CN109701607A - Skeletal isomerisation catalyst, preparation method and applications - Google Patents
Skeletal isomerisation catalyst, preparation method and applications Download PDFInfo
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Abstract
The present invention relates to a kind of straight-chain olefin skeleton isomerization catalyst, preparation method and its application in straight-chain olefin skeleton isomerization, the problems such as binder content is high, skeletal isomerization activity is low, initial reaction stage isomerization target product selectivity is low, target product selectivity " climbing the phase " is long, single pass life is short is mainly solved in preformed catalyst existing in the prior art.Low binder, high activity and highly selective skeletal isomerisation catalyst is prepared in the method for preformed catalyst of the present invention by using hydro-thermal process containing binder；A kind of preparation method of new skeletal isomerisation catalyst is provided, this method has many advantages, such as that preparation process is simple, is suitable for industrial production.The technical solution preferably solves the problems, such as this, can be used for straight-chain olefin skeleton isomerization and prepares in the industrial production of isomeric olefine.
Description
Technical field
The present invention relates to skeletal isomerisation catalyst and applied technical field more particularly to a kind of binder free shaped catalysts
The preparation method and application of agent.
Background technique
The a large amount of C 4 olefins of MTO/CTO device by-product of commercial refineries device, ethylene unit and country's rise in recent years.Carbon
Main component of the alkatetraenes after Butadiene Extraction is isobutene and n-butene.Isobutene is that the important set of C 4 olefin divides it
One, it is widely used in synthesizing methyl tertbutyl ether (MTBE), butyl rubber, methyl methacrylate (MMA) and polyisobutene etc.
In the process.Converting isobutene by skeletal isomerization for the not high n-butene of application value in by-product mixing carbon four can be excellent
Change and utilize lighter hydrocarbons resource, petroleum chemical enterprise's economic benefit can be improved.Meanwhile refinery facilities, ethylene unit and MTO/CTO device
The a large amount of light dydrocarbons of meeting by-product and the above alkene of light dydrocarbon, linear alkene therein again may be by skeletal isomerization and be converted into isomery alkene
Hydrocarbon is used for synthesizing methyl tert-amyl ether (TAME), methyl- tert hexyl ether (MTHE), isoprene rubber, styrene-isoprene-benzene
Ethylene thermoplastic's elastomer (SIS) etc..The application value of the normal olefine of this part low value can be equally promoted, petrochemical industry is improved
The economic benefit of enterprise.
Straight-chain olefin skeleton isomerization catalyst has industrialization in 1970s, mainly using aluminium oxide and other
Unformed oxide, after gradually replaced by zeolite molecular sieve catalyst, such as sial ZSM type, phosphorus sial SAPO type.Nearly 30
The result of study in year shows the FER zeolite catalyst with ten-ring duct and special FER cage, is most suitable for for straight chain alkene
Hydrocarbon skeletal isomerizations reaction.Patent EP0055529, EP0501577, US5449851, US5510560, CN103301876, CN
The FER zeolite molecular sieve catalyst n-butene to FER zeolite and modification such as 103772112, CN103769204, CN104557402
The catalytic performance of isomerization, which is given, to be affirmed, excellent properties are mainly reflected in selective height, activity are good, the selective phase of climbing is short etc.
Feature.
CN103301876 is related to a kind of preparation method of straight-chain olefin skeleton isomerization catalyst, and specific synthesis step is
By the rare earth ZSM-35 molecular sieve of synthesis, handled 0.5~10 hour at 30~90 DEG C with aqueous slkali；Obtained product wash to
After neutrality, with binder extruded moulding, with ammonium nitrate solution exchange, filter, and be washed with deionized, dry, roast；Gained
Sample steam treatment 1~8 hour at 400~700 DEG C, is prepared isomerization catalyst.At buck prepared by the present invention
Manage modified ZSM-35 molecular sieve catalyst, compared with untreated ZSM-35 molecular sieve catalyst, reaction stability
It is significantly improved.
CN 103772112 is related to a kind of method of n-butene skeletal isomerization preparing isobutene, with SiO2/Al2O3Molar ratio is
10~50 sodium potassium Hydrogen FER molecular sieve is catalyst, and the raw material containing n-butene is 300~600 DEG C in reaction temperature, and reaction is total
Pressure is 0~0.25MPa, and weight space velocity is 0.5~20h-1Under conditions of occur skeletal isomerization reaction generate isobutene.The sodium potassium
In Hydrogen FER molecular sieve, by weight percentage, Na2O content is 0.1%~0.5%, K2O content is 4.0%~6.3%.It should
Method has many advantages, such as that initial selective isobutene is high, and there is no significant selectivity " climbing the phase ".
CN103769204 is related to a kind of n-butene skeletal isomerization preparing isobutene catalyst, by after boric acid impregnation
Modified full potassium type FER molecular sieve and binder form, and in final catalyst, the weight content of modified full potassium type FER molecular sieve is
10~90%.A kind of preparation method of n-butene skeletal isomerization preparing isobutene catalyst: full potassium type FER molecular sieve is impregnated through boric acid
It is mixed after modification with binder and water, gained mixture is formed, re-dry, roasting obtain final catalyst.This method
The n-butene skeletal isomerization preparing isobutene catalyst of preparation has higher initial selective isobutene and yield.
CN104557402 is related to a kind of method of n-butene skeletal isomerization production isobutene, a) will include the following steps:
The FER type molecular sieve catalyst that Si/Al molar ratio is 50~100 is packed into reactor, is warming up to 450 under atmosphere of inert gases
~550 DEG C；B) it is passed through the gaseous mixture A of the alkene for being at least 4~5 containing a kind of carbon atom number and inert gas composition；C) in inertia
It is warming up to 600~700 DEG C under atmosphere, is preferably warming up to 600~650 DEG C；D) be passed through at least containing a kind of carbon atom number be 2~
The gaseous mixture B of 3 alkene and inert gas composition；E) it is adjusted under atmosphere of inert gases to suitable isomerization reaction condition,
It is passed through raw material containing n-butene, carries out isomerization reaction.This method has initial isobutene yield height, and significantly shortening yield " climbs
The advantages of phase ".
But zeolite powder is undersized, there is the shortcomings that difficult recycling, easy in inactivation and aggregation in practical applications, thus need
It is used after binder molding is added.The introducing meeting of binder is so that effective surface area is reduced, and introduces diffusion limitation.Without viscous
It ties and is free of binder in the zeolite granular of agent zeolite molecular sieve or contains only a small amount of binder, have compared with high zeolite content,
Therefore with bigger effective using surface, thus there may be better catalytic performance.
Patent CN85104995 discloses a kind of method that binder free method prepares ferrierite Yu other zeolite complexs,
Use modenite, Y zeolite for substrate, with silica, alkali source and the molding of tetramethyl-ammonium compound, secondary crystallization obtain complex
Zeolite molecular sieve, but be not known and point out its purposes.
Patent CN1927714 disclose it is a kind of prepare ZSM-5 zeolite catalyst with binder free method, its essence is aoxidize
By crystallizing again the zeolite crystal of topological structure identical as substrate zeolite is made, for ZSM-5 zeolite, this side in silicon bonding
Method realizes industrial production.
The method that the present invention uses binder to crystallize under the conditions of hydrothermal crystallizing, is prepared the molding FER of binder free
Zeolite, the method prepare the catalytic activity that catalyst not only increases catalyst, further increase the selectivity of catalyst, especially
It significantly improves the selectivity of initial reaction stage isobutene.
Summary of the invention
The first technical problem to be solved by the present invention is that inert component binder content existing in the prior art is high, has
Effect component molecular sieve content is low, skeletal isomerization reactivity is low, isomerization target product selectivity is low, the catalyst one way longevity
The problems such as short, selectivity " climbing the phase " is long is ordered, a kind of new skeletal isomerisation catalyst is provided, the catalyst is different for skeleton
When structureization is reacted, with binder content, low, skeletal isomerization reactivity is high, isomerization target product selectivity is high, urges
The advantages that agent single pass life is long, selectivity " climbing the phase " is short.The second technical problem to be solved by the present invention is to be prepared
The skeletal isomerisation catalyst of low binder, high activity and selectivity；Provide a kind of system of new skeletal isomerisation catalyst
Preparation Method, this method have many advantages, such as that preparation process is simple, is suitable for industrial production.
One of to solve above-mentioned technical problem, technical scheme is as follows: a kind of skeletal isomerisation catalyst, catalysis
Agent includes the molecular sieve of the structure containing ten-ring, it is characterised in that molecular sieve is Adhesive-free Molecular Sieve.
In above-mentioned technical proposal, it is preferred that Adhesive-free Molecular Sieve based on parts by weight, including 0~5 part of binder and 95
~100 parts of molecular sieve.
In above-mentioned technical proposal, it is preferred that the number of binder is 0~3 part.
In above-mentioned technical proposal, it is furthermore preferred that the number of binder is 0.1~3 part.
In above-mentioned technical proposal, it is preferred that the number of binder is 0~2 part.
In above-mentioned technical proposal, it is furthermore preferred that the number of binder is 0.1~2 part.
In above-mentioned technical proposal, it is preferred that the molecular sieve of the structure containing ten-ring be selected from SAPO-11, ZSM-22, ZSM-23,
One of MCM-22, MCM-41, MCM-48 and ZSM-35 or at least one.
In above-mentioned technical proposal, it is preferred that the molecular sieve of the structure containing ten-ring be selected from SAPO-11, ZSM-22, ZSM-23,
One of MCM-22 and ZSM-35 or at least one.
In above-mentioned technical proposal, it is preferred that the molecular sieve of the structure containing ten-ring is selected from SAPO-11 and/or ZSM-35.
In above-mentioned technical proposal, it is furthermore preferred that the molecular sieve of the structure containing ten-ring is selected from SAPO-11 and ZSM-35；With weight
Percentages are measured, the content of SAPO-11 molecular sieve is 0~20%, and the content of ZSM-35 molecular sieve is 80~100%.
In above-mentioned technical proposal, it is furthermore preferred that the molecular sieve of the structure containing ten-ring is selected from SAPO-11 and ZSM-35；With weight
Measure percentages, the content of SAPO-11 molecular sieve is to be less than or equal to 20% greater than 0, the content of ZSM-35 molecular sieve be greater than etc.
In 80 less than 100%.
In above-mentioned technical proposal, it is preferred that the molecular sieve of the structure containing ten-ring in FER topological structure molecular sieve one
Kind is at least one, and FER topological structure molecular sieve includes ferrierite, Sr-D, FU-9, NU-23 and ZSM-35.
In above-mentioned technical proposal, it is furthermore preferred that the molecular sieve of the structure containing ten-ring is selected from FER topological structure molecular sieve magnesium alkali
One of zeolite and ZSM-35 are at least one.
In above-mentioned technical proposal, it is furthermore preferred that the molecular sieve of the structure containing ten-ring is selected from ferrierite and ZSM-35；Magnesium alkali
The weight ratio of zeolite and ZSM-35 are (1:4)~(4:1).
In above-mentioned technical proposal, it is preferred that by weight percentage, 0.1~2% is also contained in skeletal isomerisation catalyst
Metal or its oxide.
In above-mentioned technical proposal, it is furthermore preferred that by weight percentage, in skeletal isomerisation catalyst also containing 0.5~
1.0% metal or its oxide.
In above-mentioned technical proposal, it is preferred that metal or its oxide are introduced by ion exchange.
In above-mentioned technical proposal, it is preferred that metal and its oxide are alkali metal and its oxide, alkaline-earth metal and its oxygen
One of compound, iron and its oxi, cobalt and its oxide, lanthanum and its oxide, gallium and its oxide are at least one.
In above-mentioned technical proposal, it is furthermore preferred that metal and its oxide are sodium and its oxide, potassium and its oxide, iron
And its one of oxide, cobalt and its oxide or at least one.
In above-mentioned technical proposal, it is preferred that the mechanical strength of binder free catalyst is not less than 6N/mm；It is preferably not low
In 8N/mm；More preferably it is not less than 10N/mm.
To solve above-mentioned technical problem two, technical scheme is as follows: a kind of system of skeletal isomerisation catalyst
Preparation Method, comprising the following steps: using one of molecular sieve of ten-ring structure or at least one powder as crystal seed, crystal seed and viscous
Presoma is obtained after knot agent mixed-forming, presoma converts molecular sieve for binder component through hydro-thermal reaction, through ammonium exchange, roasting
Binder free catalyst is obtained after burning.
In above-mentioned technical proposal, it is preferred that the silica alumina ratio of zeolite powder is 15-35, and the sial of binder component rubs
, than being 15-100, weight shared by binder component is 5~95 weight % for you, after shaping and drying, is containing inorganic base and organic amine
Aqueous solution in hydro-thermal process be converted into soap-free emulsion polymeization dosage form moulded zeolite, wherein crystallization temperature be 120~180 DEG C, crystallization time
It is 12~144 hours.
In above-mentioned technical proposal, it is preferred that binder component used: silicon source be selected from silica solution, white carbon black, waterglass or
One or more of diatomite, kaolin；Silicon source is in kaolin, the oxide of aluminium, hydroxide, aluminium salt or aluminate
One or more；Sodium source is selected from one or more of sodium hydroxide, sodium metasilicate, sodium aluminate.
The binder mentioned in technical solution in the present invention also may include kaolin or with component similar in its structure, i.e.,
As during the preparation process be added kaolin or with component similar in its structure, with other binders finally preparing finished product catalysis
Molecular sieve component is converted into during agent.
In above-mentioned technical proposal, it is preferred that when kneading extrusion, it is molten that silicon source and silicon source in binder component can be made into sial
With ZSM-35 molecular sieve original powder kneading extrusion after glue, after can also directly mixing with molecular screen primary powder, add water, silica solution or Aluminum sol
One of or at least one kneading extrusion.
In above-mentioned technical proposal, the ZSM-35 zeolite powder is Hydrogen, sodium form, potassium type, sodium potassium type or ammonium type.
In above-mentioned technical proposal, number is the composition of the binder component by mol: Na2O:SiO2=0-0.1,
H2O:SiO2=2-10, SiO2: Al2O3=15-100.
In above-mentioned technical proposal, the weight concentration of silica is 5~50% in the silica solution.
In above-mentioned technical proposal, the reaction temperature of the hydro-thermal process is 120~180 DEG C；When the described hydro-thermal process
Between be 24~144 hours.
In above-mentioned technical proposal, it is preferred that inorganic base is in the alkali metal hydroxides such as sodium hydroxide, potassium hydroxide
It is a kind of or at least one.
It states in technical solution, it is preferred that organic amine is selected from cyclohexylamine, n-butylamine, hexamethylene imine, Isosorbide-5-Nitrae cyclohexanediamine
One of or it is at least one.
To solve above-mentioned technical problem two, technical scheme is as follows: another skeletal isomerisation catalyst
Preparation method, comprising the following steps: using one of molecular sieve of ten-ring structure or at least one powder as crystal seed, crystal seed with
Presoma is obtained after binder mixed-forming, presoma converts molecular sieve for binder component through gas-solid transformation approach, hands over through ammonium
Change, roast after obtain binder free catalyst.
In above-mentioned technical proposal, binder free catalyst can also be prepared by direct tablet compressing.
Above-mentioned catalyst is used for skeletal isomerization, and using linear alkene as raw material, raw material is obtained with above-mentioned catalyst reaction
To isomerization product.
In above-mentioned technical proposal, it is preferred that linear alkene is selected from least one of butylene, amylene, hexene and heptene.
In above-mentioned technical proposal, it is preferred that butylene is one of 1- butylene, maleic, anti-butylene or a variety of.
In above-mentioned technical proposal, it is preferred that amylene is one of 1- amylene, cis- 2- amylene, trans- 2- amylene or a variety of.
In above-mentioned technical proposal, it is preferred that the weight content of linear alkene accounts for 10 parts to 100 parts of total weight score.
In above-mentioned technical proposal, it is furthermore preferred that the weight content of linear alkene accounts for 60 parts to 90 parts of total weight score.
Inactive diluent, including nitrogen, hydrogen or alkane can be contained in above-mentioned linear alkene raw material flow.
Above-mentioned linear alkene raw material, it is preferred that the weight content of diluent accounts for 0 part to 90 parts of total weight score.
Above-mentioned linear alkene raw material, it is furthermore preferred that the weight content of diluent accounts for 10 parts to 50 parts of total weight score.
In above-mentioned technical proposal, it is preferred that diene hydrocarbon content is lower than 0.5%.
In above-mentioned technical proposal, it is furthermore preferred that diene hydrocarbon content is lower than 0.1%.
In above-mentioned technical proposal, it is furthermore preferred that diene hydrocarbon content is lower than 0.01%.
In above-mentioned technical proposal, it is preferred that reaction temperature is 200~500 DEG C.
In above-mentioned technical proposal, it is furthermore preferred that reaction temperature is 280~400 DEG C.
In above-mentioned technical proposal, it is preferred that reaction pressure is 0~1.0MPa of gauge pressure.
In above-mentioned technical proposal, it is furthermore preferred that reaction pressure is 0~0.5MPa of gauge pressure.
In above-mentioned technical proposal, it is furthermore preferred that reaction pressure is 0~0.1MPa of gauge pressure.
In above-mentioned technical proposal, it is preferred that the liquid volume air speed of reaction raw materials is 0.1~20.0 hour-1。
In above-mentioned technical proposal, it is furthermore preferred that the liquid volume air speed of reaction raw materials is 1~8.0 hour-1。
In above-mentioned technical proposal, it is preferred that the liquid volume air speed of reaction raw materials is 2.0~4.0 hours-1。
Using binder free catalyst of the invention, there is more preferably stability, reaction in catalysis Stability Assessment comparison
Time, which reaches, to be still able to maintain isobutene yield for 70 days and is still able to maintain 40wt% or more, and conventional catalyst is 40 days in the reaction time
When, isobutene yield is just down to 40wt% or less；The stability of binder free catalyst of the invention, which is compared, can be improved 70%
More than, while also there is lower selectivity " climbing the phase ".Binder free catalyst of the invention is used for skeletal isomerization
When reactivity low with binder content, skeletal isomerization is high, isomerization target product selectivity is high, the catalyst one way longevity
The advantages that life is long, selectivity " climbing the phase " is short；Achieve unexpected technical effect.
Detailed description of the invention
Fig. 1 is n-butene conversion, selective isobutene, isobutene yield and the catalysis of the entire evaluation cycle of embodiment 11
Agent life diagram.
Fig. 2 is n-butene conversion, selective isobutene, isobutene yield and the catalysis of the entire evaluation cycle of comparative example 1
Agent life diagram.
Fig. 3 is the XRD spectra of 7 precursor mixture of embodiment.
Fig. 4 is the XRD spectra for -35 moulded zeolite of binderless ZSM-5 that embodiment 8 is prepared.
Fig. 5 is the XRD spectra for -35 moulded zeolite of binderless ZSM-5 that embodiment 7 is prepared.
Fig. 6 is the SEM photograph for -35 moulded zeolite of binderless ZSM-5 that embodiment 7 is prepared.
Below by embodiment and comparative example, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
Weigh sodium metasilicate, Hydrogen ZSM-35 molecular sieve (SiO2/Al2O3Molar ratio be 15), sodium aluminate, silica solution mixing squeeze
Item forms to obtain precursor mixture, again and dissolved with potassium hydroxide and Isosorbide-5-Nitrae-cyclohexanediamine after precursor mixture is dry
(C6H14N2) aqueous solution mixing, the mol ratio of mixture is 1Al2O3: 4Na2O:15SiO2:5C6H14N2: 500H2O.Then
Said mixture is transferred in crystallizing kettle, crystallization 72 hours at 160 DEG C.After products therefrom is washed with distilled water drying, warp
Adhesive-free Molecular Sieve catalyst is obtained after ammonium exchange and 550 DEG C of roastings.Concrete component is shown in Table 1.
The evaluation condition of catalyst is as follows: using carbon four is mixed after ether, (n-butene content 93.1%, remaining is butane, third
Alkane, propylene) it is raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2.0 hours-1, Catalyst packing
Under the conditions of 10 cubic metres of amount, catalyst activity is checked and rated.Evaluation results are shown in Table 1.
[embodiment 2]
100 kilograms of the Adhesive-free Molecular Sieve catalyst being prepared in Example 1,100 kilograms of Fe(NO3)39H2O
With 1000 kilograms of progress ion exchanges of deionized water, stirs at 70 DEG C 2 hours, after filtering, is dried 12 hours in 120 DEG C,
It is roasted 8 hours then at 550 DEG C, obtains iron-containing Adhesive-free Molecular Sieve catalyst, be labeled as embodiment 2.With weight percent
It counts, the content of ferro element is 0.9% in embodiment 2.
The evaluation condition of catalyst is as follows: using carbon four is mixed after ether, (n-butene content 93.1%, remaining is butane, third
Alkane, propylene) it is raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2.0 hours-1, Catalyst packing
Under the conditions of 0.1 cubic metre of amount, catalyst activity is checked and rated.Evaluation results are shown in Table 1.
[embodiment 3]
100 kilograms of the Adhesive-free Molecular Sieve catalyst being prepared in Example 1,100 kilograms of potassium nitrate and go from
1000 kilograms of progress ion exchanges of sub- water are stirred 2 hours at 70 DEG C, after filtering, are dried 12 hours in 120 DEG C, then at 550
DEG C roasting 8 hours, obtain the Adhesive-free Molecular Sieve catalyst containing potassium, be labeled as embodiment 3.By weight percentage, implement
The content of potassium element is 0.4% in example 3.
The evaluation condition of catalyst is as follows: using carbon four is mixed after ether, (n-butene content 93.1%, remaining is butane, third
Alkane, propylene) it is raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2.0 hours-1, Catalyst packing
Under the conditions of 0.1 cubic metre of amount, catalyst activity is checked and rated.Evaluation results are shown in Table 1.
[embodiment 4]
By the preparation method of embodiment 1, white carbon black, diatomite, sodium form ZSM-35 zeolite (SiO are weighed2/Al2O3Molar ratio
For 20), sodium aluminate, aluminum sulfate and silica solution mixing extruded moulding, again and dissolved with sodium hydroxide and ring after extruded moulding object is dry
Hexylamine (C6H13N aqueous solution mixing), the mol ratio of mixture are 1Al2O3: 2Na2O:20SiO2:4C6H13N:500H2O.So
Said mixture is transferred in crystallizing kettle afterwards, 175 DEG C crystallization 24 hours.After products therefrom is washed with distilled water drying,
It is roasted in air atmosphere in 550 DEG C, obtains the catalysis of -35 molded molecular sieve of binderless ZSM-5 after ammonium exchange and 550 DEG C of roastings
Agent.The concrete component of 4 gained binder free catalyst of embodiment is shown in Table 1.
The evaluation condition of catalyst is as follows: being using mixing carbon four (n-butene content 78.0%, remaining is butane) after ether
Raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2.0 hours-1, 10 cubic metres of loaded catalyst
Under the conditions of, check and rate catalyst activity.Result after choosing reaction 24 hours is listed in table 1.
[embodiment 5]
By the preparation method of embodiment 1, white carbon black, diatomite, sodium form ZSM-35 zeolite (SiO are weighed2/Al2O3Molar ratio
For 20), sodium aluminate, aluminum sulfate and silica solution mixing extruded moulding, again and dissolved with sodium hydroxide and ring after extruded moulding object is dry
Hexylamine (C6H13N aqueous solution mixing), the mol ratio of mixture are 1Al2O3: 2Na2O:20SiO2:4C6H13N:500H2O.So
Said mixture is transferred in crystallizing kettle afterwards, 175 DEG C crystallization 48 hours.After products therefrom is washed with distilled water drying,
It is roasted in air atmosphere in 550 DEG C, obtains the catalysis of -35 molded molecular sieve of binderless ZSM-5 after ammonium exchange and 550 DEG C of roastings
Agent.The concrete component of 5 gained binder free catalyst of embodiment is shown in Table 1.
The evaluation condition of catalyst is as follows: being using mixing carbon four (n-butene content 78.0%, remaining is butane) after ether
Raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2.0 hours-1, 10 cubic metres of loaded catalyst
Under the conditions of, check and rate catalyst activity.Result after choosing reaction 24 hours is listed in table 1.
[embodiment 6]
By the preparation method of embodiment 1, white carbon black, diatomite, sodium form ZSM-35 zeolite (SiO are weighed2/Al2O3Molar ratio
For 20), sodium aluminate, aluminum sulfate and silica solution mixing extruded moulding, again and dissolved with sodium hydroxide and ring after extruded moulding object is dry
Hexylamine (C6H13N aqueous solution mixing), the mol ratio of mixture are 1Al2O3: 2Na2O:20SiO2:4C6H13N:500H2O.So
Said mixture is transferred in crystallizing kettle afterwards, 175 DEG C crystallization 72 hours.After products therefrom is washed with distilled water drying,
It is roasted in air atmosphere in 550 DEG C, obtains the catalysis of -35 molded molecular sieve of binderless ZSM-5 after ammonium exchange and 550 DEG C of roastings
Agent.The concrete component of 6 gained binder free catalyst of embodiment is shown in Table 1.
The evaluation condition of catalyst is as follows: being using mixing carbon four (n-butene content 78.0%, remaining is butane) after ether
Raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2.0 hours-1, 10 cubic metres of loaded catalyst
Under the conditions of, check and rate catalyst activity.Result after choosing reaction 24 hours is listed in table 1.
[embodiment 7]
By the preparation method of embodiment 1, white carbon black, diatomite, sodium form ZSM-35 zeolite (SiO are weighed2/Al2O3Molar ratio
For 20), sodium aluminate, aluminum sulfate and silica solution mixing extruded moulding, again and dissolved with sodium hydroxide and ring after extruded moulding object is dry
Hexylamine (C6H13N aqueous solution mixing), the mol ratio of mixture are 1Al2O3: 2Na2O:20SiO2:4C6H13N:500H2O.So
Said mixture is transferred in crystallizing kettle afterwards, 175 DEG C crystallization 96 hours.After products therefrom is washed with distilled water drying,
It is roasted in air atmosphere in 550 DEG C, obtains the catalysis of -35 molded molecular sieve of binderless ZSM-5 after ammonium exchange and 550 DEG C of roastings
Agent.The concrete component of 7 gained binder free catalyst of embodiment is shown in Table 1.
The evaluation condition of catalyst is as follows: being using mixing carbon four (n-butene content 78.0%, remaining is butane) after ether
Raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2.0 hours-1, 10 cubic metres of loaded catalyst
Under the conditions of, check and rate catalyst activity.Result after choosing reaction 24 hours is listed in table 1.
[embodiment 8]
By the preparation method of embodiment 1, weighs white carbon black, diatomite, sodium aluminate, aluminum sulfate and silica solution and be stirred
To silica-alumina gel, by gained silica-alumina gel and sodium form ZSM-35 molecular sieve (SiO2/Al2O3Molar ratio is 30) extruded moulding, extrusion
Again and dissolved with sodium hydroxide and n-butylamine (C after molding is dry4H11N aqueous solution mixing), the mol ratio of mixture are
1Al2O3: 2.7Na2O:35SiO2:7C4H11N:900H2O. then said mixture is transferred in crystallizing kettle, in 150 DEG C of crystallization
72 hours.It after products therefrom is washed with distilled water drying, is roasted in air atmosphere in 550 DEG C, through ammonium exchange and 550 DEG C of roastings
After obtain -35 moulded zeolite of binderless ZSM-5.Concrete component is shown in Table 1.
The evaluation condition of catalyst is as follows: being using mixing carbon four (n-butene content 58.2%, remaining is butane) after ether
Raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2.0 hours-1, 10 cubic metres of loaded catalyst
Under the conditions of, check and rate catalyst activity.Result after choosing reaction 24 hours is listed in table 1.
[embodiment 9]
By the preparation method of embodiment 1, weighs white carbon black, diatomite, sodium aluminate, aluminum sulfate and silica solution and be stirred
To silica-alumina gel, by gained silica-alumina gel and sodium form ZSM-35 molecular sieve (SiO2/Al2O3Molar ratio is 30) extruded moulding, extrusion
Again and dissolved with sodium hydroxide and n-butylamine (C after molding is dry4H11N aqueous solution mixing), the mol ratio of mixture are
1Al2O3: 2.7Na2O:35SiO2:7C4H11N:900H2O. then said mixture is transferred in crystallizing kettle, in 160 DEG C of crystallization
72 hours.It after products therefrom is washed with distilled water drying, is roasted in air atmosphere in 550 DEG C, through ammonium exchange and 550 DEG C of roastings
After obtain -35 moulded zeolite of binderless ZSM-5.Concrete component is shown in Table 1.
The evaluation condition of catalyst is as follows: being using mixing carbon four (n-butene content 58.2%, remaining is butane) after ether
Raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2.0 hours-1, 10 cubic metres of loaded catalyst
Under the conditions of, check and rate catalyst activity.Result after choosing reaction 24 hours is listed in table 1.
The evaluation condition of catalyst is as follows: mixing carbon four (n-butene content 93.1%) after using ether as raw material；In temperature
350 DEG C, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2 hours-1, under the conditions of 10 cubic metres of loaded catalyst, examination is urged
Agent activity.The result is shown in Figure 1 of the entire evaluation cycle of catalyst.
[embodiment 10]
By the preparation method of embodiment 1, weighs white carbon black, diatomite, sodium aluminate, aluminum sulfate and silica solution and be stirred
To silica-alumina gel, by gained silica-alumina gel and sodium form ZSM-35 molecular sieve (SiO2/Al2O3Molar ratio is 30) extruded moulding, extrusion
Again and dissolved with sodium hydroxide and n-butylamine (C after molding is dry4H11N aqueous solution mixing), the mol ratio of mixture are
1Al2O3: 2.7Na2O:35SiO2:7C4H11N:900H2O. then said mixture is transferred in crystallizing kettle, in 170 DEG C of crystallization
72 hours.It after products therefrom is washed with distilled water drying, is roasted in air atmosphere in 550 DEG C, through ammonium exchange and 550 DEG C of roastings
After obtain -35 moulded zeolite of binderless ZSM-5.Concrete component is shown in Table 1.
The evaluation condition of catalyst is as follows: being using mixing carbon four (n-butene content 58.2%, remaining is butane) after ether
Raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2.0 hours-1, 10 cubic metres of loaded catalyst
Under the conditions of, check and rate catalyst activity.Result after choosing reaction 24 hours is listed in table 1.
[embodiment 11]
By the preparation method of embodiment 1, weighs white carbon black, diatomite, sodium aluminate, aluminum sulfate and silica solution and be stirred
To silica-alumina gel, by gained silica-alumina gel and sodium form ZSM-35 molecular sieve (SiO2/Al2O3Molar ratio is 30) extruded moulding, extrusion
Again and dissolved with sodium hydroxide and n-butylamine (C after molding is dry4H11N aqueous solution mixing), the mol ratio of mixture are
1Al2O3: 2.7Na2O:35SiO2:7C4H11N:900H2O. then said mixture is transferred in crystallizing kettle, in 180 DEG C of crystallization
72 hours.It after products therefrom is washed with distilled water drying, is roasted in air atmosphere in 550 DEG C, through ammonium exchange and 550 DEG C of roastings
After obtain -35 moulded zeolite of binderless ZSM-5.Concrete component is shown in Table 1.
Embodiment 11 is chosen, the stability of catalyst and climbing the phase for observation catalyst choice are checked and rated.
The evaluation condition of catalyst is as follows: being using mixing carbon four (n-butene content 58.2%, remaining is butane) after ether
Raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2.0 hours-1, 10 cubic metres of loaded catalyst
Under the conditions of, check and rate catalyst activity.Result after choosing reaction 24 hours is listed in table 1.
[embodiment 12~16]
By being used after the ZSM-35 being prepared, with the SAPO-11 molecular sieve physical mixed of the molecular sieve of the structure containing ten-ring
In skeletal isomerization, component ratio is shown in Table 2.
The evaluation condition of catalyst is as follows: mixing carbon four (n-butene content 93.1%) after using ether as raw material；In temperature
350 DEG C, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2 hours-1, under the conditions of 1.0 cubic metres of loaded catalyst, examination
Catalyst activity.Result after choosing reaction 24 hours is listed in table 2.
[embodiment 17]
By the preparation method of embodiment 1, weighs white carbon black, diatomite, sodium aluminate, aluminum sulfate and silica solution and be stirred
To silica-alumina gel, by gained silica-alumina gel and ZSM-35 molecular sieve and FU-9 molecular sieve extruded moulding, after extruded moulding object is dry
Again and dissolved with sodium hydroxide and n-butylamine (C4H11N aqueous solution mixing), the mol ratio of mixture are 1Al2O3: 2.7Na2O:
35SiO2:7C4H11N:900H2O. then said mixture is transferred in crystallizing kettle, 180 DEG C crystallization 72 hours.Products therefrom
It after being washed with distilled water drying, is roasted in air atmosphere in 550 DEG C, obtains binder free after ammonium exchange and 550 DEG C of roastings
ZSM-35 and FU-9 eutectic molded molecular sieve catalyst.The component ratio and reaction result of the binder free catalyst of embodiment 17
It is shown in Table 2.
The evaluation condition of the resulting catalyst of embodiment 17 is as follows: mixing carbon four (n-butene content 93.1%) using after ether
For raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2 hours-1, 1.0 cubes of loaded catalyst
Under the conditions of rice, catalyst activity is checked and rated.Result after choosing reaction 24 hours is listed in table 2.
[embodiment 18]
By the preparation method of embodiment 1, weighs white carbon black, diatomite, sodium aluminate, aluminum sulfate and silica solution and be stirred
To silica-alumina gel, by gained silica-alumina gel and ZSM-35 molecular sieve and Sr-D molecular sieve extruded moulding, after extruded moulding object is dry
Again and dissolved with sodium hydroxide and n-butylamine (C4H11N aqueous solution mixing), the mol ratio of mixture are 1Al2O3: 2.7Na2O:
35SiO2:7C4H11N:900H2O. then said mixture is transferred in crystallizing kettle, 180 DEG C crystallization 72 hours.Products therefrom
It after being washed with distilled water drying, is roasted in air atmosphere in 550 DEG C, obtains binder free after ammonium exchange and 550 DEG C of roastings
ZSM-35 and Sr-D eutectic molded molecular sieve catalyst.The component ratio and reaction result of the binder free catalyst of embodiment 18
It is shown in Table 2.
The evaluation condition of the resulting catalyst of embodiment 18 is as follows: mixing carbon four (n-butene content 93.1%) using after ether
For raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2 hours-1, 1.0 cubes of loaded catalyst
Under the conditions of rice, catalyst activity is checked and rated.Result after choosing reaction 24 hours is listed in table 2.
[embodiment 19]
By the preparation method of embodiment 1, weighs white carbon black, diatomite, sodium aluminate, aluminum sulfate and silica solution and be stirred
To silica-alumina gel, by gained silica-alumina gel and ZSM-35 molecular sieve and NU-23 molecular sieve extruded moulding, after extruded moulding object is dry
Again and dissolved with sodium hydroxide and n-butylamine (C4H11N aqueous solution mixing), the mol ratio of mixture are 1Al2O3: 2.7Na2O:
35SiO2:7C4H11N:900H2O. then said mixture is transferred in crystallizing kettle, 180 DEG C crystallization 72 hours.Products therefrom
It after being washed with distilled water drying, is roasted in air atmosphere in 550 DEG C, obtains binder free after ammonium exchange and 550 DEG C of roastings
ZSM-35 and NU-23 eutectic molded molecular sieve catalyst.The component ratio and reaction knot of the binder free catalyst of embodiment 19
Fruit is shown in Table 2.
The evaluation condition of the resulting catalyst of embodiment 19 is as follows: mixing carbon four (n-butene content 93.1%) using after ether
For raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2 hours-1, 1.0 cubes of loaded catalyst
Under the conditions of rice, catalyst activity is checked and rated.Result after choosing reaction 24 hours is listed in table 2.
[embodiment 20]
By the preparation method of embodiment 1, weighs white carbon black, diatomite, sodium aluminate, aluminum sulfate and silica solution and be stirred
To silica-alumina gel, by gained silica-alumina gel and ZSM-35 molecular sieve extruded moulding, again and dissolved with hydrogen-oxygen after extruded moulding object is dry
Change sodium and n-butylamine (C4H11N aqueous solution mixing), the mol ratio of mixture are 1Al2O3: 2.7Na2O:35SiO2:
7C4H11N:900H2O.Then said mixture is transferred in crystallizing kettle, 180 DEG C crystallization 144 hours.Products therefrom steams
It after distilled water washing and drying, is roasted in air atmosphere in 550 DEG C, obtains binderless ZSM-5-after ammonium exchange and 550 DEG C of roastings
35 and NU-23 eutectic molded molecular sieve catalyst.The component ratio and reaction result of the binder free catalyst of embodiment 20 are shown in
Table 2.
The evaluation condition of the resulting catalyst of embodiment 20 is as follows: mixing carbon four (n-butene content 93.1%) using after ether
For raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2 hours-1, 1.0 cubes of loaded catalyst
Under the conditions of rice, catalyst activity is checked and rated.Result after choosing reaction 24 hours is listed in table 2.
[embodiment 21~23]
By being used after the ZSM-35 being prepared, with the ferrierite molecular sieve physical mixed of the molecular sieve of the structure containing ten-ring
In skeletal isomerization, component ratio and reaction result are shown in Table 2.
The evaluation condition of catalyst is as follows: mixing carbon four (n-butene content 93.1%) after using ether as raw material；In temperature
350 DEG C, reaction pressure 0.1MPa, four liquid volume air speed of carbon 2 hours-1, under the conditions of 1.0 cubic metres of loaded catalyst, examination
Catalyst activity.Result after choosing reaction 24 hours is listed in table 2.
[embodiment 24]
Using the Adhesive-free Molecular Sieve catalyst of embodiment 1, it to be used for n-pentene skeletal isomerization.
The evaluation condition of catalyst is as follows: using n-pentene, (1- amylene content 40%, 2- amylene content 50%, remaining is
Pentane) it is raw material；At 300 DEG C of temperature, reaction pressure 0.1MPa, light dydrocarbon liquid volume air speed 1.0 hours-1, loaded catalyst
Under the conditions of 1.0 cubic metres, catalyst activity is checked and rated.Result after choosing reaction 24 hours is listed in table 3.
[embodiment 25]
Using the Adhesive-free Molecular Sieve catalyst of embodiment 1, it to be used for n-pentene skeletal isomerization.
The evaluation condition of catalyst is as follows: using n-pentene content 80%, four light dydrocarbon of carbon of n-butene content 20% mixes
Raw material；At 330 DEG C of temperature, reaction pressure 0.5MPa, raw material liq volume space velocity 1.5 hours-1, 1.0 cubes of loaded catalyst
Under the conditions of rice, catalyst activity is checked and rated.Result after choosing reaction 24 hours is listed in table 3.
[embodiment 26]
Using the Adhesive-free Molecular Sieve catalyst of embodiment 1, it to be used for n-pentene skeletal isomerization.
The evaluation condition of catalyst is as follows: using n-pentene, (1- amylene content 15%, 2- amylene content 35%, remaining is
Pentane) it is raw material；At 280 DEG C of temperature, reaction pressure 1.0MPa, light dydrocarbon liquid volume air speed 2.0 hours-1, loaded catalyst
Under the conditions of 1.0 cubic metres, catalyst activity is checked and rated.Result after choosing reaction 24 hours is listed in table 3.
[embodiment 27]
Using the Adhesive-free Molecular Sieve catalyst of embodiment 1, it to be used for n-pentene skeletal isomerization.
The evaluation condition of catalyst is as follows: using n-hexylene content 60%, remaining is that the carbon six of six alkane of carbon is raw material；?
280 DEG C of temperature, reaction pressure 0.5MPa, six liquid volume air speed of carbon 1.0 hours-1, 1.0 cubic metres of conditions of loaded catalyst
Under, check and rate catalyst activity.Result after choosing reaction 24 hours is listed in table 3.
[comparative example 1]
With raw material used in embodiment 11: sodium form ZSM-35 molecular sieve (SiO2/Al2O3Molar ratio is 30) to pinch with silica solution
The extruded moulding object of zeolite powder containing ZSM-35 and binder that extrusion obtains is closed, wherein the mass fraction of binder is 30%.
Extruded moulding object is entitled as containing the skeletal isomerisation catalyst of binder after 550 DEG C of roastings, ammonium exchange and 550 DEG C of roastings
Comparative example 1.Carbon four (n-butene content 93.1%) is mixed after using ether as raw material；At 350 DEG C of temperature, reaction pressure 0.1MPa,
Four liquid volume air speed of carbon 2 hours-1, under the conditions of 10 cubic metres of loaded catalyst, the stability and observation for checking and rating catalyst are urged
Agent selectivity is climbed the phase.The result of the entire evaluation cycle of catalyst is shown in Fig. 2.
Table 1
Table 2
Table 3
Claims (13)
1. a kind of skeletal isomerisation catalyst, catalyst includes the molecular sieve of the structure containing ten-ring, it is characterised in that catalyst is
Binder free catalyst.
2. skeletal isomerisation catalyst according to claim 1, it is characterised in that catalyst based on parts by weight, including 0
~5 parts of binders and 95~100 parts of molecular sieve.
3. skeletal isomerisation catalyst according to claim 2, it is characterised in that the number of binder is 0.1~3 part；It is excellent
It is selected as 0.1~2 part.
4. skeletal isomerisation catalyst according to claim 1, it is characterised in that the molecular sieve of the structure containing ten-ring is selected from
One of SAPO-11, ZSM-22, ZSM-23, MCM-22, MCM-41, MCM-48 and ZSM-35 or at least one.
5. skeletal isomerisation catalyst according to claim 1, it is characterised in that the molecular sieve of the structure containing ten-ring is selected from
One of FER topological structure molecular sieve or at least one, FER topological structure molecular sieve include ferrierite, Sr-D, FU-9,
NU-23 and ZSM-35.
6. skeletal isomerisation catalyst according to claim 1, it is characterised in that the mechanical strength of binder free catalyst
Not less than 6N/mm；Preferably not lower than 8N/mm；More preferably it is not less than 10N/mm.
7. the preparation method of any one of claim 1~6 skeletal isomerisation catalyst, comprising the following steps: with ten-ring
One of molecular sieve of structure or at least one powder are crystal seed, obtain presoma after crystal seed and binder mixed-forming, preceding
Drive body converts molecular sieve for binder component through hydro-thermal reaction and obtains Adhesive-free Molecular Sieve, obtains after ammonium exchange, roasting
Binder free catalyst.
8. the preparation method of skeletal isomerisation catalyst according to claim 7, it is characterised in that presoma is anti-through hydro-thermal
It is at least partly to convert when should convert binder component in molecular sieve；Preferably conversion completely.
9. the preparation method of skeletal isomerisation catalyst according to claim 7, it is characterised in that binder is selected from silicon source
And/or silicon source.
10. the preparation method of skeletal isomerisation catalyst according to claim 9, it is characterised in that it is molten that silicon source is selected from silicon
One of glue, white carbon black, waterglass or diatomite are at least one；And/or silicon source be selected from the oxide of aluminium, hydroxide,
Aluminium salt or aluminate are a kind of or at least one.
11. a kind of skeletal isomerization, using the hydro carbons comprising linear alkene component as raw material, raw material and claim 1~6 times
One skeletal isomerisation catalyst reacts to obtain isomerization product.
12. skeletal isomerization according to claim 11, it is characterised in that linear alkene is selected from butylene, amylene and hexene
One of or it is at least one.
13. skeletal isomerization according to claim 11, it is characterised in that in terms of the weight percent of hydrocarbon raw material, directly
The weight content of olefine accounts for the 10%~100% of total weight score.
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