CN1428190A - Catalyst for preparing 1,3-propanediol by hydrogenation of lactic aldehyde - Google Patents

Abstract

The present invention relates to a catalyst for 3-hydroxypropanal hydrogenation to prepare 1,3-propylene glycol. Its active component is Ni-A, in which A is any one of Cr, Zn, Mo or Fe, the weight ratio of Ni and A is: Ni:A=1:0.01-1:0.1, its carrier is molecular sieve containing Al2O3 or SiO2 or containing both them, and the weight percentage content of active component of catalyst is 30-60%. Said catalyst can help to form high-activity nickel alloy cluster active centre, and can effectively modify pore channel of catalyst, and is favorable for diffusion of 3-hydropropanal so as to greatly raise the activity of catalyst.

Description

3-3-hydroxyl propionaldehyde hydrogenation to produce 1, the catalyst of ammediol

Technical field

The present invention relates to the 3-3-hydroxyl propionaldehyde hydrogenation to produce and be equipped with 1, the catalyst of ammediol contains Ni and Cr, Zn, Mo or Fe in the activity of such catalysts component.

Background technology

1, ammediol is a kind of broad-spectrum compound, and except that can be used for producing polyurethane and the cyclic compound, it still is a poly terephthalic acid 1, the principal monomer of ammediol ester fiber.Poly terephthalic acid 1, ammediol ester fiber are the polyester kinds of excellent performance, though just come out in the fifties, but because of 1, ammediol can't be realized industrialization, makes poly terephthalic acid 1, and the development of ammediol ester fiber stays cool for many years all the time.In recent years, along with 1, the success of ammediol suitability for industrialized production, poly terephthalic acid 1, the Application and Development of ammediol ester fiber receives publicity heavily again.At present, generate the 3-hydroxy propanal by acrolein hydration, and then make 1 by hydrogenation, ammediol is one of successful suitability for industrialized production route.By prior art as can be known, 3-3-hydroxyl propionaldehyde hydrogenation to produce 1, the preferred hydrogenation catalyst of ammediol roughly is divided into following a few class: one, Raney nickel type catalyst, and can add the metal that some have promoting catalysis; Two, be the catalyst of carrier with metal oxide or active carbon, active constituent is platinum or palladium; Three, with the molecular sieve be the catalyst of carrier, active constituent is a nickel.Second and third class catalyst is mainly used in the fixed bed reactors.

As United States Patent (USP) 5,093,537 have proposed a kind of 3-of being used for 3-hydroxyl propionaldehyde hydrogenation to produce 1, and ammediol contains the Raney nickel type catalyst of Mo, and catalyst grain size is 50m μ.Catalyst consumption is that the percentage by weight of catalyst in reactant liquor is 4～6%, the concentration expressed in percentage by weight of the raw material 3-hydroxy propanal aqueous solution is 10～20%, hydrogen pressure is 1.5～6.0mpa, hydrogenation temperature is 45～95 ℃, when hydrogenation time was 15～85min, the conversion ratio of 3-hydroxy propanal reached as high as 99%.But its shortcoming is 1, and the selectivity fluctuation of ammediol is bigger, and when conversion ratio was low, selectivity can reach 100%, but rose as conversion ratio, and selectivity then obviously descends.In addition, because catalyst granules is very little, the separation of catalyst from reactant liquor be difficulty quite, needs to add diatomite in advance usually in reactant liquor and just can separate, and makes catalyst to reuse like this.

At United States Patent (USP) 5,015, proposed to be used for two kinds of fixed bed hydrogenation catalyst of 3-hydroxy propanal in 789 and 5,364,984 respectively, it consists of Ni/Al ₂O ₃/ SiO ₂And Pt/TiO ₂Ni/Al ₂O ₃/ SiO ₂Catalyst is because activity is lower, and particularly activity stability is relatively poor, and the reaction later stage needs continuous rising Hydrogen Vapor Pressure on commercial plant, the concentration of 3-hydroxy propanal can be reduced to below 0.1%.And Pt/TiO ₂Catalyst is the improvement of this catalyst, especially aspect activity stability, improves a lot, but because platinum is easy to poisoning, so high to the sulphur in the reactant liquor, phosphorus and the requirement of arsenic equal size, also can cause the increase of production cost.

Summary of the invention

Technical problem to be solved by this invention provides a kind of 3-of being used for 3-hydroxyl propionaldehyde hydrogenation to produce and is equipped with 1, the catalyst of ammediol, it not only will have higher and stable catalytic activity, selectivity preferably, and insensitive to poisonous substances such as the sulphur in the reactant liquor, phosphorus and arsenic, to overcome the defective that prior art exists.

Technical problem to be solved by this invention is achieved through the following technical solutions:

A kind of 3-3-hydroxyl propionaldehyde hydrogenation to produce that is used for is equipped with 1, the catalyst of ammediol, and its active constituent is: Ni-A

Wherein A is any among Cr, Zn, Mo or the Fe,

The weight ratio of Ni and A is: Ni: A=1: (0.01～0.1).

Carrier is for containing Al ₂O ₃Or SiO ₂, or containing both molecular sieve simultaneously, the weight percentage of catalyst activity component is 30～60%.

Component A is preferably Cr or Mo; The weight ratio of Ni and A is preferably Ni: A=1: (0.02～0.08).

Catalyst can adopt the conventional method preparation.Generally be that fine grained molecular sieve and required active metallic compound are mixed the back extruded moulding, and be cut into particle, make compound decomposition become corresponding oxide through high-temperature roasting again, use hydrogen reducing at last, reduce to room temperature after secluding air preserve standby.

Catalyst provided by the invention is owing to added aiding catalytic component A, it can help to form highly active nickel alloy cluster activated centre on the one hand, on the other hand effective modification has been carried out in the duct of catalyst, helped the diffusion of 3-hydroxy propanal, thereby activity of such catalysts is significantly improved.It is insensitive to poisonous substances such as the sulphur in the reactant liquor, phosphorus and arsenic on the other hand, and desired hydroconversion condition is also relatively gentleer, and this is very favorable to reducing the hydrogenation production cost.

The specific embodiment

To come below that the invention will be further described by embodiment, in an embodiment:

[embodiment 1～14]

Preparation of catalysts:

With nickel nitrate and a kind of water soluble compound that contains aiding catalytic component A, be mixed with the aqueous solution according to certain ratio, add the carrier of catalyst more in proportion, and stir.After reaching certain viscosity, extruded moulding dries in the shade again.For the intensity that improves catalyst and make metallic compound resolve into oxide, more respectively 80 ℃, 300 ℃, 700 ℃ roastings 3 hours, 4 hours and 5 hours.Naturally reduce to room temperature after roasting finishes, and in the reduction reactor of packing into, when Hydrogen Vapor Pressure is 0.2MPa, heat up in about 4 hours of 470 ℃ of reduction, reducing degree can be judged from the water growing amount.Reduction drops to room temperature at nitrogen atmosphere after finishing, and is kept in the water standby.

The composition of each embodiment catalyst, the starting material of component A sees Table 1.

The evaluation of catalyst:

100 grams and 25 are restrained two tubular fixed-bed reactors that catalyst are respectively charged into series connection, first reactor charge, 100 grams, second reactor charge, 25 grams.To feed first reactor after the raw material 3-hydroxy propanal aqueous solution and the hydrogen mixing preheating, keep Hydrogen Vapor Pressure to carry out hydrogenation; Enter second reactor behind the first reactor outlet material heat temperature raising, keep Hydrogen Vapor Pressure to continue hydrogenation.Material behind the hydrogenation cools off laggard promoting the circulation of qi liquid to be separated, and liquid is analyzed wherein 3-hydroxy propanal, 1, ammediol and content of by-products with capillary chromatography.

Other concrete reaction condition and reaction result of each embodiment sees Table 2.Table 1.

	Component A	The starting material of component A	Ni: A (weight ratio)	Carrier	Active constituent content (%wt.)
						Embodiment 1	????Fe	Ferric nitrate	????1∶0.04	??SiO 2-Al 2O 3	????50.9
Embodiment 2	????Zn	Zinc nitrate	????1∶0.04	??SiO 2-Al 2O 3	????50.9
						Embodiment 3	????Cr	Chromic nitrate	????1∶0.04	??SiO 2-Al 2O 3	????50.9
Embodiment 4	????Mo	Ammonium molybdate	????1∶0.02	??Al 2O 3	????50.9
						Embodiment 5	????Mo	Ammonium molybdate	????1∶0.04	??SiO 2	????50.9
Embodiment 6	????Mo	Ammonium molybdate	????1∶0.06	??SiO 2-Al 2O 3	????50.9
						Embodiment 7	????Mo	Ammonium molybdate	????1∶0.10	??SiO 2-Al 2O 3	????50.9
Embodiment 8	????Mo	Ammonium molybdate	????1∶0.08	??SiO 2-Al 2O 3	????50.9
						Embodiment 9	????Mo	Ammonium molybdate	????1∶0.04	??SiO 2-Al 2O 3	????30.0
Embodiment 10	????Mo	Ammonium molybdate	????1∶0.04	??SiO 2-Al 2O 3	????50.0
						Embodiment 11	????Mo	Ammonium molybdate	????1∶0.05	??SiO 2-Al 2O 3	????60.0
Embodiment 12	????Mo	Ammonium molybdate	????1∶0.04	??SiO 2-Al 2O 3	????40.0
						Embodiment 13	????Mo	Ammonium molybdate	????1∶0.04	??SiO 2-Al 2O 3	????55.0
Embodiment 14	????Mo	Ammonium molybdate	????1∶0.04	??SiO 2-Al 2O 3	????60.0

Table 2.

	Material concentration (wt.%)	The one-stage hydrogenation temperature (℃)	The secondary hydrogenation temperature (℃)	Air speed (hr -1)	Hydrogen Vapor Pressure (mpa)	Conversion ratio (%)	Selectivity (%)
								Embodiment 1	????12	????50	????110	????3	????6.0	????100	????100
Embodiment 2	????12	????40	????120	????3	????6.0	????100	????100
								Embodiment 3	????12	????25	????120	????3	????6.0	????100	????100
Embodiment 4	????12	????60	????120	????3	????6.0	????100	????100
								Embodiment 5	????12	????50	????120	????3	????7.0	????100	????100
Embodiment 6	????12	????50	????120	????3	????5.0	????100	????100
								Embodiment 7	????12	????50	????120	????3	????4.0	????100	????100
Embodiment 8	????10	????50	????120	????3	????6.0	????100	????100
								Embodiment 9	????18	????50	????120	????3	????6.0	????100	????100
Embodiment 10	????20	????50	????120	????3	????6.0	????100	????99
								Embodiment 11	????25	????50	????120	????3	????6.0	????100	????99
Embodiment 12	????25	????50	????130	????0.1	????6.0	????100	????99
								Embodiment 13	????25	????50	????120	????0.5	????6.0	????100	????99
Embodiment 14	????25	????50	????120	????5	????6.0	????99	????100

Claims (3)

1, a kind of 3-3-hydroxyl propionaldehyde hydrogenation to produce that is used for is equipped with 1, the catalyst of ammediol, and its active constituent is:

Ni-A

Wherein A is any among Cr, Zn, Mo or the Fe,

The weight ratio of Ni and A is:

Ni∶A＝1∶0.01～1∶0.1，

Carrier is for containing Al ₂O ₃Or SiO ₂, or containing both molecular sieve simultaneously, the weight percentage of catalyst activity component is 30～60%.

2,, it is characterized in that A is Cr or Mo according to the described catalyst of claim.

3, according to the described catalyst of claim, the weight ratio that it is characterized in that Ni and A is Ni: A=1: 0.02～1: 0.08.