CN114075452B - Process for isomerising linear olefins - Google Patents
Process for isomerising linear olefins Download PDFInfo
- Publication number
- CN114075452B CN114075452B CN202010818012.0A CN202010818012A CN114075452B CN 114075452 B CN114075452 B CN 114075452B CN 202010818012 A CN202010818012 A CN 202010818012A CN 114075452 B CN114075452 B CN 114075452B
- Authority
- CN
- China
- Prior art keywords
- acid
- isomerization process
- catalyst
- mixed solution
- washing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/703—MRE-type, e.g. ZSM-48
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L
- C07C2529/64—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- C10G2300/1022—Fischer-Tropsch products
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/22—Higher olefins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the field of isomerization of high-carbon number linear olefins, and discloses an isomerization method of linear olefins. Comprising the following steps: c in the presence of hydrogen and/or inert gas 4 ‑C 20 Linear olefins or C-containing 4 ‑C 20 The Fischer-Tropsch light oil of the linear olefin is contacted with a catalyst containing ZSM-48 molecular sieve to carry out isomerization reaction, thus obtaining the catalyst containing C 4 ‑C 20 An isoolefin product. Can realize C 8 The isomerization of the straight-chain olefin can meet the isomerization processing of the straight-chain olefin with high carbon number, and the isomerization processing of the straight-chain olefin with high carbon number is carried out on C 4 ‑C 20 The linear olefin has good isomerization activity and selectivity.
Description
Technical Field
The invention relates to the field of isomerization of linear olefins, in particular to an isomerization method of linear olefins.
Background
In petroleum cracking components, linear olefins (C) 4 -C 7 ) The application range is narrow. However, if the skeletal isomerization treatment is carried out, it can be directly used as an aid for improving the octane number of the gasoline component, and can be used as a raw material for producing alkyl ether (such as methyl tertiary butyl ether), and the alkyl ether is a very good octane number component, so that a great deal of attention is paid to how to isomerize linear olefins into isoolefins.
CN1317466a discloses a process for structurally isomerizing a linear olefin of at least 4 carbon atoms to its corresponding methyl branched isoolefin comprising contacting a hydrocarbon feedstream containing at least one said linear olefin with an isomerization catalyst at a temperature of from about 200 ℃ to about 650 ℃, the catalyst being prepared by a process comprising the steps of: (a) Mixing (i) a zeolite powder comprising at least one zeolite having at least one-dimensional pore structure with a pore size small enough to prevent dimerization of by-products and coke formation and large enough to allow the entry of linear olefins and the formation of methyl branched isoolefins, (ii) an alumina-containing binder, (iii) water, and (iv) an effective amount of an acid comprising at least one polycarboxylic acid peptizing the zeolite powder, binder, or mixture thereof, to produce a mixture; (b) Forming the mixture into one or more solid particles, and (c) calcining the particles at a temperature of about 200 ℃ to about 700 ℃. Wherein the molecular sieve is ZSM-22, ZSM-23, the adhesive is alumina and polycarboxylic acid, and the catalyst is mainly used for isomerization reaction of linear butene and pentene.
CN101376617a discloses a process for skeletal isomerization of olefins, comprising contacting an olefin-containing feedstock with a catalyst comprising beta molecular sieve under olefin skeletal isomerization reaction conditions, wherein the beta molecular sieve comprises magnesium in an amount of 0.1 to 3.5 wt% based on oxides and total molecular sieve.
CN108114735a discloses a preparation method of a linear olefin skeleton isomerization catalyst, which comprises the following specific synthesis steps: (1) The synthesized FER molecular sieve is treated with HF/NH 4 F, treating the solution at 30-90 ℃ for 0.1-10 hours; (2) Washing the product obtained in the step (1) to be neutral, extruding strips, exchanging by using an ammonium nitrate solution, filtering, washing by using deionized water, drying and roasting; (3) And (3) treating the sample obtained in the step (2) with water vapor at 400-700 ℃ for 1-8 hours to prepare the isomerization catalyst. Is used for the preparation of isobutene.
CN103102235a discloses a process for the preparation of isobutene and co-production of high octane gasoline by n-butene isomerization comprising: step A, carrying out superposition, cyclization, isomerization, hydrogen transfer, alkylation and dehydrogenation reactions on a carbon four component rich in normal butene under the action of an acid catalyst to generate a catalyst containing C 8 High octane gasoline components of isoolefins and aromatics; step B, the carbon four component rich in normal butene is inUnder the action of an acid catalyst, a selective skeletal isomerization reaction is carried out to generate isobutene; wherein the reaction temperature of the step A is 200-300 ℃, and the reaction temperature of the step B is 300-350 ℃. The preparation method of the molecular sieve isomerism catalyst containing ZSM-35 is mainly described and is applied to the preparation of isobutene.
CN106076408A discloses a normal olefin isomerization catalyst containing 50-90 mass% of molecular sieve, the balance being alumina; the molecular sieve consists of SAPO-11 and ZSM-5, wherein SAPO-11 accounts for 75-90 percent (mass) of the total molecular sieve, and ZSM-5 accounts for 10-25 percent (mass) of the total molecular sieve. Is applied to the preparation of isobutene.
CN103301876a discloses a preparation method of a linear olefin skeleton isomerization catalyst, which comprises the following specific synthesis steps: (1) Treating the synthesized rare earth ZSM-35 molecular sieve with alkali solution at 30-90 ℃ for 0.5-10 hours; (2) Washing the product obtained in the step (1) to be neutral, extruding strips, exchanging by using an ammonium nitrate solution, filtering, washing by using deionized water, drying and roasting; (3) And (3) treating the sample obtained in the step (2) with water vapor at 400-700 ℃ for 1-8 hours to prepare the isomerization catalyst.
CN107999141a discloses a hydrated alumina composition containing a ZSM-48 type molecular sieve, the composition containing hydrated alumina, a ZSM-48 type molecular sieve, and a compound having at least two proton acceptor sites, the composition
A value of 5 or less, said +.>
The values were determined using the following method: 10g of the composition was dried at 120℃in an air atmosphere for 240 minutes, the mass of the dried composition being denoted w 1 Calculating ∈A using formula I>
Value of->
(formula I).
CN109701606a discloses a skeletal isomerization catalyst comprising, in weight percent: (1) 95.5-100% of a molecular sieve containing a ten-membered ring structure; (2) 0-4.5% of a binder.
However, in the prior art, a raw material derived from petroleum refining is often treated, and the raw material contains a small amount of carbon atoms of linear olefins. Because of short chain length, the low-carbon olefin is not easy to crack, the skeletal isomerization difficulty is low, and the catalyst is mostly a Pt/molecular sieve system.
In the field of Fischer-Tropsch oil, an iron-based Fischer-Tropsch light oil component (C 4 -C 20 ) (Fischer-Tropsch light oil) contains a large amount of high carbon number (C) 8 Above) the content of the linear terminal olefin can be more than 60 weight percent. In the prior art, the processing of the component is often carried out by hydrogenation saturation, then cracking, isomerization or cracking to prepare the low-carbon olefin, so that the processing cost is increased due to long production flow, and the high-carbon components are destroyed, thereby wasting raw material resources. Therefore, it is necessary to provide an isomerization method suitable for high-carbon-number-containing olefins according to the composition characteristics of Fischer-Tropsch light oil.
Disclosure of Invention
The invention aims to solve the problem of better isomerization of high-carbon number linear olefins contained in Fischer-Tropsch light oil, and provides an isomerization method of linear olefins. In particular for the purpose of achieving Fischer-Tropsch derived light oil components, C 8 The isomerization of the above high carbon number linear olefins gives high carbon number isoolefins. The method can also realize C 4 -C 7 Isomerization of linear olefins.
In order to achieve the above object, the present invention provides a method for isomerizing a linear olefin, comprising: c in the presence of hydrogen and/or inert gas 4 -C 20 Linear olefins or C-containing 4 -C 20 The Fischer-Tropsch light oil of the linear olefin is contacted with a catalyst containing ZSM-48 molecular sieve to carry out isomerization reaction, thus obtaining the catalyst containing C 4 -C 20 An isoolefin product.
Preferably, C in the Fischer-Tropsch light oil 8 The content of the above linear olefins is 60-80 wtThe amount is percent.
Preferably, the ZSM-48 molecular sieve containing catalyst is prepared by the following method:
(1) Mixing ZSM-48 molecular sieve with alkali liquor, adding water for pulping to prepare mixed slurry, and filtering, washing and drying to obtain modified ZSM-48 molecular sieve;
(2) Mixing the modified ZSM-48 molecular sieve, an aluminum binder and water, adding acid liquor for kneading, and then performing extrusion molding to obtain a catalyst precursor;
(3) And sequentially carrying out hydrothermal treatment, washing with a mixed solution containing ammonium salt and acid and washing with water on the catalyst precursor, and drying to obtain the catalyst.
Through the technical scheme, the method provided by the invention can realize C enrichment 4 -C 20 Fischer-Tropsch light oil (C) of straight-chain olefin 8 The content of the straight-chain olefin can reach more than 60 weight percent), and the isomerization reaction is directly carried out by a catalyst containing ZSM-48 molecular sieve to obtain the isoolefin. In particular, C contained in the material can be realized 8 The straight-chain olefin is isomerized, so that the isomerization processing of the high-carbon number straight-chain olefin can be satisfied, the isomerization activity and the isomerization selectivity of the Fischer-Tropsch light oil are good, and the isomerization selectivity can reach more than 94%.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides an isomerization method of linear olefins, which comprises the following steps: c in the presence of hydrogen and/or inert gas 4 -C 20 Linear olefins or C-containing 4 -C 20 The Fischer-Tropsch light oil of the linear olefin is contacted with a catalyst containing ZSM-48 molecular sieve to carry out isomerization reaction, thus obtaining the catalyst containing C 4 -C 20 An isoolefin product.
The invention relates in particular to the isomerisation of a feed comprising high carbon number linear olefins, such as the light oil fraction obtained by Fischer Tropsch synthesis. Due to C 8 The olefin is easy to induce cracking reaction on the acid site of the catalyst, so that the difficulty of keeping the framework to isomerise only and continuously break the chain is high, and the problems of unstable catalyst performance and quick deactivation caused by coking and the like are also caused by excessive cracking reaction. The invention thus provides a process for the preparation of a light oil component comprising linear olefins (which comprise linear olefins of high carbon number, e.g. C 8 The content of the straight-chain olefin can reach 80 wt% at most), and the straight-chain olefin can be directly isomerized into the isomerized olefin by one step, so that the isomerized product can be produced by the light oil component obtained by Fischer-Tropsch synthesis compared with the isomerized olefin product with high carbon number provided by the prior art. More preferably C 8 The above linear olefins are terminal olefins, i.e., alpha-olefins. Preferably, in Fischer-Tropsch light oil, C 8 The content of the above linear olefins is 60 to 80% by weight.
In some embodiments of the invention, the conditions defining the isomerization reaction allow the catalyst to better catalyze and facilitate the isomerization process. Preferably, the isomerization reaction conditions include: the temperature is 100-400 ℃; the pressure is 0-3MPa; hydrogen and/or inert gas with C 4 -C 20 The weight ratio of the linear olefin is not more than 0.2; c (C) 4 -C 20 Weight hourly space velocity of linear olefins from 0.5 to 5h -1 . More preferably, the temperature is 200-300 ℃; the pressure is 0-0.5MPa; hydrogen and/or inert gas with C 4 -C 20 The weight ratio of the linear olefin is 0.01-0.05; c (C) 4 -C 20 Weight hourly space velocity of linear olefins from 1 to 2h -1 。
In some embodiments of the invention, the isomerisation process may be carried out in the presence of an inert gas, preferably comprising nitrogen, argon or helium, preferably the inert gas is nitrogen.
In some embodiments of the present invention, the catalyst preparation method used is provided, and the resulting catalyst is advantageous for achieving the object of the present invention. Preferably, the ZSM-48 molecular sieve containing catalyst is prepared by the following method:
(1) Mixing ZSM-48 molecular sieve with alkali liquor, adding water for pulping to prepare mixed slurry, and filtering, washing and drying to obtain modified ZSM-48 molecular sieve;
(2) Mixing the modified ZSM-48 molecular sieve, an aluminum binder and water, adding acid liquor for kneading, and then performing extrusion molding to obtain a catalyst precursor;
(3) And sequentially carrying out hydrothermal treatment, washing with a mixed solution containing ammonium salt and acid and washing with water on the catalyst precursor, and drying to obtain the catalyst.
In some embodiments of the invention, the ZSM-48 molecular sieve is selected to provide the desired reactivity in the isomerization reaction and selectivity for isomerising the reactants. Preferably, in step (1), the ZSM-48 molecular sieve is SiO 2 /Al 2 O 3 The molar ratio (silicon to aluminum ratio) is 50 to 200, preferably 60 to 150. The ZSM-48 molecular sieve with the silicon-aluminum ratio can provide high activity of isomerization reaction of long-chain linear olefins, and the requirement on the reaction temperature is low.
In some embodiments of the invention, step (1) is used to modify the ZSM-48 molecular sieve to modulate the acidic properties of the molecular sieve. Preferably, the alkali liquor is ammonia or Na 2 CO 3 Or NaOH. In some embodiments of the invention, the lye is preferably at a concentration of 0.01-0.2M, preferably 0.05-0.1M. Can regulate and control the local framework silicon-aluminum ratio of the molecular sieve. Further, the dosage regulation of the alkali liquor can meet the requirement of increasing the ratio of the strong acid content of the molecular sieve framework to the total acid content, and the reactivity and the isomerism selectivity are improved.
In some embodiments of the invention, preferably, water: ZSM-48 molecular sieve (1-20): 1, preferably (2-5): 1.
in some embodiments of the invention, preferably, the beating temperature is 25-80 ℃, preferably 40-60 ℃; the beating time is 0.5-24h, preferably 1-3h.
In some embodiments of the present invention, preferably, in step (2), the aluminum binder is selected from at least one of pseudo-boehmite, an aluminum sol, an aluminum hydroxide gel, and boehmite.
In some embodiments of the invention, preferably, the aluminum binder is as Al 2 O 3 The weight ratio of the modified ZSM-48 molecular sieve to the aluminum binder (dry basis) is from 0.1 to 4, preferably from 1 to 3, on a dry basis. In the isomerization method provided by the invention, the use amount of the ZSM-48 molecular sieve can also meet the weight ratio of the ZSM-48 molecular sieve to the total amount of the catalyst of 0.1-0.8.
In some embodiments of the invention, preferably, the acid solution is at least one of a nitric acid solution and/or phosphoric acid. Preferably the acid solution has a concentration of 1-10wt%.
In some embodiments of the invention, preferably, the acid solution may aid peptization, aid kneading and shaping the catalyst precursor. The acid solution can be used in an amount that is measured in terms of the weight ratio of acid in the acid solution to dry base powder (the sum of the modified ZSM-48 molecular sieve and the aluminum binder), preferably the weight ratio of acid to dry base powder is 0.01-0.05; the weight ratio of the total amount of water contained in the acid liquor to the water added in the step (2) to the dry powder is 0.5-0.8.
In some embodiments of the present invention, preferably, in step (3), the conditions of the hydrothermal treatment include: continuously introducing water into the catalyst precursor to treat by taking nitrogen as carrier gas, wherein the hydrothermal treatment temperature is 200-500 ℃, and preferably 300-400 ℃; the hydrothermal treatment time is 0.5-6h.
In some embodiments of the invention, the water throughput is preferably 10-50mL/h relative to 100g of the catalyst precursor.
In some embodiments of the invention, preferably, in step (3), the concentration of the ammonium salt in the mixed solution is 0.05 to 0.5M, preferably 0.1 to 0.2M, and the concentration of the acid is 0.05 to 0.5M, preferably 0.1 to 0.2M.
In some embodiments of the invention, it is preferred that the washing temperature of the mixed solution is 40-90 ℃, preferably 60-80 ℃, and the washing time of the mixed solution is 0.1-5h, preferably 0.5-1h.
In some embodiments of the present invention, preferably, the ammonium salt is at least one of ammonium sulfate, ammonium chloride, ammonium nitrate, preferably ammonium sulfate; the acid is at least one of sulfuric acid, hydrochloric acid and nitric acid, preferably sulfuric acid. The washing of the mixed solution containing ammonium salt and acid can remove Na ions that may remain in the catalyst precursor.
In some embodiments of the invention, preferably, the water washing comprises: washing with deionized water, and filtering until the pH value of the obtained filtrate is 7-8.
In some embodiments of the invention, the filter cake obtained by filtration is dried. Preferably, the temperature of the drying is 100-120 ℃ and the time is 12-24 hours.
In some embodiments of the invention, it is preferred that the catalyst has a specific surface area of 200-300m 2 Per gram, pore volume of 0.4-0.8cm 3 /g; the total acid content of the catalyst in pyridine infrared analysis is not less than 65 mu mol/g, and the strong acid content is more than 60%. The acidity measurement was performed by referring to "determination of catalyst acidity by pyridine-thermal desorption-infrared method" (Liu Xiaosa et al, industrial catalyst, 2015 (10)).
In the present invention, the pressures involved are gauge pressures.
The present invention will be described in detail by examples. In the following examples, the content and type of isomerised product was obtained by analysis of Agilent 7890A type chromatography.
The butene is helium spectrum North division product, decyl olefin and hexadecene are Aladendin reagent.
Preparation example 1
1) 200g of ZSM-48 (silicon-aluminum ratio 80) is taken and dispersed into 600g of NaOH solution with concentration of 0.1M (the mass ratio of water to ZSM-48 is about 3:1), the mixture is stirred forcefully until the mixture is uniformly dispersed, the temperature is raised to 40 ℃ and kept constant for 2 hours, the mixture is filtered and washed until the pH value of the filtrate is less than 10, and a filter cake is dried at 120 ℃ to obtain the modified ZSM-48 molecular sieve;
2) 75g of modified ZSM-48 molecular sieve is taken together with 34.7g of pseudo-boehmite (according to Al 2 O 3 Dry basis, al 2 O 3 Content 72%) and water were mixed well (modified ZSM-48 molecular sieve: the weight ratio of the pseudo-boehmite is 31) adding 60g of dilute nitric acid solution (containing 3g of nitric acid and having the weight ratio of acid to dry base powder of 0.03) slowly while stirring in a kneader, wherein the weight ratio of total water (the sum of the water addition amount and the water amount in the dilute nitric acid solution) to the dry base powder is 60, and extruding and molding by using a bar extruder after uniformly stirring to obtain a bar-shaped catalyst initial sample.
3) Placing 100g of a bar-shaped catalyst sample into a hydrothermal tube furnace, introducing deionized water under the carrying action of carrier gas, wherein the water flow is 20mL/h, heating to 300 ℃ and keeping the temperature for 2h for hydrothermal treatment; then the obtained sample is heated to 80 ℃ by 0.1M (ammonium sulfate+sulfuric acid) mixed solution and kept at the constant temperature for 1h for washing treatment; and washing with deionized water, filtering until the pH value of the obtained filtrate is 7, and finally drying to obtain the catalyst A.
Preparation example 2
1) 200g of ZSM-48 (silicon-aluminum ratio 60) is taken and dispersed into 400g of NaOH solution with concentration of 0.05M (the mass ratio of water to ZSM-48 is about 2:1), the mixture is stirred forcefully until the mixture is uniformly dispersed, the temperature is raised to 50 ℃ and kept constant for 1h, the mixture is filtered and washed until the pH value of the filtrate is less than 10, and a filter cake is dried at 120 ℃ to obtain the modified ZSM-48 molecular sieve;
2) 75g of modified ZSM-48 molecular sieve and 34.7g of pseudo-boehmite (according to Al 2 O 3 Dry basis, al 2 O 3 Content 72%) and water were mixed well (modified ZSM-48 molecular sieve: pseudo-boehmite in a weight ratio of 3:1), 60g of a dilute phosphoric acid solution (containing 5g of phosphoric acid and having a weight ratio of acid to dry base powder of 0.05) was slowly added while stirring in a kneader, wherein the weight ratio of total water to dry base powder was 50, and after uniform stirring, the mixture was extruded by a bar extruder to obtain a bar-shaped catalyst initial sample.
3) Placing 100g of a bar-shaped catalyst sample into a hydrothermal tube furnace, introducing deionized water under the carrying action of carrier gas, introducing 50mL/h of water, heating to 360 ℃ and keeping the temperature for 6h for hydrothermal treatment; then the obtained sample is heated to 60 ℃ by 0.2M (ammonium chloride+hydrochloric acid) mixed solution and kept at the constant temperature for 0.7h for washing treatment; and washing with deionized water, filtering until the pH value of the obtained filtrate is 8, and finally drying to obtain the catalyst B.
Preparation example 3
1) 200g of ZSM-48 (silicon-aluminum ratio 150) is taken and dispersed into 1000g of NaOH solution with concentration of 0.08M (the mass ratio of water to ZSM-48 is about 5:1), the mixture is stirred forcefully until the mixture is uniformly dispersed, the temperature is raised to 60 ℃ and kept constant for 3 hours, the mixture is filtered and washed until the pH value of the filtrate is less than 10, and a filter cake is dried at 120 ℃ to obtain the modified ZSM-48 molecular sieve;
2) 75g of modified ZSM-48 molecular sieve is taken together with 34.7g of pseudo-boehmite (according to Al 2 O 3 Dry basis, al 2 O 3 Content 72%) and water were mixed well (modified ZSM-48 molecular sieve: pseudo-boehmite in a weight ratio of 3:1), while stirring in a kneader, 80g of a dilute nitric acid solution (containing 1g of nitric acid in a weight ratio of acid to dry base powder of 0.01) was slowly added, wherein the weight ratio of the total water amount (sum of the water addition amount and the water amount in the dilute nitric acid solution) to the dry base powder was 80, and after uniform stirring, the mixture was extruded by a bar extruder to obtain a bar-shaped catalyst initial sample.
3) Putting 100g of a bar-shaped catalyst sample into a hydrothermal tube furnace, introducing deionized water under the carrying action of carrier gas, wherein the water flow is 80mL/h, heating to 400 ℃ and keeping the temperature for 0.5h for hydrothermal treatment; then the obtained sample is heated to 70 ℃ by 0.16M (ammonium nitrate+nitric acid) mixed solution and kept at the constant temperature for 0.5h for washing treatment; and washing with deionized water, filtering until the pH value of the obtained filtrate is 7.5, and finally drying to obtain the catalyst C.
Preparation example 4
1) 200g of ZSM-48 (silicon-aluminum ratio 80) is taken and dispersed into 600g of NaOH solution with concentration of 0.1M (the mass ratio of water to ZSM-48 is about 3:1), the mixture is stirred forcefully until the mixture is uniformly dispersed, the temperature is raised to 40 ℃ and kept constant for 2 hours, the mixture is filtered and washed until the pH value of the filtrate is less than 10, and a filter cake is dried at 120 ℃ to obtain the modified ZSM-48 molecular sieve;
2) 50g of modified ZSM-48 molecular sieve are taken together with 69.4g of pseudo-boehmite (according to Al 2 O 3 Dry basis, al 2 O 3 Content 72%) and water were mixed well (modified ZSM-48 molecular sieve: pseudo-boehmite in a weight ratio of 1:1), 60g of a dilute nitric acid solution (containing 3g of nitric acid in a weight ratio of acid to dry base powder of 0.03) was slowly added while stirring in a kneader, wherein the weight ratio of the total water amount (sum of the water addition amount and the water amount in the dilute nitric acid solution) to the dry base powder was 60, and after uniform stirring, the mixture was extrudedAnd extruding and molding by a bar machine to obtain a bar-shaped catalyst initial sample.
3) Placing 100g of a bar-shaped catalyst sample into a hydrothermal tube furnace, introducing deionized water under the carrying action of carrier gas, wherein the water flow is 20mL/h, heating to 300 ℃ and keeping the temperature for 2h for hydrothermal treatment; then the obtained sample is heated to 80 ℃ by 0.1M (ammonium sulfate+sulfuric acid) mixed solution and kept at the constant temperature for 1h for washing treatment; and washing with deionized water, filtering until the pH value of the obtained filtrate is 7, and finally drying to obtain the catalyst D.
Preparation example 5
1) 200g of ZSM-48 (silicon-aluminum ratio 200) is taken and dispersed into 600g of NaOH solution with concentration of 0.1M (the mass ratio of water to ZSM-48 is about 3:1), the mixture is stirred forcefully until the mixture is uniformly dispersed, the temperature is raised to 40 ℃ and kept constant for 2 hours, the mixture is filtered and washed until the pH value of the filtrate is less than 10, and a filter cake is dried at 120 ℃ to obtain the modified ZSM-48 molecular sieve;
2) 60g of modified ZSM-48 molecular sieve is taken together with 55.6g of pseudo-boehmite (according to Al 2 O 3 Dry basis, al 2 O 3 Content 72%) and water were mixed well (modified ZSM-48 molecular sieve: the weight ratio of pseudo-boehmite is 1.5:1), 60g of dilute nitric acid solution (containing 3g of nitric acid and the weight ratio of acid to dry base powder is 0.03) is slowly added while stirring in a kneader, wherein the weight ratio of total water (the sum of the water addition amount and the water amount in the dilute nitric acid solution) to dry base powder is 60, and after uniform stirring, the mixture is extruded and molded by a bar extruder to obtain a bar-shaped catalyst initial sample.
3) Placing 100g of a bar-shaped catalyst sample into a hydrothermal tube furnace, introducing deionized water under the carrying action of carrier gas, wherein the water flow is 20mL/h, heating to 300 ℃ and keeping the temperature for 2h for hydrothermal treatment; then the obtained sample is heated to 80 ℃ by 0.1M (ammonium sulfate+sulfuric acid) mixed solution and kept at the constant temperature for 1h for washing treatment; and washing with deionized water, filtering until the pH value of the obtained filtrate is 7, and finally drying to obtain the catalyst E.
Preparation of comparative example 1
75g of ZSM-48 molecular sieve (silicon-aluminum ratio 80) and 34.7g of pseudo-boehmite (according to Al) 2 O 3 Dry basis, al 2 O 3 Content 72%) and water were mixed well (modified ZSM-48 molecular sieve: pseudo-thin aluminiumStone weight ratio of 3:1), 60g of dilute nitric acid solution (containing 3g of nitric acid, the weight ratio of acid to dry base powder of 0.03) was slowly added while stirring in a kneader, wherein the weight ratio of total water amount to dry base powder of 60, and extrusion molding was performed by a bar extruder after uniform stirring, to obtain catalyst DB-1.
Preparation of comparative example 2
1) 200g of ZSM-48 (silicon-aluminum ratio 80) is taken and dispersed into 600g of NaOH solution with concentration of 0.1M (the mass ratio of water to ZSM-48 is about 3:1), the mixture is stirred forcefully until the mixture is uniformly dispersed, the temperature is raised to 40 ℃ and kept constant for 2 hours, the mixture is filtered and washed until the pH value of the filtrate is less than 10, and a filter cake is dried at 120 ℃ to obtain the modified ZSM-48 molecular sieve;
2) 75g of modified ZSM-48 molecular sieve is taken together with 34.7g of pseudo-boehmite (according to Al 2 O 3 Dry basis, al 2 O 3 Content 72%) and water were mixed well (modified ZSM-48 molecular sieve: pseudo-boehmite in a weight ratio of 3:1), 60g of a dilute nitric acid solution (containing 3g of nitric acid, the weight ratio of acid to dry base powder being 0.03) was slowly added while stirring in a kneader, wherein the weight ratio of total water to dry base powder was 60, and after stirring uniformly, extrusion molding was performed by a bar extruder to obtain catalyst DB-2.
Preparation of comparative example 3
1) 75g of ZSM-48 molecular sieve (silicon-aluminum ratio 80) and 34.7g of pseudo-boehmite (according to Al 2 O 3 Dry basis, al 2 O 3 Content 72%) and water were mixed well (modified ZSM-48 molecular sieve: pseudo-boehmite in a weight ratio of 3:1), slowly adding 60g of dilute nitric acid solution (containing 3g of nitric acid and having a weight ratio of acid to dry base powder of 0.03) while stirring in a kneader, wherein the weight ratio of total water to dry base powder is 60, uniformly stirring, and extruding by a strip extruder to obtain a strip catalyst initial sample;
2) Placing 100g of a bar-shaped catalyst sample into a hydrothermal tube furnace, introducing deionized water under the carrying action of carrier gas, wherein the water flow is 20mL/h, heating to 300 ℃ and keeping the temperature for 2h for hydrothermal treatment; then the obtained sample is heated to 80 ℃ by 0.1M (ammonium sulfate+sulfuric acid) mixed solution and kept at the constant temperature for 1h for washing treatment; and washing with deionized water, filtering until the pH value of the obtained filtrate is 7, and finally drying to obtain the catalyst DB-3.
Preparation of comparative example 4
1) 200g of ZSM-35 (silicon-aluminum ratio 80) is taken and dispersed into 600g of NaOH solution with concentration of 0.1M (the mass ratio of water to ZSM-48 is about 3:1), the mixture is stirred forcefully until the mixture is uniformly dispersed, the temperature is raised to 40 ℃ and kept constant for 2 hours, the mixture is filtered and washed until the pH value of the filtrate is less than 10, and a filter cake is dried at 120 ℃ to obtain the modified ZSM-35 molecular sieve;
2) 75g of modified ZSM-35 molecular sieve is taken together with 34.7g of pseudo-boehmite (according to Al 2 O 3 Dry basis, al 2 O 3 Content 72%) and water were mixed well (modified ZSM-48 molecular sieve: the weight ratio of pseudo-boehmite is 3:1), 60g of dilute nitric acid solution (containing 3g of nitric acid and the weight ratio of acid to dry base powder is 0.01) is slowly added while stirring in a kneader, wherein the weight ratio of total water (the sum of the water addition amount and the water amount in the dilute nitric acid solution) to dry base powder is 60, and after uniform stirring, the mixture is extruded by a strip extruder to obtain a strip catalyst initial sample.
3) Placing 100g of a bar-shaped catalyst sample into a hydrothermal tube furnace, introducing deionized water under the carrying action of carrier gas, wherein the water flow is 20mL/h, heating to 300 ℃ and keeping the temperature for 2h for hydrothermal treatment; then the obtained sample is heated to 80 ℃ by 0.1M (ammonium sulfate+sulfuric acid) mixed solution and kept at the constant temperature for 1h for washing treatment; and washing with deionized water, filtering until the pH value of the obtained filtrate is 7, and finally drying to obtain the catalyst DB-4.
Catalysts A-E, DB-1 through DB-4 were subjected to specific surface area, pore volume, and acidity testing and characterization, and the results are shown in Table 1. The specific surface area and the pore volume are measured by a nitrogen adsorption and desorption isotherm method; the acidity was analyzed by pyridine adsorption and desorption infrared. In the acid test result, the content of strong acid in% refers to the content of strong acid (pyridine desorption treatment at 350 ℃ C.)/total content of acid (pyridine desorption treatment at 200 ℃ C.). Times.100%.
TABLE 1
Example 1
Butene isomerization was evaluated using catalysts A-E, DB-1 through DB-4, respectively.
In a fixed bed reactor, 2.0g of catalyst is filled, carrier gas is hydrogen, the flow rate of the hydrogen is 50mL/min, and the weight hourly space velocity of butene feeding is 1.5h -1 The reaction temperature is 300 ℃, the reaction pressure is 0.1MPa, and the weight ratio of hydrogen to butene is 0.05. The continuous reaction was carried out for about 100 hours and the analysis results of the isomerised products were shown in Table 2.
TABLE 2
| Catalyst | Conversion, percent | Isobutene yield% | Isomerism selectivity,% |
| A | 45.3 | 44.2 | 97.6 |
| B | 43.3 | 41.6 | 96.1 |
| C | 47.1 | 45.7 | 97.0 |
| D | 40.5 | 38.7 | 95.6 |
| E | 41.2 | 39.9 | 96.8 |
| DB-1 | 30.0 | 26.5 | 88.3 |
| DB-2 | 33.8 | 29.9 | 88.5 |
| DB-3 | 36.8 | 33.1 | 89.9 |
| DB-4 | 38.5 | 30.4 | 79.0 |
Example 2
Decene isomerism evaluations were performed with catalysts A-E, DB-1 through DB-4, respectively.
In a fixed bed reactor, 2.0g of catalyst was loaded, the carrier gas was hydrogen, the hydrogen flow rate was 50mL/min, and the weight hourly space velocity of decene feed was 2h -1 The reaction temperature was 200℃and the reaction pressure was 0.3MPa, and the weight ratio of hydrogen to decene was 0.03. The continuous reaction was carried out for about 100 hours and the analysis results of the isomerised products were shown in Table 3.
TABLE 3 Table 3
| Catalyst | Conversion, percent | Isodecene yield% | Isomerism selectivity,% |
| A | 50.5 | 48.9 | 96.8 |
| B | 51.2 | 49.2 | 96.1 |
| C | 51.8 | 49.3 | 95.2 |
| D | 44.6 | 42.7 | 95.7 |
| E | 47.4 | 45.1 | 95.1 |
| DB-1 | 38.2 | 34.4 | 90.1 |
| DB-2 | 39.0 | 34.9 | 89.5 |
| DB-3 | 40.4 | 35.5 | 87.9 |
| DB-4 | 42.7 | 33.3 | 78.0 |
Example 3
Hexadecene isomerism was assessed with catalysts A-E, DB-1 to DB-4, respectively.
In a fixed bed reactor, 2.0g of catalyst is filled, carrier gas is hydrogen, the flow rate of the hydrogen is 50mL/min, and the weight hourly space velocity of hexadecene feeding is 1h -1 The reaction temperature is 250 ℃, the reaction pressure is 0.2MPa, and the weight ratio of hydrogen to hexadecene is 0.01. The continuous reaction was carried out for about 100 hours and the analysis results of the isomerised products are shown in Table 4.
TABLE 4 Table 4
| Catalyst | Conversion, percent | Isodecene yield% | Isomerism selectivity,% |
| A | 51.3 | 49.2 | 95.9 |
| B | 52.3 | 49.8 | 95.2 |
| C | 52.8 | 50.3 | 95.3 |
| D | 47.6 | 45.0 | 94.5 |
| E | 48.0 | 45.2 | 94.2 |
| DB-1 | 34.4 | 29.7 | 86.3 |
| DB-2 | 36.7 | 30.5 | 83.1 |
| DB-3 | 36.9 | 31.4 | 85.1 |
| DB-4 | 35.1 | 28.1 | 80.1 |
In tables 2-4 of examples 1-3, the conversion, the isomerism selectivity and the isomerism yield were calculated by the following formula:
percent conversion = [ (amount of feed normal olefins-amount of isomerised product normal olefins)/amount of feed normal olefins ] ×100%;
isomerization selectivity% = [ isomerization product isoolefin amount/(raw material normal olefin amount-isomerization product normal olefin amount) ]x100%;
the isomer yield% = (amount of isoolefin of the isomerised product/amount of normal olefin of the feed) ×100%.
Example 4
Fischer-Tropsch light oil isomerization evaluations were performed with catalysts A-E, DB-1 through DB-4, respectively.
The Fischer-Tropsch light oil composition is shown in Table 5.
In a fixed bed reactor, 2.0g of catalyst is filled, carrier gas is hydrogen, the flow rate of the hydrogen is 50mL/min, and the weight hourly space velocity of Fischer-Tropsch light oil is 2h -1 The reaction temperature was 200℃and the reaction pressure was 0.15MPa, and the weight ratio of hydrogen to Fischer-Tropsch light oil (based on the total olefin content therein, see Table 5) was 0.03. The continuous reaction was carried out for about 100 hours and the analysis results of the isomerised products are shown in Table 6.
TABLE 5
TABLE 6
| Catalyst | Conversion, percent | Isoolefin yield% | Isomerism selectivity,% |
| A | 61.2 | 57.9 | 94.6 |
| B | 63.3 | 60.9 | 96.2 |
| C | 59.0 | 55.7 | 94.5 |
| D | 56.5 | 53.2 | 94.1 |
| E | 55.6 | 52.7 | 94.8 |
| DB-1 | 38.5 | 29.5 | 76.7 |
| DB-2 | 35.4 | 27.1 | 76.5 |
| DB-3 | 37.7 | 27.2 | 72.1 |
| DB-4 | 32.9 | 25.4 | 77.2 |
Example 5
Fischer-Tropsch light oil isomerization evaluations were performed with catalysts A-E, DB-1 through DB-4, respectively.
The Fischer-Tropsch light oil composition is shown in Table 5.
In a fixed bed reactor, 2.0g of catalyst is filled, carrier gas is nitrogen, the flow rate of the nitrogen is 50mL/min, and the weight hourly space velocity of Fischer-Tropsch light oil feed is 2h -1 The reaction temperature is 200 ℃, the reaction pressure is 0.15MPa, and the weight ratio of hydrogen to total olefin in the Fischer-Tropsch light oil is 0.03. The continuous reaction was carried out for about 100 hours and the analysis results of the isomerised products are shown in Table 7.
TABLE 7
| Catalyst | Conversion, percent | Isoolefin yield% | Isomerism selectivity,% |
| A | 59.7 | 55.6 | 93.2 |
| B | 60.4 | 55.9 | 92.5 |
| C | 57.7 | 54.0 | 93.6 |
| D | 55.6 | 51.4 | 92.4 |
| E | 53.9 | 49.2 | 91.3 |
| DB-1 | 37.3 | 27.2 | 72.9 |
| DB-2 | 35.4 | 25.9 | 73.1 |
| DB-3 | 36.2 | 26.2 | 72.4 |
| DB-4 | 33.2 | 24.6 | 74.2 |
In tables 6 and 7 of examples 4 and 5, the conversion, the isomerism selectivity and the isomerism yield were calculated by the following formula:
conversion% = [ (amount of terminal olefin in fischer-tropsch light oil-amount of terminal olefin of isomerised product)/amount of normal olefin in fischer-tropsch light oil ] ×100%;
isomerization selectivity% = [ isomerization product isomerization olefin amount/(normal olefin amount in fischer-tropsch light oil-isomerization product normal olefin amount) ]x100%;
the isomer yield% = (amount of isoolefin of the isomerised product/amount of normal olefin in the fischer-tropsch light oil) ×100%.
As can be seen from the results of examples, comparative examples and tables 1 to 7, the catalysts A to E prepared by the present invention realize the reaction on C 4 -C 20 The isomerization of the linear olefin is superior to the comparison catalysts DB-1 to DB-4 in reactivity and isomerization selectivity, and has obviously better isomerization effect of the high-carbon number linear terminal olefin.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (45)
1. A process for isomerizing linear olefins comprising:
c in the presence of hydrogen and/or inert gas 4 -C 20 Linear olefins or C-containing 4 -C 20 The Fischer-Tropsch light oil of the linear olefin is contacted with a catalyst containing ZSM-48 molecular sieve to carry out isomerization reaction, thus obtaining the catalyst containing C 4 -C 20 An isoolefin product;
wherein, C in the Fischer-Tropsch light oil 8 The content of the above linear olefins is 60 to 80 wt%;
the catalyst containing ZSM-48 molecular sieve is prepared by the following method:
(1) Mixing ZSM-48 molecular sieve with alkali liquor, adding water for pulping to prepare mixed slurry, and filtering, washing and drying to obtain modified ZSM-48 molecular sieve;
(2) Mixing the modified ZSM-48 molecular sieve, an aluminum binder and water, adding acid liquor for kneading, and then performing extrusion molding to obtain a catalyst precursor;
(3) And sequentially carrying out hydrothermal treatment, washing with a mixed solution containing ammonium salt and acid and washing with water on the catalyst precursor, and drying to obtain the catalyst.
2. The isomerization process of claim 1 wherein the isomerization reaction conditions include: the temperature is 100-400 ℃; the pressure is 0-3MPa; hydrogen and/or inert gas with C 4 -C 20 The weight ratio of the linear olefin is not more than 0.2; c (C) 4 -C 20 Weight hourly space velocity of linear olefins from 0.5 to 5h -1 。
3. The isomerization process of claim 2 wherein the isomerization reaction conditions include: the temperature is 200-300 ℃; the pressure is 0-0.5MPa; hydrogen and/or inert gas with C 4 -C 20 The weight ratio of the linear olefin is 0.01-0.05; c (C) 4 -C 20 Weight hourly space velocity of linear olefins1-2h -1 。
4. The isomerization process of claim 1 wherein in step (1) the ZSM-48 molecular sieve is SiO 2 /Al 2 O 3 The molar ratio of (2) is 50-200;
and/or the alkali liquor is ammonia, na 2 CO 3 Or NaOH solution;
and/or the concentration of the alkali liquor is 0.01-0.2M;
and/or, water: ZSM-48 molecular sieve (1-20): 1, a step of;
and/or, pulping at 25-80deg.C; the pulping time is 0.5-24h.
5. The isomerization process of claim 4 wherein in step (1) the ZSM-48 molecular sieve is SiO 2 /Al 2 O 3 The molar ratio of (2) is 60-150;
and/or the concentration of the alkali liquor is 0.05-0.1M;
and/or, water: the mass ratio of the ZSM-48 molecular sieve is (2-5): 1, a step of;
and/or, pulping at 40-60deg.C; the pulping time is 1-3h.
6. The isomerization process of any one of claims 1-5 wherein in step (2) the aluminum binder is selected from at least one of pseudo-boehmite, an aluminum sol, an aluminum hydroxide gel, and boehmite;
and/or the aluminum binder is as Al 2 O 3 The weight ratio of the modified ZSM-48 molecular sieve to the aluminum binder is 0.1-4 based on dry basis: 1, a step of;
and/or the acid liquor is a nitric acid solution and/or a phosphoric acid solution.
7. The isomerization process according to claim 6, wherein in step (2), the aluminum binder is as Al 2 O 3 The weight ratio of the modified ZSM-48 molecular sieve to the aluminum binder is 1-3:1 on a dry basis.
8. The isomerization process of any one of claims 1-5, 7 wherein in step (3), the hydrothermal treatment comprises: continuously introducing water into the catalyst precursor to treat by taking nitrogen as carrier gas, wherein the hydrothermal treatment temperature is 200-500 ℃; the hydrothermal treatment time is 0.5-6h.
9. The isomerization process of claim 8 wherein the hydrothermal treatment temperature is 300-400 ℃.
10. The isomerization process of claim 8 wherein the water throughput is 10-50mL/h relative to 100g of the catalyst precursor.
11. The isomerization process of claim 9 wherein the water throughput is 10-50mL/h relative to 100g of the catalyst precursor.
12. The isomerization process of claim 6 wherein in step (3) the hydrothermal treatment comprises: continuously introducing water into the catalyst precursor to treat by taking nitrogen as carrier gas, wherein the hydrothermal treatment temperature is 200-500 ℃; the hydrothermal treatment time is 0.5-6h.
13. The isomerization process of claim 12 wherein the hydrothermal treatment temperature is 300-400 ℃.
14. The isomerization process of claim 12 or 13 wherein the water throughput is 10-50mL/h relative to 100g of the catalyst precursor.
15. The isomerization process of any one of claims 1 to 5, 7, 9 to 13 wherein in step (3), the concentration of the ammonium salt in the mixed solution is 0.05 to 0.5M and the concentration of the acid is 0.05 to 0.5M;
and/or the washing temperature of the mixed solution is 40-90 ℃; the washing time of the mixed solution is 0.1-5h.
16. The isomerization process of claim 15 wherein in step (3) the concentration of the ammonium salt in the mixed solution is 0.1-0.2M and the concentration of the acid is 0.1-0.2M;
and/or the washing temperature of the mixed solution is 60-80 ℃; the washing time of the mixed solution is 0.5-1h.
17. The isomerization process according to claim 6, wherein in step (3), the concentration of the ammonium salt in the mixed solution is 0.05 to 0.5M and the concentration of the acid is 0.05 to 0.5M;
and/or the washing temperature of the mixed solution is 40-90 ℃; the washing time of the mixed solution is 0.1-5h.
18. The isomerization process of claim 17 wherein in step (3) the concentration of the ammonium salt in the mixed solution is 0.1-0.2M and the concentration of the acid is 0.1-0.2M;
and/or the washing temperature of the mixed solution is 60-80 ℃; the washing time of the mixed solution is 0.5-1h.
19. The isomerization process according to claim 8, wherein in step (3), the concentration of the ammonium salt in the mixed solution is 0.05 to 0.5M and the concentration of the acid is 0.05 to 0.5M;
and/or the washing temperature of the mixed solution is 40-90 ℃; the washing time of the mixed solution is 0.1-5h.
20. The isomerization process of claim 19 wherein in step (3) the concentration of the ammonium salt in the mixed solution is 0.1-0.2M and the concentration of the acid is 0.1-0.2M;
and/or the washing temperature of the mixed solution is 60-80 ℃; the washing time of the mixed solution is 0.5-1h.
21. The isomerization process according to claim 14 wherein in step (3), the concentration of the ammonium salt in the mixed solution is 0.05-0.5M and the concentration of the acid is 0.05-0.5M;
and/or the washing temperature of the mixed solution is 40-90 ℃; the washing time of the mixed solution is 0.1-5h.
22. The isomerization process of claim 21 wherein in step (3) the concentration of the ammonium salt in the mixed solution is 0.1-0.2M and the concentration of the acid is 0.1-0.2M;
and/or the washing temperature of the mixed solution is 60-80 ℃; the washing time of the mixed solution is 0.5-1h.
23. The isomerization process of any one of claims 1-5, 7, 9-13, 16-22 wherein the ammonium salt is at least one of ammonium sulfate, ammonium chloride, ammonium nitrate; the acid is at least one of sulfuric acid, hydrochloric acid and nitric acid.
24. The isomerization process of claim 23 wherein the ammonium salt is ammonium sulfate; the acid is sulfuric acid.
25. The isomerization process according to claim 6, wherein the ammonium salt is at least one of ammonium sulfate, ammonium chloride, ammonium nitrate; the acid is at least one of sulfuric acid, hydrochloric acid and nitric acid.
26. The isomerization process of claim 25 wherein the ammonium salt is ammonium sulfate; the acid is sulfuric acid.
27. The isomerization process of claim 8 wherein the ammonium salt is at least one of ammonium sulfate, ammonium chloride, ammonium nitrate; the acid is at least one of sulfuric acid, hydrochloric acid and nitric acid.
28. The isomerization process of claim 27 wherein the ammonium salt is ammonium sulfate; the acid is sulfuric acid.
29. The isomerization process of claim 14 wherein the ammonium salt is at least one of ammonium sulfate, ammonium chloride, ammonium nitrate; the acid is at least one of sulfuric acid, hydrochloric acid and nitric acid.
30. The isomerization process of claim 29 wherein the ammonium salt is ammonium sulfate; the acid is sulfuric acid.
31. The isomerization process of claim 15 wherein the ammonium salt is at least one of ammonium sulfate, ammonium chloride, ammonium nitrate; the acid is at least one of sulfuric acid, hydrochloric acid and nitric acid.
32. The isomerization process of claim 31 wherein the ammonium salt is ammonium sulfate; the acid is sulfuric acid.
33. The isomerization process of any one of claims 1-5, 7, 9-13, 16-22, 24-32 wherein the water wash comprises: washing with deionized water, and filtering until the pH value of the obtained filtrate is 7-8;
and/or the temperature of the drying is 100-120 ℃ and the time is 12-24h.
34. The isomerization process of claim 6 wherein the water wash comprises: washing with deionized water, and filtering until the pH value of the obtained filtrate is 7-8;
and/or the temperature of the drying is 100-120 ℃ and the time is 12-24h.
35. The isomerization process of claim 8 wherein the water wash comprises: washing with deionized water, and filtering until the pH value of the obtained filtrate is 7-8;
and/or the temperature of the drying is 100-120 ℃ and the time is 12-24h.
36. The isomerization process of claim 14 wherein the water wash comprises: washing with deionized water, and filtering until the pH value of the obtained filtrate is 7-8;
and/or the temperature of the drying is 100-120 ℃ and the time is 12-24h.
37. The isomerization process of claim 15 wherein the water wash comprises: washing with deionized water, and filtering until the pH value of the obtained filtrate is 7-8;
and/or the temperature of the drying is 100-120 ℃ and the time is 12-24h.
38. The isomerization process of claim 23 wherein the water wash comprises: washing with deionized water, and filtering until the pH value of the obtained filtrate is 7-8;
and/or the temperature of the drying is 100-120 ℃ and the time is 12-24h.
39. The isomerization process of any one of claims 1-5, 7, 9-13, 16-22, 24-32, 34-38 wherein the catalyst has a specific surface area of 200-300m 2 Per gram, pore volume of 0.4-0.8cm 3 /g; the total pyridine infrared acid amount of the catalyst is not less than 65 mu mol/g, and the strong acid amount is more than 60%.
40. The isomerization process according to claim 6, wherein the specific surface area of the catalyst is 200-300m 2 Per gram, pore volume of 0.4-0.8cm 3 /g; the total pyridine infrared acid amount of the catalyst is not less than 65 mu mol/g, and the strong acid amount is more than 60%.
41. The isomerization process according to claim 8, wherein the specific surface area of the catalyst is 200-300m 2 Per gram, pore volume of 0.4-0.8cm 3 /g; the total pyridine infrared acid amount of the catalyst is notLess than 65 mu mol/g, and the content of the strong acid is more than 60%.
42. The isomerization process of claim 14 wherein the catalyst has a specific surface area of 200-300m 2 Per gram, pore volume of 0.4-0.8cm 3 /g; the total pyridine infrared acid amount of the catalyst is not less than 65 mu mol/g, and the strong acid amount is more than 60%.
43. The isomerization process of claim 15 wherein the catalyst has a specific surface area of 200-300m 2 Per gram, pore volume of 0.4-0.8cm 3 /g; the total pyridine infrared acid amount of the catalyst is not less than 65 mu mol/g, and the strong acid amount is more than 60%.
44. The isomerization process of claim 23 wherein the catalyst has a specific surface area of 200-300m 2 Per gram, pore volume of 0.4-0.8cm 3 /g; the total pyridine infrared acid amount of the catalyst is not less than 65 mu mol/g, and the strong acid amount is more than 60%.
45. The isomerization process of claim 33 wherein the catalyst has a specific surface area of 200-300m 2 Per gram, pore volume of 0.4-0.8cm 3 /g; the total pyridine infrared acid amount of the catalyst is not less than 65 mu mol/g, and the strong acid amount is more than 60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010818012.0A CN114075452B (en) | 2020-08-14 | 2020-08-14 | Process for isomerising linear olefins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010818012.0A CN114075452B (en) | 2020-08-14 | 2020-08-14 | Process for isomerising linear olefins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114075452A CN114075452A (en) | 2022-02-22 |
| CN114075452B true CN114075452B (en) | 2023-06-09 |
Family
ID=80280708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010818012.0A Active CN114075452B (en) | 2020-08-14 | 2020-08-14 | Process for isomerising linear olefins |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114075452B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317466A (en) * | 1993-12-29 | 2001-10-17 | 壳牌石油公司 | Process for isomerizating straight-chain olefines into isoalkene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100447115C (en) * | 2001-08-17 | 2008-12-31 | 国际壳牌研究有限公司 | Process for producing branched olefins from linear olefin/paraffin feed |
-
2020
- 2020-08-14 CN CN202010818012.0A patent/CN114075452B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317466A (en) * | 1993-12-29 | 2001-10-17 | 壳牌石油公司 | Process for isomerizating straight-chain olefines into isoalkene |
Non-Patent Citations (1)
| Title |
|---|
| 孔级ZSM-22与ZSM-48分子筛的制备及其异构化性能的研究;李昊燃;《中国优秀硕士学位论文全文数据库（电子期刊）工程科技Ⅰ辑》;20190815;第B014-511页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114075452A (en) | 2022-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4735929A (en) | Catalytic composition for the isomerization of paraffinic hydrocarbons | |
| DE2760481C2 (en) | ||
| US6417135B1 (en) | Advances in dehydrogenation catalysis | |
| CA1196624A (en) | Process for the preparation of a catalyst and process for the dehydrogenation of c.sub.2-c.sub.4 paraffins | |
| US4062905A (en) | Manufacture of light olefins | |
| US3759821A (en) | Catalytic process for upgrading cracked gasolines | |
| CN111482199A (en) | Olefin cracking catalyst, preparation method thereof and olefin cracking method | |
| US20190224652A1 (en) | Sapo-34/zsm-5@kaolin microsphere composite catalytic material and its preparation and use | |
| JPH03146135A (en) | Catalyst and method for isomerization | |
| DE2112265A1 (en) | Process for the production of a zeolite catalyst and its use | |
| US3669903A (en) | Catalytic cracking process | |
| CN106660025B (en) | Isomerization catalyst | |
| US3852189A (en) | Shape-selective conversion in the liquid phase | |
| US3873632A (en) | Alkylaromatic hydrocarbon isomerization process | |
| US3700749A (en) | Dehydrogenation process over platinum on lithiated mordenite | |
| CN113881457B (en) | Method for treating aromatic hydrocarbon-rich distillate | |
| CN114075452B (en) | Process for isomerising linear olefins | |
| CN107955639B (en) | Method for cracking hexaalkane | |
| US2830090A (en) | Production of alcohols and ethers | |
| JP6446033B2 (en) | Process for producing unsaturated hydrocarbons | |
| US4489216A (en) | Hydrocarbon isomerization | |
| CN113042097B (en) | Molecular sieve catalyst, preparation method and application thereof | |
| CN112439433B (en) | Catalyst with hydrogenation and dimerization functions and preparation method and application thereof | |
| US2911451A (en) | Production of benzene | |
| US4000210A (en) | Selective dehydrogenation of n-paraffins to n-olefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |