WO2007065323A1 - A hydrotalcite structured catalyst using al as a substrate and a preparation method thereof - Google Patents

Abstract

A hydrotalcite structured catalyst using Al as a substrate and a preparation method thereof. The active components LDHs of the structured catalyst grow on the anodic oxidization surface which will not peel off readily under thermal treatment and rehydration treatment because of the high adhesion between LDHs and anodic alumina. The anodic oxidized Al substrate is impregnated in the solution containing urea and divalent metal salts , the releasing of anion can be controlled by regulating the reaction temperature and time to adjust the decomposing rate of urea, and aluminium source is provided by anodic alumina layer to make LDHs core and grow on the Al substrate in order to obtain LDHs structured catalyst using Al as a substrate. The catalyst will not lose readily, can be separated from reactants and products easily, can be used in the industry, and realize the integration of the LDHs catalyst and reactors.

Description

 Hydrotalcite with aluminum alloy and its preparation method

 This involves Kemei's hydrotalcite chemical catalysis and its preparation methods. It involves 5 methods of hydrotalcite chemical catalysis on aluminum jackets. Background wood

 In recent years, the degree of consideration has been proposed in terms of catalysis and reaction, especially the degree of novel catalytic catalysis.

1 Chemical catalysis combines catalytic and can actually promote catalytic effect.

 At present, the idea of catalyzing the integration of the active group, Hugh and the reverse is the most important and generally accepted new thinking in the field of catalysis. Chemical catalyst and its reaction in the chemical reaction has a conducive to improvement, in countercurrent operation and catalytic reduction, etc., is particularly conducive to improving the activity and catalyst. Chemical catalysis and reaction in the end of the beg purification, and some fine chemicals have been obtained by the households. As the special characteristics of chemical catalysis have been widely accepted, it will become less and less in the phase reaction.

Hydrotalcite is also an alloy oxide (D), which is a god's son, which is 2. + A). D s has the interchangeability of elemental and homologous. The specificity of Shenhua in the chemical industry shows that it not only has sub-exchange performance but also has a catalytic property with pores and can be used as a new material with great potential in the catalytic field. In recent years, the research of unhydrotalcite has received less and more attention, and has become a fish in the field of catalysis. In particular, the compound obtained by roasting before D is calcined and the regenerated D s obtained by roasting and then rehydrating the water, the Yuhe molecules have high activity, good activity, high dispersion of active components, good regeneration, etc. The material is mainly used for catalysis Yu catalytic and oxidation near catalytic. D and the calcined material obtained by calcining the precursor Huo with its force are both present, and thus can be used for catalysis. Force catalysis is mainly used for large anti-oxide polymerization. Examples are chemical, basalization, oxidation and Ca e -Sc md and so on. Oxidation catalysts prepared at 5 s before roasting with D s have a clear gold content of 66% ~ 77% higher qualitative than similar catalysts prepared by other methods, and have a relatively high activity in most cases. In general, the oxidation near-catalysis of s is mainly used in the following reverse synthesis, high synthesis, reforming, oxidation, hydrogen, water and F c e-Topsch.

 D s shows good prospects in the field of heterogeneous catalysis research, but it also has limitations. The uniformly dispersed mixed oxide (O) and the regenerated s hugh from D s hu and / or rehydration are smaller than the size of the particles. The surface is beneficial to the full connection of the catalytic reactant base with high catalytic activity and, but the catalytic particles are formed in a small, conventional or complete method in a rapid and effective manner. The particle size increases, the reverse connection decreases, and the catalytic activity It will inevitably decline, and it will also be affected to a certain extent. In addition, the current work

 Generally, there is no stirring device, and the reminder is coming.

Combined catalysis, Yu D can be used as the catalytic performance of multi-reaction catalysis. As a result, D s catalysis and D s0 catalysis can be obtained. Only when D s is fixed on the phase of rest (also rest), can we get D s catalysis (also rest). For other purposes. a 2001 13 (16 1263, E. Ga de et al. obtained the aluminum solution of D s on the glass and obtained oxygen groups D s in a still 2002 1 (5 1580 JX. e et al. Carbonic acid D s was obtained on the D film in em.Co m 2003 2740 and a 1998 14 (10) 2890, J. ee and Yao etc. The s in the solution rests on the highly oriented pyrolytic graphite and (100 crystals. All the immobilized s are based on the synthesis of D s or the rest of the rest. There is no tightness of the closure, the capacity is peeled off, It can not be used as a chemical catalysis if it is not high. To solve it, we must first consider the force of D s and Huo Tong. If the immobilization of D s on Huo is the same as that of Tongdi, it is easy to solve.

 In 200410090816.4, the study on the surface of the polymer material has not solved the problem of lack of tightness, etc. Due to poor high temperature performance, other performance is poor, and D s high temperature roasting and other phase activity can only better catalytic performance. Polymer materials certainly do not meet the requirements of effort s reminder. In 20051011718.5, the rest of D-catalysis and its preparation methods are provided. Echo's catalysis needs the phase to be combined with the anti-vessel. Chemical materials are usually ceramics, gold and alloys. Compared with ceramics, metal has more heat, work, high strength and more powerful prospects. The metal container can be directly processed into an anti-container. If the D can be fixed on the metal surface, the resulting D s catalysis will suspend the anti-container, so it is easier to merge.

For wood, the oxidation of aluminum in an acid solution can provide aluminum on the surface of each alumino-alumina. With strong gold, you can easily turn the aluminum into the required anti-container. Surface oxidation leads to gold on the surface, and the rest can be obtained on the aluminum surface. , You can get the catalytic and anti-contained D s catalytic reaction. s Catalytic reactors are very integrated. content

 The purpose of this book is to provide hydrotalcite catalysis with aluminum sulfide. Another objective of this book is to provide various methods of catalysis with aluminum sulfide D, that is, methods for catalyzing D s oxidization on aluminum oxidized on the surface. , D s catalysis that is not easy to fall off, catalyzed by D s in work.

y ) 2 The catalysis provided by D s is based on aluminum oxide. The active group D s is coated on the aluminum oxide surface. The aluminum is provided by aluminum oxide. The active group s is

y) 2

1 . Represents gold g2. , 2.

 Z, 2.

 ,.

 Fe2 ", any preferred g or 2 of 2. The solids of x are 0.2 0.4 0 2 respectively.

 / A3. The molar ratio of 1.5 4 1 The better molar ratio 2-4 1.

 The surface of D s alumina is tightly closed in chemical catalysis

 And rehydration are not easy to fall off.

 The aluminum used is greater than 80%

 Under the steps of this system

 A. The aluminum raw material greater than 80%, cut into different sizes and shapes as needed, then clean the surface to remove oil stains, then use 0% sodium oxide solution to remove surface oxygen ~ 5. Mo． The solution is oxidized at 0.1 2 V / c 2 m under aluminum 0.15 small to form aluminum oxide on the aluminum surface. Take out the aluminum and remove the solution with a seed to get aluminum oxide.

 In the anti-container will be.

Soluble yuan and 2Y 0.0 ~ mo． The solution of 2 dissolves the ratio of urea [urea] / [Y] 3 1 in the gold solution C. Seal the anti-vessel at the ratio of 1 ~ 5 m / mo of the surface of the aluminum oxide / gold of step A to the urea solution prepared in step B at a constant temperature of 50 ~ 180C for 1 10, preferably At a temperature of 70 2 C, a constant temperature inverse 2 7 solution was taken out of aluminum, and deionized water T was used to synthesize D s without D on the surface of alumina.

 Where the aluminum of step A is greater than 80%

 The solution described in Step A is sulfuric acid, phosphoric acid, oxalic acid solution or a mixed solution thereof. Steps.

 B 中 2 2.

 9, Z 2. , 2.

 , Fe2. , 2 "of any preferred g2. Or Y C, F, B, S 2 of any preferred or

 Urea decomposition can produce O and C 2 in the solution, and the solution can provide O and C 2, so that the solution can be in the vicinity of 7 ~ 9, and it can provide the synthesis of p. The synthesis temperature of step C is not controlled. The rate and success of the control of D s Hugh's success and life.

 Aluminum is oxidized, and aluminum oxide is formed on the surface of the aqueous solution, and aluminum oxide releases A3. Of the students did not provide aluminum. Therefore, the urea fraction explains O and 2, and the particles on the alumina surface can be formed when they are saturated. Looking at the step decomposition of urea, the D s on the surface of aluminum oxide is gradually not large and can be catalyzed by aluminum sulfide.

 P E male's total reflection accessory B ke company Veco22 Fu Li exchanged external light and B ke company D8 Adva ce X

 (XR) Qualitative analysis. 1 resulting total reflection Fourier

 (ATR-FT-R) 1 Receiving 1359 Cm of kernel Aluminium carbonate D s homopolymer 2

C's special expansion and contraction. The XR obtained by 1 shows the A in 2 is very, in alumina In XR 2 of B) J appeared 003) 006) (012 (015) (018) (110) and (113). Japan Island CP -7500 and other sons (CP measured the surface made by 1 g content force 0.028 mo / 2

 m. The g / A ratio of the surface obtained by 1 was measured with E CA AB250 X Tunzi (PS) of Mido Thermo Co., Ltd. 2.31. Japan TAC S 350 Tunzi Micromirror (E morphology is made by nitrogen method. 3 is 1 The SE phases 4 and 5 of the resulting alumina surface are the surface and SE phase of 1, respectively. It is possible that there is a very dense shape on the alumina surface, that is, the thickness of the formed s thin film D is in microns.

 ATR-FT-R XR CP XPS and SE showed that a dense s film was formed on the oxygen surface of aluminum alloy, and the D s catalysis with aluminum alloy was obtained.

 s is used as a catalyst for general and rehydration activation. Solid 6 is a SE image of 8 each at 50 C 8 and 7 is a SE image of 5 hours rehydrated in carbon dioxide water at room temperature. 6 can be seen front

 However, the generated compound oxide O did not fall off, but it still looks like D s on the aluminum surface. 7 shows that the regenerated D obtained by rehydration still remains on the surface of the aluminum alloy. The 6 and 7 D s aluminum oxide surfaces have a strong chemical appearance), and they cannot fall off under the strong external force.

 Specialized (D's counter-inspection of the catalytic activity of D s catalysis. The activity of s catalysis is to rehydrate at 00C to 500C 8 at a rate of C / m to carbon dioxide water at room temperature. In the most

The amount of water. Catalytic reverse After 2 mo 69 analysis, the surface of the surface was oxidized at 005 m2 with ice-water bath temperature C. The active s catalysis reaction must be the same as the trace reaction.

 Sh dz QP2 0 phase OC analysis mixture, within.

 Solid 8 is a combination of D catalyst and catalyst. The 23.05% specialization of the inverse 2gh specialization under C is very close to the thermodynamic equilibrium specialization of embedding and reversing at temperature (Em. 1997 5217 2991 calculates the unbalanced thermal equilibrium special 23.1%). The load of D s produced in 1 is about / m2 and the active group of the medium reaction is about 029. /. , 2001, 203: 184 and. In 2000, 60 297, the 03 g s catalysis was the same, but it also reached equilibrium in about 30 h. However, the catalytic activity of D s catalysis is higher than that of D s catalysis. Because D s is not on the surface of alumina, it is well fixed and dispersed on the surface of alumina. D s catalysis can be easily or fully molecularly combined in its catalytic activity, which makes the reverse velocity and the dispersion of D s. The performance is lower than that of chemical catalysis, which reduces the inverse solution connection in the catalytic activity, so the reverse speed is not high. The chemical catalyst is used for self-combination reaction in the collection, and the use of 20 can still make the reaction less than 35 hours to balance and the catalytic recovery of D s is reduced. It shows that the loss of active group in D s catalysis is very small.

The effect of this book is that the active group D in each catalyst is provided by the aluminum oxide on the aluminum surface. The aluminum is not on the surface of the aluminum oxide, which is tightly bound and not easy to fall off. Using the method provided by this method, D s can be fixed on the aluminum alloy to obtain the D s chemical catalytic synthesis method. The active group and the anti-container are established, and the catalytic performance is established. 1 is 1 ATR-FT 2 obtained by carbonation catalysis 2 is 1 XR obtained by D s catalysis of aluminum carbonate obtained by 1

 3 is the E phase of the alumina surface obtained by 1

 The solid phase 4 is 1 obtained from the aluminum carbonate D s catalyzed surface E phase H

 5 is the SE phase catalyzed by the aluminum carbonate obtained by 1 6 is the SE phase catalyzed by the aluminum carbonate obtained by 1

 7 is 1 compared to the SE obtained from the catalysis / rehydration activation of aluminum carbonate

 8 is the specialization of the aluminum carbonate obtained by D s catalyzed activation and inversion

 9 is the E phase of the surface of the nickel-aluminum carbonate D s obtained by 5. Hugh way

 The following is combined with this step

 1

 Clean the good aluminum (99.5 to remove oil, then use 5% sodium oxide solution to remove the surface oxidation, use deionized water to clean, put it in the middle to make the solution 1. mo sulfuric acid solution lead plate, oxidize 2V / 2

 c Aluminum Oxygen Take out the aluminum and rinse each with deionized water.

Dissolve 1.923 gg () 2 6 in 750 m of submerged water and 100 g of molybdenum in a 100 m anti-vessel and then dissolve with 12.029 urea. Seal the container with the mixed solution of oxygen 02 in the above-mentioned anti-container, incubate the anti-7 solution at 70C to take out aluminum and rinse with deionized water, 24 at 10C.

 The resulting ATR-FT-R where XR 2, SE phase 3 and cluster 4 indicate that an aluminum carbonate D s film is formed on the aluminum surface.

 s centered g / A ratio 2.31, g load capacity 0.028mo / m 2

 The good aluminum 95%) ah cleaning and degreasing, then use 3% sodium hydroxide solution to remove the surface oxidation, with deionized water to clean, 0.5mo. 'Phosphoric acid solution solution, plate, oxygen 4 V / 2

 c Aluminium Oxide for 1 hour Remove aluminum water to rinse each.

 Dissolve 1923g g 32 3 in 75m water g 0 0 // in a 10 m inverse container and then dissolve 60.069 urea.

 A. Oxygen 0.5 m2 of aluminum was sealed in the mixed solution in the upper reaction container, and the temperature was inverted at 90C 3. The solution was taken out of aluminum and rinsed with deionized water for 24 hours under C.

 The g / A ratio of the intermediate D s catalyzed by the resulting aluminum carbonate D s is 0.043mo / m2 3

 Clean the good aluminum (99.99 cleaning and degreasing, and then use 8% sodium hydroxide solution to remove the surface oxide water). 2mo oxalic acid solution solution. Oxidize 1 V / cm2 aluminum, no

 . After oxidizing for 2 hours, take out aluminum water and rinse.

Put 19.23gg () in the 0 m anti-container. 6 2 dissolved in 75 m 75.0g9 of urea dissolved in the solution of 0.1g mo in the water

 Oxygen 0.5 2

 The mixed solution of the aluminum in the upper reaction container, the sealed container is inverted at a constant temperature under C, the solution is taken out of aluminum and rinsed with deionized water, 24 under C.

 The resulting g / A ratio of D in the catalytic conversion of aluminum carbonate to D is 2.59 and the measured force is 0.039 o / m 4

 Clean the good aluminum (5%) to remove oil, and then use 5% sodium hydroxide solution to oxidize the water on the surface. 1 . Acid solution solution. Oxidized 3V / cm2 aluminum plate.

 After oxidizing for 05 hours, remove aluminum water to rinse each.

 Dissolve 28.50g gC in 75m of water in the 04m / solution of 120.129 urea in a 0-reverse container. Oxidation 0.5 2 phase in the mixed solution in the above-mentioned reverse container. Seal the container at a constant temperature of 70 ° C. The solution is taken out of aluminum and rinsed with deionized water at 24 ° C.

 The obtained aluminum carbonation catalyst has a g / A ratio of D of 2.62 g and a force of 0.043 o / m.

 5

 Clean the good aluminum (99.99%) to remove oil, and then use 6% sodium oxide solution to remove the surface oxide water to clean. 2. o Oxalic acid solution solution. 15V / cm2 aluminum oxide is not steel plate. A. Oxidation 05 Take out aluminum water to rinse each.

Dissolve 21.81g like 6 in 75 m in 0 anti-vessel The solution 6006 9 urea of 0.10 mo / in the water is dissolved.

 Oxygen 05 m2 of aluminum in the mixed solution of the above-mentioned anti-vessel. Seal the container at 70 ° C. Invert the solution. Remove the aluminum and rinse with deionized water at 9 C for 24 hours.

 9 is the phase E of the resulting nickel aluminum carbonation catalyst surface, the ratio of D s / A in the catalyst is 3.43, and the loading force is 0.0 mo / m 6

 The good aluminum (99.5 was cleaned and degreased, and then 2% sodium hydroxide was used to remove the surface oxidized water to clean it. 0. Phosphoric acid solution solution. Oxidation 4V / 2

 c Aluminum is not a steel plate. A 0.5% oxidation, take out aluminum water to rinse each.

 Dissolve 2.181g () 2 6 in 75 m of sub-water in a 0 m counter vessel, sub 0. mo / solution 6.09 Urea dissolves.

 Oxygen 2

 0.2 aluminum in the mixed solution in the upper container. Seal the container at a constant temperature of 120C. Invert the solution. Take out the aluminum and rinse with deionized water for 24 hours under C.

 The ratio of s / A in the catalysis of the nickel-aluminum carbonate obtained is 2.17 loading force 0.032mo / m2

 .

Claims

 Requirement 1 The hydrotalcite catalysis with aluminum is characterized by the oxidation of aluminum and the activity D s is less than that of aluminum. The oxidation surface provides aluminum by oxidation 5 The chemical flux of activity s is A xO 2 O) where 2. .  Represents gold g2. , Z 2. , 2, Fe2. , 2. Any 3 of them are 0.2 04, 0 2 respectively.  2. Requirement 1 is the catalysis of the hydrotalcification of Ixiu.  2.  Is the formula of s 2  g "or /.  A3  Mobi 2 4 1 3． Requirement 1 is the hydrotalcite catalyst with aluminum alloy, especially the aluminum alloy is large, and the reason and the rehydration will not fall off.  4 Various methods of hydrotalcite transformation with aluminum alloy  A. Aluminum material greater than 0%. Cut to the required size and shape, then clean to remove surface oil stains, and then use 1% to 10% sodium hydroxide solution to remove surface oxidation. Use deionized water to clean the aluminum plate or not.  Solution ~ 5. O． The solution, under the oxidation of 0.1 ~ 2 V / c 2 aluminum 0. ~ 5, to form aluminum oxide on the surface of aluminum, take out the aluminum and wash away the solution with wanzi to obtain alumina  At.  Dissolve the soluble 2Y 0.001 1. mo solution in the container, and dissolve the urea [urea / Y 3 15 ratio in the gold solution Take the ratio of the aluminum oxide of aluminum oxide in step A to the ratio of 1 to 5 / mo of gold to the solution of urea prepared in step B. The anti-vessel is taken out of aluminum at a temperature of 50 C and a temperature of 1 10 , Rinse the synthesized D s with deionized water, that is, the raw coat is on the surface of alumina to get D catalysis.  5. Each method of hydrotalcite catalysis with aluminum sulfide described in claim 4 is the specific step 2 in step B.  g2 "or Y O or.  6. The various methods of hydrotalcite catalysis with aluminum as described in claim 4 are characterized in that the reaction of step C is a constant temperature reaction of 70 ~ 12 at a temperature of 70 ~ 12.