CN114917866B - Olefin adsorbent for Fischer-Tropsch light distillate oil adsorption rectification coupling process and preparation method thereof - Google Patents
Olefin adsorbent for Fischer-Tropsch light distillate oil adsorption rectification coupling process and preparation method thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 71
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 58
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 51
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000010168 coupling process Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 239000004711 α-olefin Substances 0.000 claims abstract description 29
- 230000008878 coupling Effects 0.000 claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 claims abstract description 11
- 239000002808 molecular sieve Substances 0.000 claims description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 19
- 239000003921 oil Substances 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 238000005342 ion exchange Methods 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000003795 desorption Methods 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002500 ions Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- 150000001335 aliphatic alkanes Chemical class 0.000 description 15
- 238000012856 packing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 6
- 230000000274 adsorptive effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 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 description 3
- 230000032683 aging Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 238000009495 sugar coating Methods 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 2
- -1 alkane olefin Chemical class 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
Classifications
-
- 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
- B01J20/02—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
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
- C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G7/00—Distillation of hydrocarbon oils
-
- 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
-
- 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
- C10G2300/1037—Hydrocarbon fractions
Abstract
The invention relates to an olefin adsorbent for Fischer-Tropsch light distillate oil adsorption rectification coupling separation technology and a preparation method thereof. The prepared olefin adsorbent is applied to the Fischer-Tropsch light distillate (C4-C10) adsorption rectification coupling separation process, has high saturated adsorption capacity and selectivity for olefin in the Fischer-Tropsch light distillate (C4-C10), and is applied to the adsorption rectification coupling separation process to obtain the alpha-olefin with the purity of more than 99.2% and the yield of more than 85%.
Description
Technical Field
The invention relates to the technical field of adsorption separation, in particular to an adsorbent for a Fischer-Tropsch synthetic oil adsorption rectification coupling process and a preparation method thereof.
Background
Alpha-olefin refers to mono-olefin with double bond at molecular chain end, is an important raw material for petrochemical industry, and can be used as comonomer, surfactant synthesis intermediate, plasticizer alcohol, synthetic lubricating oil, oil additive and the like, and the application is wide. At present, alpha-olefin is mainly produced through ethylene oligomerization, the process flow is simple, but byproducts are more, the energy consumption is higher, and the economy is poor. The Fischer-Tropsch synthesis light distillate oil contains a large amount of alpha-olefin, and the Fischer-Tropsch oil is mostly produced by hydrotreating or directly used as primary industrial materials at present, and the olefin component is utilized in a low value. Therefore, the invention provides the adsorbent, which is used for separating alpha-olefin in Fischer-Tropsch oil through adsorption and rectification to be used as an olefin product with high added value, so that the economic benefit of enterprises is improved.
CN201911406647.3 discloses a process for preparing Fischer-Tropsch oil alkane-alkene separation adsorbent, which comprises pre-adsorbent and main adsorbent, wherein the pre-adsorbent is used for removing oxygen-containing organic matters in Fischer-Tropsch synthetic oil, and the obtained refined alkane and alkene mixture is subjected to deep adsorption separation by the main adsorbent through a simulated moving bed process to obtain high-purity alpha-alkene
CN201911406649.2 discloses a method for separating long-chain alkane from fischer-tropsch synthetic oil, which comprises the steps of introducing raw materials into a pre-adsorption tower filled with deoxidizing adsorbent for adsorption separation to remove oxygen-containing compounds in the raw materials, so that the mass fraction of the oxygen-containing compounds is reduced to below 0.1%; then the obtained material is sent to a simulated moving bed adsorption separation system filled with alkane-alkene separation adsorbent to carry out alkane-alkene adsorption separation, and two material flows are obtained by selectively separating alpha-alkene and alkane, wherein one material flow is rich in alpha-alkene components, and the other material flow is rich in alkane components; finally, sending the alpha-olefin-rich component into a rectifying unit, and cutting the desorbent and the alpha-olefin to obtain the alpha-olefin and the desorbent, wherein the desorbent is circulated to a desorbent storage tank; and sending the alkane-rich component into a rectifying unit for cutting to obtain the desorbent and long-chain alkane cutting. The method can obtain long-chain alpha-olefin with high added value through two-stage series adsorption separation process.
As can be seen, there is no technology for separating alpha-olefin by using an adsorption rectification adsorbent and an adsorption rectification process to extract fischer-tropsch synthesized light distillate.
Disclosure of Invention
The invention relates to an adsorption rectification adsorbent for separating Fischer-Tropsch oil alkane from olefin and a preparation method thereof, and aims to overcome the defects of the prior separation technology, and provides an olefin adsorbent for a Fischer-Tropsch light distillate oil adsorption rectification coupling process and a preparation method thereof.
The invention provides an olefin adsorbent for Fischer-Tropsch light distillate adsorption rectification coupling process, which comprises 80-90 wt% of a metal ion exchanged molecular sieve adsorbent and 10-20% of an auxiliary agent, wherein n (SiO) in the framework of the metal ion exchanged molecular sieve adsorbent 2 )/n(Al 2 O 3 ) =2.2 to 2.8, the adsorbent is NH 3 The desorption temperature of the acid center in the TPD analysis is 120-300 ℃; the metal ion is one or more of Fe, cs, ti, ba, and the specific surface area of the olefin adsorbent and the molecular sieve adsorbent exchanged by the metal ion is 500-700 m 2 And/g, the pore diameter is 2-5 nm.
According to the olefin adsorbent of the present invention, preferably, the metal ion exchanged molecular sieve adsorbent has a grain size of 0.5 to 10 μm and a specific surface area of 600 to 700m 2 Per g, pore diameter of 3-4 nm, pore volume of 0.2-0.8 cm 3 /g。
According to the olefin adsorbent of the present invention, preferably, n (SiO 2 )/n(Al 2 O 3 ) =2.3 to 2.5, the adsorbent is NH 3 The desorption temperature of the acid center in the TPD analysis is 200-250 ℃.
According to the olefin adsorbent of the present invention, preferably, the metal ion exchanged molecular sieve adsorbent is prepared by dissolving aluminum, dissolving silicon, gelling, continuous crystallization, ion exchange, and molding.
According to the olefin adsorbent, preferably, the continuous crystallization step is carried out in a continuous crystallization device, the gel forming solution obtained in the gel forming step is conveyed into a raw material tank of the continuous crystallization device, the temperature of the solution is controlled to be increased to 90-120 ℃, the gel forming solution is crystallized from the raw material tank through a section of slender pipeline, the gel forming solution flows out of the device after 1-2 hours, and is dried at a high temperature after suction filtration separation, and the temperature is 120-200 ℃ for 12-24 hours.
The invention further provides a preparation method of the olefin adsorbent, which comprises the following steps:
1) Dissolving an aluminum source in water to obtain an aluminum source water solution;
2) Dissolving a silicon source in water to obtain a silicon source water solution;
3) Slowly and uniformly dripping an aluminum source water solution into a silicon source water solution in a low-temperature water bath with the temperature less than or equal to 20 ℃, continuously stirring the process, controlling the gel forming time to be less than or equal to 30 minutes, obtaining a gel forming solution, and continuously stirring for 20-40 minutes after the completion of the gel forming;
4) The gel forming solution is conveyed into a raw material tank of a continuous crystallization device, the temperature of the solution is controlled to be increased to 90-120 ℃ in the process, the gel forming solution is crystallized from the raw material tank through a section of slender pipeline, flows out of the device after 1-2 hours, is dried at high temperature after being filtered and separated, and is subjected to temperature 120-200 ℃ for 12-24 hours, so that a molecular sieve product is obtained;
5) Placing the obtained molecular sieve product in an ion exchange device for ion exchange, wherein the exchange metal ions comprise one or more of Fe, cs, ti, ba, drying, and then performing temperature programming roasting to obtain the ion exchanged molecular sieve product;
6) Finally, mixing the ion-exchanged molecular sieve product and the auxiliary agent, molding, drying and roasting to obtain the catalyst; wherein the contents of the components are as follows: 80-90 wt% of molecular sieve and 10-20% of auxiliary agent; the forming process adopts one of rolling ball and granulating to prepare the formed adsorbent with the particle size of 1-3 mm.
According to the preparation method, the molar ratio of the molecular sieve synthesis feed is preferably as follows: siO (SiO) 2 /Al 2 O 3 ＝2.0～3.0，Na 2 O/SiO 2 ＝1.0～5.0，H 2 O/SiO 2 ＝50～400。
According to the preparation method of the present invention, preferably the temperature-programmed calcination includes: heating to 250-300 ℃ in 2h, then keeping the temperature for roasting for 1.5-2.5 h, continuously programming to 450-550 ℃ in 2h, keeping the temperature for roasting for 3-5 h, and naturally cooling.
According to the application of the olefin adsorbent in the Fischer-Tropsch light distillate oil adsorption rectification coupling separation process, the olefin adsorbent is preferably filled in an adsorption rectification tower, and the adsorption rectification coupling separation process is used for obtaining the alpha-olefin with the purity of more than or equal to 99.2 percent and the yield of more than or equal to 85 percent.
According to the application of the olefin adsorbent in the Fischer-Tropsch light distillate oil adsorption, rectification and coupling separation process, the olefin adsorbent is preferably filled in an adsorption section of an adsorption rectifying tower, and the ratio of the olefin adsorbent to the filler filled in the adsorption section is 1:10-10:1.
The olefin adsorbent for the Fischer-Tropsch light distillate oil adsorption rectification coupling process and the preparation method and application thereof have the beneficial effects that compared with the prior art:
1) Aiming at the characteristics of the alkane-alkene separation and adsorption rectification process, the invention provides a special adsorbent which can obtain high-purity and high-yield alpha-olefin, can greatly reduce energy consumption and improve economic benefit;
2) The main component molecular sieve of the olefin adsorbent adopts continuous flow synthesis, the crystallization time is greatly shortened, the crystallization process has accurate temperature control, the uniformity of the synthesized molecular sieve is strong, the production cost is reduced, and the production efficiency is improved;
3) The preparation process of the adsorbent improves the selectivity and saturated adsorption capacity of the adsorbent, optimizes the separation performance of the adsorbent and reduces the process energy consumption by controlling the gel forming temperature and the roasting procedure.
Detailed Description
To further illustrate the olefin adsorbents and methods of making the olefin adsorbents for Fischer-Tropsch light distillate adsorption rectification coupling processes, the invention is described below in connection with examples, but the invention is not limited to these examples.
Example 1: preparation and application of adsorbent A
Step A: molecular sieve synthesis
1000g of sodium metaaluminate and 6200g of water are taken and stirred and dissolved in a beaker to obtain a solution (1);
taking 4170g of water glass and 3100g of water, stirring and dissolving in a beaker to obtain a solution (2);
slowly and uniformly dripping the solution (1) into the solution (2) in a low-temperature water bath (the temperature is less than or equal to 20 ℃), continuously stirring the solution in the process, controlling the gelling time to be less than or equal to 30 minutes, obtaining a gelling solution (3), and continuously stirring for 30 minutes after the gelling solution is finished;
standing and aging the gel forming solution (3) for 24 hours at 30 ℃, and then crystallizing for 1.5 hours in a continuous flow reactor at 95 ℃ to obtain a solution (4); in a continuous flow reactor, the specific process is as follows: delivering the gel forming solution into a raw material tank of a continuous flow reactor, controlling the process to heat the solution to a crystallization temperature of 95 ℃, crystallizing the gel forming solution from the raw material tank through a section of long and thin pipeline, and flowing out of the device after 1.5 h;
after crystallization, the crystallized solution (4) is filtered and separated by suction and dried for 24 hours at the temperature of 120 ℃ to obtain the pure phase molecular sieve WX-1, the grain size is 1.5-2.5 mu m, and the element n (SiO) 2 )/n(Al 2 O 3 ) Molar ratio=2.41, specific surface area 660m 2 Per g, pore diameter 2.12nm, pore volume 0.33cm 3 /g。
And (B) step (B): ion exchange modification
And loading the roasted WX-1 300g into an ion exchange column, wherein the temperature is 80 ℃, the ion exchange liquid is CsCl solution with the concentration of 1mol/L, the pumping speed is 3mL/min, the volume of the exchange liquid is 40 times that of the adsorbent, and finally, drying and roasting are carried out to obtain the exchanged molecular sieve WXJ-1. The firing procedure is shown in FIG. 1. The Cs exchange degree of WXJ-1 is 40%, the grain size is 1.5-2.5 μm, and the element n (SiO 2 )/n(Al 2 O 3 ) Molar ratio = 2.41, specific surface area 640m 2 Per g, pore diameter 2.07nm, pore volume 0.32cm 3 And/g. The acid center desorption temperature=230℃inthe NH3-TPD analysis.
Step C: shaping
Taking 250g of WXJ-1, 30g of attapulgite and 5g of sesbania powder, putting the mixture into a small sugar-coating machine for balling, continuously and slowly adding 80g of water in the process of rolling the mixture into the ball, finally obtaining 150g of balls with the particle size of 20-40 meshes, and drying and roasting the balls to obtain the final olefin adsorbent WXQ-1. Specific surface area 612m 2 Per g, pore diameter 2.01nm, pore volume 0.33cm 3 /g。
Step D: evaluation
The deoxidized Fischer-Tropsch C4-C10 fraction (the oxide content is lower than 1 mug/g) enters an adsorption rectifying tower for further alkane-alkene separation, and the adsorption rectifying tower is a packed tower and consists of five parts, namely a rectifying section, an adsorption section, a stripping section, a tower top condenser and a tower kettle reboiler. The rectifying section and the stripping section are filled with theta-ring filler to ensure that light and heavy components are fully separated, the adsorption section is filled with adsorbent and theta-ring filler (volume ratio is 6:4), and the adsorbent adopts WXQ-1. The total number of the adsorption rectifying tower is 85, the number of the adsorption section is 35, the number of the rectifying section is 20, and the number of the stripping section is 25. The C4-C10 alkane olefin raw material enters at a 35 th column plate (the middle part of an adsorption section), the operation pressure of the column top is 1atm, the mass reflux ratio is 2.5, the temperature of the column top is 45 ℃, and the temperature of the column bottom is 200 ℃. One stream is named side stream 1at tray 12 and consists essentially of a mixture of C6-C7 alkanes and C4-C5 alkenes, and the other stream is named side stream 2 at tray 72 and consists essentially of a mixture of C8-C10 alkanes and C6-C7 alkenes. The purity of each product after adsorption, rectification and separation is shown in table 3. The purity of C8-C10 alpha-olefin in the tower bottom reaches more than 99.8wt.%, and the yield reaches 95%. The two streams extracted from the side line directly enter a rectifying and refining unit for further processing.
TABLE 1 purity of the components of the streams after adsorptive rectification
The rectifying and refining unit adopts two rectifying towers to respectively treat two side streams 1 and 2, the side stream 1 enters a rectifying tower A, and a packing tower is adopted, wherein the packing type is theta-ring. The total number of plates of the rectifying tower A is 45, the operating pressure at the top of the tower is 1atm, the feeding position is the 20 th plate, and the mass reflux ratio is 1.5. And the side stream 2 enters a rectifying tower B, a packing tower is adopted, and the packing type is theta-ring. The total number of plates of the rectifying tower B is 55, the operating pressure is 1atm, the feeding position is the 30 th plate, and the mass reflux ratio is 2.3. The purity of the product stream components after rectification refining is shown in tables 2 and 3. The purity of the C4-C5 alpha-olefin product can reach 99.8wt.%, the yield reaches 94%, and the purity of the C6-C7 alpha-olefin product can reach 99.8wt.%, and the yield reaches 92%.
TABLE 2 purity of the stream components of rectifying column A
TABLE 3 purity of the stream components of rectifying column B
Example 2: preparation and application of adsorbent B
Step A: molecular sieve synthesis
1000g of sodium metaaluminate and 12880g of water are taken and stirred and dissolved in a beaker to obtain a solution (1);
3665g of water glass and 6440g of water are taken and stirred and dissolved in a beaker to obtain a solution (2);
slowly and uniformly dripping the solution (1) into the solution (2) in a low-temperature water bath (the temperature is less than or equal to 20 ℃), continuously stirring the solution in the process, controlling the gel forming time to be less than or equal to 30 minutes, obtaining the solution (3), and continuously stirring for 30 minutes after the completion of the gel forming;
standing and aging the solution (3) for 24 hours at 30 ℃, and then crystallizing the solution in a continuous flow reactor at 95 ℃ for 1.5 hours to obtain a solution (4);
after crystallization, the solution (4) is subjected to suction filtration and drying steps to obtain a pure phase molecular sieve WX-2, the crystal grain is 2.0-3.5 mu m, and the element n (SiO) 2 )/n(Al 2 O 3 ) Molar ratio=2.49, specific surface area 632m 2 Per g, pore diameter 2.07nm, pore volume 0.29cm 3 /g。
And (B) step (B): ion exchange modification
Loading roasted WX-2 300g into ion exchange column at 80deg.C with 1mol/L BaCl ion exchange solution 2 And (3) the solution is pumped at a speed of 3mL/min and is exchanged until the solution penetrates (about 4 h), and finally, the solution is dried and roasted to obtain the exchanged molecular sieve WXJ-2. The firing procedure was as in example 1. The Ba exchange degree of WXJ-2 is 30%, and the crystal grains
2.0-3.5 μm, element n (SiO 2 )/n(Al 2 O 3 ) =2.49, specific surface area 654m 2 Per g, pore diameter 2.21nm, pore volume 0.32cm 3 /g。NH 3 -acid center desorption temperature = 250 ℃ in TPD analysis.
Step C: shaping
250g of WXJ-2, 35g of kaolin and 5g of sesbania powder are put into a small sugar-coating machine for rolling and balling, 95g of water is continuously and slowly added in the process of rolling and balling, 150g of pellets with the particle size of 20-40 meshes are finally obtained, and the final olefin adsorbent WXQ-2 is obtained through drying and roasting. Specific surface area 635m 2 Per g, pore diameter 2.14nm, pore volume 0.31cm 3 /g。
Step D: evaluation
The deoxidized Fischer-Tropsch C4-C10 fraction (the oxide content is lower than 1 mug/g) enters an adsorption rectifying tower for further alkane-alkene separation, and the adsorption rectifying tower is a packed tower and consists of five parts, namely a rectifying section, an adsorption section, a stripping section, a tower top condenser and a tower kettle reboiler. The rectifying section and the stripping section are filled with theta-ring filler to ensure that light components and heavy components are fully separated, the adsorption section is filled with adsorbent and theta-ring filler (volume ratio is 7:3) in a certain proportion, and the adsorbent adopts WXQ-2. The total plate number of the adsorption rectifying tower is 95, the number of the plates of the adsorption section is 45, the number of the plates of the rectifying section is 20, and the number of the plates of the stripping section is 30. The C4-C10 alkylolefin feed was introduced at the 45 th tray (middle of adsorption stage), the overhead operating pressure was 1atm, the mass reflux ratio was 3, the overhead temperature was 48℃and the column bottom temperature was 205 ℃. One stream is named side stream 1at tray 14 and consists essentially of a mixture of C6-C7 alkanes and C4-C5 alkenes, and the other stream is named side stream 2 at tray 80 and consists essentially of a mixture of C8-C10 alkanes and C6-C7 alkenes. The purity of each product after adsorption, rectification and separation is shown in table 4. The purity of C8-C10 alpha-olefin in the tower bottom reaches 99.7wt.%, and the yield reaches 95%. The two streams extracted from the side line directly enter a rectifying and refining unit for further processing.
The rectifying and refining unit adopts two rectifying towers to respectively treat two side streams 1 and 2, the side stream 1 enters a rectifying tower A, and a packing tower is adopted, wherein the packing type is theta-ring. The total number of plates of the rectifying tower A is 35, the operating pressure at the top of the tower is 1atm, the feeding position is 15 th plate, and the mass reflux ratio is 1.7. And the side stream 2 enters a rectifying tower B, a packing tower is adopted, and the packing type is theta-ring. 60 total plates of the rectifying tower B, the operating pressure is 1atm, the feeding position is 35 th plate, and the mass reflux ratio is 2.0. The purity of the product stream components after rectification refining is shown in tables 5 and 6. The purity of the C4-C5 alpha-olefin product reaches 99.6wt.%, and the yield reaches 92%; the purity of the C6-C7 alpha-olefin product reaches 99.6wt.%, and the yield reaches 93%.
TABLE 4 purity of the components of the streams after adsorptive rectification
TABLE 5 purity of the stream components of rectifying column A
TABLE 6 purity of the stream components of rectifying column B
Example 3: preparation and application of adsorbent C
Step A: molecular sieve synthesis
1000g of sodium metaaluminate and 6200g of water are taken and stirred and dissolved in a beaker to obtain a solution (1);
taking 3789g of water glass and 3500g of water, stirring and dissolving in a beaker to obtain a solution (2);
slowly and uniformly dripping the solution (1) into the solution (2) in a low-temperature water bath (the temperature is less than or equal to 20 ℃), continuously stirring the solution in the process, controlling the gelling time to be less than or equal to 30 minutes, obtaining a gelling solution (3), and continuously stirring for 30 minutes after the gelling solution is finished;
standing and aging the gel forming solution (3) for 24 hours at 30 ℃, and then crystallizing for 1.5 hours in a continuous flow reactor at 95 ℃ to obtain a solution (4); in a continuous flow reactor, the specific process is as follows: delivering the gel forming solution into a raw material tank of a continuous flow reactor, controlling the process to heat the solution to a crystallization temperature of 98 ℃, crystallizing the gel forming solution from the raw material tank through a section of long and thin pipeline, and flowing out of the device after 1.5 h;
after crystallization, the crystallized solution (4) is filtered and separated by suction and dried for 24 hours at the temperature of 120 ℃ to obtain the pure phase molecular sieve WX-3, the grain size is 1.5-2.5 mu m, and the element n (SiO) 2 )/n(Al 2 O 3 ) Molar ratio = 2.48, specific surface area 680m 2 Per g, pore diameter 2.12nm, pore volume 0.33cm 3 /g。
And (B) step (B): ion exchange modification
Loading roasted WX-3 300g into ion exchange column at 80deg.C with ion exchange solution of Fe (Cl) 1mol/L 3 The solution is pumped at a speed of 3mL/min, the volume of the exchange liquid is 40 times that of the adsorbent, and finally the exchange liquid is dried and roasted to obtain the exchanged molecular sieve WXJ-1. The firing procedure is shown in FIG. 1. The Fe exchange degree of WXJ-3 is 60%, the grain size is 1.5-2.5 μm, and the element n (SiO 2 )/n(Al 2 O 3 ) Molar ratio = 2.58, specific surface area 610m2/g, pore diameter 2.02nm, pore volume 0.32cm 3 /g。NH 3 -acid center desorption temperature = 230 ℃ in TPD analysis.
Step C: shaping
Taking 250g of WXJ-3, 35g of attapulgite and 5g of water-soluble starch, putting into a small sugar-coating machine for balling, continuously and slowly adding 80g of water in the process of balling to finally obtain 150g of pellets with the particle size of 20-40 meshes, and drying and roasting to obtain the final olefin adsorbent WXQ-3. Specific surface area 612m 2 Per g, pore diameter 2.02nm, pore volume 0.32cm 3 /g。
Step D: evaluation
The deoxidized Fischer-Tropsch C4-C10 fraction (the oxide content is lower than 1 mug/g) enters an adsorption rectifying tower for further alkane-alkene separation, and the adsorption rectifying tower is a packed tower and consists of five parts, namely a rectifying section, an adsorption section, a stripping section, a tower top condenser and a tower kettle reboiler. The rectifying section and the stripping section are filled with Raschig ring filler to ensure that light components and heavy components are fully separated, the adsorbing section is filled with adsorbent and Raschig ring filler (volume ratio is 6:4), and the adsorbent adopts WXQ-3. The total number of the adsorption rectifying tower is 85, the number of the adsorption section is 35, the number of the rectifying section is 20, and the number of the stripping section is 25. The C4-C10 alkane olefin raw material enters at a 35 th column plate (the middle part of an adsorption section), the operation pressure of the column top is 1atm, the mass reflux ratio is 2.5, the temperature of the column top is 45 ℃, and the temperature of the column bottom is 200 ℃. The purity of each product after adsorption, rectification and separation is shown in table 7. The purity of C8-C10 alpha-olefin in the tower bottom reaches more than 99.9wt.%, and the yield reaches 96%.
TABLE 7 purity of the components of the streams after adsorptive rectification
| Raw materials wt.% | Overhead wt.% | The weight percent of the tower kettle is equal to | |
| C 4 -C 5 Alkanes | 15.11 | 99.60 | 0 |
| C 6 -C 7 Alkanes | 13.21 | 0.02 | 0 |
| C 8 -C 10 Alkanes | 18.23 | 0 | 0.08 |
| C 4 -C 5 Alpha-olefins | 12.56 | 0.02 | 0 |
| C 6 -C 7 Alpha-olefins | 14.35 | 0 | 0 |
| C 8 -C 10 Alpha-olefins | 26.54 | 0 | 99.9 |
| Other substances | 2.01 | 0.36 | 0.02 |
Example 4:
the difference from example 3 is that the adsorption section is filled with adsorbent and Raschig ring packing (volume ratio 7:3), and the purity of each product after adsorption, rectification and separation is shown in Table 8. The purity of C8-C10 alpha-olefin in the tower bottom reaches more than 99.9wt.%, and the yield reaches 98%.
TABLE 8 purity of the components of the streams after adsorptive rectification
| Raw materials wt.% | Overhead wt.% | The weight percent of the tower kettle is equal to | |
| C 4 -C 5 Alkanes | 15.11 | 99.8 | 0 |
| C 6 -C 7 Alkanes | 13.21 | 0.05 | 0 |
| C 8 -C 10 Alkanes | 18.23 | 0 | 0.08 |
| C 4 -C 5 Alpha-olefins | 12.56 | 0.05 | 0 |
| C 6 -C 7 Alpha-olefins | 14.35 | 0 | 0 |
| C 8 -C 10 Alpha-olefins | 26.54 | 0 | 99.9 |
| Other substances | 2.01 | 0.1 | 0.02 |
Comparative example 1:
the difference from example 3 is that the adsorption section is filled with olefin adsorbent only, and the purity of each product after adsorption, rectification and separation is shown in table 9. The purity of C8-C10 alpha-olefin in the tower kettle reaches more than 89.2wt.% and the yield reaches 78%.
TABLE 9 purity of the components of the streams after adsorptive rectification
Claims (10)
1. An olefin adsorbent for Fischer-Tropsch light distillate oil adsorption rectification coupling process is characterized in that:
the olefin adsorbent comprises 80-90 wt% of metal ion exchanged molecular sieve and 10-20 wt% of auxiliary agent, wherein n (SiO 2 ）/n（Al 2 O 3 ) =2.2 to 2.8; the metal ion is one or more of Fe, cs, ti, ba, and the olefin adsorbent and the metal ion exchanged molecular sieve are absorbedThe specific surface area of the adhesive agent is 500-700 m 2 /g, wherein the aperture is 2-5 nm;
the olefin adsorbent is in NH 3 The desorption temperature of the acid center in the TPD analysis is 120-300 ℃.
2. The olefin adsorbent according to claim 1, wherein the olefin adsorbent is filled in an adsorption rectifying tower and applied to a Fischer-Tropsch light distillate oil adsorption rectifying coupling separation process, and the adsorption rectifying coupling separation process obtains alpha-olefin with purity of more than or equal to 99.2% and yield of more than or equal to 85%.
3. The olefin adsorbent according to claim 1, wherein the metal ion exchanged molecular sieve has a grain size of 0.5 to 5 μm and a specific surface area of 600 to 700m 2 Per gram, pore diameter of 3-4 nm and pore volume of 0.2-0.8 cm 3 /g。
4. The olefin adsorbent of claim 1, wherein n (SiO 2 ）/n（Al 2 O 3 ) =2.3 to 2.5, the olefin adsorbent is in NH 3 The desorption temperature of the acid center in the TPD analysis is 200-250 ℃.
5. The olefin adsorbent according to claim 1, wherein the metal ion exchanged molecular sieve is prepared by dissolving aluminum, dissolving silicon, gelling, continuous crystallization, ion exchange, and molding; the continuous crystallization step is carried out in a continuous crystallization device, the gel forming solution obtained in the gel forming step is conveyed into a raw material tank of the continuous crystallization device, the temperature of the solution is controlled to be increased to be 90-120 ℃, the gel forming solution is crystallized from the raw material tank through a section of slender pipeline, flows out of the device after 1-2 hours, is dried at a high temperature after being filtered and separated, and is heated at 120-200 ℃ for 12-24 hours, so that the molecular sieve product is obtained.
6. A process for the preparation of an olefin adsorbent as claimed in claim 1, comprising the steps of:
dissolving an aluminum source in water to obtain an aluminum source water solution;
dissolving a silicon source in water to obtain a silicon source water solution;
slowly and uniformly dripping an aluminum source water solution into a silicon source water solution in a low-temperature water bath at the temperature of less than or equal to 20 ℃, continuously stirring in the process, controlling the gelling time to be less than or equal to 30 minutes, obtaining a gelling solution, and continuously stirring for 20-40 minutes after the gelling solution is finished;
conveying the gel forming solution to a raw material tank of a continuous crystallization device, controlling the temperature of the solution to be 90-120 ℃ in the process, crystallizing the gel forming solution from the raw material tank through a section of long and thin pipeline, flowing out of the device after 1-2 hours, performing suction filtration and separation, and then drying at a high temperature of 120-200 ℃ for 12-24 hours to obtain a molecular sieve product;
placing the obtained molecular sieve product in an ion exchange device for ion exchange, wherein the exchange metal ions comprise one or more of Fe, cs, ti, ba, drying, and then performing temperature programming roasting to obtain the ion exchanged molecular sieve product;
finally, mixing the ion-exchanged molecular sieve product and the auxiliary agent, molding, drying and roasting to obtain the catalyst; wherein the contents of the components are as follows: 80-90 wt% of molecular sieve and 10-20% of auxiliary agent; the forming process adopts one of rolling balls and granulating, and the particle size of the formed olefin adsorbent is 1-3 mm.
7. The method of claim 6, wherein the molar ratio of molecular sieve synthesis charge is: siO (SiO) 2 /Al 2 O 3 ＝2.0~3.0，Na 2 O/SiO 2 ＝1.0~5.0，H 2 O/SiO 2 ＝50~400。
8. The method of claim 6, wherein the temperature-programmed firing comprises: heating to 250-300 ℃ in 2h, then roasting at the maintained temperature for 1.5-2.5 h, continuously programming to 450-550 ℃ in 2h, continuously roasting at the maintained temperature for 3-5 h, and naturally cooling.
9. The application of the olefin adsorbent in the Fischer-Tropsch light distillate oil adsorption rectification coupling separation process according to claim 1, which is characterized in that the olefin adsorbent is filled in an adsorption rectification tower, and the adsorption rectification coupling separation process obtains the alpha-olefin with the purity of more than or equal to 99.2 percent and the yield of more than or equal to 85 percent.
10. The application of the olefin adsorbent in the Fischer-Tropsch light distillate oil adsorption, rectification and coupling separation process according to claim 1, wherein the olefin adsorbent is filled in an adsorption section of an adsorption rectifying tower, and the volume ratio of the olefin adsorbent to the filler filled in the adsorption section is 1:10-10:1.
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