phosphorus and other assistants. The hydrogenation reaction temperature is 220-380 ℃, the reaction pressure is 2.0-6.0 MPa, the hydrogen/oil volume ratio is 200-800, and the volume airspeed is 0.5-5.0 h-1. The Fischer-Tropsch synthetic oil mainly comprises straight-chain alkane and olefin, contains a certain amount of oxygen-containing compounds, and has extremely low aromatic hydrocarbon content. Hydrofining is mainly used for saturating olefin in the oil and improving the quality of the oil, and the literature mentions that the removal rate of substances containing oxidation is 99%, but the initial concentration of oxygen-containing compounds and the final concentration are not mentioned.
Chinese patent CN103664488 discloses an aromatic hydrocarbon methanol alkylation method for removing oxygen-containing compound journal. The invention adopts the following steps: a) the mixed raw material of benzene or toluene and methanol passes through a composite bed reactor and contacts with a catalyst to generate a material flow 1, b) the material flow 1 enters an oil-water separator after heat exchange and cooling, the lower-layer by-product water is discharged, and the upper-layer oil phase enters a stripping tower and is separated to obtain the p-xylene. The key point is that a methylation catalyst and an oxygen-containing compound removal catalyst are respectively filled in a composite bed reactor from top to bottom, and the oxidation-containing compound is converted into water or carbon dioxide through two-step reaction. The product is reported to contain less than 0.5ppm of each oxygenate. Because the reaction adopts fixed bed operation, the catalyst filling is complex, and for a fluidized bed reactor, different catalysts can be difficultly filled in the same reactor from top to bottom, so the adaptability of the method is limited.
Disclosure of Invention
The technical problem to be solved by the invention is the defects of complex process for removing oxygen-containing compounds in the process of producing mixed aromatic hydrocarbons by methanol aromatization and high oxygen-containing compounds in the treated mixed aromatic hydrocarbons in the prior art, and the invention provides a method for removing the oxygen-containing compounds in the aromatic hydrocarbons produced by methanol aromatization.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for removing oxygen-containing compounds in mixed aromatics of methanol aromatization products is characterized by comprising the following steps:
(1) after the aromatic hydrocarbon-rich material flow flowing out of the methanol aromatization reactor is separated by a three-phase separator, the gas-phase hydrocarbon returns to the methanol aromatization reactor, part of the oxygenate is dissolved in the water phase and discharged, and the oil phase rich in aromatic hydrocarbon enters the step (2);
(2) the oil phase which flows out from the three-phase separator and is rich in aromatic hydrocarbon enters an alkaline washing tower, and organic acid in the oil phase is removed after alkaline washing;
(3) the material flow flowing out of the alkaline washing tower enters a water washing tower, and oxygen-containing compounds which are easy to dissolve in water are removed through water washing;
(4) the material flow flowing out of the water washing tower enters an aromatic hydrocarbon extraction tower, and aromatic hydrocarbon and non-aromatic hydrocarbon are separated through aromatic hydrocarbon extraction and steam stripping;
(5) and (3) the aromatic hydrocarbon obtained by the aromatic hydrocarbon extraction tower enters an oxygen-containing compound adsorption tower, and the oxygen-containing compound in the aromatic hydrocarbon is removed by adsorption to obtain the mixed aromatic hydrocarbon with low oxygen-containing compound content.
In the technical scheme, in the aromatic hydrocarbon-rich material flow which is obtained from the methanol aromatization reactor and is subjected to three-phase separation, the oxygen-containing compounds mainly comprise methanol, formic acid, ethanol, acetic acid, acetaldehyde, propionaldehyde, acetone, butyraldehyde, butanone, pentanone, hexanone, alkyl phenyl ethanol and alkylphenol, and the total weight content of the oxygen-containing compounds is 100-10000 ppm in terms of the weight percentage of the aromatic hydrocarbon-rich material flow.
In the above technical solution, more preferably, in the aromatic hydrocarbon-rich stream that is obtained from the methanol aromatization reactor and subjected to three-phase separation, the total weight content of the oxygen-containing compounds is 200 to 8000ppm, in terms of the weight percentage of the aromatic hydrocarbon-rich stream.
In the above technical scheme, preferably, in the aromatic hydrocarbon-rich stream subjected to three-phase separation and coming out of the methanol aromatization reactor, the total weight content of the oxygen-containing compounds is 1000 to 4000ppm in terms of the weight percentage of the aromatic hydrocarbon-rich stream.
In the above technical scheme, preferably, in the aromatic hydrocarbon-rich stream which is separated from the methanol aromatization reactor by three phases, the weight content of the non-aromatic ketone oxygen-containing compound is 20 to 4000ppm in terms of the weight percentage of the aromatic hydrocarbon-rich stream.
In the above technical solution, more preferably, in the aromatic hydrocarbon-rich stream that is obtained from the methanol aromatization reactor and subjected to three-phase separation, the weight content of the non-aromatic ketone oxygen-containing compound is 50 to 2000ppm in terms of the weight percentage of the aromatic hydrocarbon-rich stream.
In the above technical scheme, preferably, in the aromatic hydrocarbon-rich stream which is separated from the methanol aromatization reactor by three-phase separation, the weight content of the alkylphenol is 100 to 5000ppm in terms of the weight percentage of the aromatic hydrocarbon-rich stream.
In the above technical solution, more preferably, in the aromatic hydrocarbon-rich stream that is obtained from the methanol aromatization reactor and is subjected to three-phase separation, the weight content of the alkylphenol is 200 to 2000ppm in terms of the weight percentage of the aromatic hydrocarbon-rich stream.
In the above technical solution, preferably, the weight content of the oxygen-containing compound in the treated mixed aromatic hydrocarbon is less than 5 ppm.
In the above technical solution, more preferably, the weight content of the oxygen-containing compound in the treated mixed aromatic hydrocarbon is less than 1 ppm.
In the technical scheme, the temperature of the alkaline washing tower is controlled to be 1-80 ℃, the concentration of the alkali liquor is 5-15%, and the volume ratio of the alkali liquor to the aromatic hydrocarbon material flow is 0.1: 1-1: 1, and 1-3 times of alkaline washing. The preferable temperature is 10-60 ℃, and the preferable concentration of the alkali liquor is 5-10%. The temperature of the water washing tower is 1-80 ℃, and the volume ratio of water to aromatic hydrocarbon material flow is 0.1: 1-10: 1, and 1-5 times of washing. The optimal washing temperature is 10-60 ℃, and the optimal volume ratio of water to the aromatic hydrocarbon material flow is 1: 1-5: 1. The aromatic hydrocarbon extraction tower adopts at least one of diethylene glycol ether, triethylene glycol ether, tetraethylene glycol ether, sulfolane, dimethyl sulfoxide, N-methyl pyrrolidone and formyl morpholine as an extracting agent, and the volume ratio of the extracting agent to the aromatic hydrocarbon material flow is 1: 1-20: 1. The extraction column employs conventional prior art. The oxygen-containing compound adsorption tower adopts a fixed bed or a simulated moving bed as contact equipment, preferably the simulated moving bed, and has better removal effect. The adsorbent is selected from at least one of activated carbon, porous alumina and zeolite molecular sieve, preferably porous alumina.
In the above technical scheme, preferably, the adsorbent is a mixture of activated carbon and porous alumina; more preferably, the ratio of the activated carbon to the porous alumina is (1: 5) to (5: 1).
At present, no report on removal of oxygen-containing compounds in mixed aromatics of methanol aromatization products is found, and the technical scheme provided by the invention effectively removes the oxygen-containing compounds in the mixed aromatics of the methanol aromatization reaction products by three main links of acid washing, water washing to remove the oxygen-containing compounds which are easy to dissolve in water and fine removal by using an oxygen-containing compound adsorption tower, so that the content of the oxygen-containing compounds in the mixed aromatics of the methanol aromatization reaction products is less than 1ppm, thereby reducing the influence of byproduct oxygen-containing compound impurities on the normal operation of a subsequent aromatic combination device, and improving the quality and the economic value of the mixed aromatics of the methanol aromatization products.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
The reaction product from the methanol aromatization reactor was subjected to three-phase separation to obtain an aromatic-rich stream i, the oxygenates contained therein and their content are shown in table 1.
The temperature of the alkaline washing tower is controlled to be 20 ℃, the concentration of the alkaline liquor is 10 percent, the volume ratio of the alkaline liquor to the aromatic hydrocarbon material flow is 1:1, and the number of times of alkaline washing is 1. Controlling the temperature of the water washing tower to be 20 ℃, the volume ratio of water to the aromatic hydrocarbon material flow to be 2:1, and the washing times to be 3 times. The oxygen-containing compound adsorption tower adopts a fixed bed reactor as contact equipment, and porous alumina is selected as an adsorbent. The oxygenate and its content in the aromatic hydrocarbon stream after stream i passed sequentially through the caustic wash tower, water wash tower and adsorption tower are shown in table 1.
[ example 2 ]
Using stream I from example 1, the temperature of the caustic wash tower was controlled at 40 ℃, the concentration of the caustic was controlled at 15%, the volume ratio of the caustic to the aromatic stream was 0.5:1, and the number of caustic washes was 1. Controlling the temperature of the water washing tower to be 60 ℃, the volume ratio of water to the aromatic hydrocarbon material flow to be 5:1, and the washing times to be 2 times. The oxygen-containing compound adsorption tower adopts a fixed bed reactor as contact equipment, and the adsorbent is a 4A molecular sieve. The oxygenate and its content in the aromatic hydrocarbon stream after stream i passed sequentially through the caustic wash tower, water wash tower and adsorption tower are shown in table 1.
[ example 3 ]
Using stream I from example 1, the temperature of the caustic wash tower was controlled at 40 ℃, the concentration of the caustic was controlled at 8%, the volume ratio of the caustic to the aromatic stream was 1:1, and the number of caustic washes was controlled at 3 times. Controlling the temperature of the water washing tower to be 30 ℃, the volume ratio of water to the aromatic hydrocarbon material flow to be 3:1, and the washing times to be 3 times. The oxygen-containing compound adsorption tower adopts a simulated moving bed reactor as contact equipment, and the adsorbent is a 13X molecular sieve. The oxygenate and its content in the aromatic hydrocarbon stream after stream i passed sequentially through the caustic wash tower, water wash tower and adsorption tower are shown in table 1.
[ example 4 ]
Using stream I from example 1, the temperature of the caustic wash tower was controlled at 80 ℃, the concentration of the caustic was controlled at 10%, the volume ratio of the caustic to the aromatic stream was controlled at 0.2:1, and the number of caustic washes was controlled at 2 times. Controlling the temperature of the water washing tower to be 50 ℃, the volume ratio of water to the aromatic hydrocarbon material flow to be 8:1, and washing times to be 1 time. The oxygen-containing compound adsorption tower adopts a simulated moving bed reactor as contact equipment, and the Y molecular sieve is selected as an adsorbent. The oxygenate and its content in the aromatic hydrocarbon stream after stream i passed sequentially through the caustic wash tower, water wash tower and adsorption tower are shown in table 1.
[ example 5 ]
Using stream I from example 1, the temperature of the caustic wash tower was controlled at 20 ℃, the concentration of the caustic was controlled at 10%, the volume ratio of the caustic to the aromatic stream was 0.2:1, and the number of caustic washes was 1. Controlling the temperature of the water washing tower to be 20 ℃, the volume ratio of water to the aromatic hydrocarbon material flow to be 2:1, and the washing times to be 3 times. The oxygen-containing compound adsorption tower adopts a fixed bed reactor as contact equipment, and porous alumina is selected as an adsorbent. The oxygenate and its content in the aromatic hydrocarbon stream after stream i passed sequentially through the caustic wash tower, water wash tower and adsorption tower are shown in table 1.
[ example 6 ]
Using stream I from example 1, the temperature of the caustic wash tower was controlled at 20 ℃, the concentration of the caustic was controlled at 10%, the volume ratio of the caustic to the aromatic stream was 1:1, and the number of caustic washes was 1. Controlling the temperature of the water washing tower to be 20 ℃, the volume ratio of water to the aromatic hydrocarbon material flow to be 2:1, and the washing times to be 1 time. The oxygen-containing compound adsorption tower adopts a fixed bed reactor as contact equipment, and porous alumina is selected as an adsorbent. The oxygenate and its content in the aromatic hydrocarbon stream after stream i passed sequentially through the caustic wash tower, water wash tower and adsorption tower are shown in table 1.
[ example 7 ]
Using stream I from example 1, the temperature of the caustic wash tower was controlled at 20 ℃, the concentration of the caustic was controlled at 10%, the volume ratio of the caustic to the aromatic stream was 1:1, and the number of caustic washes was 1. Controlling the temperature of the water washing tower to be 20 ℃, the volume ratio of water to the aromatic hydrocarbon material flow to be 2:1, and the washing times to be 1 time. The oxygen-containing compound adsorption tower adopts a fixed bed reactor as contact equipment, and the adsorbent is selected from activated carbon and porous alumina (weight ratio is 1: 5). The oxygenate and its content in the aromatic hydrocarbon stream after stream i passed sequentially through the caustic wash tower, water wash tower and adsorption tower are shown in table 1.
[ example 8 ]
Using stream I from example 1, the temperature of the caustic wash tower was controlled at 20 ℃, the concentration of the caustic was controlled at 10%, the volume ratio of the caustic to the aromatic stream was 1:1, and the number of caustic washes was 1. Controlling the temperature of the water washing tower to be 20 ℃, the volume ratio of water to the aromatic hydrocarbon material flow to be 2:1, and the washing times to be 1 time. The oxygen-containing compound adsorption tower adopts a fixed bed reactor as contact equipment, and the adsorbent is selected from activated carbon and porous alumina (the weight ratio is 5: 1). The oxygenate and its content in the aromatic hydrocarbon stream after stream i passed sequentially through the caustic wash tower, water wash tower and adsorption tower are shown in table 1.
Comparative example 1
Taking a material flow I rich in aromatic hydrocarbon, controlling the temperature of an alkaline washing tower to be 20 ℃, the concentration of alkaline liquor to be 10 percent, the volume ratio of the alkaline liquor to the aromatic hydrocarbon material flow to be 1:1, and carrying out alkaline washing for 1 time. The oxygen-containing compound adsorption tower adopts a fixed bed reactor as contact equipment, and porous alumina is selected as an adsorbent. The oxygenate and its content in the aromatic stream after passing the caustic wash and adsorption columns in sequence in stream i are shown in table 1.
Comparative example 2
Taking a material flow I rich in aromatic hydrocarbon, controlling the temperature of a washing tower to be 20 ℃, the volume ratio of water to the aromatic hydrocarbon material flow to be 2:1, and washing times to be 3 times. The oxygen-containing compound adsorption tower adopts a fixed bed reactor as contact equipment, and porous alumina is selected as an adsorbent. The oxygenate and its content in the aromatic stream after the stream i passed sequentially through the water wash column and the adsorption column are shown in table 1.
Comparative example 3
Taking a material flow I rich in aromatic hydrocarbon, controlling the temperature of an alkaline washing tower to be 20 ℃, the concentration of alkaline liquor to be 10 percent, the volume ratio of the alkaline liquor to the aromatic hydrocarbon material flow to be 1:1, and carrying out alkaline washing for 1 time. Controlling the temperature of the water washing tower to be 20 ℃, the volume ratio of water to the aromatic hydrocarbon material flow to be 2:1, and the washing times to be 3 times. The oxygenate and its content in the aromatic stream after passing the caustic wash and water wash column sequentially in stream i is shown in table 1.
Comparative example 4
Taking a material flow I rich in aromatic hydrocarbon, controlling the temperature of a washing tower to be 20 ℃, the volume ratio of water to the aromatic hydrocarbon material flow to be 2:1, and washing times to be 3 times. The temperature of the alkaline washing tower is controlled to be 20 ℃, the concentration of the alkaline liquor is 10 percent, the volume ratio of the alkaline liquor to the aromatic hydrocarbon material flow is 1:1, and the number of times of alkaline washing is 1. The oxygen-containing compound adsorption tower adopts a fixed bed reactor as contact equipment, and porous alumina is selected as an adsorbent. The oxygenate and its content in the aromatic hydrocarbon stream after passing stream i through the water wash tower, the caustic wash tower and the adsorption tower in sequence are shown in table 1.
TABLE 1
| Major species | Alcohols | Aldehydes | Ketones | Acids (acids) | Alkyl benzene ethanol | Alkyl phenol | Total amount of |
| Logistics I content (ppm) | 160 | 230 | 1050 | 200 | 100 | 1000 | 2740 |
| Example 1 after treatment | / | / | / | / | / | / | <1 |
| Example 2 after treatment | / | / | / | / | / | / | <1 |
| Example 3 after treatment | / | / | / | / | / | / | <1 |
| Example 4 after treatment | / | / | / | / | / | / | <1 |
| Example 5 after treatment | / | / | 1 | / | / | 1.5 | 2.5 |
| Example 6 after treatment | / | / | 1 | / | 1 | 2 | 4.0 |
| Example 7 after treatment | / | / | / | / | / | / | <1 |
| Example 8 after treatment | / | / | / | / | / | / | <1 |
| Comparative example 1 after treatment | 10 | 12 | 50 | / | 8 | 20 | 100 |
| Comparative example 2 after treatment | 5 | 6 | 20 | 1 | 3 | 23 | 58 |
| Comparative example 3 after treatment | 10 | 15 | 40 | / | 3 | 10 | 79 |
| Comparative example 4 after treatment | / | / | / | 3 | 1 | 2 | 5 |
By comparison, any one of the steps of alkali washing, water washing and adsorption is omitted, so that the content of the oxygen-containing compounds in the treated stream rich in the aromatic hydrocarbon is too high. The order of the water washing tower and the alkali washing tower is changed, the influence is small, and the content of the oxygen-containing compound is slightly increased.
[ examples 9 to 14 ]
The aromatic hydrocarbon-rich liquid streams II, III, IV, V, VI and VII containing organic oxygen-containing compounds are respectively taken, wherein the organic oxygen-containing compounds and the content thereof are shown in Table 2, the processing steps are the same as in example 1, and the oxygen-containing compounds and the content thereof in the aromatic hydrocarbon-rich streams after the processing are shown in Table 2.
Comparative example 5
And taking an organic material flow IV, controlling the temperature of the water washing tower to be 20 ℃, controlling the volume ratio of water to the aromatic hydrocarbon material flow to be 2:1, and washing for 3 times. The oxygen-containing compound adsorption tower adopts a fixed bed reactor as contact equipment, and porous alumina is selected as an adsorbent. The oxygenate and its content in the aromatic stream after passing the water wash column and the adsorption column in sequence are shown in table 2.
TABLE 2
| Major species | Alcohols | Aldehydes | Ketones | Acids (acids) | Phenylethanolic acid | Alkyl phenol | Total amount of |
| Logistics II content (ppm) | 20 | 5 | 60 | 15 | 10 | 50 | 160 |
| Level of stream III (ppm) | 500 | 1000 | 4000 | 800 | 200 | 3000 | 9500 |
| Logistics IV content (ppm) | 25 | 10 | 100 | 30 | 20 | 115 | 300 |
| Material flow V content (ppm) | 520 | 600 | 2200 | 900 | 130 | 3100 | 7430 |
| VI content of material flow (ppm) | 200 | 260 | 310 | 100 | 40 | 350 | 1260 |
| Level of stream VII (ppm) | 380 | 290 | 1400 | 270 | 150 | 800 | 3290 |
| Example 9 after treatment | / | / | / | / | / | / | <1 |
| Example 10 after treatment | / | / | 2 | / | / | 3 | 5 |
| Example 11 after treatment | / | / | / | / | / | / | <1 |
| Example 12 after treatment | / | / | 1 | / | / | 1.5 | 2.5 |
| Example 13 after treatment | / | / | / | / | / | / | <1 |
| Example 14 after treatment | / | / | / | / | / | / | <1 |
| Comparative example 5 after treatment | / | / | / | 1 | / | / | 1 |
Claims (3)
1. A method for removing oxygen-containing compounds in mixed aromatics of methanol aromatization products is characterized by comprising the following steps:
(1) after the aromatic hydrocarbon-rich material flow flowing out of the methanol aromatization reactor is separated by a three-phase separator, the gas-phase hydrocarbon returns to the methanol aromatization reactor, part of the oxygenate is dissolved in the water phase and discharged, and the oil phase rich in aromatic hydrocarbon enters the step (2); wherein, in the aromatic hydrocarbon-rich material flow which is separated by three phases and comes out from the methanol aromatization reactor, the total weight content of oxygen-containing compounds is 1000-4000 ppm in terms of the weight percentage of the aromatic hydrocarbon-rich material flow;
(2) the oil phase which flows out from the three-phase separator and is rich in aromatic hydrocarbon enters an alkaline washing tower, and organic acid in the oil phase is removed after alkaline washing; wherein the temperature of the alkaline washing tower is 1-80 ℃, the concentration of the alkaline liquor is 5-15%, the volume ratio of the alkaline liquor to the aromatic hydrocarbon material flow is 0.1: 1-1: 1, and the number of times of alkaline washing is 1-3;
(3) the material flow flowing out of the alkaline washing tower enters a water washing tower, and oxygen-containing compounds which are easy to dissolve in water are removed through water washing; wherein the temperature of the water washing tower is 1-80 ℃, the volume ratio of water to the aromatic hydrocarbon material flow is 0.1: 1-10: 1, and the washing times are 1-5;
(4) the material flow flowing out of the water washing tower enters an aromatic hydrocarbon extraction tower, and aromatic hydrocarbon and non-aromatic hydrocarbon are separated through aromatic hydrocarbon extraction and steam stripping; wherein the extractant adopted by the aromatic extraction tower is selected from at least one of diethylene glycol ether, triethylene glycol ether, tetraethylene glycol ether, sulfolane, dimethyl sulfoxide, N-methylpyrrolidone and formylmorpholine, and the volume ratio of the extractant to the aromatic stream is 1: 1-20: 1;
(5) the aromatic hydrocarbon obtained by the aromatic hydrocarbon extraction tower enters an oxygen-containing compound adsorption tower, and the oxygen-containing compound in the aromatic hydrocarbon is removed through adsorption to obtain the mixed aromatic hydrocarbon with low content of the oxygen-containing compound, wherein the oxygen-containing compound adsorption tower adopts a fixed bed or a simulated moving bed as contact equipment, and an adsorbent is selected from at least one of activated carbon, porous alumina and a zeolite molecular sieve.
2. The method of claim 1 for removing oxygenates from mixed aromatics of methanol aromatization products, characterized in that the oxygenates in the aromatics-rich stream exiting the methanol aromatization reactor are selected from the group consisting of methanol, formic acid, ethanol, acetic acid, acetaldehyde, propionaldehyde, acetone, butyraldehyde, butanone, pentanone, hexanone, alkylphenylethanol, and alkylphenols.
3. The method for removing the oxygen-containing compounds in the mixed aromatic hydrocarbons of the methanol aromatization product according to claim 1, characterized in that the oxygen-containing compound adsorption tower adopts a fixed bed or a simulated moving bed as a contact device, and the adsorbent is selected from porous alumina.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610918528.6A CN107973687B (en) | 2016-10-21 | 2016-10-21 | Method for removing oxygen-containing compounds in mixed aromatics of methanol aromatization product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610918528.6A CN107973687B (en) | 2016-10-21 | 2016-10-21 | Method for removing oxygen-containing compounds in mixed aromatics of methanol aromatization product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107973687A CN107973687A (en) | 2018-05-01 |
| CN107973687B true CN107973687B (en) | 2021-07-30 |
Family
ID=62004314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610918528.6A Active CN107973687B (en) | 2016-10-21 | 2016-10-21 | Method for removing oxygen-containing compounds in mixed aromatics of methanol aromatization product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107973687B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106608794B (en) * | 2015-10-22 | 2019-10-11 | 中国石油化工股份有限公司 | The method of oxygen-containing organic compound impurity in Arene removal logistics |
| CN112126461A (en) * | 2019-06-24 | 2020-12-25 | 内蒙古伊泰煤基新材料研究院有限公司 | Method for removing oxide in Fischer-Tropsch oil |
| CN115491229B (en) * | 2022-09-23 | 2024-03-22 | 上海兖矿能源科技研发有限公司 | Separation method of high-temperature Fischer-Tropsch synthesis light oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008014428A2 (en) * | 2006-07-28 | 2008-01-31 | Chevron Phillips Chemical Company Lp | Method of enhancing an aromatization catalyst |
| CN101823929A (en) * | 2010-04-14 | 2010-09-08 | 清华大学 | System and process for preparing aromatic hydrocarbon by converting methanol or dimethyl ether |
| CN104109555A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Alkylation product treatment method |
| CN105622306A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon with oxygen-containing compound as raw material |
-
2016
- 2016-10-21 CN CN201610918528.6A patent/CN107973687B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008014428A2 (en) * | 2006-07-28 | 2008-01-31 | Chevron Phillips Chemical Company Lp | Method of enhancing an aromatization catalyst |
| CN101823929A (en) * | 2010-04-14 | 2010-09-08 | 清华大学 | System and process for preparing aromatic hydrocarbon by converting methanol or dimethyl ether |
| CN104109555A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Alkylation product treatment method |
| CN105622306A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon with oxygen-containing compound as raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107973687A (en) | 2018-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107074676B (en) | Method for producing butadiene from ethanol in a low-water and low-energy reaction step | |
| CN1263831C (en) | Method for producing C2 and C3 olefins of hydrocarbons | |
| US10214461B2 (en) | Process and plant for producing olefins from oxygenates | |
| CN103964997B (en) | The treatment process of butylene oxidation-dehydrogenation product | |
| CN105152840A (en) | Process for refining C-4 hydrocarbon fluid | |
| CN107973687B (en) | Method for removing oxygen-containing compounds in mixed aromatics of methanol aromatization product | |
| CN107778122B (en) | Method for preparing aromatic hydrocarbon from methanol | |
| CN111646885A (en) | Method for preparing aldehyde based on hydroformylation of Fischer-Tropsch low-carbon hydrocarbon | |
| CN101337857A (en) | Integrated processing of methanol to olefins | |
| KR20060024765A (en) | Production of linear alkyl benzene | |
| RU2615160C2 (en) | Method of producing olefins and aromatic hydrocarbons | |
| CN107973677B (en) | Device and method for preparing mixed aromatic hydrocarbon with low content of oxygen-containing compound through methanol aromatization | |
| KR101512860B1 (en) | Process for production of propylene | |
| CN101333144B (en) | Method for removing dimethyl ether from olefin stream | |
| CN103664488A (en) | Arene methanol alkylation method for removing oxygen-containing compound impurities | |
| CN100575320C (en) | Extraction of oxygenates from hydrocarbon stream | |
| CN103664492A (en) | Alkylation method for methylbenzene and methyl alcohol | |
| CN103664478A (en) | Method for increasing yields of low-carbon olefins and aromatics by naphtha steam cracking | |
| US20150344381A1 (en) | Process and plant for producing olefins from oxygenates | |
| CN104672046B (en) | Method of increasing ethylene and propylene yields by freshening C-4 olefins in catalytic cracking or pyrolysis process after separation | |
| CN105218325B (en) | Preparation process of low-sulfur methyl tert-butyl ether | |
| CN103145520B (en) | Method for removing dimethyl ether from C4 material flow | |
| CN101121621B (en) | Methanol-water mixtures in olefin production via oxygenate conversion | |
| CN108779399B (en) | Process and catalyst for producing high octane components | |
| WO2014124845A1 (en) | Process and plant for producing olefins from oxygenates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |