CN103111314B

CN103111314B - Catalyst for preparing glyceryl monostearate by continuous complete hydrogenation of grease and preparation method of catalyst

Info

Publication number: CN103111314B
Application number: CN201110365245.0A
Authority: CN
Inventors: 周生虎; 王金龙
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2011-11-17
Filing date: 2011-11-17
Publication date: 2015-05-13
Anticipated expiration: 2031-11-17
Also published as: CN103111314A

Abstract

The invention relates to a catalyst for preparing glyceryl monostearate by continuous complete hydrogenation of grease and a preparation method of the catalyst. The catalyst adopts alumina as carrier, and the active ingredients of the catalyst are uniformly distributed or distributed in the shape of an eggshell on the carrier, wherein the active ingredients of the catalyst are shown by the following general formula in molar ratio: Pd0.1NaaPbMcOx, wherein M is selected from at least one of Mg, Ca, La, Ce, Y, Zr, Fe, V, Mo or W; a is not less than 0 and not more than 2; b is not less than 0 and not more than 0.2; c is more than 0 and not more than 0.3; x is the total number of oxygen atoms needed for satisfying the valence of other elements; and the carrier alumina is 60.0%-99.9% of the catalyst in weight. The catalyst disclosed by the invention has the advantages of being high in activity, long in service life and unlikely to loss; the conventional nickel-based catalyst is replaced by a palladium catalyst for being used in trickle-bed large-scale production and continuous grease hydrogenation reaction; and meanwhile, the post-treatment steps of the product can be simplified, the production capacity is improved and the operation cost is reduced.

Description

Grease serialization complete hydrogenation prepares the Catalysts and its preparation method of tristerin

Technical field

The present invention relates to a kind of catalyst, specifically a kind of Catalysts and its preparation method preparing tristerin for grease scale, serialization complete hydrogenation.

Background technology

Stearic acid plays an important role in the synthesis and process of rubber, can be used as vulcanizing activator, plasticizer, softening agent, foaming agent and releasing agent, in textile and dyeing industry, stearic acid is as uses such as dispersant, softening agent, penetrant, anti-friction composition, defoamers.Current stearic acid obtains mainly through hydrolysis edible animals and plants grease, however hydrolysis animal and plant fat obtain aliphatic acid and contain a large amount of unrighted acids, as the highest butter of stearic acid content, stearic acid content also only has 24%.Therefore, Unsaturatcd fatty acid glycerides in animal and plant fat is hydrogenated to tristerin by development oil hydrogenation catalyst, then can greatly improve stearic yield through hydrolytic process, can improve the utilization rate of animal and plant fat simultaneously.

Since 20 beginning of the century oil hydrogenations realize industrialization, people develop oil hydrogenation catalyst always, modification, perfect research, current is main research direction (US4683088 with copper nickel binary catalyst and unit nickel catalyst, CN1021106C, CNZL97205577.0, JP54094489 etc.).The antioxidative stabilizer that unit nickel catalyst cost is low, catalytic activity is high, grease after hydrogenation has height during room temperature storage, but because metallic nickel is more active, Ni can part run off in hydrogenated oil and fat, cause Ni catalyst life very short, therefore oil hydrogenation process all uses autoclave batch reactor, after reaction terminates, Ni catalyst need be filtered out from the grease after hydrogenation, cause production capacity low, not easily scale, serialization; Cu is the pro-oxidant of grease, and millionth residual quantity all will have influence on the stability of hydrogenated oil and fat, and therefore, when using copper catalyst, product postprocessing is cumbersome.Homogeneous catalyst (CN85103783A etc.) can overcome some shortcomings of nickel-base catalyst, as the catalyst of HYDROGENATION OF OILS AND FATS, active high, selective good, consumption is few, and hydrogenation temperature is low, and catalyst is reusable, but after reaction terminates, the separation difficulty of hydrogenated oil and fat and catalyst, needs special separation method, is subject to certain restrictions in large-scale industrial production, therefore, current HYDROGENATION OF OILS AND FATS research is still based on nickel-base catalyst.

Summary of the invention

The catalyst that first technical problem to be solved by this invention is to provide a kind of grease scale, serialization complete hydrogenation prepares tristerin; this catalyst have active high, the life-span long, not easily run off advantage, overcomes that traditional nickel-base catalyst easily runs off, the life-span is short, subsequent products separate complex, the not easily shortcoming such as scale, serialization.

The preparation method that second technical problem to be solved by this invention is to provide a kind of grease scale, serialization complete hydrogenation prepares the catalyst of tristerin.

The present invention solves the technical scheme that above-mentioned first technical problem adopt: a kind of grease serialization complete hydrogenation prepares the catalyst of tristerin, it is characterized in that this catalyst is take aluminium oxide as carrier, the active component of catalyst is evenly distributed or eggshell type distribution on carrier, and the active component of catalyst can represent with following general formula with molar ratio computing:

Pd _0.1Na _aP _bM _cO _x

In formula, M is selected from least one in Mg, Ca, La, Ce, Y, Zr, Fe, V, Mo or W;

Value 0≤a≤0.2 of a, value 0≤b≤0.2 of b, value 0 < c≤0.3 of c, and a, b are 0 simultaneously or are not that 0, x is for meeting the oxygen atom sum needed for other element valence;

Wherein the quality of alumina catalyst support accounts for the 60.0-99.9% of catalyst total amount.

As preferably, active component distribution in eggshell type on carrier of described catalyst.

The present invention solves the technical scheme that above-mentioned second technical problem adopt: a kind of grease serialization complete hydrogenation prepares the preparation method of the catalyst of tristerin, it is characterized in that: first will containing 3.0 × 10 ^-4at least one presoma metal salt solution in ~ 0.6mol Mg, Ca, La, Ce, Y, Zr, Fe, V, Mo or W is dissolved in the water of 120 ~ 600ml, by 1L carrier A l ₂o ₃add and wherein flood, take out, dry, roasting; Then dipping is containing 1.0 × 10 ^-4salting liquid 800 ~ the 1400ml of 0.2mol Pd, filters, washes with water, dry, roasting; Final impregnating 120 ~ 600ml is containing 2.0 × 10 ^-4the phosphoric acid hydrogen of ~ 0.4mol receives the aqueous solution, and dry, roasting obtains finished catalyst, with 1L carrier A l ₂o ₃for benchmark.

As preferably, described presoma slaine is nitrate or the acetate of Mg, Ca, La, Ce, Y, Zr, Fe, V, Mo or W, or palladium adds with palladium nitrate or chlorine palladium acid form, and vanadium adds with vanadate form, molybdenum adds with molybdate form, and tungsten adds with tungstates form.

Preferably, in described presoma slaine, magnesium, calcium, lanthanum, cerium, yttrium, zirconium, iron add with nitrate salts.

Preferred again, the salting liquid of described Pd is chlorine palladium acid solution.

Further preferably, described carrier is Raschig ring type Al ₂o ₃, appearance and size is not more than pore volume is 0.6 ~ 1.0ml/g, and specific area is 80 ~ 150m ²/ g, this carrier by mediating, shaping, roasting, the step such as reaming obtain, its loose specific weight is 200 ~ 600g/L.

Finally, described baking temperature is 80 ~ 120 DEG C, and sintering temperature is 300 ~ 700 DEG C, and the time is 2 ~ 8 hours.

Compared with prior art, the invention has the advantages that:

1) substitute traditional nickel-base catalyst in oil hydrogenation reaction with palladium catalyst, because Pd chemical stability is high, not easily run off in hydrogenated oil and fat, thus catalyst stability is high, and the life-span is long;

2) due to the high chemical stability of Pd catalyst with not easily run off, can use it in trickle bed scale, the reaction of serialization oil hydrogenation.Compared with traditional batch (-type) oil hydrogenation technique, product postprocessing step can be simplified, improve production capacity, reduce running cost;

3) the Pd catalyst of eggshell type distribution is adopted to be used in oil hydrogenation reaction, because Pd only disperses on the outer surface of the support, the catalytic activity of the catalyst that the catalytic activity of unit load amount catalyst distributes than even type is high, thus can reduce the use cost of catalyst; Simultaneously can in eliminative reaction process in the restriction of diffusion, reduce the degree of degree of depth side reaction, improve the service life of catalyst.

Detailed description of the invention

Below in conjunction with embodiment, the present invention is described in further detail.

Catalyst of the present invention can be used for the serialization complete hydrogenation of various grease, and as soybean oil, rapeseed oil, cottonseed oil, sunflower oil, castor oil, palm oil, waste oil (refining) etc., before hydrogenation experiment, the iodine number of various grease is as shown in table 1.

Table 1

Feedstock oil	Palm oil	Rapeseed oil	Soybean oil	Cottonseed oil	Sunflower oil	Castor oil	Waste oil (refining)
								Iodine number	52	101	124	106	114	85	73

In the present invention, catalyst is carry out reactivity worth evaluation in the reactor of 25.2mm at internal diameter.Catalyst is in advance through H ₂(60ml/min) reduce 1h, reduction temperature is 300 DEG C.Purge in Ar and be reduced to 200 DEG C to temperature of reactor, feedstock oil and hydrogen enter reactor through blender, and reaction pressure is 2.0 ~ 3.0MPa.The method that the iodine number of hydrogenated oil and fat adopts GB/T5532-2008 to provide records, and catalyst activity calculates with following formula:

Embodiment 1:

The lanthanum nitrate of 0.0136mol is dissolved in 353ml water.By 1L Raschig ring type Al ₂o ₃wherein, gentle agitation extremely absorbs dipping completely, 110 DEG C of oven dry, 600 DEG C of roasting 3h.Then flood the chlorine palladium acid solution 1000ml of 0.0068mol, filter, wash with water, 110 DEG C of oven dry, 500 DEG C of roasting 2h.Final impregnating 353ml is containing the dibastic sodium phosphate aqueous solution of 0.0068mol, and gentle agitation is to absorbing completely, and 110 DEG C of oven dry, 500 DEG C of roasting 2h obtain finished catalyst.Containing palladium 0.72g/L catalyst in finished catalyst, catalyst atoms consists of Pd _0.1na _0.1p _0.1la _0.2o _x.

Obtained above-mentioned catalyst is investigated through above-mentioned appreciation condition, catalyst activity and hydrogenated oil and fat determination of iodine value result as shown in table 2.

Table 2

Embodiment 2:

According to each step Kaolinite Preparation of Catalyst of embodiment 1, just change the addition of dibastic sodium phosphate, containing palladium 0.72g/L catalyst in obtained finished catalyst, catalyst atoms consists of Pd _0.1na _0.05p _0.05la _0.2o _x.The appreciation condition identical by embodiment 1 is investigated, catalyst activity and hydrogenated oil and fat determination of iodine value result as shown in table 3.

Table 3

Embodiment 3:

According to each step Kaolinite Preparation of Catalyst of embodiment 1, just replace lanthanum nitrate with cerous nitrate, containing palladium 0.72g/L catalyst in obtained finished catalyst, catalyst atoms consists of Pd _0.1na _0.1p _0.1ce _0.2o _x.The appreciation condition identical by embodiment 1 is investigated, catalyst activity and hydrogenated oil and fat determination of iodine value result as shown in table 4.

Table 4

Embodiment 4:

According to each step Kaolinite Preparation of Catalyst of embodiment 1, just replace lanthanum nitrate with ammonium molybdate, containing palladium 0.72g/L catalyst in obtained finished catalyst, catalyst atoms consists of Pd _0.1na _0.1p _0.1mo _0.2o _x.The appreciation condition identical by embodiment 1 is investigated, catalyst activity and hydrogenated oil and fat determination of iodine value result as shown in table 5.

Table 5

Embodiment 5:

According to each step Kaolinite Preparation of Catalyst of embodiment 1, in catalyst preparation process, only add the magnesium nitrate of 0.0068mol and be dissolved in 353ml water together with the lanthanum nitrate of 0.0068mol, containing palladium 0.72g/L catalyst in obtained finished catalyst, catalyst atoms consists of Pd _0.1na _0.1p _0.1mg _0.1la _0.1o _x.The appreciation condition identical by embodiment 1 is investigated, catalyst activity and hydrogenated oil and fat determination of iodine value result as shown in table 6.

Table 6

Embodiment 6:

According to each step Kaolinite Preparation of Catalyst of embodiment 1, only replace lanthanum nitrate with 0.0068mol ferric nitrate and 0.0068mol zirconium nitrate, be dissolved in 353ml water together, containing palladium 0.72g/L catalyst in obtained finished catalyst, catalyst atoms consists of Pd _0.1na _0.1p _0.1fe _0.1zr _0.1o _x.The appreciation condition identical by embodiment 1 is investigated, catalyst activity and hydrogenated oil and fat determination of iodine value result as shown in table 7.

Table 7

Embodiment 7:

According to each step Kaolinite Preparation of Catalyst of embodiment 1, only replace lanthanum nitrate with 0.0034mol calcium nitrate, 0.0068mol cerous nitrate, 0.0034mol ammonium tungstate, be dissolved in 353ml water together, containing palladium 0.72g/L catalyst in obtained finished catalyst, catalyst atoms consists of Pd _0.1na _0.1p _0.1ca _0.05ce _0.1w _0.05o _x.The appreciation condition identical by embodiment 1 is investigated, catalyst activity and hydrogenated oil and fat determination of iodine value result as shown in table 8.

Table 8

Comparative example 1:

By 1L Raschig ring type Al ₂o ₃the chlorine palladium acid solution 1000ml of dipping 0.0068mol, filters, washes with water, 110 DEG C of oven dry, 500 DEG C of roasting 2h, and containing palladium 0.72g/L catalyst in obtained finished catalyst, catalyst atoms consists of Pd _0.1o _0.1.The appreciation condition identical by embodiment 1 is investigated, catalyst activity and hydrogenated oil and fat determination of iodine value result as shown in table 9.

Table 9

Claims

1. a grease serialization complete hydrogenation prepares the preparation method of the catalyst of tristerin, it is characterized in that: this catalyst take aluminium oxide as carrier, active component distribution in eggshell type on carrier of catalyst, the active component of catalyst can represent with following general formula with molar ratio computing:

Pd _0.1Na _aP _bM _cO _x

Value 0 < a≤0.2 of a, value 0 < b≤0.2 of b, value 0 < c≤0.3 of c, x is for meeting the oxygen atom sum needed for other element valence;

Wherein the quality of alumina catalyst support accounts for the 60.0-99.9% of catalyst total amount;

First will containing 3.0 × 10 during preparation ^-4at least one presoma metal salt solution in ~ 0.6mol Mg, Ca, La, Ce, Y, Zr, Fe, V, Mo or W is dissolved in the water of 120 ~ 600ml, by 1L carrier A l ₂o ₃add and wherein flood, take out, dry, roasting; Then dipping is containing 1.0 × 10 ^-4salting liquid 800 ~ the 1400ml of ~ 0.2mol Pd, filters, washes with water, dry, roasting; Final impregnating 120 ~ 600ml is containing 2.0 × 10 ^-4the aqueous solution of ~ 0.4mol dibastic sodium phosphate, dry, roasting obtains finished catalyst, with 1L carrier A l ₂o ₃for benchmark.

2. preparation method according to claim 1, it is characterized in that described presoma slaine is nitrate or acetate, or palladium adds with palladium nitrate or chlorine palladium acid form, vanadium adds with vanadate form, molybdenum adds with molybdate form, and tungsten adds with tungstates form.

3. preparation method according to claim 2, is characterized in that in described presoma slaine, magnesium, calcium, lanthanum, cerium, yttrium, zirconium, iron add with nitrate salts.

4. preparation method according to claim 1, is characterized in that the salting liquid of described Pd is chlorine palladium acid solution.

5. preparation method according to claim 1, is characterized in that described carrier is Raschig ring type Al ₂o ₃, appearance and size is not more than pore volume is 0.6 ~ 1.0ml/g, and specific area is 80 ~ 150m ²/ g, loose specific weight is 200 ~ 600g/L.