A modified supported catalyst applied to the deacidification of methanol to hydrocarbon products

Abstract

This invention discloses a modified supported catalyst for deacidification of methanol-to-hydrocarbons (MTH) products. The catalyst preparation includes the following steps: (1) preparing a solution A containing alkali metal ions and anions; (2) adding Ce... 3+ With OH ‑ With CO3 2‑ (2) The soluble alkaline solution reacts with the precipitate, and the precipitate is dried and calcined to obtain support B; (3) Solution A and support B are mixed and loaded, and then dried and calcined to obtain the deacidification catalyst. The deacidification catalyst of the present invention can efficiently remove organic acid components from methanol-to-hydrogen product gas, the organic acid content in the product gas is less than 5 ppm, and the stability is good, without affecting the distribution of the main products of methanol-to-hydrogen. At the same time, the catalyst is simple to prepare, has low raw material cost, good mechanical strength, and is suitable for industrial application.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of deacidification catalysts for methanol to hydrocarbon products, and particularly relates to a modified supported catalyst for deacidification of methanol to hydrocarbon products. BACKGROUND

[0002] Ethylene, propylene and aromatic hydrocarbons are important chemical raw materials, and their downstream products cover various fields. Therefore, developing efficient production technology of low-carbon olefins and aromatic hydrocarbons helps to improve the economic strength of petrochemical enterprises, and is conducive to promoting the development of various fields covered by downstream products.

[0003] In the methanol to olefins (MTO), methanol to propylene (MTP) and methanol to aromatic hydrocarbons (MTA / MTX / MTPX) reactions, due to the use of acidic molecular sieve catalysts, small-molecule organic acids (mainly acetic acid and propionic acid) and a large amount of water vapor (~ 50wt.%) are often by-produced from oxygen-containing compounds such as methanol, the pH of the liquid phase product is between 3-4, and its corrosion effect on the equipment in the subsequent heat recovery and product separation unit in the industrial device cannot be ignored, and the pH of the condensed water is less than 5.0. The traditional treatment method is to add a certain concentration of NaOH solution through a metering pump for neutralization, and control the pH of the quenching water system to be greater than 7. However, the alkali injection system is not easy to control in the actual production process, and excessive injection of lye will cause damage to the tower wall and shorten the service life of the quenching tower. In addition, in order to avoid corrosion of organic acids at the dew point, the traditional MTO process reaction gas heat exchange reaches about 190-230℃, and then enters the quenching tower for water washing separation, and the heat recovery rate is reduced. Therefore, the existing treatment method of organic acid components in methanol to hydrocarbons still has many drawbacks.

[0004] Carboxylic acid ketonization reaction has been widely concerned in decarboxylation reaction, especially in the upgrading of biological oil. As a C-C coupling reaction, ketonization reaction can obtain a carbon chain-extended ketone compound by coupling 2 molecules of carboxylic acid through C-C bond, and remove 1 molecule of CO2 and 1 molecule of H2O, and the reaction temperature is usually at 300-500℃. This method not only removes small-molecule organic acids in the reaction product of methanol to hydrocarbons, but also increases the carbon chain and selectively converts organic acids into ketones. However, there is no report on the application of ketonization to the removal of organic acids in the reaction product of methanol to hydrocarbons. It can be assumed that once a suitable deacidification catalyst is obtained, and the organic acids in the reaction product of methanol to hydrocarbons can be selectively catalytically converted, the problem of corrosion of organic acids in the production of methanol to hydrocarbons can be fundamentally solved, and therefore a high-efficiency deacidification catalyst for removing organic acids in the reaction product of methanol to hydrocarbons is needed to be developed. SUMMARY

[0005] The present application aims to provide a modified supported deacidification catalyst, using which the efficient and stable removal of organic acids in the product gas of methanol to hydrocarbon can be achieved under mild conditions.

[0006] The present application first provides a modified supported catalyst, the preparation method of which comprises the following steps:

[0007] (1) preparing solution A containing alkali metal ions and anions;

[0008] (2) preparing carrier B: reacting metal ions with a soluble alkali solution containing OH - and / or CO3 2- , precipitating, drying and calcining to obtain a metal oxide carrier B;

[0009] (3) loading solution A and carrier B to prepare a deacidification catalyst.

[0010] Preferably, the anions in solution A are selected from one or more of OH - , CO3 2- , H2PO4 - .

[0011] Preferably, in the soluble alkali solution, the molar ratio of OH - to CO3 2- is (1-3):(3-1), and typically but not limitedly, for example, it can be 1:3, 1:1 or 3:1, preferably 1:1.

[0012] Preferably, the metal ions in step (2) are Ce 3+ , and the metal oxide carrier B is CeO2.

[0013] Further, the soluble alkali is selected from one or more of NaOH, KOH, Na2CO3 and K2CO3.

[0014] Further, the mass percentage of carrier B in the prepared catalyst in step (3) is 90%-96%, preferably 90%, in terms of mass content.

[0015] The present application also provides the use of the deacidification catalyst in the deacidification of methanol to hydrocarbon products, wherein the methanol to hydrocarbon products are methanol to propylene products, methanol to aromatic hydrocarbon products and / or mixed xylene and methanol to aromatic hydrocarbon products, the deacidification reaction temperature is 400-470℃, and the deacidification reaction mass space velocity is 1-3h -1 .

[0016] Compared with the prior art, the present application has the beneficial effects including:

[0017] 1) The deacidification catalyst provided by the present application has high reaction activity, improves the deacidification rate without destroying the main product, and is conducive to solving the corrosion problem of organic acids in the methanol-to-hydrocarbon product gas.

[0018] 2) The deacidification catalyst has high stability and low loss of active components.

[0019] 3) The catalyst and its active component preparation method are simple, have low raw material cost, and have good mechanical strength, and are suitable for industrial application. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 A methanol-to-propylene product gas deacidification evaluation device.

[0021] In the figure, 1 is a high-pressure feed pump, 2 is a mass flow meter, 3 is a pressure gauge, 4 is a reaction furnace, 5 is a stop valve, 6 is a check valve, 7 is a vaporization chamber, 8 is a methanol conversion reaction tube, and 9 is a deacidification reaction tube. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0023] The preparation method of the modified supported deacidification catalyst active component provided by the present application comprises the following steps:

[0024] (1) Prepare solution A, which contains alkali metal ions and anions selected from one or more of OH - , CO3 2- , and H2PO4 - ;

[0025] (2) Prepare carrier B: react Ce 3+ with a soluble alkali solution containing OH - and / or CO3 2- , precipitate, dry, and calcine to obtain the carrier CeO2;

[0026] (3) Load solution A and carrier B, dry, and calcine to obtain the deacidification catalyst active component.

[0027] In the soluble alkali solution for preparing the carrier CeO2, the molar ratio of OH - to CO3 2- is preferably 1:1.

[0028] Further, the soluble base in the prepared carrier CeO2 is selected from one or more of NaOH, KOH, Na2CO3 and K2CO3.

[0029] The prepared modified supported deacidification catalyst has a content of 90% by weight of the catalyst carrier.

[0030] The deacidification catalyst can efficiently remove organic acid components in the methanol-to-hydrocarbon product gas, and the content of organic acid in the product gas is less than 5 ppm, and the stability is good, and does not affect the main product distribution of the methanol-to-hydrocarbon. Taking the deacidification of the methanol-to-hydrocarbon product as an example, the main small-molecule organic acid component in the methanol-to-hydrocarbon product gas is acetic acid, which undergoes ketonization deacidification reaction on the deacidification catalyst prepared in the application, mainly following the following reaction path:

[0031] 2CH3COOH→CH3COCH3+H2O+CO2

[0032] In the above manner, the carboxyl group of acetic acid is removed to generate CO2, thereby reducing the acid value. Since the deacidification reaction of the catalyst mainly occurs on the surface of the catalyst, and the introduction of the modified element makes the crystal structure of the catalyst more stable, the structure of the catalyst can maintain good stability before and after the reaction.

[0033] In order to reflect the deacidification performance difference between different modified catalysts, the best catalyst is selected in the decarboxylation ketonization reaction (non-methanol conversion system) under low temperature reaction conditions (330℃). The preferred catalyst is used in the methanol-to-propylene system, the methanol-to-aromatic hydrocarbon system and the mixed xylene and methanol-to-aromatic hydrocarbon system, and the decarboxylation ketonization reaction is carried out at a deacidification reaction temperature of 400℃ or higher. The specific implementation is as follows:

[0034] Example 1

[0035] (1) Preparation of deacidification catalyst carrier 1: 43.4g of Ce(NO3)3·6H2O solid was dissolved in a certain amount of deionized water, and the metal ion concentration was 0.1mol / L. 5.6g of KOH was dissolved in a certain amount of deionized water to form a soluble base solution, and the K + The concentration was 1mol / L, and the soluble base solution was slowly added to the Ce precursor solution, and the pH of the mixed solution was controlled at about 9, and then aged for 4h. After the reaction, the precipitate was washed with water, filtered, dried and calcined to obtain the deacidification catalyst carrier 1.

[0036] (2) Acetic acid ketonization evaluation experiment of deacidification catalyst carrier 1: the above deacidification catalyst carrier 1 was loaded into a laboratory fixed bed reactor, and the feed was acetic acid. The temperature of the reactor bed was set to 330℃, the reaction pressure was atmospheric pressure, the mass space velocity was 6.1h -1, stable operation for 1 h, the conversion of acetic acid is 35.2%.

[0037] Example 2

[0038] (1) Preparation of deacidification catalyst support 2: 43.4 g of Ce(N03)3-6H20 solid was dissolved in a certain amount of deionized water, and the metal ion concentration was 0.1 mol / L. 4.2 g of KOH and 3.5 g of K2C03 were dissolved in a certain amount of deionized water to form a soluble alkali solution, and the K + The concentration was 1 mol / L, and the soluble alkali solution was slowly added to the Ce precursor solution, and the pH of the mixed solution was controlled at ~ 9, and then stirred and aged for 4 h. After the reaction, the precipitate was washed with water, filtered, dried and calcined to obtain the deacidification catalyst support 2.

[0039] (2) Evaluation experiment of acetic acid ketonization of deacidification catalyst support 2: the above deacidification catalyst support 2 was loaded into a laboratory fixed bed reactor, and the feed was acetic acid. The reactor bed temperature was set to 330°C, the reaction pressure was atmospheric pressure, and the mass space velocity was 6.1h -1 After stable operation for 1 h, the conversion of acetic acid was 48.9%.

[0040] Example 3

[0041] (1) Preparation of deacidification catalyst support 3: 43.4 g of Ce(N03)3-6H20 solid was dissolved in a certain amount of deionized water, and the metal ion concentration was 0.1 mol / L. 4.2 g of KOH and 3.5 g of K2C03 were dissolved in a certain amount of deionized water to form a soluble alkali solution, and the K + The concentration was 1 mol / L, and the soluble alkali solution was slowly added to the Ce precursor solution, and the pH of the mixed solution was controlled at ~ 9, and then stirred and aged for 4 h. After the reaction, the precipitate was washed with water, filtered, dried and calcined to obtain the deacidification catalyst support 2.

[0042] (2) Evaluation experiment of acetic acid ketonization of deacidification catalyst support 3: the above deacidification catalyst support 3 was loaded into a laboratory fixed bed reactor, and the feed was acetic acid. The reactor bed temperature was set to 330°C, the reaction pressure was atmospheric pressure, and the mass space velocity was 6.1h -1 After stable operation for 1 h, the conversion of acetic acid was 62.6%.

[0043] Example 4

[0044] (1) Preparation of deacidification catalyst support 4: 43.4 g of Ce(N03)3-6H20 solid was dissolved in a certain amount of deionized water, and the metal ion concentration was 0.1 mol / L. 1.4 g of KOH and 10.4 g of K2C03 were dissolved in a certain amount of deionized water to form a soluble alkali solution, and the K + concentration was 1 mol / L, and the soluble alkali solution was slowly added to the Ce precursor solution, and the pH of the mixed solution was controlled at about 9, and then stirred and aged for 4 h. After the reaction, the precipitate was washed with water, filtered, dried and calcined to obtain the deacidification catalyst support 4.

[0045] (2) Evaluation experiment of acetic acid ketonization of deacidification catalyst support 4: the above deacidification catalyst support 4 was loaded into a laboratory fixed bed reactor, and the feed was acetic acid. The reactor bed temperature was set to 330°C, the reaction pressure was atmospheric pressure, and the mass space velocity was 6.1h -1 After stable operation for 1 h, the acetic acid conversion rate was calculated to be 50.4%.

[0046] Example 5

[0047] (1) Preparation of deacidification catalyst support 5: 43.4 g of Ce(N03)3-6H20 solid was dissolved in a certain amount of deionized water, and the metal ion concentration was 0.1 mol / L. 1.4 g of KOH and 10.4 g of K2C03 were dissolved in a certain amount of deionized water to form a soluble alkali solution, and the K + concentration was 1 mol / L, and the soluble alkali solution was slowly added to the Ce precursor solution, and the pH of the mixed solution was controlled at about 9, and then stirred and aged for 4 h. After the reaction, the precipitate was washed with water, filtered, dried and calcined to obtain the deacidification catalyst support 4.

[0048] (2) Evaluation experiment of acetic acid ketonization of deacidification catalyst support 5: the above deacidification catalyst support 5 was loaded into a laboratory fixed bed reactor, and the feed was acetic acid. The reactor bed temperature was set to 330°C, the reaction pressure was atmospheric pressure, and the mass space velocity was 6.1h -1 After stable operation for 1 h, the acetic acid conversion rate was calculated to be 42.9%.

[0049] Example 6

[0050] (1) Preparation of deacidification catalyst 1: 1.43 g of KOH solid was dissolved in a certain amount of deionized water, and the K + concentration was 2.5 mol / L, and was added to a beaker containing 10 g of deacidification catalyst support 3 for impregnation for 24 h. After impregnation, the precipitate was washed with water, filtered, dried and calcined to obtain the deacidification catalyst 1.

[0051] (2) Deacidification catalyst 1 acetic acid ketonization evaluation experiment: the above deacidification catalyst 1 is loaded into a laboratory fixed bed reactor, and the feed is acetic acid. The reactor bed temperature is set to 330℃, the reaction pressure is atmospheric pressure, and the mass space velocity is 6.1h -1 After stable operation for 1h, the acetic acid conversion rate is calculated to be 70.1%.

[0052] Example 7

[0053] (1) Preparation of deacidification catalyst 2: 1.7g of K2CO3 solid is dissolved in a certain amount of deionized water, and the K + concentration is 2.5mol / L, and is added to a beaker containing 10g of deacidification catalyst carrier 3 for impregnation for 24h. After impregnation, the precipitate is washed with water, filtered, dried and calcined to obtain the deacidification catalyst 2.

[0054] (2) Deacidification catalyst 2 acetic acid ketonization evaluation experiment: the above deacidification catalyst 2 is loaded into a laboratory fixed bed reactor, and the feed is acetic acid. The reactor bed temperature is set to 330℃, the reaction pressure is atmospheric pressure, and the mass space velocity is 6.1h -1 After stable operation for 1h, the acetic acid conversion rate is calculated to be 56.8%.

[0055] Example 8

[0056] (1) Preparation of deacidification catalyst 3: 3.5g of KH2PO4 solid is dissolved in a certain amount of deionized water, and the K

[0057] (2) Deacidification catalyst 3 acetic acid ketonization evaluation experiment: the above deacidification catalyst 3 is loaded into a laboratory fixed bed reactor, and the feed is acetic acid. The reactor bed temperature is set to 330℃, the reaction pressure is atmospheric pressure, and the mass space velocity is 6.1h -1 After stable operation for 1h, the acetic acid conversion rate is calculated to be 40.1%.

[0058] Example 9

[0059] (1) Preparation of deacidification catalyst carrier 3: 43.4g of Ce(NO3)3·6H2O solid is dissolved in a certain amount of deionized water, and the metal ion concentration is 0.1mol / L. Then 2.8g of KOH and 6.9g of K2CO3 are dissolved in a certain amount of deionized water to form a soluble alkali solution, and the K +The soluble base solution was slowly added to the Ce precursor solution at a concentration of 1 mol / L, with the pH of the mixed solution controlled at ~9, followed by stirring and aging for 4 h. After the reaction, the precipitate was washed with water, filtered, dried, and calcined to obtain the deacidified catalyst support 3.

[0060] (2) Evaluation experiment of the deacidified catalyst support 3 for acetic acid ketonization: The above deacidified catalyst support 3 was loaded into a laboratory fixed-bed reactor, and the feed was acetic acid. The reactor bed was set to a temperature of 400°C, the reaction pressure was atmospheric pressure, the mass space velocity was 6.1 h-1, and the reaction time was 1 h. After stable operation for 1 h, the acetic acid conversion rate was calculated to be 82.5%. -1

[0061] Example 10

[0062] (1) Preparation of the deacidified catalyst 1: 1.43 g of KOH solid was dissolved in a certain amount of deionized water, and the K + The concentration was 2.5 mol / L, and it was added to a beaker containing 10 g of the deacidified catalyst support 3 for impregnation for 24 h. After impregnation, the precipitate was washed with water, filtered, dried, and calcined to obtain the deacidified catalyst 1.

[0063] (2) Evaluation experiment of the deacidified catalyst 1 for acetic acid ketonization: The above deacidified catalyst 1 was loaded into a laboratory fixed-bed reactor, and the feed was acetic acid. The reactor bed was set to a temperature of 400°C, the reaction pressure was atmospheric pressure, the mass space velocity was 6.1 h-1, and the reaction time was 1 h. After stable operation for 1 h, the acetic acid conversion rate was calculated to be 95.1%. -1

[0064] Example 11

[0065] (1) Preparation of the deacidified catalyst 2: 1.7 g of K2CO3 solid was dissolved in a certain amount of deionized water, and the K + The concentration was 2.5 mol / L, and it was added to a beaker containing 10 g of the deacidified catalyst support 3 for impregnation for 24 h. After impregnation, the precipitate was washed with water, filtered, dried, and calcined to obtain the deacidified catalyst 2.

[0066] (2) Evaluation experiment of the deacidified catalyst 2 for acetic acid ketonization: The above deacidified catalyst 2 was loaded into a laboratory fixed-bed reactor, and the feed was acetic acid. The reactor bed was set to a temperature of 400°C, the reaction pressure was atmospheric pressure, the mass space velocity was 6.1 h-1, and the reaction time was 1 h. After stable operation for 1 h, the acetic acid conversion rate was calculated to be 91.7%. -1

[0067] Example 12

[0068] ​​​(1) Preparation of deacidification catalyst 3: 3.5 g of KH2PO4 solid was dissolved in a certain amount of deionized water to obtain a K concentration of 2.5 mol / L, and then impregnated in a beaker containing 10 g of deacidification catalyst carrier 3 for 24 h. After impregnation, the precipitate was washed with water, filtered, dried and calcined to obtain the deacidification catalyst 3.

[0069] (2) Evaluation experiment of acetic acid ketonization of deacidification catalyst 3: The above deacidification catalyst 3 was loaded into a laboratory fixed bed reactor, and the feed was acetic acid. The temperature of the reactor bed was set to 400℃, the reaction pressure was atmospheric pressure, the mass space velocity was 6.1h -1 After 1 h of stable operation, the acetic acid conversion rate was calculated to be 86.4%.

[0070] Example 13

[0071] Evaluation experiment of deacidification of methanol-to-propylene product gas: As shown in the table, the deacidification reaction of methanol-to-propylene product gas was carried out in a double-tube fixed bed reaction device composed of two stainless steel reaction tubes in series. A high-pressure feed pump 1 delivered methanol to a vaporization chamber 7 and mixed it with nitrogen stably controlled by a flow meter 2. The mixture was reacted in the series of reaction tube 8 and reaction tube 9. The methanol-to-propylene catalyst (MTP) and the deacidification catalyst were placed in the reaction tube 8 and the reaction tube 9, respectively. The MTP reactor was filled with a modified molecular sieve catalyst, the reaction mass space velocity was 1h -1 , the reaction temperature was 470℃, the pressure was 0.1 MPa, nitrogen was used as the protective gas, the volume flow rate was 40 ml / min, the deacidification reactor was filled with the deacidification catalyst 1, the reaction mass space velocity was 2.61h -1 , the reaction temperature was 470℃, the pressure was 0.1 MPa, and after the reaction was stable, the pH of the liquid product was analyzed by a pH meter to be 6.2, and the acetic acid content was analyzed by gas chromatography to be less than 5 ppm, and there was no obvious effect on the main product of the methanol-to-aromatics reaction compared with the product of Comparative Example 1.

[0072] Comparative Example 1

[0073] The deacidification reactor in Comparative Example 1 was removed. The MTP reactor was filled with a modified molecular sieve catalyst, the reaction mass space velocity was 1h -1 , the reaction temperature was 470℃, the pressure was 0.1 MPa, nitrogen was used as the protective gas, the volume flow rate was 40 ml / min, and after the reaction was stable, the pH of the liquid product was analyzed by a pH meter to be 3.7, and the acetic acid content was analyzed by gas chromatography to be 1016.3 ppm.

[0074] Example 14

[0075] Evaluation experiment of deacidification of methanol-to-aromatics product gas: As shown in the table, the deacidification reaction of methanol-to-aromatics product gas was carried out in a double-tube fixed bed reaction device composed of two stainless steel reaction tubes in series. A high-pressure feed pump 1 delivered methanol to a vaporization chamber 7 and mixed it with nitrogen stably controlled by a flow meter 2. The mixture was reacted in the series of reaction tube 8 and reaction tube 9. The methanol-to-aromatics catalyst (MTO) and the deacidification catalyst were placed in the reaction tube 8 and the reaction tube 9, respectively. The MTO reactor was filled with a modified molecular sieve catalyst, the reaction mass space velocity was 1h -1 , the reaction temperature was 470℃, the pressure was 0.1 MPa, nitrogen was used as the protective gas, the volume flow rate was 40 ml / min, the deacidification reactor was filled with the deacidification catalyst 1, the reaction mass space velocity was 2.61h + , the reaction temperature was 470℃, the pressure was 0.1 MPa, and after the reaction was stable, the pH of the liquid product was analyzed by a pH meter to be 6.2, and the acetic acid content was analyzed by gas chromatography to be less than 5 ppm, and there was no obvious effect on the main product of the methanol-to-aromatics reaction compared with the product of Comparative Example 1.Figure 1 As shown, the methanol-to-aromatics product gas deacidification reaction is carried out in a double-tube fixed-bed reactor consisting of two stainless steel reaction tubes connected in series. A high-pressure feed pump 1 delivers methanol to the vaporization chamber 7, where it is mixed with nitrogen gas, which is stably controlled by a flow meter 2. The mixture then reacts in the series reaction tubes 8 and 9. The methanol-to-aromatics catalyst (MTA) and the deacidification catalyst are placed in reaction tubes 8 and 9, respectively. The catalyst packed in the MTA reactor is a modified molecular sieve catalyst, and the mass hourly space velocity (HHSV) is 1 h⁻¹. -1 The reaction temperature was 400℃, the pressure was 0.5MPa, nitrogen was used as the protective gas, the volumetric flow rate was 40ml / min, the catalyst packed in the deacidification reactor was deacidification catalyst 1, and the mass hourly space velocity (HHSV) was 1.90h. -1 The reaction temperature was 470℃ and the pressure was 0.5MPa. After the reaction stabilized, the pH of the liquid product was 6.0 as determined by pH meter analysis and the acetic acid content was less than 5ppm as determined by gas chromatography analysis. Furthermore, the main product of the methanol-to-aromatics reaction was not significantly affected by the product of Comparative Example 2.

[0076] Comparative Example 2

[0077] Remove Figure 1 The deacidification reactor in the middle. The catalyst packed in the MTA reactor is a modified molecular sieve catalyst, and the mass space velocity of the reaction is 1 h⁻¹. -1 The reaction temperature was 400℃, the pressure was 0.5MPa, nitrogen was used as a protective gas, and the volumetric flow rate was 40ml / min. After the reaction stabilized, the pH of the liquid product was 4.2 as determined by a gas pH meter, and the acetic acid content was 520.2ppm as determined by gas chromatography.

[0078] Example 15

[0079] Evaluation experiment on deacidification of products from mixed xylene and methanol to produce aromatics: such as Figure 1 As shown, the deacidification reaction of mixed xylene with methanol-to-aromatics product gas is carried out in a double-tube fixed-bed reactor consisting of two stainless steel reaction tubes connected in series. High-pressure feed pump 1 delivers methanol and mixed xylene to vaporization chamber 7, where they are mixed with nitrogen gas, which is stably controlled by flow meter 2. The mixture reacts in reaction tubes 8 and 9 connected in series. The mixed xylene-to-aromatics catalyst (XMTA) and the deacidification catalyst are placed in reaction tubes 8 and 9, respectively. The catalyst packed in the XMTA reactor is a modified molecular sieve catalyst, and the mass hourly space velocity (HHSV) is 1 h⁻¹. -1 The reaction temperature was 360℃, the pressure was 1.5MPa, nitrogen was used as the protective gas, the volumetric flow rate was 40ml / min, the catalyst packed in the deacidification reactor was deacidification catalyst 1, and the mass hourly space velocity (HHSV) was 1.47h. -1The reaction temperature was 400℃, the pressure was 1.5 MPa, and after the reaction was stable, the pH of the liquid phase product was 6.2 by pH meter analysis, the acetic acid content was less than 5 ppm by gas chromatography analysis, and there was no obvious influence on the main product of the methanol to arene reaction compared with the product of Comparative Example 3.

[0080] Comparative Example 3

[0081] removed Figure 1 The deacidification reactor in the XMTA reactor was removed. The catalyst filled in the XMTA reactor was a modified molecular sieve catalyst, the reaction mass space velocity was 1 h-1 -1 , the reaction temperature was 360℃, the pressure was 1.5 MPa, nitrogen was used as a protective gas, the volume flow rate was 40 ml / min, after the reaction was stable, the pH of the liquid phase product was 3.8 by pH meter analysis, and the acetic acid content was 767.8 ppm by gas chromatography analysis.

[0082] In summary, compared with low temperature reaction, high temperature reaction (400℃) is more conducive to the ketonization reaction of acetic acid. With carrier 3 as the best carrier, KOH, K2CO3 and KH2PO4 three different K + supported modified catalysts exhibit higher acetic acid conversion in high temperature reaction, and at the same time, it is also shown that high temperature conditions are conducive to improving the catalytic performance of different K + supported catalysts. Among them, the KOH supported catalyst has the best performance. In the methanol to propylene system, the methanol to arene system and the mixed xylene and methanol to arene system, the KOH supported catalyst can remove acetic acid at a high rate without damaging the main product, and reduce the acetic acid content to less than 5 ppm.

[0083] The above-mentioned liquid pH detection method and equipment are as follows:

[0084] The pH meter (Lei magnet PHS-25 pH meter) was used for pH detection, the detection method was based on industry standard detection, which belonged to the prior art and was common knowledge for those skilled in the art, and was not the key point of the invention, and was not described here.

[0085] The above-mentioned product organic component content determination equipment is as follows:

[0086] The gas chromatograph (Agilent GC7820A) was used to determine the components in the product, the detection method was based on industry standard detection, which belonged to the prior art and was common knowledge for those skilled in the art, and was not the key point of the invention, and was not described here.

[0087] From the comparison of the examples and the comparative examples, it can be seen that the introduction of the deacidification catalyst can efficiently remove the organic acids in the hydrocarbon product gas prepared from methanol, and has no obvious influence on the main product of the hydrocarbon prepared from methanol. Therefore, the process of the present application fundamentally solves the corrosion problem of the organic acids in the hydrocarbon product gas prepared from methanol by preparing a high-efficiency and stable deacidification catalyst and selectively catalytically converting the organic acids in the reaction product of the hydrocarbon prepared from methanol.

[0088] The above-described examples only describe the preferred modes of the present application, and do not limit the scope of the present application. Without departing from the design spirit of the present application, various modifications and improvements of the technical solutions of the present application made by those skilled in the art shall fall within the protection scope determined by the claims of the present application.

Claims

1. Use of a modified supported catalyst in the deacidification of a hydrocarbon product from methanol, characterized in that, The preparation method of the modified supported catalyst comprises the following steps: (1) preparing a solution A containing alkali metal ions and anions selected from one or more of OH - , CO3 2- , H2PO4 - ; (2) Preparation of carrier B: reacting metal ion Ce 3+ with soluble alkali solution containing OH - and / or CO3 2- , precipitating, drying and calcining to obtain metal oxide carrier B, which is CeO2; (3) loading solution A on carrier B, and drying and calcining to obtain a deacidification catalyst, the mass percentage content of carrier B in the prepared catalyst is 90%-96%; The methanol-to-hydrocarbon product is a methanol-to-propylene product or a methanol-to-aromatic product; the deacidification reaction temperature is 400-470 ℃, the deacidification reaction mass space velocity is 1-3 h -1 .

2. Use of the modified supported catalyst according to claim 1 in the deacidification of hydrocarbons produced from methanol, characterized in that: The molar ratio of OH - to CO3 2- in the soluble alkali solution in step (2) is (1-3):(3-1).

3. Use of the modified supported catalyst according to claim 1 in the deacidification of hydrocarbons produced from methanol, characterized by: In step (2), the soluble base is selected from one or more of NaOH, KOH, Na2CO3 and K2CO3.

4. Use of the modified supported catalyst according to claim 1 in the deacidification of hydrocarbons produced from methanol, characterized by: The loading mode is an equal-volume impregnation method, a precipitation impregnation method or an excess impregnation method.

5. Use of the modified supported catalyst according to claim 1 in the deacidification of hydrocarbons produced from methanol, characterized by: The calcination temperature is 400-500 ℃, and the calcination time is 4-6 h.

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