CN111686824A - In-situ regeneration method for ruthenium-based catalyst synthesized by Fischer-Tropsch fixed bed - Google Patents
In-situ regeneration method for ruthenium-based catalyst synthesized by Fischer-Tropsch fixed bed Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 196
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 132
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 238000011069 regeneration method Methods 0.000 title claims abstract description 60
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 46
- 230000008929 regeneration Effects 0.000 claims abstract description 46
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000010926 purge Methods 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- GWUAFYNDGVNXRS-UHFFFAOYSA-N helium;molecular oxygen Chemical compound [He].O=O GWUAFYNDGVNXRS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 230000008021 deposition Effects 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract description 4
- 239000002574 poison Substances 0.000 abstract description 4
- 231100000614 poison Toxicity 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000011156 evaluation Methods 0.000 description 20
- 230000000694 effects Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer Methods 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/56—Hydrocarbons
Abstract
The invention provides an in-situ regeneration method of a ruthenium-based catalyst synthesized by a fixed bed Fischer-Tropsch process, which comprises the following steps: (1) treating the Fischer-Tropsch synthesis ruthenium-based catalyst to be regenerated by using naphtha in a subcritical state; (2) purging the catalyst after naphtha treatment by using inactive gas; (3) oxidizing the purged catalyst with an oxygen-containing gas; and (4) carrying out hydrogen reduction on the oxidized catalyst to obtain the regenerated Fischer-Tropsch synthesis ruthenium-based catalyst. The in-situ regeneration method provided by the invention can realize in-situ regeneration of the ruthenium-based catalyst synthesized by the Fischer-Tropsch fixed bed, the regeneration process is simple and convenient to operate and easy to realize, and the used materials and reagents are low in price. The method eliminates the catalyst deactivation caused by carbon deposition, metal phase change and partial poison pollution, thereby achieving the purpose of prolonging the service life of the Fischer-Tropsch synthesis ruthenium-based catalyst.
Description
Technical Field
The invention relates to an in-situ regeneration method of a ruthenium-based catalyst synthesized by a fixed bed Fischer-Tropsch process, belonging to the technical field of catalysts.
Background
The Fischer-Tropsch synthesis (FTS) process is carried out by mixing synthesis gas (carbon monoxide (CO) and hydrogen (H)2) Mixed gas of (2) into liquid hydrocarbons or hydrocarbons, is one of the most important ways for the efficient conversion and utilization of non-petroleum carbon-containing resources (natural gas, coal, residual oil, biomass, etc.). In the Fischer-Tropsch synthesis process, synthesis gas is used as a primary product under the action of a catalyst to generate a series of hydrocarbons (C1-C200) with different carbon numbers, wherein the primary product is straight-chain paraffin, and some low-carbon olefins and alcohols are obtained at the same time. The initial product is further treated (such as separation, hydrocracking or hydroisomerization) to obtain oil fuels of gasoline, diesel oil and the like and chemicals of ethylene, propylene, lubricating oil, paraffin and the like with certain specifications.
The catalyst is one of the key Fischer-Tropsch synthesis technologies, and the catalysts used in the Fischer-Tropsch synthesis industry at present mainly comprise an iron-based catalyst and a cobalt-based catalyst. The iron-based catalyst is an early catalyst used in the Fischer-Tropsch synthesis industry, has the advantages of high catalytic activity and low cost, and also has higher water gas shift reaction performancePoor structural stability of the catalyst and short service life. Compared with an iron-based catalyst, the cobalt-based catalyst has the advantages of high CO hydrogenation activity, strong chain growth capacity, difficult carbon deposition and inactivation of the catalyst, less low-carbon olefin and oxygen-containing compound generated in the product, and methane (CH)4) The catalyst has the advantages of low selectivity, low water gas shift activity, mild reaction conditions and the like, and therefore, the catalyst becomes one of the most promising catalysts for Fischer-Tropsch synthesis. Compared with a cobalt-based catalyst, the ruthenium-based catalyst has the advantages of low loading capacity, higher activity, lower methane selectivity, longer service life, capability of maintaining higher conversion rate in higher water partial pressure and oxygen-containing compound atmosphere and the like, has excellent Fischer-Tropsch synthesis activity and chain growth capability, but has few ruthenium sources and high price, and has the technical problem of overhigh cost when being used for the Fischer-Tropsch synthesis catalyst.
In the Fischer-Tropsch synthesis process, the catalysts have certain service life, and the catalytic activity and the selectivity of required products of the catalysts are gradually reduced in normal use, so that the performance of the catalysts is reduced. The reasons for the performance degradation of the catalyst mainly include the pollution of the catalyst by poisons, carbon deposition of the catalyst, sintering of the catalyst, phase change of active metals, change of the structure of the catalyst and the like. The deactivated or partially deactivated catalyst can restore or partially restore the original catalytic performance through regeneration treatment, so that the service life of the catalyst is prolonged and the catalyst circulation cost is reduced through a proper catalyst treatment or regeneration process, and the method has important industrial significance. Especially for the ruthenium-based catalyst with high price, the catalyst treatment or regeneration process can greatly reduce the usage amount of the fresh ruthenium-based catalyst, thereby saving the cost.
For the catalyst treatment or regeneration process in the art, for example, patent document US5283216 discloses a method for restoring the activity of a hydrocarbon synthesis catalyst by reducing the catalyst with hydrogen in the presence of liquid hydrocarbons at a temperature and pressure at which at least 80% of the original activity can be restored. However, this method of hydrogen re-reduction has certain limitations, which is only effective for catalysts deactivated by active metal phase transition, and cannot solve the problem of catalyst deactivation caused by carbon deposition.
Patent document CN100398501C proposes a method for regenerating a fischer-tropsch slurry bed catalyst to prolong the service life of the catalyst, which mainly comprises the steps of removing hydrocarbons adsorbed by the catalyst, impregnating with a solution, oxidizing, and reducing hydrogen. Although the method for regenerating the catalyst in the patent has a certain effect on the catalyst inactivated for various reasons, the method can damage the structure of the catalyst, influence the interaction between the active metal and the carrier and the interaction between the active metal and the auxiliary agent, and has complex process operation, and the regeneration of the catalyst needs to transfer the catalyst out of the hydrogenation reactor, perform the catalyst in other special equipment and finally return the catalyst to the hydrogenation reactor.
The two catalyst regeneration methods cannot give consideration to the three methods of in-situ, good effect and simplicity and feasibility. Patent document CN1230467A discloses regenerating an in-situ deactivated catalyst in a subcritical or supercritical state by using a part of light oil fraction in a fischer-tropsch synthesis product, and then reducing the treated catalyst with a reducing gas. The method is simple and easy to implement, and the obtained catalyst has good stability and higher activity, but is only limited to Fe catalysts.
Therefore, there is still a need in the art for a method for effectively regenerating a ruthenium-based catalyst in situ by fischer-tropsch synthesis, so as to prolong the service life of the ruthenium-based catalyst and reduce the cost consumption.
Disclosure of Invention
Aiming at the technical problem, the invention provides an in-situ regeneration method of a fixed bed Fischer-Tropsch synthesis ruthenium-based catalyst, which comprises the following steps:
(1) soaking and washing a Fischer-Tropsch synthesis ruthenium-based catalyst to be regenerated in a fixed bed reactor by using naphtha in a subcritical state;
(2) purging the treated ruthenium-based catalyst by using inactive gas;
(3) oxidizing the purged ruthenium-based catalyst with an oxygen-containing gas; and
(4) and carrying out hydrogen reduction on the oxidized ruthenium-based catalyst to obtain a regenerated ruthenium-based catalyst.
Advantageous effects
In the conventional ruthenium-based catalyst regeneration method, the purpose of ruthenium-based catalyst regeneration is to eliminate catalyst deactivation caused by carbon deposition, metal phase transition and partial poison pollution, but long-chain products blocking a pore channel cannot be completely removed. In the present invention, by using naphtha in a subcritical state, long-chain products in the pore channels of the ruthenium-based catalyst can be effectively removed compared to other mineral spirits (e.g., aromatic hydrocarbon solvents, alkane solvents, etc.) under conventional processing conditions, so that the pore structure of the regenerated ruthenium-based catalyst is close to that of a fresh ruthenium-based catalyst.
Compared with the traditional catalyst regeneration method, the in-situ regeneration method for the ruthenium-based Fischer-Tropsch synthesis catalyst of the fixed bed does not need an additional purging process before naphtha treatment, and the naphtha can be directly adopted to treat the ruthenium-based Fischer-Tropsch synthesis catalyst to be regenerated. The in-situ regeneration method has simple process, and the fixed bed Fischer-Tropsch synthesized ruthenium-based catalyst is regenerated, so that the service life of the catalyst is greatly prolonged, the use amount of the fresh ruthenium-based catalyst is reduced, and the operation cost is saved.
Detailed Description
The invention provides an in-situ regeneration method of a ruthenium-based catalyst synthesized by a fixed bed Fischer-Tropsch process. The in-situ regeneration method of the fixed bed Fischer-Tropsch synthesis ruthenium-based catalyst provided by the invention comprises the following steps:
(1) soaking and washing a Fischer-Tropsch synthesis ruthenium-based catalyst to be regenerated in a fixed bed reactor by using naphtha in a subcritical state;
(2) purging the treated ruthenium-based catalyst by using inactive gas;
(3) oxidizing the purged ruthenium-based catalyst with an oxygen-containing gas; and
(4) and carrying out hydrogen reduction on the oxidized ruthenium-based catalyst to obtain a regenerated ruthenium-based catalyst.
In the method, the ruthenium-based catalyst refers to a ruthenium-based Fischer-Tropsch synthesis catalyst filled in a fixed bed reactor. In the present invention, the terms "fixed bed fischer-tropsch synthesis ruthenium-based catalyst", "fischer-tropsch synthesis ruthenium-based catalyst" and "ruthenium-based catalyst" are used interchangeably herein. In the process of the present invention, the pressures employed are gauge pressures, unless otherwise specifically indicated. Further, in the method of the present invention, the atmospheric pressure means one atmospheric pressure.
In a preferred embodiment, the ruthenium-based catalyst may be selected from supported ruthenium-based catalysts. In some embodiments, the support of the ruthenium-based catalyst can be selected from alumina, silica, titania, or a silica-alumina composite support.
The ruthenium-based catalyst before regeneration has a ruthenium loading range of 0.2 to 10% by mass. The specific surface area of the carrier is 70-500 cm2(ii) in terms of/g. In the present invention, ruthenium-based catalysts commercially available in the art can be used as the ruthenium-based catalyst.
In the invention, the fixed bed reactor is a tubular reactor, 500-10000 or more than 10000 reaction tubes are arranged in the reactor, the diameter of each reaction tube is 20-60 mm, preferably 25-50 mm, and the length is 4-15 m, preferably 6-12 m. The catalyst is uniformly filled in each reaction tube. The particle size (diameter) of the catalyst is 0.5-5 mm, preferably 1-3 mm, and the catalyst can be in the shape of column, sphere, hollow sphere, ring, saddle, trilobe, tetralobal and the like.
In the invention, naphtha is light oil for chemical raw materials, which is produced by processing crude oil or other raw materials, and the main component of the naphtha is C5-C12 alkane components. In the present invention, the naphtha used in the step (1) has a C8-C12 alkane content of 40-80 wt% and a sulfur content of not more than 100 ppm.
In the step (1), naphtha is heated and pressurized to a subcritical state before treating the ruthenium-based catalyst to be regenerated with the naphtha. In some embodiments, the naphtha in the subcritical state is at the following conditions: the temperature is 150-350 ℃, and the optimal temperature is 200-300 ℃; the pressure is 1.5 to 3.0MPa, preferably 2.0 to 2.5 MPa. The naphtha under the subcritical state can effectively remove long-chain products in the ruthenium-based catalyst pore channel, particularly heavy alkane, olefin and the like with the carbon number of more than 60, and the long-chain products are accumulated for a long time to cause pore channel blockage and reduce the catalytic efficiency. Reacting naphtha in subcritical state from fixed bed on which ruthenium-based catalyst to be regenerated is locatedInjecting from the top of the reactor, wherein the liquid airspeed is 0.1-5 h-1Preferably 0.5 to 1 hour-1More preferably 0.5 to 0.8 hour-1. In the soaking and washing process, the ruthenium-based catalyst is treated under the condition that the temperature and the pressure of the naphtha are kept unchanged, and the treated naphtha is continuously discharged from the bottom of the reactor until the discharge of the naphtha is transparent.
In the step (2), hydrocarbons remaining on the surface of the ruthenium-based catalyst after naphtha treatment are removed using an inactive gas purge. In the present invention, the inactive gas refers to a gas that does not chemically react with the fischer-tropsch synthesis ruthenium-based catalyst and naphtha, and may be nitrogen, argon, helium or a combination thereof, and is preferably nitrogen. The temperature of the inactive gas during purging is 200-400 ℃, and the preferred temperature is 250-350 ℃; the pressure is 0.1MPa to 3MPa, preferably 2MPa to 3 MPa; the gas space velocity (GHSV) is 2000-6000 h-1Preferably 3000-5000 h-1(ii) a The time is 0.5 to 2 hours, preferably 1 hour. In this step, the purging may be terminated when the volume content of total hydrocarbons in the purge gas is less than 0.05ppm, which may be detected, for example, using a tail gas detection device.
In step (3), the oxygen-containing gas reacts with the carbon deposit and other organic matters in the catalyst to remove the carbon deposit. The metal of the catalyst and organic substances such as carbon on the surface are converted into metal oxides and carbon oxides by oxidation, so that any oxygen-containing gas can be used without damaging the ruthenium-based catalyst. For step (3), when CO is in the purge gas2Less than 0.05ppm, the oxidation reaction can be terminated. The oxygen-containing gas used is oxygen, air, a heliox (e.g., a heliox in which the volume ratio of helium to oxygen is 10:90 to 30: 70), or a combination thereof, preferably air. In the step (3), the temperature of the treatment (oxidation) is 300-500 ℃, preferably 350-450 ℃; the pressure is 0.5MPa to 2MPa, preferably 1MPa to 1.5 MPa; GHSV of 2000-6000 h-1Preferably 3000-5000 h-1(ii) a The time is 0.5 to 2 hours, preferably 1 hour.
In the step (4), hydrogen is used in an amount of not less than 99% by volume, and hydrogen is also usedThe original conditions are as follows: normal pressure; the temperature is 250-450 ℃, and preferably 300-400 ℃; GHSV of 500-6000 h-1Preferably 1000 to 2000 hours-1(ii) a And (4) carrying out constant temperature treatment for 2-12 h, preferably 4-8 h.
The in-situ regeneration method provided by the invention can realize in-situ regeneration of the fixed bed ruthenium-based Fischer-Tropsch synthesis catalyst, the in-situ regeneration process is simple and convenient to operate and easy to realize, the used materials and reagents are low in price, and the interaction between metal and a carrier, and between active metal and an auxiliary agent is not changed. The method can eliminate the catalyst deactivation caused by carbon deposition, metal phase change and partial poison pollution, and remove long-chain products blocking the pore channel, thereby achieving the purpose of prolonging the service life of the Fischer-Tropsch synthesis ruthenium-based catalyst.
Examples
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified, and all reagents are Chemically Pure (CP) or more. The catalyst is self-made, and the preparation method is an excess impregnation method, namely, the carrier is put into prepared impregnation liquid containing precursor metal ions, and the finally used catalyst is obtained after the impregnation, the drying and the roasting. The ruthenium precursor contains ruthenium nitrosyl nitrate and ruthenium chloride, the drying temperature is 100 ℃, the roasting temperature is 400 ℃, the amount of ruthenium counted by metal after roasting is 0.5-6 wt%, and the balance is a carrier.
Example 1
The evaluation test of the ruthenium-based catalyst was carried out in a fixed bed reactor, and the selected ruthenium-based catalyst was prepared by an excess impregnation method, an alumina support, and a 5% Ru loading (by mass). The reduction conditions for preparing the fresh ruthenium-based catalyst before regeneration are as follows: h2，350℃，0.5MPa，GHSV＝1000h-1Keeping the temperature constant for 12 hours; the Fischer-Tropsch synthesis reaction conditions of the ruthenium-based catalyst evaluation test before and after regeneration are as follows: 210 ℃, 2MPa, GHSV of 5000h-1，H2and/CO (V: V) ═ 2: 1. The evaluation results of the ruthenium-based catalyst before and after regeneration are shown in table 1.
In-situ regeneration of ruthenium-based catalysts: in makingBefore treating the ruthenium-based catalyst with naphtha, heating and pressurizing the naphtha to 250 ℃/2.5MPa, injecting the naphtha in a subcritical state from the top end of a reactor where the ruthenium-based catalyst to be regenerated is positioned, wherein the liquid space velocity is 0.8h-1The ruthenium-based catalyst is treated under constant temperature and pressure conditions and is continuously discharged from the bottom of the reactor until the naphtha discharge is transparent. The reactor is heated to 300 ℃ and N is introduced2Blowing at 300 deg.c and 2MPa and GHSV of 3000 hr-1The time period was 1 hour. N is a radical of2Releasing pressure after purging, introducing air for oxidation, wherein the treatment temperature is 350 ℃, the pressure is 1.5MPa, and the GHSV is 3000h-1The time period was 1 hour. Releasing pressure after oxidation, reducing by hydrogen at normal pressure and 300 ℃ and GHSV of 1000h-1And keeping the temperature constant for 8 hours, and finishing regeneration to obtain the regenerated catalyst.
Example 2
The evaluation test of the ruthenium-based catalyst is carried out in a fixed bed reactor, the selected fresh ruthenium-based catalyst is prepared by an excess impregnation method, a silicon-aluminum composite carrier and 4.2% of Ru loading (by mass), and the reduction conditions for preparing the fresh ruthenium-based catalyst before regeneration are as follows: h2，300℃，0.2MPa，GHSV＝2000h-1Keeping the temperature constant for 10 hours; the Fischer-Tropsch synthesis reaction conditions of the ruthenium-based catalyst evaluation test before and after regeneration are as follows: 200 ℃, 3MPa, GHSV 6000h-1，H2and/CO (V: V) ═ 2.1: 1. The evaluation results of the ruthenium-based catalyst before and after regeneration are shown in table 1.
In-situ regeneration of ruthenium-based catalysts: before the ruthenium-based catalyst is treated by using naphtha, heating and pressurizing the naphtha at 300 ℃/2.0MPa, injecting the naphtha in a subcritical state from the top end of a reactor where the ruthenium-based catalyst to be regenerated is positioned, and ensuring that the liquid airspeed is 0.6h-1The ruthenium-based catalyst is treated under constant temperature and pressure conditions and is continuously discharged from the bottom of the reactor until the naphtha discharge is transparent. The reactor is heated to 350 ℃ and N is introduced2Blowing at 350 deg.c and 2.5MPa and GHSV of 3000 hr-1The time period was 1 hour. N is a radical of2Releasing pressure after purging, introducing air for oxidation, treating at 400 deg.C under 1.0MPa and GHSV of 3000h-1The time period was 1 hour. After oxidationReleasing pressure, reducing with hydrogen at 350 deg.C and normal pressure for 2000h-1And keeping the temperature constant for 5 hours, and finishing regeneration to obtain the regenerated catalyst.
Example 3
The evaluation test of the ruthenium-based catalyst was carried out in a fixed bed reactor, the selected fresh ruthenium-based catalyst was prepared by the excess impregnation method, the titania carrier, 4.6% Ru loading (by mass), and the reduction conditions for preparing the fresh ruthenium-based catalyst before regeneration were: h2，350℃，0.5MPa，GHSV＝1000h-1Keeping the temperature constant for 12 hours; the Fischer-Tropsch synthesis reaction conditions of the ruthenium-based catalyst evaluation test before and after regeneration are as follows: 190 ℃, 2MPa, GHSV of 5000h-1，H2and/CO (V: V) ═ 2: 1. The evaluation results of the ruthenium-based catalyst before and after regeneration are shown in table 1.
In-situ regeneration of ruthenium-based catalysts: before the ruthenium-based catalyst is treated by using naphtha, heating and pressurizing the naphtha at 300 ℃/2.5MPa, injecting the naphtha in a subcritical state from the top end of a reactor where the ruthenium-based catalyst to be regenerated is positioned, and ensuring that the liquid space velocity is 0.5h-1The ruthenium-based catalyst is treated under constant temperature and pressure conditions and is continuously discharged from the bottom of the reactor until the naphtha discharge is transparent. The reactor is heated to 300 ℃ and N is introduced2Blowing at 300 deg.c and 2.0MPa and GHSV of 4000h-1The time period was 1 hour. N is a radical of2Releasing pressure after purging, introducing air for oxidation, wherein the treatment temperature is 400 ℃, the pressure is 1.0MPa, and the GHSV is 4000h-1The time period was 1 hour. Releasing pressure after oxidation, reducing by hydrogen at normal pressure and 350 ℃ and GHSV of 2000h-1And keeping the temperature constant for 6 hours, and finishing regeneration to obtain the regenerated catalyst.
Example 4
The ruthenium-based catalyst evaluation test was carried out in a fixed bed reactor, the selected fresh ruthenium-based catalyst was prepared by the excess impregnation method, the silica support, 5% Ru loading (by mass), and the reduction conditions for preparing the fresh ruthenium-based catalyst before regeneration were: h2，250℃，0.5MPa，GHSV＝1000h-1Keeping the temperature constant for 9 hours; the Fischer-Tropsch synthesis reaction conditions of the ruthenium-based catalyst evaluation test before and after regeneration are as follows: 210 ℃, 2MPa, GHSV of 5000h-1，H2and/CO (V: V) ═ 2: 1. The evaluation results of the ruthenium-based catalyst before and after regeneration are shown in table 1.
In-situ regeneration of ruthenium-based catalysts: before using the naphtha to process the catalyst, heating and pressurizing naphtha at 200 ℃/2.5MPa, injecting the naphtha in a subcritical state from the top end of a reactor where the ruthenium-based catalyst to be regenerated is positioned, wherein the liquid space velocity is 0.7h-1The ruthenium-based catalyst is treated under constant temperature and pressure conditions and is continuously discharged from the bottom of the reactor until the naphtha discharge is transparent. The reactor is heated to 350 ℃ and N is introduced2Purging at 350 deg.C and 3.0MPa (GHSV of 5000 h)-1The time period was 1 hour. N is a radical of2Releasing pressure after purging, introducing air for oxidation, treating at 400 deg.C under 1.0MPa and GHSV of 5000h-1The time period was 1 hour. Releasing pressure after oxidation, reducing by hydrogen at normal pressure and 400 ℃ and GHSV being 1500h-1And keeping the temperature constant for 8 hours, and finishing regeneration to obtain the regenerated catalyst.
Comparative example 1
The evaluation test of the ruthenium-based catalyst was carried out in a fixed bed reactor, and the selected fresh ruthenium-based catalyst was prepared by an excess impregnation method, an alumina support, and a 5% Ru loading (by mass). The reduction conditions for preparing the fresh ruthenium-based catalyst before regeneration are as follows: h2，350℃，0.5MPa，GHSV＝1000h-1Keeping the temperature constant for 12 hours; the Fischer-Tropsch synthesis reaction conditions of the ruthenium-based catalyst evaluation test before and after regeneration are as follows: 210 ℃, 2MPa, GHSV of 5000h-1，H2and/CO (V: V) ═ 2: 1. The evaluation results of the ruthenium-based catalyst before and after regeneration are shown in table 1.
In-situ regeneration of ruthenium-based catalysts: before the ruthenium-based catalyst is treated by the dimethylbenzene, the dimethylbenzene is heated and pressurized to 250 ℃/2.5MPa, the dimethylbenzene in a subcritical state is injected from the top end of a reactor where the ruthenium-based catalyst to be regenerated is positioned, and the liquid space velocity is 0.8h-1The ruthenium-based catalyst is treated under the condition of constant temperature and pressure, and is continuously discharged from the bottom of the reactor until the xylene discharge is transparent. The reactor is heated to 300 ℃ and N is introduced2Blowing at 300 deg.c and 2MPa and GHSV of 3000 hr-1The time period was 1 hour. N is a radical of2Releasing pressure after purging, introducing air for oxidation, wherein the treatment temperature is 350 ℃, the pressure is 1.5MPa, and the GHSV is 3000h-1The time period was 1 hour. Releasing pressure after oxidation, reducing by hydrogen at normal pressure and 300 ℃ and GHSV of 1000h-1And keeping the temperature constant for 8 hours, and finishing regeneration to obtain the regenerated catalyst.
Comparative example 2
The evaluation test of the ruthenium-based catalyst is carried out in a fixed bed reactor, the selected fresh ruthenium-based catalyst is prepared by an excess impregnation method, a silicon-aluminum composite carrier and 4.2% of Ru loading (by mass), and the reduction conditions for preparing the ruthenium-based fresh catalyst before regeneration are as follows: h2，300℃，0.2MPa，GHSV＝2000h-1Keeping the temperature constant for 10 hours; the Fischer-Tropsch synthesis reaction conditions of the ruthenium-based catalyst evaluation test before and after regeneration are as follows: 200 ℃, 3MPa, GHSV 6000h-1，H2and/CO (V: V) ═ 2.1: 1. The evaluation results of the ruthenium-based catalyst before and after regeneration are shown in table 1.
In-situ regeneration of ruthenium-based catalysts: general formula (N)2Blowing at 350 deg.c and 2.5MPa and GHSV of 3000 hr-1The time period was 1 hour. Before the ruthenium-based catalyst is treated by using naphtha, heating and pressurizing the naphtha at 300 ℃/2.0MPa, injecting the naphtha in a subcritical state from the top end of a reactor where the ruthenium-based catalyst to be regenerated is positioned, and ensuring that the liquid airspeed is 0.6h-1The ruthenium-based catalyst is treated under constant temperature and pressure conditions and is continuously discharged from the bottom of the reactor until the naphtha discharge is transparent. The reactor is heated to 350 ℃ and N is introduced2Blowing at 350 deg.c and 2.5MPa and GHSV of 3000 hr-1The time period was 1 hour. N is a radical of2Releasing pressure after purging, introducing air for oxidation, treating at 400 deg.C under 1.0MPa and GHSV of 3000h-1The time period was 1 hour. Releasing pressure after oxidation, reducing by hydrogen at normal pressure and 350 ℃ and GHSV of 2000h-1And keeping the temperature constant for 5 hours, and finishing regeneration to obtain the regenerated catalyst.
The evaluation results of the ruthenium-based catalyst before and after regeneration are shown in table 1.
TABLE 1 evaluation results of ruthenium-based catalysts before and after regeneration in examples
As can be seen from Table 1, the activity and selectivity of the ruthenium-based catalyst after regeneration in examples 1 to 4 were comparable to those of the ruthenium-based catalyst before regeneration. However, in comparative example 1, when naphtha was treated by replacing xylene, the activity and selectivity of the ruthenium-based catalyst were not well maintained.
Claims (10)
1. A method for in situ regeneration of a fixed bed fischer-tropsch synthesized ruthenium-based catalyst, the method comprising:
(1) soaking and washing a ruthenium-based catalyst to be regenerated in a fixed bed reactor by using naphtha in a subcritical state;
(2) purging the soaked and washed ruthenium-based catalyst by using inactive gas;
(3) oxidizing the purged ruthenium-based catalyst with an oxygen-containing gas; and
(4) and carrying out hydrogen reduction on the oxidized ruthenium-based catalyst to obtain a regenerated ruthenium-based catalyst.
2. The process of claim 1, wherein the ruthenium-based catalyst is selected from the group consisting of a supported fischer-tropsch synthesis ruthenium-based catalyst; preferably, the loading range of ruthenium in the ruthenium-based catalyst is 0.2-10% by mass; more preferably, for the supported ruthenium-based catalyst for Fischer-Tropsch synthesis, the carrier of the catalyst is selected from alumina, silica, titania or a silicon-aluminum composite carrier, and the specific surface area of the carrier ranges from 70 cm to 500cm2/g。
3. The method according to claim 1 or 2, wherein the temperature in the subcritical state is between 150 ℃ and 350 ℃, preferably between 200 ℃ and 300 ℃; the pressure in the subcritical state is 1.5 to 3.0MPa, preferably 2.0 to 2.5 MPa.
4. The method according to any one of claims 1 to 3, wherein in the step (1), the liquid space velocity of the subcritical naphtha is 0.1 to 5h-1Preferably 0.5 to 1 hour-1More preferably 0.5 to 0.8 hour-1。
5. The method according to any one of claims 1 to 4, wherein in step (2) the non-reactive gas is selected from nitrogen, argon, helium or a combination thereof, preferably nitrogen.
6. The method according to any one of claims 1 to 5, wherein in step (2), the temperature at which the inert gas is purged is 200 to 400 ℃, preferably 250 to 350 ℃; the pressure is 0.1-3 MPa, preferably 2-3 MPa; GHSV of 2000-6000 h-1Preferably 3000-5000 h-1(ii) a The time is 0.5 to 2 hours, preferably 1 hour.
7. The process according to any one of claims 1 to 6, wherein in step (3) the oxygen-containing gas is oxygen, air, heliox or a combination thereof, preferably air.
8. The process according to any one of claims 1 to 7, wherein in step (3), the temperature of oxidation is 300 to 500 ℃, preferably 350 to 450 ℃; the pressure is 0.5-2 MPa, preferably 1-1.5 MPa; GHSV of 2000-6000 h-1Preferably 3000-5000 h-1(ii) a The time is 0.5 to 2 hours, preferably 1 hour.
9. The method according to any one of claims 1 to 8, wherein, in step (4), the volume fraction of hydrogen gas used in the hydrogen reduction is not less than 99%.
10. The method of any one of claims 1-9, wherein in step (4), the hydrogen reduction conditions are: atmospheric pressureThe temperature is 250-450 ℃, and preferably 300-400 ℃; GHSV of 500-6000 h-1Preferably 1000 to 2000 hours-1(ii) a Reducing for 2-12 h, preferably 4-8 h at constant temperature.
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