CN102019197B - Method for synthesizing kaolin microsphere in-situ crystallized product containing small crystal grain NaY molecular sieves - Google Patents
Method for synthesizing kaolin microsphere in-situ crystallized product containing small crystal grain NaY molecular sieves Download PDFInfo
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- CN102019197B CN102019197B CN2009100931144A CN200910093114A CN102019197B CN 102019197 B CN102019197 B CN 102019197B CN 2009100931144 A CN2009100931144 A CN 2009100931144A CN 200910093114 A CN200910093114 A CN 200910093114A CN 102019197 B CN102019197 B CN 102019197B
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Abstract
The invention relates to a method for synthesizing a kaolin microsphere in-situ crystallized product containing small crystal grain NaY molecular sieves. Kaolin is used as a raw material. The method comprises the following steps of: adding deionized water and sodium silicate or sodium pyrophosphate into the kaolin, mixing and slurrying, performing spray drying on the mixed slurry to prepare kaolin spray microspheres with particle diameters of 20 to 110 microns, roasting a part of the kaolin spray microspheres for 1 to 3 hours at the temperature of between 920 and 1,000 DEG C to obtain high-temperature roasted microspheres, and roasting the other part of the kaolin spray microspheres for 1 to 3 hours at the temperature of between 700 and 900 DEG C to obtain metakaolin microspheres; mixing the high-temperature roasted microspheres and the metakaolin microspheres in a mass ratio of 9:1-1:9, adding sodium silicate, directing agent, sodium hydroxide solution, deionized water and organic additive into the mixture, and crystallizing for 16 to 36 hours at the temperature of between 90 and 95 DEG C; and filtering, removing mother solution, and drying the filtrate to obtain the kaolin microsphere in-situ crystallized product containing NaY molecular sieve crystal grains of 200 to 400 nanometers.
Description
Technical field
The present invention relates to a kind of is raw material with the kaolin atomized microball, and in-situ crystallization synthesizes and contains the method that crystal grain is the kaolin microsphere in-situ crystallization thing of 200-400nm small crystal grain NaY molecular sieve.Can be used as the parent of preparation catalytic cracking catalyst with the synthetic kaolin microsphere in-situ crystallization thing of this method.
Background technology
The NaY molecular sieve is as the topmost active component of fluid catalytic cracking (FCC) catalyst, and its performance directly affects the reaction result of catalytic cracking, to the economic benefit important influence of catalytic cracking unit.The purpose of catalytic cracking reaction is exactly that macromolecular heavy charge is passed through catalytic reaction, generates the process of little molecule products such as gasoline, diesel oil, liquefied gas.
How reduction along with the oil refining profit improves catalytic cracking process purpose product yield cost-effectively, is the challenge that petroleum refining industry faces always.The particle diameter of conventional industrial NaY molecular sieve is generally at 800-1000nm, and crystal grain is big, and the duct is long, and outer surface is little, has influenced the catalytic performance of catalyst.Small crystal grain molecular sieve FCC catalyst is because the particle diameter of molecular sieve diminishes, and more activated centre is able to expose, and increase in the aperture of exposing, and micro channel shortens, and makes the big molecule of heavy oil more easily near the activated centre, and crackate more is prone to stripping, diffusion.Both improved the cracking ability of heavy oil; Reduced the secondary response of midbarrel again, yield of light oil is improved, coke yield reduces; Show good cracking activity and product selectivity (Camblor M A; Corma A.Benefits in Activity and Selectivityof Small Y Zeolite Crystallites Stabilized by a Higher Silicon-to-Aluminum Ratio bySynthesis [J] .Applied Catalysis, 1989,55:65～74).Have predictable superperformance just because of small crystal grain NaY molecular sieve, the researcher furthers investigate the synthetic of small crystal grain NaY molecular sieve both at home and abroad.
Some patent reports have been had synthesizing of small crystal grain NaY molecular sieve.US3864282 has reported that the method that adopts the hot crushing technology of physics to handle the NaY molecular sieve is reduced to below the 100nm zeolite crystal; US3755538 has invented through adding hetero atom to increase the nucleus quantity in the synthetic system, in directed agents, adds a spot of at least a elements such as B, V, P, Mo, W, Ce that are selected from, and has reduced zeolite crystal; CN1073968 discloses a kind of rare earth ion that in the crystallization system, adds to make the NaY molecular sieve of little crystal grain; CN111384, CN1160676A, CN1033503C, CN1032803C, CN1133585C and US4587115 have invented the method that reduces zeolite crystal through the optimization synthesis condition, but complicated operating process, industrializing implementation is difficult; CN1081425, CN1785808 and CN1789125 adopt two sections temperature-switching methods to prepare the small crystal grain NaY molecular sieve of 100-500nm, but operating temperature has surpassed the condition that conventional industrial crystallization temperature is lower than 100 ℃, and scrap build, running cost are higher; CN1840475 invented a kind of with crown ether add to synthetic system with the preparation small crystal grain NaY molecular sieve the preparation method, this method cost is higher; US 4778666 has invented the method that adopts the microwave method synthesis of molecular sieve, at present can't industrialization; Among the CN107438C disclosed method be in synthetic system, add can with the water-soluble organic complexing agent of aluminium salt complexing such as acetate, citric acid, ethylenediamine tetra-acetic acid etc.; US 4372931 is to become under the prerequisite of glue at low temperature with EP 0041338A disclosed method, adds monose or polysaccharide.
Though foregoing invention can make the small crystal grain NaY molecular sieve of 50-500nm, the method that adopts all synthesizes the basis with the silica-alumina gel hydro-thermal.There are some researches show (Shen Shimin, the synthetic and performance of sub-micron NaY molecular sieve, Shandong petrochemical industry; 2002,30 (1): 6～9), because the harsh reaction condition of FCC; When the crystal grain of the synthetic NaY molecular sieve of gel method drops to 500nm when following; Its stability decreases is very fast, can not satisfy the requirement of FCC catalyst to NaY molecular sieve stability, makes the application of small crystal grain NaY molecular sieve in catalytic cracking catalyst of prior art for preparing be restricted.
In the evolution of catalytic cracking catalyst; U.S. Engelhard company is the technology that the synthetic NaY molecular sieve of raw material, in-situ crystallization prepares the FCC catalyst with kaolin; Opened up the new way of a preparation high-performance catalytic cracking catalyst; A series of patents such as US 5023220, US 5559067, US 6656347, US 6716338, US 6942783, US 6943132 and US 7101473 have been authorized in application, and are wherein the most representative with the US4493902 patent that people such as Brown delivered in 1985.Research shows; Adopt conventional method; Use the kaolin in-situ crystallization method just can make crystal grain and be 400-600nm left and right sides NaY molecular sieve; Because specific molecule sieve growth course makes its hydrothermal stability apparently higher than with the synthetic 800-1000nm left and right sides NaY molecular sieve of gel method, and is especially with the obvious advantage at the mink cell focus conversion aspect.The in-situ crystallization patented technology ZL200410091494.5 of PetroChina Company Ltd. exploitation, it is characteristic and good heavy oil conversion performance about 400-600nm that prepared NaY molecular sieve has crystal grain equally.
Summary of the invention
The objective of the invention is with the kaolin atomized microball is raw material; In-situ crystallization synthesizes and contains the method that crystal grain is the kaolin microsphere in-situ crystallization thing of 200-400nm small crystal grain NaY molecular sieve, can be used as the parent of preparation catalytic cracking catalyst with the synthetic kaolin microsphere in-situ crystallization thing of this method.
Realize that technical scheme of the present invention is:
(1) with kaolin be raw material, add the making beating of deionized water and dispersant, dispersant is sodium metasilicate or sodium pyrophosphate, and addition is the 2-10% of kaolin quality, and the kaolin mass content is 25-45%, and surplus is a water;
(2) the kaolin mixed serum is prepared into the kaolin atomized microball CS of particle diameter at 20-110 μ m through spray-drying; With kaolin atomized microball CS is raw material; A part of kaolin atomized microball is obtained high-temperature roasting microballoon CP at 920-1000 ℃ of roasting 1-3h, and another part kaolin atomized microball obtains metakaolin microballoon CM at 700-900 ℃ of roasting 1-3h;
(3) with high-temperature roasting microballoon CP and metakaolin microballoon CM according to 9: 1-1: after 9 mass ratio mixes; Add sodium metasilicate, directed agents, sodium hydroxide solution, deionized water and organic additive and mix, the mass ratio that adds raw material in the mixed solution is (1.0-1.2) kaolin roasting microballoon: (5.0-12.0) sodium metasilicate: (0.3-0.7) directed agents: (1.5-4.0) sodium hydroxide solution: (0.5-1.5) deionized water; The sodium metasilicate mass concentration is 20%, and the NaOH mass concentration is 18%, and directed agents consists of in molar ratio:
(14-16) SiO
2: (0.7-1.3) Al
2O
3: (14-16) Na
2O: (300-330) H
2O, organic additive are PVP or polyvinyl alcohol, and the organic additive addition is kaolin roasting microballoon gross mass 1%-10%;
(4) in 90-95 ℃ of crystallization 16-36h;
(5) remove by filter mother liquor, it is below 10.5 that cakes with deionized water is washed till pH, the kaolin microsphere in-situ crystallization thing that to obtain a kind of NaY of comprising zeolite crystal after the drying be 200-400nm.
When mainly being employed in in-situ crystallization, the present invention adds organic solvent; The depolymerization of silicate during with the quickening hydrothermal crystallizing; Further wetting solid-liquid reaction interface disperses directed agents simultaneously, increases into nuclear volume and in-situ crystallization active sites; The kaolin microsphere in-situ crystallization product that to obtain a kind of NaY of comprising zeolite crystal be 200-400nm has reduced the crystal grain of NaY molecular sieve.This in-situ crystallization product that comprises small crystal grain NaY molecular sieve can be predicted and high performance catalytic cracking catalyst can be prepared.
Description of drawings
The sem photograph (SEM) of Fig. 1 embodiment 7 in-situ crystallization NaY molecular sieves and Comparative Examples.
The sem photograph (SEM) of Fig. 2 embodiment 8 in-situ crystallization NaY molecular sieves and Comparative Examples
The sem photograph (SEM) of Fig. 3 embodiment 9 in-situ crystallization NaY molecular sieves and Comparative Examples
The sem photograph (SEM) of Fig. 4 embodiment 10 in-situ crystallization NaY molecular sieves and Comparative Examples
The specific embodiment
The present invention does not receive the restriction of following specific embodiment.
The main analysis that relates among the embodiment is following:
The kaolin testing graininess adopts the laser particle analyzer method, and method standard is Q/SYLS 0519-2002; X-ray powder diffraction is adopted in the test of NaY molecular sieve crystallinity, and method standard is Q/SYLS 0596-2002; X-ray powder diffraction is adopted in the test of NaY molecular sieve silica alumina ratio, and method standard is Q/SYLS 0573-2002, and above method is Petroleum Chemical Engineering Institute of a CNPC standard; NaY zeolite crystal size adopts the S-4800 sem test of FDAC.
Embodiment 1-embodiment 3 is the preparation method of kaolin atomized microball.
Embodiment 1
With kaolin 2000g (burn base), sodium metasilicate 4%, adding deionized water, to be prepared into the kaolin solid content be 42% mixed serum, spray-drying obtains the kaolin atomized microball CS1 of 1840g particle diameter at 20-110 μ m.
Embodiment 2
With kaolin 2000g (burn base), sodium metasilicate 9%, adding deionized water, to be prepared into the kaolin solid content be 28% mixed serum, spray-drying obtains the kaolin atomized microball CS2 of 1710g particle diameter at 20-110 μ m.
Embodiment 3
With kaolin 2000g (burn base), sodium pyrophosphate 6%, adding deionized water, to be prepared into the kaolin solid content be 35% mixed serum, spray-drying obtains the kaolin atomized microball CS3 of 1632g particle diameter at 20-110 μ m.Embodiment 4-embodiment 8 is the preparation method of kaolin roasting microballoon.
Embodiment 4
The CS1 atomized microball is divided into two parts, and first part at 930 ℃ of following roasting 2.8h, obtain high-temperature roasting kaolin microsphere CP1, and second part at 730 ℃ of following roasting 2.8h, obtain metakaolin microballoon CM1.
Embodiment 5
The CS2 atomized microball is divided into two parts, and first part at 960 ℃ of following roasting 2.2h, obtain high-temperature roasting kaolin microsphere CP2, and second part at 780 ℃ of following roasting 2.0h, obtain metakaolin microballoon CM2.
Embodiment 6
The CS3 atomized microball is divided into two parts, and first part at 985 ℃ of following roasting 1.4h, obtain high-temperature roasting kaolin microsphere CP3, and second part at 850 ℃ of following roasting 1.5h, obtain metakaolin microballoon CM3.It is the preparation of small crystal grain NaY molecular sieve content crystallization microballoon that embodiment 7-implements 9
Embodiment 7
It is raw material that present embodiment adopts the roasting microballoon (embodiment 4) of CS1 atomized microball (embodiment 1) preparation; Carry out the preparation of small crystal grain NaY molecular sieve content crystallization microballoon; The polyvinyl alcohol addition is 8% of a roasting microspheres quality, and crystallization result sees table 1, and grain size is seen accompanying drawing 1.
It is raw material that present embodiment adopts the roasting microballoon (embodiment 5) of CS2 atomized microball (embodiment 2) preparation; Carry out the preparation of small crystal grain NaY molecular sieve content crystallization microballoon; The addition of polyvinyl alcohol is 3% of a roasting microspheres quality, and crystallization result sees table 1, and grain size is seen accompanying drawing 2.
Embodiment 9
It is raw material that present embodiment adopts the roasting microballoon (embodiment 6) of CS3 atomized microball (embodiment 3) preparation; Carry out the preparation of small crystal grain NaY molecular sieve content crystallization microballoon; The addition of PVP is 6% of a roasting microspheres quality, and crystallization result sees table 1, and grain size is seen accompanying drawing 3.
Embodiment 10 is the comparative example.
Embodiment 10
Present embodiment is the comparative example, and except that the crystallization system does not add the organic additive, other all synthesis conditions are with embodiment 9, and crystallization result sees table 1, and grain size is seen accompanying drawing 4.
The preparation result of the high NaY molecular sieve content of table 1 in-situ crystallization microballoon
Visible from table 1, after the crystallization system is introduced organic additive, the synthetic NaY molecular sieve of in-situ crystallization not only is free from side effects, and has improved degree of crystallinity and silica alumina ratio.
Visible from accompanying drawing 1, to compare with Comparative Examples, after the crystallization system was introduced organic additive, NaY zeolite crystal size obviously reduced, and main crystal grain is distributed in 200-400nm.
Claims (1)
1. synthetic method that contains the kaolin microsphere in-situ crystallization thing of small crystal grain NaY molecular sieve is characterized in that:
(1) with kaolin be raw material, add the making beating of deionized water and dispersant, dispersant is sodium metasilicate or sodium pyrophosphate, and addition is the 2-10% of kaolin quality, and kaolin stereoplasm amount content is 25-45%, and surplus is a deionized water;
(2) the kaolin mixed serum is prepared into the kaolin atomized microball of particle diameter at 20-110 μ m through spray-drying; With the kaolin atomized microball is raw material; A part of kaolin atomized microball is obtained the high-temperature roasting microballoon at 920-1000 ℃ of roasting 1-3h, and another part kaolin atomized microball obtains the metakaolin microballoon at 700-900 ℃ of roasting 1-3h;
(3) high-temperature roasting microballoon and metakaolin microballoon are pressed mass ratio 9: 1-1: after 9 the mixed; Adding sodium metasilicate, directed agents, sodium hydroxide solution, deionized water and organic additive mixes; The mass ratio that adds raw material in the mixed solution is (1.0-1.2) kaolin roasting microballoon: (5.0-12.0) sodium metasilicate: (0.3-0.7) directed agents: (1.5-4.0) sodium hydroxide solution: (0.5-1.5) deionized water; The sodium metasilicate mass concentration is 20%; NaOH mass concentration 18%, directed agents are formed:
(14-16)SiO
2∶(0.7-1.3)Al
2O
3∶(14-16)Na
2O∶(300-330)H
2O
Organic additive is a kind of in PVP and the polyvinyl alcohol, and the organic additive addition is kaolin roasting microballoon gross mass 1-10%;
(4) in 90-95 ℃ of crystallization 16-36h;
(5) remove by filter mother liquor, it is below 10.5 that cakes with deionized water is washed till pH, the kaolin microsphere in-situ crystallization thing that to obtain a kind of NaY of containing zeolite crystal after the drying be 200-400nm.
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| CN102049278B (en) * | 2009-10-27 | 2012-08-29 | 中国石油化工股份有限公司 | Small-grain Y-type molecular sieve dispersing material |
| CN102701232B (en) * | 2012-06-08 | 2014-07-09 | 西北化工研究院 | Preparation method of NaY molecular sieve |
| CN104275205B (en) * | 2013-07-12 | 2016-05-11 | 中国石油天然气股份有限公司 | A kind of preparation method of the catalyst that improves catalytic cracking diesel oil yield |
| CN104307544B (en) * | 2014-11-05 | 2016-10-26 | 吴俊荣 | The preparation method of catalytic cracking catalyst |
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| CN1334318A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for preparing full-clay high octane number catalytic cracking catalyst |
| CN1334142A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for synthesizing molecular sieve from gaolin |
| CN1533982A (en) * | 2003-03-28 | 2004-10-06 | �й�ʯ�ͻ����ɷ�����˾ | Nano-grade Y type zeolite synthesized from kaolin and its preparation metod |
| CN1778676A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Production for synthesizing high-content NaY molecular sieve from kaolin atomized microball |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1334318A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for preparing full-clay high octane number catalytic cracking catalyst |
| CN1334142A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for synthesizing molecular sieve from gaolin |
| CN1533982A (en) * | 2003-03-28 | 2004-10-06 | �й�ʯ�ͻ����ɷ�����˾ | Nano-grade Y type zeolite synthesized from kaolin and its preparation metod |
| CN1778676A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Production for synthesizing high-content NaY molecular sieve from kaolin atomized microball |
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