CN1110252A - Method for synthetizing ultramacropore molecular sieve - Google Patents

Method for synthetizing ultramacropore molecular sieve Download PDF

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CN1110252A
CN1110252A CN 94110178 CN94110178A CN1110252A CN 1110252 A CN1110252 A CN 1110252A CN 94110178 CN94110178 CN 94110178 CN 94110178 A CN94110178 A CN 94110178A CN 1110252 A CN1110252 A CN 1110252A
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molecular sieve
sio
sieve mcm
super macroporous
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CN1045424C (en
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李宏愿
王清遐
赵修松
徐龙伢
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Dalian Institute of Chemical Physics of CAS
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Abstract

A kind of synthetic method of super macroporous molecular sieve MCM-41 uses Inorganic silicon dioxide, inorganic acid, inorganic base, aluminate (or aluminium salt) are original Material, only uses a kind of structure in the synthesis process are as follows: Wherein: R1, R2 or R3 are the alkyl of C1~C5; R ' is the alkyl of C5~C24; H is OH-, and the surfactant of F-, Cl-, Br- or I- ion make directed agents. The soluble-salt containing transition metal element can also be added in that synthesis, the super macroporous molecular sieve MCM-41 containing metallic element is made.

Description

Method for synthetizing ultramacropore molecular sieve
The invention provides a kind of preparation method of molecular sieve, specifically provided a kind of method of using inorganic silicon dioxide, mineral acid, mineral alkali, aluminate (or aluminium salt) as raw material synthetizing ultramacropore molecular sieve MCM-41.
Super macroporous molecular sieve (13～200A aperture) is phase in the early 1990s, by U.S. Mobil company synthetic (U.S.P 5,057,296 and U.S.P 5,108,725) the earliest, and called after MCM-41 molecular sieve.This molecular sieve both can be used as catalyzer, can make sorbent material again, and to alkylating aromatic hydrocarbon, olefin oligomerization, cracking and hydrocracking reaction, particularly the cracking reaction to residual oil has unique catalytic performance as it.In the method for the above-mentioned synthetizing ultramacropore molecular sieve that provides,, also need a kind of additional directed agents, its reaction process complexity except that using tensio-active agent to do the directed agents.
The synthetic method that the purpose of this invention is to provide a kind of super macroporous molecular sieve MCM-41, this preparation technology is simple, simultaneously can in preparation process, directly add the salts solution that contains transition metal again, and prepare the super macroporous molecular sieve MCM-41 that contains transition metal.Metallic element join in the molecular sieve can the modulation molecular sieve performance, use to adapt in different catalyzed reactions.
The method of synthetizing ultramacropore molecular sieve MCM-41 of the present invention, use inorganic silicon dioxide, mineral acid, mineral alkali, aluminate (or aluminium salt) to add tensio-active agent and make directed agents as raw material, it is characterized in that only using in the building-up process a kind of directed agents, and no longer with additional directed agents, directed agents can be represented with following molecular structural formula:
Figure 941101789_IMG3
Wherein: R 1, R 2Or R 3Be C 1～C 5Alkyl; R ' is C 5～C 24Alkyl; H is OH -, F -, Cl -, Br -Or I -Ion.Above-mentioned silicon source is an inorganic silicon dioxide, as water glass, silicon sol or soft silica.The aluminium source is aluminate or manganese salt, as sodium metaaluminate or potassium, and Tai-Ace S 150, aluminum nitrate or aluminum oxide.Mineral acid can be used sulfuric acid, nitric acid or hydrochloric acid, mineral alkali available hydrogen sodium oxide, potassium or ammonium.
In the synthetic method of the present invention, the proportioning of above-mentioned each raw material and directed agents (by the oxide molecule ratio) is:
Al 2O 3/SiO 2≤5;
OH -/SiO 2≤2;
H 2O/SiO 2＝10～500;
R/SiO 2=0.01～1, wherein R is a directed agents.
In addition, be the performance of modulation molecular sieve, can in molecular sieve, add transition metal and make the super macroporous molecular sieve MCM-41 that contains transition metal.The transition metal that is added can be used in the building-up process and directly to add solubility and contain the salts solution of transition metal, as contains vitriol, nitrate, muriate or the acetate of one or more elements among La, Ce, Mg, Zn, Ti, Cr, Fe, Ni, Ga or the Ge.When synthesizing the super macroporous molecular sieve MCM-41 of containing metal element, the proportioning of each raw material and directed agents (by the oxide molecule ratio) is: Al 2O 3/ SiO 2≤ 5;
OH -/SiO 2≤2;
H 2O/SiO 2＝10～500;
R/SiO 2=0.01～1; M/SiO 2=0.001～0.2, wherein R is a directed agents, and M is the oxide compound of metallic element.
The detailed process that the present invention prepares super macroporous molecular sieve MCM-41 is:
(1) reaction mixture preparation: at first in proportion aluminium source material is mixed in reactor with directed agents, under agitation silicon source material is added, after stirring, add the acid solution that the alkali lye that should add or the unnecessary alkali that neutralizes should add again, after stirring, be the reaction mixture for the treatment of crystallization.As prepare the super macroporous molecular sieve MCM-41 of containing metal element, can above-mentioned add alkali or acid after, add other metal salt solution again, stir, make the reaction mixture of crystallization;
(2) with reactor sealing, be no less than to (70～200 ℃) crystallization under the fixed temperature 2 hours to 30 days complete up to crystallization;
(3) solid crystallized product is separated with mother liquor,, promptly get the synthesis type raw material through washing and dry;
(4) the former powder of synthesis type roasting in 400～650 ℃ of following air promptly gets super macroporous molecular sieve MCM-41.
The super macroporous molecular sieve MCM-41 for preparing as stated above, recording bore dia with the x-x ray small angle scattering x is 15～150 ; It is 800～1200m that the BET method records surface-area 2/ g; Pore volume is 0.6～1.2cm 3/ g; At 25 ℃ of phenenyl absorbing amounts is 10.0～20.0%wt(Ps/Po=0.016), and water regain is 50.0～75.0%wt(Ps/Po=0.026); Sample does not destroy through X-ray diffraction proof skeleton 800 ℃ of roastings 1 hour.
Below by example method afford of the present invention is further specified.
Example 1 super macroporous molecular sieve MCM-41 synthetic 1
(1) raw material:
(A) silicon sol (contains SiO 226%wt, as follows): 38.4 grams;
(B) sodium aluminate solution (contains Al 2O 31.8 mol; Na 2O 3.3 mol, as follows): 3.0 milliliters;
(C) sodium hydroxide solution (contains Na 2O 8.06 mol, as follows) 3.6 milliliters;
(D) trimethylammonium 18 alkyl ammomium chloride solution (C 18TMACl) (contain C 18TMACl 35%wt): 33.0 grams.
(2) operation steps:
Earlier with raw material (B) with (D) in 100 milliliters of stainless steel cauldrons, mix, under agitation raw material (A) is slowly added in the still, stirred 10 minutes, add raw material (C) again, continue to stir after 30 minutes, with the reactor sealing, 100 ℃ of following crystallization 72 hours, after the cooling, solid is separated from mother liquor, and solid is with the deionized water wash several, at 100 ℃ of following air dryings, roasting is 3 hours in 540 ℃ of following air, makes super macroporous molecular sieve MCM-41.Recording bore dia through the x-x ray small angle scattering x is 38 ; It is 960m that the BEF method records surface-area 2/ g, pore volume are 0.961cm 3/ g; Is 19.2%wt(Ps/Po=0.016 at 25 ℃ of following samples to the adsorptive capacity of benzene), be 73.0%wt(Ps/Po=0.026 to the adsorptive capacity of water).
Example 2 super macroporous molecular sieve MCM-41 Synthetic 2s
In example 1, only sodium hydroxide solution is contained NH with 4 grams 4OH is the aqueous ammonia to replace of 25%wt, and all the other components are constant, and product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance d=49
Figure 941101789_IMG6
, recording bore dia is 45
Example 3 super macroporous molecular sieve MCM-41 synthetic 3
In example 1, only sodium hydroxide solution is increased to 6 milliliters, all the other components are constant, and product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance d=42
Figure 941101789_IMG8
, recording bore dia is 36
Figure 941101789_IMG9
Example 4 super macroporous molecular sieve MCM-41 synthetic 4
In example 1, only sodium aluminate solution is kept to 1.5 milliliters, all the other components are constant, and product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance d=38 , recording bore dia is 32
Figure 941101789_IMG11
Example 5 super macroporous molecular sieve MCM-41 synthetic 5
In example 1, only the amount with trimethylammonium 18 alkyl ammomium chlorides is kept to 8.25 grams, and all the other components are constant, and product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance d=83
Figure 941101789_IMG12
, recording bore dia is 78
Example 6 super macroporous molecular sieve MCM-41 synthetic 6
In example 1, only silicon sol is used instead 11 grams and contained SiO 2Be the soft silica of 90%wt and the mixture of 28 ml waters, all the other components are constant, and product is super macroporous molecular sieve MCM-41, and product is basic identical in its proterties and the example 1.
Example 7 super macroporous molecular sieve MCM-41 synthetic 7
In example 1, be the potassium hydroxide solution replacement of 8.06 mol with 3.6 ml concns only with sodium hydroxide solution, all the other components are constant, and product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance d=43
Figure 941101789_IMG14
, recording bore dia is 37
Figure 941101789_IMG15
Example 8 super macroporous molecular sieve MCM-41 synthetic 8
In example 1, only trimethylammonium 6 alkyl ammomium chlorides of trimethylammonium 18 alkyl ammomium chlorides with 23.6 gram 35%wt are replaced, all the other components are constant, and product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance d=30 , recording bore dia is 23
Figure 941101789_IMG17
Example 9 super macroporous molecular sieve MCM-41 synthetic 9
(1) raw material:
(A) water glass liquid (contains SiO 23.07 mol, Na 2O 1.05 mol): 54 milliliters;
(B) sodium aluminate solution: 3 milliliters;
(C) sulphuric acid soln (contains H 2SO 44 mol): 7 milliliters;
(D) tripropyl 18 alkyl ammomium chloride solution: 33 grams
(2) operation steps:
Earlier will (B) and (D) in 200 milliliters of stainless steel synthesis reactors, mix, under agitation (A) slowly added, stirred 10 minutes, add again (C), continue to stir 30 minutes, synthesis reactor is sealed, 90 ℃ of following crystallization 120 hours, sample preparation is with example 1, and product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance d=54
Figure 941101789_IMG18
, recording bore dia is 48
Figure 941101789_IMG19
Example 10 super macroporous molecular sieve MCM-41 synthetic 10
(1) raw material:
(A) silicon sol: 21.5 grams;
(B) sodium aluminate solution: 1.2 milliliters;
(C) sodium hydroxide solution: 3.5 milliliters;
(D) trimethylammonium 18 alkyl bromination ammonium solutions: 33 grams.
(2) operation steps: with example 1.100 ℃ of following crystallization, product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance D=38A, and recording bore dia is 32A.
Example 11 super macroporous molecular sieve MCM-41 synthetic 11
In example 10, only changing crystallization temperature is 150 ℃, and crystallization time is 24 hours, and all the other conditions are constant, and product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance D=63
Figure 941101789_IMG20
, recording bore dia is 58
Figure 941101789_IMG21
The super macroporous molecular sieve MCM-41 of example 12 containing metal elements synthetic 1
(1) raw material:
(A) silicon sol: 38.4 grams;
(B) sodium aluminate solution: 3 milliliters;
(C) sodium hydroxide solution: 3.6 milliliters;
(D) trimethylammonium 18 alkyl ammomium chloride solution: 33 grams;
(E) lanthanum nitrate hexahydrate (contains La 2O 30.6 mol): 1.5 milliliters.
(2) operation steps:
Earlier with raw material (B) with (D) in 100 milliliters of stainless steel synthesis reactors, mix, under agitation slowly add in the still with (A), stir after 10 minutes, again (C) added, at last (E) added, stir after 30 minutes, with synthesis reactor sealing, 100 ℃ of following crystallization 72 hours, sample preparation was with example 1, product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance d=45 , recording bore dia is 39
Figure 941101789_IMG23
540 ℃ of roasting samples contain La 2O 32.5%wt.
Example 13 super macroporous molecular sieve MCM-41 synthetic 12
(1) raw material:
(A) silicon sol: 38.4 grams;
(B) sodium aluminate solution: 6 milliliters;
(C) solution of ammonium hydroxide (contains NH 4OH 25%): 1.86 milliliters;
(D) triethyl 20 alkyl ammomium chloride solution: 8.5 grams.
(2) operation steps:
Earlier will (B) with (D) in 100 milliliters of stainless steel synthesis reactors, mix, under agitation (A) slowly added, stirs after 10 minutes, adding (C) again, continuation stirring 10 minutes sealed synthesis reactor, 150 ℃ of following crystallization 10 days.Sample preparation is with example 1.Product is super macroporous molecular sieve MCM-41.X-ray diffraction highest peak interplanar distance d=125
Figure 941101789_IMG24
, recording bore dia is 120
Figure 941101789_IMG25
The super macroporous molecular sieve MCM-41 Synthetic 2 of example 14 containing metal elements
In example 1, only sodium aluminate solution (is contained Ga with 1.5 ml aluminium acid sodium solutions and 1.5 milliliters of sodium solution gallates 2O 31.8 mol, Na 2O 3.3 mol) mixture replaces, and all the other components are constant, and product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance d=45
Figure 941101789_IMG26
, recording bore dia is 39
Figure 941101789_IMG27
The super macroporous molecular sieve MCM-41 of example 15 containing metal elements synthetic 3
In example 12, only lanthanum nitrate hexahydrate is replaced with 1.5 milliliters of magnesium acetate solution (containing MgO 1.2 mol), all the other components are constant, and product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance d=44
Figure 941101789_IMG28
, recording bore dia is 38
The super macroporous molecular sieve MCM-41 of example 16 containing metal elements synthetic 4
In example 12, only lanthanum nitrate hexahydrate (is contained Ni with 1.5 milliliters of nickel nitrate solutions 2O 30.6 mol) replace, all the other components are constant, product is super macroporous molecular sieve MCM-41, X-ray diffraction highest peak interplanar distance d=44
Figure 941101789_IMG30
, recording bore dia is 38
Figure 941101789_IMG31
By above-mentioned example,, only use a kind of tensio-active agent just can synthesize super macroporous molecular sieve MCM-41 by method provided by the invention.Its method is simple, and is easy to operate, and cost is low.Simultaneously, contain the soluble salt of transition metal, can prepare the super macroporous molecular sieve that contains metallic element by adding.

Claims (7)

1, a kind of inorganic silicon dioxide, mineral acid, mineral alkali, aluminate (or aluminium salt) of using is raw material, and tensio-active agent is made the method for the synthetizing ultramacropore molecular sieve MCM-41 of directed agents, it is characterized in that it only uses a kind of directed agents, the useful molecules structural formula is represented:
Figure 941101789_IMG2
Wherein: R 1, R 2Or R 3Be C 1～C 5Alkyl; R ' is C 5～C 24Alkyl; H is OH -, F -, Cl -, Br -Or I -Ion.
2,, it is characterized in that used inorganic silicon dioxide, available silicon colloidal sol, water glass or soft silica according to the method for the described synthetizing ultramacropore molecular sieve MCM-41 of claim 1.
3, according to the method for the described synthetizing ultramacropore molecular sieve MCM-41 of claim 1, it is characterized in that used aluminium salt can use Tai-Ace S 150, aluminum nitrate or aluminum chloride, used aluminate can be with sodium metaaluminate or potassium.
4,, it is characterized in that used inorganic salt, available sulfuric acid, nitric acid or hydrochloric acid according to the method for the described synthetizing ultramacropore molecular sieve MCM-41 of claim 1; Mineral alkali available hydrogen sodium oxide, potassium hydroxide or ammonium hydroxide.
5,, it is characterized in that each used proportioning raw materials (by the oxide molecule ratio) is according to the method for the described synthetizing ultramacropore molecular sieve MCM-41 of claim 1:
Al 2O 3/SiO 2≤5;
OH -/SiO 2≤2;
H 2O/SiO 2＝10～500;
R/SiO 2=0.01～1, R is a directed agents.
6, according to the method for the described synthetizing ultramacropore molecular sieve MCM-41 of claim 1, it is characterized in that in building-up process, metal salt solution to be added in the material and together react, prepare the super macroporous molecular sieve MCM-41 that contains metallic element; Added metal-salt can adopt vitriol, nitrate, muriate or the acetate that contains one or more elements among La, Ce, Mg, Zn, Ti, Cr, Fe, Ni, Ga or the Ge.
7,, it is characterized in that each used proportioning raw materials (by the oxide molecule ratio) is according to the described synthetic method that contains the super macroporous molecular sieve MCM-41 of metallic element of claim 6:
Al 2O 3/SiO 2≤5;
OH -/SiO 2≤2;
H 2O/SiO 2＝10～500;
R/SiO 2=0.01～1, M/SiO 2=0.001～0.2, wherein R is a directed agents, and M is the oxide compound of metallic element.
CN 94110178 1994-04-11 1994-04-11 Method for synthetizing ultramacropore molecular sieve Expired - Fee Related CN1045424C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1074749C (en) * 1998-04-24 2001-11-14 中国石油化工总公司 Super macroporous molecular sieve modifying method
CN1074750C (en) * 1998-04-24 2001-11-14 中国石油化工总公司 Method for prepn. of super macroporous molecular sieve
CN1108988C (en) * 1999-03-17 2003-05-21 中国科学院大连化学物理研究所 Microwave synthesis of macroporous molecular sieve
CN1115299C (en) * 2000-09-07 2003-07-23 中国石油化工股份有限公司 Synthesis method or molecular sieve
CN105136208A (en) * 2015-10-16 2015-12-09 厦门铠睿智能科技有限公司 Nine-axis MEMS (Micro Electro Mechanical System) sensor
CN108238610A (en) * 2016-12-23 2018-07-03 中国石油化工股份有限公司 A kind of molecular sieve, its manufacturing method and its application

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1074749C (en) * 1998-04-24 2001-11-14 中国石油化工总公司 Super macroporous molecular sieve modifying method
CN1074750C (en) * 1998-04-24 2001-11-14 中国石油化工总公司 Method for prepn. of super macroporous molecular sieve
CN1108988C (en) * 1999-03-17 2003-05-21 中国科学院大连化学物理研究所 Microwave synthesis of macroporous molecular sieve
CN1115299C (en) * 2000-09-07 2003-07-23 中国石油化工股份有限公司 Synthesis method or molecular sieve
CN105136208A (en) * 2015-10-16 2015-12-09 厦门铠睿智能科技有限公司 Nine-axis MEMS (Micro Electro Mechanical System) sensor
CN108238610A (en) * 2016-12-23 2018-07-03 中国石油化工股份有限公司 A kind of molecular sieve, its manufacturing method and its application
CN108238610B (en) * 2016-12-23 2020-02-28 中国石油化工股份有限公司 Molecular sieve, and preparation method and application thereof

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