CN102019197A - Synthetic method of kaolin microsphere in-situ crystallization product containing small-grain NaY molecular sieve - Google Patents
Synthetic method of kaolin microsphere in-situ crystallization product containing small-grain NaY molecular sieve Download PDFInfo
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- CN102019197A CN102019197A CN2009100931144A CN200910093114A CN102019197A CN 102019197 A CN102019197 A CN 102019197A CN 2009100931144 A CN2009100931144 A CN 2009100931144A CN 200910093114 A CN200910093114 A CN 200910093114A CN 102019197 A CN102019197 A CN 102019197A
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- kaolin
- molecular sieve
- roasting
- nay molecular
- deionized water
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000005995 Aluminium silicate Substances 0.000 title claims abstract description 55
- 235000012211 aluminium silicate Nutrition 0.000 title claims abstract description 55
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 42
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002425 crystallisation Methods 0.000 title claims abstract description 40
- 230000008025 crystallization Effects 0.000 title claims abstract description 39
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 25
- 239000004005 microsphere Substances 0.000 title claims abstract description 25
- 238000010189 synthetic method Methods 0.000 title claims description 3
- 239000013078 crystal Substances 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 12
- 239000006259 organic additive Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 6
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims abstract description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 claims abstract description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims abstract description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000012452 mother liquor Substances 0.000 claims abstract description 3
- 239000011806 microball Substances 0.000 claims description 20
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- 210000002966 serum Anatomy 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000010009 beating Methods 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 24
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract 3
- 238000002156 mixing Methods 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000011268 mixed slurry Substances 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 11
- 238000004523 catalytic cracking Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004231 fluid catalytic cracking Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Abstract
The invention relates to a method for synthesizing kaolin microsphere in-situ crystallization containing small-grain NaY molecular sieve; taking kaolin as a raw material, adding deionized water and sodium silicate or sodium pyrophosphate for mixing and pulping, spray-drying the mixed slurry to prepare kaolin spray microspheres with the particle size of 20-110 mu m, roasting a part of the kaolin spray microspheres at 920-900 ℃ for 1-3h to obtain high-temperature roasted microspheres, and roasting the other part of the kaolin spray microspheres at 700-900 ℃ for 1-3h to obtain metakaolin microspheres; mixing the high-temperature roasted microspheres and the metakaolin microspheres according to the mass ratio of 9: 1-1: 9, adding sodium silicate, a guiding agent, a sodium hydroxide solution, deionized water and an organic additive, and crystallizing at 90-95 ℃ for 16-36 hours; filtering to remove the mother liquor, and drying to obtain the kaolin microsphere in-situ crystal with NaY molecular sieve crystal particles of 200-400 nm.
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 exposed, and increase in the aperture of exposing, and micro channel shortens, and makes the big molecule of heavy oil easier of the activated centre, the easier stripping of crackate, 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 by adding hetero atom to increase the nucleus quantity in the synthetic system, adds a spot of at least a elements such as B, V, P, Mo, W, Ce that are selected from directed agents, has reduced zeolite crystal; CN1073968 discloses a kind of rare earth ion that adds to make the NaY molecular sieve of little crystal grain in the crystallization system; CN111384, CN1160676A, CN1033503C, CN1032803C, CN1133585C and US4587115 have invented the method that reduces zeolite crystal by 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, synthetic and the performance of sub-micron NaY molecular sieve, the Shandong petrochemical industry, 2002,30 (1): 6～9), because the reaction condition of FCC harshness, 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.Studies show that, adopt conventional method, just can make crystal grain with the kaolin in-situ crystallization method is 400-600nm left and right sides NaY molecular sieve, because specific molecule sieve growth course, make its hydrothermal stability apparently higher than with the synthetic 800-1000nm left and right sides NaY molecular sieve of gel method, 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 feature about 400-600nm and good heavy oil conversion performance 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 filter cake is washed till pH with deionized water, 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 adopting in position crystallization, the present invention adds organic solvent, the depolymerization of silicate during with the quickening hydrothermal crystallizing, while further wetting solid-liquid reaction interface, disperse directed agents, increase 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 is not subjected to the restriction of following specific embodiment.
What relate among the embodiment mainly is analyzed as follows:
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.
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 the results are shown in 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 the results are shown in 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 the results are shown in 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 the results are shown in 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
As seen 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.
From accompanying drawing 1 as seen, 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) with high-temperature roasting microballoon and metakaolin microballoon in mass ratio 9: 1-1: after 9 ratio is 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 filter cake is washed till pH with deionized water, 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 |
| CN102701232A (en) * | 2012-06-08 | 2012-10-03 | 西北化工研究院 | Preparation method of NaY molecular sieve |
| CN104275205A (en) * | 2013-07-12 | 2015-01-14 | 中国石油天然气股份有限公司 | Preparation method of catalyst for improving yield of catalytic cracking diesel oil |
| CN104307544A (en) * | 2014-11-05 | 2015-01-28 | 吴俊荣 | Method for preparing catalytic cracking catalyst |
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| CN1163301C (en) * | 2000-07-19 | 2004-08-25 | 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 |
| 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 |
| CN1275855C (en) * | 2003-03-28 | 2006-09-20 | 中国石油化工股份有限公司 | Nano-grade Y type zeolite synthesized from kaolin and its preparation metod |
| CN100429149C (en) * | 2004-11-26 | 2008-10-29 | 中国石油天然气股份有限公司 | Preparation method for synthesizing high-content NaY molecular sieve by kaolin spray microspheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102701232A (en) * | 2012-06-08 | 2012-10-03 | 西北化工研究院 | Preparation method of NaY molecular sieve |
| CN102701232B (en) * | 2012-06-08 | 2014-07-09 | 西北化工研究院 | Preparation method of NaY molecular sieve |
| CN104275205A (en) * | 2013-07-12 | 2015-01-14 | 中国石油天然气股份有限公司 | Preparation method of catalyst for improving yield of catalytic cracking diesel oil |
| CN104307544A (en) * | 2014-11-05 | 2015-01-28 | 吴俊荣 | Method for preparing catalytic cracking catalyst |
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