CN102658174B - Mesoporous fibrous SO42-/MxOy type solid acid catalyst and its preparation method - Google Patents
Mesoporous fibrous SO42-/MxOy type solid acid catalyst and its preparation method Download PDFInfo
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Abstract
本发明公开的介孔纤维状SO4 2-/MxOy型固体酸催化剂，其特征在于在扫描电镜观察的微观形貌为纤维状，具有介孔结构，平均孔径为2.5~30.9nm，比表面积为30.4~150m2.g-1，含硫量为0.5 ~4.67μmol.m-2。本发明还公开了介孔纤维状SO4 2-/MxOy型固体酸催化剂的制备方法。本发明提供的固体酸催化剂不仅具有介孔结构，其微观形貌还为纤维状，而金属离子又是负载于其上的，加之有辅助金属盐的作用，因而锻烧时既可避免现有技术的问题，而且比表面积大，催化效果好，并可通过固液分离，进行重复利用，符合绿色环保的要求。本发明方法使用的原料温和，无毒，操作性强，易于推广，市场前景好。The mesoporous fibrous SO 4 2- /M x O y type solid acid catalyst disclosed by the present invention is characterized in that the microscopic appearance observed by the scanning electron microscope is fibrous, has a mesoporous structure, and has an average pore diameter of 2.5-30.9nm. The specific surface area is 30.4~150m 2 .g -1 , and the sulfur content is 0.5~4.67μmol.m -2 . The invention also discloses a preparation method of the mesoporous fibrous SO 4 2- /M x O y type solid acid catalyst. The solid acid catalyst provided by the invention not only has a mesoporous structure, but also has a fibrous microscopic appearance, and metal ions are loaded on it, and it also has the effect of auxiliary metal salt, so that the existing catalyst can be avoided during calcination. Technical problems, and the specific surface area is large, the catalytic effect is good, and it can be reused through solid-liquid separation, which meets the requirements of green environmental protection. The raw materials used in the method of the invention are mild, non-toxic, highly operable, easy to popularize and have good market prospects.
Description
Technical field
The invention belongs to solid acid catalyst and preparing technical field thereof, be specifically related to a kind of mesoporous fiber shape SO
4 2-/ M
xo
ytype solid acid catalyst and preparation method thereof.
Background technology
Since people's reported first such as Japanese scientist Hino in 1979 SO
4 2-/ Fe
2o
3(Hino M. et al. Reaction of butane to isobutane catalyzed by iron oxide treated with sulfate ion solid superacid catalyst. Chemical Letters after solid acid, 1979, (5): 1259-1260), SO
4 2-/ M
xo
ytype solid acid has just caused people's extensive attention.SO
4 2-/ M
xo
ytype solid super-strong acid is with some metal oxide (M
xo
y) be carrier, with SO
4 2-for the solid catalyst of loaded article, it is as a kind of new catalytic material, relatively traditional liquid acid catalyst, it is easy that it has with separation of products, non-corrosiveness, little to environmental hazard, the plurality of advantages such as can reuse, the reactions such as isomerization, alkylation, dehydration and esterification are had to higher catalytic activity simultaneously, becoming the environment-friendly catalyst with wide range of industrial applications prospect, is study hotspot (Li Peiying, the solid acid catalyst Recent Research summary of catalytic field in recent years, Chemical Industry in Guangzhou .2010,38 (12): 42-44).
Up to the present, the SO having developed
4 2-/ M
xo
ytype solid acid is broadly divided into three classes, and (Wang Yingjun, etc. SO
4 2-/ M
xo
ytype solid super-strong acid progress, Industrial Catalysis, 2008,16(2): 12-17): (1) solid acid take single oxide as carrier, as SO
4 2-/ TiO
2, SO
4 2-/ ZrO
2, SO
4 2-/ Al
2o
3deng.This class solid acid is the SO developing the earliest
4 2-/ M
xo
ytype solid acid catalyst, though it has good catalytic activity, because its specific area is little, thermally-stabilised the solid acid that is modified gradually substitutes with reusability is poor.(2) solid acid of the solid acid take composite oxides as carrier or metal ion mixing, as SO
4 2-/ TiO
2-ZrO
2, SO
4 2-/ TiO
2-Fe
2o
3, Pt-SO
4 2-/ ZrO
2, La
3+the SO of doping
4 2-/ ZrO
2-TiO
2deng.Adding of metal ion, increases the specific area of solid acid to a certain extent, has also increased the SO of carrier surface
4 2-content, has improved the catalytic activity of solid acid.But still there is the shortcoming of easy inactivation, poor heat stability in these solid acids, in preparation method, concrete synthesis condition also can affect the different structure of the final generation of its catalyst simultaneously, meeting exert an influence to the distribution of the size of acid strength and acid position, thereby has influence on the acidity of catalyst.(3) load-type solid acid take molecular sieve as carrier.For the carrier of supported solid acid, mainly contain at present the mesopore molecular sieve of MCM, SBA-15, HMS series, and active carbon, SiO
2, Al
2o
3deng.Such solid acid has advantages of porous, structural regularity and the high-specific surface area of molecular sieve carrier, but exists immobilized fastness poor, the shortcoming that inactivation is fast.Poor just because of the immobilized fastness of molecular sieve carrier load-type solid acid, the shortcoming that inactivation is fast, people have invested sight the solid acid catalyst of direct synthesising mesoporous structure.Directly synthetic meso-hole structure material, because it has higher specific area, regular pore passage structure, the pore size feature such as adjustable continuously, becomes the study hotspot of material subject.Therefore, prepare and self there is certain pore passage structure, high specific area, improve carrier surface SO
4 2-content, producing the more solid acid catalyst of polyacid active site position is SO
4 2-/ M
xo
ythe developing direction of type solid acid.
Prepare mesoporous SO
4 2-/ M
xo
ysolid acid catalysis agent method have sol-gal process and organic formwork method etc. (become to defeat, etc. the progress of solid super acid catalyst. application chemical industry, 2004,33(6): 5-8).Sol-gal process is the new method of Kaolinite Preparation of Catalyst in widespread attention in recent years, and it has improved the specific area of solid acid, thus increased sour total amount improved catalytic activity (Jin Huafeng. complex solid superacid SO
4 2-/ Ti
2-Fe
2o
3catalyze and synthesize isobutyl isobutyrate (IBIB). chemical research and application, 2003,15(1): 69-70).But blemish in an otherwise perfect thing is that the preparation cost of catalyst is high, and the solvent toxicity that forms colloidal sol is larger, affected greatly by preparation condition, pore passage structure is difficult to the shortcomings such as control, active component are easily reunited, distributing homogeneity is poor, catalytic activity is low.Organic formwork method is the another kind of new method of preparing mesoporous solid acid.Its intermediary hole SO
4 2-/ M
xo
ysynthetic multiplex liquid crystal templated method (LCT) at present, the template of use is mainly organic formwork agent: the organic polymers such as long chain quaternary (softex kw, Cetyltrimethylammonium bromide, eicosyl trimethylammonium bromide, cetylamine), block copolymer (P123), AEO (AEO-3).Though organic formwork agent can reach the object that regulates product size, mechanical performance and hot property by the chemical constitution, chain length, the functional group that change itself, but when adopting calcination to remove template surface activating agent, mesoporously easily subside, surface hydroxyl can serious condensation, cause surface-active to decline, catalytic activity is restricted, and makes mesoporous solid acid not reach higher catalytic activity and reusability in ideal.The finiteness of simultaneously selecting due to existing template and the defect of himself, make the size in mesoporous aperture and distribute waywardly, and duct order is weakened even as unordered, and these have all limited mesoporous SO
4 2-/ M
xo
ythe practical application of material.
Summary of the invention
The object of the invention is the problem existing for prior art, a kind of new mesoporous fiber shape SO is provided
4 2-/ M
xo
ytype solid acid catalyst.
Another object of the present invention is to provide a kind of above-mentioned mesoporous fiber shape SO
4 2-/ M
xo
ythe preparation method of type solid acid catalyst.
Mesoporous fiber shape SO provided by the invention
4 2-/ M
xo
ytype solid acid catalyst, is characterized in that at the microscopic appearance of scanning electron microscopic observation be fibrous, has meso-hole structure, and average pore size is 2.5 ~ 30.9nm, and specific area is 30.4 ~ 150m
2.g
-1, sulfur content is 0.5 ~ 4.67 μ mol.m
-2.
Above-mentioned mesoporous fiber shape SO provided by the invention
4 2-/ M
xo
ythe preparation method of type solid acid catalyst, is characterized in that the processing step of the method and condition are as follows:
1) 10 ~ 40 parts of materials with hide glue fibril and 5 ~ 10 parts of sodium chloride are joined in 300 ~ 800 parts of water, then with mixing acid for adjusting pH to 1.8 ~ 2.0, in 20 ~ 35 ℃ of temperature, stir 2.0h, then add 15 ~ 45 parts of main slaines and 0 ~ 15 portion of assistant metal salt, continue at 20 ~ 35 ℃ of stirring reaction 2 ~ 8h of temperature;
2) with saturated sodium bicarbonate solution, the pH of reaction system is adjusted to 3.8 ~ 4.0, then be warming up to 35 ~ 50 ℃ of stirring reaction 2 ~ 8h, cooling, filtration, be washed with water to without chlorion and detect, then use soaked in absolute ethyl alcohol 3 ~ 5h, at≤65 ℃, be dried to constant weight, obtaining load has the collagenous fibres of metal ion;
3) load is had to the collagenous fibres of metal ion in 500 ~ 1000 ℃ of calcining 2 ~ 10h, remove collagenous fibres template, adding after cooling 10 ~ 100 parts of concentration is 0.5 ~ 9.0mol/L sulfuric acid solution, in 25 ~ 35 ℃ of standing>=8h of temperature, filter, at 100 ℃, be dried to constant weight, then in 200 ~ 800 ℃ of calcining 2 ~ 8h, cooling, obtain mesoporous fiber shape SO
4 2-/ M
xo
ytype solid acid catalyst.
Described in above method, the umber of raw material is parts by weight.
Materials with hide glue fibril described in above method is that any from ox-hide, sheepskin or pigskin obtains, first according to conventional leather-making technologies such as the cleaning of raw material skin, degreasing, alkali treatment, splitting, neutralizations, to carry out specifically, to reach the object of losing hair or feathers and removing non-collagen interstitial, then with aqueous acetic acid, remove the mineral matter in skin; With glacial acetic acid-sodium acetate buffer solution, regulate again the pH to 4.8-5.0 of pelt, with after absolute ethyl alcohol or acetone dehydration, drying under reduced pressure to water content is less than 10%, finally pulverize and sieve to such an extent that particle diameter is 10-20 object materials with hide glue fibril, its water content is no more than 12%, ash is no more than 0.3%, pH in the scope of 5.0-5.5.
Any in main slaine preferably sulfuric acid zirconium, titanium sulfate or ferric sulfate described in above method.
Any in assistant metal salt preferably sulfuric acid aluminium, copper sulphate, manganese sulfate, cerous sulfate or lanthanum nitrate described in above method.
Mixed acid described in above method preferably consists of formic acid and sulfuric acid, formic acid: the mass ratio=1:9 of sulfuric acid.
In above method the 2nd) step is dried to preferably 30 ~ 65 ℃ of the temperature of constant weight; The 3rd) preferably 8 ~ 24h. of the time of repose of step
Compared with prior art, tool of the present invention has the following advantages:
1. because solid acid catalyst provided by the invention not only utilizes orderly supermolecule that materials with hide glue fibril has and natural fibre structure (can provide fiber and pore structure for the moulding of solid acid), also utilizing materials with hide glue fibril to contain several functions group (comprises-COOH,-OH ,-NH
2,-CONH
2with-CONH), can utilize process hides principle, by chemical reaction by Ti
4+, Zr
4+, Al
3+, Cr
3+deng metal ion, be dispersed in uniformly (this is for providing chemical fundamentals with the precursor of collagen fiber supported metal ion preparation preparation solid-acid material) on collagenous fiber bundle, through Overheating Treatment, remove template again, further pickling reaction obtains, thereby make the solid acid catalyst obtaining not only there is meso-hole structure, its microscopic appearance is also fibrous, for solid acid catalyst field provides a kind of new catalytic perfomance good kind.
2. because the metal ion of solid acid catalyst provided by the invention is carried on materials with hide glue fibril, thereby not only there will not be that prior art is mesoporous subsides during calcination, the serious condensation of surface hydroxyl, surface-active declines, the problem that catalytic activity is limited, and also specific area is larger, excellent catalytic effect, and can pass through Separation of Solid and Liquid, and reuse, meet the requirement of environmental protection.
3. because the inventive method is on the basis that is added with main slaine, be also added with assistant metal salt, thereby can make the specific area of obtained solid acid catalyst larger, catalytic effect is better.
4. because the inventive method can be by regulating load capacity, preparation temperature, the pickling concentration of metal ion on materials with hide glue fibril optionally prepare different mesoporous sizes, distribution, specific surface area size, sulfur content etc. have the SO of different qualities
4 2-/ M
xo
ytype solid acid catalyst, thereby can meet the demand under different application condition.
5. because the present invention can utilize the tailing of Pi Hua factory, be used as preparing the raw material of materials with hide glue fibril, thereby not only can make full use of resource, and also for new approach has been started in the utilization of materials with hide glue fibril.
6. the raw material gentleness that the present invention uses, nontoxic, preparation method's strong operability, is easy to promote, and market prospects are good.
Accompanying drawing explanation
Fig. 1 is the ZrO using in the embodiment of the present invention 1
2(a) and preparation SO
4 2-/ ZrO
2(b) infrared spectrum of solid acid catalyst.(b) 1239 cm in figure
-1, 1176cm
-1, 1091cm
-1and 1025cm
-1four absworption peaks are SO
4 2-/ ZrO
2middle S=O stretching vibration Absorption Characteristics peak, lower wave number 1091cm
-1, 1025cm
-1be absorbed as S=O key partial double bond Absorption Characteristics peak, and high wave number 1239 cm
-1, 1176cm
-1be absorbed as S-O key double covalent bonds Absorption Characteristics peak.By comparing (a) and above-mentioned characteristic peaks (b), can prove SO
4 2-not to be attached on metal oxide surface simply, but and ZrO
2form chemical bond, generated SO
4 2-/ ZrO
2.
Fig. 2 is microscopic appearance figure under the ESEM of the solid acid catalyst prepared of the embodiment of the present invention 2.The solid acid catalyst of preparation has kept the fibre structure of collagen as can be seen from Figure.
Fig. 3 is microscopic appearance figure under the ESEM of the solid acid catalyst prepared of the embodiment of the present invention 5.The solid acid catalyst of preparation has kept the fibre structure of collagen as can be seen from Figure.
Fig. 4 is the crystal phase structure figure of the X-ray diffraction of the solid acid catalyst prepared of the embodiment of the present invention 3.ZrO in figure
2for tetragonal crystal structure, have no MnO
2diffraction maximum, this illustrates MnO
2entered ZrO
2lattice has formed solid solution.
Fig. 5 is the graph of pore diameter distribution that the nitrogen adsorption for solid acid catalyst prepared of the embodiment of the present invention 10-desorption method is measured.In figure, the aperture of solid acid catalyst is about 12.3nm, and pore-size distribution is mainly at 4.0nm ~ 20nm.
Fig. 6 is that solid acid catalyst ammonia Temperature Programmed Desorption prepared by the embodiment of the present invention 8 is measured acid strength distribution map.In the time of 300 ℃ to 500 ℃, the appearance of signal peak represents that catalyst has the characteristic of moderate strength acid, and the appearance of 500 ℃ of postpeaks represents that catalyst has the characteristic of strong acid.Therefore, the SO of preparation in the embodiment of the present invention 8
4 2-/ Fe
2o
3-MnO
2solid acid catalyst is in having, the characteristic acid catalyst of strong acidity.
The specific embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
What deserves to be explained is the mesoporous fiber shape SO that following examples obtain
4 2-/ M
xo
ythe specific area of type solid acid catalyst, for average pore size, nitrogen adsorption-desorption method is measured, sulfur content barium sulfate gravimetric detemination, and specifically test data is in Table 1.
Embodiment 1
By 15 parts of particle diameters, be that 10 ~ 20 order cattle-hide collagen fibers and 5 parts of sodium chloride join in 400 parts of water, then with the mixed acid (formic acid: sulfuric acid=1:9) that formic acid and sulfuric acid form, regulate pH to 1.8, in 25 ℃ of stirring reaction 2.0h of temperature, add again 30 parts of zirconium sulfates, continue at 25 ℃ of stirring reaction 8.0h of temperature; The pH of reaction system is adjusted to 4.0 with saturated sodium bicarbonate solution, is then warming up to 45 ℃ of stirring reaction 8.0h, cooling, filter, be washed with water to without chlorion and detect, use soaked in absolute ethyl alcohol 5.0h, at 45 ℃, be dried to constant weight, obtain the collagenous fibres of load zirconium ion thereafter; There are the collagenous fibres of zirconium ion to put into Muffle furnace load, in 1000 ℃ of calcining 8.0h, add after cooling the sulfuric acid solution of 10 parts of 0.5mol/L, in 25 ℃ of standing 24h of temperature, at 100 ℃, be dried to constant weight, then proceed to Muffle furnace in 200 ℃ of calcining 4h, the cooling SO that obtains
4 2-/ ZrO
2solid acid catalyst (S1).
Embodiment 2
By 40 parts of particle diameters, be that 10 ~ 20 order cattle-hide collagen fibers and 10 parts of sodium chloride join in 800 parts of water, then with the mixed acid (formic acid: sulfuric acid=1:9) that formic acid and sulfuric acid form, regulate pH to 1.8, in 35 ℃ of stirring reaction 2.0h of temperature, add again 40 parts of zirconium sulfates and 2 parts of lanthanum nitrates, continue at 35 ℃ of stirring reaction 7.0h of temperature; The pH of reaction system is adjusted to 4.0 with saturated sodium bicarbonate solution, is then warming up to 45 ℃ of stirring reaction 4.0h, cooling, filter, be washed with water to without chlorion and detect, thereafter use soaked in absolute ethyl alcohol 3.0h, at 30 ℃, be dried to constant weight, obtaining load has the collagenous fibres of zirconium and lanthanum ion; There are the collagenous fibres of zirconium ion and lanthanum ion to put into Muffle furnace load, in 600 ℃ of calcining 10h, add after cooling the sulfuric acid solution of 100 parts of 1mol/L, in 30 ℃ of standing 12h of temperature, at 100 ℃, be dried to constant weight, then proceed to Muffle furnace in 600 ℃ of calcining 3h, the cooling SO that obtains
4 2-/ ZrO
2--La
2o
3solid acid catalyst (S2).
Embodiment 3
By 25 parts of particle diameters, be that 10 ~ 20 order cattle-hide collagen fibers and 6 parts of sodium chloride join in 600 parts of water, then with the mixed acid (formic acid: sulfuric acid=1:9) that formic acid and sulfuric acid form, regulate pH to 2.0, in 25 ℃ of stirring reaction 2.0h of temperature, add again 25 parts of zirconium sulfates and 5 parts of manganese sulfates, continue at 25 ℃ of stirring reaction 6.0h of temperature; The pH of reaction system is adjusted to 3.8 with saturated sodium bicarbonate solution, is then warming up to 50 ℃ of stirring reaction 4.0h, cooling, filter, be washed with water to without chlorion and detect, thereafter use soaked in absolute ethyl alcohol 5.0h, at 65 ℃, be dried to constant weight, obtaining load has the collagenous fibres of zirconium and manganese ion; There are the collagenous fibres of zirconium ion and manganese ion to put into Muffle furnace load, in 500 ℃ of calcining 8h, add after cooling the sulfuric acid solution of 40 parts of 5mol/L, in 25 ℃ of standing 16h of temperature, at 100 ℃, be dried to constant weight, then proceed to Muffle furnace in 400 ℃ of calcining 4h, the cooling SO that obtains
4 2-/ ZrO
2-MnO
2solid acid catalyst (S3).
Embodiment 4
By 10 parts of particle diameters, be that 10 ~ 20 order sheepskin collagenous fibres and 5 parts of sodium chloride join in 300 parts of water, then with the mixed acid (formic acid: sulfuric acid=1:9) that formic acid and sulfuric acid form, regulate pH to 2.0, in 30 ℃ of stirring reaction 2.0h of temperature, add again 15 parts of zirconium sulfates and 1 part of aluminum sulfate, continue at 30 ℃ of stirring reaction 2.0h of temperature; The pH of reaction system is adjusted to 3.9 with saturated sodium bicarbonate solution, is then warming up to 50 ℃ of stirring reaction 2.0h, cooling, filter, be washed with water to without chlorion and detect, thereafter use soaked in absolute ethyl alcohol 4.0h, at 45 ℃, be dried to constant weight, obtaining load has zirconium and aluminum ions collagenous fibres; There are zirconium ion and aluminum ions collagenous fibres to put into Muffle furnace load, in 500 ℃ of calcining 6h, add after cooling the sulfuric acid solution of 20 parts of 1mol/L, in 35 ℃ of standing 24h of temperature, at 100 ℃, be dried to constant weight, then proceed to Muffle furnace in 300 ℃ of calcining 6h, the cooling SO that obtains
4 2-/ ZrO
2-Al
2o
3solid acid catalyst (S4).
Embodiment 5
By 35 parts of particle diameters, be that 10 ~ 20 order sheepskin collagenous fibres and 8 parts of sodium chloride join in 500 parts of water, then with the mixed acid (formic acid: sulfuric acid=1:9) that formic acid and sulfuric acid form, regulate pH to 2.0, in 20 ℃ of stirring reaction 2.0h of temperature, add again 40 parts of titanium sulfates and 15 parts of aluminum sulfate, continue at 25 ℃ of stirring reaction 6.0h of temperature; The pH of reaction system is adjusted to 4.0 with saturated sodium bicarbonate solution, is then warming up to 40 ℃ of stirring reaction 7.0h, cooling, filter, be washed with water to without chlorion and detect, thereafter use soaked in absolute ethyl alcohol 5.0h, at 50 ℃, be dried to constant weight, obtaining load has titanium and aluminum ions collagenous fibres; There are titanium ion and aluminum ions collagenous fibres to put into Muffle furnace load, in 700 ℃ of calcining 2h, add after cooling the sulfuric acid solution of 30 parts of 2.0mol/L, in 25 ℃ of standing 8h of temperature, at 100 ℃, be dried to constant weight, then proceed to Muffle furnace in 300 ℃ of calcining 4h, the cooling SO that obtains
4 2-/ TiO
2--Al
2o
3solid acid catalyst (S5).
Embodiment 6
By 40 parts of particle diameters, be that 10 ~ 20 order pigskin collagen fibers and 10 parts of sodium chloride join in 500 parts of water, then with the mixed acid (formic acid: sulfuric acid=1:9) that formic acid and sulfuric acid form, regulate pH to 1.9, in 30 ℃ of stirring reaction 2.0h of temperature, add again 35 parts of titanium sulfates and 8 parts of copper sulphate, continue at 30 ℃ of stirring reaction 5.0h of temperature; The pH of reaction system is adjusted to 4.0 with saturated sodium bicarbonate solution, is then warming up to 50 ℃ of stirring reaction 4.0h, cooling, filter, be washed with water to without chlorion and detect, thereafter use soaked in absolute ethyl alcohol 4.0h, at 45 ℃, be dried to constant weight, obtaining load has the collagenous fibres of titanium and copper ion; There are the collagenous fibres of titanium ion and copper ion to put into Muffle furnace load, in 800 ℃ of calcining 3h, add after cooling the sulfuric acid solution of 50 parts of 9mol/L, in 25 ℃ of standing 18h of temperature, at 100 ℃, be dried to constant weight, then proceed to Muffle furnace in 400 ℃ of calcining 8h, the cooling SO that obtains
4 2-/ TiO
2-CuO
2solid acid catalyst (S6).
Embodiment 7
By 25 parts of particle diameters, be that 10 ~ 20 order pigskin collagen fibers and 8 parts of sodium chloride join in 600 parts of water, then with the mixed acid (formic acid: sulfuric acid=1:9) that formic acid and sulfuric acid form, regulate pH to 1.8, in 30 ℃ of stirring reaction 2.0h of temperature, add again 45 parts of titanium sulfates and 10 parts of cerous sulfates, continue at 25 ℃ of stirring reaction 3.0h of temperature; The pH of reaction system is adjusted to 3.8 with saturated sodium bicarbonate solution, is then warming up to 40 ℃ of stirring reaction 8.0h, cooling, filter, be washed with water to without chlorion and detect, thereafter use soaked in absolute ethyl alcohol 5.0h, at 60 ℃, be dried to constant weight, obtaining load has the collagenous fibres of titanium and cerium ion; There are the collagenous fibres of titanium ion and cerium ion to put into Muffle furnace load, in 900 ℃ of calcining 4h, add after cooling the sulfuric acid solution of 80 parts of 5.0mol/L, in 30 ℃ of standing 24h of temperature, at 100 ℃, be dried to constant weight, then proceed to Muffle furnace in 800 ℃ of calcining 4h, the cooling SO that obtains
4 2-/ TiO
2-CeO
22solid acid catalyst (S7).
Embodiment 8
By 30 parts of particle diameters, be that 10 ~ 20 order pigskin collagen fibers and 10 parts of sodium chloride join in 500 parts of water, then with the mixed acid (formic acid: sulfuric acid=1:9) that formic acid and sulfuric acid form, regulate pH to 1.9, in 25 ℃ of stirring reaction 2.0h of temperature, add again 40 parts of ferric sulfate and 12 parts of manganese sulfates, continue at 35 ℃ of stirring reaction 8.0h of temperature; The pH of reaction system is adjusted to 4.0 with saturated sodium bicarbonate solution, is then warming up to 35 ℃ of stirring reaction 6.0h, cooling, filter, be washed with water to without chlorion and detect, thereafter use soaked in absolute ethyl alcohol 5.0h, at 45 ℃, be dried to constant weight, obtaining load has the collagenous fibres of iron and manganese ion; There are the collagenous fibres of iron ion and manganese ion to put into Muffle furnace load, in 600 ℃ of calcining 6h, add after cooling the sulfuric acid solution of 60 parts of 1mol/L, in 25 ℃ of standing 10h of temperature, at 100 ℃, be dried to constant weight, then proceed to Muffle furnace in 500 ℃ of calcining 7h, the cooling SO that obtains
4 2-/ Fe
2o
3-MnO
2solid acid catalyst (S8).
Embodiment 9
By 10 parts of particle diameters, be that 10 ~ 20 order pigskin collagen fibers and 7 parts of sodium chloride join in 300 parts of water, then with the mixed acid (formic acid: sulfuric acid=1:9) that formic acid and sulfuric acid form, regulate pH to 1.8, in 35 ℃ of stirring reaction 2.0h of temperature, add again 15 parts of ferric sulfate and 5 parts of aluminum sulfate, continue at 25 ℃ of stirring reaction 4.0h of temperature; The pH of reaction system is adjusted to 4.0 with saturated sodium bicarbonate solution, is then warming up to 35 ℃ of stirring reaction 4.0h, cooling, filter, be washed with water to without chlorion and detect, thereafter use soaked in absolute ethyl alcohol 3.0h, at 35 ℃, be dried to constant weight, obtaining load has iron and aluminum ions collagenous fibres; There are iron ion and aluminum ions collagenous fibres to put into Muffle furnace load, in 500 ℃ of calcining 5h, add after cooling the sulfuric acid solution of 100 parts of 0.5mol/L, in 35 ℃ of standing 16h of temperature, at 100 ℃, be dried to constant weight, then proceed to Muffle furnace in 300 ℃ of calcining 5h, the cooling SO that obtains
4 2-/ Fe
2o
3-Al
2o
3solid acid catalyst (S9).
By 20 parts of particle diameters, be that 10 ~ 20 order pigskin collagen fibers and 9 parts of sodium chloride join in 400 parts of water, then with the mixed acid (formic acid: sulfuric acid=1:9) that formic acid and sulfuric acid form, regulate pH to 1.8, in 25 ℃ of stirring reaction 2.0h of temperature, add again 40 parts of ferric sulfate and 13 parts of cerous sulfates, continue at 30 ℃ of stirring reaction 8.0h of temperature; The pH of reaction system is adjusted to 3.9 with saturated sodium bicarbonate solution, is then warming up to 35 ℃ of stirring reaction 5.0h, cooling, filter, be washed with water to without chlorion and detect, thereafter use soaked in absolute ethyl alcohol 5.0h, at 45 ℃, be dried to constant weight, obtaining load has the collagenous fibres of iron and cerium ion; There are the collagenous fibres of iron ion and cerium ion to put into Muffle furnace load, in 500 ℃ of calcining 6h, add after cooling the sulfuric acid solution of 50 parts of 4.0mol/L, in 25 ℃ of standing 10h of temperature, at 100 ℃, be dried to constant weight, then proceed to Muffle furnace in 600 ℃ of calcining 4h, the cooling SO that obtains
4 2-/ Fe
2o
3-CeO
2solid acid catalyst (S10).
Embodiment 11
By 20 parts of particle diameters, be that 10 ~ 20 order cattle-hide collagen fibers and 5 parts of sodium chloride join in 500 parts of water, then with the mixed acid (formic acid: sulfuric acid=1:9) that formic acid and sulfuric acid form, regulate pH to 1.8, in 25 ℃ of stirring reaction 2.0h of temperature, add again 20 parts of titanium sulfates and 1 part of lanthanum nitrate, continue at 25 ℃ of stirring reaction 8.0h of temperature; The pH of reaction system is adjusted to 4.0 with saturated sodium bicarbonate solution, is then warming up to 35 ℃ of stirring reaction 4.0h, cooling, filter, be washed with water to without chlorion and detect, thereafter use soaked in absolute ethyl alcohol 4.0h, at 45 ℃, be dried to constant weight, obtaining load has the collagenous fibres of iron and lanthanum ion; There are the collagenous fibres of iron ion and lanthanum ion to put into Muffle furnace load, in 600 ℃ of calcining 8h, add after cooling the sulfuric acid solution of 50 parts of 1.0mol/L, in 25 ℃ of standing 20h of temperature, at 100 ℃, be dried to constant weight, then proceed to Muffle furnace in 300 ℃ of calcining 2h, the cooling SO that obtains
4 2-/ TiO
2-La
2o
3solid acid catalyst (S11).
Application examples
In there-necked flask, first add the prepared solid acid catalyst 0.1g of cyclohexane 10mL, acetic acid 1.0mL, butanols 2.0mL and embodiment 1, then at speed of agitator 400r/min, reaction temperature is to react 1.0h at 80 ℃.After having reacted, be cooled to room temperature, remove by filter catalyst.Reaction system solution, take carrene as internal standard compound, adopts gas chromatograph to measure, and the conversion ratio that calculates the butyl acetate obtaining is 96%.The catalyst of filtration is added in above reaction system again and repeated ten times, and the conversion ratio of the butyl acetate obtaining still can reach 92%.
Table 1
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| CN106631786A (en) * | 2016-12-29 | 2017-05-10 | 广州印田新材料有限公司 | Preparation process of benzoic ether plasticizer through solid acid catalysis |
| CN107008460B (en) * | 2017-04-21 | 2020-06-30 | 广州花语精细化工有限公司 | Solid catalyst for synthesizing double-long-chain ester-based quaternary ammonium salt and preparation method thereof |
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| RU2736047C1 (en) * | 2020-05-25 | 2020-11-11 | Общество с ограниченной ответственностью "Алвега" (ООО "Алвега") | Method of catalyst preparation |
| CN111939943B (en) * | 2020-07-06 | 2023-05-23 | 润泰化学（泰兴）有限公司 | Preparation method of solid acid catalyst for synthesizing biological plasticizer |
| CN116237066B (en) * | 2022-12-30 | 2024-08-16 | 河南省生物基材料产业研究院有限公司 | Solid strong acid catalyst and method for catalytic synthesis of 2, 2-di (2-furyl) propane by using same |
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| CN101347740A (en) * | 2008-08-28 | 2009-01-21 | 复旦大学 | Method for preparing SO4<2->/ZrO2-MxOy solid superacid catalyst and use |
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Non-Patent Citations (2)
| Title |
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| "Preparation of fibrous sulfated zirconia (SO42-/ZrO2) solid acid catalyst using collagen fiber as the template and its application in esterification";Yang Liao.et al;《Journal of Molecular Catalysis A: Chemical》;20110720;第347卷;第48页 Fig.1,第49页 Table 1 * |
| Yang Liao.et al."Preparation of fibrous sulfated zirconia (SO42-/ZrO2) solid acid catalyst using collagen fiber as the template and its application in esterification".《Journal of Molecular Catalysis A: Chemical》.2011,第347卷第48页 Fig.1,第49页 Table 1. |
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