CN100453459C - Amine (nitrogen) frame hybrid alkali microporous materials and method for preparing same - Google Patents

Amine (nitrogen) frame hybrid alkali microporous materials and method for preparing same Download PDF

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CN100453459C
CN100453459C CNB2004100179747A CN200410017974A CN100453459C CN 100453459 C CN100453459 C CN 100453459C CN B2004100179747 A CNB2004100179747 A CN B2004100179747A CN 200410017974 A CN200410017974 A CN 200410017974A CN 100453459 C CN100453459 C CN 100453459C
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skeleton
amine
poromerics
hydridization
molecular sieve
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CN1569634A (en
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韩爱杰
贺鹤勇
郭娟
龙英才
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Fudan University
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Abstract

The present invention relates to an amine (nitrogen) framework hybridization alkaline microporous material and a preparation method thereof, which belongs to the technical field of a microporous material. The material is obtained in a mode that crystalline or amorphous microporous materials (such as a zeolite molecular sieve, a mesopore molecular sieve, silica gel, white carbon black, etc.) are mixed with an aminating agent solution to carry out a hydrothermal reaction or a gas/solid phase reaction and replace framework oxygen by an amino group part. The solid alkalinity of a novel catalyzing material is regulated and controlled by changing the length of alkyl group carbon chains of C1-C4 of an aminating agent and using primary amine or secondary amine. The material is roasted to generate a nitrogen hybridization alkaline microporous material of which the nitrogen atom part replaces framework oxygen atoms. The material has the advantages of mild synthetic condition, good repetitiveness, simple and convenient preparation, low price and no environmental pollution, and is suitable for industrialized production.

Description

A kind of amine (nitrogen) skeleton hydridization alkalescence poromerics and preparation method thereof
Technical field
The invention belongs to the poromerics technical field, be specifically related to a kind of amine (nitrogen) skeleton hydridization alkalescence poromerics and preparation method thereof.This material has wide application prospects at aspects such as catalysis and fractionation by adsorption.
Background technology
Different with traditional solid acid zeolite, skeleton amine (nitrogen) hybridized microporous material (as zeolite molecular sieve) has the specific surface height, the solid alkaline of may command and modulation, characteristics such as shape selectivity are selected in tax, have high reactivity, highly selective, reaction conditions gentleness, product as catalyzer and be easy to advantages such as separation, be expected to become environmental friendliness catalytic material of new generation.The basic zeolite catalyzer can be used for partial oxidation and the halogen digestion and the catalysis Knoevenagel condensation etc. of hydro carbons, has good commercial application prospect aspect the synthetic fine chemical product.This material also can be used for adsorbing from the waste water that contains strong acid removes gelled acid.
J.B.Peri report (J.Phys.Chem., 1966,70 (9): 2937-2945), in advance with silicon sol after 800 ℃ of roastings, ammonia (NH 3) can be adsorbed on its surface slowly.Increase pressure and time, NH 3Adsorptive capacity can increase, can obtain NH in absorption under the pressure of 100mmHg after 8 days 3Maximal absorptive capacity, but also only be every 100A 2The NH of 1.3 to 1.4 molecules of absorption 3NH 3Replace silicon sol surface OH, form NH on the silicon sol surface 2Group.
(J.Phys.Chem., 1968,79 (8): 3071-3072), the skeleton Sauerstoffatom of the Y zeolite of Hydrogen (HY) can be by ammonia (NH under 500 ℃ of hot conditionss for the G.T.Kerr of Mobil company and G.F.Shipman report 3) replace, obtain ammonification zeolite (amidozeolite).
P.W.Lednor and R.de Ruiter report (J.Chem.Soc., Chem.Commun., 1989,320-321), ammonia (NH 3) and multi-form SiO 2(all-silica MFI zeolite and silica gel) reacts under 1100 ℃ high temperature and obtains Si 2N 2O.They find that this silica nitrogen material has alkalescence, and with its catalysis Knoevenagel condensation reaction (J.Chem.Soc., Chem.Commun., 1991,1625-1626).
J.Sjoberg and R.Pompe report (J.Am.Ceram.Soc., 1992,75 (8): 2189-2193), ammonia (NH 3) and amorphous Si O 2Just the body phase reaction can take place at 800 ℃ more than the high temperature.When temperature reached 1050 ℃, nitrogenize reached maximum, can obtain Si 2N 2O silica nitrogen material.
A.Steinz, B.Wehrle and M.Jansen newspaper logical (Zeolites, 1993,13:291-298), under the temperature more than 900 ℃, AlPO 4-5 (a kind of phosphate molecule sieves) are at NH 3Or NH 3Reaction obtains P-NH in the mixed atmosphere of/CO 2Group, the skeleton Sauerstoffatom is replaced by nitrogen-atoms.
People such as P.Grange report that nitrogenous phosphate molecule sieve (aluminophosphate oxynitrides) has alkalescence, can be used as novel catalyzer (Appl.Catal.A:Gen, 1994,114, L191-L196; Appl.Catal.A:Gen, 1996,137,9-23).
People such as M.J.Climent report (J.Catal., 1996,163:392-398; Catal.Lett., 1999,59:33-38), under 800 ℃ of high temperature phosphate aluminium molecular sieve can and ammonia gas react, the nitrogenous phosphate molecule sieve (aluminophosphateoxynitrides) that obtains is used as novel basic catalyst.They also calculated theoretically the stability of nitrogenous phosphate molecule sieve and alkalescence (J.Mol.Catal.A:1998,133:241-250).
People such as S.Ernst report (Appl.Catal.A:Gen, 2000,200:117-123), zeolite under the high temperature more than 800 ℃ (NaY) and phosphate aluminium molecular sieve can and ammonia gas react, the nitrogenous zeolite molecular sieve of preparation is used to catalysis Knoevenagel condensation reaction.
(Adv.Mater., 2001,13 (3): 192-195), mesoporous silicon and ammonia be the nitrogenous mesoporous silicon of prepared in reaction under 950 ℃ of high temperature for people such as J.El Haskouri report.
The nitrogenous poromerics of above-mentioned report all adopts the preparation of gas/solid state reaction, promptly usually under the high temperature more than 500 ℃ with ammonia to base material effect, severe reaction conditions.
Summary of the invention
The objective of the invention is to propose that a kind of catalytic performance is good, the amine of low cost of manufacture (nitrogen) skeleton hydridization alkalescence poromerics and preparation method thereof.
The amine skeleton hydridization alkalescence poromerics that the present invention proposes is the skeleton oxygen that skeleton contains 1-20% in the oxygen poromerics is substituted with amido and to obtain, and wherein amido is-NHR, or NR 1R 2, R here 1, R 2Be respectively C 1-C 4Hydro carbons.
In the above-mentioned poromerics, described skeleton contains the zeolite molecular sieve that the oxygen poromerics can be a crystalline state, aluminium phosphate molecular sieve, mesopore molecular sieve, and amorphous silica gel, white carbon black etc.
Amine is stronger than the alkalescence of ammonia, and primary amine, the hydrogen atom on the secondary amine in the amido can be used as reaction position, the Si-O-Si skeleton of the attack poromerics that takes the lead in.Therefore, reactivity ratio's ammonia height of amine reacts temperature required low.After the part skeleton Sauerstoffatom of poromerics is replaced by amine groups,, become a kind of novel micropore catalytic material because the lower electronegativity of nitrogen-atoms on the amine groups causes the alkalescence of material to strengthen.
The preparation method of above-mentioned amine (nitrogen) skeleton hydridization alkalescence poromerics is as follows:
Aqueous solution with base material and amine places reactor, carries out hydro-thermal reaction, temperature 100-200 ℃, time 10-50 hour, obtains amine and replaces the skeleton hybridized microporous material; Or the aqueous solution of amine placed the reactor bottom, base material places the upper strata, carries out hydro-thermal reaction, temperature 100-200 ℃, time 10-50 hour, the steam and the base material generation gas/solid state reaction that produce when utilizing heating were prepared into amine and replace the skeleton hybridized microporous material.
Above-mentioned amine is replaced the skeleton hybridized microporous material at 400-800 ℃ of roasting 1-3h, obtain skeleton azepine micropore catalytic material.Promptly this material has substituted the skeleton oxygen that skeleton contains 1-20% in the oxygen poromerics with nitrogen-atoms.
In the aforesaid method, described base material can adopt commodity zeolite molecular sieve, aluminium phosphate molecular sieve, mesopore molecular sieve, white carbon black or silica gel etc., base material and the reaction of amine low-temperature hydrothermal or generation gas/solid state reaction, make skeleton amine hydridization alkalescence micropore novel material, through roasting, obtain to have the skeleton azepine poromerics of alkalescence again.MFI zeolite with methylamine hydridization is an example, handles the back acid-basicity through different modes and changes and see shown in Figure 1ly, and table 1 and table 2 have provided the nitrogen content of the poromerics of data that acid-basicity changes and different modes mensuration respectively.
Preparation methods of the present invention is easy, the reaction conditions gentleness, and production cost is low, and skeleton amine (nitrogen) the hydridization alkalescence poromerics that obtains can be used as catalyzer and sorbent material, and is applied widely, has favorable industrial application prospect.
Description of drawings
Fig. 1 MFI zeolite temperature programmed desorption(TPD) (TPD) that acid-basicity changes after different modes is handled figure.Wherein, (A) NH 3/ TPD shows variation (B) CO of acid matter 2/ TPD shows the variation of alkaline matter.(a) substrate MFI zeolite among the figure; (b) the MFI zeolite of methylamine hydridization; (c) the MFI zeolite of 500 ℃ of azepineizations that roasting obtains; (d) the MFI zeolite of 800 ℃ of azepineizations that roasting obtains.
Embodiment
Further describe the present invention below by embodiment:
Embodiment 1:
Substrate MFI zeolite according to the following steps with the methylamine effect, the MFI zeolite of preparation skeleton amine hydridization:
1, the aqueous solution of methylamine is mixed with the MFI zeolite places reactor.Or the aqueous solution of methylamine placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains skeleton methylamine hydridization MFI zeolite.
3, skeleton methylamine hydridization MFI zeolite obtains skeleton azepine MFI zeolite at 500 ℃ of roasting 2h.
Embodiment 2:
Substrate MFI zeolite according to the following steps with the dimethylamine effect, the MFI zeolite of preparation skeleton dimethylamine hydridization:
1, the aqueous solution of dimethylamine is mixed with the MFI zeolite places reactor.Or the aqueous solution of dimethylamine placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 150 ℃ of baking ovens, reaction is 50 hours under self-generating pressure.
3, reaction product is washed after filtration, and oven dry at 500 ℃ of roasting 2h, obtains skeleton dimethylamine hydridization MFI zeolite.
Embodiment 3:
Substrate MFI zeolite according to the following steps with the ethamine effect, the MFI zeolite of preparation skeleton ethamine hydridization:
1, ethamine is mixed with the MFI zeolite places reactor.Or the aqueous solution of ethamine placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 10 hours under self-generating pressure, and reaction product is washed after filtration, and oven dry makes skeleton ethamine hydridization MFI zeolite.
3, this skeleton ethamine hydridization MFI zeolite at 500 ℃ of roasting 2h, obtains skeleton azepine MFI zeolite.
Embodiment 4:
Base material MCM-41 molecular sieve according to the following steps with the methylamine effect, the MCM-41 molecular sieve of preparation skeleton amine hydridization:
1, the aqueous solution of methylamine is mixed with the MCM-41 molecular sieve places reactor.Or the aqueous solution of methylamine placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 150 ℃ of baking ovens, reaction is 48 hours under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains skeleton methylamine hydridization MCM-41 molecular sieve.
3, skeleton methylamine hydridization MFI zeolite obtains skeleton azepine MCM-41 molecular sieve at 400 ℃ of roasting 2h.
Embodiment 5:
Base material MCM-41 molecular sieve according to the following steps with the dimethylamine effect, the MCM-41 molecular sieve of preparation skeleton dimethylamine hydridization:
1, the aqueous solution of dimethylamine is mixed with the MCM-41 molecular sieve places reactor.Or the aqueous solution of dimethylamine placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 20 hours under self-generating pressure.
3, reaction product is washed after filtration, and oven dry at 800 ℃ of roasting 1h, obtains skeleton azepine MCM-41 molecular sieve.
Embodiment 6:
Base material MCM-41 molecular sieve according to the following steps with the ethamine effect, the MCM-41 molecular sieve of preparation skeleton ethamine hydridization:
1, ethamine is mixed with the MCM-41 molecular sieve places reactor.Or the aqueous solution of ethamine placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 100 ℃ of baking ovens, reaction is 48 hours under self-generating pressure, and reaction product is washed after filtration, and oven dry makes skeleton ethamine hydridization MCM-41 molecular sieve.
3, this skeleton ethamine hydridization MFI zeolite at 400 ℃ of roasting 3h, obtains skeleton azepine MCM-41 molecular sieve.
Embodiment 7:
Base material silica gel according to the following steps with the methylamine effect, the silica gel of preparation skeleton amine hydridization:
1, the aqueous solution of methylamine is mixed with silica gel places reactor.Or the aqueous solution of methylamine placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains skeleton methylamine hybridisation silica gel.
3, skeleton methylamine hybridisation silica gel obtains skeleton azepine silica gel at 500 ℃ of roasting 2h.
Embodiment 8:
Base material silica gel according to the following steps with the dimethylamine effect, the silica gel of preparation skeleton dimethylamine hydridization:
1, the aqueous solution of dimethylamine is mixed with silica gel places reactor.Or the aqueous solution of dimethylamine placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 40 hours under self-generating pressure.
3, reaction product is washed after filtration, and oven dry at 800 ℃ of roasting 1h, obtains skeleton azepine silica gel.
Embodiment 9:
Base material silica gel according to the following steps with the ethamine effect, the silica gel of preparation skeleton ethamine hydridization:
1, ethamine is mixed with silica gel places reactor.Or the aqueous solution of ethamine placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 150 ℃ of baking ovens, reaction is 48 hours under self-generating pressure, and reaction product is washed after filtration, and oven dry makes skeleton ethamine hybridisation silica gel.
3, this skeleton ethamine hybridisation silica gel at 800 ℃ of roasting 2h, obtains skeleton azepine silica gel.
Embodiment 10:
The poromerics white carbon black according to the following steps with the methylamine effect, the white carbon black of preparation skeleton methylamine hydridization:
1, the aqueous solution of methylamine is mixed with white carbon black places reactor.Or the aqueous solution of methylamine placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains skeleton methylamine hydridization white carbon black.
3, skeleton methylamine hybrid material obtains skeleton azepine white carbon black at 500 ℃ of roasting 2h.
Embodiment 11:
The poromerics white carbon black according to the following steps with the dimethylamine effect, the white carbon black of preparation skeleton dimethylamine hydridization:
1, the aqueous solution of dimethylamine is mixed with white carbon black places reactor.Or the aqueous solution of dimethylamine placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry makes skeleton dimethylamine hydridization white carbon black.3. skeleton dimethylamine hydridization white carbon black at 500 ℃ of roasting 2h, obtains skeleton azepine white carbon black.
Embodiment 12:
The poromerics white carbon black according to the following steps with the ethamine effect, the white carbon black of preparation skeleton ethamine hydridization:
1, ethamine is mixed with white carbon black places reactor.Or the aqueous solution of ethamine put
Figure C20041001797400071
The reactor bottom, base material places the upper strata, and the centre separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure.
3, reaction product is washed after filtration, and oven dry at 500 ℃ of roasting 2h, obtains skeleton azepine white carbon black.
The data of table 1MFI soda acid change of properties after different modes is handled
Figure C20041001797400081
Table 2 different modes is measured the nitrogen content of poromerics
XPS Kjeldahl method for nitrogen determination The formaldehyde nitriding
Methylamine hydridization MFI 16.2％ 13.1％ 14.8％
Azepine MFI 13.8％ / /
Methylamine hydridization white carbon black 16.8％ 14％ /
The azepine white carbon black 16.2％ 12.3％ /

Claims (5)

1, a kind of amine skeleton hydridization alkalescence poromerics is characterized in that it being the skeleton oxygen that skeleton contains 1-20% in the oxygen poromerics is substituted with amido and to obtain, and wherein amido is methylamine, ethamine or dimethylamine.
2, poromerics according to claim 1 is characterized in that described skeleton contains the zeolite molecular sieve that the oxygen poromerics is a crystalline state, aluminium phosphate molecular sieve, mesopore molecular sieve, amorphous silica gel or white carbon black.
3, a kind of nitrogen skeleton hydridization alkalescence poromerics is characterized in that being prepared through 400-800 ℃ of roasting 1-3 hour by the described amine skeleton of claim 1 hydridization alkalescence poromerics.
4, a kind of preparation method of alkaline poromerics as claimed in claim 1 is characterized in that the aqueous solution of base material and amine is placed reactor, carry out hydro-thermal reaction, temperature 100-200 ℃, time 10-50 hour, obtain amine and replace the skeleton hybridized microporous material; Or amine placed the reactor bottom, and base material places the upper strata, carries out hydro-thermal reaction, and temperature 100-200 ℃, time 10-50 hour, the steam and the base material generation gas/solid state reaction that produce when utilizing heating were prepared into amine replacement skeleton hydridization micropore catalytic material.
5, a kind of preparation method of alkaline poromerics as claimed in claim 3 is characterized in that claim 4 gained material making skeleton azepine choline poromerics further through 400～800 ℃ temperature roasting 1～3 hour.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0479354A1 (en) * 1990-09-12 1992-04-08 Shell Internationale Researchmaatschappij B.V. Nitrided silica
WO2003097531A1 (en) * 2002-05-01 2003-11-27 Exxonmobil Chemical Patents Inc. Synthetic porous crystalline mcm-71, its synthesis and use

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0479354A1 (en) * 1990-09-12 1992-04-08 Shell Internationale Researchmaatschappij B.V. Nitrided silica
WO2003097531A1 (en) * 2002-05-01 2003-11-27 Exxonmobil Chemical Patents Inc. Synthetic porous crystalline mcm-71, its synthesis and use

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