CN102744097B - Low wear fluidized bed catalyst and its preparation method - Google Patents

Low wear fluidized bed catalyst and its preparation method Download PDF

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CN102744097B
CN102744097B CN201110101142.3A CN201110101142A CN102744097B CN 102744097 B CN102744097 B CN 102744097B CN 201110101142 A CN201110101142 A CN 201110101142A CN 102744097 B CN102744097 B CN 102744097B
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catalyst
aluminium
phosphorus
binding agent
preparation
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CN102744097A (en
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汪哲明
陈希强
肖景娴
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention relates to a low wear fluidized bed catalyst and its preparation method, which solves the problems of serious pollution and corrosion of the preparation process and large abrasion of a catalyst during the fluidized bed catalyst preparation in the prior art. According to the invention, by calculating the weight percentage of an oxide, the catalyst comprises the following components: a) 10%-70% of molecular sieve; b) 10-30% of silicon phosphorus aluminum composite binder; and c) 20-60% of clay. The above technical scheme better solves the problem, and can be used for industrial production of the fluidized bed catalyst.

Description

Low abrasion fluidized bed catalyst and preparation method
Technical field
The present invention relates to a kind of low abrasion fluidized bed catalyst and preparation method, special taking molecular sieve as active component, for the Catalysts and its preparation method of naphtha catalytic pyrolysis preparing ethylene and propylene fluid bed.
Background technology
Ethene, propylene are very important two kinds of petrochemical materials, and current global ethene and propylene are mainly to be produced by steam cracking process.Because traditional steam cracking reaction temperature is up to 820～1000 DEG C, process energy consumption is very high, accounts for 50% of whole ethylene industry energy consumption.This process is non-catalytic free radical thermal cracking mechanism, propylene/ethylene lower (0.4～0.6) in its product.Current, face country and petrochemical industry is proposed during 11th Five-Year to energy-saving and cost-reducing 20% requirement and the propylene demand day by day increasing, traditional steam cracking process is just standing acid test.Catalytic pyrolysis is to utilize catalyst naphtha to be carried out to the process of producing low-carbon olefins by cracking.Compared with steam cracking, catalytic pyrolysis has reaction temperature low (600-780 DEG C), energy consumption significantly reduce and product propylene/ethylene than the advantage of high (0.6～1.3).This technology occurs, for the innovation of traditional steam cracking production ethylene, propylene process has brought hope.
Patent CN101114372A provides a kind of preparation method of fluid catalyst, in its process, use the aluminium oxide of hcl acidifying and aluminium colloidal sol (by hydrochloric acid peptization alumina preparation) as compound binding agent, in spray slurry, contain a large amount of chlorine species, in the use procedure of dry, the follow-up catalyst roasting process of spraying and catalyst, to discharge a large amount of chlorine, relevant device is existed to the problem that corrosion is large of polluting.
Patent USP5366948 provides a kind of preparation method of fluid catalyst, strengthen the tear strength of catalyst, but the Davison Attrition Index of prepared catalyst is still up to 15 by introducing phosphorus component.
In the preparation process of the mentioned fluid catalyst of patent CN101455977A, also will use the aluminium oxide of acidifying, inorganic acid used is hydrochloric acid, has also introduced pollution and corrosivity chlorine element in the preparation process of catalyst.
In the catalyst that patent US5456281 patent provides, used phosphorus component and silicon components as structural reinforcing agent, but catalyst still there is the higher problem of abrasion index, abrasion index is up to more than 10.
Patent CN uses and in its process, uses the aluminium oxide of hcl acidifying and aluminium colloidal sol (by hydrochloric acid peptization alumina preparation), as compound binding agent, the wear rate of the catalyst of preparation is up to more than 1.6%/h.
In sum, fluid catalyst prepared by prior art, exist the wearing and tearing of catalyst large with preparation process in pollution larger, corrode large problem.
Summary of the invention
One of technical problem to be solved by this invention is the fluid catalyst of preparing with prior art, there is the problem that attrition of catalyst is large, a kind of new fluid catalytic cracking catalyst is provided, this catalyst has advantages of that abrasion are little, the preparation method of two catalyst corresponding with one of technical solution problem of technical problem to be solved by this invention.The method has advantages of that preparation process is polluted little and corrosion is low.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows, and a kind of low abrasion fluidized bed catalyst, comprises following component by weight percentage: a) 10～70% molecular sieve; B) compound binding agent in 10～30% siliceous source, phosphorus source, aluminium source, Ludox is taking the weight percentage of oxide as 10～90% in the compound binding agent in siliceous source, phosphorus source, aluminium source, and the mol ratio of phosphorus and aluminium is 0.5～6.0: 1; C) 20～60% kaolin.
In technique scheme, the preferred version of molecular sieve be selected from there is MFI, at least one in the molecular sieve of MEL, MTW, MWW, FAU, BETA, MOR, MTT, TON, CHA, AEL, ATO or AFO topological structure; The silicon source of compound binding agent derives from Ludox; Phosphorus source, aluminium source come from aluminium dihydrogen phosphate or at least one in the aluminium oxide of phosphoric acid acidifying; In the weight percentage of oxide, Ludox is taking the preferred scope of weight percentage of oxide as 10～50% in silicon, phosphorus, aluminium compound binding agent, and the preferred scope of the mol ratio of phosphorus and aluminium is 1.0～4.5.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of fluid catalyst of low abrasion, comprises the following steps
1) molecular sieve of aequum is mixed to making beating with water and obtain mixture I;
2) the silicon source of aequum, phosphorus source, aluminium source and water are mixed to get to compound binding agent, then add the kaolin mixing making beating of aequum to obtain mixtures II;
3) mixture I is mixed with mixtures II and emulsification is less than 5 microns to the solid particle diameter in slurries and obtains below mixtures III;
4) by mixtures III under 450～270 DEG C of conditions of inlet temperature, the spray-dried particle diameter that obtains is the microspheres with solid of 10～200 microns, then at 500～700 DEG C, roasting 2-10 hour obtains required catalyst.
Wherein, through the aluminium oxide of phosphoric acid acidifying, can react preparation in 0.5～12 hour with aluminium oxide at 30～200 DEG C with phosphoric acid.Aluminium oxide can be boehmite, a diaspore or gibbsite.The solid-liquid mass ratio of phosphate aqueous solution and aluminium oxide is 0.5～4: 1.Ludox, can be acidic silicasol, alkaline silica sol, at least one in Ludox prepared by the sodium metasilicate of acidifying or waterglass.
Adopt the preparation method in the present invention, in catalyst spray slurry, introduce free from chloride compound binding agent, substitute the alumina binder of traditional aluminium colloidal sol (by hydrochloric acid peptization alumina preparation) or hcl acidifying, in catalyst slurry with calcined catalyst, contain hardly contaminative and corrosive chlorine element, therefore preparation process is polluted little low with corrosion.The wearing valve of fluid catalyst prepared by employing this patent method is 0.8～1.2%/h, and the low 0.4～1.0%/h of catalyst preparing than existing method, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
After the ZSM-5 of aequum (MFI structure) molecular sieve, kaolin, silicon phosphorus aluminium compound binding agent and water are mixed, emulsification to the solid particle diameter in slurries is less than below 5 microns.Wherein silicon phosphorus aluminium compound binding agent is in weight hundred scores of oxide, Ludox (SiO 2weight percentage be 40%) shared ratio is 90%, phosphorus al binder is aluminium dihydrogen phosphate.By slurries, under the condition of 450 DEG C of inlet temperatures, the spray-dried particle diameter that obtains is the microspheres with solid of 10～200 microns, and then at 500 DEG C, roasting obtains required fluid catalyst for 10 hours.Catalyst is by weight percentage: 35%ZSM-5: 35% kaolin: 20% sial phosphorus compound binding agent.
[embodiment 2]
After the ZSM-22 of aequum (TON structure) molecular sieve, kaolin, compound binding agent and water are mixed, emulsification to the solid particle diameter in slurries is less than below 5 microns.Wherein silicon phosphorus aluminium compound binding agent is in weight hundred scores of oxide, Ludox (SiO 2weight percentage be 40%) shared ratio is 10%, phosphorus al binder is the aluminium oxide of phosphoric acid acidifying, the mol ratio of phosphorus and aluminium is 3.0.By slurries, under the condition of 350 DEG C of inlet temperatures, the spray-dried particle diameter that obtains is the microspheres with solid of 10～200 microns, and then at 700 DEG C, roasting obtains required fluid catalyst for 2 hours.Catalyst is 10%ZSM-22 by weight percentage: 60% kaolin: 30% sial phosphorus compound binding agent.
[embodiment 3]
After the ZSM-11 of aequum (MEL structure) molecular sieve, kaolin, compound binding agent and water are mixed, emulsification to the solid particle diameter in slurries is less than below 5 microns.Wherein silicon phosphorus aluminium compound binding agent is in weight hundred scores of oxide, Ludox (SiO 2weight percentage be 40%) shared ratio is 50%, phosphorus al binder is the aluminium oxide of phosphoric acid acidifying, the mol ratio of phosphorus and aluminium is 0.5.By slurries, under the condition of 270 DEG C of inlet temperatures, the spray-dried particle diameter that obtains is the microspheres with solid of 10～200 microns, and then at 600 DEG C, roasting obtains required fluid catalyst for 4 hours.Catalyst is 55%ZSM-11 by weight percentage: 20% kaolin: 25% sial phosphorus compound binding agent.
[embodiment 4]
After the SAPO-34 of aequum (CHA structure) molecular sieve, kaolin, compound binding agent and water are mixed, emulsification to the solid particle diameter in slurries is less than below 5 microns.Wherein silicon phosphorus aluminium compound binding agent is in weight hundred scores of oxide, Ludox (SiO 2weight percentage be 40%) shared ratio is 70%, phosphorus al binder is the aluminium oxide of phosphoric acid acidifying, the mol ratio of phosphorus and aluminium is 6.0.By slurries, under the condition of 350 DEG C of inlet temperatures, the spray-dried particle diameter that obtains is the microspheres with solid of 10～200 microns, and then at 600 DEG C, roasting obtains required fluid catalyst for 4 hours.Catalyst is by weight percentage: catalyst is by weight percentage: 60%SAPO-34: 20% kaolin: 20% sial phosphorus compound binding agent.
[embodiment 5]
After the SAPO-5 of aequum (ATO structure) molecular sieve, kaolin, compound binding agent and water are mixed, emulsification to the solid particle diameter in slurries is less than below 5 microns.Wherein silicon phosphorus aluminium compound binding agent is in weight hundred scores of oxide, Ludox (SiO 2weight percentage be 40%) shared ratio is 30%, phosphorus al binder is the aluminium oxide of phosphoric acid acidifying, the mol ratio of phosphorus and aluminium is 2.0.By slurries, under the condition of 350 DEG C of inlet temperatures, the spray-dried particle diameter that obtains is the microspheres with solid of 10～200 microns, and then at 600 DEG C, roasting obtains required fluid catalyst for 4 hours.Catalyst is by weight percentage: 70%ZSM-5: 10% kaolin: 20% sial phosphorus compound binding agent.
[embodiment 6]
After the MCM-22 of aequum (MWW structure), ZSM-23 (MTT structure), SAPO-11 (AEL structure) molecular sieve, ZSM-12 (MTW structure), SAPO-41 (AFO structure) molecular sieve, kaolin, compound binding agent and water are mixed, emulsification to the solid particle diameter in slurries is less than below 5 microns.Wherein silicon phosphorus aluminium compound binding agent is in weight hundred scores of oxide, Ludox (SiO 2weight percentage be 40%) shared ratio is 90%, phosphorus al binder is aluminium dihydrogen phosphate.By slurries, under the condition of 350 DEG C of inlet temperatures, the spray-dried particle diameter that obtains is the microspheres with solid of 10～200 microns, and then at 600 DEG C, roasting obtains required fluid catalyst for 4 hours.Catalyst is by weight percentage: 10%MCM-22: 20%ZSM-23: 15%SAPO-11: 15%ZSM-12: 10%SAPO-41: 20% kaolin: 10% sial phosphorus compound binding agent.
[embodiment 7]
After the USY of aequum (FAU structure), Beta (BEA structure), MOR (MOR structure) molecular sieve, kaolin, compound binding agent and water are mixed, emulsification to the solid particle diameter in slurries is less than below 5 microns.Wherein silicon phosphorus aluminium compound binding agent is in weight hundred scores of oxide, Ludox (SiO 2weight percentage be 40%) shared ratio is 50%, aluminium dihydrogen phosphate proportion is 25%, the aluminium oxide proportion of phosphoric acid acidifying is 25% (mol ratio of phosphorus and aluminium is 6.0).By slurries, under the condition of 350 DEG C of inlet temperatures, the spray-dried particle diameter that obtains is the microspheres with solid of 10～200 microns, and then at 600 DEG C, roasting obtains required fluid catalyst for 4 hours.Catalyst is 20%USY: 20%Beta: 20%MOR by weight percentage: 20% kaolin: 20% sial phosphorus compound binding agent.
[embodiment 8]
After the ZSM-5 of aequum (MFI structure) molecular sieve, kaolin, silicon phosphorus aluminium compound binding agent and water are mixed, emulsification to the solid particle diameter in slurries is less than below 5 microns.Wherein silicon phosphorus aluminium compound binding agent is in weight hundred scores of oxide, Ludox (SiO 2weight percentage be 40%) shared ratio is 75%, phosphorus al binder is aluminium dihydrogen phosphate.By slurries, under the condition of 350 DEG C of inlet temperatures, the spray-dried particle diameter that obtains is the microspheres with solid of 10～200 microns, and then at 500～700 DEG C, roasting obtains required fluid catalyst for 2～10 hours.Catalyst is 60%ZSM-5 by weight percentage: 25% kaolin: 15% sial phosphorus compound binding agent.
[comparative example 1]
By the ZSM-5 of aequum (MFI structure) molecular sieve, kaolin, acidifying aluminium oxide, after aluminium colloidal sol (wherein chlorine is 2.0 with the weight ratio of aluminium element) and water mix, emulsification to the solid particle diameter in slurries is less than below 5 microns.Acidifying aluminium oxide, wherein the weight ratio of HCl and aluminium oxide is 0.15, within 2 hours, makes with processing aluminium oxide at 60 DEG C of concentrated hydrochloric acids.In aluminium oxide, acidifying aluminium oxide and aluminium colloidal sol ratio be 1: 1.By slurries, under the condition of 350 DEG C of inlet temperatures, the spray-dried particle diameter that obtains is the microspheres with solid of 10～200 microns, and then at 600 DEG C, roasting obtains comparative example catalyst for 4 hours.Catalyst is 35%ZSM-5 by weight percentage: 35% kaolin: 30%Al 2o 3.
[comparative example 2]
After the ZSM-5 of aequum (MFI structure) molecular sieve, clay, aluminium colloidal sol (wherein chlorine is 2.0 with the weight ratio of aluminium element) and water are mixed, emulsification to the solid particle diameter in slurries is less than below 5 microns.Acidifying aluminium oxide, wherein the weight ratio of HCl and aluminium oxide is 0.15, within 2 hours, makes with processing aluminium oxide at 60 DEG C of concentrated hydrochloric acids.In aluminium oxide, acidifying aluminium oxide and aluminium colloidal sol ratio be 0.5: 1.By slurries, under the condition of 350 DEG C of inlet temperatures, the spray-dried particle diameter that obtains is the microspheres with solid of 10～200 microns, and then at 600 DEG C, roasting obtains comparative example catalyst for 4 hours.Catalyst is 55%ZSM-5 by weight percentage: 25% kaolin: 20%Al 2o 3.
The wearing valve of table 1 different catalysts
By relatively can finding out of embodiment and comparative example, the wearing valve of catalyst prepared by employing this patent method is 0.8～12%/h, low 0.4～the 1.0%/h of catalyst preparing than existing method, in catalyst slurry with calcined catalyst in hardly containing pollute with corrosive chlorine element, have advantages of attrition of catalyst low with preparation process pollute, corrode little.

Claims (1)

1. a preparation method for the fluid catalyst of low abrasion, step is as follows:
After ZSM-22 molecular sieve, kaolin, compound binding agent and the water of aequum are mixed, emulsification to the solid particle diameter in slurries is less than below 5 microns; Wherein silicon phosphorus aluminium compound binding agent is with the weight percent meter of oxide, and the shared ratio of Ludox is 10%, SiO in described Ludox 2weight percentage be 40%, phosphorus al binder is the aluminium oxide of phosphoric acid acidifying, the mol ratio of phosphorus and aluminium is 3.0; By slurries, under the condition of 350 DEG C of inlet temperatures, the spray-dried particle diameter that obtains is the microspheres with solid of 10～200 microns, and then at 700 DEG C, roasting obtains required fluid catalyst for 2 hours; Catalyst is 10%ZSM-22:60% kaolin by weight percentage: 30% sial phosphorus compound binding agent.
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CN104549449B (en) * 2013-10-28 2017-02-15 中国石油化工股份有限公司 Wear-resistant catalytic cracking fluidized bed catalyst and preparation method thereof
CN104549551B (en) * 2013-10-28 2017-03-29 中国石油化工股份有限公司 A kind of method for preparing microsphere FCC catalyst

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CN1704163A (en) * 2004-05-28 2005-12-07 中国石油化工股份有限公司 Molecular screen microspherical catalyst
CN101318143A (en) * 2008-06-12 2008-12-10 中国石油化工股份有限公司 Method for preparing molecular sieve fluidized bed catalyst

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US7375048B2 (en) * 2004-04-29 2008-05-20 Basf Catalysts Llc ZSM-5 additive

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1704163A (en) * 2004-05-28 2005-12-07 中国石油化工股份有限公司 Molecular screen microspherical catalyst
CN101318143A (en) * 2008-06-12 2008-12-10 中国石油化工股份有限公司 Method for preparing molecular sieve fluidized bed catalyst

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