A reforming generated oil degumming agent, its preparation method and application

Abstract

This invention discloses a reforming oil degumming agent, its preparation method, and its application. The reforming oil degumming agent of this invention, by total weight, comprises the following components: (a) 40%–94.5% molecular sieve; (b) 5%–55% binder; (c) 0.5%–8% of one or more elements selected from Group IA and Group IIA; the acid content on the outer surface of the degumming agent accounts for 3%–20% of the total acid content; and the molar ratio of the total alkali content to the total acid content of the degumming agent is 0.1–10. The reforming oil degumming agent provided by this invention can effectively remove gums, ensuring long-term operation of the bottom heater of the xylene tower and protecting the downstream catalyst from gum contamination that could shorten its lifespan.

Description

Technical Field

[0001] This invention relates to the field of degumming reformed oil, and more specifically, to a degumming agent for reformed oil in the production of aromatics, its preparation method, and its application. Background Technology

[0002] p-Xylene plays a crucial role among basic organic feedstocks. Its production process requires naphtha reforming or disproportionation followed by alkyl transfer reactions to generate a mixture of C8 aromatics. This mixture is then subjected to adsorption separation to obtain PX products. The reformed product requires further processing before entering the downstream xylene tower. C8 aromatics are separated at the top of the tower, while the bottom product undergoes disproportionation and alkyl transfer to convert it back into C8 aromatics. Therefore, the xylene tower is vital in the entire p-xylene production process, and its bottom heater is the main energy driver for the distillation and separation of the entire aromatics complex. Protecting the normal and effective operation of the xylene tower bottom heater is a critical technical aspect.

[0003] Reformed C8 aromatics and above contain olefins, impurities, and gums, which affect downstream adsorbents, equipment, and pipelines, requiring removal. Currently, aromatics from other reactions, such as catalytic cracking, generally contain olefins and must also be removed before becoming products. Industrially, hydrogenation and liquid-phase alkylation are used to remove olefins from reformed aromatics. For gum impurities, conventional adsorption with clay is used. However, as the lifespan of molecular sieve catalysts increases, the adsorption capacity of clay for gums becomes limited. Furthermore, the adsorbed gums on the catalyst's active sites will be adsorbed, significantly shortening the catalyst's deolefin removal efficiency and greatly reducing its lifespan.

[0004] CN107760362A uses activated carbon and element-modified molecular sieves with hydroxide as alkaline agents to remove colloids. Similarly, CN107760358A uses kaolin and activated carbon to remove colloids. However, the effectiveness of the prepared colloid removers is limited by the performance of the removers and needs further improvement.

[0005] CN105080619A describes the use of molecular sieve protectants containing Ca, Zn, Mg, Fe, B, Na, and K elements to treat colloids. The molecular sieves used include one or more of mordenite, Y-zeolite, clinoptilolite, ZSM-5 molecular sieve, MCM-22, MCM-56, and β-zeolite. However, its colloid removal capacity is limited, and its activity and stability are poor, failing to meet the requirements for long-term industrial operation. Summary of the Invention

[0006] To address the problem of difficult impurity removal, especially gum removal, in current reforming oil deolefins technology, which leads to scaling in subsequent distillation columns and pumps, this invention provides a reforming oil degumming agent, its preparation method, and its application. The degumming agent provided by this invention can selectively and effectively remove gum from xylene in reforming oil, significantly extending the catalyst's lifespan.

[0007] The first aspect of this invention provides a reforming oil degumming agent, comprising the following components by weight of the total degumming agent:

[0008] (a) 40%–94.5% molecular sieve;

[0009] (b) 5%–55% adhesive;

[0010] (c) 0.5% to 8% selected from one or more elements in Group IA and Group IIA;

[0011] The acid content on the outer surface of the degumming agent accounts for 3% to 20% of the total acid content; the molar ratio of the total alkali content to the total acid content of the degumming agent is 0.1 to 10.

[0012] Further, preferably, the acid content on the outer surface of the degumming agent accounts for 5% to 20% of the total acid content; more preferably, the acid content on the outer surface of the degumming agent accounts for 6% to 15% of the total acid content.

[0013] Further, preferably, the molar ratio of the total alkali content to the total acid content of the degumming agent is 0.3 to 3.0.

[0014] Further, the molecular sieve is selected from one or more of the following: mordenite, γ-zeolite, clinoptilolite, MCM-22 molecular sieve, MCM-56 molecular sieve, β-zeolite, and molecular sieves containing -ITV, -CLO, or -IFU structures; preferably, the molecular sieve is selected from one or more of the following: mordenite, USY, β-zeolite, MCM-22 molecular sieve, MCM-56 molecular sieve, ITQ-37, [Zn-Ga-PO]-CLO, or ITQ-54.

[0015] Furthermore, the molecular sieve may or may not contain the framework element M. If the molecular sieve contains the framework element M, M is selected from one or more of Al, Fe, Zn, V, Ni, Co, and Ga, preferably one or more of Zn, Ga, and Fe. The mass content of the framework element M, based on the mass of the molecular sieve, is 0.01% to 5%.

[0016] Furthermore, the Group IA element is selected from at least one of sodium, potassium, rubidium, and cesium, and the Group IIA element is selected from at least one of magnesium, calcium, strontium, and barium.

[0017] Furthermore, the carrier is selected from one or more of alumina, silicon dioxide, titanium dioxide, and zirconium oxide.

[0018] Furthermore, based on the total weight of the degumming agent, the content of the molecular sieve is 45% to 90%, the content of the binder is 8% to 55%, and the content of the Group IA metals and / or Group IIA metals, calculated as oxides, is 0.8% to 6%.

[0019] A second aspect of the present invention provides a method for preparing the above-mentioned reformed oil degumming agent, comprising the following steps:

[0020] (1) Molecular sieves were treated with steam under vacuum to obtain product I;

[0021] (2) Product I was separated by ammonium ion exchange and dried to obtain product II;

[0022] (3) Product II is mixed with Group IA metal compounds and / or Group IIA metal compounds and binder precursors, molded, and calcined to obtain the degumming agent.

[0023] Further, the molecular sieve is a molecular sieve with or without the framework element M. The molecular sieve is selected from one or more of the following: mordenite, γ-zeolite, clinoptilolite, MCM-22 molecular sieve, MCM-56 molecular sieve, β-zeolite, and molecular sieves containing -ITV, -CLO, or -IFU structures; preferably, the molecular sieve is selected from one or more of USY, β-zeolite, MCM-22 molecular sieve, ITQ-37, [Zn-Ga-PO]-CLO, or ITQ-54.

[0024] Furthermore, the Si / Al molar ratio of the molecular sieve is 2 to 90.

[0025] Furthermore, the molecular sieve contains a framework element M, which is selected from one or more of Al, Fe, Zn, V, Ni, Co, and Ga; preferably one or more of Zn, Ga, and Fe. The Si / M molar ratio in the molecular sieve is 2–150, preferably 50–120.

[0026] Furthermore, the molecular sieve can be prepared using conventional methods in the art.

[0027] Further, in step (1), the vacuum refers to an absolute pressure of 0.00001 to 0.098 MPa, and the partial pressure of the water vapor is not less than 0.001 MPa, preferably 0.001 to 0.097 MPa.

[0028] Further, in step (1), the steam treatment process is as follows: treatment under steam conditions of 120 to 380°C for 0.1 to 20 hours, preferably treatment under steam conditions of 120 to 260°C for 0.5 to 6 hours.

[0029] Furthermore, in step (1), after the steam treatment is completed, conventional steps such as washing and filtration are performed.

[0030] Furthermore, in step (2), the ammonium ion exchange is performed using conventional methods in the art. For example, the ammonium ion exchange is conducted at 35–99°C for 0.2–6.0 h, and the number of exchange cycles is 1–4. The ammonium salt used for the exchange is preferably ammonium nitrate, the concentration of the ammonium salt solution is 0.001–2.0 mol / L, and the liquid-to-solid mass ratio of product I to the ammonium salt solution is 1–10.

[0031] Further, in step (2), after the ion exchange is completed, the product undergoes conventional steps such as separation and washing, and is then dried at 50–220°C for 1–200 hours. The separation can be performed by centrifugation. The washing can be performed with deionized water until the pH value is 6–7.

[0032] Further, in step (3), the binder precursor is selected from one or more of alumina monohydrate, silica sol (solid content of 20% to 45%), and titanate. The amount of binder added, calculated as oxide, accounts for 4.99% to 55% of the total weight of the degumming agent, preferably 10% to 55%.

[0033] Further, in step (3), the Group IA metal compound and / or Group IIA metal compound are soluble compounds of the corresponding elements, wherein the Group IA element is selected from at least one of sodium, potassium, rubidium, and cesium, and the Group IIA element is selected from at least one of magnesium, calcium, strontium, and barium.

[0034] Further, in step (3), the amount of the Group IA metal and / or Group IIA metal added, calculated as oxides, accounts for 0.5% to 8% of the total weight of the degumming agent, preferably 0.8% to 6%.

[0035] Furthermore, in step (3), the molding method adopts a conventional method in the art. After mixing and molding, the degumming agent is obtained by drying and calcining. The drying temperature is 50-220℃ and the drying time is 1-200h; the calcining temperature is 450-750℃ and the calcining time is 0.5-20h.

[0036] A third aspect of the present invention provides a method for degumming reformed oil, comprising: reacting the reformed oil with the aforementioned degumming agent.

[0037] Furthermore, the olefin content of the reformed oil, calculated by the bromine index, is between 200 and 2000 mgBr / 100g, and the gum content after washing is between 1 and 50 mg / 100mL.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] 1. The reforming oil degumming agent provided by this invention can effectively remove gum by controlling the ratio of acid on the outer surface of the degumming agent to the total acid, as well as the molar ratio of total alkali to total acid. This ensures the long-term operation of the bottom heater of the xylene tower and protects the downstream catalyst from being contaminated by gum, thus preventing a shortened lifespan.

[0040] 2. The method employed in this invention first treats the molecular sieve with steam under vacuum and at a relatively low temperature to protect and improve the uniformity of pore expansion in the molecular sieve channels. Then, by combining some acidic centers with Group IA and Group IIA metal ions, basic sites are provided for the degumming agent, isolating the acidic centers and giving the degumming agent suitable acidity and alkalinity. This prevents pore blockage within the degumming agent particles due to accumulation, significantly improving the ability to remove colloids. The degumming agent prepared by this invention has a large degumming capacity, effectively removing colloids while also removing a small amount of olefins, effectively reducing the lifespan of subsequent refining agents. Detailed Implementation

[0041] The present invention will be further described below with reference to the embodiments, but the present invention is not limited to the embodiments.

[0042] In this invention, NH3-TPD is used to characterize the total acid content of molecular sieves. 100 mg of catalyst is first treated at 500 °C for 2 hours, then cooled to 100 °C to adsorb ammonia, and then the temperature is programmed to rise to 600 °C to adsorb ammonia with acid. The total acid content is then determined by titration.

[0043] The total alkali content of the molecular sieve was characterized by CO2-TPD. After low-temperature adsorption, high-temperature desorption, and alkali absorption, the total alkali content was determined by titration and calculated.

[0044] The ratio of acid content on the outer surface of the molecular sieve to total acid content was characterized using 2,6-di-tert-butylpyridine infrared spectroscopy (DTBP-FTIR) and pyridine infrared spectroscopy (Py-FTIR).

[0045] Example 1

[0046] Preparation of degumming agent:

[0047] Take 120g of BETA molecular sieve (silicon-aluminum atomic ratio 20, silicon-iron atomic ratio 120, sodium in the molecular sieve is 3% by mass as sodium oxide), treat it under water vapor conditions at 220℃ for 3 hours, the partial pressure of water vapor is 0.05MPa, and the absolute pressure is 0.09MPa; then wash and filter with water to obtain product I.

[0048] Product I was placed in an ammonium nitrate solution and exchanged 4 times at 80°C (the liquid-solid mass ratio of product I to ammonium nitrate was 3, and the exchange time was 3 hours). The solid was then separated and dried at 120°C for 20 hours to obtain product II.

[0049] Product II was mixed with alumina monohydrate (30% of the total weight of the degumming agent based on alumina) and magnesium nitrate (0.9% of the total weight of the degumming agent based on magnesium oxide), shaped, dried at 120°C for 4 hours, and calcined at 550°C for 4 hours to obtain the degumming agent.

[0050] The acid content on the outer surface of the obtained degumming agent accounted for 9.7% of the total acid content, with a total acid content of 0.23 mmol / g and a total alkali content of 0.18 mmol / g. The test results are shown in Table 1.

[0051] Degumming reaction of reformed oil:

[0052] Reformed oil with a bromine index of 1213 mgBr / 100g and a post-wash gum content of 5 mg / 100mL was used, and subjected to a heat treatment at 2.8 MPa for 5 hours. -1 At 190℃, 8.0g of degumming agent was introduced into a container. After degumming, the bromine index at the outlet reached 320mgBr / 100g, and the amount of gum was 1.5mg / 100mL. After 100 hours, the bromine index at the outlet reached 269mgBr / 100g, and the amount of gum was 1.6mg / 100mL.

[0053] Example 2

[0054] Preparation of degumming agent:

[0055] Take 120g of USY molecular sieve (silicon-aluminum ratio 6, sodium in the molecular sieve is 4.5% by mass as sodium oxide), treat it under water vapor conditions at 320℃ for 6 hours, the partial pressure of water vapor is 0.05MPa, and the absolute pressure is 0.06MPa; then wash and filter with water to obtain product I.

[0056] Product I was placed in an ammonium nitrate solution and exchanged twice at 90°C (the liquid-to-solid mass ratio of product I to ammonium nitrate was 4, and the time was 4 hours). The solid was then separated and dried at 180°C for 6 hours to obtain product II.

[0057] Product II was mixed with alumina monohydrate (20% of the total weight of the degumming agent based on alumina) and calcium nitrate (1.2% of the total weight of the degumming agent based on calcium oxide) and shaped into a mixture. The mixture was dried at 220°C for 2 hours and calcined at 500°C for 18 hours to obtain the degumming agent.

[0058] The test results of the acid content, total acid content, and total alkali content on the outer surface of the obtained degumming agent are shown in Table 1.

[0059] Degumming reaction of reformed oil:

[0060] Reformed oil with a bromine index of 1213 mgBr / 100g and a post-wash gum content of 5 mg / 100mL was used, and subjected to a heat treatment at 2.8 MPa for 6 hours. -1 At 180℃, 8.0g of degumming agent was introduced into a container. After degumming, the bromine index at the outlet reached 590mgBr / 100g, and the amount of gum was 0.2mg / 100mL. After 100 hours, the bromine index at the outlet reached 662mgBr / 100g, and the amount of gum was 0.5mg / 100mL.

[0061] Example 3

[0062] Preparation of degumming agent:

[0063] Take 120g of MCM-22 molecular sieve (silicon-aluminum molecular ratio 30, magnesium in the molecular sieve is 1.5% by mass, calculated as magnesium oxide), treat it under water vapor conditions at 120℃ for 10 hours, the partial pressure of water vapor is 0.02MPa, and the absolute pressure is 0.09MPa; then wash and filter with water to obtain product I.

[0064] Product I was placed in an ammonium nitrate solution and exchanged three times at 30°C (the liquid-to-solid mass ratio of product I to ammonium nitrate was 3, and the time was 4 hours). The solid was then separated and dried at 90°C for 18 hours to obtain product II.

[0065] Product II was mixed with sodium nitrate (0.5% of the total weight of the degumming agent based on sodium oxide) and alumina monohydrate (26% of the total weight of the degumming agent based on alumina), shaped, dried at 120°C for 4 hours, and calcined at 550°C for 4 hours to obtain the degumming agent.

[0066] The test results of the acid content, total acid content, and total alkali content on the outer surface of the obtained degumming agent are shown in Table 1.

[0067] Degumming reaction of reformed oil:

[0068] Reformed oil with a bromine index of 560 mgBr / 100g and a post-wash gum content of 2 mg / 100mL was used, and subjected to a temperature of 2.8 MPa and a humidity of 4 h⁻¹. 1 At 150℃, 8.0g of degumming agent was introduced into a container. After degumming, the bromine index at the outlet reached 320mgBr / 100g, and the amount of gum was 0.4mg / 100mL. After 100 hours, the bromine index at the outlet reached 412mgBr / 100g, and the amount of gum was 0.6mg / 100mL.

[0069] Example 4

[0070] Preparation of degumming agent:

[0071] Take 120g of MCM-56 molecular sieve (silicon-aluminum molecular ratio 27, silicon-zinc molecular ratio 100), treat it under water vapor conditions at 260℃ for 2 hours, the partial pressure of water vapor is 0.03MPa, and the absolute pressure is 0.04MPa; then wash and filter with water to obtain product I.

[0072] Product I was placed in an ammonium nitrate solution and exchanged three times at 40°C (the liquid-to-solid mass ratio of product I to ammonium nitrate was 3, and the time was 4 hours). The solid was then separated and dried at 180°C for 6 hours to obtain product II.

[0073] Product II was mixed with alumina monohydrate (25% of the total weight of the degumming agent based on alumina) and potassium chloride (0.9% of the total weight of the degumming agent based on potassium oxide) and shaped into a mixture. The mixture was dried at 90°C for 120 hours and calcined at 580°C for 2.5 hours to obtain the degumming agent.

[0074] The test results of the acid content, total acid content, and total alkali content on the outer surface of the obtained degumming agent are shown in Table 1.

[0075] Degumming reaction of reformed oil:

[0076] Reformed oil with a bromine index of 1680 mgBr / 100g and a post-wash gum content of 20 mg / 100mL was used, and subjected to a heat treatment at 1.8 MPa for 6 hours. -1 At 230℃, 8.0g of degumming agent was introduced into a container. After degumming, the bromine index at the outlet reached 630mgBr / 100g, and the amount of gum was 1.0mg / 100mL. After 100 hours, the bromine index at the outlet reached 653mgBr / 100g, and the amount of gum was 1.2mg / 100mL.

[0077] Example 5

[0078] Preparation of degumming agent:

[0079] 120g of mordenite molecular sieve (silicon-aluminum ratio 20, silicon-gallium ratio 50) was treated with steam at 160℃ for 18 hours. The partial pressure of the steam was 0.05MPa and the absolute pressure was 0.08MPa. Then, the product was washed and filtered to obtain product I.

[0080] Product I was placed in an ammonium nitrate solution and exchanged three times at 80°C (the liquid-to-solid mass ratio of product I to ammonium nitrate was 3, and the time was 4 hours). The solid was then separated and dried at 150°C for 4 hours to obtain product II.

[0081] Product II was mixed with alumina monohydrate (40% of the total weight of the degumming agent based on alumina), strontium chloride (3.0% of the total weight of the degumming agent based on strontium oxide), and silica sol (10% of the total weight of the degumming agent based on SiO2) and shaped. The mixture was dried at 150°C for 6 hours and calcined at 650°C for 2 hours to obtain the degumming agent.

[0082] The test results of the acid content, total acid content, and total alkali content on the outer surface of the obtained degumming agent are shown in Table 1.

[0083] Degumming reaction of reformed oil:

[0084] Reformed oil with a bromine index of 1680 mgBr / 100g and a post-wash gum content of 20 mg / 100mL was used, and subjected to a heat treatment at 1.8 MPa for 6 hours. -1 At 180℃, 8.0g of degumming agent was introduced into a container. After degumming, the bromine index at the outlet reached 570mgBr / 100g, and the amount of gum was 3.0mg / 100mL. After 100 hours, the bromine index at the outlet reached 780mgBr / 100g, and the amount of gum was 4.5mg / 100mL.

[0085] Example 6

[0086] Preparation of degumming agent:

[0087] 10g of ITQ-37 molecular sieve (silicon-germanium molecular ratio 70) was treated with steam at 360℃ for 3 hours. The partial pressure of the steam was 0.01MPa and the absolute pressure was 0.03MPa. Then, the product was washed and filtered to obtain product I.

[0088] Product I was placed in an ammonium chloride solution and exchanged twice at 80°C (the liquid-to-solid mass ratio of product I to ammonium chloride was 20, and the time was 4 hours). The solid was then separated and dried at 150°C for 3 hours to obtain product II.

[0089] Product II was mixed with alumina monohydrate (45% of the total weight of the degumming agent), magnesium chloride (1.0% of the total weight of the degumming agent based on magnesium oxide), and titanate (10% of the total weight of the degumming agent based on titanium oxide) and shaped. The mixture was dried at 120°C for 4 hours and calcined at 550°C for 4 hours to obtain the degumming agent.

[0090] The test results of the acid content, total acid content, and total alkali content on the outer surface of the obtained degumming agent are shown in Table 1.

[0091] Degumming reaction of reformed oil:

[0092] Reformed oil with a bromine index of 1680 mgBr / 100g and a post-wash gum content of 20 mg / 100mL was used, and subjected to a heat treatment at 1.8 MPa for 6 hours. -1 At 180℃, 2.0g of degumming agent was introduced into a container. After degumming, the bromine index at the outlet reached 1220mgBr / 100g, and the amount of gum was 10mg / 100mL. After 100 hours, the bromine index at the outlet reached 1310mgBr / 100g, and the amount of gum was 12mg / 100mL.

[0093] Example 7

[0094] Preparation of degumming agent:

[0095] Take 120g of BETA molecular sieve (silicon-aluminum atomic ratio 20, silicon-iron atomic ratio 120, sodium in the molecular sieve is 3% by mass as sodium oxide), treat it under water vapor conditions at 220℃ for 3 hours, the partial pressure of water vapor is 0.05MPa, and the absolute pressure is 0.09MPa; then wash and filter with water to obtain product I.

[0096] Product I was placed in an ammonium nitrate solution and exchanged 4 times at 80°C (the liquid-solid mass ratio of product I to ammonium nitrate was 3, and the exchange time was 3 hours). The solid was then separated and dried at 80°C for 180 hours to obtain product II.

[0097] Product II was mixed with magnesium nitrate (1.9% of the total weight of the degumming agent based on magnesium oxide) and alumina monohydrate (30% of the total weight of the degumming agent based on alumina), shaped, dried at 120°C for 4 hours, and calcined at 550°C for 4 hours to obtain the degumming agent.

[0098] The obtained degumming agent had an external surface acidity / total acidity of 6%, a total acidity of 0.12 mmol / g, and a total alkali content of 0.29 mmol / g. The test results are shown in Table 1.

[0099] Degumming reaction of reformed oil:

[0100] Reformed oil with a bromine index of 1213 mgBr / 100g and a post-wash gum content of 5 mg / 100mL was used, and subjected to a heat treatment at 2.8 MPa for 5 hours. -1 At 190℃, 8.0g of degumming agent was introduced into a container. After degumming, the bromine index at the outlet reached 470mgBr / 100g, and the amount of gum was 0.2mg / 100mL. After 100 hours, the bromine index at the outlet reached 685mgBr / 100g, and the amount of gum was 1.3mg / 100mL.

[0101] Example 8

[0102] Preparation of degumming agent:

[0103] Take 120g of USY molecular sieve (silicon-aluminum ratio 6, sodium in the molecular sieve is 2.1% by mass as sodium oxide), treat it under water vapor conditions at 320℃ for 6 hours, the partial pressure of water vapor is 0.05MPa, and the absolute pressure is 0.06MPa; then wash and filter with water to obtain product I.

[0104] Product I was placed in an ammonium nitrate solution and exchanged twice at 90°C (the liquid-to-solid mass ratio of product I to ammonium nitrate was 4, and the time was 4 hours). The solid was then separated and dried at 180°C for 6 hours to obtain product II.

[0105] Product II was mixed with alumina monohydrate (8% of the total weight of the degumming agent based on alumina) and barium nitrate (5.8% of the total weight of the degumming agent based on barium oxide) and shaped into a mixture. The mixture was dried at 120°C for 4 hours and calcined at 480°C for 18 hours to obtain the degumming agent.

[0106] The test results of the acid content, total acid content, and total alkali content on the outer surface of the obtained degumming agent are shown in Table 1.

[0107] Degumming reaction of reformed oil:

[0108] Reformed oil with a bromine index of 1960 mgBr / 100g and a post-wash gum content of 45 mg / 100mL was used, and subjected to a heat treatment at 2.8 MPa for 3 hours. -1 At 180℃, 8.0g of degumming agent was introduced into a container. After degumming, the bromine index at the outlet reached 667mgBr / 100g, and the amount of gum was 2.2mg / 100mL. After 100 hours, the bromine index at the outlet reached 857mgBr / 100g, and the amount of gum was 5.1mg / 100mL.

[0109] Comparative Example 1

[0110] Preparation of degumming agent:

[0111] Take 120g of BETA molecular sieve (silicon-aluminum atomic ratio 20, silicon-iron atomic ratio 120, sodium in the molecular sieve is 3% by mass as sodium oxide), treat it under water vapor conditions at 220℃ for 3 hours, the partial pressure of water vapor is 0.05MPa, and the absolute pressure is 0.09MPa; then wash and filter with water to obtain product I.

[0112] Product I was placed in an ammonium nitrate solution and exchanged 4 times at 80°C (the liquid-solid mass ratio of product I to ammonium nitrate was 3, and the exchange time was 3 hours). The solid was then separated and dried at 120°C for 8 hours to obtain product II.

[0113] Product II was mixed with alumina monohydrate (30% of the total weight of the degumming agent based on alumina) and molded. The mixture was dried at 120°C for 4 hours and calcined at 550°C for 4 hours to obtain the degumming agent.

[0114] The obtained degumming agent had an external surface acidity / total acidity of 9.7%, a total acidity of 0.41 mmol / g, and a total alkali content of 0.01 mmol / g. The test results are shown in Table 1.

[0115] Degumming reaction of reformed oil:

[0116] Reformed oil with a bromine index of 1213 mgBr / 100g and a post-wash gum content of 5 mg / 100mL was used, and subjected to a heat treatment at 2.8 MPa for 5 hours. -1At 190℃, 8.0g of degumming agent was introduced into a container. After degumming, the bromine index at the outlet reached 312mgBr / 100g, and the amount of gum was 4.5mg / 100mL. After 100 hours, the bromine index at the outlet reached 797mgBr / 100g, and the amount of gum was 4.9mg / 100mL.

[0117] Comparative Example 2

[0118] BETA molecular sieve (silicon-aluminum ratio 20, silicon-iron ratio 120) was directly mixed with alumina monohydrate (30% of the total weight of the degumming agent based on alumina) and shaped. The mixture was dried at 120°C for 4 hours and calcined at 550°C for 4 hours to obtain the degumming agent.

[0119] The obtained degumming agent had an external surface acidity / total acidity of 0.5%, a total acidity of 0.41 mmol / g, and a total alkali content of 0.01 mmol / g. The test results are shown in Table 1.

[0120] Degumming reaction of reformed oil:

[0121] Reformed oil with a bromine index of 1213 mgBr / 100g and a post-wash gum content of 5 mg / 100mL was used, and subjected to a heat treatment at 2.8 MPa for 5 hours. -1 At 190℃, 8.0g of degumming agent was introduced into a container. After degumming, the bromine index at the outlet reached 422mgBr / 100g, and the amount of gum was 4.7mg / 100mL. After 100 hours, the bromine index at the outlet reached 950mgBr / 100g, and the amount of gum was 4.9mg / 100mL.

[0122] Comparative Example 3

[0123] Preparation of degumming agent:

[0124] Take 120g of BETA molecular sieve (silicon-aluminum atomic ratio 20, silicon-iron atomic ratio 120, sodium in the molecular sieve is 3% by mass as sodium oxide) and treat it under normal pressure and 220℃ with 100% water vapor for 3 hours; then wash and filter with water to obtain product I.

[0125] Product I was placed in an ammonium nitrate solution and exchanged 4 times at 80°C (the liquid-solid mass ratio of product I to ammonium nitrate was 3, and the exchange time was 3 hours). The solid was then separated and dried at 120°C for 8 hours to obtain product II.

[0126] Product II was mixed with alumina monohydrate (30% of the total weight of the degumming agent based on alumina) and molded. The mixture was dried at 120°C for 4 hours and calcined at 550°C for 4 hours to obtain the degumming agent.

[0127] The obtained degumming agent had an external surface acidity / total acidity of 3.7%, a total acidity of 0.26 mmol / g, and a total alkali content of 0.01 mmol / g, as shown in Table 1.

[0128] Degumming reaction of reformed oil:

[0129] Reformed oil with a bromine index of 1213 mgBr / 100g and a post-wash gum content of 5 mg / 100mL was used, and subjected to a heat treatment at 2.8 MPa for 5 hours. -1 At 190℃, 8.0g of degumming agent was introduced into a container. After degumming, the bromine index at the outlet reached 790mgBr / 100g, and the amount of gum was 4.0mg / 100mL. After 100 hours, the bromine index at the outlet reached 1105mgBr / 100g, and the amount of gum was 4.9mg / 100mL.

[0130] Table 1

[0131]

[0132] The embodiments described above are merely detailed descriptions of the technical solutions of this invention, but the invention is not limited to the above embodiments; that is, the invention does not depend on the steps described in the above embodiments for implementation. In summary, any improvements made to this invention by those skilled in the art, including substitutions for the raw materials and additives described in this invention, and selections of specific implementation methods, all fall within the protection and disclosure scope of this invention.

Claims

1. A reforming oil degumming agent, characterized in that, Based on the total weight of the degumming agent, it includes the following components: (a) Molecular sieves with a purity of 40% to 94.5%; (b) 5% to 55% adhesive; (c) 0.5% to 8% of one or more of Group IA and Group IIA metal oxides; The acid content on the outer surface of the degumming agent accounts for 3% to 20% of the total acid content; the molar ratio of the total alkali content to the total acid content of the degumming agent is 0.1 to 10. The preparation method of the reformed oil degumming agent includes the following steps: (1) The molecular sieve was treated with steam under vacuum to obtain product I; (2) Product I was subjected to ammonium ion exchange, separated, and dried to obtain product II; (3) Product II is mixed with Group IA metal compounds and / or Group IIA metal compounds and binder precursors, molded, and calcined to obtain the degumming agent; In step (1), the steam treatment process is as follows: treatment under steam conditions of 120~380 ℃ for 0.1~20 h.

2. The degumming agent according to claim 1, characterized in that, The acid content on the outer surface of the degumming agent accounts for 5% to 20% of the total acid content; the molar ratio of the total alkali content to the total acid content of the degumming agent is 0.3 to 3.

0.

3. The degumming agent according to claim 2, characterized in that, The acid content on the outer surface of the degumming agent accounts for 6% to 15% of the total acid content.

4. The degumming agent according to claim 1, characterized in that, The molecular sieve is selected from one or more of the following: mordenite, γ-zeolite, clinoptilolite, MCM-22 molecular sieve, MCM-56 molecular sieve, β-zeolite, and molecular sieves containing -ITV, -CLO, or -IFU structures.

5. The degumming agent according to claim 4, characterized in that, The molecular sieve is selected from one or more of the following: mordenite, USY, β-zeolite, MCM-22 molecular sieve, MCM-56 molecular sieve, ITQ-37, or ITQ-54, which contain a twelve-membered ring.

6. The degumming agent according to claim 1, characterized in that, The molecular sieve contains a framework element M, selected from one or more of Zn, Ga, and Fe; the mass content of the framework element M is 0.01% to 5% based on the mass of the molecular sieve.

7. The degumming agent according to claim 1, characterized in that, The group IA elements are selected from at least one of sodium, potassium, rubidium, and cesium, and the group IIA elements are selected from at least one of magnesium, calcium, strontium, and barium.

8. The degumming agent according to claim 1, characterized in that, The molecular sieve content is 45% to 90% based on the total weight of the degumming agent, the binder content is 8% to 55%, and the content of Group IA metals and / or Group IIA metals as oxides is 0.8% to 6%.

9. A method for preparing the reforming oil degumming agent according to any one of claims 1-8, comprising the following steps: (1) The molecular sieve was treated with steam under vacuum to obtain product I; (2) Product I was subjected to ammonium ion exchange, separated, and dried to obtain product II; (3) Product II is mixed with Group IA metal compounds and / or Group IIA metal compounds and binder precursors, molded, and calcined to obtain the degumming agent; In step (1), the steam treatment process is as follows: treatment under steam conditions of 120~380 ℃ for 0.1~20 h.

10. The preparation method according to claim 9, characterized in that, In step (1), the vacuum refers to an absolute pressure of 0.03~0.098 MPa and the partial pressure of water vapor is 0.001~0.097 MPa.

11. The preparation method according to claim 9, characterized in that, In step (1), the steam treatment process is as follows: treatment under steam conditions of 120~260 ℃ for 0.5~6 h.

12. The preparation method according to claim 9, characterized in that, In step (3), the binder precursor is selected from one or more of alumina monohydrate, silica sol, and titanate.

13. A method for degumming reformed oil, comprising: The reformed oil reacts with the degumming agent described in any one of claims 1-8.

14. The method according to claim 13, characterized in that, The olefin content of the reformed oil, calculated by the bromine index, is 200-2000 mgBr / 100g, and the gum content after washing is 1-50 mg / 100mL.

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