CN101284244B - Catalyst for synthesizing the aziridine type compound - Google Patents
Catalyst for synthesizing the aziridine type compound Download PDFInfo
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Abstract
The invention discloses a modified zeolite catalyst with the component of XaYbOc(ZSM-5)d, wherein X is selected from alkali metal or alkaline earth metal, Y is selected from phosphorus or boron element, O is oxygen element; a, b, c and d are the molar ratio of X, Y, O and ZSM-5 zeolite, when d is equal to 1, a is equal to 0.01 to 0.1, b is equal to 0.001 to 0.1 and the value of c depends on a andb. The modified zeolite catalyst of the invention is used for the synthesis of ethylene imine by using monoethanolamine, which can obtain satisfactorily high yield and high selectivity. The catalyst of the invention can also be used for preparing ethylene imine compound shown in the general formula (2) by using ethanolamine compound shown in the general formula (1), wherein R1, R2, R3 and R4 are H, methyl or ethyl.
Description
Technical field
The invention belongs to catalyst field, relate to a kind of modified zeolite catalyst that is used for the synthesizing ethylene imine compound particularly.
Background technology
Aziridine is a kind of important fine chemical product, can be used for making dyestuff, agricultural chemicals, photosensitive material, softening agent, medical product or the like, and aziridine derivative and polymine have extensive use in fiber industry, also can be used for wastewater treatment etc.The initial industrial making method of aziridine is a liquid phase method, is raw material with the MEA, adopts the concentrated sulfuric acid as dehydrating agent.Need to add a large amount of concentrated bases in the reaction, cost is higher and produce a large amount of useless inorganic salts by-products, has caused the serious environmental pollution.Therefore catalytic dehydration generation aziridine method has caused extensive concern in the monoethanolamine gas-solid phase molecule.
Japan Patent JP5010593/1975 has proposed dehydration method synthesizing ethylene imines in the MEA catalytic molecular, and it mainly adopts the W oxide as catalyst, and co-catalyst is: one or more in Li, Mg, Sn, Bi, Mn, Ni and the Al oxide; U.S. Pat 4301036 has also been reported the use of catalyst in the aziridine preparation that tungsten oxide and Si oxide are formed.U.S. Pat 4289656,4301036,4337175,4358405, proposed in 4376732,4477591 with niobium (Nb)/tantalum (Ta) oxide and alkaline earth oxide with (or) iron/chromated oxide is as the method for Catalyst Production the aziridine type compound.
Above-mentioned catalyst is used for the MEA reaction, and conversion ratio is very low mostly; Even minority catalyst conversion ratio is higher, but, the selectivity of purpose product the aziridine type compound is reduced greatly owing to the generation of deaminizating and intermolecular condensation side reaction increases accessory substance; This type of catalyst is unfavorable for suitability for industrialized production because inactivation comparatively fast causes service life short simultaneously.
European patent EP 227461 has been reported a kind of siliceous composite oxide catalysts, European patent EP 228898 and EP230776 have reported the application in the dehydration in the alcamine compound catalytic molecular of a kind of phosphorous composite oxide catalysts, the use of these catalyst can solve and generate the problem that by-product is more and catalyst life is not long in the alcamine compound gas phase catalysis molecule inner dewatering reaction, but because by-product carbonyls (as: acetaldehyde) in the reaction and amine (as: ethamine) can react with the raw alcohol aminated compounds, the alcamine compound amount that causes participating in dehydration reduces, particularly carbonyls easily with alcamine compound addition reaction generation schiff bases (Schiff) compounds, influenced the further raising of aziridine product selectivity, so still need improve.
The zeolite molecular sieve that world patent WO8905797 once proposed with alkali metal or alkaline-earth metal dipping is the method for the alcamine compound intramolecular dehydration production the aziridine type compound of catalyst, but the MEA conversion ratio is very low in the example of its production aziridine, the weight selectivity of aziridines compound is up to 65%, but corresponding weight conversion ratio has only 1%, and the easy inactivation of this catalyst, be unfavorable for suitability for industrialized production.
Summary of the invention
The objective of the invention is to, develop a kind of new modified zeolite catalyst, be used for MEA or alcamine compound catalyzed gas molecule inner dewatering reaction,, satisfy industrial needs to improve the yield and the selectivity of synthesizing ethylene imines or the aziridine type compound.
Technical scheme of the present invention is as follows:
The present invention proposes a kind of modified zeolite catalyst, composed as follows:
X
aY
bO
c(ZSM-5)
d
Wherein X is selected from alkali metal or alkaline-earth metal, and Y is selected from phosphorus or boron element, and O is an oxygen element;
A, b, c, d are the mol ratios of X, Y, O, ZSM-5 zeolite, when d=1, and a=0.01～0.1, b=0.001～0.1, the c value depends on a, b.
The further preferred modified zeolite catalyst of the present invention consists of: X is selected from sodium, potassium, caesium, magnesium, calcium or barium, and Y is selected from phosphorus or boron element, and O is an oxygen element; When d=1, a=0.01～0.1, b=0.01～0.1, the c value depends on a, b.
It is as follows to prepare the used raw material of modified zeolite catalyst of the present invention:
The ZSM-5 zeolite, mean molecule quantity in 60 (because the present invention all selects silica-rich zeolite for use, calculate for convenience, its molecular weight is in the silicon dioxide molecules amount), can select in the existing commercially available prod any one for use, also can prepare (as adopting reported method in the following document: VP Shiralkar, AClearfield according to known method, Zeolites 9:363-370,1989; RAiello, F Crea, A Nastro, C Pellegrino, Zeolites 7:549-553,1987; BM Lowe, JRD Nee JL Casci, Zeolites 14:610-619,1994).The ZSM-5 zeolite can be preferably Hydrogen for Hydrogen or sodium type.The optional scope of silica alumina ratio is 25 to infinity, but consider silica-rich zeolite at high temperature stability increase and reduce gradually with silica alumina ratio, so the preferred range of silica alumina ratio is between 25-300.
Component X can be selected from oxide, hydroxide, halide or the salt (for example its nitrate, carbonate, sulfate etc.) of alkali metal or alkaline-earth metal.
Component Y can be selected from phosphoric acid (for example orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid or polyphosphoric acid), phosphate (for example, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), sodium phosphate etc.), phosphorus pentoxide, boric acid or boron oxide.
Also can use element X and the formed salt of various phosphoric acid source as component X and phosphorus.
Modified zeolite catalyst of the present invention can adopt arbitrary known method preparation of existing Preparation of Catalyst.After promptly can adopting mixing method, each component dry powder fully being mixed, add certain binding agent (as water, Ludox etc.), make after fully kneading, drying, roasting, the pulverizing; Perhaps adopt infusion process, the former powder of ZSM-5 is made carrier by adding a certain amount of binding agent (as water, Ludox etc.), flood X and Y component solution (water or ethanolic solution etc.) then, make after drying, roasting, the pulverizing.Usually the sintering temperature of catalyst is according to raw material and preparation method's difference and difference.The sintering temperature of modified zeolite catalyst of the present invention is between 450-1000 ℃, and suitable temperature is 550-900 ℃.
The modified zeolite catalyst that the present invention is proposed is used for MEA catalyzed gas molecule inner dewatering reaction synthesizing ethylene imines, can obtain gratifying high yield and high selectivity.Reaction equation is as follows:
In like manner, catalyst of the present invention also can be used for the interior dehydration of the alcamine compound gas molecule in space shown in the general formula (I) and prepares the aziridine type compound shown in the general formula (II):
Wherein:
R1, R2, R3, R4 are H, methyl or ethyl.
Adopt the catalyst of the ZSM-5 zeolite through alkali metal or alkaline-earth metal, phosphorus or boron oxide compound modification of the present invention as the synthesizing ethylene imine compound, utilize the even pore passage structure of zeolite and selected the shape selectivity, improved reaction raw materials and the product diffusion effect in catalyst pores, having limited the intermolecular condensation accessory substance simultaneously generates, particularly reduce the reaction of reaction by-product acetaldehyde and raw material or purpose product, promptly reduced the generation of Schiff bases compound by-product, thereby improved the purpose product selectivity; The tar that also can alleviate to a certain extent simultaneously in the reaction generates, and improves the yield of purpose product.
Catalytic reaction involved in the present invention can be carried out in fixed bed, fluid bed or moving-burden bed reactor.Can add inert gas dilution reaction raw materials such as nitrogen, argon gas, helium in the reaction, the volume ratio that inert gas accounts for total gas can be 10-99%, preferably 50-99%.Reaction can be carried out under normal pressure, mesolow or negative pressure, preferably reacts under normal pressure or negative pressure.Reaction temperature is generally carried out under 300-600 ℃, preferably 350-500 ℃ of reaction down.Total gas space velocity of reaction raw materials is 200-20000h
-1, 500-10000h preferably
-1Can also add components such as hydrogen, water, ammonia in the course of reaction so that stop the generation of side reaction to a certain extent.
The specific embodiment
Following example is in order to specifying the beneficial effect of using catalyst synthesizing ethylene imines of the present invention, but the present invention only limits to this absolutely not.
Employed conversion ratio in the example optionally is defined as follows:
MEA conversion ratio (mole %)=
(participating in the MEA molal quantity/MEA charging molal quantity of reaction) * 100%;
Aziridine selectivity (mole %)=
(the MEA molal quantity of the aziridine molal quantity of generation/participation reaction) * 100%.
Example 1
Catalyst proportion (stoichiometry): Na
0.04P
0.02O
0.07(ZSM-5).
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=100), it is diameter 1.2mm strip that the water of itself and appropriate amount and 1.366g three water ammonium phosphate, 1.140g sodium nitrate are fully mediated extrusion modling, be dried to constant weight in 120 ℃, pulverize behind 750 ℃ of roasting 8h to the 14-20 order and make catalyst.
Catalytic reaction is carried out in the stainless steel fixed bed reactors.Reactor inside diameter 12mm, catalyst admission space 20ml, reaction temperature: 420 ℃, inertia protection gas is nitrogen, N
2/ MEA (gas volume ratio)=10, the total air speed of reacting gas (in standard state): 3000h
-1Be reflected under the normal pressure and carry out, reaction 5h, the gas chromatographic analysis result, the MEA conversion ratio is 90%, the aziridine selectivity is 72%.
Example 2
Catalyst proportion (stoichiometry): K
0.04P
0.02O
0.07(ZSM-5).
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=100), it is diameter 1.2mm strip that the water of itself and appropriate amount and 1.366g three water ammonium phosphate, 1.354g potassium nitrate are fully mediated extrusion modling, be dried to constant weight in 120 ℃, pulverize behind 800 ℃ of roasting 4h to the 14-20 order and make catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 87%, and the aziridine selectivity is 75%.
Example 3
Catalyst proportion (stoichiometry): Mg
0.04P
0.02O
0.09(ZSM-5).
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=100), it is diameter 1.2mm strip that the water of itself and appropriate amount and 1.366g three water ammonium phosphate, 0.781g magnesium hydroxide are fully mediated extrusion modling, be dried to constant weight in 120 ℃, pulverize behind 800 ℃ of roasting 8h to the 14-20 order and make catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 90%, and the aziridine selectivity is 70%.
Example 4
Catalyst proportion (stoichiometry): Ba
0.04P
0.02O
0.09(ZSM-5).
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=100), it is diameter 1.2mm strip that the water of itself and appropriate amount and 1.366g three water ammonium phosphate, 3.500g barium nitrate are fully mediated extrusion modling, be dried to constant weight in 120 ℃, pulverize behind 850 ℃ of roasting 6h to the 14-20 order and make catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 88%, and the aziridine selectivity is 73%.
Example 5
Catalyst proportion (stoichiometry): Ca
0.04P
0.02O
0.09(ZSM-5).
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=100), it is diameter 1.2mm strip that the water of itself and appropriate amount and 1.366g three water ammonium phosphate, 3.163g four water-calcium nitrate are fully mediated extrusion modling, be dried to constant weight in 120 ℃, pulverize behind 800 ℃ of roasting 8h to the 14-20 order and make catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 88%, and the aziridine selectivity is 71%.
Example 6
Catalyst proportion (stoichiometry): Na
0.04B
0.02O
0.05(ZSM-5).
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=100), it is diameter 1.2mm strip that the water of itself and appropriate amount and 0.420g boric acid, 1.150g sodium nitrate are fully mediated extrusion modling, be dried to constant weight in 120 ℃, pulverize behind 800 ℃ of roasting 6h to the 14-20 order and make catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 71%, and the aziridine selectivity is 68%.
Example 7
Catalyst proportion (stoichiometry): Mg
0.04B
0.02O
0.07(ZSM-5).
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=100), it is diameter 1.2mm strip that the water of itself and appropriate amount and 0.420g boric acid, 3.300g magnesium nitrate hexahydrate are fully mediated extrusion modling, be dried to constant weight in 120 ℃, pulverize behind 850 ℃ of roasting 8h to the 14-20 order and make catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 68%, and the aziridine selectivity is 66%.
Example 8
Catalyst proportion (stoichiometry): Cs
0.04P
0.02O
0.07(ZSM-5).
The former powder of H-ZSM-5 (Shanghai multiple Xu Fenzishaichang) 50g (Si/Al=100) adds the water of appropriate amount, and mediating extrusion modling is diameter 1.2mm strip, is dried to constant weight in 120 ℃, pulverizes after 550 ℃ of roastings to the 14-20 order and makes carrier.Getting 20g impregnated in the solution that three water ammonium phosphate 1.367g, cesium nitrate 2.446g, distilled water 15g are made into.Fully dipping is dried to constant weight for back 120 ℃, makes catalyst behind 800 ℃ of roasting 10h.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 84%, and the aziridine selectivity is 84%.
Example 9
Catalyst proportion (stoichiometry): Cs
0.03P
0.02O
0.065(ZSM-5).
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=100), it is diameter 1.2mm strip that the water of itself and appropriate amount and 0.889g diammonium hydrogen phosphate, 1.827g cesium nitrate are fully mediated extrusion modling, be dried to constant weight in 120 ℃, pulverize behind 850 ℃ of roasting 10h to the 14-20 order and make catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 83%, and the aziridine selectivity is 75%.
Example 10
Catalyst proportion (stoichiometry): Cs
0.06P
0.02O
0.08(ZSM-5).
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=50), it is diameter 1.2mm strip that the water of itself and appropriate amount and 0.889g diammonium hydrogen phosphate, 3.482g cesium nitrate are fully mediated extrusion modling, be dried to constant weight in 120 ℃, pulverize behind 800 ℃ of roasting 2h to the 14-20 order and make catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 81%, and the aziridine selectivity is 76%.
Example 11
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=270), catalyst proportion, raw material composition, method for preparing catalyst, catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 85%, and the aziridine selectivity is 79%.
Example 12
All catalyst proportions, raw material composition, method for preparing catalyst, catalytic reaction condition and analysis condition all are same as example 8, and the 100h that turns round continuously, MEA conversion ratio are 73%, and the aziridine selectivity is 77%.
Example 13
Catalyst proportion (stoichiometry): Cs
0.06P
0.02O
0.08(ZSM-5).
The former powder of H-ZSM-5 (Catalyst Factory, Nankai Univ) 50g (Si/Al=50) adds the water of appropriate amount, and mediating extrusion modling is diameter 1.2mm strip, is dried to constant weight in 120 ℃, pulverizes after 550 ℃ of roastings to the 14-20 order and makes carrier.Get 20g and impregnated in the solution that three water ammonium phosphate 1.367g, cesium nitrate 3.482g, distilled water 15g are made into, fully flood back 120 ℃ and be dried to constant weight, behind 800 ℃ of roasting 10h, make catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 81%, and the aziridine selectivity is 77%.
Example 14
Catalyst proportion (stoichiometry): Mg
0.2P
0.1O
0.45(ZSM-5).
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=100), it is diameter 1.2mm strip that the water of itself and appropriate amount and 6.830g three water ammonium phosphate, 13.750g magnesium nitrate hexahydrate are fully mediated extrusion modling, be dried to constant weight in 120 ℃, pulverize behind 850 ℃ of roasting 8h to the 14-20 order and make catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 96%, and the aziridine selectivity is 56%.
Example 15
Catalyst proportion (stoichiometry): Mg
0.02P
0.01O
0.45(ZSM-5).
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=100), it is diameter 1.2mm strip that the water of itself and appropriate amount and 0.683g three water ammonium phosphate, 1.375g magnesium nitrate are fully mediated extrusion modling, be dried to constant weight in 120 ℃, pulverize behind 850 ℃ of roasting 8h to the 14-20 order and make catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 86%, and the aziridine selectivity is 76%.
Example 16
Catalyst proportion (stoichiometry): Mg
0.01P
0.001O
0.45(ZSM-5).
The former powder of H-ZSM-5 (the multiple Xu Fenzishaichang in Shanghai) 20g (Si/Al=100), it is diameter 1.2mm strip that the water of itself and appropriate amount and 0.068g three water ammonium phosphate, 0.688g magnesium nitrate are fully mediated extrusion modling, be dried to constant weight in 120 ℃, pulverize behind 850 ℃ of roasting 8h to the 14-20 order and make catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 65%, and the aziridine selectivity is 72%.
Case of comparative examples 1
The former powder of H-ZSM-5 (Shanghai multiple Xu Fenzishaichang) 50g (Si/Al=100) adds the water of appropriate amount, and mediating extrusion modling is diameter 1.2mm strip, is dried to constant weight in 120 ℃, pulverizes after 550 ℃ of roastings to the 14-20 order and makes catalyst.
Catalytic reaction condition and analysis condition are with example 1.The MEA conversion ratio is 100%, and the aziridine selectivity is 2.5%.
Claims (2)
1. a modified zeolite catalyst is used for the purposes of synthesizing ethylene imine compound, it is characterized in that this catalyst has following composition:
X
aY
bO
c(ZSM-5)
d，
Wherein X is selected from alkali metal or alkaline-earth metal, and Y is selected from phosphorus or boron element, and O is an oxygen element;
A, b, c, d are the mol ratios of X, Y, O, ZSM-5 zeolite, when d=1, and a=0.01～0.1, b=0.001～0.1, the c value depends on a, b;
Described the aziridine type compound structure such as general formula (II):
In the formula: R1, R2, R3, R4 are H, methyl or ethyl.
2. according to the described purposes of claim 1, it is characterized in that: X is selected from sodium, potassium, caesium, magnesium, calcium or barium in this catalyst, and Y is selected from phosphorus or boron element, and O is an oxygen element; When d=1, a=0.01～0.1, b=0.01～0.1, the c value depends on a, b.
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