CN105642340A - Preparation of catalyst excellent in low temperature etherification activity - Google Patents

Preparation of catalyst excellent in low temperature etherification activity Download PDF

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Publication number
CN105642340A
CN105642340A CN201610038602.5A CN201610038602A CN105642340A CN 105642340 A CN105642340 A CN 105642340A CN 201610038602 A CN201610038602 A CN 201610038602A CN 105642340 A CN105642340 A CN 105642340A
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catalyst
etherification
acid
preparation
activity
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柯明
颜曦明
宋昭峥
蒋庆哲
周耀文
于沛
刘强
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China University of Petroleum Beijing
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China University of Petroleum Beijing
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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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/16—Metal oxides
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a preparation method of a catalyst excellent in low temperature etherification activity. The catalyst can be used for producing ethers high-octane gasoline additives or be applied to a catalytic cracking light petrol etherification alkene-reduction process. The preparation method of the catalyst comprises the steps that firstly, pseudo-boehmite serves as binder, beta-molecular sieves serve as active components, a substrate catalyst is prepared and obtained, then the substrate catalyst is modified through a combined method of acid fluid treatment and hydro-thermal treatment, and finally the catalyst excellent in low temperature etherification activity is obtained. The etherification performance evaluation conditions of the catalyst are that the alcohol-alkene ratio is 0.7-1.3, the temperature is 50-100 DEG C, the pressure is 1-5 MPa, and the volume air speed is 0.6-3.0 h<-1>. The preparation method of the etherification catalyst is easy to operate and low in cost, and the catalyst can reach high etherification activity at the low reaction temperature and is high in selectivity, few in by-product, good in stability and easy to regenerate after inactivation.

Description

A kind of preparation with superior low-temperature etherification activity catalyst
Technical field
The invention mainly relates to a kind of preparation method with superior low-temperature etherification activity catalyst, this catalyst can be used for producing ethers high-knock rating gasoline additive or for light FCC gasoline etherificate Olefin decrease process.
Background technology
Environmental requirement in recent years is increasingly strict, and quality of gasoline upgrading paces are substantially accelerated, and strictly limits olefin(e) centent �� 24% in state's V gasoline standard, and following state VI gasoline standard will be more harsh. Domestic gasoline is essentially from catalytic cracking process, and olefin(e) centent is high, therefore, how effectively Olefin decrease, retain octane number and become the study hotspot of oil product processing industry.
Gasoline etherification technology is that catalytically cracked gasoline cuts into weight two component, with light component for raw material, with low-carbon alcohols generation etherification reaction under acidic catalyst effect, generate product alkyl ether and be in harmonious proportion with heavy constituent, finally giving and there is high-octane etherified gasoline. This technology can reach Olefin decrease and put forward high-octane dual purpose in single step reaction simultaneously, is improve one of high-level most desirable route of gasoline quality, reply country gasoline, has development and application prospect widely.
Tert amyl methyl ether(TAME) (TAME) is the desirable high-octane rating additive of another after methyl tertiary butyl ether(MTBE) (MTBE), can be prepared by iso-amylene and methanol etherification, although octane number is slightly below MTBE, but it is good with gasoline compatibility, in water, dissolubility is low, to environment nonhazardous effect, therefore, the research of TAME production technology is increasingly paid attention to by people.
External etherificate research starting relatively early, common are the NEXTAME technique etc. of the TAME technique of BP company, the CDTACOL technique of IFP, the Ethermax technique of Britain UOP, the CDTECH technique of CR&L company of the U.S., Nexte company of Finland. What studies in China was more has Fusun PetroleumCollege, Lanzhou Petrochemical academy, Qilu Petrochemical academy, Luoyang Petrochemical company etc.
Early stage catalyst for etherification mostly is homogeneous catalyst, after there is the shortcomings such as etching apparatus, product separation difficulty, contaminated environment in view of it, people develop again a series of heterogeneous catalysis in succession, such as acid large hole cation exchanger resin, solid-carrying heteropolyacid, molecular sieve etc.
Macropore strong acid cation exchanger resin is industrially applied relatively general, has acid strong, activity is high, cost is a low advantage, but poor heat stability, acid site are easy to run off, regenerate difficulty, and side reaction is more.Patent CN1348941A discloses a kind of preparation method with etherificate, selective hydrogenation and isomerization three function catalyst, and this catalyst is with acidic resins for carrier, and load active component Pt, Pd, Ni, Co and promoter prepare. Patent CN102557887A discloses a kind of preparation method synthesizing TAME catalyst, this catalyst is with macroreticular acidic cation exchange resin carrier, with one or more in Ru, Rh, Co, Mo, Ni metal or corresponding salt for major catalyst, in ii I or iv main group, one or more are for auxiliary agent. The preparation method relating to a kind of light resin catalyst in patent CN103586075A, it be by 100 parts of styrene, 5-20 part divinylbenzene, 0.1-5 part '-biphenyl diphenol and 0.1-2 part 3-(1-pyrrolidinyl) ethyl acrylate be monomer copolymerization generate polymerization Archon after, last sulfonated prepare.
Solid-carrying heteropolyacid is the catalyst that a class is relatively new, by preparing on liquid loaded by heteropoly acid to suitable porous material, not only increases specific surface area and improves catalysis activity, but still suffers from the problem run off in acid site, and complicated process of preparation, high expensive. Patent CN103787842A mentions with aluminium based metal composite oxides MgO-Al2O3��TiO2-Al2O3And ZrO2-Al2O3Deng in one or more be carrier, with one or more in phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, germanotungstic acid for active component, prepare the catalyst for etherification for synthesizing TAME by different quality than compound. Patent CN102408316A relates to a kind of method that ionic liquid is catalyst preparing TAME, the ionic liquid used is 1-methyl-3-1-Butyl-1H-imidazole borofluoride, when temperature 70 C-100 DEG C, alfin ratio 1.1-1.5, pressure 0.5MPa-0.8MPa, air speed 0.9-1.3, iso-amylene conversion per pass is more than 70%.
And molecular sieve catalysts is as a class catalyst for etherification of most prospects for commercial application, activity is lower slightly compared with resin catalyst, especially during low temperature, activity is poor, but some modified approach Molecular regulator sieve pore structure can be passed through and acid in order to improve its etherification activity, in addition the distinctive pore structure of molecular sieve has the type effect of selecting and can suppress the generation of side reaction, product colour mostly is water white transparency, selectivity is excellent, and good stability, inactivation is regeneration easily, and therefore it is the study hotspot of current etherificate researcher. Few for the patent in etherificate about molecular sieve, patent CN101138739A discloses with molecular sieve for carrier, by load active component 1-5% boron trioxide or SO4 2-/Fe2O3Solid super-strong acid prepares catalyst for etherification, reveals the advantages such as activity is high, selectivity is good, renewable for low carbon olefin hydrocarbon etherification reaction table. The preparation method that patent CN1311182A relates to a kind of Etherification of Light FCC Gasoline catalyst, including the fluorine of the �� zeolite of 60%-80%, the inorganic oxide of 10%-30% and 1%-10%. Patent CN1289751A disclose a kind of using zeolite composite to acid mesopore and large pore zeolite as catalyst, for the method that the hydration and etherification of low-carbon alkene with water/alcohol react generation ether and alcohol ether, product can mix gasoline raising octane number.
In sum, objective and the developing direction of following catalyst for etherification research is, improving catalyst activity and be selective while, to ensure that it has good stability and renewable as far as possible. Molecular sieve catalysts generally need to can be only achieved best etherification activity when 90 DEG C, but etherificate is exothermic reaction, temperature height is not only unfavorable to positive reaction, also can increase deactivation rate, affect catalyst life and stability, therefore, it is necessary to the low temperature etherification activity how improving beta-molecular sieve is furtherd investigate.
Summary of the invention
The preparation of catalyst for etherification has been carried out careful research by the present invention, it is therefore intended for preparing and has highly active catalyst for etherification under cryogenic conditions, can use it for production ethers high-knock rating gasoline additive and for light FCC gasoline etherificate Olefin decrease process.
The present invention proposes a kind of preparation method with good low temperature etherification activity catalyst, it is characterised in that: first molecular sieve is active component, and with boehmite for binding agent, sesbania powder is extrusion aid, and dust technology is that substrate catalyst prepared by peptizer. Wherein molecular sieve is to buy or homemade Hydrogen or sodium form beta-molecular sieve, and its content is the 30wt%-90wt% of substrate catalyst quality; Boehmite and sesbania powder all adopt commercially available, 10wt%-70wt% and the 1.0wt%-10.0wt% of content respectively substrate catalyst quality, add, after above-mentioned three kinds of powder mix homogeneously, the dilute nitric acid solution that appropriate concentration is 0.1mol/L-1.0mol/L, through fully kneading, extrusion, dry and after roasting, prepare substrate catalyst. Then adopt acid solution to process and substrate catalyst is modified by the mode of steam treatment compound, finally give the catalyst for etherification under low temperature with excellent activity.
Catalyst modification method of the present invention is the mode adopting acid solution facture and hydrothermal treatment consists method compound, composite pathway is probably after first substrate catalyst being carried out acid solution process to carry out hydrothermal treatment consists again, or carries out acid solution process again after first it being carried out hydrothermal treatment consists.
The acid solution used in acid solution processing method of the present invention can be one or more in hydrochloric acid, phosphoric acid, citric acid, and acid strength is 0.1mol/L-2.0mol/L, and acid treatment temperature is 20 DEG C-90 DEG C, and the acid treatment time is 1h-10h.
Hydrothermal treatment consists method of the present invention is to adopt 100% steam, and hydrothermal treatment consists temperature is 100 DEG C-700 DEG C, and the process time is 1h-8h, and vapor flow rate is 0.1mL/min-2.0mL/min.
Catalyst etherification activity evaluation of the present invention is to carry out in the micro fixed-bed reactor of self assembly. Raw material of etherification oil can be formed by normal hexane, hexene and iso-amylene 5: 3: 2 configurations in mass ratio, beds is passed through after itself and methanol mixed, etherificate appreciation condition: methanol and iso-amylene mol ratio are 0.7-1.3, reaction temperature is 50 DEG C-110 DEG C, reaction pressure is 1.0MPa-4.0MPa, and air speed is 0.6h-1-4h-1��
Catalyst for etherification prepared by the present invention can be used for producing ethers high-knock rating gasoline additive, can also be used for light FCC gasoline etherificate Olefin decrease process, this catalyst has prominent low temperature etherification activity, carry out etherification reaction at a lower temperature to be possible not only to reduce side reaction generation, make selectivity improve, and ensure that catalyst has good stability, can be regenerated by the mode of high-temperature roasting after this catalysqt deactivation in addition, preparation process is simple to operation, and cost is low.
Detailed description of the invention
Substrate catalyst preparation method of the present invention is specific as follows: beta-molecular sieve silica alumina ratio is 10-80, and specific surface area is 200m2/g-500m2/ g; Pore volume >=the 0.3cm of boehmite powder3/ g, specific surface area is 100m2/g-400m2/ g. First weighing in proportion beta-molecular sieve, boehmite and sesbania powder, wherein beta-molecular sieve content is the 30wt%-90wt% of carrier quality, it is preferred to 30wt%-80wt%, it is most preferred that for 40wt%-80wt%; Boehmite content is the 10wt%-70wt% of carrier quality, it is preferred to 20wt%-70wt%, it is most preferred that for 20wt%-60wt%; Sesbania powder content is the 1.0wt%-8.0wt% of carrier quality, it is preferred to 1.0wt%-6.0wt%, it is most preferred that for 2wt%-5wt%. Then configuring dilute nitric acid solution, concentration is 0.1mol/L-1.0mol/L, it is preferred to 0.2mol/L-0.8mol/L, it is most preferred that for 0.3mol/L-0.5mol/L.Dilute nitric acid solution is added in mixed-powder and to be extruded into bar shaped after fully mediating, be placed in the baking oven of 50 DEG C-120 DEG C dry 5h-10h, then in 400 DEG C of-650 DEG C of Muffle furnaces roasting 2h-6h, pound into 20-40 order granule after cooling standby.
It is as follows that acid solution of the present invention processes concrete operation step: initially with one or more preparation 100ml acid treating solutions in hydrochloric acid, phosphoric acid, citric acid, acid strength is 0.1mol/L-2.0mol/L, it is preferably 0.1mol/L-1.5mol/L, it is most preferred that for 0.3mol/L-1.5mol/L. Adding 10g carrier in acid solution, be subsequently placed in water bath with thermostatic control and stir, acid solution treatment temperature is 20 DEG C-90 DEG C, it is preferred to 20 DEG C-80 DEG C, it is most preferred that be 30 DEG C-80 DEG C; The acid solution process time is 1h-10h, it is preferred to 2h-10h, it is most preferred that for 4h-10h. Sucking filtration become neutrality with a large amount of deionized water wash to filtrate after acid treatment, dry 6h-10h in 60 DEG C of-110 DEG C of baking ovens, then in the Muffle furnace of 300 DEG C-600 DEG C roasting 2h-6h, standby after cooling.
Hydrothermal treatment consists method concrete operation step of the present invention is as follows: carry out hydrothermal treatment consists in homemade tubular heater, 10g carrier is added in special quartz curette, quartz curette is placed in tube furnace constant temperature zone, first in nitrogen environment, temperature is risen to predetermined hydrothermal temperature, then passed to for the 100% steam treatment scheduled time, go in nitrogen environment standby after cooling after being disposed again. Described hydrothermal temperature is 100 DEG C-700 DEG C, it is preferred to 200 DEG C-600 DEG C, it is most preferred that be 400 DEG C-500 DEG C; The hydro-thermal time is 1h-8h, it is preferred to 2h-7h, it is most preferred that for 2h-5h; Vapor flow rate is 0.1mL/min-2.0mL/min, it is preferred to 0.2mL/min-1.5mL/min, it is most preferred that for 0.4mL/min-1.0mL/min.
Etherification activity evaluation of the present invention is to carry out in homemade micro fixed-bed reactor, and tube inner diameter is 10mm, and length is 600mm, and reaction tube adopts three sections of temperature controls, loads 5mL catalyst at constant temperature zone, and remainder fills the little porcelain ball of inertia. Raw material of etherification oil is to be formed by normal hexane, hexene and iso-amylene 5: 3: 2 configurations in mass ratio, by its mixture with methanol under following reaction condition with catalyst haptoreaction: methanol and iso-amylene mol ratio are 0.7-1.3, it is preferably 0.8-1.2, it is most preferred that for 0.9-1.1; Reaction temperature is 50 DEG C-110 DEG C, it is preferred to 60 DEG C-100 DEG C, it is most preferred that be 60 DEG C-90 DEG C; Reaction pressure is 1.0MPa-5.0MPa, it is preferred to 1.0MPa-4.0MPa, it is most preferred that for 1.0MPa-3.0MPa; Volume space velocity is 0.6h-1-3.0h-1, it is preferred to 0.6h-1-2.0h-1, it is most preferred that for 0.8h-1-1.5h-1��
Further illustrate below by specific embodiment:
Embodiment 1
Beta-molecular sieve content is the 60% of substrate catalyst quality, boehmite content is the 37% of substrate catalyst quality, sesbania powder content is the 3% of substrate catalyst quality, it is the dilute nitric acid solution of 0.4mol/L that three adds concentration after being sufficiently mixed, bar shaped it is extruded into after stirring, after 110 DEG C of oven drying 12h and 550 DEG C of Muffle furnace roasting 6h, cool down and be broken into the granule of 20-40 order, finally prepare substrate catalyst.
With the phosphoric acid solution that 100ml concentration is 0.3mol/L at 60 DEG C to substrate catalyst acid treatment 10h, sucking filtration and with deionized water wash to filtrate in neutrality, then cool down standby after 110 DEG C of dry 10h and 550 DEG C of roasting 4h.
Etherificate evaluation response condition: methanol/iso-amylene mol ratio is 0.8, reaction temperature is 70 DEG C, and reaction pressure is 3MPa, and volume space velocity is 1h-1��
Embodiment 2
Substrate catalyst preparation method is identical with embodiment 1, and the difference is that it is carried out acid treatment by the phosphoric acid solution using 0.4mol/L instead, as described in Example 1, etherification activity appreciation condition is also as described in Example 1 for step.
Embodiment 3
Substrate catalyst preparation method is identical with embodiment 1, and the difference is that it is carried out acid treatment by the phosphoric acid solution using 0.5mol/L instead, as described in Example 1, etherification activity appreciation condition is also as described in Example 1 for step.
Embodiment 4
Substrate catalyst preparation method is identical with embodiment 1, and the difference is that it is carried out acid treatment by the phosphoric acid solution using 0.6mol/L instead, as described in Example 1, etherification activity appreciation condition is also as described in Example 1 for step.
Embodiment 5
Substrate catalyst preparation method is identical with embodiment 1, and the difference is that it is carried out acid treatment by the phosphoric acid solution using 0.7mol/L instead, as described in Example 1, etherification activity appreciation condition is also as described in Example 1 for step.
Embodiment 6
Substrate catalyst preparation method and embodiment 1 are identical, the difference is that using citric acid solution that 100ml concentration is 0.7mol/L instead at 80 DEG C to its acid treatment 8h, and then sucking filtration standby with cooling down after deionized water wash, dry, roasting. Etherification activity appreciation condition is also as described in Example 1.
Embodiment 7
Substrate catalyst preparation method is identical with embodiment 1, and it as described in Example 6, is carried out acid treatment the difference is that using 0.9mol/L citric acid solution instead by other steps, and etherification activity appreciation condition is as described in Example 1.
Embodiment 8
Substrate catalyst preparation method is identical with embodiment 1, and it as described in Example 6, is carried out acid treatment the difference is that using 1.1mol/L citric acid solution instead by other steps, and etherification activity appreciation condition is as described in Example 1.
Embodiment 9
Substrate catalyst preparation method is identical with embodiment 1, and it as described in Example 6, is carried out acid treatment the difference is that using 1.3mol/L citric acid solution instead by other steps, and etherification activity appreciation condition is as described in Example 1.
Embodiment 10
Substrate catalyst preparation method is identical with embodiment 1, and it as described in Example 6, is carried out acid treatment the difference is that using 1.5mol/L citric acid solution instead by other steps, and etherification activity appreciation condition is as described in Example 1.
Embodiment 11
Substrate catalyst preparation method is identical with embodiment 1, the difference is that being respectively adopted phosphoric acid and citric acid solution, carrier is carried out acid treatment, first acid treatment is carried out with 0.5mol/L phosphoric acid solution, step is as described in Example 1, until washing, sucking filtration, dry and after roasting, continuing with 1.1mol/L citric acid solution, this step is identical with embodiment 6 again, then through washing, sucking filtration, dries and cools down standby after roasting. Etherification activity appreciation condition is as described in Example 1.
Embodiment 12
Substrate catalyst preparation method is identical with embodiment 1, other steps are similar with embodiment 11, the difference is that being respectively adopted citric acid and phosphoric acid solution, it is carried out acid treatment, first acid treatment is carried out with 1.1mol/L citric acid solution, until washing, sucking filtration, dry and after roasting, again with 0.5mol/L phosphoric acid solution acid treatment, finally prepare catalyst for etherification. Etherification activity appreciation condition is as described in Example 1.
Embodiment 13
Substrate catalyst preparation method and embodiment 1 are identical, the difference is that using 100% steam that flow is 0.4ml/min instead at temperature 400 DEG C to its hydrothermal treatment consists 2h, then standby after cooling. Etherification activity appreciation condition is: methanol/iso-amylene mol ratio is 1.0, and reaction temperature is 80 DEG C, and reaction pressure is 3MPa, and volume space velocity is 1h-1��
Embodiment 14
Substrate catalyst preparation method is identical with embodiment 1, described in other steps such as embodiment 13, at 500 DEG C, it is carried out hydrothermal treatment consists 2h the difference is that changing into, then cools down standby.Etherification activity appreciation condition is also identical with embodiment 13.
Embodiment 15
Substrate catalyst preparation method and embodiment 1 are identical, described in other steps such as embodiment 13, the difference is that at 400 DEG C to its hydrothermal treatment consists 3h, then cool down standby. Etherification activity appreciation condition is identical with embodiment 13.
Embodiment 16
Substrate catalyst preparation method and embodiment 1 are identical, described in other steps such as embodiment 13, the difference is that at 400 DEG C to its hydrothermal treatment consists 4h, then cool down standby. Etherification activity appreciation condition is identical with embodiment 13.
Embodiment 17
Substrate catalyst preparation method is identical with embodiment 1, then first as described in Example 3, with the phosphoric acid solution of 0.5mol/L, substrate catalyst is carried out acid treatment, after sucking filtration, washing, dry and roasting for another example described in embodiment 15, with 100% steam treatment 3h at 400 DEG C, standby after cooling. Etherification activity appreciation condition is: methanol/iso-amylene mol ratio is 1.0, and reaction temperature is 60 DEG C, and reaction pressure is 3MPa, and volume space velocity is 1h-1��
Embodiment 18
Substrate catalyst preparation method is identical with embodiment 1, other steps are similar to embodiment 17, the difference is that first at 400 DEG C, substrate catalyst being processed 3h with 100% steam, with the phosphoric acid solution of 0.5mol/L, it is carried out acid treatment again after cooling, until sucking filtration, washing, dry and cool down standby after roasting. Etherification activity appreciation condition is identical with embodiment 17.
Embodiment 19
Substrate catalyst preparation method is identical with embodiment 1, then first as described in Example 8, with the citric acid solution of 1.1mol/L, it is carried out acid treatment, after sucking filtration, washing, dry and roasting for another example described in embodiment 15, with 100% steam hydrothermal treatment consists 3h at 400 DEG C, standby after cooling. Etherification activity appreciation condition is identical with embodiment 17.
Embodiment 20
Substrate catalyst preparation method is identical with embodiment 1, other steps are similar to embodiment 19, the difference is that first with 100% steam at 400 DEG C to its hydrothermal treatment consists 3h, after cooling again with the citric acid solution of 1.1mol/L to its acid treatment, cool down standby after sucking filtration, washing, dry and roasting. Etherification activity appreciation condition is identical with embodiment 17.
In embodiment, each catalyst etherification activity evaluation result is as shown in table 1 below.
Catalyst etherification activity evaluation result in table 1 embodiment
Table 1 result shows, acid solution is adopted to process the modification mode with hydrothermal treatment consists compound, the catalyst with superior low-temperature etherification activity can be prepared under suitable operating condition, this catalyst can reach higher etherification activity at a lower reaction temperature, selectivity is high, by-product is few, has good stability.

Claims (8)

1. a preparation method with good low temperature etherification activity catalyst, its feature includes herein below: first with boehmite for binding agent, beta-molecular sieve is active component, sesbania powder is extrusion aid, three adds peptizer dust technology after sufficiently mixing, then obtains substrate catalyst after kneading, extrusion, dry and roasting; Then adopt the mode that acid solution processes with hydrothermal treatment consists compound that substrate catalyst is modified, finally prepare and namely there is highly active catalyst for etherification under low reaction temperatures.
2. in accordance with the method for claim 1, it is characterised in that described boehmite powder is mesothyrid or macroporous type, pore volume >=0.3cm3/ g, specific surface area is 100m2/g-400m2/ g; Molecular sieve is commercially available or homemade sodium form or Hydrogen beta-molecular sieve, and silica alumina ratio is 10-80, and specific surface area is 200m2/g-500m2/g��
3. in accordance with the method for claim 1, it is characterized in that the described 10wt%-70wt% that boehmite content is substrate catalyst quality, beta-molecular sieve content is the 30wt%-90wt% of substrate catalyst quality, sesbania powder content is the 1.0wt%-10.0wt% of substrate catalyst quality, and dilute nitric acid solution concentration is 0.1mol/L-1.0mol/L.
4. in accordance with the method for claim 1, it is characterized in that described acid solution processes and the composite modified approach of hydrothermal treatment consists, can be after first substrate catalyst being carried out acid treatment, carry out hydrothermal treatment consists again, or carry out acid treatment again after first it being carried out hydrothermal treatment consists.
5. in accordance with the method for claim 1, it is characterised in that described acid solution facture is one or both in selection hydrochloric acid, phosphoric acid, citric acid, and acid strength is 0.1mol/L-2.0mol/L, and acid treatment temperature is 20 DEG C-90 DEG C, and the process time is 1h-10h.
6. in accordance with the method for claim 1, it is characterized in that described hydrothermal treatment consists method is in homemade tubular heater, adopting 100% steam is 0.1mL/min-2.0mL/min at flow, and temperature is, under 100 DEG C of-700 DEG C of conditions, substrate catalyst is processed 1h-8h.
7. catalyst etherificate performance evaluation mainly completes in micro fixed-bed reactor, and raw material of etherification oil is to be formed by normal hexane, n-hexylene and iso-amylene 5: 3: 2 configurations in mass ratio, it is contacted with catalyst with methanol mixed and reacts.
8. in accordance with the method for claim 6, it is characterised in that etherification activity appreciation condition is: alfin mol ratio is 0.7-1.3, reaction temperature is 50 DEG C-110 DEG C, and reaction pressure is 1MPa-5MPa, and air speed is 0.6h-1-3.0h-1��
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Cited By (6)

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CN106831360A (en) * 2017-01-16 2017-06-13 南京师范大学 A kind of continuous process for preparing β naphthyl methyl ethers
CN109942383A (en) * 2017-12-21 2019-06-28 中国科学院大连化学物理研究所 A kind of method of mixed phenol methanol vapor phase etherificate production compound ether
EP3527550A1 (en) * 2018-02-14 2019-08-21 INDIAN OIL CORPORATION Ltd. Process for etherification of mixed olefinic light naphtha and simultaneous reduction of methanol in the product
CN112495427A (en) * 2020-11-24 2021-03-16 宏元(江门)化工科技有限公司 Hierarchical pore molecular sieve catalyst, preparation method and application thereof in synthesis of polymethoxy dimethyl ether
CN113617385A (en) * 2021-08-18 2021-11-09 天津长芦海晶集团有限公司 Preparation method of catalyst for olefin hydration reaction
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106831360A (en) * 2017-01-16 2017-06-13 南京师范大学 A kind of continuous process for preparing β naphthyl methyl ethers
CN106831360B (en) * 2017-01-16 2020-05-05 南京师范大学 Process method for continuously preparing β -naphthyl methyl ether
CN109942383A (en) * 2017-12-21 2019-06-28 中国科学院大连化学物理研究所 A kind of method of mixed phenol methanol vapor phase etherificate production compound ether
CN109942383B (en) * 2017-12-21 2020-10-30 中国科学院大连化学物理研究所 Method for producing mixed ether by gas phase etherification of mixed phenol methanol
EP3527550A1 (en) * 2018-02-14 2019-08-21 INDIAN OIL CORPORATION Ltd. Process for etherification of mixed olefinic light naphtha and simultaneous reduction of methanol in the product
CN112495427A (en) * 2020-11-24 2021-03-16 宏元(江门)化工科技有限公司 Hierarchical pore molecular sieve catalyst, preparation method and application thereof in synthesis of polymethoxy dimethyl ether
CN112495427B (en) * 2020-11-24 2023-07-28 宏元(广东)高新材料科技有限公司 Hierarchical pore molecular sieve catalyst, preparation method and application thereof in polymethoxy dimethyl ether synthesis
CN114762832A (en) * 2021-01-12 2022-07-19 洛阳市科创石化科技开发有限公司 Preparation method and application of catalyst for producing mixed propylbenzene by alkylation of benzene and carbon tetraenes
CN114762832B (en) * 2021-01-12 2023-12-08 洛阳市科创石化科技开发有限公司 Preparation method and application of catalyst for producing mixed propylbenzene by alkylation of benzene and carbon tetraolefin
CN113617385A (en) * 2021-08-18 2021-11-09 天津长芦海晶集团有限公司 Preparation method of catalyst for olefin hydration reaction

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