CN107638889B - Method for regenerating waste hydrogenation catalyst - Google Patents
Method for regenerating waste hydrogenation catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 234
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 154
- 239000002699 waste material Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 24
- 238000000197 pyrolysis Methods 0.000 claims abstract description 76
- 239000000725 suspension Substances 0.000 claims abstract description 44
- 230000004913 activation Effects 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 22
- 230000003213 activating effect Effects 0.000 claims abstract description 10
- 239000003921 oil Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000000295 fuel oil Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 30
- 239000000428 dust Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 239000010779 crude oil Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- 238000005406 washing Methods 0.000 abstract description 6
- 239000004480 active ingredient Substances 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 4
- 239000003929 acidic solution Substances 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 73
- 239000011280 coal tar Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000009471 action Effects 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004939 coking Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011300 coal pitch Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
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- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for regenerating a waste hydrogenation catalyst. The method comprises the following steps: s1, carrying out dry distillation treatment on the waste hydrogenation catalyst to obtain a dehydrated and deoiled catalyst A and dry distillation gas; s2, activating the catalyst A to obtain a catalyst B; and S3, grinding the catalyst B to obtain the regenerated hydrogenation catalyst. The regenerated hydrogenation catalyst can be directly used in the suspension bed hydrogenation process, and can also be mixed with a new hydrogenation catalyst and then used in the suspension bed hydrogenation process. The method does not need acidic solution washing and roasting coke-removing treatment, but directly adopts dry distillation and activation treatment, thereby realizing effective compound utilization of carriers and active ingredients; and the loading performance of the carrier loading the active metal in the waste hydrogenation catalyst can not be damaged, and the catalytic hydrogenation performance of the carrier in the waste hydrogenation catalyst and the active metal loaded on the carrier in the waste hydrogenation catalyst in a suspension bed hydrogenation process is ensured.
Description
Technical Field
The invention belongs to the technical field of catalyst waste agent recovery, and particularly relates to a method for regenerating a waste hydrogenation catalyst, in particular to a method for regenerating a suspension bed waste hydrogenation composite catalyst.
Background
The suspension bed hydrogenation catalyst has a plurality of types, and the suspension bed hydrogenation composite catalyst is widely applied along with the improvement of the performance requirement of the hydrogenation catalyst. The hydrogenation composite catalyst has the performances of hydrodesulfurization, hydrocracking, hydrodenitrogenation and the like. The common composite catalyst for suspension bed hydrogenation is molybdenum-cobalt-alumina system, molybdenum-cobalt-nickel-alumina system, etc. and the heavy oil material, such as heavy oil, residual oil, high temperature coal tar, etc., is hydrogenated catalytically to light.
The hydrogenation composite catalyst after the hydrogenation process is converted into a waste catalyst. Metals such as Fe, Ni, V, Ca and the like in raw oil exist in the form of soluble metal organic compounds, and are decomposed and deposited on the surface and inside of a catalyst in the hydrogenation catalysis process to block micropores of the catalyst, and carbon is deposited on the surface and inside of the catalyst in the hydrogenation catalysis process to block micropores of the catalyst and cover metal active centers, so that the catalyst is finally deactivated.
In addition, the active centers of nickel, molybdenum and the like originally existing in the waste catalyst are all in the form of sulfide, so that the waste catalyst has flammability and toxicity, belongs to dangerous waste and needs to be treated.
The conventional catalyst treatment flow is as follows: waste catalyst burning, grinding, oxidizing roasting, alkaline leaching and recovering molybdenum and vanadium, acid leaching and recovering cobalt and nickel, and waste residue discharging. However, this flow has the following problems: 1) valuable metals such as molybdenum, nickel and the like are incompletely recovered, and the recovery rate is low; 2) 5-15% of oil is absorbed by the waste catalyst, so that oil products are wasted by burning during incineration treatment, and the environment is polluted; 3) the sulfur of the metal sulfide is oxidized in the processes of incineration and oxidizing roasting, and is converted into sulfur dioxide to pollute the environment; 4) the waste residue after treatment still contains heavy metal salt, and long-term stacking and treatment may cause secondary pollution.
Chinese patent document CN 102310005 a discloses a method for regenerating a heavy oil hydrotreating catalyst. It discloses the following steps: firstly, carrying out dry distillation on the inactivated heavy oil hydrotreating catalyst, then washing by adopting an acidic solution, and then carrying out roasting and coke removing treatment; the dry distillation temperature is 300-550 ℃; the acid solution is a solution containing hydrochloric acid, the ratio of the amount of washing acid to the amount of catalyst is 5 to 50L/Kg, and the acid concentration is 0.1 to 0.5 mol/L. Partial residual oil in the deactivated catalyst is recovered through the dry distillation step, and partial coking matter is subjected to dry distillation reaction to obtain liquid hydrocarbon, so that the recovery rate of valuable products is improved. The steps of dry distillation, acid washing, roasting and the like and proper conditions are organically combined, so that the deactivated hydrotreating catalyst is well regenerated.
However, it has been found through analysis that the technical solutions disclosed in the above patent documents have the following disadvantages: 1) the carriers and the active ingredients are not effectively utilized in a compound way in the recovery treatment process of the waste hydrogenation catalyst; 2) metal impurities are removed by acid washing, but some metal impurities can be used as active metals in the subsequent hydrogenation process, so that the metal impurities are not effectively utilized; 3) performing dry distillation on part of the coking substances to obtain liquid hydrocarbon, but effectively utilizing the rest coking substances; and then removing the carbon deposition by roasting, and not utilizing the carbon deposition.
Disclosure of Invention
Therefore, the invention aims to solve the defect that the carrier and the active ingredient are not effectively and compositely utilized in the process of recovering and treating the waste hydrogenation catalyst, and further provides the method for regenerating the waste hydrogenation catalyst, which has the advantages of simple steps, low investment cost, capability of effectively utilizing the carrier and the active ingredient in the waste hydrogenation catalyst, realization of regeneration of the waste hydrogenation catalyst and direct application of the waste hydrogenation catalyst in a hydrogenation process.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the method for regenerating the waste hydrogenation catalyst provided by the invention comprises the following steps:
s1, carrying out dry distillation treatment on the waste hydrogenation catalyst to obtain a dehydrated and deoiled catalyst A and dry distillation gas;
s2, activating the catalyst A to obtain a catalyst B;
and S3, grinding the catalyst B to obtain the regenerated hydrogenation catalyst.
The temperature of the dry distillation treatment step is 400-800 ℃, and the time is 2-2.5 h.
Further, the temperature of the dry distillation treatment step is 600-800 ℃, and the time is 2-2.5 h.
The temperature of the activation treatment step is 850-950 ℃, and the time is 0.5-2 h.
Further, the temperature of the activation treatment step is 900-950 ℃, and the time is 0.5-1 h.
Further, the activating agent adopted in the activating treatment step is water vapor.
The grinding treatment step is to grind the catalyst B to 20-200 μm.
Further, the grinding treatment step is to grind the catalyst B to 20-50 μm.
The waste hydrogenation catalyst is obtained by performing solid-liquid separation on a mixed solution of the waste catalyst and a heavy oil product discharged from the bottom of the vacuum tower after a heavy oil raw material is subjected to a suspension bed hydrogenation process.
And further, dedusting the dry distillation gas, mixing the obtained dust with the catalyst A, cooling the dedusted dry distillation gas to obtain a mixture of high-boiling-point oil and water and combustible low-boiling-point gas, and separating the mixture of the high-boiling-point oil and the water into crude oil and oily wastewater.
Further, the method comprises the following step of mixing the regenerated hydrogenation catalyst and the new hydrogenation catalyst according to the mass ratio of (2-7): 10 mixing to form a mixed hydrogenation catalyst.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the method for regenerating the waste hydrogenation catalyst provided by the embodiment of the invention, the waste hydrogenation catalyst is subjected to dry distillation treatment, activation treatment and grinding treatment in sequence to obtain the regenerated hydrogenation catalyst, and the regenerated hydrogenation catalyst can be directly used in a suspension bed hydrogenation process and can also be mixed with a new hydrogenation catalyst and then used in the suspension bed hydrogenation process. The method does not need acidic solution washing and roasting coke-removing treatment, but directly adopts dry distillation and activation treatment, thereby realizing effective compound utilization of carriers and active ingredients; and the loading performance of the carrier loading the active metal in the waste hydrogenation catalyst can not be damaged, and the catalytic hydrogenation performance of the carrier in the waste hydrogenation catalyst and the active metal loaded on the carrier in the waste hydrogenation catalyst in a suspension bed hydrogenation process is ensured.
2) According to the method for regenerating the waste hydrogenation catalyst provided by the embodiment of the invention, firstly, the waste hydrogenation catalyst is converted into the dehydrated and deoiled catalyst A and dry distillation gas through dry distillation treatment, and the metal deposited on the surface and in the waste hydrogenation catalyst is activated through the dry distillation treatment, such as metal fluidization and the like, so that the catalytic performance of the subsequent regenerated hydrogenation catalyst is improved; moreover, the dry distillation treatment can coke easily-coked substances (such as carbon) deposited on the surface and inside the waste hydrogenation catalyst into blocks, so that the activation treatment is favorable for activating the blocks into porous materials through subsequent activation treatment, micropores are prevented from being blocked, and meanwhile, the adsorption characteristic of the porous materials is exerted, and active metals are better adsorbed;
activating the catalyst A after the dry distillation treatment to obtain a catalyst B, expanding pores of the catalyst A through the activation treatment, activating the coking substance obtained after the dry distillation into a porous material, and optimizing the internal pore diameter structure of the whole catalyst B through the porous material and the catalyst A after pore expansion, so that the active metal in the hydrogenation catalyst can play a catalytic role; the temperature of the activation treatment step is limited to 850-950 ℃, the time is 0.5-2 h, the temperature and the time range are proper, the catalyst A can be effectively activated, the composite effect of the carrier and the active component is exerted, and the active metal in the subsequent regenerated hydrogenation catalyst is kept to exist in a sulfur state form;
and finally, grinding the catalyst B to 20-200 mu m through grinding treatment to prepare the regenerated hydrogenation catalyst which can be directly used in a suspension bed hydrogenation process.
3) The method for regenerating the waste hydrogenation catalyst provided by the embodiment of the invention ensures that the temperature of the dry distillation treatment is 400-800 ℃ and the time is 2-2.5 h, and finally obtains the dehydrated and deoiled catalyst A and dry distillation gas; more importantly, the coking degree of easily-coked substances deposited on the surface and inside the waste hydrogenation catalyst is controlled, and the problems that the coking degree is low, the subsequent activation treatment of the easily-coked substances is not facilitated, or the coking degree is high, the easily-coked substances are coked into large blocks, the carrier in the hydrogenation catalyst is damaged, micropores of the carrier are broken and collapsed, and the load performance of the carrier is influenced are avoided.
4) The method for regenerating the waste hydrogenation catalyst provided by the embodiment of the invention can realize the continuous use of the hydrogenation catalyst, improve the utilization efficiency of the waste hydrogenation catalyst, reduce the pollution to the environment caused by the emission or recovery of the waste hydrogenation catalyst from the source, and has great environmental protection and economic values.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific embodiments. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims.
The suspension bed hydrogenation catalyst used in the following examples and comparative examples may be a catalyst commonly used for suspension bed hydrogenation, which is well known to those skilled in the art, such as a suspension bed hydrogenation catalyst of a molybdenum-cobalt-nickel-alumina system, and the like, and may be specifically a suspension bed hydrogenation catalyst of model number HS-1 available from beijing trimerization new environment-friendly materials gmbh.
Example 1
The method for regenerating the waste hydrogenation catalyst provided by the embodiment comprises the following steps:
s1, under the action of a suspension bed hydrogenation catalyst, subjecting a heavy oil raw material, namely high-temperature coal tar, to a suspension bed hydrogenation process, and performing solid-liquid separation on a mixed solution of a waste catalyst and a heavy oil product discharged from the bottom of a vacuum tower by using an automatic back-flushing filter to obtain a filter cake, namely the waste hydrogenation catalyst;
s2, carrying out dry distillation treatment on the waste hydrogenation catalyst at 600 ℃ for 2.2h to obtain a dehydrated and deoiled catalyst A and dry distillation gas, then carrying out dust removal on the dry distillation gas, mixing the obtained dust with the catalyst A, cooling the dust-removed dry distillation gas to obtain a high-boiling-point oil and water mixture and combustible low-boiling-point gas, separating the high-boiling-point oil and water mixture through oil and water to obtain crude oil and oily wastewater, and filtering the combustible low-boiling-point gas to obtain clean combustible gas for storage and later use;
s3, carrying out steam activation treatment on the dehydrated and deoiled catalyst A at 900 ℃ for 1h to obtain a catalyst B;
s4, grinding the catalyst B to 20 mu m to obtain the regenerated hydrogenation catalyst.
Example 2
The method for regenerating the waste hydrogenation catalyst provided by the embodiment comprises the following steps:
s1, under the action of a suspension bed hydrogenation catalyst, subjecting heavy oil raw material-atmospheric residue oil to a suspension bed hydrogenation process, and performing solid-liquid separation on a mixed solution of a waste catalyst and a heavy oil product discharged from the bottom of a vacuum tower by using a plate-and-frame filter to obtain filter residue, namely the waste hydrogenation catalyst;
s2, carrying out dry distillation treatment on the waste hydrogenation catalyst at 700 ℃ for 2.1h to obtain a dehydrated and deoiled catalyst A and dry distillation gas, then carrying out dust removal on the dry distillation gas, mixing the obtained dust with the catalyst A, cooling the dust-removed dry distillation gas to obtain a high-boiling-point oil and water mixture and combustible low-boiling-point gas, separating the high-boiling-point oil and water mixture through oil and water to obtain crude oil and oily wastewater, and filtering the combustible low-boiling-point gas to obtain clean combustible gas for storage and later use;
s3, carrying out water vapor activation treatment on the dehydrated and deoiled catalyst A at 950 ℃ for 0.5h to obtain a catalyst B;
s4, grinding the catalyst B to 50 mu m to obtain the regenerated hydrogenation catalyst.
Example 3
The method for regenerating the waste hydrogenation catalyst provided by the embodiment comprises the following steps:
s1, under the action of a suspension bed hydrogenation catalyst, subjecting a mixture of heavy oil raw material, namely medium and low temperature coal tar and pitch to a suspension bed hydrogenation process, and centrifugally separating a mixed solution of a waste catalyst and a heavy oil product discharged from the bottom of a vacuum tower by using a centrifugal separator to obtain solid residues, namely the waste hydrogenation catalyst;
s2, carrying out dry distillation treatment on the waste hydrogenation catalyst at 400 ℃ for 2.5h to obtain a dehydrated and deoiled catalyst A and dry distillation gas, then carrying out dust removal on the dry distillation gas, mixing the obtained dust with the catalyst A, cooling the dust-removed dry distillation gas to obtain a high-boiling-point oil and water mixture and combustible low-boiling-point gas, separating the high-boiling-point oil and water mixture through oil and water to obtain crude oil and oily wastewater, and filtering the combustible low-boiling-point gas to obtain clean combustible gas for storage and later use;
s3, carrying out steam activation treatment on the dehydrated and deoiled catalyst A at 850 ℃ for 2h to obtain a catalyst B;
s4, grinding the catalyst B to 100 mu m to obtain the regenerated hydrogenation catalyst.
Example 4
The method for regenerating the waste hydrogenation catalyst provided by the embodiment comprises the following steps:
s1, under the action of a suspension bed hydrogenation catalyst, subjecting a mixture of a heavy oil raw material, namely medium and low temperature coal tar, and slag reduction to a suspension bed hydrogenation process, and centrifugally separating a mixed solution of a waste catalyst and a heavy oil product discharged from the bottom of a vacuum tower by using a centrifugal separator to obtain solid slag, namely the waste hydrogenation catalyst;
s2, carrying out dry distillation treatment on the waste hydrogenation catalyst at 500 ℃ for 2.4h to obtain a dehydrated and deoiled catalyst A and dry distillation gas, then carrying out dust removal on the dry distillation gas, mixing the obtained dust with the catalyst A, cooling the dust-removed dry distillation gas to obtain a high-boiling-point oil and water mixture and combustible low-boiling-point gas, separating the high-boiling-point oil and water mixture through oil and water to obtain crude oil and oily wastewater, and filtering the combustible low-boiling-point gas to obtain clean combustible gas for storage and later use;
s3, carrying out steam activation treatment on the dehydrated and deoiled catalyst A at 920 ℃ for 1.5h to obtain a catalyst B;
s4, grinding the catalyst B to 150 mu m to obtain the regenerated hydrogenation catalyst.
Example 5
The method for regenerating the waste hydrogenation catalyst provided by the embodiment comprises the following steps:
s1, under the action of a suspension bed hydrogenation catalyst, subjecting a heavy oil raw material, namely medium-low temperature coal tar, to a suspension bed hydrogenation process, and performing solid-liquid separation on a mixed solution of a waste catalyst and a heavy oil product discharged from the bottom of a vacuum tower by using a plate-and-frame filter to obtain filter residues, namely the waste hydrogenation catalyst;
s2, carrying out dry distillation treatment on the waste hydrogenation catalyst at 550 ℃ for 2.2h to obtain a dehydrated and deoiled catalyst A and dry distillation gas, then carrying out dust removal on the dry distillation gas, mixing the obtained dust with the catalyst A, cooling the dust-removed dry distillation gas to obtain a high-boiling-point oil and water mixture and combustible low-boiling-point gas, separating the high-boiling-point oil and water mixture through oil and water to obtain crude oil and oily wastewater, and filtering the combustible low-boiling-point gas to obtain clean combustible gas for storage and later use;
s3, carrying out steam activation treatment on the dehydrated and deoiled catalyst A at 930 ℃ for 1h to obtain a catalyst B;
s4, grinding the catalyst B to 200 mu m to obtain the regenerated hydrogenation catalyst.
Example 6
The method for regenerating the waste hydrogenation catalyst provided by the embodiment comprises the following steps:
s1, under the action of a suspension bed hydrogenation catalyst, subjecting a heavy oil raw material, namely medium-low temperature coal tar and high temperature coal tar, to a suspension bed hydrogenation process, and performing solid-liquid separation on a mixed liquid of the waste catalyst and a heavy oil product discharged from the bottom of a vacuum tower by using a plate-and-frame filter to obtain filter residues, namely the waste hydrogenation catalyst;
s2, carrying out dry distillation treatment on the waste hydrogenation catalyst at 700 ℃ for 2.4h to obtain a dehydrated and deoiled catalyst A and dry distillation gas, then carrying out dust removal on the dry distillation gas, mixing the obtained dust with the catalyst A, cooling the dust-removed dry distillation gas to obtain a high-boiling-point oil and water mixture and combustible low-boiling-point gas, separating the high-boiling-point oil and water mixture through oil and water to obtain crude oil and oily wastewater, and filtering the combustible low-boiling-point gas to obtain clean combustible gas for storage and later use;
s3, carrying out steam activation treatment on the dehydrated and deoiled catalyst A at 910 ℃ for 1h to obtain a catalyst B;
s4, grinding the catalyst B to 30 mu m to obtain the regenerated hydrogenation catalyst.
Comparative example 1
The method for regenerating the waste hydrogenation catalyst provided by the comparative example comprises the following steps:
s1, under the action of a suspension bed hydrogenation catalyst, subjecting a heavy oil raw material, namely high-temperature coal tar, to a suspension bed hydrogenation process, and performing solid-liquid separation on a mixed solution of a waste catalyst and a heavy oil product discharged from the bottom of a vacuum tower by using an automatic back-flushing filter to obtain a filter cake, namely the waste hydrogenation catalyst;
s2, carrying out dry distillation treatment on the waste hydrogenation catalyst at 400 ℃ for 2.5h to obtain a dehydrated and deoiled catalyst A and dry distillation gas, then carrying out dust removal on the dry distillation gas, mixing the obtained dust with the catalyst A, cooling the dust-removed dry distillation gas to obtain a high-boiling-point oil and water mixture and combustible low-boiling-point gas, separating the high-boiling-point oil and water mixture through oil and water to obtain crude oil and oily wastewater, and filtering the combustible low-boiling-point gas to obtain clean combustible gas for storage and later use;
s3, grinding the catalyst A to 20 mu m to obtain the regenerated hydrogenation catalyst.
Comparative example 2
The method for regenerating the waste hydrogenation catalyst provided by the comparative example comprises the following steps:
s1, under the action of a suspension bed hydrogenation catalyst, subjecting heavy oil raw material-atmospheric residue oil to a suspension bed hydrogenation process, and performing solid-liquid separation on a mixed solution of a waste catalyst and a heavy oil product discharged from the bottom of a vacuum tower by using a plate-and-frame filter to obtain filter residue, namely the waste hydrogenation catalyst;
s2, carrying out dry distillation treatment on the waste hydrogenation catalyst at 300 ℃ for 4h to obtain a dehydrated and deoiled catalyst A and dry distillation gas, then carrying out dust removal on the dry distillation gas, mixing the obtained dust with the catalyst A, cooling the dry distillation gas after dust removal to obtain a high-boiling-point oil and water mixture and combustible low-boiling-point gas, separating the high-boiling-point oil and water mixture through oil and water to obtain crude oil and oily wastewater, and filtering the combustible low-boiling-point gas to obtain clean combustible gas for storage and later use;
s3, carrying out water vapor activation treatment on the dehydrated and deoiled catalyst A at 950 ℃ for 0.5h to obtain a catalyst B;
s4, grinding the catalyst B to 50 mu m to obtain the regenerated hydrogenation catalyst.
Comparative example 3
The method for regenerating the waste hydrogenation catalyst provided by the comparative example comprises the following steps:
s1, under the action of a suspension bed hydrogenation catalyst, subjecting heavy oil raw material-atmospheric residue oil to a suspension bed hydrogenation process, and performing solid-liquid separation on a mixed solution of a waste catalyst and a heavy oil product discharged from the bottom of a vacuum tower by using a plate-and-frame filter to obtain filter residue, namely the waste hydrogenation catalyst;
s2, carrying out dry distillation treatment on the waste hydrogenation catalyst at 850 ℃ for 1.5h to obtain a dehydrated and deoiled catalyst A and dry distillation gas, then carrying out dust removal on the dry distillation gas, mixing the obtained dust with the catalyst A, cooling the dust-removed dry distillation gas to obtain a high-boiling-point oil and water mixture and combustible low-boiling-point gas, separating the high-boiling-point oil and water mixture through oil and water to obtain crude oil and oily wastewater, and filtering the combustible low-boiling-point gas to obtain clean combustible gas for storage and later use;
s3, carrying out water vapor activation treatment on the dehydrated and deoiled catalyst A at 950 ℃ for 0.5h to obtain a catalyst B;
s4, grinding the catalyst B to 50 mu m to obtain the regenerated hydrogenation catalyst.
Comparative example 4
The method for regenerating the waste hydrogenation catalyst provided by the comparative example comprises the following steps:
s1, under the action of a suspension bed hydrogenation catalyst, subjecting a mixture of heavy oil raw material, namely medium and low temperature coal tar and pitch to a suspension bed hydrogenation process, and centrifugally separating a mixed solution of a waste catalyst and a heavy oil product discharged from the bottom of a vacuum tower by using a centrifugal separator to obtain solid residues, namely the waste hydrogenation catalyst;
s2, carrying out dry distillation treatment on the waste hydrogenation catalyst at 700 ℃ for 2h to obtain a dehydrated and deoiled catalyst A and dry distillation gas, then carrying out dust removal on the dry distillation gas, mixing the obtained dust with the catalyst A, cooling the dry distillation gas after dust removal to obtain a high-boiling-point oil and water mixture and combustible low-boiling-point gas, separating the high-boiling-point oil and water mixture through oil and water to obtain crude oil and oily wastewater, and filtering the combustible low-boiling-point gas to obtain clean combustible gas for storage and later use;
s3, carrying out steam activation treatment on the dehydrated and deoiled catalyst A at 800 ℃ for 2h to obtain a catalyst B;
s4, grinding the catalyst B to 100 mu m to obtain the regenerated hydrogenation catalyst.
Comparative example 5
The method for regenerating the waste hydrogenation catalyst provided by the comparative example comprises the following steps:
s1, under the action of a suspension bed hydrogenation catalyst, subjecting a mixture of heavy oil raw material, namely medium and low temperature coal tar and pitch to a suspension bed hydrogenation process, and centrifugally separating a mixed solution of a waste catalyst and a heavy oil product discharged from the bottom of a vacuum tower by using a centrifugal separator to obtain solid residues, namely the waste hydrogenation catalyst;
s2, carrying out dry distillation treatment on the waste hydrogenation catalyst at 600 ℃ for 2h to obtain a dehydrated and deoiled catalyst A and dry distillation gas, then carrying out dust removal on the dry distillation gas, mixing the obtained dust with the catalyst A, cooling the dry distillation gas after dust removal to obtain a high-boiling-point oil and water mixture and combustible low-boiling-point gas, separating the high-boiling-point oil and water mixture through oil and water to obtain crude oil and oily wastewater, and filtering the combustible low-boiling-point gas to obtain clean combustible gas for storage and later use;
s3, carrying out steam activation treatment on the dehydrated and deoiled catalyst A at 1000 ℃ for 1h to obtain a catalyst B;
s4, grinding the catalyst B to 100 mu m to obtain the regenerated hydrogenation catalyst.
Experimental example 1
The regenerated hydrogenation catalysts prepared in the above examples and comparative examples are used in a heavy oil raw material suspension bed hydrogenation process, and the suspension bed hydrogenation catalytic performance of the regenerated hydrogenation catalysts is tested, wherein the specific test conditions are as follows: taking medium-low temperature coal tar as a reaction raw material, respectively adding 280g of medium-low temperature coal tar and 1% of the regenerated hydrogenation catalyst prepared in each embodiment and comparative example into a high-pressure reaction kettle with the volume of 1L, and carrying out the suspension bed hydrogenation reaction of the medium-low temperature coal tar at 450 ℃ under the condition of keeping the hydrogen pressure at 20MPa, wherein the reaction time is 1.5 h; after the reaction is finished, weighing the taken liquid oil according to the formula: the conversion rate of coal tar is less than 524 ℃ component mass (gas content)/raw oil mass x 100%, the conversion rate of inferior heavy oil is obtained, and the corresponding activity test results are shown in the following table 1:
TABLE 1
From the data in table 1 above, it can be seen that: the regenerated hydrogenation catalyst prepared by recycling through the method still keeps excellent suspension bed hydrogenation catalytic performance, the conversion rate of inferior heavy oil is slightly reduced compared with a new hydrogenation catalyst, but the regenerated hydrogenation catalyst prepared by the method has remarkable suspension bed hydrogenation catalytic performance compared with a hydrogenation catalyst which is not subjected to activation treatment, is not in the dry distillation temperature range of the invention, or is not prepared in the activation temperature range of the invention.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. A method for regenerating a waste hydrogenation catalyst comprises the following steps:
s1, carrying out dry distillation treatment on the waste hydrogenation catalyst to obtain a dehydrated and deoiled catalyst A and dry distillation gas;
s2, activating the catalyst A to form a porous material to obtain a catalyst B;
s3, grinding the catalyst B to obtain a regenerated hydrogenation catalyst;
the activating agent adopted in the activating treatment step is water vapor;
the time of the activation treatment step is 0.5h-2 h;
the temperature of the activation treatment step is 850-950 ℃.
2. The process according to claim 1, wherein the dry distillation treatment step is carried out at a temperature of 400 ℃ to 800 ℃ for a time of 2h to 2.5 h.
3. The process according to claim 2, wherein the dry distillation treatment step is carried out at a temperature of 600 ℃ to 800 ℃ for a time of 2h to 2.5 h.
4. The method according to claim 1, wherein the temperature of the activation treatment step is 900 ℃ to 950 ℃ and the time is 0.5h to 1 h.
5. The method according to any one of claims 1 to 4, wherein the grinding treatment step is to grind the catalyst B to 20 to 200 μm.
6. The method according to claim 5, wherein the grinding treatment step is to grind the catalyst B to 20 to 50 μm.
7. The method according to any one of claims 1 to 4, wherein the waste hydrogenation catalyst is obtained by subjecting a mixed solution of the waste catalyst and the heavy oil discharged from the bottom of the vacuum tower to solid-liquid separation after the heavy oil raw material is subjected to the suspension bed hydrogenation process.
8. The method according to any one of claims 1 to 4, further comprising dedusting the dry distillation gas, mixing the obtained dust with the catalyst A, and cooling the dedusted dry distillation gas to obtain a mixture of high-boiling-point oil and water and combustible low-boiling-point gas, wherein the mixture of high-boiling-point oil and water is subjected to oil-water separation to obtain crude oil and oily wastewater.
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| CN110760339A (en) * | 2019-11-04 | 2020-02-07 | 武汉金中石化工程有限公司 | Suspension bed hydrogenation residue treatment process method |
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