A process for the preparation of a catalytic cracking octane enhancer

Abstract

The application discloses a preparation method of a catalytic cracking octane value additive, and first forms a Y-type molecular sieve filter cake layer, then loads ZSM-5 molecular sieve exchanged by containing phosphorus wastewater on the Y-type molecular sieve filter cake, recovers the excess phosphorus in the filtrate through the Y-type molecular sieve filter cake layer, reduces the loss of phosphorus, and the excess phosphorus can also modify the Y-type molecular sieve, and simultaneously improves the thermal stability and hydrothermal stability of the Y-type molecular sieve. The added humic acid is a multi-element organic complex, has the function of fixing phosphorus elements, makes the phosphorus elements not easy to flow away with the filtrate, and further improves the phosphorus utilization rate. The preparation method of the catalytic cracking additive provided by the application recycles the phosphorus-containing wastewater of the additive microspheres for the molecular sieve ion exchange process, can effectively reduce the water consumption and the consumption of the phosphorus-containing exchange liquid in the additive production process, and is favorable for reducing the production cost of the additive.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of auxiliary preparation, in particular to a preparation method of a catalytic cracking octane number auxiliary. BACKGROUND

[0002] With the increasingly stringent environmental regulations and the rapid development of the automobile industry, the quality requirements of vehicle gasoline are becoming higher and higher, and are developing in the direction of clean and high-grade, and the octane number is usually used to measure the anti-knock performance of gasoline. At present, the blending components of vehicle gasoline in China are still mainly fluid catalytic cracking (FCC) gasoline, with a proportion of more than 75%, while the content of high-octane gasoline blending components such as reforming gasoline and alkylated gasoline is too low; the clean measures such as gasoline desulfurization and control of olefin content often cause a certain degree of octane number loss, and the octane number shortage contradiction is more prominent. The high or low of the octane number of catalytic cracking gasoline plays a decisive role in the overall level of gasoline octane number, and improving the octane number of catalytic cracking gasoline is the key to improving the octane number of finished gasoline. There are many ways to improve the octane number of catalytic cracking gasoline, such as using octane number increasing additives or high octane number cracking catalysts, optimizing the composition of catalytic cracking raw oil, changing the operating conditions of FCC unit, etc., among which the use of MFI structure molecular sieve containing octane number increasing additive is one of the effective ways to quickly improve the octane number of catalytic cracking gasoline. The main active component for improving the octane number of gasoline is the molecular sieve with MFI structure, which has higher efficiency in the additive than in the main agent, and because one additive can be used with different main agents to meet the needs of different users for product distribution, the flexibility is higher, so for most catalytic cracking units, using the additive with MFI structure zeolite is an effective technical approach to improve the octane number.

[0003] CN111686790A provides a low liquefied gas yield catalytic cracking gasoline octane number auxiliary and a preparation method thereof, the preparation method comprising the following steps: (1) mixing ZSM-5 molecular sieve with deionized water at a solid dry basis content of 10-30wt%, beating, then adding magnesium salt and urea, continuously stirring for 10-60min, and obtaining a molecular sieve slurry; (2) mixing clay and binder with deionized water at a solid dry basis content of 10-30wt%, beating, and obtaining a matrix slurry; (3) mixing the above-mentioned molecular sieve slurry and matrix slurry, beating, and then spray drying to form a catalytic cracking gasoline octane number auxiliary. The catalytic cracking gasoline octane number auxiliary provided by the present application has the characteristics of low liquefied gas yield, good gasoline selectivity and high octane number when used in heavy oil catalytic cracking reaction.

[0004] CN111686791A provides a catalytic cracking gasoline octane number additive and a preparation method thereof, belonging to the field of catalyst preparation. The method comprises: (1) preparation of meso-micro multi-level pore structure ZSM-5 molecular sieve: mixing the required boron-containing compound, ZSM-5 molecular sieve and deionized water according to the mass ratio of boron-containing compound to elemental boron: ZSM-5 molecular sieve: deionized water = 0.005-0.05:1:5-50, then stirring at 30-95°C for 0.5-3h for ion exchange, then filtering and washing, and calcining the obtained filter cake at 400-800°C under 100% steam for 1-3h to obtain meso-micro multi-level pore structure ZSM-5 zeolite molecular sieve, (2) mixing the meso-micro multi-level pore structure ZSM-5 molecular sieve obtained in (1), clay and binder according to solid content 10-30wt% and deionized water, then spraying, washing, filtering and drying to obtain the catalytic cracking gasoline octane number additive. The gasoline octane number additive provided by the invention has the characteristics of low liquefied gas yield and high gasoline octane number when used for catalytic cracking.

[0005] CN107224991B discloses a catalytic cracking gasoline octane number improving additive and a preparation method thereof. The catalytic cracking gasoline octane number improving additive is composed of the following components according to weight percentage: molecular sieve 0-70%, matrix 10-70%, non-metallic active substance 0-10%, binder 0-50%, and additive 0-30%, and the silicon-aluminum ratio of the molecular sieve is greater than or equal to 200. The method comprises the following steps: (1) weighing the molecular sieve, matrix, non-metallic active substance, binder, and additive according to the weight percentage of the components, mixing them to form a mixture, grinding the mixture into powder using a grinding device, and adding water to stir to form a slurry, the weight ratio of water to mixture is 1-10:1, and the slurry is placed at a temperature of 0-100°C for more than 2 hours; (2) using a stirrer to stir the slurry in step (1) at a temperature of 0-100°C for more than 1 hour to make it uniformly dispersed; (3) spray drying the slurry in step (2) at a temperature of 100-300°C to form additive particles, and screening the additive particles to obtain target particles with a particle size of ≤200μm; (4) calcining the target particles at a temperature of 300-800°C for 0-5 hours to obtain additive particles; (5) contacting the additive particles with chemical reagents at a certain temperature for a certain time to obtain a gasoline octane number improving additive. The temperature for aging in step (5) is 200-450°C, the time for aging in step (5) is 1-8 hours, and the chemical reagents in step (5) include deionized water, alkaline solution, organic alcohol, amine or phenolic compound. The catalytic cracking gasoline octane number improving additive has the characteristics of high reaction activity, high hydrothermal stability and persistence during the reaction process, and slow deactivation rate.

[0006] Patent CN1298923A discloses a catalytic cracking catalyst and its preparation method. The catalyst can not only reduce the content of olefins and sulfur in gasoline, but also increase the octane number of gasoline and the production of liquefied gas. The catalyst is composed of Y-type molecular sieve, ZSM-5 molecular sieve, carrier and binder. The Y-type molecular sieve is REY, REHY, USY or REUSY, and its content is 1-54% by weight. The ZSM-5 molecular sieve is hydrogen type, and its content is 1-20% by weight. The ZSM-5 molecular sieve is modified by zinc, gallium, rare earth elements, and the content of the modifying elements in the ZSM-5 is 0.01-20.0% by weight. The carrier is a modified carrier, and its content is 35-60% by weight. The carrier is SiO2, Al2O3, MgO, ZrO2, kaolin, diatomite, sepiolite, aluminum-magnesium spinel or their mixture. The modifying elements used for the carrier are zinc, phosphorus, rare earth elements or their mixture, and the content of the modifying elements in the carrier is 0.01-25.0% by weight. The binder is aluminum hydroxychloride sol, silicon-aluminum gel, aluminum phosphate sol or their mixture, and its content in the catalyst is 10-25% by weight. A typical preparation method of the catalytic cracking catalyst is to add the slurry of Y-type molecular sieve, ZSM-5 molecular sieve and carrier into the binder, to beat and homogenize the slurry, to control the pH value to be 2.5-4.8, to filter, to spray dry, to bake or to water wash and dry, to obtain the catalyst, or to add the modified ZSM-5 molecular sieve and Y-type molecular sieve into the mixed slurry of water glass and modified carrier, to beat and homogenize the slurry, to add aluminum sulfate solution, to age for 10 minutes at 60-95°C, to adjust the pH value to 12 with sodium metaaluminate, to add aluminum sulfate solution, to adjust the pH value to 3.5-4.8, to add ammonia water, to filter, to beat, to spray dry, to wash, to dry and to obtain the catalyst.

[0007] The phosphorus modification can significantly improve the cracking activity and stability of the ZSM-5 zeolite additive.

[0008] CN304980 discloses an additive for reducing the content of olefins in catalytic cracking gasoline and simultaneously increasing the octane number of gasoline and its preparation method. The additive is composed of ZSM-5 molecular sieve, carrier and clay. The ZSM-5 molecular sieve is modified by phosphorus, gallium, aluminum, nickel, zinc or rare earth elements.

[0009] CN107970983B provides a kind of to improve gasoline octane barrel catalytic cracking adjuvant and its preparation method, with the dry base weight of the adjuvant as the basis, the adjuvant includes 10-75 weight percentage of phosphorus-containing MFI structure molecular sieve with dry base weight, 3-40 weight percentage of phosphorus aluminum inorganic binder with dry base weight, 1-30 weight percentage of other inorganic binder with oxide, 0-60 weight percentage of second clay with dry base weight, and 0.5-15 weight percentage of metal additive selected from at least one of group VIII metal and manganese, zinc, gallium with oxide.The catalytic cracking adjuvant provided by the application has good catalytic cracking performance, and when mixed with main agent for catalytic cracking reaction of hydrocarbon oil, the octane barrel of catalytic cracking gasoline can be improved, the content of isomerized hydrocarbon in gasoline is significantly improved, and the octane of gasoline is further improved.

[0010] CN102851058B provides a kind of method for improving catalytic cracking gasoline octane value;The catalytic cracking adjuvant used is prepared by the following method: a) ZSM-5 molecular sieve with silicon-aluminum ratio of 30-150, carrier, binder, phosphorus-containing compound and one or more of potassium, iron, magnesium, calcium and manganese are added to deionized water, and are formed by beating and spraying;Or ZSM-5 molecular sieve with silicon-aluminum ratio of 30-150, carrier, binder and phosphorus-containing compound are added to deionized water, and after beating and spraying, one or more of the aqueous solution of potassium, iron, magnesium, calcium and manganese is impregnated or ion exchanged;b), the product obtained in a) is calcined at high temperature or treated with high-temperature steam;c), zinc and one or more of molybdenum and tungsten are loaded or impregnated on the product;The adjuvant has good coke selectivity, can control liquefied gas yield, reduce gasoline yield loss, improve gasoline octane value, and significantly reduce gasoline olefin content.

[0011] CN1156555C discloses an adjuvant for reducing the olefin content of catalytic cracking gasoline and simultaneously improving the octane value, and a preparation method thereof.The adjuvant is composed of 5-65 weight percentage of ZSM-5 molecular sieve, 15-60 weight percentage of carrier and 10-40 weight percentage of binder, wherein the ZSM-5 molecular sieve is hydrogen type and is modified by modified elements phosphorus, zinc and at least one rare earth element;The preparation of the adjuvant is to modify the hydrogen type ZSM-5 molecular sieve with Zn and rare earth elements, mix the modified ZSM-5 molecular sieve and carrier with aluminum phosphate sol binder, beat and homogenize, and then filter, spray dry and calcine to obtain.

[0012] In addition to the phosphorus modification of ZSM-5 zeolite, it is also reported that the introduction of phosphorus compounds into the matrix can improve the performance of octane adjuvant.

[0013] CN114904564 A discloses a catalytic cracking aid for improving gasoline octane number and a preparation method thereof. The catalytic cracking aid is composed of MFI structure molecular sieve, clay, pseudo-boehmite, phosphorus compound, binder, modified metal compound, etc. The catalytic cracking aid for improving gasoline octane number is obtained by the following preparation method: mixing the MFI structure molecular sieve after alkali treatment, water and acid uniformly, controlling the pH value of the slurry in the range of 2.0-6.5, then adding the modified metal compound and clay and beating for 15-60 min to form a mixed slurry A, adding pseudo-boehmite to form a slurry B, adjusting the pH value of the slurry B with acid in the range of 0.1-2.0, then aging at 40-60℃ for 30-60 min, cooling to below 35℃, adding the binder and phosphorus compound, homogenizing, spray drying, calcining, and washing to obtain the catalytic cracking aid for improving gasoline octane number. The preparation process of the catalytic cracking aid disclosed in the invention is simple, the solid content of the gel slurry is high, and the catalytic cracking aid can effectively improve the gasoline octane number and has a small increase in liquefied gas.

[0014] CN106179470A discloses a preparation method of a catalytic cracking aid for improving gasoline octane number. The preparation steps are as follows: (1) ZSM-5 molecular sieve is beaten with water, the solid content is controlled in the range of 35-45wt%, and a certain proportion of modifier is added and stirred uniformly. (2) A certain proportion of pseudo-boehmite is added to the slurry of step (1), and the pH value is adjusted to the range of 1.8-2.3 with acid solution. (3) A certain concentration of pseudo-boehmite slurry is added to a certain concentration of phosphoric acid solution, the reaction temperature is controlled in the range of 50-65℃, and the reaction time is >5h. (4) A certain amount of water is added to the slurry of step (3), and kaolin is added and stirred uniformly. (5) The slurry of step (2) is added to the slurry of step (4) and stirred uniformly. (6) Spray drying is performed to obtain the aid. Industrial test proves that the aid accounts for 3-10wt% of the system content, the research method octane number can be increased by 1-3 units, and the silicon-aluminum ratio of ZSM-5 molecular sieve in the aid is 100-300.

[0015] CN102049290B provides a heavy oil catalytic cracking high octane gasoline additive, 5-90% by weight of the total weight of the additive, containing 5-90% by weight of composite molecular sieve, molecular sieve is hydrogen type, wherein BETA or EU-1 molecular sieve 1-60% by weight, chemical element modified or unmodified ZSM-5 molecular sieve 1-30% by weight, containing 2-60% by weight of clay, said additive contains P (as P2O5) 7.0-15.0% by weight, wherein the precursor of P is aluminum phosphate sol; aluminum phosphate sol contains 2-10% by weight of Al and 5-15% by weight of P, pH is 1.0-2.5, content of HNO3 is 2-20% by weight. Its preparation method comprises: molecular sieve, clay is respectively mixed with water to form slurry, aluminum phosphate sol is added to the clay slurry, and then the slurry is mixed uniformly, and the slurry is spray dried into the additive slurry. The microspherical additive after spray forming is calcined, washed and dried, or only washed and dried, and the additive product can be obtained. The prepared catalytic cracking additive has obviously improved activity, and when used with main catalyst, product distribution can be improved, gasoline octane number can be increased, and gasoline yield can be increased.

[0016] In the existing catalytic cracking octane number additive production process, the additive needs to be washed with water for many times after molding, and the total phosphorus content (as P) of the waste liquid after washing of the additive exceeds the limit of "Integrated Wastewater Discharge Standard" (GB8978-1996) (first level standard: 0.5mg / l; second level standard: 1.0mg / l), and a large amount of cost is needed to treat the phosphorus-containing wastewater before discharge, otherwise, it will cause serious pollution to the environment.

[0017] The existing technology mainly focuses on improving the alkylation and aromatization performance of the catalytic cracking octane number additive and the phosphorus removal method of the phosphorus-containing wastewater, and no related report is found on the recycling of the phosphorus-containing wastewater of the octane number additive. The existing technology uses adsorbent to adsorb phosphorus to meet the discharge standard. This operation requires the adsorbent to contact with the wastewater for a long time, and the adsorbent needs to be regenerated regularly, which cannot meet the continuous production demand of the octane number additive preparation process, and seriously affects the production capacity of the octane number additive.

[0018] Therefore, how to effectively improve the phosphorus utilization rate in the production process of the octane number additive and reduce the discharge of the phosphorus-containing wastewater is an important measure for the catalyst production enterprises to reduce cost and increase benefit, and is one of the key research topics of the catalyst production enterprises. SUMMARY

[0019] The application aims to provide a preparation method of catalytic cracking octane value additive, so as to solve the problems of phosphorus loss and pollution in the production process of catalytic cracking octane value additive, realize efficient utilization of phosphorus in the preparation process of octane value additive, realize the direct discharge of waste water, and ensure the green and continuous production of octane value additive.

[0020] To achieve the above-mentioned purpose, the application provides a preparation method of catalytic cracking octane value additive, comprising the following steps:

[0021] 1) Y-type molecular sieve, humic acid and water are slurried to obtain Y-type molecular sieve slurry, the Y-type molecular sieve slurry is filtered to form a Y-type molecular sieve filter cake layer, and the weight ratio of humic acid to Y-type molecular sieve on a dry basis is 0.001-0.05;

[0022] 2) ZSM-5 molecular sieve and phosphorus-containing waste water are slurried to obtain ZSM-5 molecular sieve slurry, the ZSM-5 molecular sieve slurry is filtered through the Y-type molecular sieve filter cake layer to form a Z-Y composite filter cake layer, the Z-Y composite filter cake layer is subjected to ion exchange with a first phosphorus-containing exchange solution, and then is washed with water to obtain a Z-Y composite molecular sieve filter cake, wherein the weight ratio of the amount of the first phosphorus-containing exchange solution to the dry basis of ZSM-5 molecular sieve is 0.005-0.15, calculated based on P;

[0023] 3) the Z-Y composite molecular sieve filter cake, clay, binder and water are mixed and slurried, and then are spray dried and formed, and then are calcined and solidified to obtain additive microspheres, the additive microspheres and water are mixed and slurried, and then are filtered to form a microsphere filter cake, the microsphere filter cake is subjected to ion exchange with a second phosphorus-containing exchange solution, and then is subjected to ion exchange with a metal solution, and then is dried to obtain catalytic cracking octane value additive, wherein the weight ratio of the amount of the second phosphorus-containing exchange solution to the dry basis of the microspheres is 0.005-0.10, calculated based on P, and the weight ratio of the amount of the metal solution to the dry basis of the microspheres is 0.005-0.10, calculated based on metal elements.

[0024] In the application, the slurry conditions of the Y-type molecular sieve and water in step 1) are known to those skilled in the art, and the content of Y-type molecular sieve in the slurry is generally 100-300 g / L. The temperature of the slurry can be 10-100℃, preferably 50-90℃. The spray drying and forming and calcination and solidification conditions in step 3) are known to those skilled in the art, such as the drying temperature is room temperature to 200℃, preferably 100-150℃, the calcination and solidification temperature is 300-600℃, preferably 400-500℃, and the calcination and solidification time is 10-200 minutes, preferably 30-60 minutes.

[0025] In the application, the metal solution is a solution containing one or more of zinc, magnesium, molybdenum, tungsten and gallium.

[0026] The preparation method of the catalytic cracking octane number additive according to the present application, wherein the Y-type molecular sieve is selected from one or more of USY, REY, HY, REHY, NH4Y and REUSY.

[0027] The preparation method of the catalytic cracking octane number additive according to the present application, wherein the humic acid is selected from one or more of fulvic acid, humic acid and humin acid.

[0028] The preparation method of the catalytic cracking octane number additive according to the present application, wherein the ZSM-5 molecular sieve has a silica / alumina molar ratio greater than 100.

[0029] The preparation method of the catalytic cracking octane number additive according to the present application, wherein the ZSM-5 molecular sieve is a ZSM-5 molecular sieve modified by rare earth ions or acid.

[0030] The preparation method of the catalytic cracking octane number additive according to the present application, wherein the mass ratio of the phosphorus-containing wastewater to the ZSM-5 molecular sieve is 2-10, preferably 3-6.

[0031] The preparation method of the catalytic cracking octane number additive according to the present application, wherein the phosphorus-containing wastewater is the filtrate collected after the ion exchange of the microsphere filter cake with the second phosphorus-containing exchange solution in step 3).

[0032] The preparation method of the catalytic cracking octane number additive according to the present application, wherein the first and second phosphorus-containing exchange solutions are one or more of ammonium phosphate solution, diammonium hydrogen phosphate solution, ammonium dihydrogen phosphate solution and phosphoric acid.

[0033] The preparation method of the catalytic cracking octane number additive according to the present application, wherein the first phosphorus-containing exchange solution is prepared from the filtrate collected after the ion exchange of the microsphere filter cake with the second phosphorus-containing exchange solution in step 3).

[0034] The preparation method of the catalytic cracking octane number additive according to the present application, wherein the clay is one or more of kaolin, halloysite and montmorillonite; and the binder is one or more of aluminum sol, silicon sol and pseudo-boehmite.

[0035] The preparation method of the catalytic cracking octane number additive according to the present application, wherein steps 1) and 2) are performed on a first horizontal belt filter, which comprises a Y-type molecular sieve filter cake forming area, a ZMS-5 molecular sieve filter cake forming area, a phosphorus exchange area and a water washing area connected in series; and step 3) is performed on a second horizontal belt filter, which comprises a microsphere filter cake forming area, a phosphorus exchange area and a metal ion exchange area connected in series.

[0036] The present application has the following advantages:

[0037] The application provides a preparation method of a catalytic cracking octane number additive, and first forms a Y-type molecular sieve filter cake layer, then loads ZSM-5 molecular sieve exchanged by phosphorus-containing wastewater on the Y-type molecular sieve filter cake, recovers the excess phosphorus in the filtrate through the Y-type molecular sieve filter cake layer, reduces the loss of phosphorus, and the excess phosphorus can also modify the Y-type molecular sieve, and the thermal stability and hydrothermal stability of the Y-type molecular sieve are simultaneously improved. The humic acid added in the application is a multi-element organic complex, has the function of fixing phosphorus elements, makes the phosphorus elements not easy to flow away with the filtrate, and further improves the phosphorus utilization rate. The preparation method of the catalytic cracking additive provided by the application recycles the phosphorus-containing wastewater of the additive microspheres for the ion exchange process of the molecular sieve, can effectively reduce the water consumption and the consumption of the phosphorus-containing exchange liquid in the additive production process, is beneficial to reducing the production cost of the additive, and thus, compared with the prior art, the preparation method of the catalytic cracking octane number additive provided by the application does not need to increase additional investment, can realize the direct discharge of wastewater on the existing production device, the operation process is simple, and technical support is provided for green production and energy saving and consumption reduction of a catalyst enterprise.

[0038] In addition, the preparation method of the catalytic cracking octane number additive provided by the application is modified by magnesium, zinc, molybdenum, tungsten, gallium and the like after the additive is formed and the phosphorus exchange is completed, the stability of the molecular sieve is improved through the synergistic effect of phosphorus and metal, the acid properties of the molecular sieve and the matrix are adjusted, the coke formation probability is reduced, and excessive cracking of gasoline components is inhibited, so that the gasoline yield and the gasoline octane number are considered. BRIEF DESCRIPTION OF DRAWINGS

[0039] Figure 1 The figure is a flow chart of the molecular sieve phosphorus exchange process of the application;

[0040] Figure 2 The figure is a flow chart of the phosphorus and metal ion exchange process of the additive microspheres of the application.

[0041] In the figure, the reference signs are as follows:

[0042] 1, 5, 15 and 16 are pulp tanks;

[0043] 2, 6, 10, 13, 17, 21 and 25 are pipelines;

[0044] 3 is filter cloth;

[0045] 4 is a Y-type molecular sieve filter cake forming area

[0046] 7 is a ZSM-5 molecular sieve filter cake forming area

[0047] 8 and 23 are liquid receivers

[0048] 9, 12, 20 and 24 are containers

[0049] 14 is a water washing area

[0050] 19 is a microsphere filter cake forming area

[0051] 11,22 phosphorus exchange zone

[0052] 26 metal ion exchange zone

[0053] 27 recovery filtrate DETAILED DESCRIPTION

[0054] The present application will be described in detail below by way of examples. It is necessary to point out here that the following examples are only used to further illustrate the present application and cannot be understood as limiting the scope of protection of the present application, and those skilled in the art can make some non-essential improvements and adjustments to the present application according to the above content of the present application.

[0055] According to the method provided by the present application, the present application can be implemented according to the flow shown in Figure 1 Figure 2

[0056] I. Formation of Y-type molecular sieve filter cake

[0057] The Y-type molecular sieve, humic acid and water at 10-100°C, preferably 50-90°C are beaten to form a slurry, which is continuously loaded from the beating tank 1 through the pipeline 2 to the filter cloth 3 of the horizontal vacuum belt filter, the filter cloth continuously moves into the Y-type molecular sieve filter cake formation zone 4. The liquid receiver 8 is located below the filter cloth 3, the liquid receiver 8 is vacuumed, under the action of vacuum, the liquid in the slurry on the filter cloth 3 enters the liquid receiver 8 through the filter cloth 3. At the same time, the Y-type molecular sieve slurry on the filter cloth 3 forms a filter cake, the loading speed of the Y-type molecular sieve slurry should ensure that the thickness of the Y-type molecular sieve filter cake is 0.5-1.5 centimeters, preferably 0.8-1.5 centimeters. The vacuum degree in the vacuum box 8 makes the surface of the filter cake not crack. The vacuum degree in the vacuum box 8 is generally 0.02-0.08 MPa, preferably 0.05-0.08 MPa.

[0058] II. Formation of ZSM-5 molecular sieve filter cake

[0059] The ZSM-5 molecular sieve slurry at 50-100°C is continuously loaded from the beating tank 5 through the pipeline 6 to the Y-type molecular sieve filter cake layer of the horizontal vacuum belt filter, and moves into the ZSM-5 molecular sieve filter cake formation zone 7 with the filter cloth. The phosphorus-containing wastewater can be provided by the microsphere exchange process liquid receiver 23 described below, which can reduce the amount of water used and also recover the phosphorus in the filtrate of the catalyst microsphere ion exchange process, thereby reducing the amount of sewage discharged. At the same time, the ZSM-5 molecular sieve slurry on the filter cloth 3 forms a filter cake, and the loading speed of the ZSM-5 molecular sieve slurry should ensure that the thickness of the ZSM-5 molecular sieve filter cake is 0.5-1.5 centimeters, preferably 0.8-1.5 centimeters.

[0060] III. Composite molecular sieve ion exchange ​​

[0061] As the filter cloth 3 moves, the filter cake formed in the Y zeolite filter cake formation zone 4 and the ZSM-5 filter cake formation zone 7 enters the ion exchange zone 11, where a phosphorus-containing exchange solution at a temperature of 20-100°C, preferably 30-90°C, is added from vessel 9 through line 10. Under the action of vacuum, the phosphorus-containing exchange solution passes through the filter cake while ion exchange is carried out.

[0062] Four, washing of the composite zeolite

[0063] The washing method is known to those skilled in the art, and the filter cake obtained in the ion exchange zone 11 enters the water washing zone 14, where deionized water is added from vessel 12 through line 13. The weight ratio of deionized water to composite zeolite is generally 1-15, preferably 2-10, and the temperature of the deionized water is 20-100°C, preferably 30-90°C. Under the action of vacuum, the liquid passes through the filter cake, and the residual ions, especially anions, in the filter cake are washed away.

[0064] Five, forming and solidifying of the additive microspheres

[0065] The washed composite zeolite filter cake enters the pulping tank 15, where clay, binder and water are mixed and pulped, and the additive microspheres are formed by spraying and solidified by calcination.

[0066] Six, formation of the microsphere filter cake

[0067] The solidified additive microspheres enter the pulping tank 16, where they are pulped with water. The microsphere slurry is continuously loaded from the pulping tank 16 through line 17 onto the filter cloth 18 of a horizontal vacuum belt filter, and the filter cloth continuously moves into the microsphere filter cake formation zone 19. A liquid receiver 23 is located below the filter cloth 18, and the liquid receiver 23 is evacuated. Under the action of vacuum, the liquid in the slurry on the filter cloth 18 passes through the filter cloth 18 into the liquid receiver 23. At the same time, the microsphere slurry on the filter cloth 18 forms a filter cake, and the loading speed of the microsphere slurry should ensure that the thickness of the microsphere filter cake is 0.5-2.0 cm, preferably 0.8-1.5 cm. The vacuum degree in the vacuum box 23 is generally 0.02-0.08 MPa, preferably 0.03-0.08 MPa.

[0068] Seven, phosphorus ion exchange of the additive microspheres

[0069] As the filter cloth 18 moves, the filter cake formed in the microsphere filter cake formation zone 19 enters the ion exchange zone 22, where a phosphorus-containing exchange solution at a temperature of 20-100°C, preferably 30-90°C, is added from vessel 20 through line 21. Under the action of vacuum, the phosphorus-containing exchange solution passes through the filter cake while ion exchange is carried out.

[0070] Eight, metal ion exchange of the additive microspheres

[0071] As the filter cloth 18 is moved, the filter cake from the phosphorus exchange zone 22 is moved into the metal ion exchange zone 26. A metal-containing solution is added to the filter cake from the phosphorus exchange zone 22 from vessel 24 through line 25. The metal-containing solution is at a temperature of from 20 to 100°C, preferably from 30 to 90°C. The metal-containing solution is ion exchanged through the filter cake under the influence of vacuum.

[0072] The following examples were performed using a cloth funnel filter apparatus to illustrate the process provided by the present invention. Since the cloth funnel filter apparatus also undergoes cake formation, ion exchange, and washing, these steps are performed separately and are therefore equivalent to the continuous process performed on a belt filter.

[0073] Source of raw materials:

[0074] 1) USY molecular sieve: produced by Lanzhou Petrochemical Company, Na2O content 0.9%, unit cell constant 24.36 angstroms;

[0075] REY molecular sieve: produced by Lanzhou Petrochemical Company, Na2O content 1.1%, RE2O3 content 14.8%, unit cell constant 24.66 angstroms;

[0076] HY molecular sieve: produced by Lanzhou Petrochemical Company, Na2O content 1.5%, unit cell constant 24.39 angstroms;

[0077] NH4Y molecular sieve: produced by Lanzhou Petrochemical Company, Na2O content 1.2%, unit cell constant 24.41 angstroms;

[0078] REHY molecular sieve: produced by Lanzhou Petrochemical Company, Na2O content 1.3%, RE2O3 content 1.5%, unit cell constant 24.45 angstroms;

[0079] REUSY molecular sieve: produced by Lanzhou Petrochemical Company, Na2O content 0.8%, RE2O3 content 0.9%, unit cell constant 24.39 angstroms;

[0080] Fe-ZSM-5 molecular sieve: produced by Lanzhou Petrochemical Company, molar ratio (SiO2 / Al2O3) 400;

[0081] Zn-ZSM-5 molecular sieve: produced by Lanzhou Petrochemical Company, molar ratio (SiO2 / Al2O3) 300;

[0082] La-ZSM-5 molecular sieve: produced by Lanzhou Petrochemical Company, molar ratio (SiO2 / Al2O3) 100;

[0083] Kaolin, halloysite, montmorillonite, silica sol, pseudoboehmite, and alumina sol were all obtained from Lanzhou Petrochemical Company.

[0084] 2) Fulvic acid, humic acid, black acid, phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, yttrium oxide, magnesium oxide, white carbon black: analytical pure, all are chemical reagents.

[0085] Analysis method:

[0086] The filtrate phosphorus content was detected by ICP (Inductive Coupled Plasma Emission Spectrometer).

[0087] Comparative example 1

[0088] The sample was prepared according to the patent CN114904564A.

[0089] 1140g (dry basis) La-ZSM-5 molecular sieve was added to 2040mL deionized water, mixed and slurried, 136g sodium hydroxide was added, stirred at 25℃ for 45min, the pH value of the molecular sieve slurry was adjusted to 2.5 with hydrochloric acid, 11.4g citric acid, 46g ferric chloride were added, the slurry pH value was 0.98, stirred for 45min, then 100g phosphoric acid was added, continued to stir for 15min, 2140mL deionized water, 235g aluminum chloride, 1006g (dry basis) kaolin, 300g (dry basis) pseudo-boehmite were added, the slurry pH value was 0.66, the temperature was raised to 50℃, stirred for 1h, then the temperature was lowered to 25℃, under stirring, 521g phosphoric acid was added, continued to stir for 30min, the obtained colloidal solid content was 37% (by weight), after homogenization, spray drying, calcination and water washing, microsphere filtrate A and additive finished product D1 were obtained, wherein the phosphorus content of the microsphere filtrate A was 123mg / L.

[0090] Comparative example 2

[0091] 1) La-ZSM-5 molecular sieve was mixed and slurried with phosphorus-containing wastewater (microsphere filtrate A of comparative example 1), the mass of the microsphere filtrate A was 5 times that of the ZMS-5 molecular sieve to prepare a ZMS-5 molecular sieve slurry, the obtained ZMS-5 molecular sieve slurry was heated to 70℃ and stirred for 1h, poured into a Buchner funnel, and at the same time the filter bottle was vacuumed to 0.07MPa, forming a ZMS-5 molecular sieve filter cake with a thickness of 10mm on the filter cloth.

[0092] 2) When there was no liquid on the surface of the filter cake, 90℃ ammonium phosphate solution was immediately added, the adding speed ensured that no cracks were formed on the surface of the filter cake, and the amount of ammonium phosphate was such that the weight ratio of P to ZMS-5 molecular sieve was 0.04. When there was no liquid on the surface of the filter cake, deionized water at 80℃ was immediately added to wash the filter cake, and the weight ratio of deionized water to ZMS-5 molecular sieve was 5. Then the molecular sieve filter cake was taken out and the filtrate B was collected.

[0093] 3) The molecular sieve slurry obtained in step (2) was mixed with kaolin, alumina sol, pseudoboehmite in the ratio of 47:35:8:10 to form an additive mixture slurry;

[0094] 4) The slurry obtained in step (3) was spray dried to form additive microspheres by a conventional spray drying method for additive preparation, and the additive microspheres were calcined.

[0095] 5) The calcined additive microspheres obtained in step 4) were mixed with water to form a slurry having an additive microsphere content of 110 g / L, and the obtained slurry was heated to 60°C and poured into a Buchner funnel, while the filter bottle was vacuumed to 0.06 MPa to form a filter cake having a thickness of 10 mm on the filter cloth.

[0096] 6) When there was no liquid on the surface of the filter cake obtained in step 5) above, a zinc chloride solution having a temperature of 90°C was immediately added at a rate ensuring that no cracks were formed on the surface of the filter cake, and the amount of zinc chloride was such that the weight ratio of Zn to the microspheres was 0.03. When there was no liquid on the surface of the filter cake, the filter cake was removed and the filtrate C was collected, and the additive sample D2 was dried to obtain a phosphorus content of 158 mg / L.

[0097] Example 1

[0098] 1) USY molecular sieve was mixed with fulvic acid and water to form a molecular sieve slurry having a molecular sieve content of 180 g / L, wherein the amount of fulvic acid added was such that the weight ratio of fulvic acid to the dry basis of USY molecular sieve was 0.03:1, and the obtained molecular sieve slurry was heated to 80°C and poured into a Buchner funnel, while the filter bottle was vacuumed to 0.07 MPa to form a filter cake having a thickness of 10 mm on the filter cloth.

[0099] 2) La-ZSM-5 molecular sieve was mixed with phosphorus-containing wastewater (microsphere filtrate A of Comparative Example 1) to form a ZSM-5 molecular sieve slurry, wherein the mass of the microsphere filtrate A was 5 times that of the molecular sieve, and the obtained ZSM-5 molecular sieve slurry was heated to 70°C and stirred for 1 h, and then poured onto the USY filter cake of step 1) in a Buchner funnel, while the filter bottle was vacuumed to 0.07 MPa to form a ZSM-5 molecular sieve filter cake having a thickness of 10 mm on the filter cloth.

[0100] 3) When there was no liquid on the surface of the filter cake obtained in the above step, an ammonium phosphate solution having a temperature of 90°C was immediately added at a rate ensuring that no cracks were formed on the surface of the filter cake, and the amount of ammonium phosphate was such that the weight ratio of P to the ZSM-5 molecular sieve was 0.04. When there was no liquid on the surface of the filter cake, deionized water having a temperature of 80°C was immediately added to wash the filter cake, and the weight ratio of deionized water to the composite molecular sieve was 5. Then, the composite molecular sieve filter cake was removed and the filtrate D was collected, wherein the mass ratio of Y-type molecular sieve to ZSM-5 molecular sieve on a dry basis was 6:94.

[0101] 4) The slurry of step (3) is mixed with kaolin, alumina sol, and pseudo-boehmite in a ratio of 47:35:8:10 of molecular sieve: kaolin: alumina sol (as Al203): pseudo-boehmite to form an additive mixture slurry;

[0102] 5) The slurry of step (4) is spray dried to form additive microspheres by a conventional spray drying method for additive preparation, and the additive microspheres are calcined.

[0103] 6) The calcined additive microspheres of step 5) are mixed with water to form a slurry having an additive microsphere content of 110 g / L, and the resulting slurry is heated to 60°C and poured into a Buchner funnel while the filter bottle is vacuumed to 0.06 MPa to form a filter cake having a thickness of 10 mm on the filter cloth.

[0104] 7) When the filter cake surface is free of liquid in step 6) above, a phosphoric acid solution having a temperature of 30°C is immediately added in an amount such that the weight ratio of P to the microspheres is 0.05, and a zinc chloride solution having a temperature of 90°C is added in an amount such that the weight ratio of Zn to the microspheres is 0.03. When the filter cake surface is free of liquid, the filter cake is removed and the filtrate E is collected, and the filter cake is dried to obtain an additive sample S1, and the filtrate D has a phosphorus content of 0.8 mg / L.

[0105] Example 2

[0106] The operating steps are the same as in Example 1, except that:

[0107] Step 1) The slurry of REY molecular sieve has a content of 300 g / L, and the brown acid is added in an amount such that the weight ratio of brown acid to dry REY molecular sieve is 0.001:1, the slurry temperature is 15°C, the vacuum degree of the filter bottle is 0.08 MPa, and the filter cake has a thickness of 5 mm.

[0108] Step 2) The Fe-ZSM-5 molecular sieve is mixed with the phosphorus-containing waste water (filtrate E) to form a slurry, the amount of filtrate E is 2 times the amount of molecular sieve, the slurry temperature is 50°C, the stirring time is 2 h, the vacuum degree of the filter bottle is 0.08 MPa, and the filter cake has a thickness of 15 mm.

[0109] Step 3) The amount of diammonium hydrogen phosphate is such that the weight ratio of P to ZSM-5 molecular sieve is 0.005, the temperature of the deionized water is 100°C, and the weight ratio of deionized water to molecular sieve is 1. The molecular sieve filter cake is removed and the filtrate F is collected.

[0110] Step 4) Molecular sieve: halloysite: silica sol (as Si02) = 35:55:10.

[0111] Step 5) Spray drying and calcination.

[0112] Step 6) Microsphere content 300 g / L, slurry temperature 80°C, filter cake thickness 5 mm.

[0113] Step 7) Ammonium phosphate solution temperature 50°C, ammonium phosphate amount such that P to microsphere weight ratio is 0.005, ammonium tungstate and gallium chloride solution with W:Ga mass ratio of 3:7, (W+Ga) to microsphere weight ratio is 0.10, temperature 20°C. The filter cake is then removed and the filtrate I is collected to obtain the additive sample S2, and the filtrate F has a phosphorus content of 0.6 mg / L.

[0114] Example 3

[0115] The operating steps are the same as in Example 1, with the difference that:

[0116] Step 1) REUSY to HY dry base mass ratio 1:1, molecular sieve slurry content 100 g / L, melanocortin addition amount to dry base molecular sieve weight ratio 0.05:1, slurry temperature 100°C, filter cake thickness 15 mm.

[0117] Step 2) Zn-ZSM-5 molecular sieve is mixed with phosphorus-containing wastewater (filtrate I) to make a slurry, the amount of filtrate I being 10 times the amount of molecular sieve, slurry temperature 100°C, stirring for 0.5 h, filter cake thickness 5 mm.

[0118] Step 3) Temperature 20°C, diammonium hydrogen phosphate to molecular sieve weight ratio 0.15. Deionized water temperature 20°C, deionized water to molecular sieve weight ratio 3. The molecular sieve filter cake is removed and the filtrate J is collected.

[0119] Step 4) Molecular sieve: montmorillonite: pseudo-boehmite (as Al203) = 40:45:15.

[0120] Step 5) Spray drying, solidification.

[0121] Step 6) Additive microsphere content 100 g / L, slurry temperature 20°C, filter cake thickness 20 mm.

[0122] Step 7) Ammonium dihydrogen phosphate solution temperature 90°C, ammonium dihydrogen phosphate amount such that P to microsphere weight ratio is 0.10, magnesium nitrate to microsphere weight ratio is 0.005, temperature 100°C. The filter cake is then removed and the filtrate K is collected to obtain the additive sample S3, and the filtrate J has a phosphorus content of 0.4 mg / L.

[0123] Example 4

[0124] The operating steps are the same as in Example 1, with the difference that:

[0125] Step 1) NH4Y to REHY dry basis mass ratio of 1:3, molecular sieve slurry content of 180 g / L, humic acid and fulvic acid addition amount to molecular sieve dry basis weight ratio of 0.03:1, slurry temperature 75°C, filter bottle vacuum degree 0.04 MPa, filter cake thickness 8 mm.

[0126] Step 2) La-ZSM-5 molecular sieve mixed with phosphorus-containing wastewater (filtrate K) to make a slurry, filtrate K amount 4 times the molecular sieve, slurry temperature 70°C, stirring 1.5 h, filter bottle vacuum degree 0.04 MPa, filter cake thickness 13 mm.

[0127] Step 3) phosphoric acid to molecular sieve weight ratio of 0.01, deionized water temperature 40°C, deionized water to molecular sieve weight ratio of 8. The molecular sieve filter cake was removed and filtrate L was collected.

[0128] Step 4) molecular sieve: kaolin: aluminum sol (calculated as aluminum oxide) = 45:35:20.

[0129] Step 5) spray drying, solidification.

[0130] Step 6) additive microspheres content 170 g / L, slurry temperature 60°C, filter bottle vacuum degree 0.04 MPa, filter cake thickness 18 mm.

[0131] Step 7) diammonium hydrogen phosphate solution temperature 70°C, diammonium hydrogen phosphate amount to make P to microsphere weight ratio of 0.07, ammonium molybdate to microsphere weight ratio of 0.02, temperature 60°C, filter cake dried at 200°C and then calcined at 500°C for 1 h, then the filter cake was removed and filtrate M was collected, obtaining additive sample S4, filtrate L phosphorus content 0.5 mg / L.

[0132] Example 5

[0133] The industrial catalyst of trade name LDO-75 was used as the main catalyst, mixed with the additives prepared in Examples 1-4 and Comparative Examples 1-2 in a weight ratio of 95:5, and the mixture was aged at 800°C for 10 h with 100% steam. The catalytic performance of the mixed catalyst was evaluated on a fixed fluidized bed device using 3 million tons / year catalytic feedstock from Lanzhou Petrochemical as the evaluation oil (properties shown in Table 1). The blank was the evaluation result of the main catalyst without mixing the additive. The evaluation conditions were reaction temperature 500°C, regeneration temperature 700°C, and catalyst / oil ratio 4. The evaluation results are shown in Table 2.

[0134] Table 1 Properties of catalytic feedstock

[0135]

[0136] Table 2 Evaluation results of additives, %

[0137] Catalyst Blank D1 D2 S1 S2 S3 S4 Conversion 85.1 83.4 84.74 85.12 83.62 84.02 85.23 Dry gas 2.41 2.34 2.32 2.53 2.53 2.45 2.49 Liquefied gas 24.12 25.02 24.81 24.66 24.86 25.04 24.44 Gasoline 51.03 47.95 50.06 50.31 49.02 49.03 49.84 Diesel 10.54 11.15 10.62 10.67 11.67 11.44 11.29 Heavy oil 4.36 5.45 4.64 4.21 4.71 4.54 4.48 Coke 7.54 8.09 7.55 7.62 7.21 7.5 7.46 RON 88.8 90.1 90.2 91.1 90.4 90.2 90.4

[0138] From the results of examples S1 to S4, it can be seen that the filtrate phosphorus content obtained by the method of the present application is less than 1 mg / l, meeting the national secondary discharge standard. Compared with Comparative Example 1, the operation process of the present application is simple and can achieve direct discharge of wastewater on the existing auxiliary agent preparation device. From the evaluation data, it can be seen that the auxiliary agent prepared by the method of the present application can improve the octane number of catalytic cracking catalytic gasoline, and the auxiliary agent prepared by the method provided by the present application has low filtrate phosphorus content, does not need to be treated, can achieve direct discharge requirements, and has good operability, and has good industrial application prospect.

[0139] Of course, the present application can also have other various embodiments, and those skilled in the art can make various corresponding changes and modifications according to the present application without departing from the spirit and essence of the present application. However, these corresponding changes and modifications should all belong to the protection scope of the claims of the present application.

Claims

1. A process for the preparation of a catalytic cracking octane enhancer characterized in that, The method comprises the following steps: 1) Y zeolite, humic acid and water are slurried to obtain a Y zeolite slurry, the Y zeolite slurry is filtered to form a Y zeolite filter cake layer, and the weight ratio of the humic acid to the Y zeolite on a dry basis is 0.001-0.05; 2) ZSM-5 zeolite and phosphorus-containing wastewater are slurried to obtain a ZSM-5 zeolite slurry, the ZSM-5 zeolite slurry is filtered through the Y zeolite filter cake layer to form a Z-Y composite filter cake layer, the Z-Y composite filter cake layer is subjected to ion exchange with a first phosphorus-containing exchange solution, and then subjected to water washing to obtain a Z-Y composite zeolite filter cake, wherein the weight ratio of the amount of the first phosphorus-containing exchange solution to the ZSM-5 zeolite on a dry basis is 0.005-0.15, calculated based on P; 3) the Z-Y composite zeolite filter cake, clay, binder and water are mixed and slurried, and then spray-dried to form a catalyst microsphere, the catalyst microsphere is mixed and slurried with water, and then filtered to form a microsphere filter cake, the microsphere filter cake is subjected to ion exchange with a second phosphorus-containing exchange solution, and then subjected to ion exchange with a metal solution, and then dried to obtain a catalytic cracking octane number aid, wherein the weight ratio of the amount of the second phosphorus-containing exchange solution to the microsphere on a dry basis is 0.005-0.10, calculated based on P; and the weight ratio of the amount of the metal solution to the microsphere on a dry basis is 0.005-0.10, calculated based on metal elements.

2. The process for the preparation of a catalytic cracking octane booster according to claim 1, characterized in that, The metal solution is a solution containing one or more of zinc, magnesium, molybdenum, tungsten and gallium.

3. The process for the preparation of a catalytic cracking octane booster according to claim 1, characterized in that, The Y zeolite is selected from one or more of USY, REY, HY, REHY, NH4Y and REUSY.

4. The process for the preparation of a catalytic cracking octane booster according to claim 1, characterized in that, The humic acid is selected from one or more of yellow humic acid, brown humic acid and black humic acid.

5. The process for the preparation of a catalytic cracking octane booster according to claim 1, characterized in that, The ZSM-5 zeolite has a silica / alumina molar ratio greater than 100.

6. The process for the preparation of a catalytic cracking octane booster according to claim 1, characterized in that, The ZSM-5 zeolite is a ZSM-5 zeolite modified by rare earth ions or acid.

7. The process for the preparation of a catalytic cracking octane booster according to claim 1, characterized in that, The mass ratio of the phosphorus-containing wastewater to the ZSM-5 zeolite is 2-10.

8. The process for the preparation of a catalytic cracking octane booster according to claim 1, characterized in that, The mass ratio of the phosphorus-containing wastewater to the ZSM-5 zeolite is 3-6.

9. The process for the preparation of a catalytic cracking octane booster according to claim 1, characterized in that, The first and second phosphorus-containing exchange solutions are one or more of ammonium phosphate solution, diammonium hydrogen phosphate solution, ammonium dihydrogen phosphate solution and phosphoric acid.

10. The process for the preparation of a catalytic cracking octane booster according to claim 1, characterized in that, The clay is one or more of kaolin, halloysite and montmorillonite; and the binder is one or more of aluminum sol, silicon sol and pseudo-boehmite.

11. The process for the preparation of a catalytic cracking octane booster according to claim 1, characterized in that, Steps 1) and 2) are performed on a first horizontal belt filter machine, and the first horizontal belt filter machine comprises a Y zeolite filter cake forming area, a ZSM-5 zeolite filter cake forming area, a phosphorus exchange area and a water washing area connected in series; and step 3) is performed on a second horizontal belt filter machine, and the second horizontal belt filter machine comprises a microsphere filter cake forming area, a phosphorus exchange area and a metal ion exchange area connected in series.

Images