CN107955639A - The method of six alkane cracking of carbon - Google Patents

The method of six alkane cracking of carbon Download PDF

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Publication number
CN107955639A
CN107955639A CN201610898329.3A CN201610898329A CN107955639A CN 107955639 A CN107955639 A CN 107955639A CN 201610898329 A CN201610898329 A CN 201610898329A CN 107955639 A CN107955639 A CN 107955639A
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zsm
mercerising
carbon
small
alkane
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CN107955639B (en
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黄政
金国杰
高焕新
杨洪云
刘远林
汪超
丁琳
康陈军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—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
    • 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
    • B01J29/80—Mixtures of different zeolites
    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • 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
    • B01J29/7034—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1081—Alkanes

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

Abstract

The present invention relates to a kind of method of six alkane cracking of carbon, mainly solving the technical problems that there are catalytic activity is low and the shortcomings that stability is poor in the reaction of six alkane cracking of prior art carbon.It is of the invention to be as catalyst, catalytic reaction condition by using ZSM 12 (MTW) and modenite (MOR) symbiosis composite material：Using six alkane of carbon as raw material, reaction temperature is at 270~550 DEG C, and reaction pressure is in 0.01~1MPa, raw material crystalline zeolite catalyst haptoreaction together.Catalyst wherein used is in terms of ratio of weight and number including following components：A) 30~100 parts of silica alumina ratio Si/Al are less than 100 12 symbiosis composite molecular screen materials of mercerising/ZSM, and 12 molecular sieve ratios of ZSM are 10~50%；B) 0~70 part of binding agent, the technical solution preferably solve the problems, such as this, available in the industrial production of low-carbon alkene.

Description

The method of six alkane cracking of carbon
Technical field
The present invention relates to a kind of method for six alkane cracking of carbon.
Background technology
Current petro chemical industry has been developed as promoting one of emphasis pillar industry of development of all countries economy, and conduct Mostly important basic material --- the low-carbon alkene of the core and petrochemical industry of petrochemical industry：Ethene, propylene, its yield it is more Have become a national oil chemical industry and " barometer " of the level of economic development less.In petroleum refining industry, such as it is catalyzed The operating process such as cracking have been commercialized the main path for synthesizing light alkene from hydrocarbon-bearing material.
Since the 1960s, molecular sieve is used as catalytic cracking catalyst, since its own heat endurance is good, The characteristics of catalytic activity and high selectivity, is thus widely used in catalytic cracking reaction.It is common have A types, X-type, The zeolite molecular sieve of the single structures such as Y types, M types and ZSM types.With the continuous improvement of the quality requirement to chemical products, to boiling The catalytic performance of stone molecular sieve it is also proposed the requirement of higher.
CN102373069A discloses a kind of method for six alkane cracking of carbon, is answered using ZSM-5 and mordenite coexisting Condensation material is catalyst, but ZSM-5 is MFI, is that ten-ring is formed, and modenite is MOR, is that twelve-ring is formed, therefore ZSM-5/MOR has the composite construction that less stable is between ten-ring and twelve-ring, causes it to be used for six alkane of carbon and splits There is the problem of activity is low, stability is poor in solution reaction.
The content of the invention
The present invention relates to a kind of method for six alkane cracking of carbon, mainly solving the technical problems that prior art carbon six Alkane cracking catalytic reaction activity is low, stability is poor.The present invention provides a kind of side of six alkane cracking of carbon by mercerising/ZSM-12 Method, uses mercerising/ZSM-12 symbiosis composite molecular screen as catalyst, and the mercerising/ZSM-12 composite molecular screens have preferably steady Qualitative and catalytic activity.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of method of six alkane cracking of carbon, with Six alkane of carbon is raw material, and raw material generates the hydrocarbon of C1~C5 with catalyst haptoreaction, wherein catalyst used is with parts by weight Meter includes following components：
A) mercerising/ZSM-12 symbiosis composite molecular screens of 30~100 parts of silica alumina ratio Si/Al between 10~100；Its Middle ZSM-12 molecular sieves ratio is 10~50%；
B) 0~70 part of binding agent.
In above-mentioned technical proposal, it is preferable that carbon six alkane is included selected from n-hexane, 3- methylpentanes, 2- methylpentanes It is at least one；More preferably, n-hexane and 3- methylpentanes, ratio 1：1.
In above-mentioned technical proposal, reaction temperature preferred scope is 250~600 DEG C, and more preferably scope is 270~500 DEG C.Instead It is 0.1~1MPa to answer pressure preferred scope, and more preferably scope is 0.1~0.5MPa.Liquid phase air speed preferred scope is small for 0.01~3 When-1, when more preferably scope is 0.1~1 small-1。
In above-mentioned technical proposal, the dosages of mercerising/ZSM-12 molecular sieves is counted as 40~90 parts using hundred number of weight, preferably Ground, using the binder free mercerising without binding agent/ZSM-12 symbiosis composite molecular screens, the mechanical strength of the molecular sieve is up to 40 Ox.
In above-mentioned technical proposal, the binding agent is selected from aluminium oxide or silica.
In above-mentioned technical proposal, it is preferable that the silica alumina ratio Si/ of the mercerising/ZSM-12 symbiosis composite molecular screens Between Al is 20~80.
In above-mentioned technical proposal, the ZSM-12 part by weight of the mercerising/ZSM-12 symbiosis composite zeolites for 15~ 40%.
The preparation method of mercerising/ZSM-12 symbiosis composite molecular screens is as follows in the present invention：First by silicon source, silicon source, template Agent R and water composition mixture, mixture molar ratio composition are：Si/Al=37.5~50；H2O/SiO2=15~30；R/SiO2= 0.1~0.5；Template R is the mixture of tetraethyl ammonium hydroxide and etamon chloride, adds alkali source, is initially formed ZSM- 12 synthetic reaction system, is subsequently added into modenite, continues to be stirred until homogeneous, when 120~200 DEG C of crystallization 20~120 are small Crystallized product, washed dry the mercerising/ZSM-12 symbiosis composite molecular screens of crystallized product.The alkali source can be hydroxide Sodium, ammonium hydroxide etc..
The preparation method of catalyst is as follows in the present invention：First by the MOR/MTW symbiosis composite molecular screen and active oxygen of synthesis Change aluminium mixing, add binding agent and carry out kneading, shaping, drying, roasting, catalyst precarsor is made, then with ammonium salt solution to wherein Sodium ion swap, last drying, calcination activation, up to finished catalyst.
The present invention uses mercerising/ZSM-12 symbiosis composite molecular sieve catalysts, and ZSM-12 is MTW, is that twelve-ring is formed, Modenite is MOR, is that twelve-ring is formed, mercerising/ZSM-12 has the composite construction of stable twelve-ring, utilizes two kinds Structure interaction that may be present, at the same regulate and control mercerising/ZSM-12 symbiosis composite molecular sieve catalysts silica alumina ratio and mercerising/ The part by weight of MOR and MTW in ZSM-12 symbiosis composite molecular sieve catalysts so that the catalytic activity of reaction is than mechanical mixture It is at least high by 10%, meanwhile, reaction evaluating is basically unchanged when 400 is small, and stability is good, achieves preferable technique effect.
Below by example further instruction is given to the present invention.
Embodiment
Embodiment 1：
The preparation method of mercerising/ZSM-12 molecular sieves：
The first step, 35.22 grams of waterglass, 1.1 grams of sodium hydroxide, 6.45 grams of Solid aluminum sulfate are mixed with 141 grams of distilled water Close, then add ammonium hydroxide and (contain NH325.5wt%) 10 grams, it is uniformly mixed, is put into reaction kettle, when 180 DEG C of crystallization 48 are small, crystallization After be cooled to room temperature, by filter washing, place into baking oven in 100 DEG C it is dry 3~4 it is small when, obtain modenite original powder.
Second step, takes Ludox (wt40%) 25.6g, sodium metaaluminate 0.25g, sodium hydroxide 1g, deionized water 40g, 30wt% tetraethylammonium bromides 9.5g, 30wt% tetraethyl ammonium hydroxide 3.9g, 30wt% etamon chloride 3.25g is mixed, It is stirred at room temperature uniformly.PH to 13 is adjusted with 10% sodium hydrate aqueous solution, when standing 6 is small.Then first step synthesis is added 9 grams of modenite crystal seed, be put into after being sufficiently stirred in reaction kettle, it is dry in 100 DEG C in baking oven when 160 DEG C of crystallization 72 are small It is dry 3~4 it is small when, obtain symbiosis composite molecular screen original powder.When then crystallization 72 is small at 180 DEG C.Obtained milky slurries are spent Ion is washed 5 times, when then vacuum drying 12 is small.Obtain symbiosis composite molecular screen original powder.
36 grams of the co-crystalline zeolite of synthesis is mixed with 24 grams of aluminium oxide, mixed powder and dust technology (0.5 weight Measure %) press 80：20 weight ratio carries out kneading, shaping, drying.After when 550 DEG C of roastings 6 are small in atmosphere, up to institute of the present invention The catalyst precarsor stated.
Manufactured catalyst precarsor carries out 3 secondary ion exchanges with the ammonium nitrate solution of 10wt%, every time at 90 DEG C, lasts 3 Hour, sodium content is less than 50ppm after processing.Catalyst precarsor after above-mentioned ammonium is exchanged filters, is dry at room temperature, in air In when activation 4 is small at a temperature of 550 DEG C, be cooled to room temperature up to catalyst of the present invention.
Mercerising/ZSM-12 molecular sieve catalysts (Si/ that 1 gram of content is 60% is added in 10 milliliters of fixed bed reactors For Al molar ratios for 20) (MTW part by weight is 30%), 40% is alumina binder, and granular size is 20-40 mesh, reaction is former Material is with molar ratio 1：1 n-hexane and 3- methylpentanes, LHSV 0.5h-1, N2Molar ratio with reactant is 4:1, in normal pressure After lower 280 DEG C of reaction half an hour, the online gas chromatographic analysis of product.Hexane conversion rate is 45.43%, 3- methylpentanes Conversion ratio is 6.35%, and reaction evaluating has no conversion ratio reduction when 400 is small.
Embodiment 2：
The preparation method of mercerising/ZSM-12 molecular sieves：
The first step, 35.22 grams of waterglass, 1.1 grams of sodium hydroxide, 6.45 grams of Solid aluminum sulfate are mixed with 141 grams of distilled water Close, then add ammonium hydroxide and (contain NH325.5wt%) 10 grams, it is uniformly mixed, is put into reaction kettle, when 180 DEG C of crystallization 48 are small, crystallization After be cooled to room temperature, by filter washing, place into baking oven in 100 DEG C it is dry 3~4 it is small when, obtain modenite original powder.
Second step, takes Ludox (wt40%) 25.6g, sodium metaaluminate 0.25g, sodium hydroxide 1g, deionized water 40g, 30wt% tetraethylammonium bromides 9.5g, 30wt% tetraethyl ammonium hydroxide 3.9g, 30wt% etamon chloride 3.25g is mixed, It is stirred at room temperature uniformly.PH to 13 is adjusted with 10% sodium hydrate aqueous solution, when standing 6 is small.Then first step synthesis is added 12 grams of modenite crystal seed, be put into after being sufficiently stirred in reaction kettle, it is dry in 100 DEG C in baking oven when 160 DEG C of crystallization 72 are small It is dry 3~4 it is small when, obtain symbiosis composite molecular screen original powder.When then crystallization 72 is small at 180 DEG C.Obtained milky slurries are spent Ion is washed 5 times, when then vacuum drying 12 is small.Obtain symbiosis composite molecular screen original powder.
24 grams of the co-crystalline zeolite of synthesis is mixed with 36 grams of aluminium oxide, mixed powder and dust technology (0.5 weight Measure %) press 80：20 weight ratio carries out kneading, shaping, drying.After when 550 DEG C of roastings 6 are small in atmosphere, up to institute of the present invention The catalyst precarsor stated.
Manufactured catalyst precarsor carries out 3 secondary ion exchanges with the ammonium nitrate solution of 10wt%, every time at 90 DEG C, lasts 3 Hour, sodium content is less than 50ppm after processing.Catalyst precarsor after above-mentioned ammonium is exchanged filters, is dry at room temperature, in air In when activation 4 is small at a temperature of 550 DEG C, be cooled to room temperature up to catalyst of the present invention.
Mercerising/ZSM-12 molecular sieve catalysts (Si/ that 1 gram of content is 40% is added in 10 milliliters of fixed bed reactors For Al molar ratios for 40) (MTW part by weight is 15%), 60% is alumina binder, and granular size is 20-40 mesh, reaction is former Material is with molar ratio 1：1 n-hexane and 3- methylpentanes, LHSV 0.5h-1, N2Molar ratio with reactant is 4:1, in normal pressure After lower 300 DEG C of reaction half an hour, the online gas chromatographic analysis of product.Hexane conversion rate is 62.77%, 3- methylpentanes Conversion ratio is 9.80%.Reaction evaluating has no conversion ratio reduction when 400 is small.
Embodiment 3：
The preparation method of mercerising/ZSM-12 molecular sieves：
The first step, 35.22 grams of waterglass, 1.1 grams of sodium hydroxide, 6.45 grams of Solid aluminum sulfate are mixed with 141 grams of distilled water Close, then add ammonium hydroxide and (contain NH325.5wt%) 10 grams, it is uniformly mixed, is put into reaction kettle, when 180 DEG C of crystallization 48 are small, crystallization After be cooled to room temperature, by filter washing, place into baking oven in 100 DEG C it is dry 3~4 it is small when, obtain modenite original powder.
Second step, takes Ludox (wt40%) 25.6g, sodium metaaluminate 0.25g, sodium hydroxide 1g, deionized water 40g, 30wt% tetraethylammonium bromides 9.5g, 30wt% tetraethyl ammonium hydroxide 3.9g, 30wt% etamon chloride 3.25g is mixed, It is stirred at room temperature uniformly.PH to 13 is adjusted with 10% sodium hydrate aqueous solution, when standing 6 is small.Then first step synthesis is added 8 grams of modenite crystal seed, be put into after being sufficiently stirred in reaction kettle, it is dry in 100 DEG C in baking oven when 160 DEG C of crystallization 72 are small It is dry 3~4 it is small when, obtain symbiosis composite molecular screen original powder.When then crystallization 72 is small at 180 DEG C.Obtained milky slurries are spent Ion is washed 5 times, when then vacuum drying 12 is small.Obtain symbiosis composite molecular screen original powder.
54 grams of the co-crystalline zeolite of synthesis is mixed with 6 grams of aluminium oxide, mixed powder and dust technology (0.5 weight %) By 80：20 weight ratio carries out kneading, shaping, drying.After when 550 DEG C of roastings 6 are small in atmosphere, urged up to of the present invention Agent precursor.
Manufactured catalyst precarsor carries out 3 secondary ion exchanges with the ammonium nitrate solution of 10wt%, every time at 90 DEG C, lasts 3 Hour, sodium content is less than 50ppm after processing.Catalyst precarsor after above-mentioned ammonium is exchanged filters, is dry at room temperature, in air In when activation 4 is small at a temperature of 550 DEG C, be cooled to room temperature up to catalyst of the present invention.
It is 90% mercerising/ZSM-12 molecular sieve catalysts (Si/Al that 1 gram of content is added in 10 milliliters of fixed bed reactors Molar ratio is that 30) (MTW part by weight be 40%), 10% is silica binder, and granular size is 20-40 mesh, reaction raw materials With molar ratio 1：1 n-hexane and 3- methylpentanes, LHSV 0.5h-1, N2Molar ratio with reactant is 4:1, under normal pressure After 350 DEG C of reaction half an hour, the online gas chromatographic analysis of product.Hexane conversion rate turns for 48.07%, 3- methylpentanes Rate is 19.64%.Reaction evaluating has no conversion ratio reduction when 400 is small.
Embodiment 4：
The preparation method of mercerising/ZSM-12 molecular sieves：
The first step, 35.22 grams of waterglass, 1.1 grams of sodium hydroxide, 6.45 grams of Solid aluminum sulfate are mixed with 141 grams of distilled water Close, then add ammonium hydroxide and (contain NH325.5wt%) 10 grams, it is uniformly mixed, is put into reaction kettle, when 180 DEG C of crystallization 48 are small, crystallization After be cooled to room temperature, by filter washing, place into baking oven in 100 DEG C it is dry 3~4 it is small when, obtain modenite original powder.
Second step, takes Ludox (wt40%) 25.6g, sodium metaaluminate 0.25g, sodium hydroxide 1g, deionized water 40g, 30wt% tetraethylammonium bromides 9.5g, 30wt% tetraethyl ammonium hydroxide 3.9g, 30wt% etamon chloride 3.25g is mixed, It is stirred at room temperature uniformly.PH to 13 is adjusted with 10% sodium hydrate aqueous solution, when standing 6 is small.Then first step synthesis is added 12 grams of modenite crystal seed, be put into after being sufficiently stirred in reaction kettle, it is dry in 100 DEG C in baking oven when 160 DEG C of crystallization 72 are small It is dry 3~4 it is small when, obtain symbiosis composite molecular screen original powder.When then crystallization 72 is small at 180 DEG C.Obtained milky slurries are spent Ion is washed 5 times, when then vacuum drying 12 is small.Obtain symbiosis composite molecular screen original powder.
30 grams of the co-crystalline zeolite of synthesis is mixed with 30 grams of aluminium oxide, mixed powder and dust technology (0.5 weight Measure %) press 80：20 weight ratio carries out kneading, shaping, drying.After when 550 DEG C of roastings 6 are small in atmosphere, up to institute of the present invention The catalyst precarsor stated.
Manufactured catalyst precarsor carries out 3 secondary ion exchanges with the ammonium nitrate solution of 10wt%, every time at 90 DEG C, lasts 3 Hour, sodium content is less than 50ppm after processing.Catalyst precarsor after above-mentioned ammonium is exchanged filters, is dry at room temperature, in air In when activation 4 is small at a temperature of 550 DEG C, be cooled to room temperature up to catalyst of the present invention.
It is 50% mercerising/ZSM-12 molecular sieve catalysts (Si/Al that 1 gram of content is added in 10 milliliters of fixed bed reactors Molar ratio is that 80) (MTW part by weight be 15%), 50% is alumina binder, and grain size is 20-40 mesh, reaction raw materials with Molar ratio 1：1 n-hexane and 3- methylpentanes, LHSV 1h-1, N2Molar ratio with reactant is 4:1,400 DEG C under normal pressure After reacting half an hour, the online gas chromatographic analysis of product.Hexane conversion rate is 95.33%, 3- methylpentane conversion ratios For 35.23%.Reaction evaluating has no conversion ratio reduction when 400 is small.
Embodiment 5：
The preparation method of mercerising/ZSM-12 molecular sieves：
The first step, 35.22 grams of waterglass, 1.1 grams of sodium hydroxide, 6.45 grams of Solid aluminum sulfate are mixed with 141 grams of distilled water Close, then add ammonium hydroxide and (contain NH325.5wt%) 10 grams, it is uniformly mixed, is put into reaction kettle, when 180 DEG C of crystallization 48 are small, crystallization After be cooled to room temperature, by filter washing, place into baking oven in 100 DEG C it is dry 3~4 it is small when, obtain modenite original powder.
Second step, takes Ludox (wt40%) 25.6g, sodium metaaluminate 0.25g, sodium hydroxide 1g, deionized water 40g, 30wt% tetraethylammonium bromides 9.5g, 30wt% tetraethyl ammonium hydroxide 3.9g, 30wt% etamon chloride 3.25g is mixed, It is stirred at room temperature uniformly.PH to 13 is adjusted with 10% sodium hydrate aqueous solution, when standing 6 is small.Then first step synthesis is added 9 grams of modenite crystal seed, be put into after being sufficiently stirred in reaction kettle, it is dry in 100 DEG C in baking oven when 160 DEG C of crystallization 72 are small It is dry 3~4 it is small when, obtain symbiosis composite molecular screen original powder.When then crystallization 72 is small at 180 DEG C.Obtained milky slurries are spent Ion is washed 5 times, when then vacuum drying 12 is small.Obtain symbiosis composite molecular screen original powder.
30 grams of the co-crystalline zeolite of synthesis is mixed with 30 grams of aluminium oxide, mixed powder and dust technology (0.5 weight Measure %) press 80：20 weight ratio carries out kneading, shaping, drying.After when 550 DEG C of roastings 6 are small in atmosphere, up to institute of the present invention The catalyst precarsor stated.
Manufactured catalyst precarsor carries out 3 secondary ion exchanges with the ammonium nitrate solution of 10wt%, every time at 90 DEG C, lasts 3 Hour, sodium content is less than 50ppm after processing.Catalyst precarsor after above-mentioned ammonium is exchanged filters, is dry at room temperature, in air In when activation 4 is small at a temperature of 550 DEG C, be cooled to room temperature up to catalyst of the present invention.
Mercerising/ZSM-12 molecular sieve catalysts (Si/ that 1 gram of content is 50% is added in 10 milliliters of fixed bed reactors For Al molar ratios for 35) (MTW part by weight is 30%), 50% is silica binder, and granular size is 20-40 mesh, reaction is former Material is with molar ratio 1：1 n-hexane and 3- methylpentanes, LHSV 0.1h-1, N2Molar ratio with reactant is 4:1, in 0.5MP After pressure lower 270 DEG C of reaction half an hour, the online gas chromatographic analysis of product.Hexane conversion rate is 82.29%, 3- methyl Conversion of pentane rate is 16.44%.Reaction evaluating has no conversion ratio reduction when 400 is small.
Embodiment 6：
The preparation method of mercerising/ZSM-12 molecular sieves：
The first step, 35.22 grams of waterglass, 1.1 grams of sodium hydroxide, 6.45 grams of Solid aluminum sulfate are mixed with 141 grams of distilled water Close, then add ammonium hydroxide and (contain NH325.5wt%) 10 grams, it is uniformly mixed, is put into reaction kettle, when 180 DEG C of crystallization 48 are small, crystallization After be cooled to room temperature, by filter washing, place into baking oven in 100 DEG C it is dry 3~4 it is small when, obtain modenite original powder.
Second step, takes Ludox (wt40%) 25.6g, sodium metaaluminate 0.25g, sodium hydroxide 1g, deionized water 40g, 30wt% tetraethylammonium bromides 9.5g, 30wt% tetraethyl ammonium hydroxide 3.9g, 30wt% etamon chloride 3.25g is mixed, It is stirred at room temperature uniformly.PH to 13 is adjusted with 10% sodium hydrate aqueous solution, when standing 6 is small.Then first step synthesis is added 8.5 grams of modenite crystal seed, be put into after being sufficiently stirred in reaction kettle, when 160 DEG C of crystallization 72 are small, in 100 DEG C in baking oven When drying 3~4 is small, symbiosis composite molecular screen original powder is obtained.When then crystallization 72 is small at 180 DEG C.Obtained milky slurries are used Deionization is washed 5 times, when then vacuum drying 12 is small.Obtain symbiosis composite molecular screen original powder.
After when by the co-crystalline zeolite of synthesis, 550 DEG C of roastings 6 are small in atmosphere, up to before catalyst of the present invention Body.
Manufactured catalyst precarsor carries out 3 secondary ion exchanges with the ammonium nitrate solution of 10wt%, every time at 90 DEG C, lasts 3 Hour, sodium content is less than 50ppm after processing.Catalyst precarsor after above-mentioned ammonium is exchanged filters, is dry at room temperature, in air In when activation 4 is small at a temperature of 550 DEG C, be cooled to room temperature up to catalyst of the present invention.
Mercerising/ZSM-12 molecular sieve catalysts (Si/ that 1 gram of content is 100% is added in 10 milliliters of fixed bed reactors Al molar ratios is 35) (MTW part by weight is 20%), binder free, granular size are 20-40 mesh, and reaction raw materials are with molar ratio 1：1 n-hexane and 3- methylpentanes, LHSV 0.1h-1, N2Molar ratio with reactant is 4:1,270 under 0.5MP pressure DEG C reaction half an hour after, the online gas chromatographic analysis of product.Hexane conversion rate converts for 84.25%, 3- methylpentanes Rate is 17.03%.Reaction evaluating has no conversion ratio reduction when 400 is small.
Comparative example 1：
It is (1 that 2 grams of mechanical mixture MOR are added in 10 milliliters of fixed bed reactors with MTW mass ratioes：4) molecular sieve is urged Agent, granular size are 20-40 mesh, and reaction raw materials are with molar ratio 1：1 n-hexane and 3- methylpentanes, LHSV 0.5h-1, N2 Molar ratio with reactant is 4:1, under normal pressure after 300 DEG C of reaction half an hour, the online gas chromatographic analysis of product.Just oneself Alkane conversion ratio is that 15.57%, 3- methylpentanes conversion ratio is 8.36%.When 150 is small, conversion ratio begins to reduce reaction evaluating .
Comparative example 2：
1 gram of mercerising molecular sieve catalyst is added in 10 milliliters of fixed bed reactors, granular size is 20-40 mesh, reaction Raw material is with molar ratio 1：1 n-hexane and 3- methylpentanes, LHSV 0.5h-1, N2Molar ratio with reactant is 4:1, normal After 300 DEG C of reaction half an hour of pressure, the online gas chromatographic analysis of product.Hexane conversion rate is 11.78%, 3- methylpents Alkane conversion ratio is 12.54%.When 100 is small, conversion ratio begins to reduce reaction evaluating.
Comparative example 3：
1 gram of ZSM-12 molecular sieve catalyst is added in 10 milliliters of fixed bed reactors, granular size is 20-40 mesh, instead Raw material is answered with molar ratio 1：1 n-hexane and 3- methylpentanes, LHSV 0.5h-1, N2Molar ratio with reactant is 4:1, After normal pressure lower 300 DEG C of reaction half an hour, the online gas chromatographic analysis of product.Hexane conversion rate is 21.38%, 3- methyl Conversion of pentane rate is 7.63%.Reaction evaluating has no conversion ratio reduction when 300 is small.
Comparative example 4：
1 gram of ZSM-5/ mercerisings (MOR) molecular sieve catalyst is added in 10 milliliters of fixed bed reactors, granular size is 20-40 mesh, reaction raw materials are with molar ratio 1：1 n-hexane and 3- methylpentanes, LHSV 0.5h-1, N2With mole of reactant Than for 4:1, under normal pressure after 300 DEG C of reaction half an hour, the online gas chromatographic analysis of product.Hexane conversion rate is 82.29%, 3- methylpentane conversion ratio are 16.44%.When 350 is small, conversion ratio starts to reduce reaction evaluating.
The method of six alkane cracking of carbon of the present invention, mercerising/ZSM-12 molecular sieve catalysts are shown in the reaction The advantages of catalytic activity is high, and stability is good.

Claims (10)

1. a kind of method of six alkane cracking of carbon, using six alkane of carbon as raw material, raw material and catalyst haptoreaction generation C1~C5 Hydrocarbon, wherein catalyst used in terms of parts by weight including following components：
A) mercerising/ZSM-12 symbiosis composite molecular screens of 30~100 parts of silica alumina ratio Si/Al between 10~100；Wherein ZSM-12 molecular sieves ratio is 10~50%；
B) 0~70 part of binding agent.
2. the method for six alkane cracking of carbon according to claim 1, it is characterised in that six paraffinic feedstock of carbon connects with catalyst Tactile reaction condition is：250~600 DEG C, 0.1~1MPa of reaction pressure of reaction temperature, when liquid phase air speed 0.01~3 is small-1。
3. the method for six alkane cracking of carbon according to claim 1, it is characterised in that reaction temperature is 270~400 DEG C.
4. the method for six alkane cracking of carbon according to claim 1, it is characterised in that reaction pressure is 0.1~0.5MPa.
5. the method for six alkane cracking of carbon according to claim 1, it is characterised in that when phase air speed is 0.1~1 small-1。
6. the method for six alkane cracking of carbon according to claims 1, it is characterised in that the binding agent is selected from oxidation Aluminium or silica.
7. the method for six alkane cracking of carbon according to claims 1, it is characterised in that the mercerising/ZSM-12 symbiosis Between the silica alumina ratio Si/Al of composite molecular screen is 20~80；MTW molecular sieves liquid is ZSM-12 molecular sieves.
8. the method for six alkane cracking of carbon according to claims 1, it is characterised in that the mercerising/ZSM-12 symbiosis The ZSM-12 part by weight of composite zeolite is 15~40%.
9. the method for six alkane cracking of carbon according to claim 1, it is characterised in that mercerising/ZSM-12 in terms of parts by weight The dosage of molecular sieve is 40~90 parts, or using binder free mercerising/ZSM-12 symbiosis composite molecular screens without binding agent.
10. the method for six alkane cracking of carbon according to claim 1, it is characterised in that the mercerising/ZSM-12 symbiosis is answered The preparation method for closing molecular sieve is as follows：First by silicon source, silicon source, template R and water composition mixture, mixture molar ratio composition For：Si/Al=37.5~50；H2O/SiO2=15~30；R/SiO2=0.1~0.5；Template R for tetraethyl ammonium hydroxide with The mixture of etamon chloride, adds alkali source (such as sodium hydroxide, ammonium hydroxide etc.), is initially formed the synthetic reaction body of ZSM-12 System, is subsequently added into modenite, continues to be stirred until homogeneous, crystallized product is obtained when 120~200 DEG C of crystallization 20~120 are small, crystallizes Washed dry the mercerising/ZSM-12 symbiosis composite molecular screens of product.
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CN110479360A (en) * 2019-08-20 2019-11-22 南昌大学 The modified eutectic of structure containing MTW catalyst of transition metal element and its preparation method and application
CN113880110A (en) * 2021-10-25 2022-01-04 南昌大学 Nanometer hierarchical pore MOR/MTW eutectic molecular sieve and preparation method and application thereof

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CN110451519A (en) * 2019-08-20 2019-11-15 南昌大学 A kind of eutectic material and preparation method thereof containing MTW structure
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