CN111686793B - Composite catalyst and preparation and application thereof - Google Patents

Composite catalyst and preparation and application thereof Download PDF

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CN111686793B
CN111686793B CN202010468142.6A CN202010468142A CN111686793B CN 111686793 B CN111686793 B CN 111686793B CN 202010468142 A CN202010468142 A CN 202010468142A CN 111686793 B CN111686793 B CN 111686793B
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catalyst
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composite catalyst
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CN111686793A (en
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马保军
李欣
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Ningxia University
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Abstract

The invention discloses a composite catalyst and preparation and application thereof. The catalyst takes H-ZSM-5 as a carrier and takes ZrO 2 As active substance, into the catalystCarrying out sulfuric acid acidification treatment, introducing Ni for catalyst modification, and preparing Ni/ZrO 2 /H‑ZSM‑5/SO 4 2‑ The composite catalyst is used for alkylation of isobutane and isobutene to synthesize high-octane gasoline. Ni/ZrO of the invention 2 /H‑ZSM‑5/SO 4 2‑ The catalyst has good catalytic activity for synthesizing gasoline with high octane value by alkylation. The preparation and modification method of the catalyst is simple, the raw materials are cheap and easy to obtain, the catalyst is good in stability, and the catalyst has a good application prospect.

Description

Composite catalyst and preparation and application thereof
Technical Field
The invention relates to a Ni/ZrO 2 /H-ZSM-5/SO 4 2- The preparation of the composite catalyst and the application thereof in the reaction of synthesizing high-octane gasoline by alkylating isobutane and isobutene.
Background
The alkylate being a C 8 The mixture of isoparaffin has the advantages of high octane number, low volatility, no oxygen, no aromatic hydrocarbon and olefin, almost no sulfur and the like, is an ideal high-octane number gasoline additive, and the main sources are strong acid catalyzed isobutane and low molecular olefin (C) 3 ～C 5 Olefins, primarily butenes). The worldwide production capacity of alkylated gasoline was 67.8Mt/a, with 29.3Mt/a and 38.5Mt/a for the concentrated sulfuric acid and hydrofluoric acid processes, respectively. However, hydrofluoric acid is highly toxic and readily forms an aerosol. Therefore, its industrial application is gradually limited. For a sulfate-based process, the acid consumption can reach 70-100kg/t. The spent catalyst must be regenerated in an expensive process to remove water and tar hydrocarbons. Therefore, considerable efforts have been made to replace hydrofluoric acid or sulfuric acid with solid acids, which are easier to handle and more environmentally friendly. However, due to the environmentally hazardous nature of sulfuric acid and hydrofluoric acid, the search for new solid acid catalysts is imperative. The molecular sieve HZSM-5 has a small-pore-diameter three-dimensional pore structure having a pore size of 5.5 to 5.6A based on an atomic radius, so that a large coke precursor is difficult to form in pores, and also has appropriate acidity, thereby having wide applications. Zr-based catalysts are widely used in hydrogenation reactions due to hexagonal phase ZrO 2 Exhibit moderate acidity. The modulation of the acidity of the catalyst in the alkylation reaction of the subject has a prominent effect on the conversion rate of the alkylation reaction of the alkyl and the pore structure of the catalyst plays a decisive role in the reaction selectivity.
We are based on the acidity and pore structure of HZSM-5 molecular sieve, composited with Zr-based oxides. Adjusting the acid sites and acid strength of the catalyst and the pore structure of the composite catalyst. The supported metal improves the surface structure of the catalyst and adjusts the bonding strength of each component of the catalyst. Thereby the high-efficiency and high-selectivity catalytic alkylation reaction is realized. We design a composite catalyst with HZSM-5 as carrier and Zr-based oxide as active material, and introduce metal Ni to adjust the catalyst structure, thereby improving the alkylation performance.
Disclosure of Invention
The invention aims to provide Ni/ZrO 2 /H-ZSM-5/SO 4 2- The composite catalyst and the preparation method thereof have the advantages of simple and easy operation, and cheap and easily obtained raw materials. The prepared catalyst has good alkylation reaction performance.
The technical scheme of the invention is as follows:
ZrO used in alkylation synthesis of high-octane gasoline from isobutane and isobutene 2 the/H-ZSM-5 is sulfated, and the surface of the catalyst is loaded with Ni. Wherein ZrO 2 And the mass ratio of the H-ZSM-5 is 1-2, the load of the Ni auxiliary agent is 1.0-12.0 percent.
Preferably, zrO 2 And H-ZSM-5 at a mass ratio of 1; zrO is further preferable 2 And H-ZSM-5 in a mass ratio of 1, wherein the loading amount of the Ni auxiliary agent is 5.0 percent.
ZrO produced according to the invention 2 /H-ZSM-5/SO 4 2- Compared with a smooth H-ZSM-5 nano cubic block, the nano cubic block has larger aperture and rough surface, is beneficial to the loading and combination of metal Ni ions on one hand, and is beneficial to the adsorption of isobutene on the surface of an active site of a catalyst and the activation of a C-C bond in the reaction process on the other hand, and the conversion rate of reaction raw materials is improved. In addition, the catalyst has large aperture and is suitable for alkylation reaction to selectively generate C 8 And (4) obtaining a target product.
Further, the ZrO 2 /H-ZSM-5/SO 4 2- The composite catalyst adopts a coprecipitation method to uniformly load ZrO on H-ZSM-5 2 The concrete pretreatment steps are as follows: dispersing H-ZSM-5 in solvent, ultrasonic treating for 1 hr, washing with deionized water, and placing in 110 deg.C ovenDrying for 6 hours, taking out and grinding for standby.
Further, the ZrO 2 /H-ZSM-5/SO 4 2- The composite catalyst is subjected to sulfation treatment, the surface structure is changed, the roughness of the catalyst is increased, and the acidity is increased. The sulfating comprises the following specific steps: zrO2 is mixed with 2 the/H-ZSM-5 was dosed at 10mL (0.15 mol/L H) 2 SO 4 )/g cat Soaking for 1h, filtering, washing with deionized water, drying, and calcining in a muffle furnace at 550 ℃ for 4h.
Further, the Ni/ZrO 2 /H-ZSM-5/SO 4 2- Uniformly loading a Ni auxiliary agent by adopting an impregnation method, wherein the impregnation method comprises the following specific steps: preparing a precursor solution of nickel nitrate for later use according to the required Ni loading amount; is reacted with ZrO 2 /H-ZSM-5/SO 4 2- Dispersing in deionized water, dropwise adding the nickel nitrate solution into the dispersion liquid, and continuously stirring in the process, wherein the stirring speed is 600-1200r/min.
Further, the isobutane and the isobutene are alkylated to synthesize Ni/ZrO in the high-octane gasoline 2 /H-ZSM-5/SO 4 2- The composite catalyst is prepared by the following steps:
(1) ZrO according to 1 2 : the mass ratio of H-ZSM-5 is prepared into ZrCl 2 ·4H 2 O solution is reserved; dispersing a proper amount of H-ZSM-5 in deionized water, ultrasonically dispersing for 1H, and dissolving ZrCl in the deionized water 2 ·4H 2 Slowly adding the O solution into the H-ZSM-5 dispersion liquid, and continuously performing ultrasonic treatment and stirring in the process. Wherein the ultrasonic frequency is 40-60KHz, and the stirring speed is 600-1200r/min.
(2) Configuration 20% of NH 3 ·H 2 And O is used as a precipitator of a coprecipitation method, the dispersion is added dropwise until white flocculent gel is formed, standing and aging are carried out for 10 hours, and then filtering and deionized water washing are carried out.
(3) Drying the obtained gel-like substance in a 110 ℃ oven pot, grinding, and calcining in a muffle furnace at 550 ℃ for 4 hours to obtain ZrO 2 /H-ZSM-5。
(4) ZrO2 is mixed with 2 the/H-ZSM-5 was dosed at 10mL (0.15 mol/L H) 2 SO 4 )/g cat Soaking for 2h, filtering, washing with deionized water, drying, and calcining at 550 deg.C in muffle furnaceZrO is obtained after 4 hours 2 /H-ZSM-5/SO 4 2- 。
(5) Preparing a precursor solution of nickel nitrate for later use according to the required Ni loading amount; zrO prepared in (4) 2 /H-ZSM-5/SO 4 2- Dispersing in deionized water, dropwise adding the nickel nitrate solution into the dispersion liquid, and continuously stirring in the process, wherein the stirring speed is 600-1200r/min.
(6) Putting the dispersion liquid in the step (5) in a water bath kettle at 90 ℃ to be dried by distillation, grinding, and calcining at 550 ℃ in a muffle furnace for 4 hours to obtain Ni/ZrO 2 /H-ZSM-5/SO 4 2- And (3) compounding a catalyst.
Ni/ZrO of the invention 2 /H-ZSM-5/SO 4 2- The application of the composite catalyst in the alkylation of isobutane and isobutene to synthesize high-octane gasoline is characterized in that: the alkylation reaction of isobutane and isobutene to synthesize high-octane gasoline is carried out on a pressurized fixed bed continuous flow reactor. The alkylation reaction conditions are as follows: the reaction pressure is 1.4Mpa, the reaction temperature is 80 ℃, and the feeding flow is 2 mL.h -1 N (isobutene) to n (isobutane) molar ratio of 1. Tabletting and screening the catalyst by 40-80 meshes, activating the catalyst before reaction and then using the catalyst, wherein the activation conditions of the catalyst are as follows: activation with pure nitrogen at 400 ℃ for 2h.
Further, the molar ratio of isobutene to isobutane in the feed is 1.
Preferably, the alkylation reaction conditions are: the reaction pressure is 1.4Mpa, the reaction temperature is 80 ℃, and the feeding flow is 2mL h -1 。
Further, the raw material sampling amount is controlled by changing the flow rate of the plunger pump. The amount of product was calculated by area normalization.
The invention has the advantages of
Ni/ZrO of the invention 2 /H-ZSM-5/SO 4 2- Composite catalyst, zrO 2 the/H-ZSM-5 is the compound of non-noble metal oxide and molecular sieve, and a small amount of transition metal Ni is loaded on ZrO 2 /H-ZSM-5/SO 4 2- In addition, the conversion rate of butylene and C in alkylation reaction can be obviously enhanced 8 Selective, promoted thermal catalytic alkylation reactionThe cost is reduced.
Ni/ZrO of the invention 2 /H-ZSM-5/SO 4 2- The preparation method of the composite catalyst is simple and feasible, the raw materials are cheap and easy to obtain, the large-scale production is facilitated, the catalytic alkylation effect is good, the stability is good, and the application prospect is good.
Ni/ZrO of the invention 2 /H-ZSM-5/SO 4 2- The composite catalyst has higher C 8 And (4) selectivity. Wherein, at the best loading of Ni, the composite catalyst Ni/ZrO 2 /H-ZSM-5/SO 4 2- The maximum isobutene conversion was 95.2%, the conversion at steady state was 61.7%, the selectivity at steady state was 86.0% and the steady yield was 53.1%.
Drawings
FIG. 1 shows the 5.0% of Ni/ZrO of the composite catalyst 2 /H-ZSM-5/SO 4 2- SEM images of the individual components during the synthesis. Wherein:
a.ZrO 2 ,b.H-ZSM-5,c.H-ZSM-5/ZrO 2 /SO 4 2- ,d.ZrO 2 /SO 4 2- ,e.H-ZSM-5/SO 4 2- ,f.Ni/H-ZSM-5/ZrO 2 /SO 4 2-
FIG. 2 Ni/ZrO at different Ni loadings 2 /H-ZSM-5/SO 4 2- XRD pattern of the composite alkylation catalyst.
FIG. 3 Ni/ZrO at different Ni loadings 2 /H-ZSM-5/SO 4 2- And (3) a catalytic activity diagram of the composite catalyst.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1:
Ni/ZrO used for alkylation reaction of isobutane and isobutene to synthesize high-octane gasoline 2 /H-ZSM-5/SO 4 2- The preparation method of the composite catalyst comprises the following steps:
(1) 1.9g of zirconium chloride was weighed and dissolved in 20mL of deionized water, and stirred vigorously at room temperature for 30min until the solid was completely dissolved. 1.0g of H-ZSM-5 was weighed, dispersed in 10mL of deionized water, and ultrasonically dispersed for 1 hour. Adding the H-ZSM-5 dispersion into the aqueous solution of zirconium chloride, and continuing stirring and carrying out ultrasonic treatment for 20min (the ultrasonic frequency is 50KHz, and the stirring speed is 800 r/min). And dropwise adding ammonia water with the mass concentration of 20% into the solution, and adjusting the pH to 9.0 to generate a white gelatinous substance. Standing, aging for 10h, and filtering.
(2) And (3) drying the sample prepared in the step (1) at 100 ℃ for 4h, grinding, putting into a crucible, transferring into a muffle furnace, and calcining at 550 ℃ which is the target temperature through program temperature control in an air atmosphere. Wherein the heating rate is 3 ℃/min, the calcination time is 4h at the target temperature, the temperature is 550 ℃, and the ZrO is obtained 2 catalyst/H-ZSM-5 in which ZrO 2 And the mass ratio of H-ZSM-5 is 1.
(3) 1.0g of ZrO prepared in (2) was weighed 2 The catalyst is dispersed in 15mL of 0.15mol/L H 2 SO 4 Soaking for 1h, filtering, washing with deionized water, drying, transferring to a muffle furnace, and calcining at 550 ℃ for 4h in air atmosphere. To obtain ZrO 2 /H-ZSM-5/SO 4 2- 。
(4) 0.125g of nickel nitrate hexahydrate is weighed and dissolved in a proper amount of deionized water to prepare a saturated nickel nitrate solution, then the saturated nickel nitrate solution is stirred and added dropwise into the ZrO prepared in the step (3) 2 /H-ZSM-5/SO 4 2- Putting the solution into an ultrasonic machine for ultrasonic treatment for 30 minutes, wherein the ultrasonic frequency is 40KHz, and stirring the dispersion liquid for 30 minutes by adopting mechanical stirring, and the stirring speed is 1000r/min. Then transferring the sample into a water bath kettle, evaporating the sample in the water bath at 90 ℃ to dryness, and grinding the massive sample into powder in a mortar. And putting the sample into a crucible, transferring the crucible into a muffle furnace, calcining the sample for 4h at 550 ℃ in the air atmosphere at the heating rate of 4 ℃/min, and taking the sample out after the temperature is reduced to the room temperature. To obtain 5.0% of Ni/ZrO 2 /H-ZSM-5/SO 4 2- And (3) compounding a catalyst.
The application of the catalyst comprises the following steps:
weighing the catalyst prepared in the step (4), tabletting and granulating (40-80 meshes), uniformly mixing with quartz sand with the particle size of 40-80 meshes, filling into a fixed bed reactor, and adding into a reactor N 2 Activation is carried out for 2h at 400 ℃. And then switching the raw material with the molar ratio of isobutane/isobutene =10, injecting liquid, and injecting the sampleThe amount is 2.0mL/h/g cat The reaction temperature is 80 ℃ and the reaction pressure is 1.4Mpa. Carrier gas N 2 The flow rate is the space velocity of 1800mL/g cat Catalyzing isobutane and isobutene to alkylate and synthesize the high-octane gasoline under the condition of/h.
Example 2
A composite catalyst was prepared as in example 1, except that the amount of nickel nitrate hexahydrate added in step (4) was 0.025g, and the amount of nickel supported in the finally obtained catalyst was 1.0%, 1.0% 2 /H-ZSM-5/SO 4 2- The rest of the procedure was the same as in example 1.
Example 3
A composite catalyst was prepared as in example 1, except that the amount of nickel nitrate hexahydrate added in step (4) was 0.075g, and the final nickel loading in the resulting catalyst was 3.0%, 3.0% as Ni/ZrO 2 /H-ZSM-5/SO 4 2- The rest of the procedure was the same as in example 1.
Example 4
A composite catalyst was prepared as in example 1, except that the amount of nickel nitrate hexahydrate added in step (4) was 0.200g, and the amount of nickel supported in the finally obtained catalyst was 8.0%, 8.0% as Ni/ZrO 2 /H-ZSM-5/SO 4 2- The rest of the procedure was the same as in example 1.
Example 5
A composite catalyst was prepared as in example 1, except that the amount of nickel nitrate hexahydrate added in step (4) was 0.300g, and the amount of nickel supported in the finally obtained catalyst was 12.0%, which was taken as 12.0% 2 /H-ZSM-5/SO 4 2- The rest of the procedure was the same as in example 1.
Example 6
The composite catalyst was prepared as in example 1 except that the amount of nickel nitrate hexahydrate added in step (4) was 0 and the amount of nickel supported in the final catalyst was 0%, which was designated as ZrO 2 /H-ZSM-5/SO 4 2- The rest of the procedure was the same as in example 1.
Example 7
The preparation of the composite catalyst was the same as in example 1,except that the amount of zirconium chloride added in step (1) was 0.38g and the amount of nickel nitrate hexahydrate added in step (4) was 0. Finally preparing catalyst ZrO 2 /H-ZSM-5/SO 4 2- Medium ZrO of 2 The mass ratio of H-ZSM-5 is 1.
Example 8
A composite catalyst was prepared as in example 1, except that the amount of zirconium chloride added in step (1) was 0.63g, and the amount of nickel nitrate hexahydrate added in step (4) was 0. ZrO in the finally prepared catalyst 2 The mass ratio of H-ZSM-5 is 1.
Example 9
A composite catalyst was prepared as in example 1, except that the amount of zirconium chloride added in step (1) was 0.95g, and the amount of nickel nitrate hexahydrate added in step (4) was 0. ZrO in the finally prepared catalyst 2 The mass ratio of H-ZSM-5 is 1.
Example 10
A composite catalyst was prepared as in example 1, except that the amount of zirconium chloride added in step (1) was 3.8g, and the amount of nickel nitrate hexahydrate added in step (4) was 0. ZrO in the finally prepared catalyst 2 The mass ratio of H-ZSM-5 is 2.
Example 11 (acid treatment with different acid concentrations)
A composite catalyst was prepared as in example 1, except that the acid-treated H in step (3) 2 SO 4 The concentration was 0.05mol/L. Except that the acid concentration in the acid treatment was different, the remaining steps were the same as in example 1.
Example 12 (acid treatment with different acid concentrations)
A composite catalyst was prepared as in example 1, except that the acid-treated H in step (3) 2 SO 4 The concentration was 0.1mol/L. Except that the acid concentration in the acid treatment was different, the remaining steps were the same as in example 1.
Example 13 (acid treatment different acid concentrations)
A composite catalyst was prepared as in example 1, except thatH acid-treated in step (3) 2 SO 4 The concentration was 0.3mol/L. Except that the acid concentration in the acid treatment was different, the remaining steps were the same as in example 1.
Example 14 (acid treatment with different acid concentrations)
A composite catalyst was prepared as in example 1, except that the acid-treated H in step (3) 2 SO 4 The concentration was 1.0mol/L. Except that the acid concentration in the acid treatment was different, the remaining steps were the same as in example 1.
Example 15 (influence of reaction temperature)
The preparation of the composite catalyst was the same as in example 1 except that the reaction temperature in the catalyst application step was 20 ℃, and the remaining steps were the same as in example 1.
Example 16 (influence of reaction temperature)
The preparation of the composite catalyst was the same as in example 1 except that the reaction temperature in the catalyst application step was 40 ℃, and the remaining steps were the same as in example 1.
Example 17 (influence of reaction temperature)
The preparation of the composite catalyst was the same as in example 1 except that the reaction temperature in the catalyst application step was 60 deg.c, and the remaining steps were the same as in example 1.
Example 18 (influence of reaction temperature)
The preparation of the composite catalyst was the same as in example 1 except that the reaction temperature in the catalyst application step was 120 deg.c, and the remaining steps were the same as in example 1.
Example 19 (influence of the alkane to alkene ratio)
The preparation of the composite catalyst was the same as in example 1, except that isobutane/isobutylene =2:1, the rest of the procedure was the same as in example 1.
Example 20 (influence of the alkane to alkene ratio)
The preparation of the composite catalyst was the same as in example 1, except that isobutane/isobutylene =5:1, the rest of the procedure was the same as in example 1.
Example 21 (influence of the alkane to alkene ratio)
The preparation of the composite catalyst was the same as in example 1, except that in the catalyst application step, isobutane/isobutene =20:1, the rest of the procedure was the same as in example 1.
Example 22 (influence of the alkane to alkene ratio)
The preparation of the composite catalyst was the same as in example 1, except that in the catalyst application step isobutane/isobutylene =50:1, the rest of the procedure was the same as in example 1.
Comparative example 1
A composite catalyst was prepared as in example 1, except that the amount of cobalt nitrate added in step (4) was 0.200, and the amount of cobalt supported in the finally obtained catalyst was 5%, as noted 5.0% 2 /H-ZSM-5/SO 4 2- The rest of the procedure was the same as in example 1.
Comparative example 2
A composite catalyst was prepared as in example 1, except that the ammonium molybdate addition in step (4) was 0.825 and the molybdenum loading in the final catalyst was 5%, as 5.0% Mo/ZrO 2 /H-ZSM-5/SO 4 2- The rest of the procedure was the same as in example 1.
Comparative example 3
The composite catalyst was prepared as in example 1, except that the amount of cerium nitrate added in step (4) was 0.290, and the loading of cerium in the finally obtained catalyst was 5%, as 5.0% Ce/ZrO 2 /H-ZSM-5/SO 4 2- The rest of the procedure was the same as in example 1.
Comparative example 4
A composite catalyst was prepared as in example 1, except that the amount of copper nitrate added in step (4) was 0.160, and the copper loading in the final catalyst was 5%, as 5.0% Cu/ZrO 2 /H-ZSM-5/SO 4 2- The rest of the procedure was the same as in example 1.
Sample evaluation
Respectively loading the finished catalysts obtained in examples 1-6 and comparative examples 1-4 into a fixed bed reactor (the reduction process is the same as that in example 1), tabletting and granulating the catalyst (40-80 meshes), uniformly mixing the catalyst with quartz sand with the particle size of 40-80 meshes, and filling the mixture to be fixedIn a bed reactor, in N 2 Activation is carried out for 2h at 400 ℃. Then, the raw material with the molar ratio of isobutane/isobutene =10 is switched to the raw material, and liquid injection is carried out. The flow rate of the raw material sample introduction is 2.0mL/h/g cat The pressure is 1.4MPa, the reaction temperature is 80 ℃, and the carrier gas N is 2 The flow rate is that the space velocity is 1800mL/g cat H is used as the reference value. The isobutene conversion and C of each catalyst were examined separately 8 Selectivity and C 8 Yield. The evaluation results are shown in tables 1 and 2.
Table 1 examples 1-6 alkylation catalysis results
Figure BDA0002513336950000071
Table 2 comparative examples 1-4 alkylation catalysis results
Figure BDA0002513336950000081
And (4) surface note: con in the table. Isobutene (%) is the butene conversion rate of the alkylation reaction, wherein the initial conversion rate is data obtained after 3min of reaction, and the stable conversion rate is data obtained after 43min of reaction; in table S C8 (%) is C in the alkylation reaction product 8 Selectivity of (a); pro in the table. C8 (%) is C in the reaction product 8 The yield of (2).
From the alkylation reaction results of isobutane and isobutene of the catalysts of examples 1-6, under the same reaction conditions, with the increase of the nickel loading amount, the conversion rate of isobutane shows a trend of increasing first and then decreasing, and the reason is that the excessive loading of Ni causes the aggregation of the catalyst to cover the surface acid sites of the catalyst; however C 8 The selectivity of (C) is kept increasing with increasing nickel loading, since the increased loading of Ni produces C 8 An active center of (a); c when combining conversion and selectivity 8 The yield reached the optimum value when the amount of nickel added was 5.0%, indicating that excessive addition of Ni increased C 8 But overall reduces the yield of alkylation. Thus, the more Ni is added, the betterI.e. 5.0% Ni/ZrO 2 /H-ZSM-5/SO 4 2- The optimal catalytic performance is shown.
From the results of the alkylation reaction of isobutane with isobutylene using the composite catalysts of examples 1 and 6, it was found that ZrO was reacted under the same reaction conditions 2 /H-ZSM-5/SO 4 2- Catalyst, zrO due to addition of an appropriate amount of Ni 2 /H-ZSM-5/SO 4 2- Showing an increase in performance. This indicates that the loading of Ni is to elevate ZrO alone 2 /H-ZSM-5/SO 4 2- Important reasons for catalyst performance.
From the alkylation reaction results of isobutane and isobutylene in the catalysts of comparative examples 1-5, it can be seen that under the same reaction conditions, the catalytic performance of Ni as a metal carrier is significantly superior to that exhibited by Co, mo, ce, and Cu.
Sample evaluation
The finished catalysts obtained in examples 7 to 14 were respectively loaded in fixed bed reactors (the reduction process was the same as in example 1), tabletting and granulating the catalyst (40-80 meshes), uniformly mixing the catalyst with quartz sand with the particle size of 40-80 meshes, filling the mixture into a fixed bed reactor, and adding N 2 Activating at 400 deg.C for 2h. Then, the raw material with the molar ratio of isobutane/isobutene =10 is switched to the raw material, and liquid injection is carried out. The sample injection flow of the raw material is 2.0mL/h/g cat The pressure is 1.4MPa, the reaction temperature is 80 ℃, and the carrier gas N is 2 The flow rate is the space velocity of 1800mL/g cat H is used as the reference value. The isobutene conversion and C of each catalyst were examined separately 8 Selectivity and C 8 Yield. The evaluation results are shown in tables 3 and 4.
Table 3 examples 7-11 alkylation catalysis results
Figure BDA0002513336950000091
Table 4 examples 12-14 alkylation catalysis results
Figure BDA0002513336950000092
And (4) surface note: con in the table. Isobutene (%) is the butene conversion rate of the alkylation reaction, wherein the initial conversion rate is data obtained after 3min of reaction, and the stable conversion rate is data obtained after 43min of reaction; in table S C8 (%) is C in the alkylation reaction product 8 The selectivity of (a); pro in the table. C8 (%) is C in the reaction product 8 The yield of (A) was found.
From the results of the alkylation reactions of examples 7 to 11, it was found that ZrO produced under the same reaction conditions 2 And the ratio of H-ZSM-5 has a significant effect on the catalytic performance. H-ZSM-5 as composite catalyst carrier with large content of (ZrO) 2 : H-ZSM-5= 1), the initial conversion of isobutylene by the alkylation reaction is low, C 8 The selectivity is only 76.38 percent, because the acidic sites of the H-ZSM-5 are mainly weak acidic sites, and the conversion efficiency of catalytic butylene is low. However, zrO is excessive 2 Amount of supported (ZrO) 2 : H-ZSM-5= 2) reduces the conversion of isobutylene, possibly by ZrO, the active site of H-ZSM-5 in the composite catalyst 2 A large amount of coverage. When ZrO2 2 : H-ZSM-5=1, the composite catalyst exhibits the best catalytic effect, and at this time C 8 The yield reaches 45.26 percent.
From the alkylation reaction results of examples 12-14, it can be seen that the acid treatment step in the preparation of the composite catalyst has a significant effect on the catalyst. When the concentration of the sulfuric acid used is in the range of 0.1 to 0.3mol/L, a superior catalytic effect is exhibited. The best effect is achieved when the concentration of sulfuric acid is 0.15mol/L, and C is obtained when 8 The yield reaches 45.26 percent.
Sample evaluation
In order to examine the influence of the reaction temperature and the ratio of the alkane and the alkene of the reaction raw materials on the alkylation reaction, the finished catalysts obtained in examples 15 to 22 are respectively filled in a fixed bed reactor (the reduction process is the same as in example 1), the catalysts are uniformly mixed with quartz sand with the grain diameter of 40 to 80 meshes after being tableted and granulated (40 to 80 meshes), and the mixture is filled in the fixed bed reactor, and then N is added into the reactor 2 Activating at 400 deg.C for 2h. Then the alkane-alkene ratio of the raw materials is switched to carry out the reaction. The sample injection flow of the raw material is 2.0mL/h/g cat The pressure is 1.4MPa, the reaction temperature is 20-120 ℃, and the carrier gas is usedN 2 The flow rate is that the space velocity is 1800mL/g cat H is used as the reference value. The isobutene conversion and C of each catalyst were examined separately 8 Selectivity and C 8 Yield. The evaluation results are shown in tables 5 and 6.
TABLE 5 examples 15-18 alkylation catalysis results
Figure BDA0002513336950000101
TABLE 6 examples 19-22 alkylation catalysis results
Figure BDA0002513336950000102
And (4) surface note: con in the table. Isobutene (%) is the butene conversion rate of the alkylation reaction, wherein the initial conversion rate is data obtained after 3min of reaction, and the stable conversion rate is data obtained after 43min of reaction; in table S C8 (%) is C in the alkylation reaction product 8 Selectivity of (a); pro in the table. C8 (%) is C in the reaction product 8 The yield of (2).
From the results of the alkylation reactions of examples 15 to 18, it is clear that the reaction temperature is an important reaction condition in the alkylation reaction. The low temperature results in incomplete conversion of isobutylene and the high temperature results in polymerization of the alkylate product. The reaction effect is best when the reaction temperature is 80 ℃.
From the results of the alkylation reactions of examples 19-22, it can be seen that the olefin content in the alkylation reaction feed affects the product yield, with the highest alkylation yield of 52.22% when the ratio of the alkyl to the olefin is 10.
FIG. 1 shows the content of Ni/ZrO 2 in the composite catalyst 5.0% 2 /H-ZSM-5/SO 4 2- SEM images of the components in the synthesis process show that the structures of the sulfated ZrO2 and H-ZSM-5 are changed obviously, and the smooth surface is changed into coarse and finer particles. In particular, H-ZSM-5 is transformed from a regular hexagonal prism to a random, finer shape. ZrO (ZrO) 2 /H-ZSM-5/SO 4 2- Medium ZrO of 2 The particles are concentrated in the air and concentrated in the air,enriching and agglomerating; and when 5.0% of Ni is loaded, zrO 2 The situation of large aggregates is alleviated.
FIG. 2 shows Ni/ZrO loading with different Ni 2 /H-ZSM-5/SO 4 2- XRD pattern of the composite alkylation catalyst. From FIG. 2, it can be seen that ZrO when Ni is loaded 2 The diffraction peak of the compound is greatly reduced, and the diffraction peak of the H-ZSM-5 is also reduced. Shows that the addition of Ni reduces ZrO 2 Comparison of the crystallinity of (1) with SEM also shows that the addition of Ni makes ZrO 2 And is more dispersed. No diffraction peak of Ni species is shown in XRD, which indicates that the Ni species are uniformly dispersed and have low crystallinity.
FIG. 3 shows Ni/ZrO at different Ni loadings 2 /H-ZSM-5/SO 4 2- Catalytic activity profile of the composite alkylation catalyst. The reaction conditions are as follows: the reaction conditions are that the sample injection flow of the raw material is 2.0mL h < -1 >, the pressure is 1.4MPa and the reaction temperature is 80 ℃. As can be seen from the figure: the highest conversion rate of the added 5.0 percent of metal Ni, the highest conversion rate of isobutene is 95.20 percent, and the conversion rate is 61.69 percent in stable state; the addition of 12.0% metallic Ni reduces the butene conversion, it is the excess Ni species that covers the acidic sites of the acidic support. Increased amount of Ni added, C 8 The selectivity gradually increased, the binding conversion rate, 5.0% of Ni addition was optimal, the selectivity was 84.65% at steady state, and the yield was 52.22%.

Claims (9)

1. Ni/ZrO 2 / H-ZSM-5 / SO 4 2- The application of the composite catalyst in catalyzing isobutane and isobutene alkylation to synthesize gasoline is characterized in that: the Ni/ZrO 2 / H-ZSM-5 / SO 4 2- The composite catalyst is prepared by loading transition metal Ni into ZrO by impregnation 2 / H-ZSM-5 / SO 4 2- Then calcining in air to obtain the composite catalyst;
wherein the carriers are H-ZSM-5 and ZrO 2 Compounding according to the mass ratio of 1 2 SO 4 Or (NH) 4 ) 2 SO 4 Soaking to obtain ZrO 2 / H-ZSM-5 / SO 4 2- ；
The loading of Ni in the composite catalyst was 5.0%.
2. Use according to claim 1, characterized in that:
the preparation method of the composite catalyst comprises the following steps:
(1) The ZrO 2 One or more of zirconium nitrate, zirconium chloride and zirconium hydroxide is used as a zirconium source, ammonia water or a saturated ammonium bicarbonate solution is used as a precipitator, coprecipitation is carried out to compound with H-ZSM-5, and the catalyst is prepared by calcining;
(2) Said ZrO 2 The reaction of/H-ZSM-5 with H 2 SO 4 Or (NH) 4 ) 2 SO 4 Soaking to improve the acidity and increase the pore structure;
(3) The Ni/ZrO 2 / H-ZSM-5 / SO 4 2- The composite catalyst is prepared by taking a nickel precursor as a Ni source through an impregnation method, so that Ni is in ZrO 2 / H-ZSM-5 / SO 4 2- Wherein the loading amount of Ni is 5.0%.
3. The use as claimed in claim 2, comprising the steps of:
(1) ZrO according to desired stoichiometric ratio 2 And H-ZSM-5 with ZrCl 2 ·4H 2 O solution is reserved, and the mass concentration of the solution is 0.01 g/mL-0.1 g/mL; dispersing 1.0g of H-ZSM-5 in 10-30 mL of deionized water, ultrasonically dispersing for 1-2H, and ZrCl 2 ·4H 2 Slowly adding the O solution into the H-ZSM-5 dispersion liquid, and continuously performing ultrasonic treatment and stirring in the process; wherein the ultrasonic frequency is 40-60KHz, and the stirring speed is 600-1200 r/min;
(2) preparing NH with the mass concentration of 10-30% 3 ·H 2 Adding O solution or saturated ammonium bicarbonate solution as precipitant of coprecipitation method, and dripping the dispersion solution of (1) to form white flocculent gel with pH of 8.5-9.5; standing and aging for 8-10 h;
(3) drying the obtained gel-like substance in an oven pan at 90-110 deg.C; grinding and calcining at 300-600 ℃ for 3-6 h in a muffle furnace to obtain ZrO 2 / H-ZSM-5；
(4) ZrO2 is mixed with 2 The amount of the/H-ZSM-5 is 10 to 20 mL/g cat The concentration of H is 0.05-1.0 mol/L 2 SO 4 Or at 10-20 mL/g cat Saturation (NH) at Normal temperature 4 ) 2 SO 4 Soaking in solution for 0.5-3 h, with cat representing ZrO 2 H-ZSM-5; filtering, washing solid matters with deionized water, drying, and calcining in a muffle furnace at 300-600 ℃ for 3-6 h; to obtain ZrO 2 / H-ZSM-5 / SO 4 2- ；
(5) Preparing a nickel precursor saturated solution for later use according to the required Ni loading amount; zrO preparation of 1.0g of the catalyst prepared in (4) 2 / H-ZSM-5 / SO 4 2- Dispersing in 10-30 mL deionized water; dropwise adding the prepared nickel nitrate solution into the dispersion liquid while stirring, wherein the stirring speed is 600-1200 r/min;
(6) putting the dispersion liquid in the step (5) in a water bath kettle at 70-95 ℃ to be dried by distillation, grinding, and calcining in a muffle furnace at 300-600 ℃ for 3-6 h; obtaining Ni/ZrO 2 / H-ZSM-5 / SO 4 2- And (3) compounding a catalyst.
4. Use according to claim 3, characterized in that:
in the step (3), the calcining temperature is 500-600 ℃, and the calcining time is 4 h;
step (4) wherein H 2 SO 4 In a concentration of 0.1 to 0.3mol/L H 2 SO 4 The calcination temperature is 500-600 ℃ and the calcination time is 4 h;
placing the dispersion liquid in the step (6) at 85-90 ℃; the calcining temperature is 500-600 ℃, and the calcining time is 4h.
5. Use according to claim 2, characterized in that: the nickel precursor is one or more of nickel sulfate, nickel nitrate, nickel chloride and nickel hydroxide.
6. Use according to claim 1, characterized in that: the reaction of isobutane and isobutene alkylated synthetic gasoline is carried out on a pressurized fixed bed continuous flow reactor; alkylation reaction conditionsComprises the following steps: the reaction pressure is 0.8-2.0 Mpa; the reaction temperature is 20-120 ℃; the feeding flow is 1.0-3.0 mL h -1 / g cat (ii) a n (isobutene) and n (isobutane) in a molar ratio of 1:20.
7. use according to claim 6, characterized in that: the alkylation reaction conditions are as follows: the reaction pressure is 1.0-1.5 Mpa; the reaction temperature is 80-120 ℃; feed flow 2.0mL h -1 / g cat (ii) a n (isobutene) to n (isobutane) molar ratio 1.
8. Use according to claim 1 or 6, characterized in that: tabletting and screening the catalyst for 40-80 meshes, wherein the catalyst is used after being activated before reaction, and the activation conditions of the catalyst are as follows: activating with pure nitrogen at 200-500 deg.C for 1-5 h.
9. Use according to claim 1, characterized in that:
supports H-ZSM-5 and ZrO 2 And (2) compounding the components in a mass ratio of 1.
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