CN111437889A - Regeneration method of catalyst of hydrogenation system for producing hydrogen peroxide by anthraquinone process - Google Patents
Regeneration method of catalyst of hydrogenation system for producing hydrogen peroxide by anthraquinone process Download PDFInfo
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- 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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- 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
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
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Abstract
The invention belongs to the technical field of chemical production, and particularly relates to a regeneration method of a catalyst of a hydrogenation system for producing hydrogen peroxide by an anthraquinone process, which comprises the steps of material returning, washing of a mixed solution of aromatic hydrocarbon and trioctyl phosphate, steam purging, nitrogen drying, screening outside a tower, refilling, hot water circulation, steam purging, hydrogen activation and aromatic hydrocarbon soaking circulation; soaking the mixture of hot arene and trioctyl phosphate solution and circulating the mixture through a circulating washing pump to dissolve and separate anthraquinone and its degradation product adsorbed on the surface of the catalyst and in the micropores; then, removing alumina powder, alkali liquor and impurities in the catalyst by steam blowing accompanied with hot desalted water; the impurities such as dry alumina powder, catalyst powder, broken ceramic balls and the like are screened out after being discharged and swept by a vibrating screen and a fan, so that the regeneration effect and the regeneration activity of the catalyst are improved; after the hot saturated steam purging oxidation and hydrogen reduction, the aromatic hydrocarbon is soaked, so that the activity of the catalyst is further improved, and the service life of the catalyst is prolonged.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a regeneration method of a catalyst of a hydrogenation system for producing hydrogen peroxide by an anthraquinone process.
Background
The anthraquinone process of producing hydrogen peroxide solution with 2-ethyl anthraquinone and tetrahydro 2-ethyl anthraquinone as carrier and trioctyl phosphate and heavy arene as solvent includes the steps of hydrogenation, oxidation, extraction, post-treatment and preparation. The hydrogenation process mainly functions in that working solution and hydrogen gas flow downwards in a hydrogenation tower provided with a catalyst bed layer in a cocurrent mode to carry out hydrogenation reaction. The hydrogenation tower is divided into an upper section, a middle section and a lower section, and after the catalyst bed layer operates for a period of time, the activity is reduced or inactivated, and regeneration treatment is needed. The commonly used regeneration method is a steam method, i.e. organic impurities and inorganic impurities adsorbed on the catalyst are washed clean by steam to restore the activity of the catalyst, and the steam regeneration process comprises material returning, steam regeneration, nitrogen drying and activation. The problems of the existing steam method for catalyst regeneration are as follows: (1) only steam is used for blowing, alkali liquor, anthraquinone and anthraquinone degradation products adsorbed in catalyst micropores cannot be effectively dissolved and separated, so that the catalyst micropores are blocked, and the regeneration effect is poor; (2) alumina powder on the surface of the catalyst, catalyst powder in the bed layer and damaged ceramic balls cannot be effectively removed, so that the pressure difference of the bed layer is increased, and the activity of the catalyst is reduced; (3) after the catalyst is regenerated, cold nitrogen is adopted for drying, the treatment time is long, the effect is poor, and the activity of the regenerated catalyst is influenced.
In the prior art, for example, a Chinese patent with an authorization publication number of 'CN 1111448C' discloses a palladium catalyst regeneration method, and the technical scheme is that a waste catalyst filled in a stainless steel sieve is cleaned by hot water with the temperature close to 100 ℃, part of organic impurities and most of inorganic impurities are washed, then the waste catalyst is drained, enters a roasting furnace for roasting, and finally is discharged from the furnace, cooled and packaged; the technical scheme can prolong the service life of the palladium catalyst, but needs to adopt a roasting furnace for roasting treatment, correspondingly increases regeneration equipment and regeneration procedures, is inconvenient to operate and is easy to cause damage to the palladium catalyst.
Further, for example, a Chinese patent with an issued publication number of "CN 104511315B" discloses a method for regenerating a palladium catalyst for hydrogenation reaction; in the technical scheme, the method has the advantages that aromatic hydrocarbon washing is added before steam washing, hot water washing and tower external washing are added after steam washing, so that impurities adsorbed on the palladium catalyst pellets are fully dissolved and separated, ceramic balls and crushed slag in the palladium catalyst are removed, the regeneration effect is improved, and the regeneration activity of the palladium catalyst is improved. The activated palladium catalyst is softened by aromatic hydrocarbon, so that the activity of the catalyst is further improved, the optimization of hydrogenation reaction operation is facilitated, and the service life of the palladium catalyst is prolonged. Although the technical scheme optimizes the catalyst regeneration operation and improves the regeneration effect, the technical scheme does not relate to the removal of impurities such as anthraquinone, alumina powder, catalyst powder, alkali liquor and the like adsorbed by the catalyst, and can influence the activity of the regenerated catalyst; meanwhile, corresponding equipment is required to be added for washing treatment outside all the towers, so that the operation is inconvenient; aromatic hydrocarbon is flammable and explosive, and certain potential safety hazard exists; aromatic hydrocarbon is easy to volatilize and has certain harm to human bodies.
Also, as disclosed in chinese patent publication No. CN104475175A, a method for regenerating a palladium catalyst used in the production of hydrogen peroxide by an anthraquinone process is disclosed, wherein the catalyst is removed from a fixed bed after being washed with steam, washed with 50 ℃ aromatic hydrocarbon until the surface of the catalyst is smooth and free of organic attachments, washed with desalted water and dried in the sun, so that impurities adsorbed on the palladium catalyst beads are sufficiently dissolved and separated, and simultaneously, ceramic beads and crushed slag in the palladium catalyst are removed, thereby improving the regeneration effect of the palladium catalyst and the regeneration activity of the palladium catalyst. Although the technical scheme optimizes the regeneration operation of the palladium catalyst and improves the regeneration effect, the anthraquinone adsorbed by the palladium catalyst cannot be dissolved and separated out by soaking and washing the aromatic hydrocarbon in the technical scheme. Corresponding equipment is added for the aromatic hydrocarbon soaking washing and desalted water washing treatment outside the tower, so that the operation is inconvenient and the treatment time is long; aromatic hydrocarbon is flammable and explosive, and certain potential safety hazard exists; aromatic hydrocarbon is easy to volatilize and has certain harm to human bodies.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a regeneration method of a catalyst of a hydrogenation system for producing hydrogen peroxide by an anthraquinone process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a regeneration method of a catalyst of a hydrogenation system for producing hydrogen peroxide by an anthraquinone process comprises the following steps:
(1) returning the hydrogenated liquid;
pumping all working solution of a catalyst bed layer in a hydrogenation tower into an alkaline preparation kettle for washing, and blowing the working solution of the catalyst bed layer with nitrogen to be clean, wherein the pressure is kept at 0.05-0.1 MPa;
(2) soaking the mixed solution of aromatic hydrocarbon and trioctyl phosphate for circular washing;
adding mixed solution of aromatic hydrocarbon and trioctyl phosphate into the hydrogenation tower through a regeneration liquid inlet and a regeneration steam distributor, heating to 45-50 ℃, and adding the mixed solution at the temperature of 200-250m3Continuously circulating the flow of the flow/h, filtering the flow by a filter, indirectly supplementing and pumping and washing the mixed solution of the aromatic hydrocarbon and the trioctyl phosphate, and circulating the mixed solution until the mixed solution is qualified;
(3) saturated steam purging;
adding water vapor into the hydrogenation tower through a regeneration liquid inlet and a regeneration steam distributor, simultaneously adding desalted water, and controlling the temperature of the catalyst bed layer to be 100-110 ℃; the steam amount is 1 ton of steam consumed per ton of catalyst per hour, and the steam is swept until the catalyst is qualified;
(4) circularly drying and cooling by nitrogen;
after the steam washing is stopped, introducing nitrogen from a nitrogen inlet, and slowly purging for 4 hours by using the nitrogen until the water discharge is reduced; drying by using a circulator and hot nitrogen circulating blowing, wherein the temperature of the nitrogen is controlled at 110 ℃ of 100-; stopping heating with nitrogen gas when the sewage is drained and no water exists, and circularly cooling to 25 ℃;
(5) discharging the catalyst in the tower and screening;
discharging the catalyst in the hydrogenation tower, screening by a vibrating screen and a fan, screening out alumina dust, catalyst powder, crushed ceramic balls and anthraquinone particles carried by a catalyst bed layer, putting a few parts of the screened catalyst with serious agglomeration into an aromatic hydrocarbon washing tank for washing, and then washing, filtering and airing by using desalted water;
(6) refilling;
refilling the screened, agglomerated and washed catalyst into a catalyst bed layer of the hydrogenation tower for continuous use;
(7) hot water circulation washing;
desalted water is added into the hydrogenation tower through a regeneration liquid inlet and is heated to 60-70 ℃ at the temperature of 200-3The flow rate of the/h is continuously circulated, and solid impurities are filtered by a filter; indirect replacement is needed during circulation till the desalted water is clear and transparent;
(8) steam purging and nitrogen drying;
adding steam into the hydrogenation tower through a regeneration liquid inlet and a regeneration steam distributor, and controlling the temperature of a catalyst bed layer to be 100-110 ℃; the steam amount is that each ton of catalyst consumes 1 ton of steam per hour, stop the steam to let in after the condensed water is clear and transparent; then a circulator is used for hot nitrogen circulating blowing and drying, the temperature of the nitrogen is controlled at 110 ℃ of 100-;
(9) activating hydrogen;
after the catalyst is qualified by the replacement of nitrogen, introducing hydrogen into the hydrogenation tower to activate the catalyst, wherein the amount of the hydrogen is controlled to be 100-fold and 200Nm3The activation temperature is 55-70 ℃, and the activation time is 19-21 h;
(10) soaking in aromatic hydrocarbon;
before use, hot aromatic hydrocarbon at 40-45 ℃ is introduced into the hydrogenation tower through a working solution inlet for soaking, so that the aromatic hydrocarbon flows through a catalyst bed layer, and circulation or soaking is carried out for 8-10h under the protection of nitrogen.
Preferably, in the step (2), the mixed solution of the aromatic hydrocarbon and the trioctyl phosphate is prepared by mixing the aromatic hydrocarbon and the trioctyl phosphate according to a volume ratio of 1: (3-4) mixing, wherein the aromatic hydrocarbon is C9 and C10 fractions, the content of the aromatic hydrocarbon is more than or equal to 96 percent, and the total sulfur content is less than or equal to 5 ppm; the content of trioctyl phosphate is more than or equal to 99 percent.
Compared with the prior art, the invention has the following technical effects:
the regeneration method of the catalyst of the hydrogenation system for producing hydrogen peroxide by the anthraquinone process, provided by the invention, comprises the steps of soaking the catalyst in a hot mixed solution of aromatic hydrocarbon and trioctyl phosphate under the protection of nitrogen, and circulating the catalyst by a circulating washing pump to fully dissolve and separate anthraquinone and degradation products thereof adsorbed on the surface and in micropores of the catalyst; further removing alumina powder, alkali liquor and impurities in the catalyst by steam blowing accompanied with hot desalted water; the impurities such as dry alumina powder, catalyst powder, broken ceramic balls and the like are further effectively screened out by discharging and sweeping through an electric vibrating screen and an axial flow fan, so that the regeneration effect and the regeneration activity of the catalyst are improved; after the hot saturated steam purging oxidation and hydrogen reduction, the aromatic hydrocarbon soaking treatment further improves the activity of the catalyst, is beneficial to optimizing the hydrogenation reaction operation, and prolongs the service life of the catalyst.
Drawings
FIG. 1 is a flow chart of a method of regenerating a catalyst according to the present invention;
FIG. 2 is a schematic view of the catalyst bed and the inlets for the various materials in the hydrogenation column of the present invention;
FIG. 3 is a schematic view of a catalyst bed in the present invention;
the reference numbers in the figures illustrate: the method comprises the following steps of 1-a hydrogenation tower, 2-a regenerated steam distributor, 3-a working liquid inlet, 4-a hydrogen inlet, 5-a nitrogen inlet, 6-a regenerated liquid inlet, 7-a catalyst bed layer, 8-a regenerated outlet, 9-a palladium catalyst layer, 10-an inert ball layer, 11-a steel wire mesh and 12-a supporting ball layer.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
FIG. 1 is a flow chart showing a method for regenerating a catalyst according to the present invention; the regeneration method comprises the processes of material returning, aromatic hydrocarbon and trioctyl phosphate mixed solution washing, steam purging, nitrogen drying, tower external screening, refilling, hot water circulation, steam purging, hydrogen activation and aromatic hydrocarbon soaking circulation. By combining the soaking circulation of the mixed solution of the aromatic hydrocarbon and the trioctyl phosphate, the saturated steam regeneration and the hot water circulation, the regeneration method of the catalyst is optimized, the damage of the catalyst is reduced, and the activity and the use method of the regenerated catalyst are improved. In the invention, the catalyst is a palladium catalyst.
Fig. 3 is a schematic diagram of a catalyst bed layer in the present invention, which includes an inert ball layer 10, a steel wire mesh 11, a palladium catalyst layer 9, a steel wire mesh 11 and a support ball layer 12, which are sequentially disposed in a hydrogenation tower 1 from top to bottom;
in one embodiment of the present invention, the inert balls of the inert ball layer 10 are
The ceramic ball of (1) is supported by the ball layer
Ceramic ball layer of
Is composed of ceramic ball layer, and
the ceramic ball layer is positioned at
On the ceramic ball layer.
The regeneration step of the present invention is specifically described below with reference to FIG. 2:
(1) returning the hydrogenated liquid;
pumping all working solution of a catalyst bed layer 7 in a hydrogenation tower 1 into an alkaline preparation kettle for washing, and blowing the working solution of the catalyst bed layer 7 with nitrogen to be clean, and keeping the pressure at 0.05-0.1 MPa;
(2) soaking the mixed solution of aromatic hydrocarbon and trioctyl phosphate for circular washing;
adding the mixed solution of aromatic hydrocarbon and trioctyl phosphate into the hydrogenation tower 1 through a regeneration liquid inlet 6 and a regeneration steam distributor 2, heating to 45-50 ℃, and adding the mixed solution at the temperature of 200-3Continuously circulating the flow of the flow/h, filtering the flow by a filter, indirectly supplementing and pumping and washing the mixed solution of the aromatic hydrocarbon and the trioctyl phosphate, and circulating the mixed solution until the mixed solution is qualified;
in the invention, a regenerated steam distributor 2 is arranged at the upper part of a catalyst bed layer 7 in a hydrogenation tower 1, the regenerated steam distributor 2 consists of a main pipe and a plurality of branch pipes, the branch pipes are positioned at two opposite sides of the main pipe, the main pipe extends to the outside of the hydrogenation tower 1, the lower parts of the branch pipes are provided with distribution holes, and the upper part of the main pipe is provided with gas-liquid holes; the regenerated steam distributor 2 sprays the mixed solution of the aromatic hydrocarbon and the trioctyl phosphate onto the catalyst bed layer 7 from the distribution holes and the gas-liquid holes uniformly.
In the step, mainly using the principle that the mixed solution of arene and trioctyl phosphate and anthraquinone are similar and compatible to dissolve anthraquinone, dissolving and separating anthraquinone in catalyst micropores to improve the activity of the catalyst, controlling the temperature at 45-50 ℃ for circulation, and filtering by a filter to remove solid impurities; the circulation temperature is controlled mainly because the dissolution temperature of the hydroanthraquinone is about 40 ℃, and the hydroanthraquinone in the catalyst micropores can not be dissolved and separated out due to the excessively low circulation temperature; meanwhile, the aromatic hydrocarbon is inflammable and explosive due to overhigh temperature, so that nitrogen is introduced for protection during circulation.
Further, in the step (2), the mixed solution of the aromatic hydrocarbon and the trioctyl phosphate is prepared by mixing the aromatic hydrocarbon and the trioctyl phosphate according to a volume ratio of 1: (3-4) mixing, wherein the aromatic hydrocarbon is C9 and C10 fractions, the content of the aromatic hydrocarbon is more than or equal to 96 percent (measured by a sulfonation method), and the total sulfur content is less than or equal to 5 ppm; the content of trioctyl phosphate is more than or equal to 99 percent. Specifically, the arene is dissolved 2-ethyl anthraquinone and degradation products thereof, and the trioctyl phosphate is dissolved hydroanthraquinone;
(3) saturated steam purging;
adding water vapor into the hydrogenation tower 1 through a regeneration liquid inlet 6 and a regeneration steam distributor 2, simultaneously adding desalted water, and controlling the temperature of a catalyst bed layer 7 to be 100-110 ℃; the steam amount is 1 ton of steam consumed per ton of catalyst per hour, in the process, the consumption of desalted water is mainly determined according to the temperature of the catalyst bed layer 7, and the steam is swept until the desalted water is qualified;
in the above steps, the catalyst is purged by using saturated steam, mainly the catalyst is oxidized and regenerated by using oxygen in the saturated steam, and the appropriate desalted water is added into the steam to better wash solid impurities such as alumina powder, catalyst powder and alkali liquor carried in the catalyst bed layer 7. (4) Circularly drying and cooling by nitrogen;
after steam washing is stopped, introducing nitrogen through a nitrogen inlet 5, and slowly purging for 4 hours by using the nitrogen, wherein the circulating amount of the nitrogen is determined according to the temperature of a catalyst bed layer 7 until the water discharge amount is reduced; drying by using a circulator and hot nitrogen circulating blowing, wherein the temperature of the nitrogen is controlled at 110 ℃ of 100-; stopping heating with nitrogen gas when the sewage is drained and no water exists, and circularly cooling to 25 ℃;
in the specific operation, the nitrogen heater is adopted to heat the nitrogen, and the hot nitrogen circulation has better water removal effect and shorter circulation time than the cold nitrogen circulation.
(5) Discharging the catalyst in the tower and screening;
discharging the catalyst in the hydrogenation tower 1, screening alumina dust, catalyst powder, crushed ceramic balls and anthraquinone particles carried by a catalyst bed layer 7 by a vibrating screen and a fan, putting a few parts of the screened catalyst with serious agglomeration into an aromatic hydrocarbon washing tank for washing, and then washing, filtering and airing by using desalted water;
(6) refilling;
the screened, agglomerated and washed catalyst is refilled into the catalyst bed layer 7 of the hydrogenation tower 1 for continuous use;
(7) hot water circulation washing;
desalted water is added into the hydrogenation tower 1 through a regeneration liquid inlet 6 and heated to 60-70 ℃ at the temperature of 200-3The flow rate of the/h is continuously circulated, and solid impurities are filtered by a filter; indirect replacement is needed during circulation till the desalted water is clear and transparent;
in the step, the alkali liquor adsorbed by the catalyst can be dissolved and separated, and meanwhile, impurities can be further filtered.
(8) Steam purging and nitrogen drying;
adding steam into the hydrogenation tower 1 through a regeneration liquid inlet 6 and a regeneration steam distributor 2, and controlling the temperature of a catalyst bed layer 7 to be 100-; the steam amount is that each ton of catalyst consumes 1 ton of steam per hour, stop the steam to let in after the condensed water is clear and transparent; then a circulator is used for hot nitrogen circulating blowing and drying, the temperature of the nitrogen is controlled at 110 ℃ of 100-; this is to activate the reduction catalyst with hydrogen at a high temperature (25 ℃ in the case of hydrogen activation of the procatalyst) to improve the activity of the regenerated catalyst.
(9) Activating hydrogen;
after the catalyst is qualified by replacing with nitrogen, introducing hydrogen into the hydrogenation tower 1 by using a hydrogen inlet 4 to activate the catalyst, wherein the amount of the hydrogen is controlled at 100-200Nm3The activation temperature is 55-70 ℃, and the activation time is 19-21 h;
(10) soaking in aromatic hydrocarbon;
before use, hot aromatic hydrocarbon at 40-45 ℃ is introduced into the hydrogenation tower 1 through a working solution inlet 3 for soaking, so that the aromatic hydrocarbon flows over a catalyst bed layer 7, and circulation or soaking is carried out for 8-10 hours under the protection of nitrogen. The surface and micropores of the catalyst are softened and wetted by the aromatic hydrocarbon, so that anthraquinone macromolecular substances in the working solution are prevented from entering catalyst channels to influence the activity of the catalyst; meanwhile, the selectivity of the catalyst can be improved by adopting arene softening.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (2)
1. A regeneration method of a catalyst of a hydrogenation system for producing hydrogen peroxide by an anthraquinone process is characterized by comprising the following steps:
(1) returning the hydrogenated liquid;
pumping all working solution of a catalyst bed layer in a hydrogenation tower into an alkaline preparation kettle for washing, and blowing the working solution of the catalyst bed layer with nitrogen to be clean, wherein the pressure is kept at 0.05-0.1 MPa;
(2) soaking the mixed solution of aromatic hydrocarbon and trioctyl phosphate for circular washing;
adding mixed solution of aromatic hydrocarbon and trioctyl phosphate into the hydrogenation tower through a regeneration liquid inlet and a regeneration steam distributor, heating to 45-50 ℃, and adding the mixed solution at the temperature of 200-250m3Continuously circulating the flow of the flow/h, filtering the flow by a filter, indirectly supplementing and pumping and washing the mixed solution of the aromatic hydrocarbon and the trioctyl phosphate, and circulating the mixed solution until the mixed solution is qualified;
(3) saturated steam purging;
adding water vapor into the hydrogenation tower through a regeneration liquid inlet and a regeneration steam distributor, simultaneously adding desalted water, and controlling the temperature of the catalyst bed layer to be 100-110 ℃; the steam amount is 1 ton of steam consumed per ton of catalyst per hour, and the steam is swept until the catalyst is qualified;
(4) circularly drying and cooling by nitrogen;
after the steam washing is stopped, introducing nitrogen from a nitrogen inlet, and slowly purging for 4 hours by using the nitrogen until the water discharge is reduced; drying by using a circulator and hot nitrogen circulating blowing, wherein the temperature of the nitrogen is controlled at 110 ℃ of 100-; stopping heating with nitrogen gas when the sewage is drained and no water exists, and circularly cooling to 25 ℃;
(5) discharging the catalyst in the tower and screening;
discharging the catalyst in the hydrogenation tower, screening by a vibrating screen and a fan, screening out alumina dust, catalyst powder, crushed ceramic balls and anthraquinone particles carried by a catalyst bed layer, putting a few parts of the screened catalyst with serious agglomeration into an aromatic hydrocarbon washing tank for washing, and then washing, filtering and airing by using desalted water;
(6) refilling;
refilling the screened, agglomerated and washed catalyst into a catalyst bed layer of the hydrogenation tower for continuous use;
(7) hot water circulation washing;
desalted water is added into the hydrogenation tower through a regeneration liquid inlet and is heated to 60-70 ℃ at the temperature of 200-3The flow rate of the/h is continuously circulated, and solid impurities are filtered by a filter; indirect replacement is needed during circulation till the desalted water is clear and transparent;
(8) steam purging and nitrogen drying;
adding steam into the hydrogenation tower through a regeneration liquid inlet and a regeneration steam distributor, and controlling the temperature of a catalyst bed layer to be 100-110 ℃; the steam amount is that each ton of catalyst consumes 1 ton of steam per hour, stop the steam to let in after the condensed water is clear and transparent; then a circulator is used for hot nitrogen circulating blowing and drying, the temperature of the nitrogen is controlled at 110 ℃ of 100-;
(9) activating hydrogen;
after the catalyst is qualified by the replacement of nitrogen, introducing hydrogen into the hydrogenation tower to activate the catalyst, wherein the amount of the hydrogen is controlled to be 100-fold and 200Nm3The activation temperature is 55-70 ℃, and the activation time is 19-21 h;
(10) soaking in aromatic hydrocarbon;
before use, hot aromatic hydrocarbon at 40-45 ℃ is introduced into the hydrogenation tower through a working solution inlet for soaking, so that the aromatic hydrocarbon flows through a catalyst bed layer, and circulation or soaking is carried out for 8-10h under the protection of nitrogen.
2. The method for regenerating a catalyst used in a hydrogenation system for producing hydrogen peroxide by an anthraquinone process according to claim 1, wherein in the step (2), the mixed solution of the aromatic hydrocarbon and the trioctyl phosphate is prepared by mixing the aromatic hydrocarbon and the trioctyl phosphate in a volume ratio of 1: (3-4) mixing, wherein the aromatic hydrocarbon is C9 and C10 fractions, the content of the aromatic hydrocarbon is more than or equal to 96 percent, and the total sulfur content is less than or equal to 5 ppm; the content of trioctyl phosphate is more than or equal to 99 percent.
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| CN113289694A (en) * | 2021-06-28 | 2021-08-24 | 广西田东达盛化工科技有限公司 | Method for regenerating palladium catalyst in production of hydrogen peroxide by anthraquinone process |
| CN113413834A (en) * | 2021-06-17 | 2021-09-21 | 杭州名鑫双氧水有限公司 | Method for prolonging service cycle of palladium catalyst of hydrogenation tower and hydrogenation tower system thereof |
| CN114046450A (en) * | 2021-10-28 | 2022-02-15 | 山东宏旭化学股份有限公司 | Two-in-one system and method for purging and replacing hydrocyanic acid pipeline |
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| CN115430465A (en) * | 2021-06-01 | 2022-12-06 | 中国石油化工股份有限公司 | Regeneration method of anthraquinone hydrogenation catalyst |
| CN115430465B (en) * | 2021-06-01 | 2024-01-05 | 中国石油化工股份有限公司 | Regeneration method of anthraquinone hydrogenation catalyst |
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| CN115745770A (en) * | 2022-12-08 | 2023-03-07 | 聊城鲁西双氧水新材料科技有限公司 | Method and system for recovering anthraquinone from inactivated alumina |
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