CN103447056B - Preparation method of lithium phosphate catalyst and application thereof in catalyzing propylene oxide isomerization - Google Patents

Preparation method of lithium phosphate catalyst and application thereof in catalyzing propylene oxide isomerization Download PDF

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CN103447056B
CN103447056B CN201310367158.8A CN201310367158A CN103447056B CN 103447056 B CN103447056 B CN 103447056B CN 201310367158 A CN201310367158 A CN 201310367158A CN 103447056 B CN103447056 B CN 103447056B
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lithium phosphate
preparation
phosphate catalyst
propylene oxide
catalyst
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CN103447056A (en
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马卫华
蒋微
王涛
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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Abstract

The invention discloses a preparation method of a lithium phosphate catalyst. The preparation method comprises the steps of respectively dissolving Na3PO4.12H2O and LiOH.H2O, and simultaneously pouring the Na3PO4.12H2O and the LiOH.H2O into a container under water bath and stirring to be uniform, wherein pouring is completed in 30s; carrying out stirring reaction on the Na3PO4.12H2O and the LiOH.H2O for 60-120 minutes, then standing for ageing, washing a reaction product until the pH value is 11.5, and reducing pressure and carrying out suction filtration so as to obtain a filter cake; placing the obtained filter cake in the last step into a vacuum drying chamber to dry for 6h, and calcining the filter cake in a muffle furnace so as to obtain the lithium phosphate catalyst. Compared with the prior art, the preparation method provided by the invention has the advantages that the adding speed of Li3PO4 provided by the invention is controlled through adopting a combining-adding type charging mode, meanwhile, the proper ageing time is controlled, the lithium phosphate with high catalytic efficiency is obtained through vacuum drying and low temperature calcination, the product is white and is hollow and spherical, and the average particle diameter is 700nm; the technical process of the preparation method is short, the catalysis propylene oxide conversion rate is high and can achieve about 90%-95%, and meanwhile, the allyl alcohol selectivity also keeps to be 91%-96%.

Description

The preparation of lithium phosphate catalyst and the application in catalyze propylene oxide isomerization thereof
Technical field
The present invention relates to a kind of environment-friendly materials preparation method, particularly a kind of preparation method of lithium phosphate catalyst, belong to inorganic chemistry and environment protection catalytic Material Field.
Background technology
At occurring in nature, propenyl is mainly present in garlic oil with allyl sulphide, diallyl trisulfide form, or is present in mustard oil with isothiocyanate forms.Since 1856, since being synthesized by the method for iodopropylene saponification, propenyl industrial process mainly contains allyl chloride hydrolysis method, methacrylaldehyde reducing process, allyl acetate Hydrolyze method and propylene oxide isomerization method 4 kinds, wherein propenyl is prepared in propylene oxide isomerization again two kinds of methods, is respectively vapor phase method and slurry reaction method.
Gas phase propylene oxide isomerization method: expoxy propane is through vaporization, enter reactor through distributor after preheating, and this method has that technique is simple, yield is high, corrosion-free to equipment, pollute the advantages such as generation without " three wastes ".Al 2o 3, ZrO 2, TiO 2and Li 3pO 4all propenyl can be generated as the propylene oxide isomerization of catalyst gas phase Deng amphoteric oxide.At present, be lithium phosphate as the most effective catalyst of catalyze propylene oxide isomerization reaction, so it have also been obtained commercial Application widely at present.
Comparatively detailed description has been carried out in the preparation evolution of United States Patent (USP) to lithium phosphate catalyst.In order to obtain more efficient lithium phosphate catalyst, US 4342666, the patents such as US 4720598, US5262371, US 5600033 are the different Li having prepared pH value, calcination temperature and condition(s) of calcination and be carrier with Al2O3, Y zeolite, HZSM-5, asbestos and silica gel respectively 3pO 4, and their catalyze propylene oxide are carried out isomerization reaction, the conversion ratio obtaining expoxy propane be 55%-78% not etc., and propenyl is selective in the scope of 70 ~ 94%.Although the application of lithium phosphate catalyst is very extensive abroad, lower conversion ratio and instability selective or occurred resistance for catalyst popularization at home.
In process with precipitation method Kaolinite Preparation of Catalyst, there is a lot of influence factor can affect the performance of catalyst.Alkaline lithium hydroxide solution is slowly added drop-wise in sodium phosphate aqueous solution by traditional lithium phosphate catalyst, carries out precipitation reaction, afterwards can with the washing of a large amount of deionized waters to catalyst pH value to setting value.But the difference of charging sequence can cause the difference of pH in whole precipitation reaction process, and also addition can make up this well.The difference of digestion time also has larger impact to the catalytic effect of catalyst in addition.
The present invention is directed to above all situations, by the feed way of feed change liquid and increase digestion time, be intended to synthesizing efficient rate, low cost, pollution is little, the life-span is long lithium phosphate catalyst.
Summary of the invention
The problems such as and propenyl selective instability lower by the conversion ratio of lithium phosphate catalyst gas phase propylene oxide isomerization reaction that the present invention is directed to provide a kind of Li 3pO 4the synthetic method of catalyst, to obtain higher conversion ratio and more stable allyl alcohol is selective.
The technical solution realizing the object of the invention is: a kind of preparation of lithium phosphate catalyst, comprises the following steps:
Step 1, by Na 3pO 412H 2o and LiOHH 2o dissolves respectively, under water-bath, to pour in container simultaneously and to stir, being finished down in 30s;
Still aging after step 2, stirring reaction 60-120 minute, washing product to pH value is 11.5, obtains filter cake after decompress filter;
Step 3, the filter cake that upper step obtains is placed in the dry 6h of vacuum drying chamber, then in Muffle furnace, calcines to obtain lithium phosphate catalyst.
Bath temperature described in step 1 is 50-80 DEG C, is more preferably 60-70 DEG C; Described Na 3pO 412H 2o and LiOHH 2with molar ratio computing OH in O -: PO 4 -3=4:1;
Digestion time described in step 2 is 2-3h; Described washing adopts 50-60 DEG C of hot water.
Baking temperature described in step 3 is 110-130 DEG C, and calcination temperature is 300-400 DEG C, most preferably is 320-330 DEG C, and calcination time is 5-6h.
An application for lithium phosphate catalyst, is placed in tubular reactor by above-mentioned lithium phosphate catalyst, passes into the expoxy propane after vaporization, and carrier gas is N 2, control reaction temperature in 250-320 DEG C, preferred 280-310 DEG C.
Compared with prior art, Li provided by the invention 3pO 4by adopting " and adding " type feed way and controlling to add speed, simultaneously in addition suitable digestion time, then after vacuum drying and Lower temperature calcination, obtain the lithium phosphate with greater catalytic efficiency, product be white, and hollow sphere, average grain diameter is 700nm.This preparation method's technological process is short, and catalyze propylene oxide conversion ratio is high, can reach about 90%-95%, and meanwhile, allyl alcohol is selective also to be remained between 91%-96%.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of lithium phosphate of the present invention.
Fig. 2 is that lithium phosphate of the present invention is at propylene oxide isomerization technique for applying flow chart.
Fig. 3 is the SEM figure of the embodiment of the present invention 1 lithium phosphate.
Fig. 4 is the XRD figure of the embodiment of the present invention 1 lithium phosphate.
Detailed description of the invention
Lower routine embodiment further illustrates the present invention.
Embodiment 1:
Take the LiOHH of 60.3g 2the Na of O, 136.8g 3pO 412H 2they are placed in the beaker of two 250mL by O respectively, respectively add hot water 125mL, stir until dissolve.By sodium radio-phosphate,P-32 solution and lithium hydroxide solution rapid) join in the there-necked flask of 500mL, be finished down in 30s, the rotating speed simultaneously controlling stirring rod is 370r/min, and bath temperature is 65 DEG C.By this mixture stirring reaction 1h after dripping, carried out ripening 3h more afterwards.
The sample obtained is washed, until pH value is 11.5, then decompress filter.Be placed on afterwards in vacuum drying chamber, dry 6h at the temperature of 120 DEG C.Finally sample is inserted 320 DEG C of calcination 6h in Muffle furnace, obtain required white lithium phosphate catalyst, flow process as shown in Figure 1.
Lithium phosphate compressing tablet after having prepared is sieved, makes it to form 10-20 object particle.Afterwards these particles are added catalytic reaction in tubular reactor, expoxy propane and N 2pass in reactor after vaporization after mixing, control in-furnace temperature with temperature controller is 290 DEG C simultaneously, and the expoxy propane after vaporization is with mass space velocity 3 h -1pass in reacting furnace, the reaction time is 4h, and idiographic flow as shown in Figure 2.Isomerization reaction product condensation at-6 DEG C, by composition contained inside gas chromatographic detection after collection, the product gas-chromatography obtained is analyzed.The activity of catalyst and effectiveness are by epoxypropane conversion rate, and allyl alcohol productive rate that is selective and allyl alcohol is evaluated, shown in I-II:
X A = F A 0 - F A F A 0 - - - ( I )
S P = F P F A 0 - F A - - - ( II )
In formula, F a0for reaction starts the amount of front raw material, i.e. expoxy propane initial amount; F afor the amount of course of reaction Raw, i.e. expoxy propane surplus; F pfor the amount of target product, this patent is allyl alcohol.
Be 92.4% by calculating the average conversion of catalyst, average selectivity is 92.7%, in table 1.
Known by Fig. 3, this catalyst is the chondritic of hollow, and particle size is 400-1000nm, and average grain diameter is 700nm.This catalyst is the block Lithiophilite of synthesis as shown in Figure 4, and No. ICDD is 25-1030.
Embodiment 2:
Other process conditions are with embodiment 1, and changing digestion time is 2 hours, and is tested by propylene oxide isomerization, and the average conversion obtaining catalyst propylene oxide isomerization is 90.2%, and the average selectivity of allyl alcohol is 91.8%, in table 1.
Embodiment 3:
Other process conditions are with embodiment 1, and changing digestion time is 2.5 hours, and is tested by propylene oxide isomerization, and the average conversion obtaining catalyst propylene oxide isomerization is 91.1%, and the average selectivity of allyl alcohol is 91.4%, in table 1.
Comparative example 1:
Take a hydronium(ion) lithia (LiOHH 2o) 60.3g, sodium phosphate dodecahydrate (Na 3pO 412H 2o) 136.8g, is placed in the beaker of two 250mL respectively by it, respectively add the hot water of 125mL, stir.Get the constant pressure funnel that two specifications are consistent, two kinds of solution are added wherein respectively, be placed in there-necked flask, the rate of addition of adjustment two funnels, instill lentamente in flask, control time for adding at about 2h, and keep rate of addition basically identical, stirring reaction under the water-bath of 65 DEG C, all the other experimental procedures are with example one.
The benchmark test of catalyst also with example one, the conversion ratio after catalyst propylene oxide isomerization and allyl alcohol is selective is respectively 80.2% and 90.7%.
Comparative example 2:
The preparation process reference example 1 of catalyst, but sodium radio-phosphate,P-32 solution is placed in there-necked flask in advance.In permanent liquid funnel, add lithium hydroxide solution afterwards, adjust permanent liquid hopper valve, make it slowly be added drop-wise in there-necked flask, control time for adding at about 2h.
Repeat the propylene oxide isomerization experiment of embodiment 1.The conversion ratio obtaining expoxy propane is 88.9%, and selective is 90.2%.
Comparative example 3:
The preparation process reference example 1 of catalyst, but lithium hydroxide solution is placed in there-necked flask in advance.In permanent liquid funnel, add sodium radio-phosphate,P-32 solution afterwards, adjust permanent liquid hopper valve, make it slowly be added drop-wise in there-necked flask, control rate of addition at about 2h.
Repeat the propylene oxide isomerization experiment of embodiment 1.The conversion ratio obtaining expoxy propane is 61.5%, and selective is 73.4%.
Comparative example 4:
Repeat the overall step of embodiment 1, change the digestion time of lithium phosphate into 1h, obtain the lithium phosphate catalyst that digestion time is 1 hour, and tested by propylene oxide isomerization, the performance obtaining catalyst is: epoxypropane conversion rate is 83.9%, and the selective of allyl alcohol is 89.5%.
Comparative example 5:
Repeat the overall step of embodiment 1, change the digestion time of lithium phosphate into 4h, obtain the lithium phosphate catalyst that digestion time is 4 hours, and tested by propylene oxide isomerization, the performance obtaining catalyst is: epoxypropane conversion rate is 88.4%, and the selective of allyl alcohol is 91.8%.
Comparative example 6:
Repeat the overall step of embodiment 2, change the digestion time of lithium phosphate into 5h, obtain the lithium phosphate catalyst that digestion time is 5 hours, and tested by propylene oxide isomerization, the performance obtaining catalyst is: epoxypropane conversion rate is 83.2%, and the selective of allyl alcohol is 89.7%.
Embodiment 1 and comparative example 1,2,3 are for by the lithium phosphate catalyst obtained by different charging sequence and feed time.The performance of these catalyst is different, with embodiment 1, i.e. and the good catalytic activity of " fast and add " type lithium phosphate catalyst.By embodiment 1-3 and comparative example 4-6, show that digestion time optionally affects catalyst activity and propenyl.Table 1 summarizes the activity of various catalyst and the selective impact of allyl alcohol.
The comparison of various lithium phosphate catalyst during table 1 propylene oxide isomerization becomes allyl alcohol to react
Compared to comparative example 1, reactant adds speed and has certain influence to lithium phosphate catalytic performance; Compared to comparative example 2, the lithium phosphate prepared by prior art, the isomerized ability of its catalyze propylene oxide will comparatively embodiment 1 be slightly poor; Compared to comparative example 3, " salt enters alkali " type lithium phosphate is for the most unfavorable isomerization reaction; Compared to comparative example 4-6, suitable digestion time for catalyst preparation be necessary because it can increase the catalytic performance of lithium phosphate.

Claims (8)

1. a preparation method for lithium phosphate catalyst, is characterized in that comprising the following steps:
Step 1, by Na 3pO 412H 2o and LiOHH 2o dissolves respectively, under water-bath, to pour in container simultaneously and to stir, being finished down in 30s, wherein, and described Na 3pO 412H 2o and LiOHH 2with molar ratio computing OH in O -: PO 4 -3=4:1;
Still aging after step 2, stirring reaction 60-120 minute, washing product to pH value is 11.5, obtains filter cake after decompress filter;
Step 3, the filter cake that upper step obtains is placed in the dry 6h of vacuum drying chamber, then in Muffle furnace, calcines to obtain lithium phosphate catalyst.
2. the preparation method of lithium phosphate catalyst according to claim 1, is characterized in that the bath temperature described in step 1 is 50-80 DEG C.
3. the preparation method of lithium phosphate catalyst according to claim 1, is characterized in that the bath temperature described in step 1 is 60-70 DEG C.
4. the preparation method of lithium phosphate catalyst according to claim 1, is characterized in that the digestion time described in step 2 is 2-3h; Described washing adopts 50-60 DEG C of hot water.
5. the preparation method of lithium phosphate catalyst according to claim 1, it is characterized in that the baking temperature described in step 3 is 110-130 DEG C, calcining heat is 300-400 DEG C, and calcination time is 5-6h.
6. the preparation method of lithium phosphate catalyst according to claim 1, is characterized in that the calcining heat described in step 3 is 320-330 DEG C.
7. the application of lithium phosphate catalyst in catalyze propylene oxide isomerization, it is characterized in that lithium phosphate catalyst according to claim 1 to be placed in tubular reactor, pass into the expoxy propane after vaporization, carrier gas is N 2, control the reaction temperature of reactor in 250-320 DEG C.
8. the application of lithium phosphate catalyst according to claim 7 in catalyze propylene oxide isomerization, is characterized in that the reaction temperature 280-310 DEG C of described reactor.
CN201310367158.8A 2013-08-22 2013-08-22 Preparation method of lithium phosphate catalyst and application thereof in catalyzing propylene oxide isomerization Expired - Fee Related CN103447056B (en)

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CN106582733B (en) * 2016-12-06 2019-10-25 湖北大学 A kind of preparation method of the nano-oxide load lithium phosphate catalyst for pilot scale reaction
CN106673958B (en) * 2016-12-06 2019-09-10 湖北大学 Pilot-scale propylene oxide gas phase isomerization fixed bed process prepares the method and system of allyl alcohol

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JPH07116083B2 (en) * 1987-06-25 1995-12-13 ダイセル化学工業株式会社 Method for producing allyl alcohol
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