CN109092353B - Yield-increasing propylene additive and preparation method thereof - Google Patents
Yield-increasing propylene additive and preparation method thereof Download PDFInfo
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- CN109092353B CN109092353B CN201811014063.7A CN201811014063A CN109092353B CN 109092353 B CN109092353 B CN 109092353B CN 201811014063 A CN201811014063 A CN 201811014063A CN 109092353 B CN109092353 B CN 109092353B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a preparation method of a yield-increasing propylene additive, which comprises the following steps: (1) removing the template agent in the SAPO molecular sieve synthesis mother liquor to obtain refined mother liquor; (2) and mixing the refined mother liquor, a carrier, a ZSM-5 molecular sieve and water to form slurry, and spraying, curing and forming the slurry to obtain the propylene yield-increasing additive. The invention provides a new application of SAPO molecular sieve synthetic mother liquor, which has the advantages of easily obtained raw materials, simple preparation process and capability of effectively reducing the production cost.
Description
Technical Field
The invention relates to the technical field of catalytic assistants, in particular to a yield-increasing propylene assistant and a preparation method thereof.
Background
At present, the traditional preparation route of low-carbon olefins (ethylene, propylene and the like) is mainly naphtha cracking, and the traditional preparation route has the defects of high energy consumption and excessive dependence on petroleum. At present, the Methanol To Olefin (MTO) is the most promising process route for preparing olefins by taking naphtha as a raw material, and recently, a round of MTO project construction is also developed in China.
The silicoaluminophosphate molecular Sieve (SAPO) has higher selectivity to low-carbon olefin, and the SAPO molecular sieve as an active component shows the most excellent catalytic performance in an MTO catalyst, and the output of the SAPO molecular sieve is increased with the continuous promotion of the industrialization of an MTO project.
However, in the production process of SAPO molecular sieves, a large amount of mother liquor wastewater containing phosphorus, aluminum, silicon and other elements and a template agent is generated, and it is a common practice to subject the mother liquor wastewater to a sewage treatment or to a proper separation treatment to extract useful components in the mother liquor wastewater and then to a sewage disposal. Under the condition that the requirements for saving resources and protecting environment are increasingly strict, the resource utilization and pollution-free treatment of the SAPO molecular sieve synthetic mother liquor are urgent.
Disclosure of Invention
The applicant researches and discovers that the treatment means of the prior SAPO molecular sieve synthesis mother liquor mainly comprises the following three types: (1) the SAPO molecular sieve is used as a raw material for synthesizing SAPO; (2) the catalyst is used as a Methanol To Olefin (MTO) catalyst raw material; (3) the components are separated or the pollution-free treatment is realized by physical means such as distillation, rectification, evaporation, concentration, cooling crystallization and the like, or chemical methods such as strong alkali, flocculating agent sedimentation and the like, or biochemical treatment and the like. The existing processing means are still more limited.
The invention aims to provide a new way for comprehensively utilizing SAPO molecular sieve synthesis mother liquor, and particularly relates to a catalytic cracking auxiliary agent for producing propylene with increased yield by using SAPO molecular sieve synthesis mother liquor.
The technical scheme of the invention is as follows:
the preparation method of the yield-increasing propylene additive comprises the following steps:
(1) removing the template agent in the SAPO molecular sieve synthesis mother liquor to obtain refined mother liquor;
(2) and mixing the refined mother liquor, a carrier, a ZSM-5 molecular sieve and water to form slurry, and spraying, curing and forming the slurry to obtain the propylene yield-increasing additive.
Wherein, the removal of the template agent in the step (1) includes but is not limited to distillation, flocculation precipitation and extractive distillation.
In one embodiment of the present invention, the method for preparing the SAPO molecular sieve synthesis mother liquor in step (1) comprises the following steps:
(1) mixing an aluminum source and water to prepare a mixed solution with a solid content of 10-40%, uniformly stirring at 20-40 ℃, refining the slurry by using a homogenizer until the median particle size D50 is 0.5-1.5 mu m, and then carrying out spray drying on the slurry to obtain a granular aluminum source with the median particle size D50 of 10-100 mu m;
(2) mixing phosphoric acid and water, stirring at the speed of 500r/min at the temperature of 20-50 ℃ in a water bath, adding a silicon source, stirring uniformly, slowly adding the granular aluminum source, continuously stirring, slowly adding a template agent, increasing the stirring speed to 900r/min at the speed of 700 and 900r/min, and stirring for 5-20 hours to obtain gel;
(3) heating the gel to 165-185 ℃, cooling after the crystallization reaction is completed, and performing solid-liquid separation to obtain a liquid part, namely SAPO molecular sieve synthesis mother liquor; preferably, the crystallization reaction time is 50-80 h.
Wherein the aluminum source is selected from pseudo-boehmite and the like which are conventionally selected in the field; the silicon source is selected from silica sol and the like which are conventionally selected in the field; the template agent is selected from tetraethyl ammonium hydroxide aqueous solution with mass concentration of 20-40%.
Further, in the step (1), the SAPO molecular sieve synthesis mother liquor is a liquid obtained after solid-liquid separation of one or more symbionts in the SAPO molecular sieve with a six-membered ring, eight-membered ring, ten-membered ring or ten-membered wrinkled ring and twelve-membered ring structure.
Further, the SAPO molecular sieve with the six-membered ring structure is a symbiont of one or more of SAPO-20, SAPO-25 and SAPO-28. Wherein, the symbiont refers to that in the field of molecular sieve synthesis, other molecular sieves are associated in the synthesis process of a certain molecular sieve.
Further, the SAPO molecular sieve with the eight-membered ring structure is a symbiont of one or more of SAPO-17, SAPO-18, SAPO-26, SAPO-33, SAPO-34, SAPO-35, SAPO-39, SAPO-42, SAPO-43, SAPO-44 and SAPO-47.
Further, the SAPO molecular sieve with the ten-membered ring or ten-membered wrinkled ring structure is a symbiont of one or more of SAPO-11, SAPO-31 and SAPO-41.
Further, the SAPO molecular sieve with the twelve-membered ring structure is a symbiont of one or more of SAPO-5, SAPO-36, SAPO-37, SAPO-40 and SAPO-46.
In one embodiment of the present invention, in the step (1), the solid content of the distillation residue is 10 to 40%.
In one embodiment of the present invention, in the step (1), the distillation residue contains, on a dry basis, 40 to 80% of phosphorus pentoxide, 5 to 30% of alumina, and 1 to 10% of silica. The balance being other ingredients.
In the step (2), the mass ratio of the distillation residual liquid, the carrier and the ZSM-5 molecular sieve is 10-40: 10-60: 20-60.
In one embodiment of the present invention, in the step (2), the carrier is one or more of kaolin, halloysite, magnesium aluminum hydrotalcite, montmorillonite, bentonite, attapulgite, diatomite, and sepiolite. Furthermore, the clay may be subjected to physical or/and chemical treatment in advance, such as one or more of grinding, calcination activation, acid or/and alkali treatment, rare earth modification, phosphorus modification and intercalation treatment.
In one embodiment of the present invention, in the step (2), the ZSM-5 molecular sieve is one or more of an H-ZSM-5 molecular sieve or/and a modified ZSM-5 molecular sieve. Further, the modified ZSM-5 molecular sieve is prepared by modifying water vapor or/and elements. Furthermore, the element is modified by one or more of phosphorus, gallium, iron, silver, zinc, calcium, magnesium and rare earth elements.
In one embodiment of the present invention, in the step (2), the silica-alumina ratio of the ZSM-5 molecular sieve is 20 to 1000.
In one embodiment of the present invention, in the step (2), the slurry has a solid content of 40 to 70%. Preferably 45 to 65%.
In step (2), the curing and forming temperature is 400-600 ℃, and the time is 0.5-5 h.
The invention also provides a preparation method of the yield-increasing propylene additive.
In the present invention, the method for distilling the SAPO molecular sieve synthesis mother liquor can adopt a distillation method well known to those skilled in the art to recover the template. For example, the distillation may be carried out by a single-effect evaporator, a double-effect evaporator, a triple-effect quadruplex evaporator, a concentration evaporator, a falling film evaporator, and for example, atmospheric distillation or reduced pressure distillation may be employed in the distillation.
In the present invention, the methods of beating, mixing, forming slurry and spray forming can be both methods of beating and spray forming well known to those skilled in the art. The clay, the distillation residue of the SAPO molecular sieve synthesis mother liquor, the ZSM-5 molecular sieve and chemical water are mixed and slurried, for example, in a stirred tank, and the slurry is spray-dried, for example, by pressure type or centrifugal type spray-drying to obtain a microspherical catalyst. The order of addition of the raw materials during pulping is not limited in the present invention.
In the present invention, the curing and molding can be performed by a method known to those skilled in the art. The spray microspheres may be calcined, for example, in a rotary kiln, tunnel kiln or roaster.
The invention has the beneficial effects that:
(1) the invention introduces SAPO molecular sieve synthetic mother liquor, saves partial raw materials in the preparation process of the catalytic cracking assistant for increasing the propylene yield, also saves the post-treatment process of the SAPO molecular sieve synthetic mother liquor, saves the investment and reduces the environmental pollution.
(2) In the invention, the steps of ammonium salt slurry washing and drying after roasting and curing of the spray microspheres in the prior art are omitted, the water consumption, the energy consumption, the production period and the production cost in the preparation process of the catalytic cracking assistant for increasing the yield of the propylene are greatly reduced, and the discharge of ammonia nitrogen wastewater is avoided;
(3) the invention provides a new application of SAPO molecular sieve synthetic mother liquor, which has the advantages of easily obtained raw materials, simple preparation process and capability of effectively reducing the production cost.
(4) In the invention, the highly dispersed phosphorus, aluminum and silicon contained in the SAPO molecular sieve synthesis mother liquor are highly compatible with the carrier and the ZSM-5 molecular sieve, so that the dispersion uniformity of a matrix component and an active component in the catalytic cracking auxiliary agent is increased, the acting force between the carrier matrix and the ZSM-5 molecular sieve is enhanced, the wear resistance of the product is effectively improved, and the realization of industrial production is ensured.
(5) The inventor also unexpectedly finds that after a small amount of SAPO molecular sieve microcrystals which are difficult to separate and exist in the SAPO molecular sieve synthesis mother liquor are introduced into the catalytic cracking assistant for increasing the yield of the propylene, the octane number of gasoline and the yield of the propylene can be further improved.
Detailed Description
The following describes a method for producing a catalytic cracking aid for increasing propylene yield by using a SAPO molecular sieve synthesis mother liquor, but the invention is not limited to the specific examples.
The production area and specification of raw materials are as follows:
1. the kaolin, halloysite, magnalium hydrotalcite, montmorillonite, bentonite, attapulgite, diatomite and sepiolite are selected and used as solid, and all the solid products are industrial qualified products.
P-ZSM-5 (silica to alumina molar ratio of 27), P-Zn-ZSM-5 (silica to alumina molar ratio of 27), H-ZSM-5 (silica to alumina molar ratio of 27), conventional propylene production increasing catalytic cracking assistant (commercial brand SD-BX1, sodium oxide 0.16%), conventional catalytic cracking catalyst base (commercial brand REZEL-1, rare earth oxide 5.4%, sodium oxide 0.16%, BET specific surface area 290 m)2The pore volume of the water drop method is 0.39mL/g) are all industrial qualified products, and are produced by Sichuan Runjin and New catalytic Material Co. High silicon ZSM-5(NKF-5-260, silica to alumina molar ratio of 260), industrial grade, Tianjin Minghua catalyst, Inc.
SAPO molecular sieve synthesis mother liquor: refer to the patent CN106276970A (as example 1-6) to obtain SAPO molecular sieve crystal bloom system, after liquid-solid separation, obtain SAPO molecular sieve synthesis mother liquor, and after simple distillation to recover template agent, obtain distillation residue, the solid content of the distillation residue is 10% -40%, and the distillation residue contains 40% -80% phosphorus pentoxide, 5% -30% alumina and 1% -10% silicon dioxide.
(II) analysis method in example:
(1) aging of the catalyst: the catalytic cracking assistant for increasing the propylene by weight comprises the following components: the catalytic cracking catalyst is prepared by adding a propylene auxiliary agent into a main agent according to the proportion of 10 weight percent to 90 weight percent, and simulating the cracking performance of an industrial balancing agent by hydrothermal aging on a multi-sample catalyst rotary hydrothermal aging device produced by Beijing Hewler-Sanji green chemistry science and technology limited, wherein the aging conditions are as follows: 800 ℃ and 100% H2O (g) aging for 17h under an atmosphere.
(2) Evaluation of catalyst reaction Performance: the aged catalyst was used to evaluate the reaction performance of the catalyst on an ACE (advanced Cracking evaluation) apparatus of Kayser corporation, USA. The properties of the raw oil are shown in Table 1, the reaction temperature is 530 ℃, and the mass ratio of the oil to the catalyst is 5.
TABLE 1 Properties of the stock oils
(3) The physical and chemical properties of the catalyst are analyzed by the following methods, and specific operation methods disclosed by corresponding documents can be specifically referred to:
the chemical composition is as follows: an XRF method is adopted, reference is made to literature analysis and test technology and instruments, 2009,02: 118-;
specific surface area: according to the reference standard GB/T5816-1995, a nitrogen adsorption method is adopted;
pore volume: the standard RIPP 28-90 is determined by a water drop method, and is described in the literature, "petrochemical analysis method: RIPP test methods, ed in Yankee et al, science publishers, 1990, p 71-72;
bulk density: the measurement is carried out by a measuring cylinder method, and the standard RIPP 31-90 is shown in the literature, "petrochemical analysis method: RIPP test methods, ed. Yang Cui et al, science publishers, 1990, p 87;
abrasion index: the method is characterized in that a goose diameter tube method is adopted for determination, and standard RIPP 29-90 is obtained according to the petrochemical analysis method: RIPP test methods, ed in Yankee et al, science publishers, 1990, p 73-75;
particle size distribution: the method adopts a laser particle size method for testing, refers to the particle size analysis error and correction of a catalytic cracking catalyst in the literature, and refers to the annual meeting of petroleum refining academia of the Chinese petroleum institute 2005, Guo Yao Qing, Zhu Yuxia, Zhang lian Rong, and the like.
Example 1
And distilling the SAPO molecular sieve synthetic mother liquor to obtain distillation residual liquid of the SAPO molecular sieve synthetic mother liquor. Under the stirring condition, adding chemical water (controlling the solid content of the final slurry to be 41 percent), distillation raffinate of SAPO molecular sieve synthetic mother liquor and attapulgite into a stirring kettle, stirring for 45min, adding an H-ZSM-5 molecular sieve, stirring for 90min, and mixing the attapulgite and the SAPO molecular sieve in the proportion of attapulgite: distillation residue of SAPO molecular sieve synthesis mother liquor (on a dry basis): ZSM-5 molecular sieve 22: 28: 50, spraying and forming the slurry after gelling, and curing the obtained spray microspheres at 450 ℃ for 5 hours to obtain the catalytic cracking assistant for increasing the propylene yield, which is recorded as BX-1.
Example 2
And distilling the SAPO molecular sieve synthetic mother liquor to obtain distillation residual liquid of the SAPO molecular sieve synthetic mother liquor. Adding chemical water (controlling the solid content of the final slurry to be 47%), distillation residual liquid of SAPO molecular sieve synthetic mother liquor and montmorillonite into a stirring kettle under the stirring condition, stirring for 60min, adding a P-Zn-ZSM-5 molecular sieve, stirring for 60min, and mixing the montmorillonite, the montmorillonite and the SAPO molecular sieve synthetic mother liquor according to the mixing ratio based on the dry basis of the catalytic cracking auxiliary agent for increasing the propylene: distillation residue of SAPO molecular sieve synthesis mother liquor (on a dry basis): ZSM-5 molecular sieve 31: 25: 44, spraying and forming the slurry after gelling, and curing the obtained spray microspheres at 500 ℃ for 3.5 hours to obtain the catalytic cracking assistant for increasing the propylene yield, which is recorded as BX-2.
Example 3
And distilling the SAPO molecular sieve synthetic mother liquor to obtain distillation residual liquid of the SAPO molecular sieve synthetic mother liquor. Under the stirring condition, adding chemical water (controlling the solid content of the final slurry to be 53%), distillation residual liquid of SAPO molecular sieve synthetic mother liquor, P-ZSM-5 molecular sieve and kaolin into a stirring kettle, stirring for 120min, wherein the mixing ratio is kaolin calculated by the catalytic cracking auxiliary agent dry basis for increasing the propylene: distillation residue of SAPO molecular sieve synthesis mother liquor (on a dry basis): ZSM-5 molecular sieve 38: 23: and 39, spraying and forming the slurry after gelling, and curing the obtained spray microspheres at 550 ℃ for 3 hours to obtain the catalytic cracking assistant for increasing the propylene yield, which is recorded as BX-3.
Comparative example 1
The yield-increasing propylene additive is prepared according to the method of the embodiment 3, except that after the distillation raffinate is separated by a high-speed centrifuge to remove SAPO molecular sieve microcrystals, the distillation raffinate is mixed with other raw materials, pulped, sprayed, roasted and cured to obtain the yield-increasing propylene catalytic cracking additive, which is marked as BX-4.
The reaction performance of the catalytic cracking assistant for increasing propylene prepared in examples 1-3 and comparative example 1 was evaluated on an ACE evaluation apparatus, and the product distribution is shown in table 2.
TABLE 2 ACE evaluation results of catalytic cracking assistants for propylene production increase
As can be seen from Table 2, compared with the industrial contrast agent SD-BX1, the catalytic cracking assistant for increasing the yield of propylene prepared by the method of the invention has the advantages that the yield of propylene is obviously improved (at least 1.4 units higher than that of the industrial contrast agent SD-BX 1), and the octane number of gasoline is obviously increased (at least 1.4 units higher than that of the industrial contrast agent SD-BX 1). Meanwhile, as shown in the evaluation data of comparative example 1, the small amount of SAPO molecular sieve microcrystals which are difficult to separate and exist in the SAPO mother liquor can be introduced into the catalytic cracking assistant for increasing the propylene to further improve the gasoline octane number and the propylene yield (compared with example 3, the propylene yield and the research octane number are respectively improved by 1.1 unit and 1.0 unit). The data show that the catalytic cracking assistant for increasing the yield of the propylene, which is produced by utilizing the SAPO molecular sieve to synthesize the mother liquor, has excellent performance.
The physicochemical performance index comparison table 3 of the catalytic cracking assistant for increasing propylene and the industrial contrast agent SD-BX1 prepared in examples 1-3 and comparative example 1.
TABLE 3 physicochemical Properties of catalytic cracking auxiliary for increasing propylene yield
As can be seen from Table 3, compared with the comparison example 1 and the industrial contrast agent SD-BX1, the catalytic cracking assistant for increasing the yield of propylene prepared by the method of the invention has the advantages of low sodium oxide content, high specific surface, large pore volume, and bulk density and particle size distribution equivalent to that of industrial products, and particularly has excellent wear resistance (the smaller the wear index, the better the mechanical strength of the catalyst), which can improve the wear resistance of the assistant in industrial devices, prolong the service life of the assistant and create higher economic benefits.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (10)
1. The preparation method of the yield-increasing propylene additive is characterized by comprising the following steps:
(1) removing the template agent in the SAPO molecular sieve synthesis mother liquor to obtain refined mother liquor;
(2) and mixing the refined mother liquor, a carrier, a ZSM-5 molecular sieve and water to form slurry, and spraying, curing and forming the slurry to obtain the propylene yield-increasing additive.
2. The method for preparing a propylene stimulation adjuvant according to claim 1, wherein: the method for preparing the SAPO molecular sieve synthesis mother liquor in the step (1) comprises the following steps:
(1) mixing an aluminum source with water, and spray-drying to obtain a granular aluminum source;
(2) mixing phosphoric acid and water, sequentially adding a silicon source, a granular aluminum source and a template agent, and mixing to obtain gel;
(3) heating the gel, performing crystallization reaction, and performing solid-liquid separation to obtain a liquid part, namely SAPO molecular sieve synthesis mother liquor; preferably, the crystallization reaction time is 50-80 h.
3. The method for preparing a propylene stimulation adjuvant according to claim 1, wherein: in the step (1), the solid content of the refined mother liquor is 10-40%.
4. The method for preparing a propylene stimulation adjuvant according to claim 1, wherein: in the step (1), the refining mother liquor contains 40-80% of phosphorus pentoxide, 5-30% of alumina and 1-10% of silicon dioxide on a dry basis.
5. The method for preparing a propylene stimulation adjuvant according to claim 1, wherein: in the step (2), the mass ratio of the refined mother liquor, the carrier and the ZSM-5 molecular sieve is 10-40: 10-60: 20-60.
6. The method for preparing a propylene stimulation adjuvant according to claim 1, wherein: in the step (2), the carrier is one or more of kaolin, halloysite, magnesium-aluminum hydrotalcite, montmorillonite, bentonite, attapulgite, diatomite and sepiolite.
7. The method for preparing a propylene stimulation adjuvant according to claim 1, wherein: in the step (2), the ZSM-5 molecular sieve is one or more of an H-ZSM-5 molecular sieve and a modified ZSM-5 molecular sieve modified by steam or/and elements.
8. The method for preparing a propylene stimulation adjuvant according to claim 1, wherein: in the step (2), the silicon-aluminum ratio of the ZSM-5 molecular sieve is 20-1000.
9. The method for preparing a propylene stimulation adjuvant according to claim 1, wherein: in the step (2), the solid content of the slurry is 40-70%.
10. The propylene yield increasing aid prepared by the method according to any one of claims 1 to 9.
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| CN101204666B (en) * | 2006-12-19 | 2011-03-30 | 石大卓越科技股份有限公司 | Catalytic cracking propylene-increasing catalyst and preparation method thereof |
| CN101462741B (en) * | 2007-12-20 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite by in situ crystallization |
| US20130225893A1 (en) * | 2011-08-30 | 2013-08-29 | Shell Oil Company | Process for the preparation of olefins |
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Address after: 614000 group 3, Miaoer village, Jinsu Town, Wutongqiao District, Leshan City, Sichuan Province Patentee after: Runhe catalyst Co.,Ltd. Address before: 614803 group 3, Miaoer village, Jinsu Town, Wutongqiao District, Leshan City, Sichuan Province Patentee before: SICHUAN REZEL CATALYSTS NEW MATERIAL Co.,Ltd. |
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Denomination of invention: An additive for increasing propylene production and its preparation method Effective date of registration: 20210607 Granted publication date: 20210219 Pledgee: Chengdu SME financing Company Limited by Guarantee Pledgor: Runhe catalyst Co.,Ltd. Registration number: Y2021510000090 |
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Date of cancellation: 20220512 Granted publication date: 20210219 Pledgee: Chengdu SME financing Company Limited by Guarantee Pledgor: Runhe catalyst Co.,Ltd. Registration number: Y2021510000090 |