CN102008969A - Hydrogen type montmorillonite-supported ruthenium catalyst as well as preparation method and application method thereof - Google Patents

Abstract

The invention belongs to the technical field of catalyst preparation, in particular to hydrogen type montmorillonite-supported ruthenium catalyst as well as a preparation method and application method thereof. The hydrogen type montmorillonite-supported ruthenium catalyst comprises an active component RuCl3 and a carrier atlapulgite, wherein the capacity of the active component RuCl3 is 0.5-10% calculated in mass; and the carrier atlapulgite is montmorillonite which is subject to acid treatment and is in a layer structure. The preparation method comprises the following steps: (1) exchanging sodium; (2) preparing hydrogen pillared montmorillonite; (3) preparing Ru-supported atlapulgite catalyst; and (4) activating. The catalyst provided by the invention can be used for diaminodiphenyl-methane catalytic hydrogenation reaction. In the invention, the atlapulgite with low cost is taken as a carrier, thus reducing the cost of the catalyst, improving recycling rate of precious metals, and lowering consumption of the catalyst.

Description

Hydrogen montmorillonite load ruthenium catalyst, preparation method and application process

Technical field

The catalyst preparation technical field that belongs to of the present invention relates to a kind of support type Ru catalyst, preparation method's and methods for using them.

Background technology

4,4 '-two amidos-dicyclohexyl methyl hydride (being called for short PACM) are the synthetic methylene dicyclohexyl vulcabond intermediates of (being called for short PICM), generally by 4,4 '-two amido diphenyl methanes (being called for short MDA) liquid phase catalytic hydrogenation preparation.PICM belongs to the aliphatic category isocyanates of not flavescence, is mainly used in aspects such as PU elastomer, coating, leather, and its goods are better than HDI at aspect of performance.Its preparation usually divides following several steps to carry out: at first prepare diamines by aniline and formaldehyde condensation, i.e. and two amido diphenyl methanes (abbreviation MDA), and then hydrogenation becomes two amido dicyclohexyl methyl hydrides (PACM) in the presence of catalyst.At last become PICM through phosgenation reaction with the preparation of other aliphatic isocyanates is the same.Its reaction equation is as follows:

1. 4, the preparation of 4 '-MDA

；

2. 4, the hydrogenation of 4 '-MDA (preparation of PACM)

；

3. PACM and phosgene reaction prepare PICM

；

。

        

As can be seen, be committed step with synthetic PACM in this route.At present, the method for hydrogenation of generally acknowledging is hydrogenation under the metallic catalyst of ruthenium and rhodium composition with MDA and hydrogen, the purposes of the metallic catalyst that mixes is to select 5% ~ 50%(mass fraction in advance), it mainly is the ratio of anti--trans isomer of 14% ~ 28%, this is because MDA produces three kinds of isomers when hydrogenation, promptly anti--anti-, anti--suitable, suitable-suitable, its structural formula is as follows:

(anti--suitable)

(anti--anti-)

(suitable-suitable).

The composition of isomers has determined the character and the purposes of itself and subsequent product thereof, and be difficult to obtain the PACM that single or specific isomers is formed by separation means, therefore industrial PACM product is various stereomeric mixtures and is accustomed to using anti--trans isomer content to define specification and the purposes of PACM, instead-trans isomer content 20% is hereinafter referred to as PACM-20, be mainly used in the preparation aliphatic polyurethane, instead-trans isomer content about 50% is called PACM-50, is mainly used in the preparation polyamide.

Anti-low-anti-PACM makes catalyst with MDA hydrogenation by ruthenium, proposes unnecessary anti--trans isomer then and obtain from reactor product, and the PICM that is made by PACM-20 is a liquid diisocyanate stable under a kind of room temperature.On the contrary, its anti--trans isomer content of PACM-50 is near 50%, at room temperature is solid by the corresponding PICM of its production.Therefore, for the production of isocyanates and in the further application aspect the polyurethane, in PICM synthetic, PACM-20 is better than PACM-50.

Whitman finds in his research report, the Ru catalyst has unique selectivity on preparation PACM stereoisomer mixture, and the Ru catalyst is under low relatively temperature, can promote the high yield of aromatic nitrogen compound effectively to a step hydrogenation reaction of corresponding hexamethylene fatty amine, so in the ruthenium reaction that just is used in body series very early.

Adopt the catalyst of dipping evaporation preparation, be carried on the inert carrier by metal usually, suitable inert carrier comprises charcoal, calcium carbonate, rare earth oxide, alundum (Al, diatomite, titanium dioxide, silica etc.But these researchs do not relate to Preparation of catalysts and the application that contains montmorillonite carrier.

Imvite class catalyst is widely used in organic reaction as a kind of effective solid acid catalyst.Up to the present, this class catalyst has been successfully applied to substitution reaction, addition reaction, oxidation reaction and rearrangement reaction etc.

Along with improving constantly of imvite modified technology, the purposes of atlapulgite is more and more wider, except traditional decolouring field, atlapulgite has wide application prospect in fields such as preparation solid acid catalyst and alkaline bentonites, as publication number is that the Chinese patent of CN200510101332.X discloses alkaline calcium bentonite and preparation method thereof, " Chinese Journal of Inorganic Chemistry " 2007 the 6th phase 1111-1116 page or leaf has been reported water-resistance solid acid SO42--TiO2-Clay Preparation of catalysts and application, all be that raw material carries out modification with the atlapulgite, how much directly related the effect of modification and the tradable hydrionic quantity of the interlayer of atlapulgite is.

Summary of the invention

The technical problem to be solved in the present invention is under the prerequisite of not using Noble Metal Rhodium Rh, and a kind of catalyst and preparation method of the MDA of being used for catalytic hydrogenation reaction is provided, and this catalyst is a load Ru slaine on sour pillared montmorillonite carrier.

The present invention is achieved by the following technical solutions:

Described Hydrogen montmorillonite load ruthenium catalyst of the present invention, by active component RuCl ₃Form with the carrier atlapulgite, wherein active component RuCl ₃Load capacity be 0.5% ~ 10% in mass; Be preferably 5% ~ 10%, wherein said carrier atlapulgite is for adopting acid-treated imvite with layer structure.

The preparation method of above-mentioned Hydrogen montmorillonite load ruthenium catalyst, carry out according to following step:

(1) sodium exchange:

To be sized to 200 purpose Ca base montmorillonites mixes with distilled water, be stirred to pulpous state, add again and be equivalent to the NaCl crystal of 0.1 ~ 1 times of native dry weight consumption by weight, add thermal agitation 2h at 60 ℃, after natridization reaction finishes, centrifugal filtration, with deionized water washing sediment to there not being chlorion, 80 ℃ of oven dry obtain the Na base montmorillonite;

(2) preparation of hydrogen pillared montmorillonite:

It is 10 ~ 30%H that above-mentioned Na base montmorillonite is soaked in volume fraction ₂SO ₄In the solution, isothermal reaction 2 ~ 7 hours, reaction temperature is 50 ~ 100 ℃, the mass ratio of sulfuric acid and sodium-based montmorillonite is 2 ~ 5:1; Soil paste after the activation is filtered, and it is to grind after 4 ~ 5,105 ℃ of oven dry that filter cake is washed till pH value with distilled water, and mistake 200 orders promptly get the carrier atlapulgite;

(3) active clay loaded Ru Preparation of catalysts:

According to the load capacity of ruthenium is 5～10% to determine required RuCl in mass ₃Total amount, and be dissolved in wiring solution-forming in the distilled water, adopt excessive infusion process in solution, to add the carrier atlapulgite, constantly be stirred to color and shoal; It is neutral transferring pH with NaOH; Extremely neutral with distilled water washing, suction filtration, flush away NaCl, drying;

(4) activation:, use H at 250 ~ 500 ℃ in the required above-mentioned ruthenium catalyst of ratio weighing of catalytic hydrogenation reaction ₂Reduction 1 ~ 5h; Make load Ru catalyst.

The above-mentioned load Ru Application of Catalyst method for preparing, its step is as follows:

Support type Ru catalyst is joined in the autoclave with the MDA that is dissolved in oxolane (THF), wherein catalyst consumption is the 4wt% of reaction system, temperature rises to 120 ℃, control reaction pressure 5.5MPa ~ 8 MPa under 1200r/min stirs, reacted 1 ~ 20 hour, utilize the control hydrogen, the control reaction process; Question response finishes, and closes heating, feeds cooling water, when temperature of reaction kettle is lower than 45 ℃, stops to stir release, discharging; Wash out remaining catalyst then, product obtains with vacuum filtration.

The present invention uses cheap atlapulgite as carrier, has reduced the cost of catalyst, has improved the noble metal recovery utilization rate, has reduced the consumption of catalyst.

The specific embodiment

Embodiment 1:

The preparation of catalyst 1

With granularity is 200 purpose Ca type imvites (available from Zhejiang Feng Hong new material limited company), adds distilled water by solid-to-liquid ratio 1:10, is stirred to pulpous state; Add the NaCl crystal be equivalent to imvite quality 6%, add thermal agitation 2h at 60 ℃, centrifugation, with deionized water washing sediment to there not being Cl ^-, 80 ℃ of oven dry are ground, and cross 200 orders and obtain the imvite of Na type;

Take by weighing the imvite of Na type, it is soaked in volume fraction is 10%H ₂SO ₄In the solution, press m (imvite) down for 100 ℃: V (10%H ₂SO ₄)=l (g): 30 (ml), stirring reaction 6h filters the soil paste after the activation, and it is to grind after 4 ~ 5,105 ℃ of oven dry that filter cake is washed till pH value with distilled water, and mistake 200 orders promptly get atlapulgite.

The 1.9g atlapulgite is joined in the beaker that contains the 10g deionized water, stir 5min.Get 0.2703g ruthenic chloride (RuCl ₃) be dissolved in the deionized water, under stirring condition, solution is scattered on the atlapulgite equably.It is neutral regulating the pH value with NaOH solution, uses the deionized water cyclic washing then, filters, and does not have Cl to filtrate ^-Exist.The catalyst that makes in 200 ℃ in air drying 4 hours, in the presence of hydrogen in 250 ℃ of following reductase 12s hour.Make 5%Ru/ activated bauxite catalyst 1.

Embodiment 2:

The preparation of catalyst 2

With embodiment 1.Different is that dried sample is used H at 500 ℃ ₂Reductase 12 hour.Make required support type 5%Ru/ activated bauxite catalyst 2.

Embodiment 3:

The preparation of catalyst 3

With granularity is 200 purpose Ca type imvites, adds distilled water by solid-to-liquid ratio 1:10, is stirred to pulpous state; Add the NaCl crystal be equivalent to imvite quality 6%, add thermal agitation 2h at 60 ℃, centrifugation, with deionized water washing sediment to there not being Cl ^-, 80 ℃ of oven dry are ground, and cross 200 orders and obtain the imvite of Na type;

Take by weighing the imvite of Na type, it is soaked in volume fraction is 30%H ₂SO ₄In the solution, press m (imvite) down for 100 ℃: V (30%H ₂SO ₄)=l (g): 30 (ml), stirring reaction 6h filters the soil paste after the activation, and it is to grind after 4 ~ 5,105 ℃ of oven dry that filter cake is washed till pH value with distilled water, and mistake 200 orders promptly get atlapulgite.

The 1.9g atlapulgite is joined in the beaker that contains the 10g deionized water, stir 5min.Get 0.2703g ruthenic chloride (RuCl ₃) be dissolved in the deionized water, under stirring condition, solution is scattered on the atlapulgite equably.It is neutral regulating the pH value with NaOH solution, uses the deionized water cyclic washing then, filters, and does not have Cl to filtrate ^-Exist.The catalyst that makes in 200 ℃ in air drying 4 hours, in the presence of hydrogen in 250 ℃ of following reductase 12s hour.Make the 5%Ru/ activated bauxite catalyst.

Embodiment 4:

The preparation of catalyst 4

With embodiment 3.Different is that dried sample is used H at 500 ℃ ₂Reductase 12 hour.Make required support type 5%Ru/ activated bauxite catalyst 4.

Embodiment 5 load Ru Application of Catalyst methods:

In the stainless steel autoclave of band stirring, adding 4,4 '-MDA 5 g, add auxiliary agent, the above-mentioned 5%Ru/ activated bauxite catalyst of 0.2g.The envelope still, stirring is opened in leak detection, and the maintenance rotating speed is 1200r/min, uses H ₂The air of replacement reaction kettle three times, heating reactor to 120 ℃ feeds hydrogen again to 8.0MPa under Hydrogen Vapor Pressure 5.0MPa, keeps the required pressure of reaction to finish until reaction.Take out reactant liquor, remove by filter catalyst, filtrate is adopted gas chromatographic analysis, calculates target product yield with internal standard method.Product the results are shown in table 1 through gas chromatographic analysis in the foregoing description.

The data declaration of table 1, after the acidification by certain hour, raising with acid concentration, reaction yield improves thereupon, this may be the layer structure that the sulfuric acid of low concentration helps keeping imvite, the sulfuric acid of high concentration makes the structural deterioration of imvite, helps the load of reagent, thereby improves reactive activity;

Catalyst activity during high-temperature activation reduces, and this may be because too high sintering temperature makes the activated centre of catalyst surface run off, thereby causes catalytic activity to descend.

Claims (4)

1. Hydrogen montmorillonite load ruthenium catalyst is characterized in that being made up of active component RuCl3 and carrier atlapulgite, and wherein the load capacity of active component RuCl3 is 0.5% ~ 10% in mass; Wherein said carrier atlapulgite is for adopting acid-treated imvite with layer structure.

2. Hydrogen montmorillonite load ruthenium catalyst according to claim 1 is characterized in that wherein the load capacity of active component RuCl3 is 5% ~ 10% in mass.

3. the preparation method of Hydrogen montmorillonite load ruthenium catalyst is characterized in that carrying out according to following step:

(1) sodium exchange:

To be sized to 200 purpose Ca base montmorillonites mixes with distilled water, be stirred to pulpous state, add again and be equivalent to the NaCl crystal of 0.1 ~ 1 times of native dry weight consumption by weight, add thermal agitation 2h at 60 ℃, after natridization reaction finishes, centrifugal filtration, with deionized water washing sediment to there not being chlorion, 80 ℃ of oven dry obtain the Na base montmorillonite;

(2) preparation of hydrogen pillared montmorillonite:

It is 10 ~ 30%H that above-mentioned Na base montmorillonite is soaked in volume fraction ₂SO ₄In the solution, isothermal reaction 2 ~ 7 hours, reaction temperature is 50 ~ 100 ℃, the mass ratio of sulfuric acid and sodium-based montmorillonite is 2 ~ 5:1; Soil paste after the activation is filtered, and it is to grind after 4 ~ 5,105 ℃ of oven dry that filter cake is washed till pH value with distilled water, and mistake 200 orders promptly get the carrier atlapulgite;

(3) active clay loaded Ru Preparation of catalysts:

According to the load capacity of ruthenium is 5～10% to determine required RuCl in mass ₃Total amount, and be dissolved in wiring solution-forming in the distilled water, adopt excessive infusion process in solution, to add the carrier atlapulgite, constantly be stirred to color and shoal; It is neutral transferring pH with NaOH; Extremely neutral with distilled water washing, suction filtration, flush away NaCl, drying;

(4) activation:, use H at 250 ~ 500 ℃ in the required above-mentioned ruthenium catalyst of ratio weighing of catalytic hydrogenation reaction ₂Reduction 1 ~ 5h; Make load Ru catalyst.

4. the application process of Hydrogen montmorillonite load ruthenium catalyst is characterized in that step is as follows:

Support type Ru catalyst is joined in the autoclave with the MDA that is dissolved in oxolane (THF), wherein catalyst consumption is the 4wt% of reaction system, temperature rises to 120 ℃, control reaction pressure 5.5MPa ~ 8 MPa under 1200r/min stirs, reacted 1 ~ 20 hour, utilize the control hydrogen, the control reaction process; Question response finishes, and closes heating, feeds cooling water, when temperature of reaction kettle is lower than 45 ℃, stops to stir release, discharging; Wash out remaining catalyst then, product obtains with vacuum filtration.