CN1179358A - Ni-B amorphous alloy catalyst, its preparing process and application - Google Patents
Ni-B amorphous alloy catalyst, its preparing process and application Download PDFInfo
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Abstract
A supported catalyst is composed of non-crystal Ni-B alloy (0.1-30 Wt.%) and porous carrier (70-99.9 Wt.%) and is prepared by allowing Ni-containing porous carrier material to contact with the BH4 solution with 0.5-10 mole concentration and 0.1-10 of atomic ratio of B to Ni in a temp range from a temp higher than setting point of solution to 100 deg. C. Said catalyst has higher thermal stability and can be used for hydrogenation reaction of various compounds containing unsaturated functional radicals.
Description
The invention relates to an amorphous alloy catalyst, a preparation method and application thereof, in particular to an amorphous alloy catalyst containing nickel and boron, and a preparation method and application thereof.
In the research of amorphous alloy catalyst, the following two problems need to be solved: in order to solve the above problems, many beneficial attempts have been made to increase the specific surface area of the amorphous alloy catalyst and to maintain the amorphous state of the catalyst during the catalytic process, i.e., to improve the thermal stability of the amorphous alloy catalyst.
CN1073726A adopts a method of pre-alloying aluminum, rare earth, phosphorus and nickel or cobalt or iron, rapidly quenching the alloy and removing aluminum in the alloy by using sodium hydroxide to prepare the large-specific-surface Ni/Co/Fe-RE-P amorphous alloy catalyst, wherein the specific surface of the catalyst can reach 50-130 m2In grams, the hydrogenation activity is higher than that of Raney Ni catalysts which are widely used in industry.
2.5M KBH was reported in Journal of Catalysis 150, 434-438, 19944The aqueous solution is added dropwise into 0.1M nickel acetate ethanol solution under stirring at 25 ℃, 6 ml of 8M ammonia water and a large amount of distilled water are sequentially used for washing and precipitating, and the amorphous Ni-B ultrafine particle catalyst is obtained, and the specific surface of the catalyst can also reach 29.7M2In terms of/g, however, the thermal stability of such Ni-B ultrafine particles is low.
In Applied Catalysis 37, 339-343, 1988, it has been reported that Ni and P are deposited on silicon oxide by chemical plating (chemical plating) to prepare an amorphous Ni-P alloy catalyst supported on silicon oxide, the specific surface area of the catalyst can reach 85 m2The supported Ni-P amorphous alloy catalyst has relatively large specific surface area and raised heat stability.
However, the research results of the preparation rule of Ni-B amorphous alloy prepared by the chemical reduction method reported in J.Phys.chem.97, 8504-8511, 1993 show that divalent metal ions and a reducing agent BH4 -The reaction in aqueous solution consists of three separate reactions as follows:
since the above three reactions are fast, if the carrier and the reaction solution are simply mixed together by the electroless plating method, it is difficult to ensure that the formed Ni-B amorphous alloy is supported on the carrier, not to mention that the Ni-B amorphous alloy is uniformly dispersed on the carrier. Because of the problems of the supporting technology, no report of the supported Ni-B amorphous alloy is found so far.
One of the purposes of the invention is to provide a Ni-B amorphous alloy catalyst which has higher thermal stability and larger specific surface simultaneously on the basis of the prior art; the second purpose of the invention is to provide a preparation method of the catalyst; the invention also aims to provide the application of the catalyst in hydrogenation reaction of compounds containing unsaturated functional groups.
The catalyst provided by the invention comprises the following components: 0.1-30.0 wt% of Ni-B amorphous alloy and 70.0-99.9 wt% of porous carrier material, wherein the atomic ratio of Ni and B is 0.5-10.0.
The preparation method of the catalyst provided by the invention comprises the steps of mixing a porous carrier material containing nickel with BH with the molar concentration of 0.5-10.0 in the temperature range of being higher than the freezing point of a solution to 100 DEG C4 -The ionic solution is contacted according to the boron-nickel feeding atomic ratio of 0.1-10.0.
The application of the catalyst provided by the invention refers to the application of the catalyst in hydrogenation reaction of compounds containing unsaturated functional groups.
The catalyst provided by the invention preferably comprises 1.0-12.0 wt% of Ni-B amorphous alloy and 88.0-99.0 wt% of porous carrier material.
According to the catalyst provided by the invention, the atomic ratio of nickel to boron is preferably 1.0-8.0.
According to the catalyst provided by the invention, the porous carrier material refers to a non-oxidative porous carrier material, preferably one or more of porous inorganic oxide, activated carbon, zeolite and molecular sieve; the porous inorganic oxide refers to oxides of elements in the IIA group, IVB group, VIB group, IIIA group and IVA group of the element table, wherein one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, magnesium oxide and calcium oxide is/are preferred; the zeolite and molecular sieve refer to various types of silicon-aluminum zeolite and heteroatom molecular sieve, such as A-type zeolite, X-type zeolite, Y-type zeolite, ZSM series zeolite, mordenite, Beta zeolite, omega zeolite, phosphorus-aluminum molecular sieve, titanium-silicon molecular sieve and the like; preferred porous support materials are silica, alumina or activated carbon.
The specific surface of the catalyst provided by the invention is changed along with the size of the specific surface of the carrier, and the specific surface can be 10-1000 m2A concentration of 100 to 1000 m2Per gram.
According to the catalyst provided by the invention, the active component nickel exists completely as amorphous nickel, and when an X-ray diffraction spectrum measured by using a CuK α target shows that a wider diffusion peak (shown as 1 in figure 1) exists at the temperature of 45 ℃ at 2 theta, but the diffusion peak becomes less and less obvious with the reduction of loading amount (shown as 2-6 in figure 1), in some cases, the peak shape of the diffusion peak is changed due to different carriers, when active carbon is used as a carrier, the diffusion peak shape is sharper (shown as figure 2), in other cases, the diffusion peak can be covered by the diffraction peak of the carrier at the same position (shown as figures 3 and 4).
The preparation method of the catalyst provided by the invention comprises the following specific steps:
(1) impregnating a porous support material with a predetermined amount of a soluble nickel salt solution and then drying; or directly adopting a commercial nickel-containing porous carrier material;
(2) the nickel-containing porous carrier material is mixed with BH with the molar concentration of 0.5-10.0 in the temperature range from the temperature higher than the freezing point of the solution to 100 DEG C4 -Solution contact of BH, wherein4 -The amount of the boron is such that the atomic ratio of boron to nickel in the carrier is 0.1-10.0;
(3) the solid product was washed with distilled water until free of acid groups.
Wherein, the nickel salt solution refers to an aqueous solution or an alcoholic solution of nickel salt, the nickel salt is selected from one or more of nickel chloride, nickel sulfate and soluble nickel carboxylate, and nickel chloride or nickel acetate is preferred.
The porous carrier material is preferably dried at 90 to 200 ℃ for more than 3 hours in advance.
The impregnation of the nickel may be carried out by impregnation methods generally used in the preparation of the catalyst, preferably by saturation impregnation.
The BH containing4 -Ionic solutions are solutions containing BH4 -An aqueous or alcoholic solution of (b), said BH4 -The ionic precursor is selected from KBH4Or NaBH4Or a mixture thereof, the boron-nickel atomic ratio is preferably 1.5 to 3.0.
The preparation of a porous nickel-containing support material with BH4 -The ionic solution may be contacted by mixing the two solutions directly or by contacting the solution with BH4 -The ionic solution is slowly added dropwise to the support material, preferably in a slowly dropwise manner.
The temperature of the contact reaction is generally controlled to be in the range of from the freezing point temperature of the solution to 100 ℃ and preferably from room temperature to 50 ℃ for energy saving, although the temperature of the contact reaction can be also controlled to be higher than 100 ℃.
When the catalyst provided by the invention is used for hydrogenation reaction of the compound containing the unsaturated functional group, the compound containing the unsaturated functional group can be alkene, alkyne, aromatic hydrocarbon, nitro compound, carbonyl compound, carboxyl compound and nitrile. The hydrogenation reaction comprises a saturated hydrogenation reaction and a selective hydrogenation reaction, in particular to the selective hydrogenation reaction of trace acetylene in ethylene. The process conditions for the hydrogenation reaction are those which are common to each reaction.
The catalyst provided by the invention has the following advantages:
(1) the thermal stability of the catalyst is good, the catalyst provided by the invention has three phase change peaks in the crystallization process, the peak temperatures are respectively 175, 280 and 362-445 ℃, and the three phase change peak temperatures of Ni-B amorphous ultrafine particles prepared by the prior art (J.catal.150, 434-438, 1994) are respectively only 144.1, 253.4 and 341.4 ℃, which shows that the catalyst provided by the invention has higher thermal stability than Ni-B amorphous ultrafine particles, and the properties of the amorphous alloy can be more easily maintained in the catalysis process.
(2) The specific surface of the catalyst is changed with different carriers, so that the specific surface of the catalyst can be arbitrarily adjusted by using different carriers, and the specific surface of the catalyst can be adjustedCan be up to 1000 m2Specific surface area of Ni-B amorphous ultrafine particle can only reach 29.7 m2About one gram, the specific surface of the large-surface Ni-RE-P amorphous alloy catalyst can only reach 130 m2Per gram.
(3) For example, when the catalyst loaded with 4.19 wt% Ni-B amorphous alloy (nickel content is 3.97 wt%), the Ni-La-P large surface amorphous alloy catalyst disclosed in CN1073726A and the conventional polycrystalline nickel catalyst containing 5 wt% nickel are respectively used in the hydrogenation reaction of styrene at 60 ℃, the conversion rate of styrene of the catalyst provided by the invention can reach 16.54 wt%, which is equivalent to that of the unsupported Ni-La-P large surface amorphous alloy catalyst (styrene conversion rate is 16.60 wt%), while the conversion rate of styrene is only 0.1 wt% when the polycrystalline nickel catalyst is used, which shows that, on one hand, the activity of the catalyst provided by the invention is more than 165 times that of the conventional polycrystalline nickel catalyst, on the other hand, although the activity of the catalyst provided by the invention is equivalent to that of the Ni-La-P large surface amorphous alloy catalyst, however, the content of nickel in the catalyst provided by the invention is only 3.97 weight percent, and the content of nickel in the Ni-La-P large-surface amorphous alloy catalyst is up to 87.4 weight percent, which shows that the relative content of active nickel playing a role in catalyzing reaction in the catalyst provided by the invention is greatly higher than that of the Ni-La-P large-surface amorphous alloy catalyst.
The preparation method of the catalyst provided by the invention abandons the traditional BH in solution4 -A process for reducing nickel by impregnating a porous support material with nickel and then using a BH4 -The solution reduces nickel which is uniformly dispersed in a porous carrier material, and the generated Ni-B amorphous alloy can not only be loaded in the porous carrier material, but also the dispersion of the alloy in the carrier is relatively uniform, which is incomparable with the prior art, such as an electroless plating method.
FIG. 1 is SiO2X-ray of supported Ni-B amorphous alloy catalystA diffraction spectrum;
FIG. 2 is an X-ray diffraction spectrum of the Ni-B amorphous alloy catalyst with activated carbon as a carrier according to the present invention;
FIG. 3 shows delta-Al of the present invention2O3X-ray diffraction spectrum of Ni-B amorphous alloy catalyst as carrier;
FIG. 4 shows gamma-Al as a component of the present invention2O3X-ray diffraction spectrum of Ni-B amorphous alloy catalyst as carrier;
FIG. 5 is SiO solid solution provided by the present invention2DSC curves of catalysts with different Ni and B contents as carriers;
FIG. 6 is a graph of acetylene conversion over time for the selective hydrogenation of trace amounts of acetylene in ethylene over different catalysts.
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Examples 1 to 18
The invention provides a preparation method of Ni-B amorphous alloy catalyst.
(1) Carrier
The carrier 1 used (number Z)1) Is coarse pore silica gel (Qingdao ocean factory product) and carrier 2 (serial number Z)2) Is fine-pored silica gel (Qingdao ocean factory product), and carrier 3 (number Z)3) Is granular activated carbon (product of Beijing Guanghua Wood factory), and carrier 4 (number Z)4) Is delta-alumina obtained by calcining spherical alumina (from Changling catalyst works) used as a carrier for CB-8 catalyst at 900 deg.C for 4 hr, and carrier 5 (No. Z)5) Is gamma-alumina, which is obtained by calcining spherical alumina (produced in Changling catalyst works) used as a CB-8 catalyst carrier at 650 deg.C for 4 hours, and carrier 6 (No. Z)6) Is gamma-alumina, which is obtained by calcining spherical alumina (produced in Changling catalyst works) used as a CB-6 catalyst carrier at 650 deg.C for 4 hours, and a carrier 7 (No. Z)7) Is gamma-alumina which is an elongated alumina (long-ridge catalysis)Product of pharmaceutical factory) is calcined at 650 ℃ for 4 hours, the carrier Z is obtained1～Z7The physicochemical properties of (A) are shown in Table 1. Wherein the crystalline phase is determined by X-ray diffraction; the specific surface and pore volume are measured by a low-temperature nitrogen adsorption BET method, and the L acid content is measured by an infrared pyridine adsorption method according to the method described in Industrial catalyst analysis and test characterization, P353-360, Hydrocarbon processing Press, 1990.
TABLE 1
| Carrier numbering | Type of support | Specific surface area, rice2Per gram | Pore volume, ml/g | Crystalline phase | Amount of acid, A/g cm2 |
| Z1 Z2 Z3 Z4 Z5 Z6 Z7 | SiO2 SiO2 Activated carbon Al2O3 Al2O3 Al2O3 Al2O3 | 401 672 888 124 153 190 175 | 0.95 0.39 0.56 0.49 0.47 0.49 0.44 | Amorphous form Amorphous form Amorphous form δ γ γ γ | 1.7 0.4 - 4.8 13.1 17.3 13.4 |
(2) Preparation of the catalyst
Weighing different carriers in a certain amount respectively, drying at 100-150 ℃, weighing nickel acetate tetrahydrate in a certain amount respectively to prepare nickel acetate solutions, soaking the nickel acetate solutions in the different carriers, and drying at 120 ℃ to obtain nickel-containing carriers; separately weighing quantitative KBH4And formulating into an aqueous solution of KBH4Dropwise adding the solution into a nickel-containing carrier at room temperature, immediately carrying out the reaction and releasing hydrogen, after the dropwise addition is finished, after no hydrogen is released, indicating that the reaction is finished, washing the obtained solid product by using distilled water until no acid radicals are released, wherein the obtained catalyst is numbered from A to R, the using amount of each substance in the preparation process is listed in Table 2, the composition and the physicochemical properties of the catalysts A to R are shown in Table 3, wherein the catalyst A has an X-ray diffraction line shown as 1 in FIG. 1, the catalyst B has an X-ray diffraction line shown as 2 in FIG. 1, the catalyst C has an X-ray diffraction line shown as 3 in FIG. 1, the catalysts D, G, H, I, J and L have an X-ray diffraction line shown as 4 in FIG. 1, the catalysts E and K have an X-ray diffraction line shown as 5 in FIG. 1, the catalyst F has an X-ray diffraction line shown as 6 in FIG. 1, and the catalysts M and N have an X-ray diffraction line shown in FIG., catalyst O has an X-ray diffraction pattern as shown in FIG. 3, and catalysts P, Q and R have an X-ray diffraction pattern as shown in FIG. 4.
The method comprises the steps of dissolving the contents of boron and nickel in a catalyst by a microwave digestion method, measuring the contents on a Jarrel-Ash 1000 type inductively coupled plasma direct-reading spectrometer (ICP), measuring an X-ray diffraction spectrum of the catalyst by a CuK α target on a Japan science D/MAX-2A type X-ray diffractometer under the conditions that the tube voltage is 40V, the tube current is 35 mA, an emission slit (D&S) ═ 1 DEG, a receiving slit (R&S) ═ 0.5 mm and an anti-divergence slit (S&S) ═ 1 DEG, measuring a Ni color filter, and measuring the specific surface area and the pore volume of the catalyst on a U.S. micromerics ASAP 2400 physical adsorption apparatus by a low-temperature nitrogen adsorption method.
TABLE 2
| Examples of the invention Numbering | Carrier | Nickel acetate solution | KBH4Solutions of | Feeding B/Ni Atomic ratio | |||
| Species of | Dosage, gram | Acetic acid tetrahydrate Amount of nickel in grams | The amount of water is used, milliliter (ml) | KBH4By using Amount, g | The amount of water is used, milliliter (ml) | ||
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 | Z1 Z1 Z1 Z1 Z1 Z1 Z1 Z1 Z1 Z1 Z1 Z2 Z3 Z3 Z4 Z5 Z6 Z7 | 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 | 4.0 3.0 2.0 1.0 0.5 0.2 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.95 1.0 1.0 1.0 1.0 | 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 6.0 8.0 5.0 5.0 5.0 5.0 5.0 | 2.16 1.62 1.08 0.54 0.27 0.11 0.65 0.54 0.43 0.33 0.22 0.54 0.54 0.52 0.54 0.54 0.54 0.54 | 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 8.0 10.0 7.0 7.0 7.0 7.0 7.0 | 2.5 2.5 2.5 2.5 2.5 2.5 3.0 2.5 2.0 1.5 1.0 2.5 2.5 2.5 2.5 2.5 2.5 2.5 |
TABLE 3
| Example numbering | Catalyst numbering | Ni and B content in catalyst | Specific surface rice2Per gram | ||
| Ni content is high | B weight percent | Atomic ratio of Ni/B | |||
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 | A B C D E F G H I J K L M N O P Q R | 8.94 7.27 5.90 3.97 1.51 0.56 3.33 3.30 3.05 2.40 1.50 2.37 3.08 4.03 3.88 3.91 3.46 3.85 | 0.37 0.36 0.31 0.22 0.06 0.03 0.22 0.22 0.20 0.14 0.08 0.23 0.08 0.27 0.17 0.46 0.50 0.12 | 4.57 3.82 3.60 3.42 3.62 3.53 2.70 2.70 2.85 3.17 3.55 1.86 7.33 3.00 4.32 1.56 1.27 5.67 | 301 321 324 341 384 395 364 365 367 374 385 451 815 131 129 177 201 194 |
As can be seen from tables 1-3:
(1) in the preparation of catalysts, e.g. reducing agents (BH)4 -) The use amount is small, namely when the feeding B/Ni atomic ratio is small, the contents of Ni and B on the catalyst are both low, most of nickel ions are not reduced, the contents of Ni and B on the catalyst are rapidly increased along with the increase of the use amount of a reducing agent, but when the feeding B/Ni atomic ratio is more than 2.5, the trend of increasing the content of Ni in the catalyst is not obvious; when the B/Ni atomic ratio is more than 2.0, the boron content in the catalyst is substantially constant, and thus the catalyst can be prepared by using a lower or higher feed B/Ni atomic ratioThe Ni-B amorphous alloy catalyst provided by the invention is prepared, but the feeding B/Ni atom ratio is smaller, so that more Ni ions can not be reduced, the yield can be greatly reduced, and the cost of the catalyst can be increased when the feeding B/Ni atom ratio is too high, so that the feeding B/Ni atom ratio is reasonably controlled within the range of 1.5-3.0. (see examples 7-11).
(2) Compared with examples 8, 12, 13, 15-18, it can be seen that under the condition that the amounts of Ni and the reducing agent are the same, the compositions of Ni-B amorphous alloys in catalysts prepared on different types of carriers are different, and the compositions of Ni-B amorphous alloys in catalysts prepared on the same type of carriers are also greatly different due to different properties of the same type of carriers. The surface area and pore structure of the carrier can influence the mass transfer process of the reduction reaction and thus influence the composition of the catalyst, generally, the larger the acid content of the carrier is, the stronger the acid strength is, the larger the content of B in the catalyst prepared under the same conditions is, and thus the conditionsfor preparing Ni-B amorphous alloy catalysts should be different for different carrier materials.
(3) The specific surface of the Ni-B amorphous alloy catalyst provided by the invention depends on the specific surface of the carrier, and the specific surface with expected value can be obtained by loading the amorphous alloy on a proper carrier, for example, the specific surface of example 13 is prepared to be as high as 815 m2The specific surface area of the Ni-B amorphous alloy catalyst per gram is difficult to achieve by the prior art.
Comparative example 1
Ni-P/SiO2Amorphous alloy reference catalyst
Ni-P/SiO2The supported amorphous alloy catalyst S is provided by Dengjing et al, and the preparation method is shown in Appl. catal.37, 339-340, 1988, and the supported amorphous alloy catalyst S comprises 11.70 wt% of Ni, 1.3 wt% of P and the balance of SiO2The Ni and P contents are dissolved by microwave digestion method and measured on Jannel-Ash-1000 type inductively coupled plasma direct-reading spectrometer (ICP).
Comparative example 2
Preparing the large-surface Ni-La-P amorphous alloy reference catalyst.
The amorphous Ni-La-P alloy catalyst T with large surface area was prepared under the conditions and the amounts of the respective components described in example 6 of CN1073726A, and its composition was Ni87.4 wt%, La 0.4 wt%, and P12.2 wt% as measured by ICP, and its specific surface area was 91 m as measured by the same method as in examples 1 to 182Per gram.
Comparative example 3
Preparation of polycrystalline nickel reference catalyst.
Weighing 5 g of the carrier Z1Soaking in 9.82 g of 8.35 wt% nickel nitrate solution, stoving at 100 deg.c for 4 hr, roasting at 500 deg.c for 3 hr, and reducing with hydrogen at 460 deg.c for 4 hr to obtain reference catalyst
Catalyst u, containing Ni5 wt%, Ni content was also measured by ICP method.
Examples 19 to 25
The following examples illustrate the thermal stability of the catalysts provided by the present invention.
5 mg of each of the catalysts B, C, D, E, L, M, N was weighed, and a DSC curve and a crystallization temperature thereof were measured on a differential scanning analyzer (DSC) of a Du Pont2100 thermal analysis system at a temperature increase rate of 10 ℃/min under a nitrogen atmosphere, the DSC curves of the catalysts B, C, D and E are shown as 7, 8, 9 and 10 in FIG. 5, respectively, and the maximum crystallization temperature of each of the catalysts is shown in Table 4.
As can be seen from FIG. 5, the catalyst provided by the invention has three phase-change peaks after being heated, the peak temperatures of the three phase-change peaks are respectively positioned near 175 ℃, 280 ℃ and 390 ℃, and as the content of the Ni-B amorphous alloy in the catalyst increases, the enthalpy change values of the phase-change processes represented by 175 ℃ and 280 ℃ increase. It can be seen from the results in table 4 that the third crystallization peak temperature (i.e. the highest crystallization peak temperature) of the catalyst is related to the composition of the Ni-B amorphous alloy in the catalyst, and the higher the content of B in the Ni-B amorphous alloy, the higher the highest peak temperature, and further, the thermal stability of the catalyst provided by the present invention is significantly higher than that of the Ni-B ultrafine amorphous alloy, for example, the three crystallization peak temperatures of the catalyst provided by the present invention are respectively 175, 280 and 362-445 ℃, while the three crystallization peak temperatures of the Ni-B ultrafine amorphous alloy are only 144.1, 253.4 and 341.4 ℃ (see j.catal.150, 435, 1994).
TABLE 4
| Example numbering | Catalyst numbering | Catalyst Ni/B atomic ratio | Peak crystallization temperature |
| 19 20 21 22 23 24 25 | B C D E L M N | 3.82 3.60 3.42 3.62 1.86 7.33 3.00 | 394 388 408 398 445 362 391 |
The following examples and comparative examples illustrate the use of the catalysts of the present invention in hydrogenation of various compounds containing unsaturated functional groups and the activity of the catalysts, the hydrogenation reactions selected were as follows:
(1) selective hydrogenation reaction of trace acetylene in ethylene
The seven reactions described above represent essentially all types of hydrogenation reactions for compounds containing unsaturated functional groups.
Examples 26 to 28
The catalyst provided by the invention is applied to selective hydrogenation reaction of trace acetylene in ethylene.
The hydrogenation reaction is carried out on a continuous micro-reactor, the inner diameter of the reactor is 3 mm, the length of the reactor is 2000 mm, the used catalyst is D, M, N, the catalyst loading is 0.04 g, the used raw material gas comprises 1.65 mol% of acetylene, 95.79 mol% of ethylene and 2.56 mol% of hydrogen, the reaction conditions are that the reaction temperature is 110 ℃, the reaction pressure is 10.0 MPa, and the gas volume space velocity is 9000 h-1The gas compositions before and after the reaction were analyzed on line by gas chromatography, and when the hydrogenation catalyst was N, D, M, the time-dependent changes in the acetylene conversion were shown as 11, 12, and 13 in fig. 6, respectively.
Comparative examples 4 to 6
The following comparative examples illustrate that the catalyst of the present invention has significantly higher activity in the selective hydrogenation of trace amounts of acetylene in ethylene than the prior art catalysts.
The apparatus, materials and reaction conditions used in the hydrogenation reaction were the same as those in examples 26 to 28 except that the catalysts used were the reference catalysts S, T and U prepared in comparative examples 1, 2 and 3, respectively, and the acetylene conversion rates with time were as shown in FIGS. 6, 14, 15 and 16, respectively.
Example 29
The catalyst provided by the invention is applied to the reaction of preparing methylcyclohexane by hydrogenating toluene.
Hydrogenation was carried out in a 100 ml batch reactor by charging 50 ml of 20% by weight toluene in cyclohexane solution and 0.2 g of catalyst D into the reactor, charging 1.0 mpa hydrogen into the reactor, evacuating, repeating the charging three times to displace the air in the reactor, then charging 4.0 mpa hydrogen, heating to 140 ℃ and reacting at a stirring rate of 64 times/min for 1 hour, cooling, taking out the reacted mixture, and analyzing by gas chromatography, the results are shown in table 5.
Comparative example 7
This comparative example illustrates the activity of the catalyst provided by the present invention in the reaction of hydrogenation of toluene to methylcyclohexane.
The reaction apparatus, raw materials and reaction conditions were the same as in example 29 except that the catalyst used was the large-surface Ni-La-P amorphous alloy catalyst T prepared in comparative example 2, and the reaction results are shown in table 5.
TABLE 5
| Example numbering | Catalyst and process for preparing same | Percent conversion of toluene is high% |
| 29 Comparative example 7 | D T | 19.74 20.01 |
Example 30
The catalyst provided by the invention is applied to the reaction of preparing ethylbenzene by hydrogenating styrene.
The hydrogenation of styrene was carried out as described in example 29, using 50 ml of styrene, 0.2 g of catalyst D, 60 ℃ and 0.5 h of reaction time, and the results of the reaction are given in Table 6, following the same procedure as in example 29.
Comparative examples 8 to 9
The following comparative examples illustrate the activity of the catalyst of the present invention in the hydrogenation of styrene to ethylbenzene.
The reaction apparatus, raw materials and reaction conditions were the same as in example 30 except that the catalysts used were the reference catalysts T and U prepared in comparative examples 2 and 3, respectively, and the reaction results are shown in Table 6.
TABLE 6
| Example numbering | Catalyst and process for preparing same | Percent conversion of styrene is |
| 30 Comparative example 8 Comparative example 9 | D T U | 16.54 16.60 0.10 |
Example 31
The catalyst provided by the invention is applied to the reaction for preparing the hexanediamine by the hydrogenation reaction of the adiponitrile.
Adiponitrile hydrogenation was carried out as described in example 29 using 50 ml of 15 wt.% adiponitrile in ethanol as the starting material, 0.2 g of catalyst D, 100 ℃ as the reaction temperature, 1 hour of reaction time, and the remaining operating conditions were the same as in example 29, and the reaction results are shown in Table 7.
Comparative example 10
This comparative example illustrates the activity of the catalyst provided by the present invention in the hydrogenation of adiponitrile to hexanediamine.
The reaction apparatus, raw materials and reaction conditions were the same as in example 31 except that the catalyst used was the reference catalyst T prepared in comparative example 2, and the reaction results are shown in Table 7.
TABLE 7
| Example numbering | Catalyst and process for preparing same | The conversion rate of ethanedinitrile is heavy% |
| 31 Comparative example 10 | D T | 20.91 25.95 |
The results intables 5 to 7 show that (1) the activity of the catalyst provided by the invention in the hydrogenation reaction is equivalent to that of the large-surface Ni-La-P amorphous alloy catalyst described in CN1073726A, but the Ni-B amorphous alloy in the catalyst provided by the invention only accounts for 4.19 wt%, the nickel content is only 3.97 wt%, and the nickel content in the large-surface Ni-La-P amorphous alloy catalyst is up to 87.4 wt%, which indicates that the relative content of active nickel playing a role in catalyzing the reaction in the catalyst provided by the invention is greatly higher than that of the Ni-La-P large-surface amorphous alloy catalyst, and (2) the activity of the catalyst provided by the invention in the hydrogenation reaction of styrene is more than 165 times of that of the traditional polycrystalline nickel catalyst, and the nickel content is lower than that of the polycrystalline nickel catalyst. In conclusion, the catalyst provided by the invention is a low-nickel high-efficiency catalyst and has incomparable advantages compared with the prior art.
Example 32
The catalyst provided by the invention is applied to the reaction of preparing aniline by nitrobenzene hydrogenation.
The hydrogenation was carried out as described in example 29, starting with 50 ml of a 20% by weight solution of nitrobenzene in isopropanol, catalyst D in a charge of 0.2 g, a reaction temperature of 89 ℃ and a reaction time of 1 hour, the other operating conditions being as in example 29, and the results are given in Table 8.
TABLE 8
| Example numbering | Catalyst and process for preparing same | Nitrobenzene conversion, weight% |
| 32 | D | 1.97 |
Example 33
The catalyst provided by the invention is applied to the reaction of preparing cyclohexanol by hydrogenating cyclohexanone.
The hydrogenation was carried out as described in example 29, starting with 50 ml of a 30% by weight cyclohexane solution of cyclohexanone, the catalyst D was charged in an amount of 0.2 g, the reaction temperature was 95 ℃ and the reaction time was 1 hour, the other operating conditions were the same as in example 29, and the reaction results are given in Table 9.
TABLE 9
| Example numbering | Catalyst and process for preparing same | Conversion of Cyclohexanone, weight% |
| 33 | D | 0.49 |
Example 34
The catalyst provided by the invention is applied to the phenylacetylene hydrogenation reaction.
The hydrogenation was carried out as described in example 29, starting with 50 ml of a 15% by weight cyclohexane solution of phenylacetylene, the catalyst D was charged in an amount of 0.2 g, the reaction temperature was 22 ℃ and the reaction time was 0.5 hours, the other operating conditions were the same as in example 29, and the reaction results are shown in Table 10.
| Example numbering | Catalyst and process for preparing same | The conversion rate of phenylacetylene is heavy% | Styrene selectivity is heavy% |
| 34 | D | 5.71 | 100 |
Claims (12)
1. The Ni-B amorphous alloy catalyst is characterized by comprising 0.1-30.0 wt% of Ni-B amorphous alloy and 70.0-99.9 wt% of porous carrier material, wherein the atomic ratio of Ni to B is 0.5-10.0.
2. The catalyst according to claim 1, wherein the composition is 1.0 to 12.0 wt% Ni-B amorphous alloy and 88.0 to 99.0 wt% porous carrier material.
3. The catalyst according to claim 1 or 2, wherein the specific surface area of the catalyst is 10 to 1000 m2Per gram.
4. The catalyst according to claim 3, wherein the specific surface area of the catalyst is 100 to 1000 m2Per gram.
5. The catalyst according to claim 1 or 2, wherein the atomic ratio of Ni and B is 1.0 to 8.0.
6. The catalyst according to claim 1 or 2, wherein the porous carrier material is selected from one or more of porous inorganic oxides, activated carbon, zeolites and molecular sieves.
7. The catalyst according to claim 4, characterized in that the porous support material is silica, activated carbon or alumina.
8. A process for preparing the catalyst of claim 1, which comprises contacting a porous nickel-containing support material with a molar concentration of 0.5 to 10.0 of BH in the temperature range from above the freezing point of the solution to 100 ℃4 -The solution of ions is contacted with Niaccording to the B and Ni feeding atomic ratio of 0.1-10.0.
9. The method of claim 8, wherein the BH that comprises4 -Ionic solutions are solutions containing BH4 -Ionic aqueous or alcoholic solutions, BH4 -The ionic precursor is selected from KBH4Or NaBH4Or mixtures thereof.
10. The method of claim 8 or 9, wherein the B to Ni charge atomic ratio is 1.5 to 3.0.
11. The method of claim 8 or 9, wherein the contacting is atAt room temperature to 50 ℃, adding BH4 -The ionic solution is slowly added dropwise to the nickel-containing support material.
12. The catalyst of claim 1 used for the catalytic hydrogenation of compounds containing unsaturated functional groups.
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| CN 96120054 CN1061269C (en) | 1996-10-15 | 1996-10-15 | Ni-B amorphous alloy catalyst, its preparing process and application |
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| CN 96120054 CN1061269C (en) | 1996-10-15 | 1996-10-15 | Ni-B amorphous alloy catalyst, its preparing process and application |
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| CN1061269C CN1061269C (en) | 2001-01-31 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099910C (en) * | 1999-08-31 | 2003-01-29 | 中国石油化工集团公司 | Process for preparing carried non-crystal alloy catalyst |
| CN1099909C (en) * | 1999-08-31 | 2003-01-29 | 中国石油化工集团公司 | Process for preparing non-crystal Ni-B alloy catalyst |
| CN100357286C (en) * | 2005-12-13 | 2007-12-26 | 天津市瑞凯科技发展有限公司 | Process for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfuralcohol |
| WO2011032474A1 (en) * | 2009-09-21 | 2011-03-24 | Wang Xiaoqi | Method for preparing halofuginone derivative |
| CN101664682B (en) * | 2008-09-05 | 2011-12-28 | 中国石油化工股份有限公司 | Non-noble metal supported selective hydrogenation catalyst and preparation method and application thereof |
| CN103952719A (en) * | 2014-03-28 | 2014-07-30 | 中国科学院物理研究所 | Catalyst used for preparation of hydrogen through water electrolysis, and preparation method thereof |
| CN105032429A (en) * | 2015-07-28 | 2015-11-11 | 湖北荆楚理工科技开发有限公司 | Benzoic acid hydrogenation catalyst prepared through micro-wave heating and preparation method |
| CN105798323A (en) * | 2016-03-18 | 2016-07-27 | 西北师范大学 | Method for preparing transition metal-boron alloy material with large specific surface area on ball milling-assisted interface |
-
1996
- 1996-10-15 CN CN 96120054 patent/CN1061269C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099910C (en) * | 1999-08-31 | 2003-01-29 | 中国石油化工集团公司 | Process for preparing carried non-crystal alloy catalyst |
| CN1099909C (en) * | 1999-08-31 | 2003-01-29 | 中国石油化工集团公司 | Process for preparing non-crystal Ni-B alloy catalyst |
| CN100357286C (en) * | 2005-12-13 | 2007-12-26 | 天津市瑞凯科技发展有限公司 | Process for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfuralcohol |
| CN101664682B (en) * | 2008-09-05 | 2011-12-28 | 中国石油化工股份有限公司 | Non-noble metal supported selective hydrogenation catalyst and preparation method and application thereof |
| WO2011032474A1 (en) * | 2009-09-21 | 2011-03-24 | Wang Xiaoqi | Method for preparing halofuginone derivative |
| US8569492B2 (en) | 2009-09-21 | 2013-10-29 | Xiaoqi WANG | Method for preparing halofuginone derivative |
| CN103952719A (en) * | 2014-03-28 | 2014-07-30 | 中国科学院物理研究所 | Catalyst used for preparation of hydrogen through water electrolysis, and preparation method thereof |
| CN105032429A (en) * | 2015-07-28 | 2015-11-11 | 湖北荆楚理工科技开发有限公司 | Benzoic acid hydrogenation catalyst prepared through micro-wave heating and preparation method |
| CN105798323A (en) * | 2016-03-18 | 2016-07-27 | 西北师范大学 | Method for preparing transition metal-boron alloy material with large specific surface area on ball milling-assisted interface |
| CN105798323B (en) * | 2016-03-18 | 2018-04-06 | 西北师范大学 | The method that ball milling assistant interface prepares bigger serface transition metal boron alloy material |
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| CN1061269C (en) | 2001-01-31 |
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