CN108212179A - For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel - Google Patents

For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel Download PDF

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CN108212179A
CN108212179A CN201711410329.5A CN201711410329A CN108212179A CN 108212179 A CN108212179 A CN 108212179A CN 201711410329 A CN201711410329 A CN 201711410329A CN 108212179 A CN108212179 A CN 108212179A
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metal felt
catalyst particle
biodiesel
step
preparation method
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CN201711410329.5A
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CN108212179B (en
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石文英
李红宾
孙茂文
秦龙威
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河南工程学院
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053Sulfates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053Sulfates
    • B01J27/055Sulfates with alkali metals, copper, gold or silver
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/10Solids characterised by their surface properties or porosity
    • B01J35/1004Surface area
    • B01J35/1023500-1000 m2/g
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11CFATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10Ester interchange
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels
    • Y02E50/13Bio-diesel

Abstract

The invention discloses a kind of for producing the preparation method of the immobilized catalyst particle metal felt of biodiesel, it is intended to solve the problems, such as that existing poor catalyst stability, service life are low, catalytic efficiency is low.The present invention includes the following steps:Metal felt absolute ethyl alcohol, water are cleaned by ultrasonic, dried;By ZrOCl2·8H2O and nitrate are configured to mixed aqueous solution, and it is 9~10 to add in ammonium hydroxide to pH value of solution while stirring, obtains flocky precipitate, stands at room temperature, is filtered, washed to no Cl later, filter cake is obtained, is dried, grinds, obtain powder;The powder is added to H2SO4In solution, mixture is formed;Metal felt after drying is added in the mixture, is dried after immersion, later under an inert atmosphere 400~600 DEG C roasting 3~7 h to get.Immobilized catalyst particle metal felt catalytic efficiency and high mechanical strength, stability prepared by the present invention are good, service life is long and simple for process, easily realizes industrialization production.

Description

For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

Technical field

The present invention relates to biodiesel catalysis technical fields, and in particular to a kind of immobilized catalysis for being used to produce biodiesel The preparation method of particle metal felt.

Background technology

Biodiesel is that the fatty acid alkyl monoesters of ester exchange reaction preparation are carried out by triglycerides and short chain alcohol.Biological bavin The nontoxic, combustion process that oil has many advantages, such as more cleans, biological degradability is good, is used for a kind of clean, alternative ordinary diesel oil Green fuel.At present, polymer film catalysis method is a kind of preferable method in biodiesel oil preparing process.It is urged as heterogeneous One kind of change method, polymer film catalysis method overcome heterogeneous catalysis by the regulation and control of the load capacity of membrane material design and catalyst Agent it is more it is insufficient, have the advantages that it is more, such as:Polymer film catalytic activity is high, and selectivity is good, and product post processing is few, to ring Border is pollution-free and can re-use.But the temperature in use of polymer film only has 200~300 DEG C, it will for some temperature Ask higher reaction and do not apply to, and polymer film easily dissolving either swelling in solvent or reactant so that it makes Use service life reduction.

Metal felt is called stainless steel sintering felt, is through nonwoven using extremely fine metallic fiber (diameter is accurate to micron) It is paved, folded match after formed through high temperature sintering.Metal felt reason different pore size layer forms gradient pores and high with filtering accuracy, receives dirt The characteristics of capacity is big;Metal felt has three-dimensional netted, porous structure, therefore it is big with porosity height, large specific surface area, aperture Small the features such as being evenly distributed, metal felt is more at present is used as filtering material, and patent document CN 103949168B are public It has opened using standby porous metal film of stainless steel fibre sintering felt and preparation method thereof, the porous metal film is in stainless steel Adhere to one layer of ferronickel complex hydroxide film on fiber sintering felt serving matrix, water flux can reach 4650Lm− 2·min− 1·MPa− 1, separation accuracy can reach 0.3 μm or so, and the porous metal film is mainly used for separation of solid and liquid.Patent document CN 103801156 A report a kind of multiple layer metal fiber sintering felt serving, are by crude metal fibrous filter layer and thin metallic fiber filter Layer and form, it is fine that the outside of the crude metal fibrous filter layer and thin metal fiber filter layer has been sintered control of two-dimensional braided metal respectively Layer is tieed up, the multiple layer metal fiber sintering felt serving is for high temperature air filtration, polymer melt filtering, viscose filtering and beer hair Filtering in ferment technique.

For a long time, scientific research personnel is dedicated to studying application of the metal felt in terms of filtering, and in catalytic field application Research is then less.

Invention content

The technical problem to be solved in the present invention is to provide a kind of simple for process, at low cost, environment amenable for producing The preparation method of the immobilized catalyst particle metal felt of biodiesel, the immobilized catalyst particle metal felt machinery prepared by the present invention are strong Degree is high, stability is good, service life is long, catalytic activity and efficient.

Metal felt not only has the good characteristics such as metals against corrosion, high rigidity, but also has the characteristics such as the flexible folding of textile, With the woven reticular structure of nonwoven process can effectively make up metal Netease block up, rapid wear, weakness easy to break, have high temperature resistant, High voltage bearing feature.Compared with polymer film carrier, metal felt has higher mechanical strength, chemical stability and thermostabilization Property.The temperature in use of metal felt is up to 600~800 DEG C, can be used in the strong solvents such as strong acid-base.

Catalyst particle is immobilized in metal felt surface and hole by the present invention using metal felt as carrier by high temperature sintering Portion prepares the metal felt of immobilized catalyst particle.Present invention process is simple, and a variety of catalyst particles can be used to carry out immobilized, system For the catalytic metal felt for going out suitable differential responses;The present invention can use the metal felt of different pore size(Grade, submillimeter level, Micron order, submicron order, nanoscale)Or the process conditions of different immobilized catalyst particle sintering, to regulate and control catalytic metal felt Specific surface area so as to improve the conversion ratio of reaction, is suitable for other catalysis reactions such as esterification or ester exchange reaction.It will Immobilized catalyst particle metal felt prepared by the present invention is in the production of biodiesel and related esterification, what is had to urge Change effect.

In order to solve the above technical problems, the present invention adopts the following technical scheme that:

Design it is a kind of for produce biodiesel immobilized catalyst particle metal felt preparation method, which is characterized in that including with Lower step:

(1)By metal felt first with absolute ethyl alcohol, after be cleaned by ultrasonic with water, dry later;

(2)By ZrOCl2 ·8H2O:Nitrate=1:1~3:1 molar ratio, by the ZrOCl2 ·8H2O and nitrate are prepared Into mixed aqueous solution, it is 9~10 to add in ammonium hydroxide to pH value of solution while stirring, obtains the mixture of flocky precipitate generation;

(3)By step(2)Middle gained mixture is stood at room temperature, is filtered, is washed to no Cl later-, finally taken out Filter, obtains filter cake;

(4)By step(3)Middle gained filter cake is dried, grinds, and obtains powder;

(5)By step(4)Middle gained powder is added to H2SO4In solution, mixture is formed;

(6)By step(1)Metal felt after middle drying is added to step(5)In middle gained mixture, dried after impregnating 12~36h It is dry, be warming up to 400~600 DEG C under an inert atmosphere later, 3~7 h of roasting to get.

Preferably, in the step(1)In, the material of the metal felt is stainless steel, inconel, resistance to hydrochloric acid are Ni-based Alloy.

Preferably, in the step(1)In, the porosity of the metal felt is 40~80%, specific surface area for 100~ 5000m2/g。

Preferably, in the step(1)In, the time being cleaned by ultrasonic in absolute ethyl alcohol and water is 15 min.

Preferably, in the step(2)In, the nitrate is Zn (NO3)2·6H2O、Cu(NO3)3·3H2O、Al (NO3)3· 9H2O and Fe (NO3)3 ·9H2One kind in O.

Preferably, in the step(3)In, time of repose control is 20~30h.

Preferably, in the step(4)In, drying temperature control for 100~120 DEG C, drying time control for 10~ 14h。

Preferably, in the step(5)In, the H2SO4A concentration of 0.5mol/L of solution, the H2SO4The body of solution Product(mL):The quality of powder(g)=2~10.

Preferably, in the step(6)In, the inert atmosphere be in ammonia, nitrogen, hydrogen, argon gas at least It is a kind of.

Preferably, in the step(6)In, heating rate control is 2~10 DEG C/min.

Compared with prior art, advantageous effects of the invention are:

1. immobilized catalyst particle metal felt catalytic activity height prepared by the present invention, large specific surface area, high catalytic efficiency, and repeat to make The catalytic performance that used time has still had.

2. immobilized catalyst particle metal felt high mechanical strength prepared by the present invention, stability is good, service life is long, solve The problem of existing poor catalyst stability, service life are low, mechanical strength and catalytic efficiency are low.

3. immobilized catalyst particle metal felt prepared by the present invention can use under high temperature and high corrosion environment, solve existing There is the problems such as polymer film temperature in use is low, perishable.

4. simple for process, easily controllable, the achievable continuous production of the present invention;It manufactures at low cost;Easily technique is put Greatly, industrialization production is realized.

5. the waste liquid generated during present invention process is few, environmentally friendly, small to equipment corrosion;It is prepared immobilized to urge Change particle metal felt to be easily recycled and regenerate.

6. the present invention can effectively control the structure size in prepared metal felt hole;By using the metal of different pore size Felt(Grade, submillimeter level, micron order, submicron order, nanoscale)Or the process conditions of different immobilized catalyst particle sintering, Regulate and control the specific surface area of catalytic metal felt, and then improve the catalytic performance of metal felt, provided for metal felt continuous catalytic reaction Important technical support has important research value and extensive prospects for commercial application.

Description of the drawings

The SEM figures of metal felt when Fig. 1 is the not immobilized catalyst particle prepared by embodiment 1;

Fig. 2 is the SEM figures of the metal felt of the immobilized catalyst particle prepared by embodiment 1.

Specific embodiment

Illustrate the specific embodiment of the present invention with reference to the accompanying drawings and examples, but following embodiment is used only in detail It describes the bright present invention in detail, does not limit the scope of the invention in any way.

Involved instrument and equipment is routine instrument device unless otherwise instructed in the examples below;Involved Raw material is commercially available convenient source unless otherwise instructed;Involved test method is conventional method unless otherwise instructed.

Embodiment 1:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

1)It is 60% by porosity, specific surface area 1000m2The stainless steel metal felt of/g, which is placed in absolute ethyl alcohol, to be impregnated, is ultrasonic 15 min are cleaned, is then cleaned by ultrasonic 15 min with deionized water, is dried for standby.

2)By ZrOCl2 ·8H2O and Zn (NO3)2·6H2O is according to molar ratio 1:1 is configured to aqueous solution, under magnetic agitation The pH to 9~10 of the aqueous solution is adjusted with concentrated ammonia liquor, the mixture of flocky precipitate generation is obtained, by the mixture In room temperature ageing for 24 hours, it filters, washing to no Cl-, finally filtered, obtain filter cake, by the filter cake be placed in drying box in 110 DEG C of dry 12h obtain powder object, and taking-up is cooled to room temperature, and the powder object is ground, after finely ground, by 5 g institutes State the H that powder object is added to 30 mL 0.5mol/ L2SO4In solution, mixed solution is formed.

3)By 1)Metal felt 10g after middle drying is dipped into 2)In middle gained mixed solution, immersion is dried afterwards for 24 hours.It will dry Metal felt after dry is placed in the tube furnace for being connected with hydrogen, and under the heating rate of 2 DEG C/min, 5h is roasted after being warming up to 500 DEG C, Finally obtain immobilized SO4 2-/ZrO2The metal felt of catalyst particle.

Embodiment 2:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

It will be unlike embodiment 1:The ZrOCl2 ·8H2O and Zn (NO3)2·6H2The molar ratio of O is:2:1, it finally obtains Immobilized SO4 2-/ZrO2The metal felt of-ZnO catalyst particles;Remaining and 1 all same of embodiment.

Embodiment 3:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

As different from Example 1:With Fe (NO3)3 ·9H2Zn (NO in O alternate embodiments 13)2·6H2O is finally obtained Immobilized SO4 2-/ZrO2-Fe2O3The metal felt of catalyst particle;Remaining and 1 all same of embodiment.

Embodiment 4:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

As different from Example 1:With Cu (NO3)3·3H2Zn (NO in O alternate embodiments 13)2·6H2O is finally obtained solid Carry SO4 2-/ZrO2The metal felt of-CuO catalyst particles;Remaining and 1 all same of embodiment.

Embodiment 5:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

As different from Example 1:With Al (NO3)3· 9H2Zn (NO in O alternate embodiments 13)2·6H2O is finally obtained solid Carry SO4 2-/ZrO2The metal felt of-CuO catalyst particles;Remaining and 1 all same of embodiment.

Embodiment 6:The catalytic performance of immobilized different catalyst particle metal felts prepared by embodiment 1-5

10g soybean oils and 6g methanol are mixed, add in the immobilized metal felt for having catalyst particle prepared by 1.2g embodiments 1-5, 65 DEG C are heated with stirring to, condensing reflux 5h.After reaction, unreacted methanol is steamed, isolates the gold of immobilized catalyst particle Belong to felt and glycerol liquor, obtain crude product biodiesel, by washing and distilling, obtain refined biometric diesel oil, immobilized different catalysis The catalytic performance of metal felt see the table below 1 under particle.

The catalytic performance of metal felt under the immobilized different catalyst particles of table 1

Catalyst particle SO4 2-/ZrO2 SO4 2-/ZrO2-ZnO SO4 2-/ZrO2-Fe2O3 SO4 2-/ZrO2-CuO SO4 2-/ZrO2-ZnO Fatty acid methyl ester conversion rate(%) 92.36 93.28 94.75 93.90 95.13

Embodiment 7:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

As different from Example 1:With the stainless steel metal felt in inconel metal felt alternate embodiment 1;Remaining and reality Apply 1 all same of example.

Embodiment 8:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

As different from Example 1:With the stainless steel metal felt in hastelloy metal felt alternate embodiment 1;Remaining With 1 all same of embodiment.

Embodiment 9:The prepared catalytic performance for obtaining immobilized catalyst particle metal felt of embodiment 1,7,8

After 5g gutter oils, the mixing of 15g methanol, the immobilized metal for having catalyst particle prepared by 1.2g embodiments 1,7,8 is added in Felt is heated with stirring to 70 DEG C, condensing reflux 5h.After reaction, unreacted methanol is steamed, isolates immobilized catalyst particle Metal felt and glycerol liquor obtain crude product biodiesel, by washing and distilling, obtain refined biometric diesel oil, different metal felt The catalytic performance of the metal felt of immobilized catalyst particle prepared by type see the table below 2.

Influence of the 2 different metal felt type of table to catalytic esterification performance

Metal felt type Stainless steel Inconel Hastelloy Fatty acid methyl ester conversion rate(%) 92.36 95.86 96.14

Embodiment 10:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

As different from Example 1:The specific surface area of the stainless steel metal felt is 100 m2/g;Remaining is homogeneous with embodiment 1 Together.

Embodiment 11:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

As different from Example 1:The specific surface area of the stainless steel metal felt is 500 m2/g;Remaining is homogeneous with embodiment 1 Together.

Embodiment 12:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

As different from Example 1:The specific surface area of the stainless steel metal felt is 2000 m2/g;Remaining is homogeneous with embodiment 1 Together.

Embodiment 13:The catalytic performance of immobilized catalyst particle metal felt prepared by embodiment 10,1,11,12

After 5g acidification oils, the mixing of 10g methanol, add in prepared by 1.2g embodiments 1,10,11,12 immobilized has catalyst particle Metal felt is heated with stirring to 60 DEG C, condensing reflux 5h.After reaction, unreacted methanol is steamed, isolates immobilized catalytic particles The metal felt and glycerol liquor of son, obtain crude product biodiesel, by washing and distilling, obtain refined biometric diesel oil, stainless steel The different specific surface areas of metal felt see the table below 3 to the catalytic performance influence of biodiesel.

The 5g acidification oils and 10g methanol in above-mentioned steps are substituted with 6g acetic acid and 9.6g ethyl alcohol, adds in the quality of metal felt For 1.44g, remaining is identical with above-mentioned biodiesel preparation process, obtains ethyl acetate product, stainless steel metal felt not on year-on-year basis Surface area see the table below 3 to the catalytic performance influence of ethyl acetate.

The different specific surface areas of 3 stainless steel metal felt of table influence catalytic performance

Metal felt specific surface area(m2/g) Ethyl acetate conversion ratio(%) Fatty acid methyl ester conversion rate(%) 100 25.69 40.35 500 30.30 52.68 1000 71.45 92.36 2000 73.94 95.45

Embodiment 14:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

As different from Example 1:With Cu (NO3)2·6H2Zn (NO in O alternate embodiments 13)2·6H2O is obtained immobilized SO4 2-/ZrO2- CuO catalyst particle metal felts;Remaining and 1 all same of embodiment.

Embodiment 15:The immobilized catalyst particle metal felt catalytic performance of different access times prepared by embodiment 14

The two is mixed according to lard 5g, methanol 20g, adds in the immobilized metal for having catalyst particle prepared by 1.2g embodiments 14 Felt is heated with stirring to 60 DEG C, condensing reflux 6h.After reaction, unreacted methanol is steamed, isolates immobilized catalyst particle Metal felt and glycerol liquor obtain crude product biodiesel, by washing and distilling, obtain refined biometric diesel oil.By embodiment 14 The immobilized catalyst particle metal felt prepared is by above-mentioned steps using 5 times, and each catalytic performance of immobilized catalyst particle metal felt is such as Shown in the following table 4.

The lard and methanol in above-mentioned steps are substituted with 6g acetic acid and 14.8g butanol, the quality for adding in metal felt is 1.44g, remaining is identical with above-mentioned biodiesel preparation process, obtains butyl acetate product, and immobilized catalyst particle metal felt makes altogether With 5 times, each catalytic performance of immobilized catalyst particle metal felt is as shown in table 4 below.

The catalytic performance of 4 immobilized catalyst particle metal felt access times of table

Access times Butyl acetate conversion ratio(%) Fatty acid methyl ester conversion rate(%) 1 76.88 94.86 2 76.63 94.46 3 76.52 94.28 4 76.43 94.15 5 76.32 94.20

Embodiment 16:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

As different from Example 1:Roasting time is 4h;Remaining and 1 all same of embodiment.

Embodiment 17:For producing the preparation method of the immobilized catalyst particle metal felt of biodiesel

As different from Example 1:Roasting time is 6h;Remaining and 1 all same of embodiment.

Embodiment 18:The catalytic performance of immobilized catalyst particle metal felt prepared by different roasting times

The catalytic performance of immobilized catalyst particle metal felt prepared by embodiment 16,1,17 see the table below 5.

The catalytic performance of the different roasting time metal felts of table 5

Roasting time(h) 4 5 6 Fatty acid methyl ester conversion rate(%) 92.36 95.48 96.82

Embodiment 19:The SEM figures of immobilized catalyst particle metal felt prepared by embodiment 1

To in embodiment 1 not immobilized catalyst particle when metal felt carry out SEM tests, as a result such as attached drawing 1.To solid in embodiment 1 It carries the metal felt after catalyst particle and carries out SEM tests, as a result such as attached drawing 2.

Attached drawing 1,2 can be seen that the metal felt of immobilized catalyst particle by metallic fiber and full of containing in its surface, hole, gap By catalyst particle form.

The present invention is described in detail above in conjunction with drawings and examples, still, those of skill in the art Member can also carry out each design parameter in above-described embodiment it is understood that under the premise of present inventive concept is not departed from Change, forms multiple specific embodiments, is the common variation range of the present invention, is no longer described in detail one by one herein.

Claims (10)

1. a kind of preparation method for the immobilized catalyst particle metal felt for being used to produce biodiesel, which is characterized in that including following Step:
(1)By metal felt first with absolute ethyl alcohol, after be cleaned by ultrasonic with water, dry later;
(2)By ZrOCl2 ·8H2O:Nitrate=1:1~3:1 molar ratio, by the ZrOCl2 ·8H2O and nitrate are prepared Into mixed aqueous solution, it is 9~10 to add in ammonium hydroxide to pH value of solution while stirring, obtains the mixture of flocky precipitate generation;
(3)By step(2)Middle gained mixture is stood at room temperature, is filtered, is washed to no Cl later-, finally taken out Filter, obtains filter cake;
(4)By step(3)Middle gained filter cake is dried, grinds, and obtains powder;
(5)By step(4)Middle gained powder is added to H2SO4In solution, mixture is formed;
(6)By step(1)Metal felt after middle drying is added to step(5)In middle gained mixture, dried after impregnating 12~36h It is dry, be warming up to 400~600 DEG C under an inert atmosphere later, 3~7 h of roasting to get.
2. it is according to claim 1 for producing the preparation method of the immobilized catalyst particle metal felt of biodiesel, it is special Sign is, in the step(1)In, the material of the metal felt is stainless steel, inconel, hastelloy.
3. it is according to claim 1 for producing the preparation method of the immobilized catalyst particle metal felt of biodiesel, it is special Sign is, in the step(1)In, the porosity of the metal felt is 40~80%, and specific surface area is 100~5000m2/g。
4. it is according to claim 1 for producing the preparation method of the immobilized catalyst particle metal felt of biodiesel, it is special Sign is, in the step(1)In, the time being cleaned by ultrasonic in absolute ethyl alcohol and water is 15 min.
5. it is according to claim 1 for producing the preparation method of the immobilized catalyst particle metal felt of biodiesel, it is special Sign is, in the step(2)In, the nitrate is Zn (NO3)2·6H2O、Cu(NO3)3·3H2O、Al(NO3)3· 9H2O With Fe (NO3)3 ·9H2One kind in O.
6. it is according to claim 1 for producing the preparation method of the immobilized catalyst particle metal felt of biodiesel, it is special Sign is, in the step(3)In, time of repose control is 20~30h.
7. it is according to claim 1 for producing the preparation method of the immobilized catalyst particle metal felt of biodiesel, it is special Sign is, in the step(4)In, drying temperature control is 100~120 DEG C, and drying time control is 10~14h.
8. it is according to claim 1 for producing the preparation method of the immobilized catalyst particle metal felt of biodiesel, it is special Sign is, in the step(5)In, the H2SO4A concentration of 0.5mol/L of solution, the H2SO4The volume mL of solution:Powder Quality g=2~10 of shape object.
9. it is according to claim 1 for producing the preparation method of the immobilized catalyst particle metal felt of biodiesel, it is special Sign is, in the step(6)In, the inert atmosphere is selected from least one of ammonia, nitrogen, hydrogen, argon gas.
10. it is according to claim 1 for producing the preparation method of the immobilized catalyst particle metal felt of biodiesel, It is characterized in that, in the step(6)In, heating rate control is 2~10 DEG C/min.
CN201711410329.5A 2017-12-23 Preparation method of immobilized catalytic particle metal felt for producing biodiesel CN108212179B (en)

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