CN114686254B - Regeneration method of oxygen-containing compound adsorbent - Google Patents
Regeneration method of oxygen-containing compound adsorbent Download PDFInfo
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- CN114686254B CN114686254B CN202011643620.9A CN202011643620A CN114686254B CN 114686254 B CN114686254 B CN 114686254B CN 202011643620 A CN202011643620 A CN 202011643620A CN 114686254 B CN114686254 B CN 114686254B
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 114
- 239000001301 oxygen Substances 0.000 title claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 title claims abstract description 18
- 238000011069 regeneration method Methods 0.000 title claims description 89
- 238000000034 method Methods 0.000 claims abstract description 49
- 230000001172 regenerating effect Effects 0.000 claims abstract description 17
- 230000008929 regeneration Effects 0.000 claims description 67
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 40
- 239000002808 molecular sieve Substances 0.000 claims description 32
- 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 32
- 230000008569 process Effects 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 description 46
- 239000007788 liquid Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 230000009471 action Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000012855 volatile organic compound Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002912 waste gas Substances 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000010730 cutting oil Substances 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0262—Compounds of O, S, Se, Te
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
-
- 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
- C10G25/12—Recovery of used adsorbent
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A method for regenerating an oxygenate adsorbent, comprising: the temperature of the oxygen-containing compound adsorbent is programmed to 50-150 ℃; C6-C12 alkane is added and the C6-C12 alkane is contacted with the oxygenate adsorbent sufficiently to regenerate the oxygenate adsorbent. The method can regenerate the adsorbent for multiple times, prolong the service life of the adsorbent and reduce the production cost.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a regeneration method of an oxygen-containing compound adsorbent.
Background
At present, the adsorption and recycling of the oxygen-containing compounds in the Fischer-Tropsch oil by using a molecular sieve adsorbent are key technologies for realizing the industrial scale-up of the removal of the oxygen-containing compounds and the separation of alkane and alkene.
CN110420628A discloses a zeolite molecular sieve regenerating device and regenerating method, placing zeolite molecular sieve saturated by adsorbing VOC in a microwave digestion tank, starting a temperature controller and setting temperature, starting a microwave generator, heating the zeolite molecular sieve, and recording time; and turning off the microwave generator every 1min, taking out the zeolite molecular sieve, weighing until the weight of the zeolite molecular sieve is not changed any more, and finishing regeneration.
CN108855021 a discloses a 13X molecular sieve activation regeneration method, which comprises the following steps: (1) soaking in a mixed solvent: soaking the molecular sieve by using a mixed solvent; (2) trimming the composite salt solution: soaking the molecular sieve obtained in the step (1) by sequentially using a solution containing an Al ion source and a solution containing a Na ion source under an acidic condition, uniformly stirring, and standing; (3) washing: washing the molecular sieve after the trimming of the compound salt solution by deionized water until the washing solution becomes neutral; (4) drying: removing the organic solvent and water from the molecular sieve after washing; (5) inert gas gradient elution: under the protection of inert gas, heating up in stages, and eluting; (6) low oxygen atmosphere oxidation: heating to a certain temperature, and introducing low-oxygen atmosphere for oxidation; (7) inert gas hot purging.
CN11013558A discloses a method for regenerating adsorbent based on cyclic heating mode, which comprises constructing an adsorption tower, a blower, a gas tank and a heat exchanger into a closed cyclic body after the adsorption process of the adsorption tower is completed; repeatedly circulating the gas in the circulating body by using the blower, and heating the circulating gas to a set temperature when the circulating gas passes through the heat exchanger; detecting the pressure and the temperature of the circulating gas, stopping the blower after the pressure reaches the set pressure, and starting a vacuum pump to extract desorption gas from the circulating body to negative pressure; repeating the steps until the adsorbent does not produce desorption gas; and supplementing a certain amount of dry cold air to the circulating body, circularly cooling the adsorbent, vacuumizing, and repeating until the adsorption and desorption processes are completed.
CN105944674a discloses a method for regenerating a poisoned carbon molecular sieve, which comprises the following steps: s100: acid washing: placing the poisoned carbon molecular sieve in hydrochloric acid solution for full soaking; s200: washing: rinsing the poisoned carbon molecular sieve after acid washing with clear water for 2-3 times; s300: and (3) cleaning a solvent: placing the carbon molecular sieve subjected to water washing and poisoning into an organic solvent for fully soaking: s400: and (3) hole adjustment: and (3) placing the poisoned carbon molecular sieve in a nitrogen environment, and adjusting the pore at 600-750 ℃.
CN110935281a discloses an adsorption and regeneration device and method for a solid adsorbent for adsorbing volatile organic compounds, wherein the device and method adsorb waste gas containing volatile organic compounds by using the solid adsorbent, and regenerate the solid adsorbent saturated by adsorption by using the waste gas containing volatile organic compounds after heating, so as to obtain waste gas with increased concentration of volatile organic compounds, and absorb the waste gas with increased concentration of volatile organic compounds by using an absorbent with absorption capacity for volatile organic compounds after cooling, so as to obtain the waste gas with reduced concentration of volatile organic compounds for reuse as regeneration gas. And cooling the regenerated solid adsorbent with higher temperature by using the waste gas containing volatile organic compounds, stopping cooling when the temperature of the solid adsorbent is reduced to a certain temperature, and re-adsorbing by using the solid adsorbent.
CN107376883a discloses a method for regenerating activated carbon by adsorption saturation, which comprises the following steps: adding an alkaline solvent or an alkaline regenerated solvent and activated carbon saturated by adsorption into a container provided with a heating device and a stirring device for mixing to obtain an alkaline mixture; performing solid-liquid separation on the obtained alkaline mixture to obtain active carbon to be treated, and recycling an alkaline regenerated solvent generated in the solid-liquid separation process; adding the obtained active carbon to be treated and an acidic solvent or an acidic regenerated solvent into a container provided with a heater and a stirrer for mixing to obtain an acidic mixture; carrying out solid-liquid separation on the obtained acid mixture to obtain active carbon to be washed, and recycling an acid regenerated solvent generated in the solid-liquid separation process; and washing the obtained activated carbon to be washed by using water to obtain regenerated activated carbon and recycling the regenerated activated carbon to treat wastewater containing benzoic acid, wherein acidic water generated in the water washing process is recycled after acid is added.
For the regeneration process of the molecular sieve adsorbent of the oxygen-containing compound in the Fischer-Tropsch oil, the existing regeneration process has the following problems: 1. the regeneration cycle evaluation performance is poor; 2. the process is complex and the energy consumption is high.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for regenerating an oxygen-containing compound adsorbent, which can improve the regeneration efficiency of the oxygen-containing compound adsorbent.
The invention adopts the following technical scheme:
a method for regenerating an oxygenate adsorbent, comprising:
the temperature of the oxygen-containing compound adsorbent is programmed to 50-150 ℃;
C6-C12 alkane is added and the C6-C12 alkane is contacted with the oxygenate adsorbent sufficiently to regenerate the oxygenate adsorbent.
In some embodiments, the regeneration process is shown to be performed in situ in a fixed bed reactor containing an oxygenate adsorbent.
In some embodiments, the C6-C12 alkane is introduced into the C6-C12 alkane from the bottom of the fixed bed reactor and contacted with the adsorbent bed.
In some embodiments, the temperature programming rate is 0.5-3 ℃/min (e.g., 1.0 ℃/min, 1.5 ℃/min, 2.0 ℃/min, or 2.5 ℃/min).
In some embodiments, the C6-C12 alkane is reacted with the oxygenate adsorbent for a period of time ranging from 100 to 500 minutes (e.g., 200 minutes, 300 minutes, or 400 minutes).
In some embodiments, the pressure employed increases and the temperature employed decreases as the number of alkane carbons employed decreases in the regeneration process.
In some embodiments, the alkane used in the regeneration process is dodecane, the pressure used is atmospheric, and the temperature used is 80-150 ℃.
In some embodiments, the alkane used in the regeneration process is n-hexane or n-octane at a pressure of 3.5 to 4.5MPa and a temperature of 50 to 70 ℃.
In some embodiments, the regeneration method further comprises: carbonyl-containing impurities in the C6-C12 alkane are removed before the C6-C12 alkane is added.
In some embodiments, carbonyl-containing impurities are removed using a molecular sieve adsorbent.
Compared with the prior art, the regeneration method of the oxygen-containing compound adsorbent adopts a fixed bed dynamic adsorption separation technology, can be carried out in situ in a fixed bed reactor, and has the advantages of high regeneration efficiency, simple operation, economy and environmental protection; the method can regenerate the adsorbent for multiple times, prolong the service life of the adsorbent and reduce the production cost.
Drawings
The following drawings are only for purposes of illustration and explanation of the present invention and are not intended to limit the scope of the invention. Wherein:
FIG. 1 shows a temperature programming process with a regeneration temperature of 80℃in an embodiment of the present invention;
FIG. 2 is a temperature programming process with a regeneration temperature of 100℃in an embodiment of the present invention;
FIG. 3 is a temperature programming process with a regeneration temperature of 120℃in an embodiment of the present invention;
FIG. 4 is a temperature programming process with a regeneration temperature of 150℃in an embodiment of the present invention;
FIG. 5 shows a temperature programming process with a regeneration temperature of 50℃in an embodiment of the present invention;
FIG. 6 is a temperature programming process with a regeneration temperature of 60℃in an embodiment of the present invention;
FIG. 7 is a temperature programming process with a regeneration temperature of 70℃in an embodiment of the present invention;
FIG. 8 is a temperature programming process with a regeneration temperature of 70℃in an embodiment of the present invention;
FIG. 9 shows the temperature programming process at a regeneration temperature of 120℃in the comparative example of the present invention.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or parameter, step, or the like described in the embodiment is included in at least one embodiment according to the present invention. Thus, references to "one embodiment according to the present invention," "in an embodiment," and the like, in this specification are not intended to specify the presence of stated features but rather are intended to be included in particular embodiments, if they are used in the same sense. It will be appreciated by those of skill in the art that the specific features, structures or parameters, steps, etc. disclosed in one or more of the embodiments of the invention may be combined in any suitable manner.
Aiming at the defects existing in the prior art, the invention provides the regeneration method of the oxygen-containing compound adsorbent, which has low cost, is reasonable and practical and is easy to industrialize. The oxygenate adsorbent in the present invention refers to a molecular sieve for adsorbing oxygenates, such as 3A, 4A, 5A, 10X, 13X type molecular sieves. The invention utilizes C6-C12 alkane (such as n-hexane, n-heptane, n-octane, n-nonane, n-decane, dodecane and the like) to regenerate and utilize the molecular sieve adsorbent which is adsorbed and poisoned.
In the following examples, the adsorbent is used to adsorb oxygenates in a C11-C16 cut oil and the saturated adsorbent is regenerated, wherein the oxygenates in the C11-C16 cut oil comprise one or more of alcohols, aldehydes, acids, ketones, esters.
The C6-C12 alkane used in regeneration is subjected to carbonyl removal by utilizing a dynamic adsorption mode, and specifically comprises the following steps:
1. filling an adsorbent: filling a new activated adsorbent 13X molecular sieve into an adsorption tube with the inner diameter of 45mm and the length of 67.8X 2cm, and filling up and down with quartz cotton, wherein the filling amount of the adsorbent is 2156ml;
2. feeding liquid: carrying out dynamic adsorption experiments by C6-C12 alkane sample injection;
3. sampling: sampling under the condition that no liquid leakage is confirmed;
4. carbonyl analysis: analyzing the carbonyl number content in the sampling liquid, and finding out a penetration point to obtain carbonyl-free alkane.
In the following examples 1 to 4, dodecane was used as a regeneration medium, and the regeneration temperature was selected to be 80℃to 150 ℃.
Example 1
(1) The 13X molecular sieve adsorbent is paved in a special sintering spoon for a muffle furnace (ensuring that the particle layer is thinner), the roasting amount is about 70g each time, the shape of the adsorbent is spherical, and the granularity is 0.85. Roasting the adsorbent at 700 ℃ for 6 hours, naturally cooling to 150 ℃ in a muffle furnace, and taking out and placing the adsorbent in a dryer for standby. (muffle furnace temperature rise rate is 2 ℃/min, setting lower rate to prevent the change of the adsorbent structure);
(2) The packing height of the adsorbent was determined by the constant temperature zone (h=13.7 cm) of the high temperature furnace, the fixed bed adsorption tube packing amount was 45.32g, and the packing volume was 70.81ml. The upper and lower openings of the adsorbent bed layer are filled with quartz cotton;
(3) And the primary water is used as a calibration medium, and the calibration system is positioned in a closed space. Experiment (calibration error caused by loss of standing primary water weight) maintain airspeed v=0.996 h -1 The volumetric flow rate of the C11-C16 cutting oil was calculated as v=0.27 ml/min based on the bed particle packing volume. The calibration time of the feed pump is 2 hours, the weight gain of the primary water is recorded every ten minutes, and 12 groups of weight data are fitted to determine the accurate flow of the feed pump. Accurate flow V after calibration 1 ＝0.272ml/min；
(4) C11-C16 cutting oil is pumped into the adsorption tower, the flow rate is 2.48ml/min, the time is 59min (calculated by the liquid outlet time of the adsorption tower), and the saturated adsorption (carried out at normal temperature and normal pressure) is completed. And calibrating primary water by using a C11-C16 cutting oil discharge system to carry out an adsorption experiment. C11-C16 cutting oil enters a bed layer from the lower part of a fixed bed adsorption tower, oxygen-containing compounds in the C11-C16 cutting oil are adsorbed through an adsorbent bed layer, the oxygen-containing compounds are collected from the top of the adsorption tower, carbonyl analysis is carried out on sampling liquid at the same time interval so as to determine the adsorption condition of the adsorbent bed layer, the adsorption curve is drawn by taking time as an abscissa and the carbonyl base as an ordinate, and the adsorption capacity corresponding to the penetration point of the adsorbent is determined;
(5) As shown in fig. 1, a fixed bed regeneration device is provided to perform temperature programming, and the temperature rising rate is: and (3) heating to 80 ℃ at 0.9 ℃/min, introducing dodecane from the bottom of the fixed bed reactor, contacting with an adsorbent bed, wherein the flow rate of the dodecane is 4.02ml/min, regenerating under normal pressure, wherein the action time of the dodecane is 285min, the temperature programming process is 60min, and then closing the device to restore to normal temperature, thus obtaining the regenerated product. Dodecane is collected as a liquid at the top of the adsorption column.
The cycle evaluation experiment is specifically as follows: regeneration 52 adsorption-regeneration cycles, the regeneration efficiency was still 91.3%. From the results, the adsorption effect of the regenerated adsorbent is not obviously different from that of the fresh adsorbent, so that the method can regenerate the adsorbent for multiple times, prolong the service life of the adsorbent and reduce the production cost.
Example 2
In this example, the 13X molecular sieve adsorbent had a particle size of 1.15mm, and steps (1) - (4) were the same as in example 1.
In step (5), as shown in fig. 2, a fixed bed regeneration device is provided to perform temperature programming, and the temperature rate is increased: 1.25 ℃/min, heating to 100 ℃, introducing dodecane from the bottom of the fixed bed reactor, contacting with an adsorbent bed, regenerating under normal pressure at the dodecane flow of 4.04ml/min, wherein the dodecane action time is 285min, programming the temperature for 60min, and then closing the device to restore normal temperature, namely, the regeneration is completed. Dodecane is collected as a liquid at the top of the adsorption column.
The cycle evaluation experiment is specifically as follows: regeneration is carried out for 52 times of adsorption-regeneration cycles, and the regeneration efficiency is still 96.3 percent. From the results, the adsorption effect of the regenerated adsorbent is not obviously different from that of the fresh adsorbent, so that the method can regenerate the adsorbent for multiple times, prolong the service life of the adsorbent and reduce the production cost.
Example 3
In this example, the 13X molecular sieve adsorbent had a particle size of 1mm, and steps (1) - (4) were the same as in example 1.
In step (5), as shown in fig. 3, a fixed bed regeneration device is provided to perform temperature programming, and the temperature rate is increased: 1.58 ℃/min, heating to 120 ℃, introducing dodecane from the bottom of the fixed bed reactor, contacting with an adsorbent bed, regenerating under normal pressure at the dodecane flow of 4.04ml/min, wherein the dodecane action time is 285min, programming the temperature for 60min, and then closing the device to restore normal temperature, namely, the regeneration is completed. Dodecane is collected as a liquid at the top of the adsorption column.
The cycle evaluation experiment is specifically as follows: regeneration is carried out for 55 times of adsorption-regeneration cycles, and the regeneration rate is still kept at 96.4 percent. From the results, the adsorption effect of the regenerated adsorbent is not obviously different from that of the fresh adsorbent, so that the method can regenerate the adsorbent for multiple times, prolong the service life of the adsorbent and reduce the production cost.
Example 4
In this example, the 13X molecular sieve adsorbent had a particle size of 1mm, and steps (1) - (4) were the same as in example 1.
In step (5), as shown in fig. 4, a fixed bed regeneration device is provided to perform temperature programming, and the temperature rate is increased: 2.1 ℃/min, heating to 150 ℃, introducing dodecane from the bottom of the fixed bed reactor, contacting with an adsorbent bed, regenerating under normal pressure at the dodecane flow of 4.05ml/min, wherein the dodecane action time is 285min, programming the temperature for 60min, and then closing the device to restore normal temperature, namely, the regeneration is completed. Dodecane is collected as a liquid at the top of the adsorption column.
The cycle evaluation experiment is specifically as follows: regeneration is carried out for 42 times of adsorption-regeneration cycles, and the regeneration rate is still kept at 91.4 percent. From the results, the adsorption effect of the regenerated adsorbent is not obviously different from that of the fresh adsorbent, so that the method can regenerate the adsorbent for multiple times, prolong the service life of the adsorbent and reduce the production cost.
In the following examples 5-7, n-hexane was used as a regeneration medium, the system was set at 3.5-4.5MPa, and the regeneration temperature was selected at 50℃to 70 ℃.
Example 5
In this example, the 13X molecular sieve adsorbent had a particle size of 0.85mm, and steps (1) - (4) were the same as in example 1.
In step (5), as shown in fig. 5, a fixed bed regeneration device is provided to perform temperature programming, and the temperature rate is increased: heating to 50 ℃ at 0.5 ℃/min, and preparing the system under 3.5MPa. Introducing n-hexane from the bottom of the fixed bed reactor, contacting with the adsorbent bed, regenerating under pressure at a flow rate of 3.15ml/min, wherein the n-hexane action time is 120min, the temperature programming process is 50min, closing the device to relieve pressure, and recovering to normal temperature to obtain the regenerated product. N-hexane is collected as a liquid at the top of the adsorption column.
The cycle evaluation experiment is specifically as follows: regeneration is carried out for 36 times, and the regeneration rate is still kept at 98.4 percent. From the results, the adsorption effect of the regenerated adsorbent is not obviously different from that of the fresh adsorbent, so that the method can regenerate the adsorbent for multiple times, prolong the service life of the adsorbent and reduce the production cost.
Example 6
In this example, the 13X molecular sieve adsorbent had a particle size of 1.15mm, and steps (1) - (4) were the same as in example 1.
In step (5), as shown in fig. 6, a fixed bed regeneration device is provided to perform temperature programming, and the temperature rate is increased: heating to 60 ℃ at 0.5 ℃/min, and preparing the system under 4.0MPa. Introducing n-hexane from the bottom of the fixed bed reactor, contacting with the adsorbent bed, regenerating under pressure at a flow rate of 3.15ml/min, wherein the n-hexane action time is 120min, the temperature programming process is 70min, closing the device to relieve pressure, and recovering to normal temperature to obtain the regenerated product. N-hexane is collected as a liquid at the top of the adsorption column.
The cycle evaluation experiment is specifically as follows: regeneration is carried out for 45 times of adsorption-regeneration cycles, and the regeneration rate is still kept at 99.2 percent. From the results, the adsorption effect of the regenerated adsorbent is not obviously different from that of the fresh adsorbent, so that the method can regenerate the adsorbent for multiple times, prolong the service life of the adsorbent and reduce the production cost.
Example 7
In this example, the 13X molecular sieve adsorbent had a particle size of 1mm, and steps (1) - (4) were the same as in example 1.
In step (5), as shown in fig. 7, a fixed bed regeneration device is provided to perform temperature programming, and the temperature rate is increased: heating to 70 ℃ at 0.5 ℃/min, and preparing the system under 4.5MPa. Introducing n-hexane from the bottom of the fixed bed reactor, contacting with the adsorbent bed, regenerating under pressure at a flow rate of 3.15ml/min, wherein the n-hexane action time is 120min, the temperature programming process is 90min, closing the device to relieve pressure, and recovering to normal temperature to obtain the regenerated product. N-hexane is collected as a liquid at the top of the adsorption column.
The cycle evaluation experiment is specifically as follows: regeneration is carried out for 49 times of adsorption-regeneration cycles, and the regeneration rate is still kept at 97.8 percent. From the results, the adsorption effect of the regenerated adsorbent is not obviously different from that of the fresh adsorbent, so that the method can regenerate the adsorbent for multiple times, prolong the service life of the adsorbent and reduce the production cost.
Example 8
In the embodiment, n-octane is used as a regeneration medium, the system is provided with 4.0MPa, and the regeneration temperature is selected to be 70 ℃.
In this example, the 13X molecular sieve adsorbent had a particle size of 1mm, and steps (1) - (4) were the same as in example 1.
In step (5), as shown in fig. 8, a fixed bed regeneration device is provided to perform temperature programming, and the temperature rate is increased: heating to 70 ℃ at 0.5 ℃/min, and preparing the system under 4.0MPa. Introducing n-octane from the bottom of the fixed bed reactor, contacting with the adsorbent bed, regenerating under pressure at the flow rate of 3.2ml/min, wherein the n-octane has the action time of 120min, the temperature programming process is 90min, closing the device to relieve pressure, and recovering the normal temperature to finish the regeneration. The carbonyl-free n-octane is collected in liquid form at the top of the adsorption tower.
The cycle evaluation experiment is specifically as follows: regeneration 59 adsorption-regeneration cycles, the regeneration rate was still maintained at 97.2%. From the results, the adsorption effect of the regenerated adsorbent is not obviously different from that of the fresh adsorbent, which indicates that the adsorbent can be regenerated repeatedly, the service life of the adsorbent is prolonged, and the production cost is reduced.
Comparative example
In this example pentadecane was used as regeneration medium, the regeneration temperature being selected at 120 ℃. In this example, the 13X molecular sieve adsorbent had a particle size of 1mm, and steps (1) - (4) were the same as in example 1.
In step (5), as shown in fig. 9, a fixed bed regeneration device is provided to perform temperature programming, and the temperature rate is increased: heating to 120 ℃ at 0.5 ℃/min. Pentadecane is introduced from the bottom of the fixed bed reactor and contacted with the adsorbent bed, the pentadecane flow is 3.2ml/min, the pentadecane action time is 120min, the temperature programming process is 190min, and the normal temperature is recovered, namely, the regeneration is completed. The carbonyl-free pentadecane is collected as a liquid at the top of the adsorption column.
The cycle evaluation experiment is specifically as follows: the regeneration was performed 16 times with a regeneration rate of 39.2%. From the above results, the adsorption effect of the regenerated adsorbent is significantly different from that of the fresh adsorbent.
The pretreatment of the adsorbent ensures that the 13X-type adsorbent has higher adsorption capacity, thereby being beneficial to accelerating the adsorption rate and prolonging the service life of the adsorbent; the fixed bed adsorption tower is used, the operation is simple and easy, and the process flow is simple. The adsorption can be carried out at normal temperature to obtain high adsorption capacity, and the regeneration method is simple and feasible and has long service life. The invention has reasonable and practical design, reduces the cost, saves the resources, improves the economic benefit production efficiency and is suitable for popularization and use.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (8)
1. A method for regenerating an oxygenate adsorbent, comprising:
the temperature of the oxygen-containing compound adsorbent is programmed to 50-120 ℃;
adding a C6-C12 alkane, and fully contacting the C6-C12 alkane with an oxygen-containing compound adsorbent to regenerate the oxygen-containing compound adsorbent;
wherein the C6 alkane is normal alkane;
the regeneration process is performed in situ in a fixed bed reactor containing an oxygenate adsorbent;
in the regeneration method, as the carbon number of the adopted alkane is reduced, the adopted pressure is increased, and the adopted temperature is reduced;
wherein, alkane adopted in the regeneration method is dodecane, the adopted pressure is normal pressure, and the adopted temperature is 80-120 ℃; the alkane adopted in the regeneration method is normal hexane or normal octane, the adopted pressure is 3.5-4.5MPa, and the adopted temperature is 50-70 ℃.
2. The regeneration process of claim 1, wherein the C6-C12 alkane is introduced from the bottom of the fixed bed reactor and contacted with the adsorbent bed.
3. The regeneration method according to claim 1, wherein the temperature-programmed temperature-raising rate is 0.5 to 3 ℃/min.
4. A regeneration method according to claim 3, wherein the temperature-programmed rate of temperature rise is 1.0 ℃/min, 1.5 ℃/min, 2.0 ℃/min or 2.5 ℃/min.
5. The regeneration process according to claim 1, wherein the C6-C12 alkane is reacted with the oxygenate adsorbent for a period of time ranging from 100 to 500 minutes.
6. The regeneration process according to claim 5, wherein the C6-C12 alkane is reacted with the oxygenate adsorbent for 200min, 300min or 400min.
7. The regeneration method according to claim 1, wherein the regeneration method further comprises: carbonyl-containing impurities in the C6-C12 alkane are removed before the C6-C12 alkane is added.
8. The regeneration process of claim 7, wherein the carbonyl-containing impurities are removed using a molecular sieve adsorbent.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2122588A (en) * | 1982-06-26 | 1984-01-18 | Unilever Plc | Regenerating spent adsorbents |
| US5041693A (en) * | 1989-08-10 | 1991-08-20 | Uop | Separation of normal paraffins and the regeneration of zeolitic molecular sieves used therein |
| CN104402663A (en) * | 2014-11-05 | 2015-03-11 | 中国石油大学(北京) | Advanced alkane purifying method for removing impurities |
| CN107057752A (en) * | 2017-06-06 | 2017-08-18 | 中国石油化工集团公司 | A kind of method of lighter hydrocarbons deeply de-aromatizing |
| CN111001382A (en) * | 2019-12-31 | 2020-04-14 | 中海油天津化工研究设计院有限公司 | Fischer-Tropsch oil alkane and alkene separation adsorbent and preparation method thereof |
| CN111100683A (en) * | 2019-12-31 | 2020-05-05 | 中海油天津化工研究设计院有限公司 | Separation method of long-chain alkane-olefin in Fischer-Tropsch synthetic oil |
| CN111996030A (en) * | 2020-08-11 | 2020-11-27 | 中海油天津化工研究设计院有限公司 | Method for in-situ regeneration of simulated moving bed adsorbent |
| CN112121779A (en) * | 2019-06-25 | 2020-12-25 | 内蒙古伊泰煤基新材料研究院有限公司 | Method and apparatus for regenerating adsorbent for removing oxide in FT synthetic oil |
-
2020
- 2020-12-31 CN CN202011643620.9A patent/CN114686254B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2122588A (en) * | 1982-06-26 | 1984-01-18 | Unilever Plc | Regenerating spent adsorbents |
| US5041693A (en) * | 1989-08-10 | 1991-08-20 | Uop | Separation of normal paraffins and the regeneration of zeolitic molecular sieves used therein |
| CN104402663A (en) * | 2014-11-05 | 2015-03-11 | 中国石油大学(北京) | Advanced alkane purifying method for removing impurities |
| CN107057752A (en) * | 2017-06-06 | 2017-08-18 | 中国石油化工集团公司 | A kind of method of lighter hydrocarbons deeply de-aromatizing |
| CN112121779A (en) * | 2019-06-25 | 2020-12-25 | 内蒙古伊泰煤基新材料研究院有限公司 | Method and apparatus for regenerating adsorbent for removing oxide in FT synthetic oil |
| CN111001382A (en) * | 2019-12-31 | 2020-04-14 | 中海油天津化工研究设计院有限公司 | Fischer-Tropsch oil alkane and alkene separation adsorbent and preparation method thereof |
| CN111100683A (en) * | 2019-12-31 | 2020-05-05 | 中海油天津化工研究设计院有限公司 | Separation method of long-chain alkane-olefin in Fischer-Tropsch synthetic oil |
| CN111996030A (en) * | 2020-08-11 | 2020-11-27 | 中海油天津化工研究设计院有限公司 | Method for in-situ regeneration of simulated moving bed adsorbent |
Non-Patent Citations (1)
| Title |
|---|
| 王凌云 ; 王兰芝 ; .预处理和再生条件对载铜13X吸附剂脱硫性能的影响.石油与天然气化工.2008,37(4),300-303. * |
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