CN1240194A - Template agent preparation for synthesizing silico-aluminium zeolite and application thereof - Google Patents

Template agent preparation for synthesizing silico-aluminium zeolite and application thereof Download PDF

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CN1240194A
CN1240194A CN 99112979 CN99112979A CN1240194A CN 1240194 A CN1240194 A CN 1240194A CN 99112979 CN99112979 CN 99112979 CN 99112979 A CN99112979 A CN 99112979A CN 1240194 A CN1240194 A CN 1240194A
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reaction
hexanolactam
template
zeolite
hydrogen
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CN1113812C (en
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王清遐
谢素娟
徐龙伢
白杰
吴治华
张连英
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a template agent for synthesizing MCM-22 silica-aluminium zeolite. Said template agent is a mixture mainly containing 76-84 wt% of hexamethylene imine, 1-10 wt.% of caprolactam and water. The silicon dioxide, sulfate, hydroxide of alkali metal or alkaline-earth methal, the invented template agent and deionized water are used as raw materials, and under the condition of temperature of 100-200 deg.C, the above-mentioned raw materials are crystallized for 1-15 days and hydrothermally synthesized into the molecular sieve. Said invention can greatly reduce its cost.

Description

A kind of lamina membranacea agent preparation and application that is used for synthesizing Si-Al zeolite
The invention relates to the process of the synthetic MCM-22 Si-Al zeolite of a kind of cheapness.Specifically, providing a kind of is template with the liquid mixture, the process of the synthetic MCM-22 Si-Al zeolite that is raw material with the oxyhydroxide and the deionized water of silicon-dioxide, aluminate, basic metal or alkaline-earth metal.
The MCM-22 zeolite is a kind of mesopore zeolite (USP4,954,325) that U.S. Mobil company succeeded in developing in the early 1990s.It is made up of two independently not mutual crosslinked channel system, and one of hole system is two-dimentional sinusoidal duct, and two of hole system is oval-shaped supercage.MCM-22 zeolite particular structure feature, make it bring into play outstanding effect in refining of petroleum and field of petrochemical industry, as catalytic cracking of hydrocarbon (USP5,085,762), benzene/ethylene alkylation (USP5,334,795), isoparaffin/olefin alkylation (USP4,992,615) and methyl alcohol/alkene system higher hydrocarbons (USP4,956,514) or the like.The template of at present synthetic MCM-22 zeolite is a hexamethylene imine substantially, is template if adopt other material, as (USP5,173,281) such as hexahydroaniline, cyclopentamine, then produces the stray crystal phase.About by the existing reported in literature of hexanolactam gas phase hydrogenation preparing hexamethylene radical imine, USP2 wherein, 181,140; Japanese kokai publication sho 49-86385,53-28188; DT2837290; Patent disclosures such as Brit.1570647 employing copper-chromic oxide, cobalt aluminium alloy, Raney-Co, support catalyzer such as copper and copper-zinc, at 200～260 ℃, under the condition of pressure 2.0～9.0MPa, hexanolactam can be converted into hexamethylene imine, yield can reach 90～98%.But above-mentioned related catalyst life is all introduced in detail, in fact the life-span all lower, therefore be difficult in industrial production, use.In the CN97116969.5 patent, disclose a kind of hexanolactam gas phase hydrogenation Preparation of catalysts method that is used for, it is characterized in that this catalyzer is Cu-MnO-Al 2O 3System, each composition weight content is CuO 30～50%, MnO5～20%, Al 2O 330～50%, can add one or more oxide compounds that auxiliary agent Zn, Ca, Mg, Ba or karat gold belong to, the weight percentage that the addition of auxiliary agent accounts for catalyzer is: ZnO 0～20%, CaO, MgO, BaO or K 2O is 0～10%.Adopt above-mentioned catalyzer to carry out the hexanolactam hydrogenation reaction, 200～270 ℃ of temperature of reaction, hydrogen pressure 0.5～2.0MPa, hexanolactam air speed 0.15h -1Condition under, transformation efficiency can reach more than 98%, the work-ing life of catalyzer can be above 3 months.
The object of the present invention is to provide a kind of template of MCM-22 Si-Al zeolite, it can make the synthetic cost of MCM-22 Si-Al zeolite significantly reduce.
The invention provides a kind of template that is used for synthetic MCM-22 Si-Al zeolite, it is characterized in that template for mainly containing (weight percent) 76～84% hexamethylene imines, 1～10% hexanolactam, surplus is the mixture of water.
The present invention also provides in the presence of hydrogenation catalyst, and hexanolactam and H-H reaction are converted into hexamethylene imine and water mixture, i.e. the method for above-mentioned template is characterized in that:
(1) series connection, multistage, cold shock fixed-bed reactor are adopted in the hexanolactam hydrogenation reaction, this reactor is divided into n conversion zone (n=2～6), hexanolactam adds from first section top, hydrogen is divided into the n section and enters, 2 to n sections add room temperature hydrogen, directly, control the bed reaction temperature rising with each conversion zone top thermal material heat exchange;
(2) hydrogenation conditions is: 200～300 ℃ of temperature of reaction, the hydrogen dividing potential drop 0.2～2.0MPa of reaction, hydrogen and hexanolactam mol ratio 20～1000, hexanolactam volume space velocity (under 70 ℃) 0.05～0.5h -1
(3) reaction effluent is after cooling and gas-liquid separation, and hydrogenator is returned in the compressed machine supercharging of the hydrogen that obtains; The liquid mixture that obtains (L) can be directly as zeolite molecular sieve synthesis material (template).
The invention provides the application of above-mentioned template in synthetic MCM-22 Si-Al zeolite reaction, it is characterized in that: adopting oxyhydroxide, template and the deionized water of silicon-dioxide, aluminate, basic metal or alkaline-earth metal is raw material, under 100～200 ℃, crystallization 1～15 day, hydro-thermal synthesizes molecular sieve; The proportioning raw materials of this zeolite synthesis (molecular ratio) scope is: SiO 2/ Al 2O 3=8～80; R/Al 2O 3=0.5～80; OH -/ Al 2O 3=0.1～80; M/Al 2O 3=0.1～160; H 2O/Al 2O 3=50～8000; Wherein R is the organism in the template, and M is basic metal or alkaline-earth metal.
The preferable proportioning raw materials of MCM-22 Si-Al zeolite synthetic of the present invention (molecular ratio) scope is SiO 2/ Al 2O 3=8～60; R/Al 2O 3=1.0～30; OH -/ Al 2O 3=1.0～30; M/Al 2O 3=1.0～60; H 2O/Al 2O 3=100～3000.
The present invention has been owing to used the template of a kind of hexamethylene imine without rectifying as synthetic MCM-22 zeolite, thereby can reduce the cost of synthetic MCM-22 zeolite significantly.Synthetic MCM-22 zeolite of the present invention has the X-ray diffract spectral line of table 1.
Table 1 the present invention and USP4, the comparison * of the X-ray diffract spectral line of MCM-22 in 954,325
Spacing d (A) USP4, MCM-22 diffraction peak relative intensity I/I in 954,325 o(×100) MCM-22 diffraction peak relative intensity I/L among the present invention o(×100)
??12.36±0.2 ????M-VS ????VS
??11.03±0.2 ????M-S ????S
??8.83±0.14 ????M-VS ????S-VS
??6.86±0.14 ????W-M ????M
??6.18±0.12 ????M-VS ????S-VS
??6.00±0.10 ????W-M ????M
??5.54±0.10 ????W-M ????M
??4.92±0.09 ????W ????W
??4.64±0.08 ????W ????W
??4.41±0.08 ????W-M ????M
??4.25±0.08 ????W ????W
??4.10±0.07 ????W-S ????M
??4.06±0.07 ????W-S ????M
??3.91±0.07 ????M-VS ????M-VS
??3.75±0.06 ????W-M ????M
??3.56±0.06 ????W-M ????M
??3.42±0.06 ????VS ????VS
??3.30±0.05 ????W-M ????M
??3.20±0.05 ????W-M ????M
??3.14±0.05 ????W-M ????M
* W, M, S and VS represent the weak, medium, strong and very strong of diffraction peak respectively, and its numerical range is W=0～20, M=20～40, S=40～60, VS=60～100.
The present invention will be further described below by example.
Example 1: the preparation of template
In a series connection, multistage, cold shock fixed-bed reactor, be divided into four sections 280ml hydrogenation catalyst JH-01 that pack into (production of the Dalian Chemistry and Physics Institute), respectively adorn 70ml for one to four section, hydrogen is divided into four parts and enters from every section top, and hexanolactam adds from first section top.The temperature of reaction of controlling each section is 265 ℃, reaction pressure 1.0MPa, total hydrogen and the mol ratio of hexanolactam 90, the liquid air speed 0.1h of total hexanolactam -1Obtain the transformation efficiency 98% of hexanolactam, contain 82.5% (w) hexamethylene imine, 2.0% (w) hexanolactam, 0.5% (w) by product and 15.0% (w) water in the product liquid, this liquid mixture called after L 1
Example 2: the preparation of template
In a series connection, multistage, cold shock fixed-bed reactor, be divided into four sections 300ml hydrogenation catalyst JH-02 that pack into (Fushun No.3 Petroleum Factory's production), respectively adorn 75ml for one to four section, hydrogen is divided into four parts and adds.Controlling each section temperature of reaction is 280 ℃, reaction pressure 1.5MPa, total hydrogen and the mol ratio of hexanolactam 250, the liquid air speed of total hexanolactam (under 70 ℃) 0.12h -1, obtain the transformation efficiency 95% of hexanolactam, contain 80.1% (w) hexamethylene imine, 4.8% (w) hexanolactam, 0.6% (w) by product and 14.5% (w) water in the product liquid, this liquid mixture called after L 2
Example 3: the preparation of template
The place of production of hydrogenation reaction system and catalyzer, loadings and type of feed are identical with example 2.Controlling each section temperature of reaction is 240 ℃, reaction pressure 0.5MPa, total hydrogen and the mol ratio of hexanolactam 500, total hexanolactam liquid air speed 0.15h -1, obtain the transformation efficiency 92% of hexanolactam, contain 77.7% (w) hexamethylene imine, 7.9% (w) hexanolactam, 0.3% (w) by product and 14.1% (w) water in the product liquid, this liquid mixture called after L 3
Synthesizing of example 4:MCM-22 zeolite
(1) raw material:
A. sodium aluminate solution [contains 16.8% (w) Al 2O 3, 24% (w) Na 2O, as follows]: 3 grams;
B. sodium hydroxide solution [containing 10% (w) NaOH, as follows]: 3.8 milliliters;
C. liquid mixture L 1(product of example 1): 6.7 grams;
D. deionized water: 115 milliliters;
E. solid silica [contains 95.7% (w) SiO 2, as follows]: 9.4 grams.
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=30; OH -/ Al 2O 3=6.6; H 2O/Al 2O 3=1350; Na/Al 2O 3=6.6; R/Al 2O 3=11.5 (R refers to L 1In organism).
(2) operation steps:
Earlier with raw material (A) with (B) in 200 milliliters of stainless steel cauldrons, mix, under agitation with raw material (C) with (D) add in the still successively, stirred 5 minutes, add raw material (E) again, continue to stir after 20 minutes, reactor is sealed, 152 ℃ of following crystallization 7 days, after the cooling, with solid and mother liquor with the 5000rpm centrifugation, solid through deionized water wash to pH8～9,120 ℃ of following dry airs 8 hours, 540 ℃ of following air roastings 3 hours make the MCM-22 Si-Al zeolite, and its X-ray diffraction spectral line is shown in table 2; SiO 2/ Al 2O 3Be 20.8 (molecular ratios, as follows); It is 458m that the BET method records specific surface area 2/ g; The adsorptive capacity of normal hexane and hexanaphthene is respectively 15.5% (w) and 13.6% (w) (adsorption conditions is 25 ℃, and adsorbate dividing potential drop 20mmHg is as follows), and the adsorptive capacity of water is 14.0% (w) (adsorption conditions is 25 ℃, and adsorbate dividing potential drop 12mmHg is as follows).
The X-ray diffraction spectral line of sample in table 2 example 4
Spacing d () Diffracted intensity I/I o(×100) Spacing d () Diffracted intensity I/I o(×100)
????12.47 ????89 ????4.23 ????12
????11.10 ????57 ????4.11 ????27
????8.84 ????69 ????4.07 ????38
????6.87 ????21 ????3.92 ????59
????6.21 ????57 ????3.75 ????38
????6.01 ????23 ????3.56 ????29
????5.56 ????33 ????3.42 ????100
????4.99 ????10 ????3.31 ????32
????4.66 ????13 ????3.21 ????35
????4.38 ????25 ????3.11 ????25
Synthesizing of example 5:MCM-22 zeolite
In example 4, change liquid mixture into L 2(product of example 2), add-on are 7.2 grams, and the add-on of sodium hydroxide changes 2.6 milliliters into, and the add-on of deionized water changes 107.1 milliliters into, and the add-on of silicon-dioxide changes 9.1 grams into, and all the other components are constant, and the mole of reaction mixture consists of: SiO 2/ Al 2O 3=29; OH -/ Al 2O 3=6.0; H 2O/Al 2O 3=1250; Na/Al 2O 3=6.0; R/Al 2O 3=12.5 (R refers to L 2In organism).Crystallization time 9.5 days, product are the MCM-22 molecular sieve.Sample is basic identical through X-ray diffraction spectral line and the table 2 of 540 ℃ of following air roastings after 3 hours; SiO 2/ Al 2O 3Be 20.1; It is 452m that the BET method records specific surface area 2/ g; The adsorptive capacity of normal hexane, hexanaphthene and water is respectively 15.1% (w), 13.7% (w) and 14.3% (w).
Synthesizing of example 6:MCM-22 zeolite
In example 4, use the synthetic Fu of 1 liter instead, liquid mixture changes L into 3(example 3 products), add-on are 20.2 grams, and the add-on of sodium metaaluminate changes 10.1 grams into, and the add-on of sodium hydroxide changes 9.8 milliliters into, and the add-on of deionized water changes 581.1 milliliters into, and the add-on of silicon-dioxide changes 33.4 grams into.The mole of reaction mixture consists of: SiO 2/ Al 2O 3=32; OH -/ Al 2O 3=6.2; H 2O/Al 2O 3=2000; Na/Al 2O 3=6.2; R/Al 2O 3=10.5 (R refers to L 3In organism).Crystallization time 7.5 days, product are the MCM-22 molecular sieve.Sample is shown in table 3 through the X-ray diffraction spectral line of 540 ℃ of following air roastings after 3 hours; SiO 2/ Al 2O 3Be 22.2; It is 450m that the BET method records specific surface area 2/ g; The adsorptive capacity of normal hexane, hexanaphthene and water is respectively 14.9% (w), 12.8% (w) and 13.5% (w).
The X-ray diffraction spectral line of sample in table 3 example 6
Spacing d () Diffracted intensity I/I o(×100) Spacing d () Diffracted intensity I/I o(×100)
????12.34 ????95 ????4.18 ????18
????11.04 ????56 ????4.09 ????32
????8.80 ????70 ????4.05 ????38
????6.85 ????21 ????3.90 ????62
????6.18 ????61 ????3.74 ????39
????6.00 ????22 ????3.56 ????30
????5.53 ????32 ????3.41 ????100
????4.94 ????9 ????3.29 ????32
????4.64 ????14 ????3.19 ????37
????4.37 ????29 ????3.11 ????26
Synthesizing of example 7:MCM-22 zeolite
In example 4, with liquid mixture L 1The purity that rectifying obtains is that 99% hexamethylene imine is a template, and add-on is 4.7 grams, and the add-on of sodium hydroxide changes 1.4 milliliters into, and the add-on of deionized water changes 118.2 milliliters into, and all the other components are constant, and the mole of reaction mixture consists of: SiO 2/ Al 2O 3=30; OH -/ Al 2O 3=5.4; H 2O/Al 2O 3=1350; Na/Al 2O 3=5.4; R/Al 2O 3=9.5 (R refers to hexamethylene imine).Crystallization time 8 days, product are the MCM-22 molecular sieve.Sample is shown in table 4, SiO through the X-ray diffraction spectral line of 540 ℃ of following air roastings after 3 hours 2/ Al 2O 3Be 22.0; It is 461m that the BET method records specific surface area 2/ g; The adsorptive capacity of normal hexane, hexanaphthene and water is respectively 15.6% (w), 13.4% (w) and 14.5% (w).
The X-ray diffraction spectral line of sample in table 4 example 7
Spacing d () Diffracted intensity I/I o(×100) Spacing d () Diffracted intensity I/I o(×100)
????12.46 ????64 ????4.22 ????15
????11.16 ????41 ????4.11 ????28
????8.92 ????50 ????4.07 ????39
????6.88 ????21 ????3.92 ????62
????6.19 ????42 ????3.75 ????38
????6.03 ????20 ????3.57 ????29
????5.56 ????24 ????3.43 ????100
????4.95 ????11 ????3.31 ????30
????4.66 ????14 ????3.21 ????30
????4.40 ????33 ????3.12 ????23

Claims (4)

1. template that is used for synthetic MCM-22 Si-Al zeolite is characterized in that template for mainly containing (weight percent) 76～84% hexamethylene imines, 1～10% hexanolactam, and surplus is the mixture of water.
2. the preparation method of the described template of claim 1 in the presence of hydrogenation catalyst, is converted into hexamethylene imine and water with hexanolactam and H-H reaction, and reaction effluent obtains gas and product liquid through gas-liquid separation, it is characterized in that:
(1) series connection, multistage, cold shock fixed-bed reactor are adopted in the hexanolactam hydrogenation reaction, this reactor is divided into n conversion zone (n=2～6), hexanolactam adds from first section top, hydrogen is divided into the n section and enters, 2 to n sections add room temperature hydrogen, directly, control the bed reaction temperature rising with each conversion zone top thermal material heat exchange;
(2) hydrogenation conditions is: 200～300 ℃ of temperature of reaction, the hydrogen dividing potential drop 0.2～2.0MPa of reaction, hydrogen and hexanolactam mol ratio 20～1000, hexanolactam volume space velocity (under 70 ℃) 0.05～0.5h -1
(3) reaction effluent is after cooling and gas-liquid separation, and hydrogenator is returned in the compressed machine supercharging of the hydrogen that obtains; The liquid mixture that obtains (L) can be directly as zeolite molecular sieve synthesis material (template).
3. the application of the described template of claim 1 in synthetic MCM-22 Si-Al zeolite reaction, it is characterized in that: the oxyhydroxide, template and the deionized water that are employing silicon-dioxide, aluminate, basic metal or alkaline-earth metal are raw material, under 100～200 ℃, crystallization 1～15 day, hydro-thermal synthesizes molecular sieve; The proportioning raw materials of this zeolite synthesis (molecular ratio) scope is: SiO 2/ Al 2O 3=8～80; R/Al 2O 3=0.5～80; OH -/ Al 2O 3=0.1～80; M/Al 2O 3=0.1～160; H 2O/Al 2O 3=50～8000; Wherein R is the organism in the template, and M is basic metal or alkaline-earth metal.
4. according to the application of the described template of claim 3 in synthetic MCM-22 Si-Al zeolite reaction, it is characterized in that: synthetic proportioning raw materials (molecular ratio) scope is SiO 2/ Al 2O 3=8～60; R/Al 2O 3=1.0～30; OH -/ Al 2O 3=1.0～30; M/Al 2O 3=1.0～60; H 2O/Al 2O 3=100～3000.
CN 99112979 1999-06-04 1999-06-04 Template agent preparation for synthesizing silico-aluminium zeolite and application thereof Expired - Fee Related CN1113812C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1116228C (en) * 2000-06-15 2003-07-30 中国石油化工集团公司 Method for synthesizing MCM-22 molecular sieve
CN100336724C (en) * 2004-05-17 2007-09-12 中国科学院大连化学物理研究所 Method for synthesizing fine grain MCM-22 molecular sieve
CN116119680A (en) * 2023-01-17 2023-05-16 西南科技大学 Method for solidifying nonferrous metal tailings by using 4A zeolite and solidified body thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1116228C (en) * 2000-06-15 2003-07-30 中国石油化工集团公司 Method for synthesizing MCM-22 molecular sieve
CN100336724C (en) * 2004-05-17 2007-09-12 中国科学院大连化学物理研究所 Method for synthesizing fine grain MCM-22 molecular sieve
CN116119680A (en) * 2023-01-17 2023-05-16 西南科技大学 Method for solidifying nonferrous metal tailings by using 4A zeolite and solidified body thereof

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