CN114405463A - Preparation method of FAU and LTA composite crystal adsorbent for separation of coal-based Fischer-Tropsch synthetic oil alkane and alkene - Google Patents
Preparation method of FAU and LTA composite crystal adsorbent for separation of coal-based Fischer-Tropsch synthetic oil alkane and alkene Download PDFInfo
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- CN114405463A CN114405463A CN202111556774.9A CN202111556774A CN114405463A CN 114405463 A CN114405463 A CN 114405463A CN 202111556774 A CN202111556774 A CN 202111556774A CN 114405463 A CN114405463 A CN 114405463A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000013078 crystal Substances 0.000 title claims abstract description 41
- 238000000926 separation method Methods 0.000 title claims abstract description 33
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 31
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 17
- 239000003245 coal Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003921 oil Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 239000000084 colloidal system Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 33
- 239000004711 α-olefin Substances 0.000 abstract description 15
- 238000003795 desorption Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000006317 isomerization reaction Methods 0.000 abstract description 2
- 230000001360 synchronised effect Effects 0.000 abstract description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 12
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 8
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004440 Isodecyl alcohol Substances 0.000 description 1
- 239000004439 Isononyl alcohol Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OBDUMNZXAIUUTH-UHFFFAOYSA-N tetradec-2-ene Chemical compound CCCCCCCCCCCC=CC OBDUMNZXAIUUTH-UHFFFAOYSA-N 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of FAU/LTA composite crystal adsorbent for separating alkane and alkene in coal-based Fischer-Tropsch synthetic oil, which comprises the steps of standing and crystallizing a certain amount of silicon source, aluminum source, inorganic base and water to prepare a guiding agent, strongly stirring the certain amount of silicon source, aluminum source, inorganic base and water to form colloid, adding a small amount of guiding agent, rapidly heating to 90-105 ℃ for crystallization for a certain time, and molding the prepared FAU/LTA composite crystal molecular sieve by using a binder ball to obtain the FAU/LTA composite crystal adsorbent, wherein the adsorbent has the characteristics of large synthesis window, simple synthesis process, high production efficiency, high adsorption, high crushing strength, high alpha-olefin selectivity, high adsorption and desorption rate, small using amount of the desorbent, low separation capacity and the like, and can obviously reduce the isomerization rate of alpha-olefin in the adsorption and separation processes, realizing the high-efficiency synchronous separation of alpha-olefin, isoolefin and alkane.
Description
Technical Field
The invention relates to the technical field of adsorption separation, in particular to a preparation method of a FAU/LTA composite crystal adsorbent for separating coal-based Fischer-Tropsch synthetic oil alkane and alkene.
Background
The industrial F-T synthetic oil technology mainly adopts two processes of fluidized bed high-temperature synthesis and fixed bed low-temperature synthesis, and the two processes mainly have different product distribution except for different temperatures. The high temperature technology mainly produces gasoline and light hydrocarbon, and the low temperature technology mainly produces diesel oil and wax. The low-temperature F-T synthetic oil is complex in components, mainly comprises alpha-olefin, normal alkane, alcohol, ketone, aldehyde, ester and other oxygen-containing compounds, and generally comprises 40-60% of the mass fraction of the alpha-olefin and 3-10% of the mass fraction of the oxide in the low-temperature synthetic Fischer-Tropsch oil. Alpha olefin is a mono-olefin with double bonds at the molecular chain end, is one of important basic raw materials in petrochemical industry, is produced through petrochemical and coal chemical routes, and has important application in the aspects of preparing linear low-density polyethylene, linear high-density polyethylene, industrial synthetic lubricating oil, isononyl alcohol, isodecyl alcohol, detergents and the like. The F-T crude oil is mainly used for primary chemical raw materials or fuel oil, and has low economic benefit and market competitiveness when the oil price is at a low price for a long time. If the long-chain alpha-olefin in the F-T synthetic oil is separated, the long-chain olefin with high added value can be obtained, and products with high added value such as clean and high-quality aviation kerosene, lubricating oil base oil or special solvent oil can be produced, so that the economy of the prior art of the coal-based F-T synthetic oil is improved, and the market risk resistance capability is improved.
Currently, alpha olefin is generally produced by a coal-based Fischer-Tropsch oil through two modes of an extraction rectification process and an adsorption separation process, wherein the extraction rectification process has high requirement on the number of layers of rectification tower plates, the equipment investment is large, the separation energy consumption in the extraction rectification process is large, an X molecular sieve or an A type molecular sieve is generally adopted as an adsorbent in the adsorption separation process, the silica-alumina ratio of the X molecular sieve is generally 2.5-3.0, the crystallinity is lower in the X molecular sieve synthesis process with the silica-alumina ratio lower than 2.5, the adsorption capacity is lower, the treatment amount of adsorption raw materials is lower, and the Li is passed through the X molecular sieve with the silica-alumina ratio of 2.0+N available in air after exchange2、O2Separation, the A type molecular sieve changes the pore size according to different kinds of cation exchange and is generally used for C2～C6And (3) adsorbing and separating the normal isomeric hydrocarbons.
USP2866835 uses 5A molecular sieve to separate C in catalytic gasoline at 80-230 DEG C6～C7The fraction of the olefin component can enrich about 4% of the olefin in the raw material to a concentration of 55%. The process adopts fixed bed adsorption separation, uses butylene as a desorbent, and needs intermittent operation, and in addition, the method has low concentration of enriched olefin, is mixed olefin and has low utilization value.
USP3510423 and C10～C15The mixture of alkane and olefin is used as raw material, olefin is separated by 8-bed simulated moving bed adsorption separation process, and the adsorbent adopts X or Y type molecular sieve exchanged by AgThe purity of the olefin product can reach 98 percent. The adsorbent provided by the method has better olefin separation degree, but the dosage of the desorbent is larger, and the separation energy consumption is larger.
CN101652339B discloses a separation C4The olefin process includes feeding n-butene, isobutene, n-butane, isobutane and other components, and intermittent adsorption separation to obtain high purity n-C4An olefin. The method can only separate the olefin component in a specific distillation section, and has poor industrial application prospect.
CN101462919B discloses a separation method of olefin for producing a cleaning agent, wherein the raw material for adsorption separation is C9～C20With a desorbent using C6～C8And (3) a cycloalkane. The adsorption separation process adopts a simulated moving bed adsorption separation method.
CN109627137B adopts an extraction and rectification mode to separate olefin from the light distillate oil of coal-based Fischer-Tropsch synthesis, the purity of the olefin can reach 99.7 percent, but the method has complex process flow, large dosage of an extracting agent and extremely high energy consumption of the process, and only olefin with single component can be separated.
The existing alkane and alkene separation adsorbent generally has the problem of low adsorption selectivity and can not meet the requirement of producing high-purity alpha-alkene. In order to solve the problems in the prior art, a preparation method of the adsorbent for separating the high-purity alpha-olefin, which has the advantages of simple production process, low production cost, high alpha-olefin product purity and wide raw material application range, needs to be provided.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a FAU/LTA composite crystal adsorbent for separating coal-based Fischer-Tropsch synthetic oil alkane and alkene.
The invention is realized by the following technical scheme:
a preparation method of a FAU and LTA composite crystal adsorbent for separating coal-based Fischer-Tropsch synthetic oil alkane and alkene comprises the following steps:
(1) synthesizing a guiding agent: SiO in molar ratio2/Al2O3＝10～20，M2O/SiO2＝0.8～2.0，H2O/SiO2Respectively weighing a certain amount of silicon source, aluminum source, inorganic base and water, uniformly mixing, and standing at 30 ℃ for 12-48 h, wherein M is Na or K;
(2) gelling: SiO in molar ratio2/Al2O3＝2.4～3.0，M2O/SiO2＝0.9～1.8，H2O/SiO2Feeding materials according to the proportion of 30-80, respectively weighing a certain amount of silicon source, aluminum source, inorganic base and water, and violently stirring and mixing a guiding agent uniformly;
(3) and (3) crystallization: rapidly heating to 90-105 ℃ in the stirring process of the colloid forming system, stopping stirring, standing and crystallizing for 4-12 hours;
(4) washing and drying: washing the crystallized material with deionized water until the pH value of the effluent is less than 10, and drying at 120 ℃ for 12h to obtain the FAU/LTA composite crystal molecular sieve;
(5) molding and roasting: and (3) forming the dried composite crystal molecular sieve and the binder through rolling balls to prepare the FAU/LTA composite crystal adsorbent.
According to the method provided by the invention, the silicon source is one or more of silica sol, sodium silicate and white carbon black, the aluminum source is one or more of sodium metaaluminate, aluminum hydroxide and soluble aluminum salt, and the inorganic alkali is one of sodium hydroxide and potassium hydroxide.
According to the method provided by the invention, the addition amount of the guiding agent in the step (2) is 0.1-10% of the total weight of the gelling and feeding materials.
The method provided by the invention is the FAU/LTA composite crystal molecular sieve SiO in the step (4)2/Al2O32.0 to 2.8, preferably SiO2/Al2O32.2 to 2.6.
The method provided by the invention is characterized in that the FAU/LTA composite crystal molecular sieve in the step (4) has a grain size of 0.1-5.0 μm, and the preferable grain size is 0.8-2.0 μm.
In the method provided by the invention, the binder in the step (5) is one or more of kaolin, attapulgite, pseudoboehmite and silica sol.
The invention also provides the FAU/LTA composite crystal adsorbent prepared by the method, wherein the particle size of the adsorbent is 0.4-2.0 mm, and the preferred particle size of the adsorbent is 0.5-1.0 mm.
The FAU/LTA composite crystal adsorbent has a 200N crushing rate of 0.1-5%.
The invention further provides application of the FAU/LTA composite crystal adsorbent prepared by the method in separation of coal-based Fischer-Tropsch synthetic oil alkane and alkene.
The invention has the following innovation points and advantages:
1. aiming at the characteristics of high alpha-olefin content and a small amount of isomerized olefin in coal-based Fischer-Tropsch synthetic oil, the invention provides the FAU and LTA composite crystal alkane and alkene separation adsorbent which can be used for a Fischer-Tropsch oil alkane and alkene separation simulated moving bed process, obviously improves the purity of an alpha-olefin product, reduces the isomerization rate of the alpha-olefin in the adsorption separation process, and realizes the efficient synchronous separation of the alpha-olefin, the isomerized olefin and alkane;
2. the adsorbent has the characteristics of large synthesis window, simple synthesis process, high production efficiency, high adsorption capacity, high crushing strength, high alpha-olefin selectivity, high adsorption and desorption rate, small consumption of the desorbent, low separation energy consumption and the like.
Drawings
FIG. 1 is an XRD spectrum of FAU/LTA composite crystal adsorbent for separation of coal-based Fischer-Tropsch synthetic oil alkane and alkene.
Detailed Description
In order to make the technical means, innovative features, objectives and effects of the present invention easily understood, the present invention will be further described with reference to the following detailed drawings, but the present invention is not limited thereto.
The XRD spectrum of the FAU/LTA composite crystal adsorbent is shown in figure 1.
The evaluation performance data of the adsorbents in the examples were determined by the following methods:
the separation performance of the adsorbent was calculated by dynamic pulse test. The single-column dynamic pulse test can be used for measuring the separation coefficient of the adsorbent and characterizing the adsorption and desorption rate, and is one of the main methods for evaluating the performance of the adsorbent. A stainless steel straight pipe with the specification of phi 10 multiplied by 1mm and the length of 1200mm is used as an adsorption column in a laboratory, the loading amount of an adsorbent is 60ml, oil bath heating and heat preservation are adopted, an inlet at the upper end of the adsorption column is connected with feeding, and an outlet at the lower end of the adsorption column is connected with a back pressure valve and is connected with an effluent collector. The raw material and the desorbent are pumped into the adsorption column by a trace plunger pump, the pressure of the system is controlled by a back pressure valve, and the effluent is collected after air cooling. The raw materials of the pulse liquid used for the adsorbent test are 30% of hexene-1 + 30% of octene-1 + 20% of n-hexane + 20% of n-octane and 30% of dodecene-1 + 30% of tetradecene-1 + 20% of dodecane + 20% of tetradecane by mass fraction, and corresponding to the two pulse liquids, the desorbent is respectively n-decane or n-octane, so that the desorbent has a boiling point difference with the pulse liquid, and the desorbent is convenient to separate and recycle.
The dynamic pulse test method comprises the steps of filling the activated adsorbent into an adsorption column, vibrating and filling, introducing a desorbent to remove gas in a system, raising the pressure to 1.0MPa, and gradually raising the temperature to the specified temperature. Then, 6ml of pulse liquid is fed quickly, the desorbent is continuously fed in and is desorbed at the same space velocity, and a desorption liquid sample is taken every 5min of feeding of the desorption liquid and is analyzed by gas chromatography to form the composition. By taking the feeding volume of the desorption agent for desorption as an abscissa and the concentration of each component of the pulse liquid as an ordinate, a peak-shaped curve of the content of each component changing along with the dosage of the desorption agent can be drawn. The curve gives the desorption feed volume, i.e.retention volume V, from the midpoint of the half-peak width of the components to zeroRThe retention volume of any component is in direct proportion to the partition coefficient at adsorption equilibrium, which reflects the adsorption equilibrium condition of each component, and the ratio of the net retention volumes of the two components, namely the adsorption selectivity beta value, is also called the separation coefficient. The larger the value of β, the better the separation of the two components. The half-peak width W1/2 of the envelope curve of each component provides information on the mass transfer rate, and the narrower the half-peak width is, the faster the adsorption and desorption rate of the component by the adsorbent is.
Example 1
The FAU/LTA composite crystal adsorbent of the invention is prepared and tested for performance.
(1) Synthesizing a guiding agent: 72.53g of water glass (SiO) were weighed out separately2The mass fraction is 22.63 percent and Na26.97 percent of O, 4.93g of sodium metaaluminate, 9.24g of sodium hydroxide and 46.59g of water, and standing for 12 hours at 30 ℃ after uniform mixing;
(2) gelling: 386.48g of water glass (SiO) is weighed respectively2The mass fraction is 22.63 percent and Na26.97 percent of O), 109.51g of sodium metaaluminate, 18.1g of sodium hydroxide, 519.83g of water and 1.22g of guiding agent are stirred vigorously and mixed uniformly;
(3) and (3) crystallization: rapidly heating to 90 ℃ in the stirring process of the colloid forming system, stopping stirring, standing and crystallizing for 12 hours;
(4) washing and drying: washing the crystallized material with deionized water until the pH value of the effluent is less than 10, and drying at 120 ℃ for 12h to obtain the FAU/LTA composite crystal molecular sieve;
(5) molding and roasting: taking 100g and 15.8g of kaolin of the dried composite crystal molecular sieve, and carrying out rolling ball molding to prepare the FAU/LTA composite crystal adsorbent A-1, wherein the particle size of the adsorbent is 0.4mm, and the crushing rate of the adsorbent 200N is 4.8%.
In the single-column pulse test, 30% of hexene-1 + 30% of octene-1 + 20% of n-hexane + 20% of n-octane was used as a pulse liquid, and n-decane was used as a desorbent, and the measured adsorbent adsorption performance was shown in table 1.
Example 2
An adsorbent was prepared as in example 1, except that the gel forming charge was 260.44g of silica Sol (SiO)228.6 percent of mass fraction), 65.97g of aluminum hydroxide, 56.4g of potassium hydroxide, 700.86g of water and 1.55g of guiding agent are stirred vigorously and mixed uniformly, then the mixture is kept stand and crystallized for 8 hours at 95 ℃, 100g of washed and dried composite crystal molecular sieve and 18.72g of attapulgite rolling balls are taken for forming to prepare the composite crystal adsorbent A-2, the particle size of the adsorbent is 0.6mm, and the crushing rate of the adsorbent 200N is 3.7 percent.
In the single-column pulse test, 30% of hexene-1 + 30% of octene-1 + 20% of n-hexane + 20% of n-octane was used as a pulse liquid, and n-decane was used as a desorbent, and the measured adsorbent adsorption performance was shown in table 1.
Example 3
An adsorbent was prepared according to the method of example 1, except that the gel-forming charge was 162.53g of silica, 36.92g of aluminum sulfate, 57.34g of sodium hydroxide, 770.5g of water, 2.17g of directing agent, vigorously stirred and mixed uniformly, then left to stand at 100 ℃ for crystallization for 6h, and 100g and 12.72g of silica Sol (SiO) were taken as the composite crystal molecular sieve after washing and drying228.6 percent of mass fraction) of the ball, and obtaining the composite crystal adsorbent A-3, wherein the particle size of the adsorbent is 0.8mm, and the crushing rate of the adsorbent 200N is 3.1 percent.
In the single-column pulse test, 30% of hexene-1 + 30% of octene-1 + 20% of n-hexane + 20% of n-octane was used as a pulse liquid, and n-decane was used as a desorbent, and the measured adsorbent adsorption performance was shown in table 1.
Example 4
An adsorbent was prepared as in example 1, except that the guiding agent charge was 29.01g of water glass (SiO)2The mass fraction is 22.63 percent and Na26.97 percent of O, 0.99g of sodium metaaluminate, 14.87g of sodium hydroxide and 76.15g of water, and standing for 48 hours at 30 ℃ to prepare the composite crystal adsorbent A-4, wherein the particle size of the adsorbent is 1.2mm, and the crushing rate of the adsorbent 200N is 2.1 percent.
The single column pulse test uses 30% dodecene-1 + 30% tetradecene-1 + 20% dodecane + 20% tetradecane as the pulse liquid and n-octane as the desorbent, and the measured adsorbent adsorption performance is shown in table 1.
Example 5
An adsorbent was prepared as in example 2, except that the guiding agent charge was 25.61g of silica Sol (SiO)228.6 percent of mass fraction), 0.99g of sodium metaaluminate, 14.87g of sodium hydroxide and 76.15g of water, and standing for 36 hours at 30 ℃ to prepare the composite crystal adsorbent A-5, wherein the particle size of the adsorbent is 1.4mm, and the crushing rate of the adsorbent 200N is 5.1 percent.
The single column pulse test uses 30% dodecene-1 + 30% tetradecene-1 + 20% dodecane + 20% tetradecane as the pulse liquid and n-octane as the desorbent, and the measured adsorbent adsorption performance is shown in table 1.
TABLE 1
| Example number | 1 | 2 | 3 | 4 | 5 |
| Sorbent numbering | A-1 | A-2 | A-3 | A-4 | A-5 |
| βHexene-1/n-hexane | 1.58 | 1.67 | 1.74 | - | - |
| βOctene-1/n-octane | 1.46 | 1.52 | 1.53 | - | - |
| Hexene-1 half Width, mL | 32.97 | 31.68 | 33.88 | - | - |
| Octen-1 half Width, mL | 20.51 | 20.32 | 22.14 | - | - |
| βDodecene/dodecane | - | - | - | 1.85 | 1.88 |
| βTetradecene/tetradecane | - | - | - | 1.58 | 1.61 |
| half-Width of dodecene, mL | - | - | - | 33.87 | 32.54 |
| Tetradecene half-peak Width, mL | - | - | - | 21.69 | 21.30 |
| Kinds of desorbents | N-decane | N-decane | N-decane | N-octane | N-octane |
Claims (10)
1. A preparation method of a FAU/LTA composite crystal adsorbent for separating coal-based Fischer-Tropsch synthetic oil alkane and alkene is characterized by comprising the following steps:
(1) synthesizing a guiding agent: SiO in molar ratio2/Al2O3＝10～20，M2O/SiO2＝0.8～2.0，H2O/SiO2Respectively weighing a certain amount of silicon source, aluminum source, inorganic base and water, uniformly mixing, and standing at 30 ℃ for 12-48 h, wherein M is Na or K;
(2) gelling: SiO in molar ratio2/Al2O3＝2.4～3.0，M2O/SiO2＝0.9～1.8，H2O/SiO2Feeding materials according to the proportion of 30-80, respectively weighing a certain amount of a silicon source, an aluminum source, inorganic base, water and a guiding agent, and violently stirring and uniformly mixing;
(3) and (3) crystallization: rapidly heating to 90-105 ℃ in the stirring process of the colloid forming system, stopping stirring, standing and crystallizing for 4-12 hours;
(4) washing and drying: washing the crystallized material obtained in the step (3) with deionized water until the pH value of an effluent is less than 10, and drying to obtain the FAU/LTA composite crystal molecular sieve;
(5) molding and roasting: and (4) forming the FAU/LTA composite crystal molecular sieve obtained in the step (4) and a binder through rolling balls to obtain the FAU/LTA composite crystal adsorbent.
2. The preparation method according to claim 1, wherein the silicon source is one or more of silica sol, water glass and white carbon black; the aluminum source is one or more of sodium metaaluminate, aluminum hydroxide and soluble aluminum salt, and the inorganic alkali is one of sodium hydroxide and potassium hydroxide.
3. The preparation method of claim 1, wherein the guiding agent in step (2) is added in an amount of 0.1-10% of the total weight of the gel-forming charge.
4. The method according to claim 1, wherein the FAU/LTA composite crystal molecular sieve SiO in the step (4)2/Al2O32.0 to 2.8, preferably 2.2 to 2.6.
5. The method according to claim 1, wherein the FAU/LTA composite crystal molecular sieve in the step (4) has a grain size of 0.1-5.0 μm.
6. The method according to claim 1, wherein the FAU/LTA composite crystal molecular sieve in the step (4) has a grain size of 0.8-2.0 μm.
7. The preparation method according to claim 1, wherein the binder in step (5) is one or more of kaolin, attapulgite, pseudoboehmite, and silica sol.
8. An FAU/LTA composite crystal adsorbent prepared by the preparation method of any one of claims 1 to 7, wherein the particle size of the FAU/LTA composite crystal adsorbent is 0.4-2.0 mm, and the preferred particle size of the adsorbent is 0.5-1.0 mm.
9. The FAU/LTA composite crystal adsorbent as set forth in claim 8, wherein the FAU/LTA composite crystal adsorbent has a 200N crush rate of 0.1-5%.
10. Use of the FAU/LTA composite crystal adsorbent according to claim 8 in the separation of alkanes and alkenes from coal-based Fischer-Tropsch synthetic oils.
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