CN110605125B - Light alkane isomerization catalyst and preparation method thereof - Google Patents
Light alkane isomerization catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 37
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000002244 precipitate Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000012188 paraffin wax Substances 0.000 claims description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical group Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 17
- 229910052742 iron Inorganic materials 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 10
- 229910052733 gallium Inorganic materials 0.000 description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229940044658 gallium nitrate Drugs 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- B01J35/615—
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- B01J35/633—
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- B01J35/635—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/274—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C5/2743—Acids of sulfur; Salts thereof; Sulfur oxides
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
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Abstract
The invention relates to the field of solid super acidic catalysts, and discloses a light alkane isomerization catalyst and a preparation method thereof, wherein the method comprises the steps of (1) dissolving soluble salt containing Fe, soluble salt containing Ga and soluble salt containing Zr in solution containing a surfactant to obtain mixed solution; (2) under the condition of stirring, dropwise adding an ammonia water solution into the mixed solution to obtain a suspension containing precipitates; (3) carrying out hydrothermal reaction on the suspension containing the precipitate, and washing, filtering and drying after the hydrothermal reaction is finished to obtain a Fe-Ga doped zirconium hydroxide precursor; (4) soaking a Fe-Ga doped zirconium hydroxide precursor into a sulfuric acid solution, drying and roasting; (5) and (4) soaking the roasted product obtained in the step (4) by using a solution containing soluble Pt salt, drying and roasting to obtain the light alkane isomerization catalyst. The invention increases the specific surface area and pore volume of the zirconium hydroxide precursor and improves the isomerization performance of light alkane of the catalyst.
Description
Technical Field
The invention relates to the field of solid super acidic catalysts, in particular to a light alkane isomerization catalyst and a preparation method thereof.
Background
With the gradual application of the VI high-standard gasoline in the V nation nationwide, the provision of high-octane isomerized oil without olefin and aromatic hydrocarbon in the isomerization production of light paraffin must be rapidly developed. The light alkane in the Fischer-Tropsch naphtha is isomerized and converted into an isomerized gasoline component with high added value, so that the benefit of the naphtha part is greatly improved, the added value of the Fischer-Tropsch product is improved, the market competitiveness of the Fischer-Tropsch product is enhanced, and the market environment of the Fischer-Tropsch product is also met.
The isomerization of light paraffin is generally carried out under the hydrogen condition, and is a process for generating corresponding isoparaffin from normal paraffin, and the reaction belongs to a mild reversible exothermic reaction. Thus, low temperatures favor the formation of isomeric products. The metal oxide type solid super acidic catalytic material has the advantages of stronger acidity, higher thermal stability, easy separation from reaction products, environmental friendliness, no corrosion to equipment, regeneration and the like, and particularly can catalyze the alkane isomerization reaction at low temperature, so the metal oxide type solid super acidic catalytic material is considered as the most promising isomerization catalyst and has wide application prospect. For example, Pt-SO 4 2- /ZrO 2 The catalyst is a low-temperature isomerization catalyst with high activity and selectivity, and can produce the isomerized oil with higher octane number level. The preparation parameters of the zirconium hydroxide precursor of the catalyst can influence ZrO 2 Thereby affecting the reactivity of the catalyst.
At present, the method commonly used for preparing sulfated zirconia catalysts is a zirconium salt hydrolysis precipitation method, and the preparation process is approximately Zr salt precipitation, Zr (OH) 4 Drying, sulfate radical impregnation, drying roasting, Pt impregnation and drying roasting. For example, in the literature reports of Monoclinic and Tetragonal High Surface Area Surface treated zirconia in titanium isometrization: CO addition and Catalysis solutions, and Journal of Catalysis 2001,198: 277) 285, Sulfated ZrO with High specific Surface Area is prepared by hydrothermal method at 150 ℃ for 2-20 hours respectively 2 Meanwhile, the product has higher butane isomerization performance. However, ZrO produced by the method 2 The activity is poor in C5 and C6 isomerization reactions due to the fact that the monoclinic phase is taken as the main phase.
CN1395995A discloses a super acidic material with high specific surface area mesopores and a preparation method thereof. The super acidic material is composed of a sulfidized metal oxide (e.g., ZrO 2 /SO 4 2- ) With P123 orP84 or P65 or polyethylene glycol as surfactant, and water and soluble salt of metal oxide are mixed in certain proportion, and the mixture is aged, sulfurized and calcined to prepare super acid material with specific surface area of 150-200m 2 Between/g, it is also more difficult to promote the adsorption and desorption of the alkane in the catalyst and to obtain a super acidic material which is only monoclinic phase.
SO 4 2- /ZrO 2 The surface doping assistant of (2) is one of the means for improving the isomerization performance of the catalyst. For example, CN106140198A discloses a Fe and W doped SO 4 2- /ZrO 2 The invention relates to a type catalyst, which is prepared by dropwise adding an ammonia water solution into a mixed solution of Zr and Fe for coprecipitation, filtering and washing the precipitate, putting the precipitate into a drying oven for drying to obtain a zirconium hydroxide precursor doped with Fe, and then impregnating sulfuric acid and Pt, drying, roasting and reducing with a mixed gas to obtain the corresponding catalyst. The preparation process is complex, the prepared tetragonal phase doped monoclinic phase catalyst has low and unstable isomerization reaction activity, the conversion rate of isomeric alkane is not high, the conversion rate of n-pentane is only 57.2 percent at most, the production cost is high, a certain amount of carbon species still remain on the surface after the catalyst is roasted in the atmosphere of hydrogen and nitrogen mixed gas, and the activity of the catalyst is also influenced to a certain degree.
Disclosure of Invention
The invention aims to solve the problems of small specific surface area of a light paraffin isomerization catalyst, low n-hexane conversion rate, low selectivity of a target reaction product 2,2-DMB and the like in the prior art, and provides a preparation method of the light paraffin isomerization catalyst.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a light paraffin isomerization catalyst, comprising the steps of:
(1) dissolving soluble salt containing Fe, soluble salt containing Ga and soluble salt containing Zr in solution containing a surfactant to obtain mixed solution;
(2) under the condition of stirring, dropwise adding an ammonia water solution into the mixed solution to obtain a suspension containing a precipitate;
(3) carrying out hydrothermal reaction on the suspension containing the precipitate, and washing, filtering and drying after the hydrothermal reaction is finished to obtain a Fe-Ga doped zirconium hydroxide precursor;
(4) soaking a Fe-Ga doped zirconium hydroxide precursor into a sulfuric acid solution, drying and roasting;
(5) and (4) soaking the roasted product obtained in the step (4) by using a solution containing soluble Pt salt, drying and roasting to obtain the light alkane isomerization catalyst.
In a second aspect, the invention provides a light paraffin isomerization catalyst prepared by the method, wherein the catalyst is Fe and Ga-doped tetragonal SO loaded with Pt 4 2- /ZrO 2 A catalyst.
The method of the invention utilizes a surfactant, a coprecipitation method and a hydrothermal treatment method to synthesize the solid super acidic catalyst with tetragonal phase crystals, promotes the adsorption and desorption of alkane in the catalyst by increasing the specific surface area and pore volume of a zirconium hydroxide precursor, and simultaneously leads the auxiliary agents Fe and Ga to be uniformly doped in the tetragonal phase SO 4 2- /ZrO 2 In the catalyst. The light paraffin isomerization catalyst can be used for the hydroisomerization reaction of normal paraffin, such as the isomerization reaction of normal hexane, and can improve the conversion rate of the normal hexane and the selectivity of a target reaction product 2, 2-DMB.
Drawings
Fig. 1 is an XRD spectrum of the light paraffin isomerization catalyst prepared in examples 1 and 2.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a preparation method of a light paraffin isomerization catalyst, which comprises the following steps:
(1) dissolving soluble salt containing Fe, soluble salt containing Ga and soluble salt containing Zr in solution containing a surfactant to obtain mixed solution;
(2) under the condition of stirring, dropwise adding an ammonia water solution into the mixed solution to obtain a suspension containing a precipitate;
(3) carrying out hydrothermal reaction on the suspension containing the precipitate, and washing, filtering and drying after the hydrothermal reaction is finished to obtain a Fe-Ga doped zirconium hydroxide precursor;
(4) soaking a Fe-Ga doped zirconium hydroxide precursor into a sulfuric acid solution, drying and roasting;
(5) and (4) soaking the roasted product obtained in the step (4) by using a solution containing soluble Pt salt, drying and roasting to obtain the light alkane isomerization catalyst.
The invention simultaneously utilizes the surfactant and the hydrothermal treatment method to increase the specific surface area and the pore volume of the zirconium hydroxide precursor and obtain the Fe and Ga doped SO with high specific surface area 4 2- /ZrO 2 The catalyst is formed, and simultaneously, the auxiliary agents Fe and Ga can be uniformly doped in tetragonal-phase ZrO 2 In the base catalyst, the isomerization performance is very good, and especially the conversion rate of C6 and the selectivity of a target product are very high.
According to the invention, in order to improve the isomerization reaction activity and facilitate the doping of the auxiliary agents Fe and Ga, in the step (1), the mass ratio of the soluble salt containing Fe, the soluble salt containing Ga and the soluble salt containing Zr is 1: 2.5-3.5: 70-90.
According to the invention, the soluble salt containing Zr is zirconium oxychloride, the soluble salt containing iron can be ferric nitrate, and the soluble salt containing Ga can be gallium nitrate.
According to the invention, in order to avoid agglomeration and collapse of the zirconium hydroxide precursor and further increase the specific surface area and pore volume of the zirconium hydroxide precursor, in the step (1), the content of the surfactant in the solution containing the surfactant is 0.1-0.5 wt%, and the solvent is water and ethanol. Preferably, the volume ratio of the water to the ethanol is 1: 0.5-2.
According to the invention, the surfactant is preferably polyethylene glycol, which is not particularly limited in the invention and can be selected according to the prior art, for example, PEG400 and PEG600, the addition of polyethylene glycol facilitates the subsequent roasting and the slow release of Fe in the formation process of zirconium hydroxide precursor 3+ And Ga 3+ And the uniform doping of Fe and Ga is promoted.
According to the present invention, in order to avoid agglomeration of the suspension containing precipitates, in step (2), the stirring speed is preferably 650-950r/min, and the dropping time is preferably 30-50 min.
According to the invention, in order to improve the dispersibility and doping amount of Fe and Ga, in the step (2), the concentration of the ammonia water solution is preferably 1-7mol/L, and the pH of the suspension containing the precipitate is 9.8-10.5.
According to the invention, in order to better build a tetragonal phase structure and make the structure more stable, in the step (3), the hydrothermal reaction condition is that the hydrothermal temperature is 60-150 ℃ and the hydrothermal reaction lasts for 5-36 h.
According to a preferred embodiment, the specific surface area of the Fe-Ga doped zirconium hydroxide precursor obtained in step (3) is 300-500m 2 Per g, pore volume of 0.4-0.6cm 3 /g。
According to the present invention, in order to prevent the active metal element from being sintered, in step (4), the concentration of the sulfuric acid solution is preferably 0.1 to 1.0mol/L, and the amount of the sulfuric acid solution used is 5 to 30mL per 1g of the Fe — Ga doped zirconium hydroxide precursor. In the step, the roasting temperature is preferably 600-800 ℃, and the roasting time is preferably 2-12 h.
According to the present invention, in the step (5), the impregnation is preferably performed such that the Pt loading amount is 0.01 to 0.10 wt%, which is advantageous for improving the carbon deposition phenomenon. In the step, the roasting temperature is preferably 400-700 ℃, the roasting time is 3-10h, the specific surface area and the pore volume of the light paraffin isomerization catalyst can be increased, the contents of Fe and Ga on the surface are increased, the surface acid content is reduced, the surface carbon content of the catalyst is reduced, and the isomerization reaction activity of the light paraffin isomerization catalyst is improved.
According to the present invention, the conditions of the drying in the above steps may include: the temperature is 100-130 ℃, and the time is 12-24 h. And the specific drying conditions for each step may be the same or different.
The invention also provides a light paraffin isomerization catalyst prepared by the method. The catalyst prepared by the method is Pt-loaded Fe and Ga-doped tetragonal SO 4 2- /ZrO 2 A catalyst.
The method utilizes a surfactant, a coprecipitation method and a hydrothermal treatment method to synthesize the solid super acidic catalyst with tetragonal phase crystals, promotes the adsorption and desorption of alkane in the catalyst by increasing the specific surface area and pore volume of a precursor of the catalyst, and simultaneously leads an auxiliary agent Fe and Ga to be uniformly doped in tetragonal SO 4 2- /ZrO 2 In the catalyst.
The present invention will be described in detail below by way of examples. In the following examples, the test methods and raw materials are referred to as follows:
specific surface area and pore volume of the catalyst by N 2 Measured by an adsorption-desorption method;
in the case where no particular mention is made, commercially available products are used as the starting materials.
Example 1
Uniformly stirring 100mL of water, 100mL of ethanol and 0.556g of polyethylene glycol (PEG400) to obtain a solution containing a surfactant; dissolving 50g of zirconium oxychloride, 0.7g of ferric nitrate and 2.0g of gallium nitrate in the solution containing the surfactant to obtain a mixed solution; under the stirring condition with the rotating speed of 800r/min, ammonia water with the concentration of 6moL/L is dripped into the mixed solution for 40 minutes to hydrolyze the mixed solution to generate precipitate, and suspension containing the precipitate is obtained; putting the suspension containing the precipitate into a hydrothermal kettle, performing hydrothermal treatment at 110 ℃ for 22h, taking out the suspension from the hydrothermal kettle, filtering, washing the precipitate with ethanol, and drying at 110 ℃ for 24h to obtain a Fe-Ga-doped zirconium hydroxide precursor, wherein the pore structure parameters of the zirconium hydroxide precursor are shown in Table 1; soaking Fe-Ga doped zirconium hydroxide precursorSoaking in 0.5mol/L sulfuric acid (15 mL of sulfuric acid solution relative to 1g of Fe-Ga-doped zirconium hydroxide precursor), drying at 110 deg.C for 24h, and calcining at 700 deg.C for 3 h; finally using H 2 PtCl 6 Is impregnated with the calcined product, then dried at 110 ℃ for 24 hours and calcined at 500 ℃ for 3 hours to prepare Fe and Ga doped tetragonal phase SO loaded with 0.5 wt% of Pt 4 2- /ZrO 2 The XRD spectrum of the catalyst is shown in figure 1. As can be seen from FIG. 1, the tetragonal phase SO 4 2- /ZrO 2 Standard tetragonal phase ZrO appears in XRD spectrogram of catalyst 2 Characteristic peak of (2).
Example 2
Taking 125mL of water, 125mL of ethanol and 0.556g of polyethylene glycol (PEG400), and uniformly stirring to obtain a solution containing a surfactant; dissolving 60g of zirconium oxychloride, 0.7g of ferric nitrate and 2g of gallium nitrate in the solution containing the surfactant to obtain a mixed solution; under the stirring condition with the rotating speed of 950r/min, 6moL/L ammonia water is dripped into the mixed solution for 30 minutes to be hydrolyzed to generate precipitate, and suspension containing the precipitate is obtained; putting the suspension containing the precipitate into a hydrothermal kettle, performing hydrothermal treatment at 110 ℃ for 22h, taking out the suspension from the hydrothermal kettle, filtering, washing the precipitate with ethanol, and drying at 110 ℃ for 24h to obtain a Fe-Ga-doped zirconium hydroxide precursor, wherein the pore structure parameters of the zirconium hydroxide precursor are shown in Table 1; soaking a Fe-Ga doped zirconium hydroxide precursor in 0.3mol/L sulfuric acid (the amount of a sulfuric acid solution is 15mL relative to 1g of the zirconium hydroxide precursor) for 1 hour by stirring, drying at 110 ℃ for 24 hours, and roasting at 700 ℃ for 3 hours; finally using H 2 PtCl 6 Is impregnated with the aqueous solution of (a), then dried at 110 ℃ for 24 hours and calcined at 500 ℃ for 3 hours to obtain Fe-and Ga-doped tetragonal phase SO loaded with 0.5 wt% Pt 4 2- /ZrO 2 The XRD spectrum of the catalyst is shown in figure 1. As can be seen from FIG. 1, the tetragonal phase SO 4 2- /ZrO 2 Standard tetragonal phase ZrO appears in XRD spectrogram of catalyst 2 Characteristic peak of (2).
Example 3
Taking 125mL of water, 125mL of ethanol and 0.556g of polyethylene glycol (PEG600), and uniformly stirring to obtainA solution containing a surfactant; dissolving 60g of zirconium oxychloride, 0.7g of ferric nitrate and 2g of gallium nitrate in the solution containing the surfactant to obtain a mixed solution; under the stirring condition with the rotating speed of 800r/min, 6moL/L ammonia water is dripped into the mixed solution for 40 minutes to hydrolyze the mixed solution to generate precipitate, and suspension containing the precipitate is obtained; putting the suspension containing the precipitate into a hydrothermal kettle, performing hydrothermal treatment at 130 ℃ for 22h, taking out the suspension from the hydrothermal kettle, filtering, washing the precipitate with ethanol, and drying at 110 ℃ for 24h to obtain a Fe-Ga-doped zirconium hydroxide precursor, wherein the pore structure parameters of the zirconium hydroxide precursor are shown in Table 1; soaking the Fe-Ga doped zirconium hydroxide precursor into 0.8mol/L sulfuric acid (the dosage of sulfuric acid solution is 15mL relative to 1g of Fe-Ga doped zirconium hydroxide precursor) while stirring for 1 hour, drying for 24 hours at 110 ℃, and roasting for 3 hours at 700 ℃; finally using H 2 PtCl 6 Is impregnated with the aqueous solution of (a), then dried at 110 ℃ for 24 hours and calcined at 500 ℃ for 3 hours to obtain Fe-and Ga-doped tetragonal phase SO loaded with 0.5 wt% Pt 4 2- /ZrO 2 A catalyst. Standard tetragonal phase ZrO also appears in the XRD spectrum 2 Characteristic peak of (2).
Comparative example 1
A light paraffin isomerization catalyst was prepared as in example 1 except that gallium nitrate was replaced with manganese nitrate to produce a catalyst having the pore structure parameters of the zirconium hydroxide precursor shown in table 1.
Comparative example 2
A light paraffin isomerization catalyst was prepared according to the procedure of example 1 except that polyethylene glycol (PEG400), a surfactant, was not added to prepare a catalyst whose pore structure parameters of the zirconium hydroxide precursor are shown in table 1.
Comparative example 3
A light paraffin isomerization catalyst was prepared by following the procedure of example 1 except that the suspension containing the precipitate was not subjected to hydrothermal reaction to prepare a catalyst whose pore structure parameters of the zirconium hydroxide precursor are shown in table 1.
Test example
The performance evaluation of the catalysts obtained in examples 1 to 3 and comparative examples 1 to 3 was carried out continuouslyThe method is carried out on a micro-reaction-chromatographic device, n-hexane is taken as a reaction raw material, and the reaction conditions are as follows: the pressure is 2MPa, the temperature is 160 ℃, the hydrogen-hydrocarbon molar ratio is 5, and the volume space velocity is 4.0h -1 The catalysts prepared in examples 1 to 3 and comparative examples 1 to 3 were evaluated, and the results of the conversion of C6 and the selectivity of 2,2-DMB are shown in Table 1.
TABLE 1
As can be seen from the results of table 1, the preparation methods of examples 1 to 3 effectively improved the specific surface area and pore volume of the catalyst, and at the same time, the prepared catalyst enabled the conversion (8h) of C6 to reach 93% or more and the selectivity of the target product 2,2-DMB to reach 38% or more, compared to comparative examples 1 to 3.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A preparation method of a light paraffin isomerization catalyst is characterized by comprising the following steps:
(1) dissolving soluble salt containing Fe, soluble salt containing Ga and soluble salt containing Zr in solution containing a surfactant to obtain mixed solution;
(2) under the condition of stirring, dropwise adding an ammonia water solution into the mixed solution to obtain a suspension containing a precipitate;
(3) carrying out hydrothermal reaction on the suspension containing the precipitate, and washing, filtering and drying after the hydrothermal reaction is finished to obtain a Fe-Ga doped zirconium hydroxide precursor;
(4) soaking a Fe-Ga doped zirconium hydroxide precursor into a sulfuric acid solution, drying and roasting;
(5) dipping the roasted product obtained in the step (4) in a solution containing soluble Pt salt, drying and roasting to prepare a light alkane isomerization catalyst;
wherein the surfactant is polyethylene glycol.
2. The production method according to claim 1, wherein in the step (1), the mass ratio of the Fe-containing soluble salt, the Ga-containing soluble salt and the Zr-containing soluble salt is 1: 2.5-3.5: 70-90; and/or the soluble salt containing Zr is zirconium oxychloride.
3. The method according to claim 1, wherein in the step (1), the surfactant-containing solution contains 0.1 to 0.5% by weight of a surfactant, and the solvent is water or ethanol; and/or the volume ratio of the water to the ethanol is 1: 0.5-2.
4. The preparation method as claimed in claim 1, wherein in the step (2), the stirring speed is 650-950r/min, and the dropping time is 30-50 min.
5. The production method according to claim 1, wherein in the step (2), the concentration of the aqueous ammonia solution is 1 to 7mol/L, and the pH of the suspension containing the precipitate is controlled to 9.8 to 10.5.
6. The method according to claim 1, wherein in the step (3), the hydrothermal reaction conditions include: the temperature is 60-150 ℃ and the time is 5-36 h.
7. The preparation method as claimed in any one of claims 1 to 6, wherein, in the step (3), the specific surface area of the Fe-Ga doped zirconium hydroxide precursor is 300-500m 2 Per g, pore volume of 0.4-0.6cm 3 /g。
8. The production method according to claim 1, wherein in the step (4), the concentration of the sulfuric acid solution is 0.1 to 1.0 mol/L; the dosage of the sulfuric acid solution is 5-30mL relative to 1g of the Fe-Ga doped zirconium hydroxide precursor;
and/or the roasting temperature is 600-800 ℃, and the roasting time is 2-12 h.
9. The production method according to claim 1, wherein in the step (5), the impregnation is performed so that the loading amount of Pt is 0.01 to 0.10 wt%;
and/or the roasting temperature is 400-700 ℃, and the roasting time is 3-10 h.
10. A light paraffin isomerization catalyst produced by the production method described in any one of claims 1 to 9.
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