CN106799256B - alkane isomerization catalyst and preparation method thereof - Google Patents
alkane isomerization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a paraffin isomerization catalyst and a preparation method thereof. The catalyst consists of a silicoaluminophosphate composite molecular sieve and one or more of non-noble metals Co, Ni, Mo and W with the content of 1-50 wt%. The silicoaluminophosphate composite molecular sieve has a mixed crystal phase of SAPO-11 and a silicoaluminophosphate salt, and an X-ray diffraction spectrum of the silicoaluminophosphate composite molecular sieve has at least the following diffraction peaks, wherein a2 theta value represents the position of the diffraction peak, and 2 theta/°: 8.14 +/-0.2, 9.48 +/-0.2, 12.49 +/-0.1, 13.24 +/-0.2, 15.70 +/-0.2, 16.32 +/-0.2, 17.56 +/-0.2, 17.87 +/-0.1, 19.02 +/-0.2, 20.46 +/-0.2, 21.10 +/-0.2, 21.66 +/-0.1, 22.18 +/-0.2, 22.60 +/-0.2, 22.76 +/-0.2, 23.22 +/-0.2, 24.74 +/-0.2, 27.86 +/-0.1, 28.49 +/-0.1, 33.03 +/-0.1 and 33.41 +/-0.1. When the catalyst is used for alkane and alkane isomerization reaction, compared with the catalyst generally adopted in the prior art, the catalyst has better catalytic activity.
Description
Technical Field
the invention relates to a paraffin isomerization catalyst, in particular to a paraffin isomerization catalyst consisting of a silicoaluminophosphate composite molecular sieve and non-noble metal with the content of 1-50 wt%.
The invention also relates to a preparation method of the catalyst.
Background
Early paraffin isomerization catalysts, primarily liquid acid catalystsSuch as AlCl3-HCl french catalyst, sulfuric acid and liquid super acid catalyst. These liquid acid catalysts have high isomerization performance and typically achieve near equilibrium conversion at room temperature to 90 c, but have poor selectivity and insufficient stability. In addition, it has been almost eliminated at present due to strong corrosion of equipment and severe pollution of the environment. From the last 40 s, bifunctional solid catalysts were gradually developed and applied to the alkane isomerization process.
The double-function solid catalyst consists of two parts of hydrogenation-dehydrogenation component and acid carrier. The hydro-dehydrogenation component can be divided into two categories, including: 1. single metal or multi-metal composite systems such as Pt, Pd, Rh, Ir, Ni, and the like; 2. transition metal sulfide systems, such as sulfides of Ni-Co, Ni-W, Ni-Mo, and the like. Acidic carriers can be classified into the following three categories: 1. amorphous single or complex metal oxides, e.g. halide-treated Al2O3、SiO2/Al2O3ZrO of superacid2/SO4 2-、WO3/ZrO2Etc.; 2. silicoaluminophosphate molecular sieves, such as Y, Beta, ZSM-5, ZSM-22, and the like; 3. the aluminum phosphate molecular sieves, such as SAPO-5, SAPO-11, SAPO-31, SAPO-41, and the like. Compared with amorphous oxides and super acids, the molecular sieve shows excellent performances in the aspects of shape selection selectivity, stability, poisoning resistance and carbon deposition resistance. Therefore, isomerization catalysts based on molecular sieves as supports are widely used.
molecular sieves refer to materials that have sieving capability in terms of molecular size. Because of the regular pore structure and the unique surface property, the catalyst is widely applied to the fields of catalysis, ion exchange, adsorption, separation and the like. The molecular sieve material which is recognized by human beings firstly is natural zeolite, the twenty century and the fortieth, Barrer R M and the like realize the artificial synthesis of the molecular sieve for the first time, and then a large amount of molecular sieve materials are artificially synthesized in succession, however, along with the development of the industry, the performance and the structure of the molecular sieve are higher in many fields, so that the development of a novel molecular sieve material is particularly significant.
Aluminium phosphateMolecular sieve (AlPO)4-n) is a new class of molecular sieve materials developed in the last 80 th century. The framework of such molecular sieves is strictly made of PO4 +And AlO4 -The tetrahedra are alternately composed, without exchangeable charges and therefore without acidity, and have extremely limited applications in catalytic reactions. The silicoaluminophosphate molecular sieve (SAPO-n) can be generated by isomorphous substitution of silicon on the framework of the silicoaluminophosphate molecular sieve, so that the silicoaluminophosphate molecular sieve has acidity due to unbalance of framework charges. At the same time, since AlPO is also maintained4The pore channel structure of-n makes SAPO-n have great application prospect in catalysis. Currently, a variety of SAPO-n's have been used in chemical industrial processes, particularly in petroleum refining related catalytic processes. For example, SAPO-34 is applied in the process of preparing olefin from methanol, SAPO-11 is applied in the process of modifying diesel oil and dewaxing lubricating oil, and the like.
The SAPO-11 molecular sieve has an AEL structure, belongs to an orthorhombic system, has a space group of Ima2 and has a unit cell parameter ofThe skeleton is mainly composed of PO4 +、AlO4 -And SiO4The tetrahedrons are mutually interwoven to form the structure, and the structure is provided with an oval ten-membered ring one-dimensional straight channel with the size of the channelTypical X-ray diffraction pattern data are shown in table 1.
TABLE 1
Diffraction peak intensity, w-m: < 20; m is 20-70; s is 70-90; vs 90-100
The synthesis of silicoaluminophosphate molecular sieve SAPO-11 can be found in various patent reports, such as US4440871, US4310440, US4943324, US5208005, EP146384, CN99109681, etc. In these patents, a hydrothermal synthesis method is adopted to synthesize pure-phase SAPO-11. Because of the structural characteristics of AEL framework, SAPO-11 molecular sieve prepared by various reported synthetic methods can only form weak acid sites and medium-strong acid sites, namely NH3-TPD-NH3The desorption peaks only appear around 180 ℃ and 280 ℃ (as shown in figure 2), and respectively represent weak acid positions and medium acid positions. Continuing to increase the amount of silicon substitution only increases the number of these two acid sites and does not produce a stronger acid site, i.e., at NH3The desorption peak around 400 ℃ appears in the TPD graph.
in the process of SAPO-11 acting on isomerization of long paraffin, the performance of the catalyst is determined by the ten-membered ring one-dimensional straight channel of SAPO-11 and the acidity thereof. The more acidic, the higher the catalyst activity and the lower the reaction temperature required to achieve the target conversion. Therefore, the synthesis of the SAPO-11 with strong acid sites or the SAPO-11 composite molecular sieve with strong acid sites can possibly expand the further application of the molecular sieve in the isomerization and cracking catalytic processes. The isomerization of the alkane prepared based on the molecular sieve shows more excellent performance.
Disclosure of Invention
The invention aims to provide a paraffin isomerization catalyst, which consists of a silicoaluminophosphate composite molecular sieve and non-noble metal; wherein the mass content of the non-noble metal is 1-20 wt%;
Wherein the silicoaluminophosphate composite molecular sieve has 0.3-0.7 nm micropores and a BET specific surface area of 100-300 m2A pore volume of 0.1 to 0.5mL/g, and an X-ray diffraction spectrum having at least the following diffraction peaks,
The 2 θ value represents a diffraction peak position, 2 θ/°: 8.14 +/-0.2, 9.48 +/-0.2, 12.49 +/-0.1, 13.24 +/-0.2, 15.70 +/-0.2, 16.32 +/-0.2, 17.56 +/-0.2, 17.87 +/-0.1, 19.02 +/-0.2, 20.46 +/-0.2, 21.10 +/-0.2, 21.66 +/-0.1, 22.18 +/-0.2, 22.60 +/-0.2, 22.76 +/-0.2, 23.22 +/-0.2, 24.74 +/-0.2, 27.86 +/-0.1, 28.49 +/-0.1, 33.03 +/-0.1 and 33.41 +/-0.1.
The non-noble metal is one or more of Co, Ni, Mo or W.
the mass content of the non-noble metal is preferably 2-20 wt%.
The invention also provides a method for preparing the alkane isomerization catalyst, which comprises the following steps:
a) mixing an aluminum source, a phosphorus source and water, and uniformly stirring to prepare a precursor mixture A; standing and aging the precursor mixture A at 0-30 ℃ for 0-12 h;
b) Adding organic amine into the precursor mixture A after standing and aging, adding a silicon source after stirring to be uniform, and continuously stirring to be uniform to form a precursor mixture B, wherein in the precursor mixture B, the ratio of aluminum source: a phosphorus source: silicon source: organic amine with Al2O3:P2O5:SiO2the organic amine is calculated, the molar ratio is 1: 0.1-5: 0.01-5: 0.1-5;
c) Heating the prepared precursor mixture B to 120-250 ℃ for crystallization, wherein the crystallization time is 8-48 h;
d) After crystallization is finished, cooling the reactant to room temperature, filtering, washing and drying to obtain a solid, namely the silicoaluminophosphate composite molecular sieve;
e) One or more than two methods of dipping, precipitation, adhesive bonding by adding a binder or mechanical pressing are adopted to realize the combination of non-noble metal and the silicoaluminophosphate composite molecular sieve, and the mixture is roasted at 400-600 ℃;
f) Before use, the calcined catalyst is subjected to reduction treatment.
The phosphorus source is one or more than two of phosphoric acid or ammonium phosphate, ammonium monohydrogen phosphate or ammonium dihydrogen phosphate in phosphate;
the non-noble metal is one or more of Co, Ni, Mo or W.
The aluminum source is one or two of pseudo-boehmite or hydrated alumina;
The organic amine is one or more than two of aliphatic amine, aromatic amine, alcohol amine and quaternary ammonium salt compounds;
The silicon source is one or more than two of fumed silica, silica sol, water glass, solid silica gel and amorphous silica.
In the step a), the precursor mixture A is preferably kept stand and aged for 0-8 h at the temperature of 0-25 ℃.
In step B), preference is given to Al in the conditioned precursor mixture B2O3:P2O5:SiO2The organic amine is present in a molar ratio of 1:0.5 to 2:0.1 to 1:0.5 to 2.
In the step c), the preferable conditions are that the crystallization temperature is 160-220 ℃ and the crystallization time is 12-36 h.
The organic amine is preferably an aliphatic amine.
combining the non-noble metal and the silicoaluminophosphate composite molecular sieve in the step e), and adopting non-noble metal acid, metallate, chloride, nitric acid compound, ammonia complex, carbonyl complex or mixture thereof as raw materials.
In the step f), the reduction treatment is carried out in the presence of hydrogen or a mixed gas of hydrogen and an inert gas at a reduction temperature of 100-600 ℃.
a) mixing an aluminum source, a phosphorus source and water, and uniformly stirring to prepare a precursor mixture A; standing and aging the precursor mixture A at 0-30 ℃ for 0-12 h;
b) Adding organic amine into the precursor mixture A, stirring the mixture until the mixture is uniform, adding a silicon source into the mixture, and continuously stirring the mixture until the mixture is uniform to form a precursor mixture B, wherein Al in the precursor mixture B2O3:P2O5:SiO2The organic amine is in a molar ratio of 1: 0.1-5: 0.01-5: 0.1-5;
c) Heating the prepared precursor mixture B to 120-250 ℃ for crystallization, wherein the crystallization time is 8-48 h;
d) After crystallization is finished, cooling the reactant to room temperature, filtering, washing and drying to obtain a solid, namely the silicoaluminophosphate composite molecular sieve;
e) the combination of the VIII group noble metal and the silicoaluminophosphate composite molecular sieve is realized by adopting the existing chemical and physical methods of dipping, precipitation, adhesive addition, mechanical pressing and the like, and the roasting is carried out at 400-600 ℃;
f) Before use, the calcined catalyst is subjected to reduction treatment.
The method comprises the step of standing and aging the precursor mixture A for 0-8 hours at the temperature of 0-25 ℃.
The method described, wherein Al is present in the precursor mixture B2O3:P2O5:SiO2the organic amine is present in a molar ratio of 1:0.5 to 2:0.1 to 1:0.5 to 2.
The method, wherein the phosphorus source is ammonium phosphate, ammonium monohydrogen phosphate or ammonium dihydrogen phosphate in phosphoric acid or phosphate.
The method, wherein the aluminum source is pseudo-boehmite or hydrated alumina.
The method comprises the step of preparing an organic amine, wherein the organic amine is one or more of aliphatic amine, aromatic amine, alcohol amine and quaternary ammonium salt compounds.
In the method, the silicon source is one or more of fumed silica, silica sol, water glass, solid silica gel and amorphous silica.
The method comprises the steps of crystallizing at the temperature of 160-220 ℃ for 12-36 hours.
The method according to (1), wherein the organic amine is an aliphatic amine.
In the method, the non-noble metal acid, metal acid salt, chloride, nitric acid compound, ammonia complex, carbonyl complex or the mixture thereof is used as the raw material in the step e.
In the method, the reducing atmosphere in the step f is hydrogen or a mixed gas of hydrogen and inert gas, and the reducing temperature is 100-600 ℃.
Compared with pure SAPO-11 synthesized by the existing known means, the silicoaluminophosphate composite molecular sieve has stronger acidity and more acid content.
therefore, compared with the catalyst prepared by the prior art and based on pure SAPO-11 as a carrier, the alkane isomerization catalyst prepared by the invention has the following characteristics:
(1) SAPO-11 crystalline phase with higher strength, namely, a large number of ten-membered ring one-dimensional straight channels with AEL structures are maintained; meanwhile, the crystal phase of the layered silicoaluminophosphate is also provided;
(2) Has a large number of strong acid sites;
(3) When the catalyst is used for long-chain paraffin isomerization reaction, the activity is higher, and the reaction temperature required for achieving high conversion rate of long-chain paraffin is lower.
drawings
FIG. 1 is an X-ray diffraction spectrum of pure SAPO-11 prepared in comparative example 1
FIG. 2 is NH of pure SAPO-11 prepared by comparative example 13-TPD profile
FIG. 3 is an X-ray diffraction pattern of a composite molecular sieve of silicoaluminophosphate in the catalyst for isomerization of hydrocarbons prepared in example 1 of the present invention
FIG. 4 shows NH of composite molecular sieve of silicoaluminophosphate in a catalyst for isomerization of paraffins prepared in example 1 of the present invention3-TPD profile
Detailed Description
The invention will be further described with reference to specific examples, but it should be understood that the invention is not limited thereto.
Comparative example 1
Weighing 114g of aluminum isopropoxide, dissolving in 200g of deionized water, and uniformly stirring and mixing; weighing 130g of phosphoric acid, dissolving in 100g of deionized water, and uniformly mixing; dropwise adding a phosphoric acid solution to an aluminum isopropoxide solution which is kept in a stirring state to form a precursor mixture A; 57g of di-n-propylamine is weighed and dripped into the A, and the mixture is stirred uniformly; weighing about 45g of silica sol (30 wt%), dropwise adding into the A, and uniformly stirring to form a precursor mixture B; putting the B into a reaction kettle with the volume of 1L, starting heating up for crystallization, wherein the crystallization temperature is 200 ℃, and keeping for 24 hours; and after crystallization is finished, washing and filtering the product until the filtrate is neutral, and drying the filtered product in an oven at 120 ℃ for 24 hours to obtain the pure SAPO-11 molecular sieve. The X-ray diffraction spectrum is shown in figure 1, and the acid characterization result is shown in figure 2; the X-ray diffraction peak positions are summarized in table 2.
Comparative example 2
100g of the pure SAPO-11 molecular sieve prepared in comparative example 1 was taken and mixed with 30g of gamma-Al2O3Mixing, adding 80g 5 wt% HNO3And (3) kneading the solution, extruding into strips, naturally drying, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 8 hours to obtain the molecular sieve carrier. 20mL of Ni (NO) containing 0.5g/mL of Ni3)2100g of the above-described support was impregnated with the solution to obtain a 10 wt% Ni/SAPO-11 catalyst, numbered A1. The results of the catalytic reaction evaluation are shown in Table 3.
Example 1
Weighing 70g of pseudo-boehmite, dissolving in 200g of deionized water, and stirring and mixing uniformly; weighing 130g of phosphoric acid, dissolving in 100g of deionized water, and uniformly mixing; dropwise adding a phosphoric acid solution to the pseudoboehmite solution which is kept in a stirring state to form a precursor mixture A; aging the A at 10 ℃ for 4 h; weighing 57g of diisopropylamine, dropwise adding the diisopropylamine into the solution A, and uniformly stirring; weighing about 45g of silica sol (30 wt%), dropwise adding into the A, and uniformly stirring to form a precursor mixture B; putting the B into a reaction kettle with the volume of 1L, starting heating up for crystallization, wherein the crystallization temperature is 200 ℃, and keeping for 24 hours; and after crystallization is finished, washing and filtering the product until the filtrate is neutral, and drying the filtered product in an oven at 120 ℃ for 24 hours to obtain the silicon-aluminum phosphate composite molecular sieve SC 1. The X-ray diffraction spectrum is shown in figure 3, and the acid characterization result is shown in figure 4; the X-ray diffraction peak positions are summarized in table 2.
Example 2
Weighing 70g of pseudo-boehmite, dissolving in 200g of deionized water, and stirring and mixing uniformly; weighing 130g of phosphoric acid, dissolving in 100g of deionized water, and uniformly mixing; dropwise adding a phosphoric acid solution to the pseudoboehmite solution which is kept in a stirring state to form a precursor mixture A; aging the A at 0 ℃ for 2 h; 57g of di-n-propylamine is weighed and dripped into the A, and the mixture is stirred uniformly; weighing about 45g of silica sol (30 wt%), dropwise adding into the A, and uniformly stirring to form a precursor mixture B; putting the B into a reaction kettle with the volume of 1L, starting heating up for crystallization, wherein the crystallization temperature is 200 ℃, and keeping for 24 hours; and after crystallization is finished, washing and filtering the product until the filtrate is neutral, and drying the filtered product in an oven at 120 ℃ for 20 hours to obtain the silicon-aluminum phosphate composite molecular sieve SC 1. The X-ray diffraction peak positions are summarized in table 2.
Example 3
Weighing 70g of pseudo-boehmite, dissolving in 200g of deionized water, and stirring and mixing uniformly; weighing 130g of phosphoric acid, dissolving in 100g of deionized water, and uniformly mixing; dropwise adding a phosphoric acid solution to the pseudoboehmite solution which is kept in a stirring state to form a precursor mixture A; aging the A at 0 ℃ for 8 h; 57g of di-n-propylamine is weighed and dripped into the A, and the mixture is stirred uniformly; weighing about 23g of silica sol (30 wt%), dropwise adding into the A, and uniformly stirring to form a precursor mixture B; putting the B into a reaction kettle with the volume of 1L, starting heating up for crystallization, wherein the crystallization temperature is 200 ℃, and keeping for 24 hours; and after crystallization is finished, washing and filtering the product until the filtrate is neutral, and drying the filtered product in an oven at 120 ℃ for 18h to obtain the silicon-aluminum phosphate composite molecular sieve SC 1. The X-ray diffraction peak positions are summarized in table 2.
example 4
Weighing 70g of pseudo-boehmite, dissolving in 200g of deionized water, and stirring and mixing uniformly; weighing 130g of phosphoric acid, dissolving in 100g of deionized water, and uniformly mixing; dropwise adding a phosphoric acid solution to the pseudoboehmite solution which is kept in a stirring state to form a precursor mixture A; aging the A at 0 ℃ for 6 h; weighing 57g of diisopropylamine, dropwise adding the diisopropylamine into the solution A, and uniformly stirring; weighing about 66g of silica sol (30 wt%), dropwise adding into the A, and uniformly stirring to form a precursor mixture B; putting the B into a reaction kettle with the volume of 1L, starting heating up for crystallization, wherein the crystallization temperature is 200 ℃, and keeping for 26 hours; and after crystallization is finished, washing and filtering the product until the filtrate is neutral, and drying the filtered product in an oven at 120 ℃ for 24 hours to obtain the silicon-aluminum phosphate composite molecular sieve SC 1. The X-ray diffraction peak positions are summarized in table 2.
Example 5
Weighing 70g of pseudo-boehmite, dissolving in 200g of deionized water, and stirring and mixing uniformly; weighing 130g of phosphoric acid, dissolving in 100g of deionized water, and uniformly mixing; dropwise adding a phosphoric acid solution to the pseudoboehmite solution which is kept in a stirring state to form a precursor mixture A; aging the A at 5 ℃ for 6 h; weighing 57g of diisopropylamine, dropwise adding the diisopropylamine into the solution A, and uniformly stirring; weighing about 66g of silica sol (30 wt%), dropwise adding into the A, and uniformly stirring to form a precursor mixture B; putting the B into a reaction kettle with the volume of 1L, starting heating up for crystallization, wherein the crystallization temperature is 200 ℃, and keeping for 26 hours; and after crystallization is finished, washing and filtering the product until the filtrate is neutral, and drying the filtered product in an oven at 120 ℃ for 24 hours to obtain the silicon-aluminum phosphate composite molecular sieve SC 1. The X-ray diffraction peak positions are summarized in table 2.
Example 6
Weighing 84g of pseudo-boehmite, dissolving in 200g of deionized water, and stirring and mixing uniformly; weighing 130g of phosphoric acid, dissolving in 100g of deionized water, and uniformly mixing; dropwise adding a phosphoric acid solution to the pseudoboehmite solution which is kept in a stirring state to form a precursor mixture A; aging the A at 0 ℃ for 6 h; weighing 69g of diisopropylamine, dropwise adding the diisopropylamine into the solution A, and uniformly stirring; weighing about 66g of silica sol (30 wt%), dropwise adding into the A, and uniformly stirring to form a precursor mixture B; putting the B into a reaction kettle with the volume of 1L, starting heating up for crystallization, wherein the crystallization temperature is 200 ℃, and keeping for 26 hours; and after crystallization is finished, washing and filtering the product until the filtrate is neutral, and drying the filtered product in an oven at 120 ℃ for 24 hours to obtain the silicon-aluminum phosphate composite molecular sieve SC 1. The X-ray diffraction peak positions are summarized in table 2.
Example 7
Weighing 84g of pseudo-boehmite, dissolving in 200g of deionized water, and stirring and mixing uniformly; weighing 130g of phosphoric acid, dissolving in 100g of deionized water, and uniformly mixing; dropwise adding a phosphoric acid solution to the pseudoboehmite solution which is kept in a stirring state to form a precursor mixture A; aging the A at 5 ℃ for 8 h; weighing 69g of di-n-propylamine, dropwise adding the di-n-propylamine into the solution A, and uniformly stirring; weighing about 44g of silica sol (30 wt%), dropwise adding into the A, and uniformly stirring to form a precursor mixture B; putting the B into a reaction kettle with the volume of 1L, starting heating up for crystallization, wherein the crystallization temperature is 200 ℃, and keeping for 24 hours; and after crystallization is finished, washing and filtering the product until the filtrate is neutral, and drying the filtered product in an oven at 120 ℃ for 24 hours to obtain the silicon-aluminum phosphate composite molecular sieve SC 1. The X-ray diffraction peak positions are summarized in table 2.
Example 8
Weighing 84g of pseudo-boehmite, dissolving in 200g of deionized water, and stirring and mixing uniformly; weighing 156g of phosphoric acid, dissolving in 100g of deionized water, and uniformly mixing; dropwise adding a phosphoric acid solution to the pseudoboehmite solution which is kept in a stirring state to form a precursor mixture A; aging the A at 0 ℃ for 7 h; weighing 69g of di-n-propylamine, dropwise adding the di-n-propylamine into the solution A, and uniformly stirring; weighing about 66g of silica sol (30 wt%), dropwise adding into the A, and uniformly stirring to form a precursor mixture B; putting the B into a reaction kettle with the volume of 1L, starting heating up for crystallization, wherein the crystallization temperature is 210 ℃, and keeping for 24 hours; and after crystallization is finished, washing and filtering the product until the filtrate is neutral, and drying the filtered product in an oven at 120 ℃ for 24 hours to obtain the silicon-aluminum phosphate composite molecular sieve SC 1. The X-ray diffraction peak positions are summarized in table 2.
Table 2 examples the X-ray diffraction peak positions and intensities of silicoaluminophosphate composite molecular sieves
Diffraction peak intensity, w-m: < 20; m is 20-70; s is 70-90; vs 90-100
Example 9
100g of the silicoaluminophosphate composite molecular sieve prepared in example 1 was taken and mixed with 30g of gamma-Al2O3Mixing, adding 80g 5 wt% HNO3And (3) kneading the solution, extruding into strips, naturally drying, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 8 hours to obtain the molecular sieve carrier. 10mL of Ni (NO) containing 0.5g/mL of Ni3)2100g of the above support was impregnated in solution to produce 5 wt% Ni/SC1 catalyst, numbered B1. The results of the catalytic reaction evaluation are shown in Table 3.
Example 10
100g of the silicoaluminophosphate composite molecular sieve SC1 prepared in example 2 was mixed with 30g of gamma-Al2O3mixing, adding 80g 5 wt% HNO3And (3) kneading the solution, extruding into strips, naturally drying, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 8 hours to obtain the molecular sieve carrier. 20mL of Ni (NO) containing 0.5g/mL of Ni3)2100g of the above support was impregnated in solution to produce 10 wt% Ni/SC1 catalyst, numbered B2. The results of the catalytic reaction evaluation are shown in Table 3.
Example 11
100g of the silicoaluminophosphate composite molecular sieve SC1 prepared in example 3 was mixed with 30g of gamma-Al2O3mixing, adding 80g 5 wt% HNO3solution, kneading, extruding, air drying, drying at 120 deg.C for 4 hr, and calcining at 550 deg.C for 8 hr to obtain the final productand (4) screening the carrier. 10mL of Ni (NO) containing 0.5g/mL of Ni3)2And 10mL of W0.3 g/mL (NH)4)6H2W12O40100g of the above support was impregnated in solution to make 5 wt% Ni-3 wt% W/SC1 catalyst, numbered B3. The results of the catalytic reaction evaluation are shown in Table 3.
Example 12
100g of the silicoaluminophosphate composite molecular sieve SC1 prepared in example 4 was mixed with 30g of gamma-Al2O3Mixing, adding 80g 5 wt% HNO3and (3) kneading the solution, extruding into strips, naturally drying, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 8 hours to obtain the molecular sieve carrier. 30mL of Ni (NO) containing 0.5g/mL of Ni3)2And 30mL of Mo-containing 0.1g/mL (NH)4)6Mo7O24100g of the above support was impregnated in solution to produce 15 wt% Ni-3 wt% Mo/SC1 catalyst, numbered B4. The results of the catalytic reaction evaluation are shown in Table 3.
example 13
100g of the silicoaluminophosphate composite molecular sieve SC1 prepared in example 5 was mixed with 30g of gamma-Al2O3Mixing, adding 80g 5 wt% HNO3And (3) kneading the solution, extruding into strips, naturally drying, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 8 hours to obtain the molecular sieve carrier. With 20mL of Co (NO) containing 0.5g/mL of Co3)2And 10mL of W0.3 g/mL (NH)4)6H2W12O40100g of the above carrier was impregnated with the solution to obtain 10 wt% Co-3 wt% W/SC1 catalyst, numbered B5. The results of the catalytic reaction evaluation are shown in Table 3.
TABLE 3 evaluation results of different catalysts
| Catalyst and process for preparing same | reaction temperature (. degree.C.)) | Conversion (%) | Isomerization selectivity (%) | isomerization yield (%) |
| A1 | 340 | 68.0 | 92.7 | 63.0 |
| B1 | 330 | 90.3 | 80.1 | 72.3 |
| B2 | 325 | 89.4 | 81.8 | 73.1 |
| B3 | 320 | 89.6 | 80.2 | 71.9 |
| B4 | 330 | 91.8 | 78.0 | 71.6 |
| B5 | 325 | 89.9 | 80.4 | 72.3 |
Example 14
Evaluation of catalytic reaction:
Raw materials: n-dodecane; reaction conditions are as follows: 10mL of fixed bed reactor, the reaction temperature is 300-370 ℃, the reaction pressure is 8MPa, and the space velocity is 1h-1The hydrogen-oil ratio was 200 nL/nL. The catalysts prepared in examples 9 to 13 were used in amounts of 8g, respectively, and the evaluation results of each catalyst are shown in Table 3.
Claims (11)
1. A catalyst for isomerization of paraffins, characterized in that: consists of a silicoaluminophosphate composite molecular sieve and non-noble metal;
wherein the mass content of the non ~ noble metal is 1 ~ 20 wt%;
wherein the silicoaluminophosphate composite molecular sieve has 0.3 ~ 0.7nm micropores and a BET specific surface area of 100 ~ 300m2a pore volume of 0.1 ~ 0.5mL/g, and an X-ray diffraction spectrum having at least the following diffraction peaks,
The value of 2 ϴ represents diffraction peak position, 2 ϴ/°: 8.14 +/-0.2, 9.48 +/-0.2, 12.49 +/-0.1, 13.24 +/-0.2, 15.70 +/-0.2, 16.32 +/-0.2, 17.56 +/-0.2, 17.87 +/-0.1, 19.02 +/-0.2, 20.46 +/-0.2, 21.10 +/-0.2, 21.66 +/-0.1, 22.18 +/-0.2, 22.60 +/-0.2, 22.76 +/-0.2, 23.22 +/-0.2, 24.74 +/-0.2, 27.86 +/-0.1, 28.49 +/-0.1, 33.03 +/-0.1 and 33.41 +/-0.1.
2. The catalyst of claim 1, wherein: the non-noble metal is one or more of Co, Ni, Mo or W.
3. the catalyst according ~ claim 1 or 2, wherein the non-noble metal is present in an amount of 2 ~ 20 wt%.
4. A method of preparing the catalyst of claim 1, wherein: the method comprises the following steps:
a) mixing an aluminum source, a phosphorus source and water, and uniformly stirring to prepare a precursor mixture A, wherein the precursor mixture A is kept stand and aged for 2 ~ 12h at the temperature of 0 ~ 30 ℃;
b) adding organic amine into the precursor mixture A after standing and aging, adding a silicon source after stirring to be uniform, and continuously stirring to be uniform to form a precursor mixture B, wherein in the precursor mixture B, the ratio of aluminum source: a phosphorus source: silicon source: organic amine with Al2O3: P2O5: SiO2the organic amine is calculated, the molar ratio is 1:0.1 ~ 5:0.01 ~ 5:0.1 ~ 5;
c) heating the prepared precursor mixture B to 120 ~ 250 ℃ for crystallization, wherein the crystallization time is 8 ~ 48 h;
d) After crystallization is finished, cooling the reactant to room temperature, filtering, washing and drying to obtain a solid, namely the silicoaluminophosphate composite molecular sieve;
e) one or more than two methods of dipping, precipitation, adhesive bonding by adding a binder or mechanical pressing are adopted to realize the combination of non ~ noble metal and the silicoaluminophosphate composite molecular sieve, and the mixture is roasted at 400 ~ 600 ℃;
f) before use, the roasted catalyst is subjected to reduction treatment;
the phosphorus source is one or more than two of phosphoric acid or ammonium phosphate, ammonium monohydrogen phosphate or ammonium dihydrogen phosphate in phosphate;
The aluminum source is one or two of pseudo-boehmite or hydrated alumina;
The organic amine is one or more than two of aliphatic amine, aromatic amine, alcohol amine and quaternary ammonium salt compounds;
the non-noble metal is one or more of Co, Ni, Mo or W;
The silicon source is amorphous silicon dioxide.
5. the method according to claim 4, wherein the precursor mixture A in step a) is left to stand and age at 0 ~ 25 ℃ for 2 ~ 8 h.
6. The method of claim 4, wherein: al in the precursor mixture B in step B)2O3: P2O5: SiO2the organic amine is present in a molar ratio of 1:0.5 ~ 2:0.1 ~ 1:0.5 ~ 2.
7. the preparation method according to claim 4, wherein the crystallization temperature in step c) is 160 ~ 220 ℃, and the crystallization time is 12 ~ 36 h.
8. The method of claim 4, wherein: the organic amine is aliphatic amine.
9. The method of claim 4, wherein: combining the non-noble metal and the silicoaluminophosphate composite molecular sieve in the step e), and adopting non-noble metal acid, metallate, chloride, nitric acid compound, ammonia complex, carbonyl complex or mixture thereof as raw materials.
10. the method according to claim 4, wherein in the step f), the reduction treatment is carried out in a reducing atmosphere of hydrogen or a mixed gas of hydrogen and an inert gas at a reducing temperature of 100 ~ 600 ℃.
11. The method of claim 4, wherein: the silicon source is one or more than two of gas-phase white carbon black, silica sol, water glass and solid silica gel.
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